Method and apparatus for producing liquid containing fine bubbles

Abstract

One embodiment of the present disclosure is a method for producing a liquid containing fine bubbles, the method comprising: a generation step of generating droplets containing fine bubbles by atomizing the liquid with ultrasonic irradiation; and a recovery step of recovering the droplet into the recovery container by using a recovery mechanism including the recovery container.

Description

Technical Field

[0001] The present disclosure relates to a method and an apparatus for producing a liquid containing fine bubbles. Background Art

[0002] In recent years, technologies that apply the properties of minute bubbles such as microbubbles with a diameter of the micrometer order and nanobubbles with a diameter of the nanometer order are being developed. In particular, bubbles with a diameter of 100 μm or less are defined as fine bubbles, bubbles with a diameter of 1.0 μm to 100 μm are defined as microbubbles, and bubbles with a diameter of 1.0 μm or less are defined as ultrafine bubbles, and various useful properties of these fine bubbles have been confirmed. Please note that in this specification, ultrafine bubbles are abbreviated by the English initials UFB.

[0003] The patent documents listed below disclose technologies for generating fine bubbles and technologies for producing liquids containing fine bubbles. In these patent documents, after dissolving a desired gas in a liquid, such dissolved gas is precipitated by a dissolution-precipitation method to produce a liquid containing ultrafine bubbles, and in the step of obtaining water containing dissolved gas, bubbling or the like is generally used.

[0004] Citation List

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent No. 6118544

[0007] Patent Document 2: Japanese Patent No. 4456176

[0008] Patent Document 3: Japanese Patent Application Publication No. 2018-65124

[0009] Patent Document 4: Japanese Patent Application Publication No. 2015-116555 Summary of the invention

[0010] However, in the manufacturing method of the above patent document, most of the loaded gas flows out into the atmosphere without being dissolved in the liquid. In addition, when a method (such as a cyclone method) is used to reduce the bubble size of the desired gas in the liquid, millibubbles and microbubbles that exist in a mixed manner will float or disappear and flow out into the gas layer. Therefore, there is a situation where most of the gas flows out to the gas phase side and is wasted. In addition, the manufacturing method described in the above patent document requires a large amount of gas as a raw material, and thus requires a gas cylinder, etc.

[0011] In view of the above-mentioned problems, an object of the present disclosure is to provide a technology for efficiently producing a liquid containing fine bubbles.

[0012] One embodiment of the present disclosure is a method for manufacturing a liquid containing fine bubbles, the method comprising: a generation step of generating droplets containing fine bubbles by atomizing the liquid by ultrasonic irradiation; and a recovery step of recovering the droplets into a recovery container by using a recovery mechanism including a recovery container.

[0013] The present disclosure can efficiently produce fine bubbles.

[0014] Further features of the present disclosure will become more apparent from the following description of embodiments with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] [ Figure 1 ] Figure 1 This is a diagram for explaining a method for producing a liquid containing fine bubbles.

[0016] [ Figure 2 ] Figure 2 This is a diagram showing a state before a liquid containing fine bubbles is produced.

[0017] [ Figure 3 ] Figure 3 It is a diagram showing the state during the production of a liquid containing fine bubbles.

[0018] [ Figure 4 ] Figure 4 This is a diagram showing a state where the production of the liquid containing fine bubbles is completed.

[0019] [ Figure 5 ] Figure 5 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0020] [ Figure 6 ] Figure 6 It is a diagram showing the state during the production of a liquid containing fine bubbles.

[0021] [ Figure 7 ] Figure 7 This is a diagram showing a state where the production of the liquid containing fine bubbles is completed.

[0022] [ Figure 8 ] Figure 8 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0023] [ Fig. 9 ] Fig. 9 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0024] [ Fig.10] Fig.10 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0025] [ Fig.11 ] Fig.11 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0026] [ Fig.12 ] Fig.12 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0027] [ Fig.13 ] Fig.13 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0028] [ Fig.14 ] Fig.14 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0029] [ Fig.15 ] Fig.15 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0030] [ Fig.16 ] Fig.16 This is a diagram showing an example of use in which the recovery mechanism for liquid containing fine bubbles is tilted.

[0031] [ Fig.17 ] Fig.17 This is a diagram showing a recovery mechanism in which the wall has flexibility.

[0032] [ Fig.18 ] Fig.18 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0033] [ Fig.19 ] Fig.19 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0034] [ Fig. 20 ] Fig. 20 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles by indirect piezoelectric atomization.

[0035] [ Fig.21 ] Fig.21 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles by indirect piezoelectric atomization.

[0036] [ Fig. 22 ] Fig. 22 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles covered with a recovery container.

[0037] [ Fig.23 ] Fig.23 This is a diagram showing an example of a device for producing a liquid containing fine bubbles, which includes a plurality of transducers (atomized FB generating device) that emit ultrasonic waves.

[0038] [ Fig.24 ] Fig.24 This is a diagram for explaining a method for producing a liquid containing fine bubbles.

[0039] [ Fig.25 ] Fig.25 This is a diagram showing a state before a liquid containing fine bubbles is produced.

[0040] [ Fig.26 ] Fig.26 It is a diagram showing the state during the production of a liquid containing fine bubbles.

[0041] [ Fig. 27 ] Fig. 27 This is a diagram showing a state where the production of the liquid containing fine bubbles is completed.

[0042] [ Fig.28 ] Fig.28 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0043] [ Fig.29 ] Fig.29 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0044] [ Fig.30 ] Fig.30 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0045] [ Fig.31 ] Fig.31 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0046] [ Fig.32 ] Fig.32 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0047] [ Fig.33 ] Fig.33 This is a diagram showing an example of an apparatus for producing a liquid containing fine bubbles.

[0048] [ Fig.34 ] Fig.34 This is a diagram showing an example of a device for producing a liquid containing fine bubbles, which includes a plurality of transducers (atomized FB generating device) that emit ultrasonic waves. DETAILED DESCRIPTION

[0049] Hereinafter, embodiments according to the present disclosure will be described. Please note that the following embodiments are exemplary and are not intended to impose unnecessary limitations on the spirit of the present disclosure. In addition, in the present specification, fine bubbles (abbreviated as FB) refer to small bubbles composed of gas. In addition, a liquid containing fine bubbles refers to a liquid containing fine bubbles as small bubbles. It is also assumed that the gas of the fine bubbles is composed of one or more components, and the proportion of the gas components can also be adjusted by controlling the gas components in the recovery mechanism of the liquid containing fine bubbles. The desired gas component may exist in the liquid as fine bubbles, or may exist in a state dissolved in the liquid.

[0050] <Overview of Production of Liquid Containing Fine Bubbles>

[0051] In the following, by using Figure 1 A method for producing a liquid containing fine bubbles by irradiating the liquid with ultrasonic waves is described. Figure 1 (a) shows an overview of an apparatus for producing a liquid containing fine bubbles by irradiating the liquid with ultrasonic waves. Figure 1 (b) is extraction Figure 1 (a) is a diagram of region Ib and shows a hypothetical diagram in a liquid irradiated with ultrasonic waves. Figure 1 (c) shows a surface wave formed in the process of producing a liquid containing fine bubbles.

[0052] like Figure 1 As shown in (a), since the atomized FB generating device 101 that generates fine bubbles by atomizing the liquid irradiates the liquid with ultrasonic waves from the inside of the liquid, the molecules in the liquid vibrate in the propagation direction of the sound, thereby alternately generating high-pressure areas and low-pressure areas. In the low-pressure area, the pressure of the liquid molecules is lower than the vapor pressure, as shown in FIG. Figure 1 As shown in (b), fine bubbles 103, which are small bubbles of dissolved gas, are generated. Regarding the fine bubbles generated in the liquid, there are bubbles that are formed by the combination of fine bubbles and are released to the outside of the liquid by repeated expansion and contraction due to the influence of ultrasonic waves. In addition, there are bubbles that are broken by the pressure caused by vibration due to the influence of ultrasonic waves. Therefore, it is considered that small fine bubbles are relatively easy to remain in the liquid.

