WO2010134551A1 - Gas-liquid mixture - Google Patents

Abstract

Provided is a gas-liquid mixture wherein the gas in a solution is present as bubbles which remain stable over a long period of time. The gas-liquid mixture has bubbles present in a liquid comprising molecules that form hydrogen bonds, and the distance between hydrogen bonds in the molecule at the liquid-foam interface is made shorter than the distance between hydrogen bonds of the molecules that constitute the liquid when the liquid is at room temperature and normal pressure. This makes it possible to surround the bubbles with liquid molecules that form strong hydrogen bonds, and for the bubbles to exist in a stable manner within the liquid. Liquids that may be used include water, liquids comprising molecules having either an O-H bond, an N-H bond, a (halogen)-H bond or an S-H bond, and liquids comprising molecules having a carboxyl group.

Description

Gas-liquid mixture

The present invention relates to a gas-liquid mixture in which gas is present as stable bubbles in the liquid.

Conventionally, a gas-liquid mixture in which fine bubbles are dispersed in a liquid is known. In particular, micro-bubble water in which micro-order size bubbles are mixed with water and nano-bubble water in which nano-order size bubbles are mixed with water are extremely small in size compared to normal bubbles, and therefore have unique properties. And has been attempted to be used in various fields (see, for example, Patent Document 1).

However, the fine bubbles in the liquid tend to disappear when dissolved or coalesced, making it difficult to stably exist in the liquid. For this reason, gas is continuously supplied to the liquid for bubbling, or a strong force is applied to agitate to generate bubbles, and the liquid is used so that the generated bubbles do not disappear. Yes. Further, as the size of the bubbles becomes nano-order and the size of the bubbles becomes finer, the bubbles are more difficult to be generated and more easily disappeared, and it is more difficult to use the liquid in which the bubbles are dispersed.

Patent Documents 2 to 4 disclose that nanobubbles are stabilized by rapidly reducing microbubbles. In the methods of these documents, a part of microbubbles is reduced by applying a force of strength, and both ions having opposite signs attracted to an aqueous solution near the interface by ions adsorbed on the gas-liquid interface and electrostatic attractive force. The ions are concentrated in a minute volume at a high concentration to act as a shell surrounding the microbubbles, and the nanobubbles are stabilized by inhibiting diffusion of the gas in the microbubbles into the aqueous solution. However, in order to stabilize nanobubbles, it is necessary to generate an electrostatic force at the gas-liquid interface, so the presence of an electrolyte is indispensable. In solutions such as pure water in which an electrolytic substance is not dissolved, nanobubbles are prevented. It could not exist stably.

Also, since only a part of the microbubbles is reduced, there is a problem that the distribution amount of nanobubbles is small and it is difficult to obtain the effect. Furthermore, since the nanobubbles are stabilized by ions surrounding the bubble, it is not easy to control the stable state of the bubble by dissolving or coalescing the bubble, and the use of a gas-liquid mixture is not possible. It was limited.

Patent Document 5 discloses that nanobubbles are generated by electrolyzing water and then applying ultrasonic waves. However, in the electrolysis of water, the gas is limited to hydrogen and oxygen, the amount of gas generated by electrolysis is small, and the generated bubbles are not stabilized. And the bubbles could not be stably maintained over a long period of time.

JP 2008-156320 A JP 2005-245817 A JP 2005-246293 A JP 2005-246294 A JP 2003-334548 A

The present invention has been made in view of the above points, and an object of the present invention is to provide a gas-liquid mixture in which gas is present in a liquid as a high-density and stable bubble over a long period of time. is there.

The gas-liquid mixture of the present invention is a gas-liquid mixture in which bubbles are present in a liquid composed of molecules that form hydrogen bonds, and the distance between hydrogen bonds of molecules present at the interface with the liquid bubbles is It is characterized by being shorter than the hydrogen bond distance of the molecules constituting the liquid when the liquid is at normal temperature and pressure.

In the above gas-liquid mixture, the liquid is preferably water.

In the gas-liquid mixture described above, the liquid is a liquid composed of molecules having at least one of OH bond, NH bond, (halogen) -H bond, and SH bond. It is preferable.

Further, in the above gas-liquid mixture, the liquid is preferably a liquid composed of molecules having a carboxyl group.

In the gas-liquid mixture, it is preferable that the concentration of the gas contained in the gas-liquid mixture is equal to or higher than the saturated dissolution concentration of the liquid.

Moreover, in the gas-liquid mixture, it is preferable that the pressure of the gas forming the bubbles is 0.12 MPa or more.

According to the gas-liquid mixture of the present invention, the distance between hydrogen bonds at the bubble interface is shortened, so that the bubbles can be surrounded by liquid molecules that form strong hydrogen bonds. Since the molecule forms a strong shell and encloses the bubble, it does not collapse even if the bubbles collide with each other, and can counteract the pressure from the liquid with the stress from the inside of the bubble, causing the bubble to disappear in the liquid It can exist stably without being combined with each other. And since this hydrogen bond is stable over a long period of time, it becomes possible to use the gas-liquid mixture in which bubbles existed stably over a long period of time. Further, nano-order size bubbles can be generated at a density far exceeding the conventional level and can be stably present in the gas-liquid mixture.

It is a graph which shows the difference of the infrared absorption spectrum of the gas-liquid mixed liquid using nitrogen and water, and nitrogen saturated water. It is a graph which shows the gas volume contained in a gas-liquid liquid mixture. It is a photograph of the gas-liquid mixed solution by a scanning electron microscope (SEM). It is the schematic which shows an example of a gas-liquid mixture manufacturing apparatus, (a) is the whole schematic, (b) is a partial schematic. (A) to (c) are each a schematic view showing a part of the gas-liquid mixture manufacturing apparatus. (A) to (d) are each a schematic view showing a part of the gas-liquid mixed liquid production apparatus. It is the schematic which shows a part of gas-liquid mixture manufacturing apparatus. It is the schematic which shows another example of a gas-liquid liquid mixture manufacturing apparatus. It is the schematic which shows an example of the gas utilization system using a gas-liquid liquid mixture. It is the schematic which shows another example of the gas utilization system using a gas-liquid liquid mixture. It is a conceptual explanatory drawing of the gas-liquid interface of the bubble in a gas-liquid mixed liquid. It is a graph which shows stability of a gas-liquid liquid mixture. It is a conceptual explanatory drawing which shows the model which utilizes gas with a gas-liquid liquid mixture.

Hereinafter, modes for carrying out the invention will be described.

For the gas-liquid mixture of the present invention, a liquid composed of molecules that form hydrogen bonds is used. A hydrogen bond is a bond that stabilizes the system in a molecule that has a high electronegativity atom and a hydrogen atom, because the hydrogen atom approaches the high electronegativity atom of another molecule. . Bubbles are present in the liquid forming the gas-liquid mixture, and in the liquid molecules existing around the bubbles, that is, at the interface with the bubbles, the distance of hydrogen bonding between the molecules is (25 ° C., 1 atm (0.1013 MPa)), which is shorter than the hydrogen bond distance of the molecules constituting the liquid. In this way, when the gas-liquid mixture exists under normal temperature and normal pressure conditions, the hydrogen bond distance at the bubble interface becomes shorter than the normal hydrogen bond distance at normal temperature and normal pressure, thereby It will be surrounded by liquid molecules that form strong hydrogen bonds. And the liquid molecule which formed this hydrogen bond turns into a firm shell, and encloses a bubble. As a result, even if the bubbles collide with each other, they will not collapse, and the pressure from the liquid can be countered by the stress from the inside of the bubbles, so the bubbles can be held without disappearing or coalescing in the liquid. Is something that can be done. In other words, it is different from conventional bubbles that are stable with surface tension.

The size of the bubbles contained in the gas-liquid mixture is not particularly limited, but is preferably finer, and can be a micro-order of 1000 μm or less (so-called microbubbles). In addition, those having a nano-order of 1 to 1000 nm (so-called nanobubbles) can be preferably used. Since the buoyancy does not substantially act on the nano-order size bubbles, the bubbles do not rise and separate from the liquid, so that the bubbles can exist stably over a long period of time. Even if the bubble is smaller or larger than this range, the bubble may not be stabilized. In addition, the bubble size can be measured by a scanning electron microscope (SEM), and the average particle diameter of the bubbles can be obtained by averaging the particle diameters of the bubbles obtained by the measurement. By the way, the liquid mixed with microbubbles is cloudy and can be discriminated visually. However, the liquid mixed with nanobubbles is colorless and transparent (or the color of the liquid when the liquid is colored) and can be discriminated visually. Can not.

