JP2018086632A - Bubble generation member, device and method - Google Patents
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- 239000011148 porous material Substances 0.000 claims abstract description 63
- 239000012528 membrane Substances 0.000 claims abstract description 36
- 239000002101 nanobubble Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 31
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- 230000000694 effects Effects 0.000 claims description 12
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
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- 239000007789 gas Substances 0.000 description 37
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 24
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
本発明は、多孔質の部材を用いて、マイクロバブルやナノバブルを発生することができる気泡発生部材及び気泡発生装置並びに気泡発生方法に関するものである。 The present invention relates to a bubble generating member, a bubble generating device and a bubble generating method capable of generating microbubbles and nanobubbles using a porous member.
従来、マイクロバブルやナノバブルを発生する技術として、多孔質部材等を用いた各種の技術が提案されている。
例えば、シラスバルーンの焼結体からなる多孔質管を用いた技術、陽極酸化法にてポーラスアルミナを形成する技術、振動オリフィス部材を用いた技術、マイクロバブル噴出基板を用いた技術、注入井の先端に多孔質部材を配置した技術、ナノサイズの開口径を有する貫通孔を備えた生成チャンバの技術などが開示されている（特許文献１〜６参照）。
Conventionally, various techniques using a porous member or the like have been proposed as techniques for generating microbubbles and nanobubbles.
For example, a technology using a porous tube made of a sintered Shirasu balloon, a technology of forming porous alumina by an anodic oxidation method, a technology using a vibrating orifice member, a technology using a microbubble ejection substrate, A technique in which a porous member is arranged at the tip, a technique of a generation chamber provided with a through hole having a nano-sized opening diameter, and the like are disclosed (see Patent Documents 1 to 6).
しかしながら、例えば多孔質基材の表面に多孔質膜を設けて、液体中にマイクロバブルやナノバブルを発生させる場合には、十分な検討がなされていないのが現状である。
例えば、多孔質基材に高い圧力で空気を供給してマイクロバブルやナノバブルを発生させる場合には、多孔質膜が使用中に剥がれる等の問題が発生することなどが考えられ、マイクロバブルやナノバブルを安定して発生させることは容易ではない。
However, for example, when a porous film is provided on the surface of a porous substrate to generate microbubbles or nanobubbles in a liquid, sufficient investigation has not been made.
For example, when air is supplied to a porous substrate at a high pressure to generate microbubbles or nanobubbles, problems such as peeling of the porous film during use may occur. It is not easy to stably generate.
本発明は、前記課題に鑑みてなされたものであり、その目的は、マイクロバブルやナノバブルを安定して発生させることができる気泡発生部材及び気泡発生装置並びに気泡発生方法を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a bubble generating member, a bubble generating device, and a bubble generating method capable of stably generating microbubbles and nanobubbles.
（１）本発明の第１局面は、多孔質基材と、多孔質基材の内側及び外側の少なくとも一方に、多孔質基材より微細な細孔を有する１又は複数の多孔質膜と、を備えた構造体を有し、構造体の多孔質基材側から多孔質膜側に気体を供給して、液体中にマイクロバブル及びナノバブルの少なくとも一方の大きさの気泡を発生させる気泡発生部材に関するものである。 (1) A first aspect of the present invention is a porous substrate, and one or a plurality of porous membranes having finer pores on at least one of the inside and outside of the porous substrate than the porous substrate; A bubble generating member that has a structure provided with gas and supplies gas from the porous substrate side to the porous membrane side of the structure to generate bubbles of at least one size of microbubbles and nanobubbles in the liquid It is about.
この気泡発生部材は、構造体の最表面の多孔質膜の平均細孔径が０．３ｎｍ〜１μｍであり、且つ、多孔質膜の厚みが５０μｍ以下である。
本第１局面では、気泡発生部材の構造体の最表面の多孔質膜の平均細孔径が０．３ｎｍ〜１μｍであり、且つ、多孔質膜の厚みが５０μｍ以下であるので、液体中にマイクロバブルやナノバブルのような微細の気泡を容易に発生させること（即ち供給すること）ができる。
In this bubble generating member, the average pore diameter of the porous film on the outermost surface of the structure is 0.3 nm to 1 μm, and the thickness of the porous film is 50 μm or less.
In the first aspect, the average pore diameter of the porous film on the outermost surface of the structure of the bubble generating member is 0.3 nm to 1 μm, and the thickness of the porous film is 50 μm or less. Fine bubbles such as bubbles and nanobubbles can be easily generated (that is, supplied).
特に、多孔質膜の厚みが５０μｍ以下と薄いので、多孔質膜は多孔質基材側に凹凸に沿って密着している。そのため、多孔質基材側から多孔質膜に圧力を加えて気体を供給したり、長期間に渡って気体を供給しても、多孔質膜が剥離しにくく、よって、安定して微細な気泡を供給できるという効果を奏する。 In particular, since the thickness of the porous film is as thin as 50 μm or less, the porous film is in close contact with the porous substrate side along the unevenness. Therefore, even if gas is supplied by applying pressure to the porous membrane from the porous substrate side, or even if gas is supplied over a long period of time, the porous membrane is difficult to peel off. There is an effect that can be supplied.
なお、多孔質膜の厚みとしては、３０００ｎｍ（即ち３μｍ）以上を採用できる。
（２）本発明の第２局面では、構造体の最表面の多孔質膜の平均細孔径が０．３ｎｍ〜５ｎｍであり、且つ、多孔質膜の厚みが５μｍ以下である。
The thickness of the porous film can be 3000 nm (that is, 3 μm) or more.
(2) In the second aspect of the present invention, the average pore diameter of the porous film on the outermost surface of the structure is 0.3 nm to 5 nm, and the thickness of the porous film is 5 μm or less.
本第２局面では、構造体の最表面の多孔質膜の平均細孔径が０．３ｎｍ〜５ｎｍであるので、例えば洗浄・殺菌作用を有するとされているナノバブル等を効率良く発生させることができる。 In the second aspect, since the average pore diameter of the porous film on the outermost surface of the structure is 0.3 nm to 5 nm, it is possible to efficiently generate, for example, nanobubbles that are supposed to have a cleaning / sterilizing action. .
（３）本発明の第３局面では、多孔質基材と最表面の多孔質膜との間に、多孔質基材と最表面の多孔質膜との間の平均細孔径を有する多孔質の中間膜を備えるとともに、中間膜の平均細孔径が４ｎｍ〜０．５μｍであり、且つ、中間膜の厚みが４μｍ〜３００μｍである。 (3) In the third aspect of the present invention, a porous material having an average pore diameter between the porous substrate and the outermost porous film is between the porous substrate and the outermost porous film. While having an intermediate film, the average pore diameter of the intermediate film is 4 nm to 0.5 μm, and the thickness of the intermediate film is 4 μm to 300 μm.
本第３局面では、上述した構成の中間膜は、例えば多孔質基材の平均細孔径と最表面の多孔質膜との平均細孔径との差が大きすぎる場合には、その間においてバッファーの役目を有しており、多孔質基材の細孔内に多孔質膜の成分が侵入するのを抑制することができる。 In the third aspect, when the difference between the average pore diameter of the porous substrate and the average pore diameter of the outermost porous film is too large, for example, the intermediate film having the above-described configuration serves as a buffer between them. It can suppress that the component of a porous membrane penetrate | invades in the pore of a porous base material.
（４）本発明の第４局面では、多孔質基材の平均細孔径が０．５μｍ〜５００μｍである。
本第４局面は、多孔質基材の平均細孔径が０．５μｍ〜５００μｍであるので、気体が流れ易いという効果がある。
(4) In 4th aspect of this invention, the average pore diameter of a porous base material is 0.5 micrometer-500 micrometers.
In the fourth aspect, since the average pore diameter of the porous substrate is 0.5 μm to 500 μm, there is an effect that gas easily flows.
（５）本発明の第５局面では、多孔質基材の平均細孔径が０．５μｍ〜５０μｍである。
本第５局面では、多孔質基材の平均細孔径が０．５μｍ〜５０μｍ（より好ましくは０．５μｍ〜５μｍ）であるので、強度が大きいという効果がある。
(5) In the fifth aspect of the present invention, the porous substrate has an average pore diameter of 0.5 μm to 50 μm.
In the fifth aspect, since the average pore diameter of the porous substrate is 0.5 μm to 50 μm (more preferably 0.5 μm to 5 μm), there is an effect that the strength is large.
（６）本発明の第６局面では、構造体の最表面の多孔質膜は、分子篩効果を有する膜又はナノ孔を有する多孔質膜である。
本第６局面は、最表面の多孔質膜に形成された細孔を例示している。なお、ナノ孔のサイズとしては、０．３ｎｍ〜５ｎｍの大きさが挙げられる。
(6) In the sixth aspect of the present invention, the porous film on the outermost surface of the structure is a film having a molecular sieving effect or a porous film having nanopores.
The sixth aspect illustrates the pores formed in the outermost porous film. In addition, as a size of a nanopore, the magnitude | size of 0.3 nm-5 nm is mentioned.
（７）本発明の第７局面では、構造体の最表面の多孔質膜は、陽極酸化金属膜、ゼオライト膜、カーボン膜、又はγ−アルミナ膜である。
本第７局面は、最表面の多孔質膜を例示している。
(7) In the seventh aspect of the present invention, the outermost porous film of the structure is an anodized metal film, a zeolite film, a carbon film, or a γ-alumina film.
The seventh aspect illustrates the outermost porous film.
ここで、ゼオライト膜とは、全体がゼオライトで構成されるかゼオライトを主成分（最大の成分）とする膜である。同様に、カーボン膜とは、全体がカーボンで構成されるかカーボンを主成分とする膜である。同様に、γ−アルミナ膜とは、全体がγ−アルミナで構成されるかγ−アルミナを主成分とする膜である。 Here, the zeolite membrane is a membrane composed entirely of zeolite or having zeolite as a main component (maximum component). Similarly, the carbon film is a film composed entirely of carbon or mainly composed of carbon. Similarly, the γ-alumina film is a film composed entirely of γ-alumina or mainly composed of γ-alumina.