[0053] It is believed that the reasons for the atomization phenomenon at the gas-liquid interface are: Figure 1 As shown in (c), a surface wave is formed. When the vibration amplitude of the surface wave exceeds the critical point, any wave crest is destroyed, generating small droplets, thereby causing atomization. The "atomization" mentioned here refers to the generation of droplets 104 containing fine bubbles, that is, fine mist liquid.

[0054] In the case of atomization at the gas-liquid interface, a liquid containing fine bubbles is atomized and droplets are generated at the same time, which significantly produces a pressure relaxation effect. For this reason, fine bubbles are newly generated during atomization, and droplets containing the fine bubbles thus generated are generated. In the case where the droplets atomized in this way are small, ultrafine bubbles (abbreviated as UFB), that is, small fine bubbles, are selectively generated because large fine bubbles do not exist in the droplets. Thereafter, a liquid containing fine bubbles can be produced by recovering the droplets containing fine bubbles. Please note that when using Figure 2 In the case of the illustrated construction, since the recovery container 106 is sealed and the entire device is covered, droplets containing fine bubbles can be generated by irradiating the liquid with ultrasonic waves, and the droplets thus generated can be recovered as liquid containing fine bubbles without leaking to the outside.

[0055] As a method of atomizing a liquid by irradiating the liquid with ultrasonic waves, it is preferred that the thickness of the liquid provided on the vibrator is less than or equal to 15 cm, but this depends on the output and intensity of the vibrator used to irradiate the liquid with ultrasonic waves. In the case where the thickness of the liquid exceeds 15 cm, since the irradiation intensity of the ultrasonic waves for atomization increases, there is a concern that it may affect the liquid medium. In the case of water as a specific example of the liquid, there is a concern that the water molecules will become hydroxyl radicals, and the hydroxyl radicals will react with, for example, dissolved nitrogen as an atmospheric component to generate nitrogen oxide ions.

[0056] Note that the method of producing a liquid containing fine bubbles by applying ultrasonic vibration is not limited to the above method. Fig.24 Describe a method that differs from the above method. Fig.24 (a) is a perspective view of an atomized FB generating device 201 that generates fine bubbles by utilizing vibrations caused by the influence of ultrasonic waves, and Fig.24 (b) is a top view of the atomized FB generating device 201. Fig.24 As shown in (a), there is a grid 202 as fine holes in the central part of the upper surface of the atomizing FB generating device 201 having a cylindrical shape. These holes penetrate from the bottom side of the atomizing FB generating device 201, and liquid is supplied from the bottom side by capillary force, etc. The ultrasonic vibration of the vibrator 203 arranged at the peripheral part of the grid 202 is applied to the supplied liquid to generate fine droplets (so-called atomization). It is believed that in this case, the dissolved gas contained in the liquid becomes fine bubbles, i.e., small bubbles, due to the rapid change in pressure caused by the ultrasonic vibration. In addition, it is also believed that while becoming fine droplets (being atomized), the liquid absorbs the gas in the space, thereby generating fine bubbles.

[0057] In order to prevent fine bubbles from being released and diffusing to the outside of the liquid during recovery, the average value of the relative humidity derived from the droplet composition in the space is set to be greater than or equal to 80%, so that the diffusion prevention effect can be expected. In the case where the average value is less than 80%, the droplets containing fine bubbles will evaporate, so only a small amount of liquid can be recovered, resulting in a problem of reduced recovery. In addition, when the weight ratio of the liquid containing fine bubbles to the raw liquid of the liquid containing fine bubbles is less than 80%, there is a concern that the atomized droplets will flow out of the manufacturing device, resulting in a problem of reduced yield.

[0058] As the gas in the recovery mechanism, unless otherwise specified, the air in the manufacturing device installation environment can be used; however, the gas is not limited to air. Other possible gases in the recovery mechanism include oxygen, nitrogen, hydrogen, ozone, helium, carbon dioxide, methane, ethane, propane, butane, chlorine, chlorine dioxide, etc., and mixed gases of these gases. In addition, dry air (air obtained by removing moisture from the above air) and clean dry air (air obtained by removing particles from the above dry air) are also preferred. Please note that clean dry air can be obtained by using a recovery mechanism inserted with a dust filter, a mist filter, a heater for removing moisture, etc. A chemical filter can be installed on such a recovery mechanism.

[0059] In the case of using ozone-containing gas as the gas in the recovery mechanism, although there is no particular limitation, it is preferred that an ozone gas generating unit that generates ozone gas by a discharge system or ultraviolet irradiation is provided in the recovery mechanism to create an ozone-containing atmosphere inside the recovery mechanism. It is preferred to create an ozone-containing atmosphere because the risk of generating nitrogen oxides is reduced when ozone gas is generated in the atmosphere by ultraviolet irradiation. As a light source, it is preferred that light can emit light having an absorption wavelength of oxygen molecules, and it is more preferred that light can emit light having a wavelength of less than or equal to 240nm, and a known light source can also be used. For example, a low-pressure mercury lamp using quartz as glass is representative, and similar effects can be obtained using the latest mercury-free ozone lamp. Specifically, such lamps include excimer lamps, CARE222 (manufactured by Ushio, Inc.), and the like. Of course, in order to use light of these wavelengths without blocking, a transmissive material such as quartz glass can be used as a component to be used in the optical path.

[0060] In addition, when the ozone-containing fine bubble water is produced, the ozone can be deactivated in the recovery mechanism by using a known chemical method such as a manganese-based catalyst or activated carbon. However, it is also preferred to use a general-purpose germicidal lamp that can emit light with a wavelength of 254nm (i.e., the absorption wavelength of ozone) in the recovery mechanism to deactivate the ozone.

[0061] Note that as a liquid contact member for the UFB liquid containing ozone after ultraviolet irradiation, it is preferable to use an ozone-resistant material. As an ozone-resistant material, it is preferable to use titanium as a metal, a fluorine-based polymer (PFA, PTFE, etc.) as a resin, quartz as a glass, etc.

[0062] The liquid to be atomized by ultrasonic irradiation is not particularly limited, and can be water, an organic liquid, an ionic liquid, etc., but preferably water. The means for supplying the liquid to be atomized by ultrasonic irradiation is not particularly limited. For example, when water is used as the liquid to be atomized, water can be supplied to the tank in batches, or water can be supplied from a water pipe through a pipeline, or moisture in the atmosphere can be supplied as condensed water using a Peltier element or the like. By shaking and stirring the liquid to be atomized by ultrasonic irradiation under the desired gas atmosphere, water dissolved with the desired gas is generated according to Henry's law. Under an oxygen atmosphere, 45ppm of oxygen-containing water can be obtained. On the other hand, under an ambient atmosphere, water dissolved with about 8.4ppm of oxygen can be generated at room temperature.

[0063] Water includes water that has been purified to have a high purity (ultrapure water), tap water, hard water, etc. In addition, water may contain solutes dissolved therein (electrolytes formed by dissociation of sodium chloride, silver nitrate, etc., free chlorine, amino acids, sugars, buffers, dyes, etc.), and may also contain dispersed bodies (pigments, dispersants, cells, bubbles, emulsions, titanium oxide, emulsifiers, etc.).

[0064] In addition, a mixed solution of water and an organic liquid can also be used. The water-soluble organic solvent to be used is not particularly limited, but specific examples thereof include the following: alkyl alcohols having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and tert-butanol, amides such as N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylformamide, and N,N-dimethylacetamide, ketones or ketoalcohols such as acetone and diacetone alcohol, cyclic ethers such as tetrahydrofuran and dioxane, ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol.

[0065] 1,2-Butanediol, 1,3-Butanediol and 1,4-Butanediol. In addition, diols such as 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol and thiodiethylene glycol.

[0066] Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether. In addition, lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and triethylene glycol monobutyl ether.

[0067] Polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Triols such as glycerol, 1,2,6-hexanetriol and trimethylolpropane.

[0068] Note that the water-soluble organic solvents listed above may be used alone, or two or more thereof may be used in combination.