One of the liquids preferably used for the gas-liquid mixture is water. The water molecule is a hydrogen bond of O ... H, that is, a hydrogen bond is formed between an oxygen atom of one water molecule and a hydrogen atom of another water molecule, and water is used as the liquid of the gas-liquid mixture. Then, this hydrogen bond in the liquid becomes stronger at the bubble interface, and the bubbles can be further stabilized. In addition, water is abundant in supply sources, can be obtained stably, is safe for the human body, and since water with dispersed bubbles has a wide range of applications, it is possible to obtain a highly useful gas-liquid mixture. It can be done. In the present invention, the water is not limited to high-purity water, and any water can be used including water and sewage systems, ponds, seawater, and the like. That is, any material that contains water as a liquid may be used.

As described above, in the gas-liquid mixed solution, it is one of preferable modes that the liquid is water. In that case, the hydrogen bonds of O ... H formed by water molecules, that is, the bonds between oxygen atoms of one water molecule and hydrogen atoms of another water molecule become stronger, and the bubbles can be further stabilized. At the same time, since water in which bubbles are dispersed has a wide range of applications, it is possible to obtain a gas-liquid mixture having high utility value.

Further, the liquid is a liquid composed of molecules having at least one of (halogen) -H bond and SH bond such as OH bond, NH bond, FH bond and Cl-H bond. It is also preferable. These bonds are bonds between atoms and hydrogen atoms having a sufficiently large electronegativity with respect to hydrogen atoms, such as OH ... O, NH ... N, FH ... F and Cl-H ... Cl. (Halogen) -H ... (halogen), SH ... S, etc., are formed, and these hydrogen bonds can surround the bubbles and stabilize the bubbles. A typical liquid having an OH bond is water, but other examples include alcohols such as hydrogen peroxide, methanol and ethanol, and glycerin. Examples of the liquid having an N—H bond include ammonia. Examples of those having a (halogen) -H bond include HF (hydrogen fluoride) having an FH bond and HCl (hydrogen chloride) having a Cl-H bond. Moreover, H ₂ S (hydrogen sulfide) can be given as an example having an S—H bond.

As described above, in the gas-liquid mixture, the liquid is a liquid composed of molecules having one or more of OH bond, NH bond, (halogen) -H bond, and SH bond. This is one of the preferred forms. In that case, the bubbles can be stabilized by surrounding the bubbles by strong hydrogen bonds such as OH ... O, NH ... N, (halogen) -H ... (halogen), and SH ... S. Can be obtained.

It is also preferable that the liquid is a liquid composed of molecules having a carboxyl group. The carboxyl group has a carbonyl oxygen atom with high electronegativity, and the carbonyl oxygen atom in one carboxyl group and a hydrogen atom in another carboxyl group form a strong hydrogen bond to surround the bubble. Therefore, it is possible to obtain a gas-liquid mixture in which bubbles are stably present. Examples of the liquid composed of molecules having a carboxyl group include carboxylic acids such as formic acid and acetic acid.

As described above, in the gas-liquid mixed solution, it is one of preferable modes that the liquid is a liquid composed of molecules having a carboxyl group. In that case, since the oxygen atom in the carboxyl group and the hydrogen atom in the other carboxyl group form a strong hydrogen bond and surround the bubble, a gas-liquid mixture in which the bubble is stably present can be obtained. .

The gas used for the gas-liquid mixture is not particularly limited, and various gases can be used. For example, gases such as air, carbon dioxide, nitrogen, oxygen, ozone, argon, hydrogen, helium, methane, propane, and butane can be used singly or in combination.

The gas concentration contained in the gas-liquid mixture is preferably equal to or higher than the saturated dissolution concentration of the liquid. If a saturated gas amount or a large amount of gas exceeding it is held in the liquid, a high-concentration gas contained in the liquid can be used, and the utility value of the gas-liquid mixture can be increased. . More preferably, a saturated dissolved amount of gas is dissolved in the gas-liquid mixed liquid, and bubbles are present in the saturated dissolved liquid. If the gas is dissolved in the saturated dissolution amount, it becomes possible to stabilize the gas in the form of bubbles without dissolving them and to hold them in the liquid as bubbles. In other words, a gas-liquid mixed solution in which a gas is present in excess of the saturated dissolution amount has a gas dissolved at a saturated concentration in the liquid, and the bubbles do not collapse or dissolve, and the bubbles are more stably contained in the liquid. Can be present. Thus, when the concentration of the gas contained in the gas-liquid mixture increases, the bubbles can be stabilized in a state where the distance of hydrogen bonding is shortened, and various activities (physiological activity, detergency, etc.) The action becomes stronger and the utility value can be further increased. The amount of gas in the gas-liquid mixture can be calculated from the amount of mass change by separating the gas from the gas-liquid mixture as shown in the examples described later.

Thus, in the gas-liquid mixture, it is preferable that the concentration of the gas contained in the gas-liquid mixture is equal to or higher than the saturated dissolution concentration of the liquid. In that case, by maintaining a large amount of gas in or above the saturated dissolution amount in the liquid, the hydrogen bond with a short distance at the bubble interface is stabilized, and a high concentration gas contained in the liquid is used. It is possible to increase the utility value of the gas-liquid mixture.

Moreover, in the gas-liquid mixture, it is preferable that the pressure of the gas forming the bubbles is 0.12 MPa or more. In that case, a stronger interface structure can be formed by maintaining the bubbles at a high internal pressure, and in the stationary state, stable bubbles are formed and an impact is once applied to the gas-liquid mixture. Then, the shell of the liquid formed by hydrogen bonds collapses due to the force of the internal pressure, and the bubbles merge and foam, so this foaming can be used and the utility value of the gas-liquid mixture can be increased. It is possible.

As described above, it is preferable that the pressure of the gas forming the bubbles, that is, the internal pressure of the bubbles is 0.12 MPa or more, but it is higher than the internal pressure of the bubbles given by the Young Laplace equation (the following equation). A pressure is preferred.

Young Laplace's formula ΔP = 2σ / r
[ΔP: rising pressure inside the bubble, σ: surface tension, r: bubble radius]

When the internal pressure of the bubbles becomes such a pressure, the bubbles are maintained at a higher internal pressure, and a stronger interface structure can be formed. Therefore, stable bubbles can be formed in a stationary state. . On the other hand, once an impact is applied to the gas-liquid mixture, the balance of the internal pressure force is disrupted, the liquid shell in which hydrogen bonds are formed collapses, the bubbles merge, foam and escape from the liquid Therefore, this foaming can be used. The internal pressure of the bubbles in the gas-liquid mixed liquid can be calculated by applying the total gas amount in the gas-liquid mixed liquid and the gas volume calculated from the density to the gas equation of state as shown in the examples described later.

The distance between the hydrogen bonds of the liquid molecules at the interface with the bubbles can be set as appropriate depending on the liquid used, but is 99% or less when the distance between hydrogen bonds at room temperature and normal pressure is 100%. Is preferred. When the hydrogen bond distance falls within this range, the bubbles can be surrounded and stabilized by a hard shell of hydrogen bonds. If the distance between hydrogen bonds is longer than this, there is a possibility that bubbles cannot be stabilized and exist. Considering the interatomic distance, the lower limit of the hydrogen bond distance is 95%. The hydrogen bond distance at the bubble interface in the gas-liquid mixture can be calculated by analyzing the infrared absorption spectrum (IR) of the gas-liquid mixture as shown in the examples described later.

By the way, water having a hydrogen bond distance of the above-mentioned distance usually has an ice or hydrate crystal structure. However, in the gas-liquid mixed liquid of the present invention, the above-mentioned locally at the bubble interface. A hydrogen bond with a short distance is formed, and a normal hydrogen bond is formed in other liquids. That is, a hard shell of liquid molecules is formed by hydrogen bonds at a short distance at the bubble interface to prevent the bubbles from coalescing and disappearing, and at other than the bubble interface, liquid exists in a normal state and normal temperature At normal pressure, fluidity is ensured, and it is easy to use liquid in which stable bubbles are present.

In the gas-liquid mixture of the present invention, when water is used as the liquid, the zeta potential becomes negative. For example, in the examples described later, the area of the bubble interface existing in a volume of 1 cm ³ is 0.6 to 1. the 2m ² about. Such characteristics can be used in various fields.

Next, the production of the gas / liquid mixture of the present invention will be described.

In the production of the gas-liquid mixture, the liquid into which the gas has been injected is pressurized at a pressure rate ΔP ₁ / t (ΔP ₁ : pressure increase, t: time) of 0.17 MPa / sec or more. At that time, the pressure of the liquid is set to 0.15 MPa or more by pressurization. Thereafter, the pressure is gradually reduced to atmospheric pressure by setting the upper limit of the pressure reduction rate ΔP ₂ / t (ΔP ₂ : pressure reduction amount, t: time) in the entire piping while feeding the liquid. Thereby, a liquid in which nano-sized bubbles are mixed can be generated.