また、γ−アルミナ膜の平均細孔径としては約４ｎｍ、カーボン膜の平均細孔径としては約０．４ｎｍ、シリカ膜（ゼオライト膜）の平均細孔径としては約０．５６〜０．５４ｎｍが挙げられる。 The average pore diameter of the γ-alumina film is about 4 nm, the average pore diameter of the carbon film is about 0.4 nm, and the average pore diameter of the silica film (zeolite membrane) is about 0.56 to 0.54 nm. It is done.
なお、陽極酸化金属膜とは、例えばアルミニウムやシリコン等を陽極酸化して形成した細孔を有する膜である。また、これ以外に、ＳＰＧ(シラスポーラスガラス)からなる多孔質膜を採用できる。 The anodized metal film is a film having pores formed by, for example, anodizing aluminum or silicon. In addition, a porous film made of SPG (shirasu porous glass) can be used.
（８）本発明の第８局面では、多孔質基材及び多孔質膜のうち、少なくとも多孔質基材はセラミックス製である。
本第８局面は、多孔質基材及び多孔質膜の材料を例示している。セラミックス製の部材の場合には、圧力等の応力に強く、変形・劣化しにくいので好適である。
(8) In the eighth aspect of the present invention, at least the porous substrate of the porous substrate and the porous film is made of ceramics.
The eighth aspect exemplifies materials for the porous substrate and the porous membrane. In the case of a ceramic member, it is suitable because it is resistant to stresses such as pressure and hardly deforms or deteriorates.
ここで、セラミックス製の多孔質基材とは、全体が例えばアルミナ等のセラミックスで構成されるかセラミックスを主成分（最大の成分）とするものである。
（９）本発明の第９局面は、第１〜第８局面のいずれかに記載の１又は複数の気泡発生部材と、気泡発生部材を液中に保持する構成と、気泡発生部材の多孔質基材側に気体を供給する構成と、を備えた気泡発生装置である。
Here, the ceramic porous substrate is composed entirely of ceramics such as alumina or has ceramics as a main component (maximum component).
(9) A ninth aspect of the present invention includes one or a plurality of bubble generating members according to any one of the first to eighth aspects, a configuration in which the bubble generating member is held in a liquid, and a porosity of the bubble generating member. And a structure for supplying gas to the substrate side.
この気泡発生装置により、液体中にマイクロバブルやナノバブルのような微細の気泡）を容易に発生させること（即ち供給すること）ができる。
また、気泡発生部材は、多孔質基材側から多孔質膜に圧力を加えて気体を供給したり、長期間に渡って気体を供給しても、多孔質膜が剥離しにくいので、この気泡発生装置によって、安定して微細な気泡を供給できるという効果を奏する。
This bubble generating device can easily generate (that is, supply) fine bubbles such as microbubbles and nanobubbles) in the liquid.
In addition, since the bubble generating member is difficult to peel off even if gas is supplied by applying pressure to the porous membrane from the porous substrate side, or even if gas is supplied over a long period of time, this bubble generating member With the generator, there is an effect that fine bubbles can be supplied stably.
（１０）本発明の第１０局面では、気体を供給側と気泡を発生させる側との間に、圧力差を発生させる機能を有する。
このように、圧力差を発生させることにより（つまり、高い圧力で気体を供給することにより）、微差な気泡を効率良く発生させることができる。
(10) The tenth aspect of the present invention has a function of generating a pressure difference between the gas supply side and the bubble generation side.
In this way, by generating a pressure difference (that is, by supplying gas at a high pressure), it is possible to efficiently generate fine bubbles.
（１１）本発明の第１１局面では、最表面の多孔質膜に、液流又は振動を付与する機能を有する。
このように、最表面の多孔質膜に液流又は振動を付与することにより、微細な気泡を効率良く発生させることができる。
(11) In an eleventh aspect of the present invention, the outermost porous film has a function of imparting a liquid flow or vibration.
Thus, by providing a liquid flow or vibration to the porous film on the outermost surface, fine bubbles can be generated efficiently.
（１２）本発明の第１２局面は、第１〜第８局面のいずれかに記載の気泡発生部材を用い、構造体の多孔質基材側から多孔質膜側に気体を供給して、液体中にマイクロバブル及びナノバブルの少なくとも一方の大きさの気泡を発生させる気泡発生方法である。 (12) In a twelfth aspect of the present invention, a gas is supplied from the porous substrate side of the structure to the porous membrane side using the bubble generating member according to any of the first to eighth aspects, and a liquid This is a bubble generation method for generating bubbles having a size of at least one of microbubbles and nanobubbles.
この気泡発生方法により、液体中にマイクロバブルやナノバブルのような微細の気泡を容易に発生させること（即ち供給すること）ができる。
この気泡発生方法では、使用する気泡発生部材に多孔質基材側から多孔質膜に圧力を加えて気体を供給したり、長期間に渡って気体を供給しても、多孔質膜が剥離しにくいので、この気泡発生方法によって、安定して微細な気泡を供給できるという効果を奏する。
By this bubble generation method, it is possible to easily generate (that is, supply) fine bubbles such as microbubbles and nanobubbles in the liquid.
In this bubble generation method, even if gas is supplied to the bubble generation member used by applying pressure to the porous membrane from the porous substrate side, or the gas is supplied over a long period of time, the porous membrane peels off. Since it is difficult, this bubble generating method has an effect of stably supplying fine bubbles.
＜以下に、本発明の各構成について説明する＞
・マイクロバブルとは、気泡の直径がマイクロナノバブル、ナノバブルより大きく、１０μｍ以下のものである。
<Each configuration of the present invention will be described below>
Microbubbles are those having a bubble diameter larger than micronanobubbles and nanobubbles and not more than 10 μm.
・マイクロナノバブルとは、気泡の直径が数百ｎｍ以上１０μｍ以下のものである。
・ナノバブルとは、気泡の直径が数百ｎｍ以下（例えば１０００ｎｍ以下）のものである。
-Micro-nano bubbles are those having a bubble diameter of several hundred nm or more and 10 μm or less.
Nanobubbles are those having a bubble diameter of several hundred nm or less (for example, 1000 nm or less).
・平均細孔径を求める方法としては、１ｎｍ以下の細孔については、物理吸着の影響が小さくなる温度域で分子径の異なるガスの透過率を測定して、各透過率を有効分子サイズに対してプロットする方法（NKＰ法；NormalizedKnudsen-basedPermeance法）が挙げられる。 -As a method for obtaining the average pore size, for pores of 1 nm or less, the permeability of gases having different molecular diameters is measured in a temperature range where the influence of physical adsorption is small, and each transmittance is compared to the effective molecular size. And a plotting method (NKP method; Normalized Knudsen-based Permeance method).
また、１ｎｍ以上の細孔を有する場合には、ナノパームポロメトリー法やバブルポイント法で算出することができる。
さらに、数十ｎｍ程度以上の細孔を有する場合には、走査型電子顕微鏡（ＳＥＭ）や透過型電子顕微鏡（ＴＥＭ）などの観察により算出することができる。
Moreover, when it has a 1 nm or more pore, it can calculate by the nano palm porometry method or the bubble point method.
Furthermore, when it has pores of about several tens of nanometers or more, it can be calculated by observation with a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like.
・各膜の厚みは、気泡発生部材を厚み方向に破断し、ＳＥＭ画像等による画像解析から求めることができる。なお、本開示では、厚みの値としては、例えば５点を測定した平均値を用いることができる。 The thickness of each film can be obtained from image analysis using an SEM image or the like by breaking the bubble generating member in the thickness direction. In the present disclosure, as the thickness value, for example, an average value obtained by measuring five points can be used.
・気泡発生部材の形状としては、筒状、Ｕ字型筒、平板型などが挙げられるが、気泡を発生できる限りは、形状には特に制限はない。また、各種の形状の気泡発生部材において、最表面の多孔質膜は、多孔質基材のどちら側に設けてもよい。 -Examples of the shape of the bubble generating member include a cylindrical shape, a U-shaped tube, and a flat plate shape, but the shape is not particularly limited as long as bubbles can be generated. Moreover, in various shapes of bubble generating members, the outermost porous film may be provided on either side of the porous substrate.
・多孔質基材の表面に形成する多孔質膜としては、例えば１又は２層が挙げられるが（例えば中間膜と最表面の多孔質膜）、それ以上であってもよい。
・気体としては、酸素ガス、水素ガス、ヘリウムガスなど、細孔を通過可能であって、液体中にマイクロバブルやナノバブルなどの微細な気泡が発生するものであれば、特に限定はない。
-As a porous film | membrane formed on the surface of a porous base material, although 1 or 2 layers are mentioned, for example (for example, intermediate film and outermost porous film), more than that may be sufficient.
The gas is not particularly limited as long as it can pass through pores, such as oxygen gas, hydrogen gas, and helium gas, and fine bubbles such as microbubbles and nanobubbles are generated in the liquid.
・液体としては、純水、塩化ナトリウム水溶液、界面活性剤添加水溶液、エタノールなどが挙げられるが、マイクロバブルやナノバブルなどの微細な気泡が発生するものであれば、特に限定はない。 Examples of the liquid include pure water, an aqueous solution of sodium chloride, a surfactant-added aqueous solution, and ethanol, but are not particularly limited as long as fine bubbles such as microbubbles and nanobubbles are generated.
次に、本発明の気泡発生部材及び気泡発生装置並び気泡発生方法の実施形態について説明する。
［１．第１実施形態］
［１−１．気泡発生部材の構成］
まず、第１実施形態の気泡発生部材について説明する。
Next, an embodiment of the bubble generating member, the bubble generating device and the bubble generating method of the present invention will be described.
[1. First Embodiment]
[1-1. Configuration of bubble generating member]
First, the bubble generating member of the first embodiment will be described.
図１に示すように、第１実施形態の気泡発生部材は、マイクロバブルやナノバブルを発生させる多孔質の構造体である気泡発生管３と、気泡発生管３の先端側（図１の右側）を閉塞する先端部材５と、気泡発生管３の後端側（図１の左側）に取り付けられた後端部材７とを備えている。 As shown in FIG. 1, the bubble generating member of the first embodiment includes a bubble generating tube 3 that is a porous structure that generates microbubbles and nanobubbles, and a tip side of the bubble generating tube 3 (right side in FIG. 1). And a rear end member 7 attached to the rear end side (left side in FIG. 1) of the bubble generating tube 3.