[0069] Furthermore, as the liquid of the gas solution, a liquid derived from a living body, specifically, blood, cerebrospinal fluid, etc. can also be used.

[0070] The ultrasonic radiating unit for atomization is not particularly limited, but piezoelectric materials are preferred. Piezoelectric materials are widely used in applications such as actuators, vibrators for emitting ultrasonic waves, micro power supplies, high voltage generating devices, etc. Many piezoelectric substances used in these applications are so-called PZT materials, and are oxides containing lead (Pb), zirconium (Zr) and titanium (Ti). For this reason, from the perspective of environmental issues, the development of lead-free piezoelectric materials has been ongoing.

[0071] Lead-free piezoelectric materials include, for example, Ba-based perovskite oxides represented by the general formula BaM'O3. Although M' represents an element or a crystal mixture composed of two or more elements in a certain composition ratio, the general formula BaM'O3 must be satisfied so that the charge becomes neutral. Piezoelectric materials represented by BaM'O3 include, for example, BaTiO3 that has a tetragonal structure at near room temperature.

[0072] As the ultrasonic irradiation unit, a commercially available unit can be used. For example, such units include the immersion ultrasonic atomization unit IM1-24 manufactured by SEIKO GIKEN INC., the cordless fragrance diffuser MJ-CAD1 44486320 manufactured by Ryohin Keikaku Co., Ltd. (commercially available as a humidifier), etc., but are not limited to these. As an ultrasonic atomization generating device of a commercially available product, an atomizer, etc. are also preferred examples. In addition, the following method is also preferred: a liquid as a liquid raw material containing fine bubbles is separated from a liquid phase of a piezoelectric atomization unit that emits ultrasonic waves, and the liquid is indirectly piezoelectrically atomized. The liquid phase of the piezoelectric atomization unit that emits ultrasonic waves is not particularly limited, but preferably QUAVA mini manufactured by KAIJO Corporation, etc. In addition, the oscillator frequency is not particularly limited, but preferably 1.6MHz.

[0073] In addition, as an example of improving acid resistance, alkali resistance, solvent resistance, and corrosion resistance (such as ozone water), it is also preferred to cover the liquid contact member of the piezoelectric element with a fluorine-based resin, a titanium-based member, or a glass member such as quartz.

[0074] <Manufacturing of Liquid Containing Fine Bubbles>

[0075] Hereinafter, the method of using Figure 1 (a) is a process for producing a liquid containing fine bubbles using a production apparatus having the structure shown.

[0076] Figure 2 1 shows the state before the manufacturing device starts to operate. In this state, by energizing the atomized FB generating device 101, ultrasonic vibration starts, as shown in FIG. Figure 3 As shown, ultrasonic vibration is applied to the liquid to generate a liquid column to cause atomization, so that droplets of the liquid containing fine bubbles float and spread. Figure 4 As shown in (a), by recovering the floating and diffused droplets using a recovery mechanism, a liquid containing fine bubbles 105 is obtained. Figure 4 (b) is extraction Figure 4 This is an enlarged view of region IVb in (a), and shows the fine bubbles 103 thus recovered.

[0077] Here, as a different form from the manufacturing apparatus described so far, a Figures 5 to 9 A production apparatus having a configuration in which a recovery mechanism is provided as a unit separate from a production mechanism is described. Figure 5 1 shows the state before the manufacturing device starts to operate. In this state, the atomized FB generating device 101 is powered on to start ultrasonic vibration and apply ultrasonic vibration to the liquid 102. Then, as shown in FIG. Figure 6 As shown, a liquid column is generated to cause atomization, so that liquid droplets 104 containing fine bubbles float and diffuse. Figure 7 As shown in (a), by recovering the floating and diffused droplets into the recovery container 106, a liquid containing fine bubbles 105 is obtained. Figure 7 (b) is extraction Figure 7 This is an enlarged view of region VIIb in (a) and shows fine bubbles 103 in a liquid containing fine bubbles 105.

[0078] like Figures 5 to 7 As shown, by separating the recovery mechanism into a unit different from the vibrator side where the fine bubbles are generated, the liquid containing the fine bubbles can be prevented from returning to the vibrator side. In this way, as described above, the fine bubbles can be prevented from bursting due to pressure when they are affected by the vibration due to being affected by the ultrasonic wave again.

[0079] Please note that as a unit for atomizing liquid, in addition to Figure 3 In addition to the types of immersion shown, other types include Figure 8 The type shown in the figure, in which a liquid introduction channel and a liquid film are arranged on the surface of the piezoelectric atomizing element, and the liquid is supplied to the surface of the piezoelectric atomizing element by capillary action for atomization. In addition, various types of units can also be used, such as Fig. 9The float type piezoelectric element shown includes a float for making the piezoelectric element float to act in a liquid surface layer, so as to maintain a distance between the surface of the piezoelectric element and the air-liquid interface.

[0080] In addition, the above description is a basic description based on the configuration of the manufacturing apparatus shown in the figure, and by appropriately adding the configuration of the manufacturing apparatus, the productivity of the liquid containing fine bubbles can also be improved.

[0081] As one example, Fig.10 The structure of recovering liquid containing fine bubbles by bringing floating and diffused liquid droplets into contact with a medium (intermedium) having a partial mesh structure is shown. Only the liquid droplets can be recovered by contacting with the mesh structure.

[0082] Also, as another example, Fig.11 The structure for recovering the liquid containing fine bubbles by using a recovery fan is shown. By using the recovery fan, the liquid 105 containing fine bubbles can be directly recovered in the recovery container 106.

[0083] And, as another example, Fig.12 A structure equipped with a blower, a liquid supply tank, a liquid column growth inhibition plate, a water level sensor, a fractionation tube, an exhaust fan and a water collection port is shown. By arranging the blower and the exhaust fan, the efficiency of the atomized aerosol moving to the recovery mechanism is improved. In addition, by arranging the liquid supply tank and the water level sensor, the liquid level of the raw material can be controlled during the operation of the manufacturing device, the dry burning of the piezoelectric atomization unit can be suppressed, and continuous operation for a long time can be achieved. In addition, by arranging the liquid column growth inhibition plate, it is expected to prevent the bulk liquid other than the fine droplets from scattering. In addition, by arranging the fractionation tube on the connecting pipe, it is expected to efficiently convert the fine droplets in the atomized state into bulk liquid and recover the bulk liquid. In addition, by arranging the fractionation tube in the connection part with the exhaust fan, it is also expected to suppress the atomized fine droplets from flowing out to the outside of the manufacturing device. In addition, by arranging the water collection port including the stopcock, the liquid containing fine bubbles can be collected without opening the manufacturing device.

[0084] Fig.13 An example is shown below: a pump, a gas tank, a valve, and a three-way stopcock are provided to control and adjust the gas composition in a recovery mechanism including a recovery container 106. By placing the recovery container in a decompressed state with a pump while the valve is closed, and phage is applied to the gas composition filled in the gas tank with the desired gas type in the desired proportion, the gas composition in the recovery container 106 can be controlled to a desired atmosphere. Thereafter, by opening the valve, atomizing the liquid 102 by ultrasonic irradiation, and recovering the bulk liquid, a liquid containing fine bubbles of the desired gas composition can be produced. Alternatively, as Fig.12As shown, by also arranging a unit and a stirring unit having the same structure on the mist FB generating device 101 side, it is possible to control the desired gas component to be obtained from the stage of the dissolved gas component in the raw material liquid.

[0085] Fig.14 An example of a device for producing a liquid containing fine bubbles of ozone is shown. The liquid containing fine bubbles of ozone can be produced by using an ozone generator provided in a recovery container 106 in a recovery mechanism, adjusting the atmosphere in the recovery mechanism to a desired ozone gas concentration, then atomizing the liquid 102, and recovering the bulk liquid.