FIG. 4 is a schematic view showing an example of an apparatus for producing a gas-liquid mixed solution. This gas-liquid mixed liquid manufacturing apparatus is an apparatus for continuously manufacturing a gas-liquid mixed liquid by pumping liquid, taking out the liquid held at atmospheric pressure (0.1 MPa) from the liquid storage tank 12 and pumping it. A pressurizing unit 1 that pressurizes the gas, a gas supply unit 2 that supplies a gas to the liquid, a gas-liquid mixing unit 3 that mixes the supplied gas with fine liquids, and a liquid in the gas-liquid mixing unit 3 A defoaming section 4 for removing large bubbles present in the gas, a decompression section 5 for gradually depressurizing the liquid from which the large bubbles have been removed by the defoaming section 4 to an atmospheric pressure without generating large bubbles, And a discharge portion 7 for discharging the liquid, and each portion is provided connected to the flow path 6.

The pressurizing unit 1 pumps the liquid to the gas-liquid mixing unit 3 and can be constituted by, for example, a pump 11 that sucks the liquid from the liquid storage tank 12 as in this device. It can also be composed of piping that sends out pressure. The gas supply unit 2 supplies gas to the liquid by being connected to the flow path 6. For example, when supplying air as gas, the other end of the tubular body whose one end is opened to the atmosphere is connected. The gas supply unit 2 can be formed by connecting to the flow path 6. Or when supplying oxygen, ozone, hydrogen, nitrogen, a carbon dioxide, argon etc. as gas, the gas supply part 2 can also be formed by connecting the cylinder etc. which enclosed these gas to the flow path 6. FIG. Moreover, when supplying ozone, you may make it connect the gas supply part 2 to an ozone generator, and supply the ozone produced | generated from air. The connection position of the gas supply unit 2 to the flow path 6 may be a position upstream of the gas-liquid mixing section 3 and is connected to the flow path 6 upstream of the pressurizing section 1 as in this device. Alternatively, it may be either connected to the flow path 6 on the downstream side of the pressurizing unit 1.

The gas-liquid mixing unit 3 mixes the pumped liquid and the gas supplied to the liquid, and converts the gas into fine bubbles by pressurization to disperse and mix in the liquid. The gas-liquid mixing unit 3 can be configured by applying a stirring force by changing the cross-sectional area of the flow path, or if the liquid is flowing in the flow path 6 with the liquid being stirred, 6 can also be configured. When the gas supply unit 2 is in the flow path 6 on the upstream side of the pressurizing unit 1 as in this apparatus, the pressurizing unit 1 constituted by the pump 11 or the like may also be used as the gas-liquid mixing unit 3.

When pressurization and mixing of gas and liquid are performed by the pump 11, the liquid can be rapidly pressurized and mixed, so that a gas-liquid mixture having a strong bubble interface structure can be reliably generated. Moreover, it is also preferable that the gas-liquid mixing unit 3 is constituted by a Venturi tube. In that case, the liquid can be rapidly pressurized and mixed with a simple configuration.

In the gas-liquid mixing unit 3, the liquid and gas are mixed under high pressure conditions. As a result, hydrogen bonds having a shorter bond distance are formed around the bubbles, and the bubbles can be covered with the shell of the hydrogen bonds, and the gas can be stabilized as fine bubbles.

By the pressurization unit 1 and the gas-liquid mixing unit 3 as described above, a strong pressure is suddenly applied to the liquid into which the gas is injected, and the bubbles existing in the liquid are subdivided into fine nano-sized bubbles. And dispersed in the liquid. In addition, a strong interface structure is formed by liquid molecules at the interface of the bubbles that have become high pressure due to a sudden pressure change. At that time, when the pressurization rate ΔP ₁ / t (ΔP ₁ : pressure increase, t: time) is 0.17 MPa / sec or more, the bubbles are subdivided to generate fine nano-sized bubbles. The pressure of the gas-liquid mixed liquid when it is sent out from the gas-liquid mixing part 3 to the defoaming part 4 becomes 0.15 MPa or more, thereby generating nano-sized bubbles with a strong structure at the bubble interface Is something that can be done. In consideration of substantial pressurization conditions, the upper limit of the pressurization rate ΔP ₁ / t is 167 MPa / sec, and the upper limit of the pressure of the pressurized gas-liquid mixture is 50 MPa.

FIG. 4B is a schematic view of the main part showing an example of a specific form of the pump 11. The pump 11 a pressurizes the liquid by the rotation of the rotating body 21, and the rotating blades 22 attached to the rotating body 21 continuously rotate to pump the pump outlet 27 through the pump passage chamber 23 from the pump inlet 26. The liquid is sent out in the direction of flow to and pressurized. In the figure, the white arrow indicates the flow direction of the liquid, and the solid line arrow indicates the rotation direction of the rotating body 21. The pump 11a includes four rotary blades 22. Further, the rotating shaft 25 of the rotating body 21 is arranged so as to be deviated toward the pump outlet 27 side from the cylindrical center of the pump wall 24 formed in a cylindrical shape, and is provided as an eccentric shaft. The volume of the second flow path chamber 23b of the pump flow path chamber 23 is formed smaller than the volume of the first flow path chamber 23a due to the eccentricity of the rotary shaft 21, and the pump flow path chamber is arranged along the liquid flow direction. The volume of 23 is gradually reduced.

Then, the liquid fed to the pump flow passage chamber 23 is pressurized is fed by rotating blades 22, large bubbles B _B due to rapid pressure changes bubbles B _N of subdivided by fine nano-sized generated . That is, the liquid sent from the first flow path chamber 23a to the second flow path chamber 23b along with the rotation of the rotating body 21 is rapidly compressed and pressurized as the volume of the pump flow path chamber 23 becomes smaller. Nano-sized bubbles _BN are generated by the pressure. Further, in the illustrated pump 11a, a shearing force is applied when the liquid passes between the inner surface of the pump wall 24 and the tip of the rotor blade 22, and the liquid is pressurized while being sheared by the clearance. At this time, the gas (large bubbles B _B ) mixed in the liquid is sheared by the shearing force applied to the liquid and becomes finer nano-sized bubbles (B _N ). The distance narrowest part between the inner surface of the pump wall 24 and the tip portion of the rotor blades 22, i.e. the clearance distance L _C is preferably 5 [mu] m ~ 2 mm. Thus, according to the pump 11a using the rotator 21, it is possible to form nano-sized bubbles by shearing the gas injected into the liquid while being rapidly pressurized with the rotator 21 with a strong force. A gas-liquid mixture having a strong bubble interface structure can be generated more reliably.

It is preferable that the rotational speed of the rotating body 21 of the pump 11 is 100 rpm or more. At this time, it becomes 1/2 rotation or more in 0.3 seconds. By having such a rotational speed, it is possible to reliably generate nano-sized bubbles in which the hydrogen bond distance is shortened by injecting a gas having a saturation dissolution concentration or more into the liquid.

Pressurization by the pressurizing unit 1 and the gas-liquid mixing unit 3 can be performed multiple times by providing a plurality of pressurizing units 1 or gas-liquid mixing units 3. By pressurizing the liquid a plurality of times while feeding the liquid, the pressurization can be performed by a plurality of pumps 11 and venturi pipes, and the liquid is strongly pressurized to generate a gas-liquid mixture having a strong bubble interface structure. It is something that can be done. Specifically, the pressurizing unit 1 can be configured with a pump 11 as shown in FIG. 4, and the gas-liquid mixing unit 3 can be configured with one or more pumps 11 or Venturi tubes.

The defoaming section 4 removes relatively large bubbles from the liquid mixed with the gas as described above, and may be composed of a tubular body or the like in which the bubbles are removed by raising their buoyancy. it can. Since the removed bubbles become gas and accumulate on the upper part, the removed gas can be removed by the gas removing unit 8. Bubbles rising by buoyancy are micro-order sizes, that is, bubbles having a diameter exceeding 1 μm, and by removing such relatively large bubbles, nano-sized bubbles that are fine bubbles are present in the liquid. Thus, a gas-liquid mixed solution having a strong interface structure can be obtained.

Specifically, the degassing part 4 can be configured as shown in FIG. (A) is formed so as to be substantially horizontal to the ground surface (on a plane substantially perpendicular to the direction of gravity) continuously with the gas-liquid mixing unit 3, and the bubbles B in the liquid Lq are It shows an example of a tubular body that is lifted up to remove bubbles B. (B) is formed so that the shape combined with the gas-liquid mixing unit 3 and the gas-liquid mixing unit 3 is a reverse L-shape when viewed from the front, and the flow direction of the liquid Lq is downward (the direction of gravity) In this example, the bubbles B are removed by raising the bubbles B in the liquid Lq to the liquid level by the buoyancy. Further, (c) is separated from the gas-liquid mixing unit 3, and the flow direction of the liquid Lq is set downward (substantially the same direction as the direction of gravity), and the bubbles B in the liquid Lq are raised to the liquid level by the buoyancy. This shows an example of a tubular body that is made to remove bubbles B.