詳しくは、図２に示すように、先端部材５は、気泡発生管３に外嵌するキャップ状の金属製の第１加締ナット１１と、第１加締ナット１１に螺合する金属製の第１ボルト１３と、第１加締ナット１１と第１ボルト１３との間に配置された樹脂製の第１ａフェルール１５及び第１ｂフェルール１７と、を備えている。 Specifically, as shown in FIG. 2, the tip member 5 is made of a cap-shaped metal first caulking nut 11 that is externally fitted to the bubble generating tube 3, and a metal that is screwed into the first caulking nut 11. A first bolt 13 and a resin-made first a ferrule 15 and first b ferrule 17 disposed between the first caulking nut 11 and the first bolt 13 are provided.
このうち、第１加締ナット１１は、板状部分１１ａと板状部分１１ｂの外周部分から軸方向（図２の左右方向）に伸びる外周部材１１ｂとからなる。第１ボルト１３は、後端側に凹部１３ａを備えるとともに先端側が閉塞されている。第１ａフェルール１５は円環状であり、第１ｂフェルール１７は円筒で外周側がテーパ形状である。 Among these, the 1st crimping nut 11 consists of the outer peripheral member 11b extended in an axial direction (left-right direction of FIG. 2) from the outer peripheral part of the plate-shaped part 11a and the plate-shaped part 11b. The 1st volt | bolt 13 is equipped with the recessed part 13a in the rear-end side, and the front end side is obstruct | occluded. The 1a ferrule 15 is annular, the 1b ferrule 17 is cylindrical, and the outer peripheral side is tapered.
従って、第１加締ナット１１と第１ボルト１３とを螺合させることにより、第１ａフェルール１５及び第１ｂフェルール１７が押圧されて、気泡発生管３と第１加締ナット１１や第１ボルト１３（従って先端部材５）との隙間が閉塞される。これによって、気泡発生管３の先端側から（マイクロバブルやナノバブルでない）空気等の気体が、水等の液体側に漏れないようになっている。 Therefore, by screwing the first caulking nut 11 and the first bolt 13, the first a ferrule 15 and the first b ferrule 17 are pressed, and the bubble generating tube 3, the first caulking nut 11, and the first bolt are pressed. 13 (therefore, the tip member 5) is closed. This prevents gas such as air (not microbubbles or nanobubbles) from leaking from the tip side of the bubble generating tube 3 to the liquid side such as water.
一方、後端部材７は、気泡発生管３に外嵌するキャップ状の金属製の第２加締ナット２１と、第２加締ナット２１に螺合する金属製の第２ボルト２３と、第２加締ナット２１と第２ボルト２３との間に配置された（先端部材５と同様な）樹脂製の第１ｂフェルール２５及び第１ｂフェルール２７と、を備えている。 On the other hand, the rear end member 7 includes a cap-shaped metal second caulking nut 21 fitted on the bubble generating tube 3, a metal second bolt 23 screwed into the second caulking nut 21, A first b ferrule 25 and a first b ferrule 27 made of resin (similar to the tip member 5) are provided between the two caulking nut 21 and the second bolt 23.
このうち、第２加締ナット２１は、板状部分２１ａと板状部分２１ｂの外周部分から軸方向に伸びる外周部材２１ｂとからなる。第２ボルト２３は、先端側に凹部２３ａを備えるとともに後端側に通気管２３ｂが設けられ、凹部２３ａと通気管２３ｂとは貫通孔２３ｃにより連通している。 Among these, the 2nd crimping nut 21 consists of the outer peripheral member 21b extended in the axial direction from the outer peripheral part of the plate-shaped part 21a and the plate-shaped part 21b. The second bolt 23 has a recess 23a on the front end side and a vent pipe 23b on the rear end side. The recess 23a and the vent pipe 23b communicate with each other through a through hole 23c.
従って、第２加締ナット２１と第２ボルト２３とを螺合させることにより、第２ａフェルール２５及び第２ｂフェルール２７が押圧されて、気泡発生管３と第２加締ナット２１や第２ボルト２３（従って後端部材７）との隙間が閉塞される。これによって、気泡発生管３の後端側から（マイクロバブルやナノバブルでない）空気等の気体が、水等の液体側に漏れないようになっている。 Therefore, by screwing the second caulking nut 21 and the second bolt 23, the 2a ferrule 25 and the 2b ferrule 27 are pressed, and the bubble generating tube 3, the second caulking nut 21 and the second bolt are pressed. 23 (therefore, the rear end member 7) is closed. This prevents gas such as air (not microbubbles or nanobubbles) from leaking from the rear end side of the bubble generating tube 3 to the liquid side such as water.
なお、第２ボルト２３には、軸方向に貫通する貫通孔２３ｃが形成されているので、通気管２３ｂの後端側から例えば空気を供給することによって、気泡発生管３の軸方向に貫通する中心孔２９に空気を供給することができる。 Since the second bolt 23 has a through hole 23c penetrating in the axial direction, for example, air is supplied from the rear end side of the vent pipe 23b so as to penetrate the bubble generating pipe 3 in the axial direction. Air can be supplied to the center hole 29.
次に、気泡発生管３の構成について説明する。
気泡発生管３は、例えば外径φ５ｍｍ×厚み１ｍｍ×長さ５０ｍｍの円筒形状の管である。
Next, the configuration of the bubble generating tube 3 will be described.
The bubble generating tube 3 is, for example, a cylindrical tube having an outer diameter of 5 mm, a thickness of 1 mm, and a length of 50 mm.
この気泡発生管３は、軸中心側より、円筒形状の多孔質基材３１、円筒形状の多孔質膜（即ち中間膜）３３、円筒形状の最表面の多孔質膜（例えばカーボン膜）３５が順に積層されたものである。なお、気泡発生管３の構成は、これに限定される訳ではなく、後述する実施例に示されるように各種の構成を採用できる。 The bubble generating tube 3 includes a cylindrical porous substrate 31, a cylindrical porous film (that is, an intermediate film) 33, and a cylindrical outermost porous film (for example, a carbon film) 35 from the axial center side. They are stacked in order. Note that the configuration of the bubble generating tube 3 is not limited to this, and various configurations can be adopted as shown in the embodiments described later.
このうち、多孔質基材３１は、例えばセラミック製（例えばアルミナ製）であり、その平均細孔径は０．５μｍ〜５００μｍの範囲である。なお、多孔質基材３１の平均細孔径が０．５μｍ〜５０μｍであるとより好ましい。 Among these, the porous substrate 31 is made of, for example, ceramic (for example, made of alumina), and the average pore diameter is in the range of 0.5 μm to 500 μm. In addition, it is more preferable that the average pore diameter of the porous substrate 31 is 0.5 μm to 50 μm.
中間膜３３、例えばセラミック製（例えばアルミナ製）の中間膜３３であり、その平均細孔径は４ｎｍ〜０．５μｍの範囲である。また、この中間膜３３の厚みは、４μｍ〜３００μｍの範囲である。 The intermediate film 33 is, for example, an intermediate film 33 made of ceramic (for example, made of alumina), and the average pore diameter is in the range of 4 nm to 0.5 μm. The thickness of the intermediate film 33 is in the range of 4 μm to 300 μm.
なお、中間膜３３を、内側の第１多孔質膜及び外側の第２多孔質膜の２層で構成してもよい（図示せず）。この場合、第１多孔質膜と第２多孔質膜との平均細孔径は同じでもよいが、外側（第２多孔質膜）は、内側（第２多孔質膜）より平均細孔径が小さいことが望ましい。 In addition, you may comprise the intermediate film 33 by two layers, an inner side 1st porous film and an outer side 2nd porous film (not shown). In this case, the average pore size of the first porous membrane and the second porous membrane may be the same, but the outer side (second porous membrane) has a smaller average pore size than the inner side (second porous membrane). Is desirable.
最表面の多孔質膜３５は、多数のナノ孔を有する薄膜（例えばカーボン膜）である。この最表面の多孔質膜３５は、平均細孔径が０．３ｎｍ〜１μｍであり、その厚みは３μｍ〜５０μｍである。なお、最表面の多孔質膜３５の平均細孔径が０．３ｎｍ〜５ｎｍであると、より好ましい。 The outermost porous film 35 is a thin film (for example, a carbon film) having a large number of nanopores. The outermost porous film 35 has an average pore diameter of 0.3 nm to 1 μm and a thickness of 3 μm to 50 μm. It is more preferable that the average pore diameter of the outermost porous film 35 is 0.3 nm to 5 nm.
なお、各構成の平均細孔径の大小については、多孔質基材３１＞中間膜３３＞最表面の多孔質膜（例えばカーボン膜）３５の関係がある。
なお、気泡発生管３の軸方向における長さとしては例えば８３ｍｍ、気泡発生管３のうち先端部材５と後端部材７との挟まれた露出部分の長さとしては例えば２５ｍｍを採用できるが、適宜変更してもよい。
The average pore diameter of each component has a relationship of porous substrate 31> intermediate film 33> outermost porous film (for example, carbon film) 35.
The length of the bubble generating tube 3 in the axial direction can be 83 mm, for example, and the length of the exposed portion between the tip member 5 and the rear end member 7 of the bubble generating tube 3 can be 25 mm, for example. You may change suitably.
例えば最表面の多孔質膜３５がセラミック製の多孔質膜である場合には、気泡発生管３の軸方向における長さとしては例えば７５ｍｍ、気泡発生管３の露出部分の長さとしては例えば１７ｍｍ採用できる。
［１−２．気泡発生装置の構成］
次に、第１実施形態の気泡発生装置について説明する。
For example, when the outermost porous membrane 35 is a ceramic porous membrane, the length of the bubble generating tube 3 in the axial direction is, for example, 75 mm, and the length of the exposed portion of the bubble generating tube 3 is, for example, 17 mm. Can be adopted.
[1-2. Configuration of bubble generator]
Next, the bubble generator of 1st Embodiment is demonstrated.