[0086] Fig.15 An example is shown in which a liquid tank is provided inside the recovery container 106. Liquid is stored in the liquid tank, the mist FB generating device 101 is attached to the liquid tank, and the entire liquid tank is covered with the recovery container 106. Fig.16 Shown by tilt Fig.15 An example of using the recycling mechanism shown to improve recycling efficiency. Fig.17 An example is shown in which a flexible material is used for the wall of the recovery container 106. By providing flexibility, the recovery container 106 can be deformed by applying force from the outside to generate an internal airflow, thereby efficiently recovering the atomized liquid droplets from the inside of the liquid tank.

[0087] Fig.18 This is a diagram showing an example of a production apparatus for a liquid containing fine bubbles, which can adjust the dissolved gas component and the gas component and partial pressure in a recovery container.

[0088] Fig.19 An example of a manufacturing device in which a liquid tank for supplying a raw material liquid and a recovery mechanism for fine bubbles are integrated is shown. As shown in the figure, the manufacturing device is covered with a recovery container 106. By integrating the liquid tank for supplying a raw material liquid and the recovery mechanism, it is expected that the manufacturing device can be miniaturized and lightweight.

[0089] Fig. 20 1 is a diagram showing an example of a manufacturing device for separating liquids. Specifically, the manufacturing device separates a first liquid from a second liquid, the first liquid being used as a raw material for a liquid containing fine bubbles, and the second liquid being irradiated with ultrasonic waves. By irradiating the second liquid with ultrasonic waves, the first liquid is indirectly piezoelectrically atomized. This configuration is advantageous in the case of generating fine bubbles in such a liquid that corrodes an ultrasonic generating unit.

[0090] Here, by using Fig.25 To describe by using Fig.24 The manufacturing apparatus shown shows a process for manufacturing a liquid containing fine bubbles.

[0091] Fig.25 It shows the state of the manufacturing device before it starts operating. Fig.25 As shown, a storage chamber 204 for storing water is installed on the bottom surface of the recovery container 106 of the manufacturing device. The atomized FB generating device 201 is installed on the storage chamber 204. Inside the storage chamber 204, a sponge is placed at a position corresponding to the upper part of the stored water. The water inside the storage chamber 204 is supplied to the atomized FB generating device 201 through the sponge by capillary force and the like, and reaches the grid 202. Fig.25 In the state shown, the mist FB generating device 201 is powered on to start ultrasonic vibration. The ultrasonic vibration is applied so that the droplets of the liquid containing fine bubbles are formed as shown in FIG. Fig.26 Then, as Fig. 27 As shown, the floating and diffused droplets are recovered by the recovery mechanism. Figure 4 As in the case of (a), a liquid containing fine bubbles 105 is obtained. The storage chamber 204 and the space where droplets of the liquid containing fine bubbles are accumulated are covered with the wall surface of the recovery container 106.

[0092] Please note that the manufacturing device using the atomized FB generating device 201 is not limited to Fig.25 Here, we will use Figures 28 to 30 Describes a form different from the above. Figures 28 to 30 In, relative to Fig.25 The atomizing FB generating device 201 is installed in a form with a changing direction so that the direction of the generated mist is different.

[0093] Fig.28 Shown with Fig.25 The state before the different manufacturing devices start to operate. By energizing the mist FB generating device 201 in this state, ultrasonic vibration starts. Then, ultrasonic vibration is applied to the liquid, causing droplets of the liquid containing fine bubbles to float and spread. Fig.28 As shown, since the mist FB generating device 201 is installed horizontally, the droplets of the liquid containing fine bubbles will fall due to their own weight, and the fallen liquid can be recovered using the recovery container 106.

[0094] Fig.29 and Fig.28 The same as in the figure shows the state before the manufacturing device starts to operate, but Fig.28 In contrast, the atomized FB generating device 201 is installed obliquely downward. In this state, by energizing the atomized FB generating device 201, ultrasonic vibration starts, and when ultrasonic vibration is applied to the liquid, droplets of the liquid containing fine bubbles float and spread. After that, the droplets of the liquid containing fine bubbles fall due to their own weight and accumulate in the recovery container 106. The user can recover the liquid containing fine bubbles accumulated in the recovery container 106.

[0095] Fig.30 and Fig.28 , Fig.29 The same as in the figure shows the state before the manufacturing device starts to operate, but Fig.28 , Fig.29 In contrast, the atomized FB generating device 201 is shown in a form in which it is installed downward. In this state, by energizing the atomized FB generating device 201, ultrasonic vibration starts, and when ultrasonic vibration is applied to the liquid, droplets of the liquid containing fine bubbles float and spread. After that, the droplets of the liquid containing fine bubbles fall due to their own weight and accumulate in the recovery container 106. The user can recover the liquid containing fine bubbles accumulated in the recovery container 106. Please note that in Fig.29 or Fig.30 In the form of, since the water in the storage chamber 204 moves downward due to its own weight, the water can reach the grid 202 even if a sponge is not inserted in the storage chamber 204. Note that although the form of providing one atomized FB generating device 201 is shown in this example, the manufacturing device may include a plurality of atomized FB generating devices 201. For example, Fig.34 As shown, the manufacturing device may include three atomization FB generating devices 201 .

[0096] exist Fig.25 In the form of, the droplets of the liquid containing fine bubbles may adhere to the surface of the grid 202 in some cases, thereby causing the liquid to fail to be discharged. Figures 28 to 30 In each form, since the possibility of droplets of the liquid containing fine bubbles adhering to the surface of the grid 202 is reduced, it is possible to prevent a decrease in productivity due to discharge failure. In addition, in the case where the gas contained in the liquid containing fine bubbles to be produced is active oxygen such as ozone, Figures 28 to 30 In each form, since the mist FB generating device 201 can be installed on the upper part of the recovery container 106, the degradation of the mist FB generating device 201 can be suppressed.

[0097] Hereinafter, the humidity in the recovery mechanism (recovery container 106, etc.) will be described. The humidity described in this specification is relative humidity, and the atmosphere in which the gas component whose relative humidity is to be obtained is completely absent in the recovery mechanism is regarded as 0%, and the atmosphere in which the gas component condenses in the recovery mechanism is regarded as 100%. In the case where the target liquid is water, the humidity can be observed by using a general hygrometer. However, in the case where the target liquid is not water, it is necessary to confirm that there is no liquid component in the recovery container when fine bubbles are started to be made. In this confirmation, a method of confirming the target liquid component, etc. using a gas detection tube is useful. After confirmation, the liquid containing fine bubbles is started to be made, and the state in which condensation occurs in the recovery mechanism is regarded as a state in which the relative humidity of the target liquid is 100%. Therefore, after this state, during the time period in which fine bubbles are generated by energizing atomization, the state in which the relative humidity is 100% continues. Therefore, the "average value of relative humidity" in this specification refers to the average value of the relative humidity in the recovery mechanism space from the start of making the liquid containing fine bubbles to the end of making.

[0098] (Description of specific example)

[0099] Hereinafter, the method of using a Figure 2 The fine bubble production device of the device shown produces a liquid containing fine bubbles under various conditions during production and examines the results of the fine bubble-containing liquid thus produced.

[0100] In order to measure the fine bubbles in the produced liquid containing fine bubbles, a measuring instrument (model: SALD-7500) manufactured by Shimadzu Corporation was used. The raw liquid before the fine bubbles were generated was used as a comparison object. The average particle size (expressed as the number of particles), concentration (the cumulative number of bubbles with a particle size of 20 μm or less per milliliter) and particle size distribution (the ratio (dw / dn) of the average molecular weight (dn) expressed as the number of particles to the average particle size (dw) expressed as the volume, with a minimum value of 1) of the fine bubbles contained in the liquid containing fine bubbles were measured.

[0101] In order to quantify the components in the liquid to be analyzed, PACK TEST manufactured by KYORITSU CHEMICAL-CHECK Lab., Corp. was used. In order to analyze the live bacteria contamination, Biochecker manufactured by SAN-AIOIL CO., LTD. was used. In order to measure the amount of dissolved oxygen, DO Meter (HQ30D) manufactured by HACH was used. For pH measurement, LAQUA pH meter manufactured by HORIBA was used. In addition, in the experiment under the atmosphere, the gas atmosphere was set to 21% oxygen and 79% nitrogen, and the concentration of the dissolved gas component was calculated based on the measurement result of the oxygen concentration.