The decompression unit 5 gradually reduces the pressure of the liquid mixed with gas to atmospheric pressure without generating large bubbles. When the liquid mixed with gas by pressurization as described above is in a high-pressure state and is discharged to the outside under atmospheric pressure as it is, bubbles in the gas-liquid mixture are combined due to a sudden pressure drop. May become a gas and be discharged from the liquid, and cavitation may occur. Therefore, the decompression unit 5 is provided, and when the gas-liquid mixture in a pressurized state is sent out, the decompression unit 5 gradually reduces the pressure to atmospheric pressure and then discharges it. The decompression unit 5 is configured to decompress while reducing the upper limit of the decompression speed ΔP ₂ / t (ΔP ₂ : decompression amount, t: time) over the entire piping while sending a liquid in which gas is mixed. ing. Thus, the gas-liquid mixture can be taken out without erasing or coalescing the nano-sized bubbles while maintaining the structure of the strong bubble interface.

The decompression unit 5 can be configured as shown in FIG. 6, and specifically, the flow path 6 whose flow path cross-sectional area gradually decreases as shown in FIG. In this way, the flow path 6 in which the cross-sectional area of the flow path gradually decreases gradually, or the gas-liquid mixing in the high pressure state (P ₁ ) due to the pressure loss in which the pressurized liquid flows in the flow path 6 as in (c). The flow path 6 whose flow path length (L) is adjusted so as to reduce the pressure of the liquid gradually (P ₂ , P ₃ ,...) To the atmospheric pressure (P _n ), and (d) Thus, it can be configured by a plurality of pressure regulating valves 9 provided in the flow path 6.

For example, when the decompression unit 5 as shown in FIG. 6A or 6B is used, the flow path 6 upstream of the decompression unit 5 has an inner diameter of 20 mm, and the decompression unit 5 has a channel length of about 1 cm to At 10 m, the inner diameter can be gradually reduced from 20 mm to 4 mm so that the cross-sectional area of the flow path can be reduced. The decompression section 5 can be set to have an inlet inner diameter / outlet inner diameter = 2 to 10 or an inner diameter reduction value per cm can be set to about 1 to 20 mm. At this time, when the gas-liquid mixture is sent to the decompression unit 5 at a flow rate of 4 × 10 ⁻⁶ m / s or more, the pressure is reduced by 1.0 MPa at a maximum decompression speed of 2000 MPa / sec or less without erasing nano-sized bubbles. The gas-liquid mixture can be depressurized to atmospheric pressure.

The discharge part 7 discharges the decompressed liquid. As shown in FIG. 7, an extension channel 10 can be provided between the discharge unit 7 and the decompression unit 5 in order to ensure a sufficient pressure of the liquid in the pressurization unit 1. That is, the total pressure loss including the decompression unit 5 is calculated, the pressure required to pressurize the liquid and gas in the gas-liquid mixing unit 3 by the indentation pressure from the pressurization unit 1, and the total pressure loss The extended flow path 10 may be added to the flow path 6 with the flow path length adjusted so that the pressure loss of this difference occurs. In order to secure the indentation pressure, it may be possible to provide a throttling portion or the like. However, if the indentation pressure is adjusted by the throttling portion or the like, bubbles may collapse due to a sudden pressure change. However, if the extension channel 10 is provided in this way, the gas-liquid mixture can be discharged while the bubbles are stabilized.

In the gas-liquid mixed liquid manufacturing apparatus configured as described above, the liquid is pumped by the pressurizing unit 1, and the gas is supplied to the liquid by the gas supply unit 2 and injected. Then, the liquid into which the gas has been injected is pressurized by the pressurizing unit 1 and the gas-liquid mixing unit 3 at a pressurization rate ΔP ₁ / t (ΔP ₁ : pressure increase, t: time) of 0.17 MPa / sec or more. The liquid pressure is set to 0.15 MPa or more. That is, the pressure of the liquid when being sent out from the gas-liquid mixing unit 3 to the defoaming unit 4 is 0.15 MPa or more. Thereafter, after removing bubbles exceeding the nano size in the gas-liquid mixture in the degassing part 4, a pressure reduction rate ΔP having a maximum pressure reduction rate of 2000 MPa / sec or less while sending the liquid to the pressure reduction part 5 and the downstream flow path 6. _The pressure is gradually reduced to atmospheric pressure at ₂ / t (ΔP ₂ : reduced pressure amount, t: time). Thereby, a gas-liquid mixed liquid in which nano-sized bubbles are stably present can be generated, and the gas-liquid mixed liquid of the present invention can be obtained.

Although the pressure in the gas-liquid mixing part 3 can be set as appropriate, it is preferable that the absolute pressure exceeds 0.1 MPa (atmospheric pressure). Thereby, the distance of a hydrogen bond can be shortened reliably. The flow path 6 on the downstream side of the gas-liquid mixing unit 3 can be formed in a tube having an inner diameter of about 2 to 50 mm. As a result, the gas-liquid mixture can be discharged with a relatively thick channel cross-sectional area, and the clogging of the pipe as in the case where the channel 6 is configured by a narrow path can be prevented, and the gas-liquid mixture can be used. It can be made easier.

FIG. 8 is a schematic view showing another example of an apparatus for producing a gas-liquid mixed solution. This gas-liquid mixture manufacturing apparatus is configured as a gas-liquid mixing tank 13 in which the pressurizing unit 1 and the gas-liquid mixing unit 3 are combined, and the liquid supplied with gas in the gas-liquid mixing tank 13 is set to 0.・ Pressure is applied at a pressure rate ΔP ₁ / t (ΔP ₁ : pressure increase, t: time) of 17 MPa / sec or more, and the liquid pressure is increased to 0.15 MPa or more to contain bubbles having a strong interface structure. The gas-liquid mixture to be produced is produced in a batch system, and after removing large bubbles from the gas-liquid mixture at the defoaming section 4, the gas-liquid mixture is sent to the decompression section 5 and the pressure is reduced to a maximum decompression speed of 2000 MPa. The pressure is reduced to atmospheric pressure at a pressure reduction rate ΔP ₂ / t (ΔP ₂ : pressure reduction amount, t: time) of / sec or less, and the gas-liquid mixture is discharged from the discharge part 7. The gas-liquid mixing tank 13 which is a closed system is sent out and pressurized in a batch manner, and is stirred by a stirring blade 14 or the like provided in the gas-liquid mixing tank 13 so that the liquid Lq and the gas are mixed. Are mixed under high pressure conditions. As a result, hydrogen bonds having a shorter bond distance are formed around the bubbles, and the bubbles can be covered with the shell of the hydrogen bonds, and the gas can be stabilized as fine bubbles. Then, the gas-liquid mixed liquid of the present invention can be obtained by sending the generated gas-liquid mixed liquid to the defoaming section 4, the decompression section 5 and the discharge section 7 configured in the same manner as the apparatus of FIG. It is.

Next, a description will be given of “a method of using a gas-liquid mixture” that uses a gas in the gas-liquid mixture.

As described above, the gas-liquid mixture of the present invention is one in which bubbles are covered with a hydrogen bond shell, but this hydrogen bond shell collapses due to external force, and gas is applied by applying external force. The generated gas can be used for various purposes. In other words, the gas is enveloped by a strong shell of hydrogen bonds, and the bubbles stably held in the liquid have a high internal pressure.When an external force is applied, the bubbles collapse to generate gas and dissolve in the liquid. Or release from liquid. Since the generated gas can be used for various purposes, a large amount of gas can be held in the liquid, and the gas can be efficiently generated from the liquid and used.

Examples of the external force applied to the gas-liquid mixture include temperature control for changing the temperature, irradiation with ultrasonic waves, infrared rays, and microwaves. By applying these external forces, it is possible to efficiently generate gas in the gas-liquid mixture.

FIG. 9 is an example of a gas utilization system using a gas-liquid mixture. The gas utilization system generates a gas-liquid mixture in which the gas is present as nano-sized bubbles in the liquid, generates gas from the gas-liquid mixture, and in the gas-liquid mixture present as bubbles The gas is used by dissolving or releasing the gas in a liquid.