図４に示すように、気泡発生装置４１は、水等の液体（Ｌ）を収容する容器４３と、容器４３内に収容された液体中に、気泡発生管３が浸かるように配置された気泡発生部材１と、容器４３内に配置されたポンプ４５とを備えている。 As shown in FIG. 4, the bubble generating device 41 includes a container 43 that stores a liquid (L) such as water, and a bubble that is disposed so that the bubble generating tube 3 is immersed in the liquid stored in the container 43. The generating member 1 and a pump 45 disposed in the container 43 are provided.
また、容器４３外には、空気等の気体（ガス：Ｇ）が充填されたボンベ（又はコンプレッサ）４７が配置され、このボンベ４７から、気泡発生部材１の後端部材７の通気管２３ｂに気体が供給されるようになっている。 Further, a cylinder (or compressor) 47 filled with a gas (gas: G) such as air is disposed outside the container 43, and from this cylinder 47 to the vent pipe 23 b of the rear end member 7 of the bubble generating member 1. Gas is supplied.
さらに、容器４３外には、ポンプ４５を駆動する電源４９が配置され、このポンプ４５によって、水流（液流）が気泡発生部材１の気泡発生管３に当たるように送られる。なお、この液流を当てる構成は省略してもよい。或いは、モータ等によって、気泡発生部材１を振動させてもよい。 Further, a power source 49 for driving the pump 45 is disposed outside the container 43, and a water flow (liquid flow) is sent by the pump 45 so as to hit the bubble generating tube 3 of the bubble generating member 1. In addition, you may abbreviate | omit the structure which applies this liquid flow. Alternatively, the bubble generating member 1 may be vibrated by a motor or the like.
そして、気泡発生装置４１によって、マイクロバブルやナノバブルのような微細な気泡（Ｋ）を発生させる場合には、ボンベ４７から気泡発生部材１の気泡発生管３の中心孔２９に気体を供給する。このとき、ポンプ４５によって、液流を気泡発生管３に当てるようにする。 When the bubble generating device 41 generates fine bubbles (K) such as micro bubbles and nano bubbles, gas is supplied from the cylinder 47 to the center hole 29 of the bubble generating tube 3 of the bubble generating member 1. At this time, the liquid flow is applied to the bubble generating tube 3 by the pump 45.
気体は、気泡発生管３において、多孔質基材３１、中間膜３３、最表面の多孔質膜（カーボン膜）３５を透過し、それによって液中に微細な気泡が発生する。
なお、どのような大きさの気泡が発生するかは、主として、最表面の多孔質膜３５の細孔の大きさ（即ち平均細孔径）によるので、細孔の大きさを調整することによって、マイクロバブルやナノバブルを発生させることが可能である。
［１−３．効果］
次に、第１実施形態の効果を説明する。
The gas permeates through the porous substrate 31, the intermediate film 33, and the outermost porous film (carbon film) 35 in the bubble generating tube 3, thereby generating fine bubbles in the liquid.
Note that the size of the bubble that is generated mainly depends on the size of the pores in the outermost porous film 35 (that is, the average pore diameter). Therefore, by adjusting the size of the pores, It is possible to generate micro bubbles and nano bubbles.
[1-3. effect]
Next, effects of the first embodiment will be described.
（１）第１実施形態では、気泡発生部材１の最表面の多孔質膜３５の平均細孔径が０．３ｎｍ〜１μｍであり、且つ、その多孔質膜３５の厚みが５０μｍ以下であるので、液体中にマイクロバブルやナノバブルのような微細の気泡を容易に発生させることができる。 (1) In the first embodiment, the average pore diameter of the porous film 35 on the outermost surface of the bubble generating member 1 is 0.3 nm to 1 μm, and the thickness of the porous film 35 is 50 μm or less. Fine bubbles such as microbubbles and nanobubbles can be easily generated in the liquid.
特に、最表面の多孔質膜３５の厚みが５０μｍ以下と薄いので、その多孔質膜３５は多孔質基材３１側の表面の開口による凹凸に沿って密着している。そのため、多孔質基材３１側から多孔質膜３５に圧力を加えて気体を供給したり、長期間に渡って気体を供給しても、多孔質膜３５が剥離しにくく、よって、安定して微細な気泡を供給できるという効果を奏する。 In particular, since the thickness of the outermost porous film 35 is as thin as 50 μm or less, the porous film 35 is in close contact with the irregularities formed by the opening on the surface of the porous substrate 31. Therefore, even if pressure is applied to the porous membrane 35 from the porous base material 31 side to supply gas or gas is supplied over a long period of time, the porous membrane 35 is difficult to peel off, and thus stable. There is an effect that fine bubbles can be supplied.
（２）第１実施形態では、多孔質基材３１と最表面の多孔質膜３５との間に中間膜３３を備えているので、多孔質基材３１と最表面の多孔質膜３５との間においてバッファーの役目を有し、多孔質基材３１の細孔内に多孔質膜３５の成分が侵入するのを抑制できる。 (2) In the first embodiment, since the intermediate film 33 is provided between the porous substrate 31 and the outermost porous film 35, the porous substrate 31 and the outermost porous film 35 It can serve as a buffer, and can prevent the components of the porous film 35 from entering the pores of the porous substrate 31.
（３）第１実施形態では、気泡の発生量が多く、最大の発生量で例えば約１６９０億個／ｍｌのナノバブルの発生が可能である。
（４）第１実施形態では、ほぼ均一な細孔から気泡を発生させることで、単分散のナノバブルの生成が可能である。
(3) In the first embodiment, the amount of bubbles generated is large, and for example, about 169 billion nanoml / ml can be generated at the maximum amount.
(4) In the first embodiment, it is possible to generate monodisperse nanobubbles by generating bubbles from substantially uniform pores.
（５）また、使用する気泡発生部材１の数量を増加させたり、気泡発生管３の外側の表面積を大きくすることにより、細孔の数を多くすることができるので、多くのナノバブルを短時間で発生させることができる。 (5) Moreover, since the number of pores can be increased by increasing the number of bubble generating members 1 to be used or increasing the surface area outside the bubble generating tube 3, many nanobubbles can be removed in a short time. Can be generated.
（６）なお、水以外の液体に対しても、ナノバブル等を添加することができる。
［２．第２実施形態］
次に、第２実施形態について説明するが、第１実施形態と同様な内容の説明は省略又は簡略化する。
(6) Nanobubbles can be added to liquids other than water.
[2. Second Embodiment]
Next, the second embodiment will be described, but the description of the same contents as the first embodiment will be omitted or simplified.
図５に示すように、本第２実施形態の気泡発生部材５１は、第１実施形態と同様な気泡発生管５３の軸方向の両端に、第１実施形態と同様な後端部材５５、５７を取り付けたものである。 As shown in FIG. 5, the bubble generating member 51 of the second embodiment has rear end members 55 and 57 similar to those of the first embodiment at both ends in the axial direction of the bubble generating tube 53 similar to that of the first embodiment. Is attached.
この気泡発生部材５１では、一方の後端部材５５から気泡発生管５３に気体（Ｇ）を供給し、他方の後端部材５５から残余の気体を排出する。
なお、気泡を発生させる液体は、気泡発生部材５１の周囲を囲む容器５９内に供給され、両後端部材５５、５７は、容器５９内に配置される。
In the bubble generation member 51, the gas (G) is supplied from one rear end member 55 to the bubble generation tube 53, and the remaining gas is discharged from the other rear end member 55.
The liquid for generating bubbles is supplied into a container 59 surrounding the bubble generating member 51, and both rear end members 55 and 57 are disposed in the container 59.
本第２実施形態は、第１実施形態と同様な効果を奏する。
［３．第３実施形態］
次に、第３実施形態について説明するが、第１実施形態と同様な内容の説明は省略又は簡略化する。
The second embodiment has the same effects as the first embodiment.
[3. Third Embodiment]
Next, the third embodiment will be described, but the description of the same contents as the first embodiment will be omitted or simplified.
図６に示すように、本第３実施形態の気泡発生部材６１は、先端側（図３の下方）が閉塞された試験管形状の気泡発生管６３と、気泡発生管５３の後端側の開口部に取り付けられた（第１実施形態と同様な）後端部材６５とを備えたものである。 As shown in FIG. 6, the bubble generating member 61 of the third embodiment includes a test tube-shaped bubble generating tube 63 whose front end (downward in FIG. 3) is closed, and a rear end side of the bubble generating tube 53. A rear end member 65 (similar to the first embodiment) attached to the opening is provided.
この気泡発生部材６１では、後端部材６５から気泡発生管６３に気体（Ｇ）を供給することにより、気泡発生管６３の外側の液中に気泡を供給することができる。
本第３実施形態は、第１実施形態と同様な効果を奏する。
［４．実施例］
次に、具体的な各実施例について説明する。
In the bubble generating member 61, the gas can be supplied into the liquid outside the bubble generating tube 63 by supplying the gas (G) from the rear end member 65 to the bubble generating tube 63.
The third embodiment has the same effects as the first embodiment.
[4. Example]
Next, specific examples will be described.
＜実施例１＞
実施例１では、前記第１実施形態と同様に、多孔質基材の表面に中間膜と最表面の多孔質膜とを備えた気泡発生部材を用いて、気泡発生装置にて気泡を発生させた。
<Example 1>
In Example 1, as in the first embodiment, bubbles are generated by a bubble generating device using a bubble generating member having an intermediate film and an outermost porous film on the surface of a porous substrate. It was.
実施例１では、外径１２ｍｍ×内径９ｍｍ×長さ１１０ｍｍ、平均細孔径が３μｍ、気孔率４０％のアルミナ製の多孔質基材を用いた。
また、多孔質基材の表面に、平均細孔径１５０ｎｍ、厚み１８０ｎｍのアルミナ製の中間膜を形成した。詳しくは、多孔質基材を、アルミナ粒子が分散したスラリー中に漬けた後に取り出し、乾燥した後に１２００℃で焼成して中間膜を形成した。
In Example 1, an alumina porous substrate having an outer diameter of 12 mm, an inner diameter of 9 mm, a length of 110 mm, an average pore diameter of 3 μm, and a porosity of 40% was used.
Further, an alumina intermediate film having an average pore diameter of 150 nm and a thickness of 180 nm was formed on the surface of the porous substrate. Specifically, the porous substrate was taken out after being immersed in a slurry in which alumina particles were dispersed, dried, and then fired at 1200 ° C. to form an intermediate film.