[0102] The evaluation items and evaluation criteria are as follows.

[0103] As an index of the storage stability of the FB-containing liquid, the change rate of the UFB concentration after one week at room temperature was obtained and evaluated.

[0104] The determination criteria are as follows.

[0105] A...greater than or equal to 80%

[0106] B...greater than or equal to 50% and less than 80%

[0107] C...greater than or equal to 10% and less than 50%

[0108] D...less than 10%

[0109] As an index of the production efficiency of the FB-containing liquid, the ratio of the weight of the recovered liquid to the weight of the raw material liquid was obtained and evaluated. The evaluation criteria are as follows.

[0110] A...greater than or equal to 95%

[0111] B...greater than or equal to 80% and less than 95%

[0112] C...greater than or equal to 10% and less than 80%

[0113] D...less than 10%

[0114] As an index of the stable productivity of the FB-containing liquid, the reduction rate of the consumption of the raw material liquid per unit time, that is, the reduction rate of the consumption with time relative to the initial state, was obtained and evaluated. The evaluation criteria were as follows.

[0115] A...100%

[0116] B...greater than or equal to 50% and less than 100%

[0117] C...greater than or equal to 10% and less than 50%

[0118] D...less than 10%

[0119] In addition, the bactericidal effect of the FB-containing liquid was examined. Specifically, a comparative test with ultrapure water was conducted by using Biochecker in which a test liquid containing the FB-containing liquid was added to a suspension containing Escherichia coli and Staphylococcus aureus. The evaluation criteria are as follows.

[0120] A...greater than or equal to 99%

[0121] B...greater than or equal to 80% and less than 99%

[0122] C...greater than or equal to 50% and less than 80%

[0123] D...less than 50%

[0124] Moreover, the ozone concentration was also checked. Based on the color reaction with Trinder's reagent by oxidative coupling, the dissolved ozone concentration in the initial state before the FB-containing liquid was manufactured and after the FB-containing liquid was stored was determined. Note that in the case where the concentration reached the upper limit of the measured concentration, the liquid was diluted with ultrapure water and the concentration was obtained by concentration conversion. The test liquid was sealed in a PFA container without a gas phase and stored at room temperature for one week. The evaluation criteria for the ozone concentration after a period of time are described below.

[0125] A...≥2ppm

[0126] B...greater than or equal to 1ppm and less than 2ppm

[0127] C...greater than or equal to 0.1ppm and less than 1ppm

[0128] D...less than 0.1ppm

[0129] (Example 1)

[0130] As the piezoelectric element of the atomization FB generating device 101 for generating ultrasonic waves, a piezoelectric atomization element (1.6 MHz) manufactured by SEIKO GIKEN INC. was used. The piezoelectric element was placed in a 500 ml beaker and 300 ml of ultrapure water was poured in. The height of the piezoelectric element was adjusted so that the distance between the gas-liquid interface and the surface of the piezoelectric element was 3.5 cm. By using Figure 2 The manufacturing device shown manufactures a liquid containing fine bubbles. The average value of the relative humidity in the recovery container during manufacturing (referred to as the average relative humidity) is 99%. Please note that in the following examples, unless otherwise specified, the average relative humidity is greater than or equal to 80%. In addition, the weight ratio of the liquid containing fine bubbles as the recovered liquid to the consumption of the raw material liquid related to the manufacturing is 99%. Please note that in the following examples, unless otherwise specified, the weight ratio of the liquid containing fine bubbles to the raw material liquid is greater than or equal to 80%.

[0131] (Example 2)

[0132] As in Example 1, a piezoelectric atomizing element (1.6 MHz) manufactured by SEIKO GIKEN INC. was used as a piezoelectric element for generating ultrasonic waves. The piezoelectric element was placed in a 500 ml beaker and 300 ml of ultrapure water was poured in. The height of the piezoelectric element was adjusted so that the distance between the gas-liquid interface and the surface of the piezoelectric element was 3.5 cm. In the recovery of the liquid containing fine bubbles, the piezoelectric element was used to generate a piezoelectric atomizing element (1.6 MHz). The piezoelectric element was placed in a 500 ml beaker and 300 ml of ultrapure water was poured in. The height of the piezoelectric element was adjusted so that the distance between the gas-liquid interface and the surface of the piezoelectric element was 3.5 cm. Fig.10The liquid containing fine bubbles is manufactured by using a manufacturing device of the recovery container 106 having a 1 mm mesh structure as shown. The average relative humidity in the recovery container during manufacturing is 99%. The weight ratio of the liquid containing fine bubbles as the recovered liquid to the consumption of the raw material liquid related to the manufacturing is 99%. Please note that the pore size of the mesh in the mesh structure is preferably any value within the range of greater than or equal to 1 mm and less than or equal to 3 mm.

[0133] (Example 3)

[0134] As in Example 1, as a piezoelectric element for generating ultrasonic waves, a piezoelectric atomizing element (1.6 MHz) manufactured by SEIKO GIKEN INC. was used. The piezoelectric element was placed in a 500 ml beaker, and 300 ml of ultrapure water was poured into it. The setting height of the piezoelectric element was adjusted so that the distance between the gas-liquid interface and the surface of the piezoelectric element was 3.5 cm. In the recovery of the liquid containing fine bubbles, the liquid containing fine bubbles was produced by using a manufacturing device including a recovery container to which a device such as Fig.11 The rotating blades (fan) shown in the figure are used to suck in and recover the mist. The average relative humidity in the recovery container during manufacturing is 99%. In addition, the weight ratio of the liquid containing fine bubbles as the recovery liquid to the consumption of the raw material liquid related to the manufacturing is 99%.

[0135] (Example 4)

[0136] use Figure 5 The manufacturing device shown. As a piezoelectric element of the atomization FB generating device 101 for generating ultrasonic waves, a piezoelectric atomization element (1.6MHz) manufactured by SEIKO GIKEN INC. is used. The piezoelectric element is set in a 500ml detachable double-necked flask, and 300ml of ultrapure water is poured in. The setting height of the piezoelectric element is adjusted so that the distance between the gas-liquid interface and the surface of the piezoelectric element is 3.5cm. Insert the power cord into one neck of the double-necked flask, provide a connecting tube at the other neck, and provide a recovery container 106 at the front end of the connecting tube. The recovery mechanism including the recovery container 106 is constructed as a closed system so that the ambient atmosphere does not flow into it. Please note that "closed system" refers to a system in which the exchange of substances with the outside world is restricted. A liquid containing fine bubbles is manufactured by using this manufacturing device. The average relative humidity in the recovery container during manufacturing is 99%. In addition, the weight ratio of the liquid containing fine bubbles as the recovered liquid to the consumption of the raw material liquid related to the same manufacturing is 99%.

[0137] (Example 5)

[0138] In Example 4, the height of the piezoelectric element is adjusted so that the distance between the gas-liquid interface and the surface of the piezoelectric element is 15 cm. In addition, in order to introduce ozone into the gas component in the recovery mechanism of the closed system, an ozone generator is provided in the recovery mechanism, and a water collection port, a valve, an ozone quencher and a pump are provided, such as Fig.14 shown.

[0139] The ozone generator used is not particularly limited, and any unit can be used. Specifically, although a manufacturing unit using ultraviolet irradiation (a low-pressure mercury lamp or a Xe excimer lamp with quartz tube glass, etc.), a discharge unit, etc. can be used, ozonation by surface discharge is adopted in this example. Although the ozone quencher is not particularly limited as long as the ozone quencher can adsorb or decompose ozone into oxygen (for example, manganese oxide or a 254nm ultraviolet lamp), activated carbon is used in this example.

[0140] A liquid containing ozone-containing fine bubbles was produced in the same manner as in Example 4 except for the above changes.

[0141] (Example 6)

[0142] In Example 4, a liquid containing fine bubbles was produced in the same manner as in Example 4, except that the setting height of the piezoelectric element was adjusted so that the distance between the gas-liquid interface and the surface of the piezoelectric element became 16 cm.