In this gas utilization system, a gas-liquid mixed liquid generating device 30 that generates a gas-liquid mixed liquid mixed with a liquid in the form of bubbles of nano-size gas, and a gas-liquid mixed generated by the gas-liquid mixed liquid generating apparatus 30 An external force supply unit 31 is provided that applies external force to the liquid and breaks bubbles to dissolve the gas into the liquid or generate the gas from the liquid. The gas-liquid mixed liquid generating device 30 and the external force donating unit 31 are continuously arranged. Therefore, in this gas utilization system, it is possible to easily generate the gas-liquid mixed liquid and use the gas.

The gas-liquid mixed liquid generating apparatus 30 generates a gas-liquid mixed liquid, and can have the same configuration as the gas-liquid mixed liquid manufacturing apparatus in FIGS. In the drawing, the apparatus has substantially the same configuration as that of the apparatus of FIG. 4 that continuously generates the gas-liquid mixed liquid, but the points that are different from the apparatus of FIG. 4 will be described.

The gas-liquid mixed liquid generating apparatus 30 includes a pipe connecting portion 18 that connects the flow path 6 to a liquid supply source 16 outside the apparatus. This pipe connection part 18 is comprised by the adjustment valve etc. which can be opened and closed and can adjust water quantity and water pressure. The liquid supply source 16 is constituted by the liquid storage tank 12, the water pipe 16a, and the like. Further, the pressurizing unit 1 and the gas-liquid mixing unit 3 are constituted by a pump 11 in the same body. Further, a gas return unit 15 is provided between the gas removal unit 8 and the gas supply unit 2. The gas return part 15 is for returning the gas from the gas removal part 8 to the gas supply part 2 and putting it in again, and is formed by a pipe body for sending the gas. In the illustrated form, the gas return unit 15 is connected to the gas path of the gas supply unit 2. By providing the gas return portion 15 in this way, the gas that has not been bubbled can be used effectively without being discarded, and when a harmful or dangerous gas is used, the gas leaks to the outside. This can prevent the environment from being polluted and dangerous.

The external force providing unit 31 applies an external force to the gas / liquid mixture generated by the gas / liquid mixture generation apparatus 30 to break up bubbles in the gas / liquid mixture to generate gas, and dissolve the gas in the liquid. A gas is diffused from a liquid. Even if you try to use the gas that has become bubbles in the liquid as it is for cleaning, sterilization, oxygen supply, etc., because the gas is in bubbles, the gas does not contact the object, and the desired effect cannot be obtained. there is a possibility. Moreover, since gas exists stably as a bubble, gas cannot be taken out as it is. However, when an external force is applied by the external force supply unit 31, a large amount of gas held as bubbles in the liquid is dissolved in the liquid, and nano-sized bubbles are combined into micro-sized bubbles or more. The released gas is released from the liquid, and the dissolved or released gas can be used.

In the form of FIG. 9, the external force supply unit 31 includes a container 33 for storing the gas-liquid mixture and an external force applying means 32 for applying an external force to the gas-liquid mixture, and the gas-liquid mixture generation apparatus The gas-liquid mixed solution containing nano-sized bubbles generated at 30 is sent to the container 33 in a desired amount batch-type. As the external force applying means 32, an external force can be applied as an impact to the gas-liquid mixture using means such as temperature control, ultrasonic waves, infrared rays, microwaves, and stirring. For example, the external force applying means 32 is constituted by a heater such as a heater or a cooling heat exchanger when the temperature control means is used, by an ultrasonic vibrator when using the ultrasonic wave, and when using infrared rays. In the case of using an infrared irradiator and using a microwave, it can be formed of a microwave oscillator.

When applying external force with temperature control, the temperature of the gas-liquid mixture is changed by heating or cooling the gas-liquid mixture.

When applying external force by heating, turn on heating means such as a heater to raise the temperature of the gas-liquid mixture stored at room temperature and normal pressure. The gas-liquid mixture whose temperature has been raised causes the interface structure to collapse due to the increase in internal energy, causing bubbles to collapse, or the bubbles to collide violently and form bubbles that are larger than micro size. Will occur. And this gas melt | dissolves in a liquid, and gas discharge | releases from a liquid. The temperature to be heated can be appropriately set in accordance with the gas generation speed. For example, when the gas is generated by rapidly collapsing bubbles, the stored gas-liquid mixture is 10 When heating up to about 30 ° C or higher and gradually generating bubbles by causing bubbles to collapse, heat the stored gas-liquid mixture to rise to about 1-10 ° C or higher. To do.

Also, when applying external force by cooling, turn on the cooling heat exchanger to lower the temperature of the gas-liquid mixture stored at normal temperature and pressure. The gas-liquid mixture whose temperature has been lowered increases the saturated dissolution concentration of the gas by cooling, and the bubbles collapse to dissolve more gas in the liquid. As the cooling temperature, for example, cooling is performed so that the temperature of the gas-liquid mixture is about 1 to 30 ° C. and the temperature is lowered. Alternatively, external force may be applied by alternately performing heating and cooling.

Thus, by generating gas by temperature control, gas can be easily generated and used. That is, when the gas-liquid mixture is produced at room temperature, the gas-liquid mixture can be heated or cooled to collapse the nano-sized bubbles and dissolve or release the gas. When the gas / liquid mixture is produced at a low temperature, the gas / liquid mixture can be returned to room temperature to collapse the nano-sized bubbles to dissolve or release the gas. Therefore, it is possible to control the retention and generation of gas only by controlling the temperature of the gas-liquid mixture.

Also, when applying an external force with ultrasonic waves, when the ultrasonic generator is turned on, ultrasonic vibration is applied from the ultrasonic transducer to the gas-liquid mixture, and the internal energy of the vibrated gas-liquid mixture increases and the interface is increased. The structure collapses and the bubbles collapse, or the bubbles collide violently and the bubbles merge to form a large micro-sized bubble or more, generating gas. And this gas melt | dissolves in a liquid, and gas discharge | releases from a liquid. The frequency of the ultrasonic wave is preferably 16 kHz or more and less than 2.4 GHz. Even if the frequency range is larger or smaller than this, the effect of collapsing bubbles may be reduced.

Thus, by applying an external force with ultrasonic waves, gas can be easily generated and used. In addition, the ultrasonic wave can be easily switched on and off, and an external force can be applied instantaneously, and the gas in the gas-liquid mixture can be obtained only in the required amount and time. Gas can be generated abruptly by a strong impact, and gas generation can be easily controlled.

In addition, when external force is applied by infrared rays, when the infrared irradiator is turned on, infrared rays are given to the gas-liquid mixture from the irradiation port, the internal energy of the gas-liquid mixture irradiated with infrared rays increases, and the interface structure collapses. Bubbles collapse, or bubbles collide violently and bubbles merge to form large micro-sized or larger bubbles, generating gas. And this gas melt | dissolves in a liquid, and gas discharge | releases from a liquid. The infrared wavelength is preferably 3 to 1000 μm. Even if the wavelength range is larger or smaller than this, the effect of collapsing bubbles may be reduced.

Thus, by applying an external force with infrared rays, gas can be easily generated and used. Infrared rays can be easily switched on and off, and the gas in the gas-liquid mixture can be obtained in a necessary amount and time. Moreover, it is possible to gradually generate gas by infrared rays, and it is possible to continuously generate and use the gas.

In addition, when external force is applied by microwaves, when the microwave generator is turned on, microwave vibration is applied from the microwave oscillator to the gas-liquid mixture, and the internal energy of the gas-liquid mixture to which the vibration wave is applied is The interface structure collapses and the bubbles collapse, or the bubbles collide violently and the bubbles merge to form a large micro-sized bubble or more. And this gas melt | dissolves in a liquid, and gas discharge | releases from a liquid. The frequency of the microwave is preferably a frequency of 915 KHz, 2.4 to 2.5 GHz, or 5.7 to 5.9 GHz. If the frequency range is out of this range, the effect of collapsing bubbles may be reduced.

Thus, by applying an external force with microwaves, gas can be easily generated and used. Further, the microwave can be easily switched on and off, and the gas in the gas-liquid mixture can be obtained in a necessary amount and time. Further, gas can be generated gradually or suddenly by microwaves, and gas generation can be easily controlled.

In the gas-liquid mixture, as described above, the gas-liquid mixture is present as bubbles by collapsing the bubbles of the gas-liquid mixture using the external force applying means 32 such as temperature control, ultrasonic waves, infrared rays, and microwaves. A large amount of gas can be instantly dissolved in a liquid or released from the liquid by these means, and the gas can be generated and used easily and efficiently.

In the illustrated embodiment, the external force applying means 32 is provided in contact with the gas-liquid mixed solution. However, the external force applying means 32 is provided outside the container 33 so that it is not contacted from the outside of the container 33. An external force may be applied to the gas-liquid mixture.