なお、アルミナ粒子の大きさ（平均粒径）を操作することにより、多孔質基材や中間膜の孔の大きさ、すなわち平均細孔径を操作することができる。
さらに、中間膜の表面に、最表面の多孔質膜として、γ−アルミナ膜（平均細孔径：約４ｎｍ、濡れ角度：１５°、露出部分の長さ：２５ｍｍ）を形成した。
In addition, by manipulating the size (average particle size) of the alumina particles, it is possible to manipulate the size of the pores of the porous substrate or the intermediate film, that is, the average pore size.
Further, a γ-alumina film (average pore diameter: about 4 nm, wetting angle: 15 °, exposed portion length: 25 mm) was formed as the outermost porous film on the surface of the intermediate film.
詳しくは、蒸留水を加熱、撹拌しアルミニウムアルコキシド（ＡＬＴＳＢ）を加えて加水分解を行ない、塩酸を加えてγ−アルミナゾルを調整した。このゾル液にＰＶＡ溶液を加えて濃度を調整した。このゾル液中に中間膜を備えた多孔質基材を浸漬し、外側表面に膜を形成した。乾燥後に５００℃で焼成してγ−アルミナ膜（最表面の多孔質膜）を得た。 Specifically, distilled water was heated and stirred, aluminum alkoxide (ALTSB) was added for hydrolysis, and hydrochloric acid was added to prepare γ-alumina sol. The PVA solution was added to this sol solution to adjust the concentration. A porous substrate provided with an intermediate film was immersed in the sol solution to form a film on the outer surface. After drying, it was fired at 500 ° C. to obtain a γ-alumina film (the outermost porous film).
なお、焼成条件（温度、時間）を調整することによりγ−アルミナ膜の平均細孔径を操作することができる。
そして、上述した気泡発生部材を水中に配置した気泡発生装置を用いて、ヘリウムガスを供給（即ち印加）し、徐々に昇圧した所、０．７ＭＰａで肉眼で確認可能なマイクロバブルの発生を確認した。但し、ポンプは使用しなかった。
The average pore diameter of the γ-alumina membrane can be manipulated by adjusting the firing conditions (temperature, time).
Then, helium gas was supplied (that is, applied) using the bubble generating device in which the bubble generating member described above was placed in water, and when the pressure was gradually increased, generation of microbubbles that could be visually confirmed at 0.7 MPa was confirmed. did. However, no pump was used.
なお、水はマグネティックスターラーで１０００ＲＰＭで撹拌しているものの、気泡発生管から気泡の剥離は見られなかった。
また、スポイトで水流を与えて気泡が成長する前に剥離するようにした所、１時間ほどで水は透明な状態からレーザー光の散乱現象が確認された状態となった。これはナノバブルにみられる特徴である。
Although water was stirred at 1000 RPM with a magnetic stirrer, no peeling of bubbles was observed from the bubble generating tube.
In addition, when a bubble was applied before the bubbles grew by applying a water flow with a dropper, the water was in a transparent state, and the laser light scattering phenomenon was confirmed in about 1 hour. This is a characteristic seen in nanobubbles.
なお、散乱を確認するために、水に照射するレーザー光としては、最大１ｍＷ、波長５３２ｎｍ、クラス２ レーザーを用いた（以下同様）。
＜実施例２＞
実施例２では、前記第１実施形態と同様に、多孔質基材の表面に中間膜と最表面の多孔質膜とを備えた気泡発生部材を用いて、気泡発生装置にて気泡を発生させた。なお、実施例１と同様な内容の説明は省略する。
In addition, in order to confirm scattering, as a laser beam irradiated to water, a maximum of 1 mW, a wavelength of 532 nm, and a class 2 laser were used (the same applies hereinafter).
<Example 2>
In Example 2, as in the first embodiment, bubbles are generated by a bubble generating device using a bubble generating member having an intermediate film and an outermost porous film on the surface of a porous substrate. It was. Note that the description of the same contents as in the first embodiment is omitted.
実施例２では、外径６ｍｍ×内径４ｍｍ×長さ５０ｍｍ、平均細孔径が３μｍ、気孔率４０％のアルミナ製の多孔質基材を用いた。
中間膜としては、平均細孔径１５０ｎｍ、厚み１８４ｎｍのアルミナ製の中間膜を形成した。なお、中間膜としては、更に例えば厚み１８０ｎｍの膜の表面に厚み４ｎｍの膜を形成して２重構造としてもよい。
In Example 2, an alumina porous substrate having an outer diameter of 6 mm, an inner diameter of 4 mm, a length of 50 mm, an average pore diameter of 3 μm, and a porosity of 40% was used.
As the intermediate film, an alumina intermediate film having an average pore diameter of 150 nm and a thickness of 184 nm was formed. As the intermediate film, for example, a double structure may be formed by forming a film having a thickness of 4 nm on the surface of a film having a thickness of 180 nm.
最表面の多孔質膜としては、カーボン膜（平均細孔径：約０．４ｎｍ、濡れ角度：８０°、露出部分の長さ：２５ｍｍ）を形成した。
詳しくは、木タールをＴＨＦ溶媒で０．１％に希釈したカーボン膜前駆体溶液中に、中間膜を備えた多孔質基材を浸漬し、その後８０℃で乾燥処理を行ない中間膜の表面に樹脂のコート層を形成した。また、再度、同様な前駆体のコート操作を行なった。２度のコート操作を終えた後にＮ２気流下、７００℃、２時間炭化処理を行ないカーボン膜を得た。
A carbon film (average pore diameter: about 0.4 nm, wetting angle: 80 °, exposed portion length: 25 mm) was formed as the outermost porous film.
Specifically, a porous base material provided with an intermediate film is immersed in a carbon film precursor solution in which wood tar is diluted to 0.1% with a THF solvent, and then a drying treatment is performed at 80 ° C. on the surface of the intermediate film. A resin coating layer was formed. The same precursor coating operation was performed again. After completing the coating operation twice, carbonization treatment was performed at 700 ° C. for 2 hours under an N 2 stream to obtain a carbon film.
なお、炭化温度の変更又はカーボン膜の前駆体種（樹脂の種類）を変更することにより、カーボン膜の多孔組織、ひいては平均細孔径を操作することが可能である。
そして、上述した気泡発生部材を水中に配置した気泡発生装置を用いて、ヘリウムガスを印加し、徐々に昇圧した所、０．５ＭＰａで肉眼で確認可能なマイクロバブルの発生を確認した。但し、ポンプは使用しなかった。
In addition, it is possible to manipulate the porous structure of the carbon film, and hence the average pore diameter, by changing the carbonization temperature or changing the precursor type (resin type) of the carbon film.
Then, using a bubble generating device in which the bubble generating member described above was placed in water, helium gas was applied and the pressure was gradually increased, and generation of microbubbles that could be visually confirmed at 0.5 MPa was confirmed. However, no pump was used.
なお、水はマグネティックスターラーで１０００ＲＰＭで撹拌しているものの、気泡発生管から気泡の剥離は見られなかった。
また、スポイトで水流を与えて気泡が成長する前に剥離するようにした所、１時間ほどで水は透明な状態であるが、レーザー光の散乱現象が確認された状態となった。これはナノバブルにみられる特徴である。
Although water was stirred at 1000 RPM with a magnetic stirrer, no peeling of bubbles was observed from the bubble generating tube.
In addition, when water was applied with a dropper to separate the bubbles before growing, the water was transparent in about 1 hour, but the laser light scattering phenomenon was confirmed. This is a characteristic seen in nanobubbles.
＜実施例３＞
実施例３では、前記第１実施形態と同様に、多孔質基材の表面に中間膜と最表面の多孔質膜とを備えた気泡発生部材を用いて、気泡発生装置にて気泡を発生させた。なお、実施例２と同様な内容の説明は省略する。
<Example 3>
In Example 3, as in the first embodiment, bubbles are generated by a bubble generator using a bubble generating member having an intermediate film and an outermost porous film on the surface of a porous substrate. It was. In addition, description of the same content as Example 2 is abbreviate | omitted.
前記実施例２と同様に、カーボン膜を備えた気泡発生部材を用い、水に界面活性剤を数滴添加して同様の操作を行った所、０．３５ＭＰａで肉眼で確認可能なマイクロバブルの発生を確認した。 Similar to Example 2, a bubble generating member equipped with a carbon film was used, and when a similar operation was performed by adding a few drops of surfactant to water, microbubbles that could be visually confirmed at 0.35 MPa were observed. The occurrence was confirmed.
また、水をマグネティックスターラーで１０００ＲＰＭで撹拌したところ、気泡発生管から気泡は容易に剥離することが確認された。さらに、１時間撹拌後、レーザー光で確認した所、光の散乱現象が確認できた。 Moreover, when water was stirred with a magnetic stirrer at 1000 RPM, it was confirmed that the bubbles were easily separated from the bubble generating tube. Furthermore, after stirring for 1 hour, a light scattering phenomenon was confirmed when confirmed with a laser beam.
＜実施例４＞
実施例４では、前記第１実施形態と同様に、多孔質基材の表面に中間膜と最表面の多孔質膜とを備えた気泡発生部材を用いて、気泡発生装置にて気泡を発生させた。なお、実施例２と同様な内容の説明は省略する。
<Example 4>
In Example 4, as in the first embodiment, bubbles are generated by a bubble generating device using a bubble generating member having an intermediate film and an outermost porous film on the surface of a porous substrate. It was. In addition, description of the same content as Example 2 is abbreviate | omitted.
前記実施例２と同様に、カーボン膜を備えた気泡発生部材を用い、純水に塩化ナトリウムを溶解させて１０ｍＭに調整した溶液１Ｌに酸素ガスを印加した。なお、本実施例４では、溶液に気泡発生部材を浸漬後に酸素ガスを流した。 In the same manner as in Example 2, a bubble generating member equipped with a carbon film was used, and oxygen gas was applied to 1 L of a solution adjusted to 10 mM by dissolving sodium chloride in pure water. In Example 4, oxygen gas was flowed after the bubble generating member was immersed in the solution.