[0143] (Example 7)

[0144] In Example 4, Fig.19 As shown, a liquid containing fine bubbles was produced in the same manner as in Example 4, except that a production apparatus covered with a recovery container was used.

[0145] (Example 8)

[0146] In Example 4, the liquid containing fine bubbles was manufactured in the same manner as in Example 4 except that ultrapure water was replaced with a 58 vol% ethanol aqueous solution. Note that in the recovery mechanism before manufacturing the liquid containing fine bubbles, the gas concentration of the ethanol component was confirmed to be 0% using an alcohol detection tube, and the relative humidity of the water was also set to 40%. Based on this result, the relative humidity in the recovery mechanism before manufacturing the 58 vol% ethanol aqueous solution was calculated to be 23.2%. In addition, at the completion of manufacturing, the liquid component ratio of the manufactured and recovered liquid containing fine bubbles was similar to that of the raw material before manufacturing. It was thus confirmed that for the target liquid (58 vol% ethanol aqueous solution in this example), the average relative humidity was 99% when the state when condensation occurred during manufacturing was regarded as 100%.

[0147] (Example 9)

[0148] In Example 4, a liquid containing fine bubbles was produced in the same manner as in Example 4, except that the distance between the gas-liquid interface and the surface of the piezoelectric element was changed to 10 cm.

[0149] (Example 10)

[0150] In Example 4, a liquid containing fine bubbles was produced in the same manner as in Example 4, except that the distance between the gas-liquid interface and the surface of the piezoelectric element was changed to 11 cm.

[0151] (Example 11)

[0152] In Example 4, a liquid containing fine bubbles was produced in the same manner as in Example 4, except that the average relative humidity in the recovery container during production was changed to 88%.

[0153] (Example 12)

[0154] In Example 4, a liquid containing fine bubbles was produced in the same manner as in Example 4, except that ultrapure water was changed to tap water.

[0155] (Example 13)

[0156] In Example 4, a liquid containing fine bubbles was produced in the same manner as in Example 4, except that ultrapure water was changed to hard water.

[0157] (Example 14)

[0158] In Example 4, a liquid containing fine bubbles was produced in the same manner as in Example 4, except that the ultrapure water was changed to rainwater.

[0159] (Example 15)

[0160] In Example 4, a liquid containing fine bubbles was produced in the same manner as in Example 4, except that ultrapure water was changed to seawater.

[0161] (Example 16)

[0162] In Example 4, Fig.12 As shown, a blower, a liquid supply tank, a liquid column growth inhibition plate, a water level sensor, a fractionation tube, an exhaust fan and a water collection port are provided. Otherwise, a liquid containing fine bubbles is manufactured in the same manner as in Example 4.

[0163] Please note that the average relative humidity in the recovery container during production was 80%, and the weight ratio of the liquid containing fine bubbles to the raw material liquid was 80%.

[0164] (Example 17)

[0165] In Example 4, Fig.17As shown in the example, the recovery container wall is given flexibility and a water collection port is provided in the recovery container. In addition, the liquid containing fine bubbles is produced in the same manner as in Example 4. By giving flexibility, the shape of the recovery container is appropriately changed to generate airflow in the recovery container. This can shorten the time required for recovering a predetermined amount by atomization by 5%.

[0166] (Example 18)

[0167] In Example 1, Fig.21 As shown, the recovery mechanism is constructed as follows: an ozone generator is provided in the recovery mechanism, and by using a piezoelectric element (manufactured by KAIJO Corporation), the first liquid is directly irradiated with 1.6 MHz ultrasonic waves and the second liquid (raw liquid) phase is indirectly irradiated, and the recovery mechanism includes a liquid supply tank. Otherwise, a liquid containing fine bubbles is produced in the same manner as in Example 4.

[0168] The ozone generator is not particularly limited, and any unit can be used. Specifically, although a manufacturing unit using ultraviolet irradiation (a low-pressure mercury lamp with quartz tube glass or a Xe excimer lamp, etc.), a discharge unit, etc. can be used, in this example, a low-pressure mercury lamp (output 5W) with a wavelength of 172nm is used.

[0169] (Example 19)

[0170] In Example 4, the gas components in the closed system manufacturing device were replaced with argon gas for manufacturing. To replace with argon gas, use Fig.13 The manufacturing device shown in the figure is degassed by using a pump while the valve in the recovery container is opened, and then the gas components of the manufacturing device are replaced with argon gas from a gas tank filled with argon gas by rotating the three-way cock. Although this operation can be performed once, it is more efficient to perform the replacement by performing this operation multiple times, such as Fig.18 As shown, it is also effective to provide an independent closed space on the raw material liquid side and perform the above-mentioned replacement operation while stirring the raw material liquid.

[0171] A liquid containing fine bubbles was produced in the same manner as in Example 4 except for the above changes.

[0172] (Example 20)

[0173] In Example 4, the gas components in the closed system manufacturing device are replaced with pure air for manufacturing. In order to replace with pure air, use Fig.13The manufacturing device shown in the figure is degassed by using a pump while the valve in the recovery container is open, and then the gas components of the closed system manufacturing device are replaced with pure air from a gas tank filled with pure air by rotating the three-way cock. Please note that pure air refers to a gas that is mainly composed of two components, oxygen and nitrogen, by removing carbon dioxide, nitrogen oxides, THC, sulfur dioxide, etc. as much as possible.

[0174] A liquid containing fine bubbles was produced in the same manner as in Example 4 except for the above changes.

[0175] (Example 21)

[0176] In Example 4, the gas components in the closed system manufacturing device are replaced with oxygen for manufacturing. To replace with oxygen, use Fig.13 The manufacturing apparatus shown is deaerated by using a pump while the valve in the recovery container is opened, and then the gas components of the closed system manufacturing apparatus are replaced with oxygen from a gas tank filled with oxygen by rotating the three-way cock.

[0177] A liquid containing fine bubbles was produced in the same manner as in Example 4 except for the above changes.

[0178] (Example 22)

[0179] In Example 4, the gas components in the closed system manufacturing device are replaced with nitrogen for manufacturing. To replace with nitrogen, use Fig.13 The manufacturing apparatus shown is deaerated by using a pump while the valve in the recovery container is opened, and then the gas components of the closed system manufacturing apparatus are replaced with nitrogen from a gas tank filled with nitrogen by rotating the three-way cock.

[0180] A liquid containing fine bubbles was produced in the same manner as in Example 4 except for the above changes.

[0181] (Example 23)

[0182] In Example 4, the gas components in the closed system manufacturing device are replaced with CO2 for manufacturing. To replace with CO2, use Fig.13 The manufacturing apparatus shown in the figure is degassed by using a pump while the valve in the recovery container is open, and then the gas composition of the closed system manufacturing apparatus is replaced with CO2 from a gas tank filled with CO2 by rotating the three-way cock. Please note that the CO2 concentration is derived by the membrane glass electrode method using the correlation curve between the CO2 gas concentration in the water dissolved with CO2 and the pH value of the water dissolved with CO2 and a carbon dioxide gas concentration meter.

[0183] A liquid containing fine bubbles was produced in the same manner as in Example 4 except for the above changes.

[0184] (Example 24)

[0185] In Example 4, the gas components in the closed system manufacturing device are replaced with hydrogen. In order to replace the hydrogen, use Fig.13 The manufacturing apparatus shown is deaerated by using a pump while the valve in the recovery container is opened, and then the gas components of the closed system manufacturing apparatus are replaced with hydrogen from a gas tank filled with hydrogen by rotating the three-way cock.

[0186] A liquid containing fine bubbles was produced in the same manner as in Example 4 except for the above changes.

[0187] (Example 25)

[0188] In Example 4, an ultraviolet lamp with a wavelength of 254 nm is provided to replace Fig.14 The ozone generator shown in the embodiment is provided, and a water collection port and a valve are provided in the recovery container. Otherwise, a liquid containing fine bubbles is produced in the same manner as in Example 4. Note that the ultraviolet lamp used is not particularly limited. The ultraviolet irradiation using the ultraviolet lamp is for the purpose of eliminating bacteria in the installation environment of the manufacturing device.