The external force application by the external force application means 32 may be continuous or intermittent. When external force is continuously applied, a large amount of gas in the gas-liquid mixture can be generated and used at once. On the other hand, when external force is intermittently applied, the gas can be gradually dissolved or released, and the gas in the liquid can be used continuously.

In the system shown in FIG. 9, an external force is applied to the gas-liquid mixture at the desired timing to dissolve or release the gas, which is used for ozone sterilization, cleaning of precision parts, oxygen supply to the living body, etc. can do. Further, the gas can be confined for a long time with the gas-liquid mixture, and the gas can be taken out from the liquid and used by applying an external force at the timing of use, and can be used for storage, storage, transportation, etc. of the gas.

FIG. 10 is a schematic diagram showing another example of the embodiment of the gas utilization method using the gas-liquid mixture of the present invention, and shows an example of the gas utilization system. This system includes a gas-liquid mixed liquid generating device 30 that generates a gas-liquid mixed liquid mixed with a liquid in the form of nano-sized bubbles in a cooled state, and a container 33 that stores the gas-liquid mixed liquid in a cooled state. Is provided.

In addition to the apparatus shown in FIG. 9, the gas-liquid mixed liquid generating apparatus 30 is provided with a liquid cooling section 17 in a liquid flow path between the pipe connecting section 18 and the gas supply section 2. Further, in this system, unlike the system of FIG. 9, the external force applying means 32 is not provided in the container. The liquid cooling unit 17 is formed, for example, by winding a cooling heat exchanger around the flow path 6 and attaching it. The liquid sent from the liquid supply source 16 is cooled by the liquid cooling unit 17, and a gas-liquid mixed solution is generated while being cooled. That is, the gas-liquid mixture is generated at a temperature lower than normal temperature. Then, this cooled gas-liquid mixture is discharged from the discharge portion 7 to the container 33 and stored. The cooling temperature only needs to be such that the temperature of the liquid is not higher than room temperature, and can be, for example, 0 to 25 ° C. The gas-liquid mixed liquid may be stored by cooling so as to maintain the cooling state, or may be stored without maintaining the cooling state. When stored with cooling, the bubbles can be stably held for a long time. The gas may be used while the gas-liquid mixed liquid is stored in the container 33, or may be used by spraying the gas-liquid mixed liquid on an object such as a human body or a cleaning object. Then, the temperature of the gas-liquid mixture rises due to the outside air temperature or the temperature of the object, the bubbles in the liquid collapse, the gas dissolves, and the gas is released as bubbles of micro size or larger. This generated gas is used for various purposes.

In this system, the gas-liquid mixture in the cooled state comes into contact with the object, changes the temperature of the gas-liquid mixture at the temperature of the object, and the gas is dissolved or generated in the immediate vicinity of the object. And since gas can be utilized, the efficiency of gas utilization can be improved. Further, the gas-liquid mixture in a cooled state can be stored while being cooled, and the stored gas-liquid mixture can be given to the object. In that case, it is possible to use the gas-liquid mixed solution by moving it to a place where it is desired to use without moving the apparatus, and it is possible to easily use the gas.

In the gas utilization method using the gas-liquid mixed solution, a method using a gas utilization system in which the gas-liquid mixed solution generated from the gas-liquid mixed solution generating device 30 is put in a container and external force is applied as it is. Although explained, the utilization method of gas is not restricted to the method using the above-mentioned gas utilization system. For example, the produced gas / liquid mixture may be stored, the gas / liquid mixture may be taken out when necessary, and an external force may be applied to generate gas.

The gas-liquid mixture of the present invention holds a gas such as carbon dioxide, nitrogen, oxygen, ozone, and argon as fine bubbles in the liquid, and these gases are stably present in the liquid at a high concentration. Therefore, it can be used in the environmental field, the manufacturing / industrial field, the energy field, the agriculture / forestry / fishery field, the food field, the household field, the medical field, and other various fields.

For example, in the environmental field, the oxygen abundance in the water area is increased by supplying a gas-liquid mixture in which oxygen is bubbled and present in high concentrations in closed water areas such as the sea, rivers, lakes, ponds, and dam lakes. Water purification can be performed, and similarly, it can be used for oxygen supply in septic tanks, sewerage facilities, and human waste processing facilities. Moreover, harmful substances and oil contamination can be treated by supplying oxygen to the soil.

In the manufacturing and industrial fields, it can be used for cleaning precision parts by jetting or dipping a gas-liquid mixture containing oxygen bubbles in high concentration. In addition, by supplying a gas-liquid mixture in which oxygen bubbles are present at a high concentration to a factory wastewater treatment facility, wastewater treatment can be performed by improving the amount of oxygen, or ozone bubbles are present at a high concentration. By supplying the gas-liquid mixture, the waste water can be subjected to ozone treatment. Moreover, it can utilize for oxygen supply for fermentation and culture | cultivation promotion of fermented food in a food factory. It can also be used to supply oxygen and ozone to circulating water filtration systems such as commercial baths, pools, and aquariums. Oxygen and ozone for factory painting process circulating water, factory cleaning process circulating water, and cooling circulating water It can be used for purification by supply. Furthermore, a gas-liquid mixture is generated by mixing toxic gas generated in factories with water as bubbles, and the toxic gas is processed by processing the gas-liquid mixture containing this high-concentration toxic gas. You can also.

In the energy field, natural gas, hydrocarbons such as methane, butane, ethane, propane, etc., oxygen, nitrogen, hydrogen, ozone, etc. are present in the liquid as bubbles, so that these gases are stably maintained at a high concentration. be able to. And, by cooling or compressing such a gas-liquid mixture, it is solidified or slurried to produce a gas hydrate, and by this gas hydrate, transportation of gas, storage and transportation of fresh food products, It can be used for plant cultivation, carbonated drinks, and fuel.

In the agriculture, forestry and fisheries field, by supplying a gas-liquid mixture with high concentration of oxygen bubbles to agricultural, fishery and livestock wastewater, the oxygen content is improved and used for water purification and flotation separation of filth. be able to. In addition, by using a gas-liquid mixed solution in which oxygen bubbles are present at a high concentration as agricultural water or fishery water, it is possible to promote the germination and growth of plants and the growth of seafood. Furthermore, by supplying a gas-liquid mixed liquid in which oxygen bubbles are present at a high concentration in the ginger, oxygen can be supplied during transport of live fish. It can also be used for agricultural wastewater treatment.

In the food field, gas-liquid mixtures containing bubbles such as oxygen and carbon dioxide can be used as food processing water and food washing water, and there are bubbles of inert gases such as nitrogen, helium, and argon. It can be used to prevent food spoilage using a gas-liquid mixture.

In the household field, wastewater treatment by improving the amount of oxygen can be performed efficiently by supplying a gas-liquid mixed solution containing oxygen bubbles at a high concentration to a septic tank for domestic wastewater. Moreover, a carbon dioxide bath can be formed by supplying a gas-liquid mixed liquid in which bubbles of carbon dioxide exist at a high concentration to the bathtub. Moreover, a gas-liquid liquid mixture can be utilized for drinks and cosmetics.

In the medical field, use gas-liquid mixtures with high concentrations of oxygen bubbles and gas-liquid mixtures with high concentrations of carbon dioxide bubbles for beverages, cancer treatment, stone destruction, etc. Can do.

In other fields, a gas-liquid mixed solution can be used as oxygen water for beverages and carbonated water for beverages. Furthermore, a gas-liquid mixture can be used as ozone water used in various fields such as sterilization, decolorization, deodorization, and organic matter decomposition.

Hereinafter, the present invention will be described by way of examples.

[Example 1]
[Production of gas-liquid mixture]
Using the apparatus of FIG. 4, pure water was used as the liquid, and various gases described later were used as the gas to produce a gas-liquid mixed solution.

As the gas-liquid mixing device, an apparatus in which the pressurizing unit 1 and the gas-liquid mixing unit 3 are combined with a pump 11 was used. As the pump 11, a pump 11 a as shown in FIG.

The ratio of gas to liquid (the amount of gas injected into the liquid) was set to 1: 1 as a volume ratio (volume ratio). Moreover, the rotation speed of the rotary body 21 of the pump 11 was set to 1700 rpm. Under this condition, gas is injected into water at atmospheric pressure (0.1 MPa) and then pressurized at a pressure rate ΔP ₁ /t=28.3 MPa / sec. The pressure of the gas-liquid mixture at the time of delivery became 0.6 MPa. Under such conditions, it is considered that the gas is injected into the liquid exceeding the saturated dissolution concentration, the hydrogen bond distance is shortened, and a strong bubble interface structure is formed. This condition (pressurizing condition) is considered to be the best condition at present.