また、ポンプを用い、２００Ｌ／ｈ（流速：０．５２ｍ／ｓ）の水流をカーボン膜に当て、酸素ガスの印加圧（供給する圧力）を下記表１に示すように変更して、１時間印加した後に、同様にレーザー光で確認した所、光の散乱現象が確認できた。 Further, using a pump, a water flow of 200 L / h (flow rate: 0.52 m / s) was applied to the carbon membrane, and the applied pressure (supply pressure) of oxygen gas was changed as shown in Table 1 below, and 1 hour After the application, it was confirmed with a laser beam in the same manner that the light scattering phenomenon was confirmed.
そして、下記表１に示すように酸素ガスを供給する圧力を変更して作成した溶液（試料No.1-1〜1-3）を、ＮａｎｏＳｉｇｈｔＬＭ１０Ｖ−ＨＳ／Ｍａｌｖｅｒｎ社（ＣＭＯＳカメラ、紫色レーザー（波長４０５ｎｍ、＜６０ｍＷ））にて分析した所、下記表１の結果が得られた。 Then, as shown in Table 1 below, solutions prepared by changing the pressure for supplying oxygen gas (Sample Nos. 1-1 to 1-3) were prepared using NanoSight LM10V-HS / Malvern (CMOS camera, purple laser (wavelength 405 nm, <60 mW)), the results shown in Table 1 below were obtained.
この表１において、圧力とは酸素ガスの供給圧力を示し、散乱「○」とはレーザー光を照射した場合に散乱が見られたこと（即ちナノバブルが発生していること）を示している。Ｍｅａｎは平均値であり、Ｍｏｄｅは最頻値である。Ｄ１０、Ｄ５０、Ｄ９０は、それぞれ気泡を小さいものから数えた場合に、気泡の数が１０％、５０％、９０％における気泡の大きさを示している。（以下同様）
なお、図７は試料No.1-1の結果を示し、図８は試料No.1-2の結果を示し、図９は試料No.1-3の結果を示す。なお、各図において、横軸は発生した気泡の大きさ（径）であり、縦軸は１ｍｌ当たりの検出された粒子（気泡）数量（気泡数／ｍｌ）である。また、各図において、グラフが上下の幅を有しているのは、測定誤差を示しており、その測定誤差の領域内にて示す実線（白線）が、測定値（５個のサンプル）の平均を示している。（以下同様）
この表１及び図７〜図９から明らかなように、実施例４では、粒の揃った微細な気泡が得られることが分かる。
In Table 1, the pressure indicates the supply pressure of oxygen gas, and the scattering “◯” indicates that scattering was observed when laser light was irradiated (that is, nanobubbles were generated). Mean is an average value and Mode is a mode value. D10, D50, and D90 indicate the bubble sizes when the number of bubbles is 10%, 50%, and 90%, respectively, when the bubbles are counted from the smallest. (The same applies hereinafter)
7 shows the result of sample No. 1-1, FIG. 8 shows the result of sample No. 1-2, and FIG. 9 shows the result of sample No. 1-3. In each figure, the horizontal axis represents the size (diameter) of the generated bubbles, and the vertical axis represents the number of detected particles (bubbles) per 1 ml (number of bubbles / ml). Also, in each figure, the graph has a vertical width indicating a measurement error, and the solid line (white line) shown in the measurement error area is the measurement value (5 samples). Shows the average. (The same applies hereinafter)
As is apparent from Table 1 and FIGS. 7 to 9, in Example 4, it can be seen that fine bubbles with uniform grains can be obtained.
＜実施例５＞
実施例５では、前記第１実施形態と同様に、多孔質基材の表面に中間膜と最表面の多孔質膜とを備えた気泡発生部材を用いて、気泡発生装置にて気泡を発生させた。なお、実施例２と同様な内容の説明は省略する。
<Example 5>
In Example 5, as in the first embodiment, bubbles are generated by a bubble generator using a bubble generating member having an intermediate film and an outermost porous film on the surface of a porous substrate. It was. In addition, description of the same content as Example 2 is abbreviate | omitted.
前記実施例２と同様に、カーボン膜を備えた気泡発生部材を用い、純水に塩化ナトリウム１０ｍＭ、ラウリル硫酸トリエタノールアミン２ｍＭを加えて調整した溶液１Ｌに酸素ガスを０．７ＭＰａで印加した。 In the same manner as in Example 2, a bubble generating member equipped with a carbon film was used, and oxygen gas was applied at 0.7 MPa to 1 L of a solution prepared by adding 10 mM sodium chloride and 2 mM lauryl sulfate triethanolamine to pure water.
また、ポンプを用い、２００Ｌ／ｈ（流速：０．５２ｍ／ｓ）の水流をカーボン膜に当て、酸素ガスを７時間印加し、同様にレーザー光で確認した所、光の散乱現象が確認できた。 Also, using a pump, a water flow of 200 L / h (flow rate: 0.52 m / s) was applied to the carbon film, oxygen gas was applied for 7 hours, and when confirmed with laser light, the light scattering phenomenon could be confirmed. It was.
そして、酸素ガスの供給によって作成した溶液を、前記Ｍａｌｖｅｒｎ社製のＣＭＯＳカメラ及び紫色レーザーにて分析した所、下記表２及び図１０の結果が得られた。なお、図１０は表２の試料No.2-1の分析結果を示している。 And when the solution created by supply of oxygen gas was analyzed with the said Malvern CMOS camera and purple laser, the result of following Table 2 and FIG. 10 was obtained. FIG. 10 shows the analysis result of Sample No. 2-1 in Table 2.
この表２及び図１０から明らかなように、実施例５では、粒の揃った非常に微細な気泡が得られることが分かる。
また、下記表３では、試料No.2-1について、酸素ガスの印加圧力及び光の散乱現象と、前記Ｍａｌｖｅｒｎ社製のＣＭＯＳカメラ及び紫色レーザーの分析結果を示す。なお、図１１は表３の試料No.2-1の分析結果を示している。
As is apparent from Table 2 and FIG. 10, in Example 5, it can be seen that very fine bubbles with uniform grains can be obtained.
Table 3 below shows the applied pressure of oxygen gas and the light scattering phenomenon, and the analysis results of the above-mentioned Malvern CMOS camera and violet laser for sample No. 2-1. FIG. 11 shows the analysis result of Sample No. 2-1 in Table 3.
この表３及び図１１から明らかなように、粒の揃った非常に微細な気泡が得られることが分かる。
なお、この表３において、前記ＣＭＯＳカメラ及び紫色レーザーにて分析した結果が、前記表２と異なるのは、径時変化による差異である。
As is apparent from Table 3 and FIG. 11, it can be seen that very fine bubbles with uniform grains can be obtained.
In Table 3, the results of analysis with the CMOS camera and the violet laser are different from those in Table 2 because of the difference due to the change with time.
＜実施例６＞
実施例６では、前記第１実施形態と同様に、多孔質基材の表面に中間膜と最表面の多孔質膜とを備えた気泡発生部材を用いて、気泡発生装置にて気泡を発生させた。なお、実施例２と同様な内容の説明は省略する。
<Example 6>
In Example 6, as in the first embodiment, bubbles are generated by a bubble generating device using a bubble generating member having an intermediate film and an outermost porous film on the surface of a porous substrate. It was. In addition, description of the same content as Example 2 is abbreviate | omitted.
前記実施例２と同様に、カーボン膜を備えた気泡発生部材を用い、純水に塩化ナトリウム塩化ナトリウムを溶解させて１０ｍＭに調整した溶液１Ｌに、水素ガスを０．７ＭＰａで印加した。 Similarly to Example 2, hydrogen gas was applied at 0.7 MPa to 1 L of a solution in which sodium chloride sodium chloride was dissolved in pure water and adjusted to 10 mM using a bubble generating member provided with a carbon film.
また、ポンプを用い、２００Ｌ／ｈ（流速：０．５２ｍ／ｓ）の水流をカーボン膜に当て、水素ガスを５時間印加し、同様にレーザー光で確認した所、光の散乱現象が確認できた。 In addition, using a pump, a water flow of 200 L / h (flow rate: 0.52 m / s) was applied to the carbon film, hydrogen gas was applied for 5 hours, and similarly confirmed with laser light, light scattering phenomenon could be confirmed. It was.
また、水素濃度を確認する為、メチレンブルー試薬を用い滴定した所、０．４ｐｐｍの水素濃度であった。
そして、水素ガスに供給によって作成した溶液を、前記Ｍａｌｖｅｒｎ社製のＣＭＯＳカメラ及び紫色レーザーにて分析した所、下記表４及び図１２の分析結果が得られた。
Moreover, in order to confirm hydrogen concentration, when it titrated using the methylene blue reagent, it was 0.4 ppm hydrogen concentration.
And when the solution created by supplying hydrogen gas was analyzed with the said Malvern CMOS camera and purple laser, the analysis result of following Table 4 and FIG. 12 was obtained.
この表４及び図１２から明らかなように、実施例６では、粒の揃った非常に微細な気泡が得られることが分かる。
＜実施例７＞
実施例７では、前記第１実施形態と同様に、多孔質基材の表面に中間膜と最表面の多孔質膜とを備えた気泡発生部材を用いて、気泡発生装置にて気泡を発生させた。なお、実施例２と同様な内容の説明は省略する。
As is apparent from Table 4 and FIG. 12, in Example 6, it can be seen that very fine bubbles with uniform grains can be obtained.
<Example 7>
In Example 7, as in the first embodiment, bubbles are generated by a bubble generating device using a bubble generating member having an intermediate film and an outermost porous film on the surface of a porous substrate. It was. In addition, description of the same content as Example 2 is abbreviate | omitted.
前記実施例２と同様に、カーボン膜を備えた気泡発生部材を用い、純水に塩化ナトリウム塩化ナトリウムを溶解させて１０ｍＭに調整した溶液１Ｌに、酸素ガスを０．５ＭＰａで印加した。 In the same manner as in Example 2, using a bubble generating member equipped with a carbon film, oxygen gas was applied at 0.5 MPa to 1 L of a solution prepared by dissolving sodium chloride sodium chloride in pure water to 10 mM.