[0189] A liquid containing fine bubbles was produced in the same manner as in Example 4 except for the above changes.

[0190] (Example 26)

[0191] In Example 4, an ultraviolet lamp with a wavelength of 185 nm is provided to replace Fig.14 The ozone generator shown in the embodiment is provided with a water collection port and a valve. Otherwise, a liquid containing fine bubbles is produced in the same manner as in the embodiment 4.

[0192] A liquid containing fine bubbles was produced in the same manner as in Example 4 except for the above changes.

[0193] (Example 27)

[0194] In Example 4, an ultraviolet lamp with a wavelength of 172 nm is provided to replace Fig.14 The ozone generator shown in the embodiment is provided with a water collection port and a valve. Otherwise, a liquid containing fine bubbles is produced in the same manner as in the embodiment 4.

[0195] (Example 28)

[0196] In Example 4, Fig. 22 The atmosphere communication port and the water collection port shown are provided, and the liquid containing fine bubbles is produced by using the fine bubble-containing liquid production device covered by the recovery container 106.

[0197] A liquid containing fine bubbles was produced in the same manner as in Example 4 except for the above changes.

[0198] (Example 29)

[0199] In Example 4, a liquid introduction channel is provided, such as Figure 8 As shown in FIG. 1 , a vibrator, namely, a mist FB generating device 101 is disposed just below the liquid film. A liquid containing fine bubbles is produced in the same manner as in Example 4 except for the above.

[0200] (Example 30)

[0201] In Example 4, Fig. 9 As shown in the example, the mist FB generating device 101 is arranged so as to float in the liquid. Otherwise, the liquid containing fine bubbles is produced in the same manner as in Example 4.

[0202] (Example 31)

[0203] By using Fig.25 A manufacturing device of the structure shown is used to manufacture a liquid containing fine bubbles, and the manufacturing device is equipped with a self-made atomization FB generating device 201. Regarding the atomization FB generating device 201, as a so-called grid-type atomization generator, a transducer used in an ultrasonic humidifier is used. It is known to use this to generate droplets of about 10μm. As a liquid, ultrapure water is used. When manufacturing a liquid containing fine bubbles, the average value of the relative humidity in the recovery container (called the average relative humidity) is 99%. Please note that unless otherwise specified in the following examples, the average relative humidity is greater than or equal to 80%. In addition, the weight ratio of the liquid containing fine bubbles as the recovered liquid to the consumption of the raw material liquid related to the manufacturing is 99%. Please note that unless otherwise specified in the following examples, the weight ratio of the liquid containing fine bubbles to the raw material liquid is greater than or equal to 80%.

[0204] (Example 32)

[0205] By using Fig.28 A manufacturing device of the structure shown in the figure is used to manufacture a liquid containing fine bubbles, and the manufacturing device is equipped with an atomized FB generating device 201. Other conditions are the same as those in Example 31. By installing the atomized FB generating device 201 horizontally, the time required to recover a predetermined amount of liquid containing fine bubbles can be shortened by 10% compared with Example 31.

[0206] (Example 33)

[0207] By using Fig.29A manufacturing device of the structure shown in the figure is used to manufacture a liquid containing fine bubbles, and the manufacturing device is equipped with an atomized FB generating device 201. Other conditions are the same as those in Example 31. By tilting the atomized FB generating device 201, the time required to recover a predetermined amount of liquid containing fine bubbles can be shortened by 20% compared with Example 31.

[0208] (Example 34)

[0209] By using Fig.30 A manufacturing device of the structure shown in the figure is used to manufacture a liquid containing fine bubbles, and the manufacturing device is equipped with an atomized FB generating device 201. Other conditions are the same as those in Examples 31 to 33. By installing the atomized FB generating device 201 downward, the time required to recover a predetermined amount of liquid containing fine bubbles can be shortened by 30% compared with Example 31.

[0210] (Example 35)

[0211] In Example 34, a liquid containing fine bubbles is produced in the same manner as in Example 34, except that ultrapure water is replaced with tap water.

[0212] (Example 36)

[0213] In Example 34, a liquid containing fine bubbles is produced in the same manner as in Example 34, except that ultrapure water is replaced by hard water.

[0214] (Example 37)

[0215] In Example 34, a liquid containing fine bubbles is produced in the same manner as in Example 34, except that ultrapure water is replaced with rainwater.

[0216] (Example 38)

[0217] In Example 34, a liquid containing fine bubbles is produced in the same manner as in Example 34, except that ultrapure water is replaced by seawater.

[0218] (Example 39)

[0219] In Example 34, the recovery mechanism is constructed as follows: an ozone generator is arranged in the recovery mechanism to increase the ozone concentration in the space of the recovery container, and Fig.31 As shown, the generated droplets can be directly irradiated with ozone. Otherwise, a liquid containing fine bubbles is produced in the same manner as in Example 34.

[0220] There is no particular limitation on the ozone generator, and any unit can be used. Specifically, although a manufacturing unit using ultraviolet irradiation (a low-pressure mercury lamp with quartz tube glass or a Xe excimer lamp, etc.), a discharge unit, etc. can be used, in this example, a low-pressure mercury lamp (output 5W) with a wavelength of 172nm is used.

[0221] (Example 40)

[0222] In Example 34, the gas components in the closed system manufacturing device are replaced with oxygen for manufacturing. In order to replace with oxygen, use Fig.32 The manufacturing apparatus shown is deaerated by using a pump while the valve in the recovery container is opened, and then the gas components of the closed system manufacturing apparatus are replaced with oxygen from a gas tank filled with oxygen by rotating the three-way cock.

[0223] A liquid containing fine bubbles is produced in the same manner as in Example 34 except for the above changes.

[0224] (Example 41)

[0225] In Example 39, the gas components in the closed system manufacturing apparatus are replaced with nitrogen, and a liquid containing fine bubbles is manufactured.

[0226] (Example 42)

[0227] In Example 39, the gas components in the closed system manufacturing apparatus are replaced with hydrogen, and a liquid containing fine bubbles is manufactured.

[0228] (Example 43)

[0229] In Example 39, the gas components in the closed system manufacturing apparatus are replaced with argon gas, and a liquid containing fine bubbles is manufactured.

[0230] (Example 44)

[0231] In Example 39, the gas components in a closed system manufacturing apparatus are replaced with helium, and a liquid containing fine bubbles is manufactured.

[0232] (Example 45)

[0233] In Example 34, after replacing the gas components in the closed system manufacturing device with oxygen, an ozone generator is used to provide a space with a high concentration of ozone, such as Fig.33 As shown, the liquid containing fine bubbles is produced by starting the atomized FB generating device 201. Fig.33 Not shown, but Fig.14 The recovery mechanism has a water collection port, a valve, an ozone quencher and a pump.

[0234] (Comparative Example 1)

[0235] In Example 4, an attempt was made to recover the liquid containing fine bubbles without providing a recovery mechanism including the recovery container 106 and the like (see Figure 5 ). The local relative humidity of the joint part with the recovery mechanism (not actually connected to the recovery container 106) is 81%. Note that the relative humidity in the space where the liquid is atomized and diffused is 40% in the initial state, and the average relative humidity at the time of manufacture is 78%. Although attempts have been made to manufacture and recover bulk liquids by using this device, recovery is difficult.

[0236] (Comparative Example 2)

[0237] In Example 4, the installation height of the piezoelectric element was adjusted so that the distance between the gas-liquid interface and the surface of the piezoelectric element was 30 cm. Other than this, an attempt was made to produce a liquid containing fine bubbles in the same manner as in Example 4. Note that the formation of a water column and turbidity of the gas phase were not observed at the liquid-gas interface.

[0238] (Comparative Example 2)

[0239] In Example 4, the piezoelectric element was changed to a 267 Hz probe type. Otherwise, an attempt was made to produce a liquid containing fine bubbles in the same manner as in Example 4. Note that at the liquid-gas interface, the formation of a water column and turbidity of the gas phase were not observed.