Further, the flow path 6 on the upstream side of the decompression unit 5 has an inner diameter of 20 mm. As the decompression unit 5, as shown in FIG. 6 (a), one having an inner diameter that gradually decreases in three stages is used. Specifically, the inner diameter is 14 mm, 8 mm, 4 mm, and each length is about 3.3 mm (decompression). The total length of the part 5 was approximately 1 cm) and was composed of three flow path pipe parts. In addition, a hose having an inner diameter of 4 mm (outer diameter of 6 mm) is used as the flow path 6 and the extension flow path 10 on the downstream side of the decompression unit 5, and the combined length of the downstream flow path 6 and the extension flow path 10 is as follows. It was set to be 2 m. Under this condition, the decompression unit 5 decompresses the gas-liquid mixture at a maximum decompression speed of 60 MPa / sec and a time of 0.0025 seconds, and further, 1 MPa / sec, time in the downstream channel 6 and the extension channel 10. The gas-liquid mixed liquid was depressurized in 0.5 seconds, and a gas-liquid mixed liquid reduced in pressure to atmospheric pressure (0.1 MPa) was obtained from the discharge part 7 which is the tip of the hose. Note that, under such conditions, a gas-liquid mixed liquid in which gas is injected into the liquid exceeding the saturated dissolution concentration and the hydrogen bond distance is shortened and the structure of the bubble interface is strengthened can be stably generated. It is considered a thing. This condition (decompression condition) is considered to be the best condition at the present time.

[Hydrogen bond distance]
FIG. 1 shows the difference between an infrared absorption spectrum of a gas-liquid mixed solution (nitrogen mixed water) using pure water as a liquid and nitrogen as a gas and nitrogen saturated water in which nitrogen is dissolved in pure water at a saturated dissolution concentration. It is a graph to show. It is known that the infrared absorption band due to OH stretching vibration of water usually has an absorption maximum in the vicinity of 3400 cm ⁻¹ , but as shown in the graph, the gas-liquid mixture of the present invention has an absorption maximum of OH stretching vibration. Is shifted to around 3200 cm ⁻¹ . When the absorption maximum is 3400 cm ⁻¹ , the hydrogen bond distance is 0.285 nm. On the other hand, when the absorption maximum is 3200 cm ⁻¹ , the hydrogen bond distance is known to be 0.277 nm, which is shorter than the normal hydrogen bond distance at room temperature and normal pressure, and is structured ice or hydrate. It was concluded that the water was close to the rate.

[Gas volume]
Pure water was used as the liquid, and nitrogen, hydrogen, methane, argon, or carbon dioxide was used as the gas, and the amount of gas present as bubbles in the gas-liquid mixture was measured by the following method. The production of the gas / liquid mixture was performed using the gas / liquid mixture production apparatus in the same manner as described above.
(1) Various gases were mixed with pure water having a conductivity of 0.1 μS / cm at 25 ° C. to obtain a gas-liquid mixture.
(2) In order to separate large bubbles having a diameter of 1 μm or more from water, the gas-liquid mixture was allowed to stand at 25 ° C. for 1 day. As for the standing time, from the Stokes' law, the bubble rising speed: V = d ² × g / (18 × γ)
(D: bubble diameter, g: gravitational acceleration, γ: kinematic viscosity coefficient)
From this equation, the rate of rise of bubbles of 1 μm is about 2.4 × 10 ⁻⁴ m / s. For example, if the water depth of the container at rest is 50 mm, Bubbles can be removed.
(3) The mass of the gas-liquid mixture was measured with an analytical balance having a minimum measured value of 1 mg.
(4) A gas-liquid mixture and a stirrer of a stirrer are placed in a PE + nylon resin vinyl bag with low gas permeability and moisture permeability, and the vinyl bag is sealed with a sealer in a state where there is no air in the bag. .
(5) Immediately after sealing, the mass of the vinyl bag in which the gas-liquid mixture was sealed was measured with an analytical balance.
(6) The vinyl bag in which the gas / liquid mixture at 25 ° C. was sealed by a hot stirrer was heated to 45 ° C., and the gas / liquid mixture was stirred for about 5 hours. By this temperature rise and stirring, fine bubbles and gas dissolved at a saturated dissolution concentration of 45 ° C. or higher were separated from the gas-liquid mixture and collected on the top of the vinyl bag.
(7) The set temperature of the hot stirrer was set to 25 ° C. at room temperature of 25 ° C., and the mixture was stirred for several hours so that a liquid having a saturated solubility of 25 ° C.
(8) Using an analytical balance, the mass of the vinyl bag in which gas and liquid were enclosed was measured.
(9) The mass of the gas-liquid mixture and the amount of change in the mass of the liquid caused by the buoyancy caused by the gas separated from the gas-liquid mixture by heating and stirring were obtained from three mass measurements. The mass change amount is the same as the mass of air having the same volume as the gas volume separated from the gas-liquid mixture, and the volume and mass of the separated gas can be calculated from this value.

FIG. 2 is a graph showing the gas volume measured in this way. The lower region of each bar graph is the amount of gas that was present as the measured bubble, and the upper region is the saturated amount of gas that follows Henry's law. As shown in the graph, for example, in the case of a gas-liquid mixture using hydrogen and water, 17.6 mL of hydrogen is dissolved in 1 L of pure water at 25 ° C. as a saturated dissolution amount, and 528 mL of gas exists as fine bubbles. It was confirmed. That is, the amount of gas contained in the gas-liquid mixture was 30 times the saturated dissolution amount. Similarly, the amount of gas contained in the gas-liquid mixture with respect to the saturated dissolution amount was 36 times for nitrogen, 17 times for methane, 16 times for argon, and 1.9 times for carbon dioxide. As described above, the gas-liquid mixed liquid can hold the gas in the liquid at a high concentration equal to or higher than the saturated dissolution concentration, and the high-concentration gas-liquid mixed liquid can be used in various fields. is there.

[Bubble size]
A gas-liquid mixture produced in the same manner as above was instantly frozen, cleaved with a cutter in a vacuum, and methane / ethylene flowed through the fractured surface to discharge, producing a hydrocarbon film (replica film) with transferred irregularities. . A conductive osmium thin film was applied to the replica film, dried sufficiently, and observed with a scanning electron microscope (SEM).

FIG. 3 is an example of a photograph observed by SEM for a gas-liquid mixture of nitrogen and pure water. Similarly, by observing photographs, it was confirmed that when nitrogen, hydrogen, methane, argon, carbon dioxide was used as the gas, the bubble size of the gas-liquid mixture was 100 nm in diameter distribution peak. The bubbles in the gas-liquid mixture of the above gas and pure water could not be accurately detected by a particle size distribution measuring apparatus such as a dynamic scattering method using a laser.

[Internal pressure of bubbles]
The pressure inside the bubbles was calculated from the total amount of gas in the gas-liquid mixture. Table 1 shows the total amount of gas and the internal pressure of bubbles calculated from the total amount of gas in a gas-liquid mixed solution of nitrogen, methane, or argon and 25 ° C. pure water.

The internal pressure of the gas in the bubbles is calculated by the following method.
The equation of state of gas is
PV / T = (const)
(P: internal pressure, V: volume, T: internal temperature)
When T is constant, PV = (const)
It is represented by

And the volume of bubbles in the gas-liquid mixture can be calculated from the density of the gas-liquid mixture,
The relationship of atmospheric pressure × total gas volume = bubble internal pressure × total gas volume in liquid is established, and the internal gas pressure in the bubbles is calculated by applying the above measured gas amount to this relational expression. The pressure value is as follows.

For example, if the gas is nitrogen,
Assuming that the volume of water in 1 liter of gas-liquid mixture is w1 liter and the volume of gas in water is w2 liter,
The following relational expression holds for the volume.

w1 + w2 = 1 liter (Formula A)

In addition, the following relational expression holds for the mass.

w1 × density of water + w2 ÷ 22.4 (liter) × 28 (molecular weight) = measured mass (Formula B)
Water density: 997.1g / L for pure water at normal temperature and pressure
22.4 liters: volume of 1 mol of gas Measured mass: 988.3 as shown in Table 1

Solving the above two equations (Equations A and B),
Since w2 = 8.84 × 10 ^ (-3) is calculated,

Internal pressure of gas = atmospheric pressure x total volume of gas ÷ total volume of gas in liquid = 0.1 x (value in Table 1) ÷ w2
= 0.1 × 0.56 ÷ (8.84 × 10 ^ (-3))
= 6.3 MPa
It becomes.

In the above calculation, it was assumed that the internal temperature of the bubble was constant (normal temperature), but the actual internal temperature of the bubble is also expected to be higher than the atmospheric temperature (normal temperature). It can be predicted from the gas state equation that the pressure is higher than the above calculation result.