また、ポンプを用い、例えば２００Ｌ／ｈ（流速：０．５２ｍ／ｓ）の水流などをカーボン膜に当て、水素ガスを印加する時間、流速、膜の状態を操作して、同様にレーザー光で確認した所、光の散乱現象が確認できた。 Also, using a pump, for example, a water flow of 200 L / h (flow rate: 0.52 m / s) is applied to the carbon film, and the time for applying hydrogen gas, the flow rate, and the state of the film are manipulated. As a result, light scattering phenomenon was confirmed.
また、各試料の溶液を、前記Ｍａｌｖｅｒｎ社製のＣＭＯＳカメラ及び紫色レーザーにて分析した所、下記表５及び図１３〜図１７の分析結果が得られた。なお、図１３は試料No.1-3-2の分析結果を示し、図１４は試料No.1-4の分析結果を示し、図１５は試料No.1-5の分析結果を示し、図１６は試料No.1-6の分析結果を示し、図１７は試料No.1-7の分析結果を示す。 Moreover, when the solution of each sample was analyzed with the said Malvern CMOS camera and a purple laser, the analysis result of following Table 5 and FIGS. 13-17 was obtained. 13 shows the analysis result of sample No. 1-3-2, FIG. 14 shows the analysis result of sample No. 1-4, FIG. 15 shows the analysis result of sample No. 1-5, 16 shows the analysis result of sample No. 1-6, and FIG. 17 shows the analysis result of sample No. 1-7.
また、実施例７では、予め気泡発生部材に酸素ガスを印加してから、溶液に浸漬することを基本に行った（表５では乾燥で示す）。また、一部は気泡発生部材に溶液を浸漬後に酸素ガスを印加した（表５では不乾燥で示す）。なお、試料No.1-0-2は、酸素ガスを供給しないブランクである。 In Example 7, oxygen gas was applied to the bubble generating member in advance and then immersed in the solution (shown as dry in Table 5). In some cases, oxygen gas was applied after immersing the solution in the bubble generating member (shown as non-drying in Table 5). Sample No. 1-0-2 is a blank that does not supply oxygen gas.
この表５及び図１３〜１７から明らかなように、実施例７では、粒の揃った非常に微細な気泡が得られることが分かる。
また、下記表６に、試料No.１-4と試料No.１-5の実験条件及び前記ＣＭＯＳカメラ及び紫色レーザーにて分析した結果を記す。なお、図１８が試料No.1-4の分析結果を示し、図１９が試料No.1-5の分析結果を示す。
As apparent from Table 5 and FIGS. 13 to 17, in Example 7, it can be seen that very fine bubbles with uniform grains can be obtained.
Table 6 below shows the experimental conditions of Samples Nos. 1-4 and Nos. 1-5 and the results of analysis using the CMOS camera and the violet laser. 18 shows the analysis result of sample No. 1-4, and FIG. 19 shows the analysis result of sample No. 1-5.
この表６及び図１８、図１９から明らかなように、粒の揃った非常に微細な気泡が得られることが分かる。
なお、この表６において、前記ＣＭＯＳカメラ及び紫色レーザーにて分析した結果が、前記表５と異なるのは、径時変化による差異である。
As is apparent from Table 6 and FIGS. 18 and 19, it can be seen that very fine bubbles with uniform grains can be obtained.
In Table 6, the results of analysis using the CMOS camera and the violet laser are different from those in Table 5 because of the difference due to the change with time.
＜実施例８＞
実施例８では、前記第１実施形態と同様に、多孔質基材の表面に中間膜と最表面の多孔質膜とを備えた気泡発生部材を用いて、気泡発生装置にて気泡を発生させた。なお、実施例２と同様な内容の説明は省略する。
<Example 8>
In Example 8, as in the first embodiment, bubbles are generated by a bubble generating device using a bubble generating member having an intermediate film and an outermost porous film on the surface of a porous substrate. It was. In addition, description of the same content as Example 2 is abbreviate | omitted.
前記実施例２と同様に、カーボン膜を備えた気泡発生部材を用い、下記表７に示す条件にて、純水１Ｌに酸素ガスを印加した。そして、酸素ガスを印加した水に対して、同様にレーザー光で光の散乱現象を確認した。また、この水を、前記Ｍａｌｖｅｒｎ社製のＣＭＯＳカメラ及び紫色レーザーにて分析した。その結果を下記表７に記す。 Similarly to Example 2, oxygen gas was applied to 1 L of pure water using a bubble generating member equipped with a carbon film under the conditions shown in Table 7 below. And the light scattering phenomenon was similarly confirmed with the laser beam with respect to the water which applied oxygen gas. Moreover, this water was analyzed with the said CMOS camera and violet laser made from Malvern. The results are shown in Table 7 below.
なお、表７の試料のうち、試料No.3-2-1は、水中に浸漬する際に、加圧しながら浸漬したものである。試料No.3-2-2は、加圧せずに水中に浸漬した後にガス加圧したものである。 Of the samples in Table 7, sample No. 3-2-1 was immersed while being pressurized when immersed in water. Sample No. 3-2-2 was gas-pressurized after being immersed in water without being pressurized.
この表７から明らかなように、実施例８では、粒の揃った非常に微細な気泡が得られることが分かる。
＜実施例９＞
実施例９では、前記第１実施形態と同様に、多孔質基材の表面に中間膜と最表面の多孔質膜とを備えた気泡発生部材を用いて、気泡発生装置にて気泡を発生させた。なお、実施例１と同様な内容の説明は省略する。
As is apparent from Table 7, it can be seen that in Example 8, very fine bubbles with uniform grains can be obtained.
<Example 9>
In Example 9, as in the first embodiment, bubbles are generated by a bubble generating device using a bubble generating member having an intermediate film and an outermost porous film on the surface of a porous substrate. It was. Note that the description of the same contents as in the first embodiment is omitted.
前記実施例１と同様に、γ−アルミナ膜を備えた気泡発生部材を用い、下記表９に示す条件にて、純水１Ｌに酸素ガスを印加した。そして、酸素ガスを印加した水に対して、同様にレーザー光で光の散乱現象を確認した。また、この水を、前記Ｍａｌｖｅｒｎ社製のＣＭＯＳカメラ及び紫色レーザーにて分析した。その結果を下記表８に記す。 In the same manner as in Example 1, an oxygen gas was applied to 1 L of pure water using a bubble generating member provided with a γ-alumina film under the conditions shown in Table 9 below. And the light scattering phenomenon was similarly confirmed with the laser beam with respect to the water which applied oxygen gas. Moreover, this water was analyzed with the said CMOS camera and violet laser made from Malvern. The results are shown in Table 8 below.
なお、表９の試料のうち、試料No.4-1-2は、水中に浸漬する際に、加圧しながら浸漬したものである。試料No.4-1-2は、加圧せずに水中に浸漬した後にガス加圧したものである。 Of the samples shown in Table 9, sample No. 4-1-2 was immersed while being pressurized when immersed in water. Sample No. 4-1-2 was gas-pressurized after being immersed in water without being pressurized.
この表８から明らかなように、実施例９では、粒の揃った非常に微細な気泡が得られることが分かる。
＜実施例１０＞
実施例１０では、前記第１実施形態と同様な多孔質基材と中間膜とγ−アルミナ膜とを備えるとともに、γ−アルミナ膜の表面に、更に最表面の多孔質膜としてシリカ膜（即ちゼオライト膜）を備える気泡発生部材を用いて、気泡発生装置にて気泡を発生させた。なお、実施例１と同様な内容の説明は省略する。
As is apparent from Table 8, it can be seen that in Example 9, very fine bubbles with uniform grains can be obtained.
<Example 10>
In Example 10, the same porous substrate, intermediate film, and γ-alumina film as those in the first embodiment were provided, and a silica film (that is, the outermost porous film) was further formed on the surface of the γ-alumina film. Bubbles were generated by a bubble generator using a bubble generating member provided with a zeolite membrane. Note that the description of the same contents as in the first embodiment is omitted.
実施例１０では、最表面の多孔質膜として、平均細孔径０．３ｎｍ、厚み５μｍのシリカ膜を用いた。
このシリカ膜は、γ-アルミナ膜の表面に、下記の方法で形成した。
In Example 10, a silica film having an average pore diameter of 0.3 nm and a thickness of 5 μm was used as the outermost porous film.
This silica film was formed on the surface of the γ-alumina film by the following method.
まず、テトラエトキシシランを硝酸存在下で加水分解して、シリカゾルを調整した。このシリカゾル液をエタノールで希釈して、水濃度が１％となるよう調整した。
次に、前記γ―アルミナ膜付きの多孔質基材を、シリカゾル液中に浸漬し、γ―アルミナ膜の表面に、シリカ膜前駆体を形成し、乾燥を経て、３００℃で１時間焼成してシリカ膜を得た。
First, tetraethoxysilane was hydrolyzed in the presence of nitric acid to prepare a silica sol. This silica sol solution was diluted with ethanol to adjust the water concentration to 1%.
Next, the porous substrate with the γ-alumina film is immersed in a silica sol solution to form a silica film precursor on the surface of the γ-alumina film, dried, and fired at 300 ° C. for 1 hour. Thus, a silica film was obtained.
なお、テトラエトキシシランの構造を基準に官能基などを導入した派生化合物を用いることで、シリカ膜の平均細孔径を操作することができる。
そして、シリカ膜を備えた気泡発生部材を用い、下記表９に示す条件にて、純水１Ｌに酸素ガスを印加した。
In addition, the average pore diameter of a silica film can be manipulated by using a derivative compound having a functional group or the like introduced based on the structure of tetraethoxysilane.
Then, oxygen gas was applied to 1 L of pure water using a bubble generating member provided with a silica film under the conditions shown in Table 9 below.
その後、酸素ガスを印加した水に対して、同様にレーザー光で散乱現象を確認した。また、この水を、前記Ｍａｌｖｅｒｎ社製のＣＭＯＳカメラ及び紫色レーザーにて分析した。その結果を下記表９に記す。 Thereafter, the scattering phenomenon was similarly confirmed with laser light for water to which oxygen gas was applied. Moreover, this water was analyzed with the said CMOS camera and violet laser made from Malvern. The results are shown in Table 9 below.
なお、表９の試料のうち、試料No.5-1-2は、水中に浸漬する際に、加圧しながら浸漬したものである。試料No.5-1-2は、加圧せずに水中に浸漬した後にガス加圧したものである。 Of the samples shown in Table 9, sample No. 5-1-2 was immersed while being pressurized when immersed in water. Sample No. 5-1-2 was gas-pressurized after being immersed in water without being pressurized.