[0240] (Comparative Examples 4 and 5)

[0241] In Example 4, using Fig. 22 The same apparatus for producing a liquid containing fine bubbles is covered with a recovery container 106 having an atmospheric communication port, and further, a bubble size reduction device connected to the exhaust port of an air pump is provided at the bottom of the water tank. Specifically, a gas phase and a water phase are separated by using a microporous membrane in the middle, and air is introduced through the micropores by pressurizing the gas phase side using an air pump to prepare a UFB liquid containing air. As the microporous membrane, a filter membrane with a molecular weight cutoff of 1000 (Minimate manufactured by PALL) is used.

[0242] Furthermore, an electrolytic ozone generator (Ozone Buster manufactured by Kansai Automation Equipment Co., Ltd.) was placed in the liquid in the water tank.

[0243] By using the above device, a device was prototyped that produces ozone by electrolysis and dissolves it, reduces the bubble size by an air pump and mixes submicron-sized fine bubbles, and diffuses atomized ice by irradiation with ultrasonic waves. Then, by using this device, the dissolved ozone concentration and UFB concentration in the liquid containing fine bubbles were derived and the properties of the liquid containing fine bubbles were identified.

[0244] In Comparative Example 4, a liquid containing fine bubbles produced by using water retained in the device in a state where 50% of the water loaded before the operation was sprayed was evaluated. In Comparative Example 5, 40% of the water loaded before the operation was sprayed into the indoor space, and the recovery and evaluation of the bulk liquid by recovering the mist were attempted. In Comparative Example 4, the production efficiency, stable productivity, and stability of the dissolved ozone concentration of the UFB were insufficient. In addition, in Comparative Example 5, the recovery of the bulk liquid was inherently difficult.

[0245] A table summarizing the above-described Examples and Comparative Examples is described below.

[0246] [Table 1]

[0247]

[0248] [Table 2]

[0249]

[0250] [Table 3]

[0251]

[0252] [Table 4]

[0253]

[0254] [Table 5]

[0255]

[0256] [Table 6]

[0257]

[0258] The present disclosure is not limited to the above embodiments, and various changes and modifications may be made without departing from the spirit and scope of the present disclosure. Therefore, the appended claims are intended to disclose the scope of the present disclosure.

[0259] This application claims priority based on Japanese Patent Application No. 2022-128243 filed on August 10, 2022 and Japanese Patent Application No. 2023-105067 filed on June 27, 2023, the entire descriptions of which are incorporated herein by reference.

Claims

1. A method for producing a liquid containing fine bubbles, comprising: a generating step of generating droplets containing fine bubbles by atomizing the liquid by irradiating the liquid with ultrasonic waves; as well as A recovery step of recovering the liquid droplets into a recovery container by using a recovery mechanism including a recovery container.

2. The manufacturing method according to claim 1, wherein: Inside the recovery container, the average value of the relative humidity during the production of the liquid containing fine bubbles is 80% or more, wherein the average value of the relative humidity when the liquid condenses is regarded as 100%.

3. The manufacturing method according to claim 1 or 2, wherein: In the generating step, a transducer for irradiating the liquid contained in the liquid tank with ultrasonic waves is used.

4. The manufacturing method according to claim 3, wherein: The thickness of the liquid on the vibrator is less than or equal to 15 cm.

5. The manufacturing method according to claim 3, wherein: The liquid tank is provided with a liquid introduction channel for guiding the liquid onto the surface of the oscillator by capillary action.

6. The manufacturing method according to claim 3, wherein: A float is attached to the vibrator, and The vibrator floats in the liquid.

7. The manufacturing method according to claim 3, wherein: In the recovery step, the liquid droplets come into contact with a medium included in the recovery mechanism, so that the liquid droplets are recovered into the recovery container.

8. The manufacturing method according to claim 7, wherein: The medium partially has a mesh structure.

9. The manufacturing method according to claim 8, wherein: The mesh of the mesh structure has a pore size of greater than or equal to 1 mm.

10. The manufacturing method according to claim 3, wherein: A fan is attached to the recycling container, and In the recovery step, the liquid droplets come into contact with the rotating fan, thereby recovering the liquid droplets into a recovery container.

11. The manufacturing method according to claim 3, wherein: The liquid tank is attached with a blower, a liquid supply tank, a liquid column growth inhibition plate and a water level sensor. The recovery mechanism comprises: an exhaust fan connected to the recovery container through a fractionation pipe; and a water collection port attached to the recovery container, and The liquid tank is connected to the recovery container through a fractionation pipe.

12. The manufacturing method according to claim 3, wherein: The recovery mechanism includes: a pump, a gas tank and a three-way cock, which are used to adjust the gas composition and partial pressure inside the recovery container to recover the droplets.

13. The manufacturing method according to claim 3, wherein: Recycling facilities are in closed systems where material exchange with the outside world is limited.

14. The manufacturing method according to claim 13, wherein: The recovery mechanism includes a water collection port, valve, ozone quencher and pump, and An ozone generator is attached inside the recovery container.

15. The manufacturing method according to claim 14, wherein: The ozone generator includes a unit for emitting ultraviolet rays.

16. The manufacturing method according to claim 3, wherein: Cover the tank with a recovery container, and A water collection port is attached to the recovery container.

17. The manufacturing method according to claim 16, wherein: The walls of the recovery container are flexible.

18. The manufacturing method according to claim 3, wherein: The liquid tank is equipped with a pump, a gas tank, a three-way cock and a stirring unit, and The recovery mechanism includes: a pump, a gas tank, a three-way cock and a water collection port, which are used to adjust the gas composition and partial pressure inside the recovery container to recover the droplets.

19. The manufacturing method according to claim 3, wherein: The liquid tank supplied with liquid in the generating step is integrated with the recovery mechanism.

20. The manufacturing method according to claim 1 or 2, wherein: In the generating step, a transducer for irradiating ultrasonic waves to a first liquid contained in a liquid tank is used, and The ultrasonic wave is directly irradiated on the first liquid, thereby indirectly irradiating the second liquid different from the first liquid, so that the second liquid is atomized.

21. The manufacturing method according to claim 1, wherein: The recovery mechanism includes a liquid storage chamber and a generating device for generating atomized fine bubbles. The generating device includes a grid and a vibrator, and In the generation step, liquid is supplied to the grid, and ultrasonic waves are irradiated to the supplied liquid by a transducer.

22. The manufacturing method according to claim 21, wherein: In the recovery step, the liquid droplets come into contact with the recovery mechanism so that the liquid droplets are recovered into the recovery container.

23. The manufacturing method according to claim 21 or 22, wherein: The generating device includes a grid located on an upper surface thereof, and The generating device is installed in a transverse direction, and the direction of generating droplets is in a transverse direction.

24. The manufacturing method according to claim 23, wherein: The generating device has a cylindrical shape.

25. The manufacturing method according to claim 21 or 22, wherein: The generating device includes a grid located on an upper surface thereof, and The generating device is installed downward, and the direction of generating droplets is in the downward direction.

26. The manufacturing method according to claim 25, wherein: The generating device has a cylindrical shape.

27. The manufacturing method according to claim 21 or 22, wherein: Recycling facilities are in closed systems where material exchange with the outside world is limited.

28. The manufacturing method according to claim 21 or 22, wherein: The recovery mechanism includes a water collection port, valve, ozone quencher and pump, and An ozone generator is attached inside the recovery container.

29. The manufacturing method according to claim 28, wherein: The ozone generator includes a unit for emitting ultraviolet rays.

30. The manufacturing method according to claim 21 or 22, wherein: Cover the reservoir with a recovery container, and A water collection port is attached to the recovery container.

31. A device for producing a liquid containing fine bubbles, comprising: a generating unit for generating liquid droplets including fine bubbles by atomizing the liquid by irradiating with ultrasonic waves; as well as The recovery mechanism is used to recover the liquid droplets into a recovery container.

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