By the way, generally, the internal pressure of bubbles is calculated as follows. The bubbles are pressurized by the interfacial tension between the gas-liquid interface, and this interfacial tension is derived by Young Laplace's equation (the following equation).

ΔP = 2σ / r
(ΔP: rising pressure, σ: surface tension, r: bubble radius)
According to this equation, for example, in the case of a bubble having a diameter of 100 nm, the bubble internal pressure is 3 MPa.

On the other hand, the internal pressure in the gas-liquid mixed liquid is 6.3 MPa in the case of nitrogen, for example, as shown in Table 1. In this gas-liquid mixed liquid, bubbles having a diameter of 100 nm are dispersed as shown in the SEM photograph. Therefore, it was confirmed that the bubbles of the gas-liquid mixture had an internal pressure that was about twice or more the value calculated from the Young Laplace equation. Therefore, it was concluded that a stronger interface structure was formed at the bubble interface.

 

FIG. 11 is a conceptual explanatory diagram for explaining the mechanism by which the gas-liquid mixed liquid is stabilized. As shown in the drawing, a protective film M having a boundary film structure (crystal structure) is formed at the interface between the bubble B and the liquid Lq by bonding of strong water molecules such as ice or hydrate whose hydrogen bond distance is shorter than usual. Therefore, it is considered that the mass transfer between the gas and liquid is suppressed, and the bubbles are in a stable state. The internal pressure of the bubbles (nanobubbles) in the gas-liquid mixture of nitrogen, methane, and argon is higher than the pressure obtained from the Young Laplace equation and is about twice or more. As described above, the hydrogen bonding distance at the bubble interface is short and the internal pressure of the bubble is increased, so that the bubble becomes a stable gas-liquid mixture. In addition, since the internal pressure of the bubbles is high, when an external force that increases the internal pressure is applied, the bubbles are likely to collapse, the bubbles can be easily collapsed, and the gas can be dissolved and released, and the gas can be used. .

[Bubble distribution]
The amount of bubble distribution (number) was calculated from Table 1.

When the gas is nitrogen, the total amount of bubbles returned to the atmosphere (0.1 MPa) is 0.56 L, and the internal pressure of the bubbles is 6.3 MPa. Therefore, the total volume V1 of bubbles in water is assumed to change isothermally, PV From = const V1 = 0.56 × 0.1 ÷ 6.3
It becomes.

Since the bubbles are spheres with a radius r = 50 nm, the volume V2 per bubble is V2 = 4/3 × π × r ^ 3.
It becomes.

From the above, the number of bubbles per liter of water n = V1 ÷ V2 = 1.7 × 10 ^ 16 is calculated.

Similarly, the number of bubbles per liter of water is calculated as 1.8 x 10 ^ 16 when the gas is methane and 1.7 x 10 ^ 16 when argon is used.

“^” Is a symbol of “power”, and for example, “10 ^ n” is “10 ⁿ ” (10 to the power of n).

[Stability of gas-liquid mixture]
FIG. 12 shows the supersaturation as the gas abundance ratio in the gas-liquid mixture with respect to the saturated dissolution concentration when the gas-liquid mixture produced by mixing air with pure water is sealed in a glass bottle and stored at a constant temperature. It is a graph to display. From the graph, it can be seen that the degree of supersaturation is almost constant (about 6) even after 400 hours, and hardly changes. Since gas is dissolved at a saturated concentration in the liquid, the gas exceeding the saturated concentration is considered to be a bubble. Therefore, it was confirmed that the gas-liquid mixture of the present invention is stable.

[External force by heating]
When the gas-liquid mixture prepared as described above is heated by a heater and the temperature of the gas-liquid mixture is increased from 25 ° C. to 40 ° C., the nano-sized bubbles collapse with the increase in temperature, and are visually observed. Bubbles that were larger than the micro size that could be confirmed were generated. It was confirmed that the liquid became cloudy with micro-order bubbles and gas was released from the liquid surface.

FIG. 13 is a conceptual explanatory diagram illustrating a mechanism by which bubbles in the gas-liquid mixed liquid collapse. This figure shows a case where ozone (O ₃ ) is used as the gas. Nano-sized bubbles B exist stably in the gas-liquid mixture as shown in (a), but as shown in (b), external force is applied as an impact by temperature control, ultrasonic waves, infrared rays, microwaves, etc. Bubbles collapse when pushed. At that time, a large amount of gas present in the bubbles is instantly dissolved in the liquid, and a gas saturated solution is generated. In addition, the bubbles are combined by collision and become bubbles of micro size or larger, and are lifted by buoyancy to release the gas. Thus, according to the gas-liquid mixture, a large amount of gas can be stored in the gas-liquid mixture, and this large amount of gas can be used by being dissolved or released at the timing at which it is desired to use. is there.

[External force by ultrasonic waves]
The gas-liquid mixed solution produced as described above was irradiated with ultrasonic waves at an output of 100 W using a 40 kHz Langevin type vibrator. With the instantaneous irradiation of about 0.05 seconds, the nano-sized bubbles collapsed and bubbles of a micro size or larger that can be visually confirmed were instantaneously generated. By irradiating ultrasonic waves for several seconds (about 0.5 to 30 seconds), almost all of the nano-sized bubbles collapsed and bubbles of micro-size or larger that can be visually confirmed were rapidly generated. It was confirmed that the liquid became cloudy with micro-order bubbles and gas was released from the liquid surface.

Similarly, it was confirmed that gas was released from the liquid surface when the ultrasonic wave was irradiated with an ultrasonic generator of 100, 200, 400, or 800 kHz. On the other hand, the release of gas could not be confirmed by ultrasonic irradiation at 2.4 GHz.

[External force by microwave]
Using a microwave power application device with an output of 300 W to 300 kW in the 2450 MHz band and irradiation for several seconds (about 0.1 to 20 seconds), it was confirmed that gas was released from the liquid surface over the entire output.

In the microwave irradiation by magnetron, it is considered that the energy level rises because the vibrator between the molecules of the liquid molecule absorbs the vibration energy and vibrates, the hydrogen bond is broken, and the gas is released. Even in a microwave with a frequency of 915 KHz or 5.7 to 5.9 GHz, hydrogen bonding at the bubble interface becomes unstable, the bubble collapses, and gas is considered to be released from the liquid surface.

[External force by infrared rays]
In particular, far-infrared rays having a wavelength of 3 μm to 1 mm absorb electromagnetic waves at the bubble interface and are given thermal energy, so that the bond distance of strong hydrogen bonds is increased and the bubble internal temperature is increased. For this reason, the bubble collapses naturally, and the bubble can be collapsed by far-infrared rays to release the gas from the liquid surface.

[Example 2]
[Cooled gas-liquid mixture]
A gas / liquid mixture using air and water was generated in a cooled state (5 ° C.) using the gas / liquid mixture generating apparatus 30 of FIG. It was confirmed that when this gas-liquid mixture was stored in a container so as to be in contact with the atmosphere at normal temperature and pressure, the saturated dissolution concentration of gas in water could be maintained for one week or more. In other words, even if the dissolved gas is gradually released from the liquid, the nano-sized bubbles gradually collapse to compensate for the amount of released gas and dissolve in the liquid, so the liquid exists while maintaining the saturated dissolution concentration. It was confirmed that it can be made.

DESCRIPTION OF SYMBOLS 1 Pressurization part 2 Gas supply part 3 Gas-liquid mixing part 4 Defoaming part 5 Depressurization part 6 Channel 7 Discharge part 8 Gas removal part 11 Pump 17 Liquid cooling part 21 Rotor 30 Gas-liquid mixed-liquid production | generation apparatus 31 External force provision part 32 External force applying means 33 Container

Claims (6)

1. A gas-liquid mixture in which bubbles are present in a liquid composed of molecules that form hydrogen bonds, and the distance between hydrogen bonds of molecules present at the interface with the liquid bubbles is determined when the liquid is at normal temperature and pressure. A gas-liquid mixed liquid characterized by being shorter than the hydrogen bond distance of molecules constituting the liquid.
2. The gas-liquid mixture according to claim 1, wherein the liquid is water.
3. 2. The gas-liquid according to claim 1, wherein the liquid is a liquid composed of molecules having any one or more of OH bond, NH bond, (halogen) -H bond, and SH bond. Mixture.
4. The gas-liquid mixture according to claim 1, wherein the liquid is a liquid composed of molecules having a carboxyl group.
5. The gas-liquid mixture according to any one of claims 1 to 4, wherein the concentration of the gas contained in the gas-liquid mixture is equal to or higher than the saturated dissolution concentration of the liquid.
6. 6. The gas-liquid mixed liquid according to claim 1, wherein the pressure of the gas forming the bubbles is 0.12 MPa or more.

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