この表９から明らかなように、実施例１０では、粒の揃った非常に微細な気泡が得られることが分かる。
＜実施例１１＞
実施例１１では、前記第１実施形態と同様に、多孔質基材の表面に中間膜と最表面の多孔質膜とを備えた気泡発生部材を用いて、気泡発生装置にて気泡を発生させた。なお、実施例２と同様な内容の説明は省略する。
As is apparent from Table 9, in Example 10, it can be seen that very fine bubbles with uniform grains can be obtained.
<Example 11>
In Example 11, as in the first embodiment, bubbles are generated by a bubble generating device using a bubble generating member having an intermediate film and an outermost porous film on the surface of a porous substrate. It was. In addition, description of the same content as Example 2 is abbreviate | omitted.
前記実施例２と同様に、カーボン膜を備えた気泡発生部材を用い、下記表１０に示す条件にて、エタノールに酸素ガスを印加した。
そして、この酸素ガスを印加した溶液に対して、同様にレーザー光で光の散乱現象を確認した。また、この溶液を、前記Ｍａｌｖｅｒｎ社製のＣＭＯＳカメラ及び紫色レーザーにて分析した。その結果を下記表１０に記す。
Similarly to Example 2, oxygen gas was applied to ethanol under the conditions shown in Table 10 below using a bubble generating member provided with a carbon film.
And the light scattering phenomenon was similarly confirmed with the laser beam with respect to the solution to which this oxygen gas was applied. Further, this solution was analyzed with the above-mentioned Malvern CMOS camera and violet laser. The results are shown in Table 10 below.
この表１１から明らかなように、実施例１１では、粒の揃った非常に微細な気泡が得られることが分かる。
＜実施例１２＞
前記実施例１０と同様なシリカ膜（即ちゼオライト膜）を備えた気泡発生部材を用い、下記表１１に示す条件にて、純水１Ｌに酸素ガスを印加した。
As is apparent from Table 11, it can be seen that in Example 11, very fine bubbles with uniform grains can be obtained.
<Example 12>
An oxygen gas was applied to 1 L of pure water under the conditions shown in Table 11 below using a bubble generating member having the same silica membrane (that is, a zeolite membrane) as in Example 10.
そして、酸素ガスを印加した水に対して、同様にレーザー光で光の散乱現象を確認した。また、この水を、前記Ｍａｌｖｅｒｎ社製のＣＭＯＳカメラ及び紫色レーザーにて分析した。その結果を下記表１１に記す。 And the light scattering phenomenon was similarly confirmed with the laser beam with respect to the water which applied oxygen gas. Moreover, this water was analyzed with the said CMOS camera and violet laser made from Malvern. The results are shown in Table 11 below.
この表１１から明らかなように、実施例１２では、粒の揃った非常に微細な気泡が得られることが分かる。
＜実施例１３＞
実施例１３では、前記第１実施形態と同様に、多孔質基材の表面に各種の中間膜と各種の最表面の多孔質膜とを備えた複数の気泡発生部材の試料を作製した。なお、実施例１と同様な内容の説明は省略する。
As can be seen from Table 11, in Example 12, very fine bubbles with uniform grains can be obtained.
<Example 13>
In Example 13, as in the first embodiment, samples of a plurality of bubble generating members having various intermediate films and various outermost porous films on the surface of the porous substrate were prepared. Note that the description of the same contents as in the first embodiment is omitted.
具体的には、実施例１と同様な多孔質基材の表面に、下記表１２に示す中間膜（中間膜Ｃ、中間膜Ｂ、中間膜Ａ）と最表面の多孔質膜とを形成した。そして、各試料の中間膜や最表面の多孔質膜の平均細孔径や膜厚を調べた。その結果を同じく下記表１２に記す。 Specifically, an intermediate film (intermediate film C, intermediate film B, intermediate film A) shown in Table 12 below and the outermost porous film were formed on the surface of the same porous substrate as in Example 1. . Then, the average pore diameter and film thickness of the intermediate film and the outermost porous film of each sample were examined. The results are also shown in Table 12 below.
なお、表１２のシリカ膜（ゼオライトＭＦＩ型、シリカライトワン）、耐水性ゼオライト膜（ゼオライトＭＯＲ型）については、それぞれ異なる平均細孔径（(1)と（2）の２種）を有するものがある。
［５．他の実施形態］
本発明は前記実施形態になんら限定されるものではなく、本発明を逸脱しない範囲において種々の態様で実施しうることはいうまでもない。
The silica membranes (zeolite MFI type, silicalite one) and water-resistant zeolite membranes (zeolite MOR type) shown in Table 12 have different average pore sizes (two types (1) and (2)). is there.
[5. Other Embodiments]
It goes without saying that the present invention is not limited to the above-described embodiment, and can be implemented in various modes without departing from the present invention.
（１）例えば、筒状の多孔質基材を用いる場合には、その内側又は外側に、中間膜や最表面の多孔質膜を設けてもよい。
この場合には、最表面の多孔質膜の無い側から気体を供給し、最表面の多孔質膜から液体にマイクロバブルやナノバブルを供給する。
(1) For example, when a cylindrical porous substrate is used, an intermediate film or an outermost porous film may be provided on the inner side or the outer side.
In this case, gas is supplied from the side having no porous film on the outermost surface, and microbubbles or nanobubbles are supplied from the outermost porous film to the liquid.
（２）また、第１実施形態では、気泡発生管に水流を当てたが、水流を当てないようにしてもよい。或いは、気泡発生部材（従って気泡発生管）を振動させてもよい。
（３）さらに、第１実施形態では、気泡発生管に所定圧力にて気体を供給したが、気泡発生管に大気を導入してもよい。この場合も、微細な気泡が発生するが、水流を当てたり、振動を与えることが好ましい。
(2) Moreover, in 1st Embodiment, although the water flow was applied to the bubble generation tube, you may make it not apply a water flow. Alternatively, the bubble generating member (and hence the bubble generating tube) may be vibrated.
(3) Furthermore, in the first embodiment, the gas is supplied to the bubble generating tube at a predetermined pressure, but the atmosphere may be introduced into the bubble generating tube. In this case as well, fine bubbles are generated, but it is preferable to apply a water flow or to vibrate.
（４）気体を気泡発生管に供給するタイミングとしては、気泡発生管を液につけた状態で気体を供給してよいが、気体を気泡発生管に供給する状態で、液中に投入してもよい。
（５）気体が供給される液体は容器内に充填されたものでもよく、或いは、連続して液体が供給される流動状態のものでもよい。
(4) As the timing for supplying the gas to the bubble generating tube, the gas may be supplied with the bubble generating tube attached to the liquid. However, even if the gas is supplied to the bubble generating tube, Good.
(5) The liquid supplied with the gas may be filled in the container, or may be in a fluidized state where the liquid is continuously supplied.
（６）前記実施形態の構成を適宜組み合わせることができる。
（７）本発明は、洗浄、浄水、衛生管理、工業分野、医療分野、食品分野、農業分野、水産・漁業分野、畜産分野、スポーツ分野など、各種の分野に適用することができる。
(6) The configurations of the above embodiments can be combined as appropriate.
(7) The present invention can be applied to various fields such as cleaning, water purification, hygiene management, industrial field, medical field, food field, agricultural field, fishery / fishery field, livestock field, and sports field.
１…気泡発生部材
３…気泡発生管
３１…多孔質基材
３３…中間膜
３５…最表面の多孔質膜（例えばカーボン膜）
DESCRIPTION OF SYMBOLS 1 ... Bubble generating member 3 ... Bubble generating pipe 31 ... Porous base material 33 ... Intermediate film 35 ... Outermost porous film (for example, carbon film)
Claims (12)
該構造体の前記多孔質基材側から前記多孔質膜側に気体を供給して、液体中にマイクロバブル及びナノバブルの少なくとも一方の大きさの気泡を発生させる気泡発生部材において、
前記構造体の最表面の前記多孔質膜の平均細孔径が０．３ｎｍ〜１μｍであり、且つ、該多孔質膜の厚みが５０μｍ以下である気泡発生部材。 A structure comprising: a porous substrate; and one or more porous films having finer pores than the porous substrate on at least one of the inside and outside of the porous substrate,
In the bubble generating member for supplying a gas from the porous substrate side of the structure to the porous membrane side to generate bubbles of at least one size of microbubbles and nanobubbles in the liquid,
A bubble generating member in which an average pore diameter of the porous film on the outermost surface of the structure is 0.3 nm to 1 μm, and a thickness of the porous film is 50 μm or less.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003265939A (en) * | 2002-03-13 | 2003-09-24 | Yasushi Takeda | Apparatus and method for generating air bubble, and apparatus and method for producing fine particle |
| JP2008514428A (en) * | 2004-10-01 | 2008-05-08 | ヴェロシス，インク． | Multiphase mixing process using microchannel process technology |
| JP2011224461A (en) * | 2010-04-19 | 2011-11-10 | Hang-Ichi:Kk | Microbubble generator |
| WO2013088667A1 (en) * | 2011-12-16 | 2013-06-20 | パナソニック株式会社 | System and method for generating nanobubbles |
| JP2016140801A (en) * | 2015-01-30 | 2016-08-08 | 株式会社ノリタケカンパニーリミテド | Microbubble generating tool and generator of microbubble-containing liquid |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003265939A (en) * | 2002-03-13 | 2003-09-24 | Yasushi Takeda | Apparatus and method for generating air bubble, and apparatus and method for producing fine particle |
| JP2008514428A (en) * | 2004-10-01 | 2008-05-08 | ヴェロシス，インク． | Multiphase mixing process using microchannel process technology |
| JP2011224461A (en) * | 2010-04-19 | 2011-11-10 | Hang-Ichi:Kk | Microbubble generator |
| WO2013088667A1 (en) * | 2011-12-16 | 2013-06-20 | パナソニック株式会社 | System and method for generating nanobubbles |
| JP2016140801A (en) * | 2015-01-30 | 2016-08-08 | 株式会社ノリタケカンパニーリミテド | Microbubble generating tool and generator of microbubble-containing liquid |
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