JP2009160508A - Ozone water forming apparatus, ozone water forming method, ozone water, ozone aqueous solution, and ozone water or ozone aqueous solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To increase dissolved efficiency and reaching concentration by dissolving ozone gas into water or an aqueous solution, and suppressing self-decomposition of ozone molecules in bubbles by thermal energy caused by sonoluminescence action generated at mixing, and to miniaturize an ozone water forming apparatus and to form highly concentrated ozone water with high effect by providing a gas cooling device cooling sucked and introduced ozone-containing gas by an ejector and keeping the gas at low temperature. <P>SOLUTION: In the ozone water forming apparatus and ozone water forming method, ozone gas is injected to water or raw water of liquid passing from a water flow-in channel upstream of the ejector through an orifice part or a gas sucking and introducing pipe connection part, and gas is mixed with liquid to form ozone water or ozone aqueous water. The gas cooling device is provided, and ozone gas is cooled to 0°C or lower in the gas sucking and introducing pipe from an ozonizer to the ejector, and introduced into the ejector. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an ozone water generating device, an ozone water generating method, ozone water, an ozone aqueous solution, and ozone water or an ozone aqueous solution, in which ozone gas is introduced into raw water and gas-liquid mixed to generate ozone water or an ozone aqueous solution.

  Ozone is extremely dangerous and harmful to humans and animals in the gas phase. Ozone bubbles are dissolved in water to form a liquid phase that can be used for sterilization and sterilization of food surfaces, water purification, cleaning of precision parts such as semiconductor wafers and liquid crystal panels, resist stripping, and surface modification. In addition to its high safety compared to the phase, it is widely used as an oxidation technique that is easy to control and as an environmentally friendly cleaning technique with no persistence.

  In order to enhance the effect of ozone water, a technique capable of increasing the concentration of ozone by dissolving it in water is required, and there is a need for a means for generating ozone water and an aqueous ozone solution more efficiently. Various methods have been proposed in order to efficiently generate ozone water or an aqueous ozone solution at a high concentration.

  For example, in Japanese Patent Application Laid-Open No. 2005-334797, oxygen or air before being discharged and ozonized in an ozonizer is cooled by a Peltier cooling device to increase the efficiency of discharge, and oxygen and moisture in the air are removed by a dehumidifying effect by cooling. A method of increasing the stability of discharge by dehumidifying has been proposed. Similarly, Japanese Patent Application Laid-Open No. 2003-47825 and Japanese Patent Application Laid-Open No. 5-97405 are different in the method, but the air or oxygen source is cooled and dehumidified before discharge in the ozonizer, and the ozone generation efficiency is improved in the downstream discharge. It is proposed to raise.

  The cooling of these raw material gases has the effect of increasing the efficiency of ozone generation and extending the life of the discharge device by reducing the amount of water supplied to the discharge device. However, the ozone-containing gas after discharge is instantly heated by the heat energy generated by the high-pressure discharge, and depending on the device flow, the ambient environment temperature may vary between the discharge device and the downstream mixing device (ejector or injector). And the heat exchange in the supply pipe was equal to the outside air temperature, and it became a state of several to several tens of degrees Celsius and was mixed with water and liquid later. As the ozone gas temperature rises, the phenomenon shown by the Henry constant that ozone is self-decomposing occurs, and the efficiency of being dissolved and retained in water when it is sent into the water as gas is reduced.

  Furthermore, in these patent documents, cavitation of ozone gas bubbles occurs in the water and liquid mixed in the ejector orifice, and the sonoluminescence phenomenon that occurs accompanying this, that is, the influence of thermal energy generation due to bubble compression, There was nothing to consider. The flow of the raw material gas-cooled ozone water generator is shown in FIG.

    On the other hand, when ozone water is generated by the gas-liquid mixing method, cooling the water to increase the dissolution efficiency is a widely practiced method as proposed in, for example, JP-A-2006-102576. As in the case of gas cooling, it has been put into practical use in view of the physical properties of self-decomposition due to the rise in ozone temperature indicated by the Henry constant. However, when cooling water or an aqueous solution, although there are some differences depending on what is added, it is impossible to maintain the water temperature below the temperature range where water freezes. It is the limit to hold.

    In addition, as in the case of gas cooling, there has been no example in which generation of thermal energy due to the sonoluminescence phenomenon and its influence are taken into consideration. A flow diagram of the water-cooled ozone water generator is shown in FIG. In addition, by applying ultrasonic waves to microbubble bubbles such as ozone that have been generated with a fine diameter in advance, the bubbles shrink, and the bubble contraction phenomenon called crushing causes ultrahigh pressure and ultrahigh temperature in the bubbles. Japanese Patent Laid-Open No. 2005-245817 proposes that ozone water containing extremely fine bubbles having a bubble diameter of 50 to 500 nm can be generated.

However, even in this method by the crushing action, thermal energy is generated by the sonoluminescence phenomenon, which is an instant that cannot be measured, but it is extremely high temperature, and therefore, it is considered that ozone is decomposed and the concentration is lowered. It was not.
JP 2005-334797 A JP 2003-47825 A JP-A-5-97405 JP 2006-102576 A JP-A-2005-245817

  This invention dissolves ozone gas in water or an aqueous solution using a gas-liquid mixing device called an ejector or an injector, and suppresses the self-decomposition of ozone molecules in the bubbles due to the thermal energy generated by the sonoluminescence action generated during mixing. , Ozone water generator, ozone water generator, ozone water, ozone aqueous solution with a gas cooling device that can cool and keep the ozone-containing gas sucked into the ejector for the purpose of increasing the dissolution efficiency and concentration , And ozone water or an aqueous ozone solution, and it is possible to reduce the size of the ozone water generator and to produce highly effective high-concentration ozone water.

  In order to solve the above problems and achieve the object, the present invention is configured as follows.

The invention described in claim 1
From the inflow water channel on the ejector to the downstream drainage channel through the orifice part or the gas suction introduction pipe connection part, the ozone gas is caused to flow from the suction introduction pipe connected in the vicinity of the orifice part to the passing water or raw liquid water, An ozone water generator that generates ozone water or an aqueous ozone solution by gas-liquid mixing.
An ozone water generator comprising a gas cooling device for cooling ozone gas to a low temperature of 0 ° C. or less and introducing it into the ejector in a gas suction introduction pipe path from the ozonizer to the ejector. .

The invention described in claim 2
From the inflow water channel on the ejector to the downstream drainage channel through the orifice part or the gas suction introduction pipe connection part, the ozone gas is caused to flow from the suction introduction pipe connected in the vicinity of the orifice part to the passing water or raw liquid water, It is an ozone water generation method that generates ozone water or an ozone aqueous solution by gas-liquid mixing.
A method for generating ozone water comprising a gas cooling device, wherein ozone gas is cooled to a low temperature of 0 ° C. or lower and introduced into the ejector in a gas suction introduction pipe path from the ozonizer to the ejector.

The invention according to claim 3
The raw water is water that does not contain at least one of tap water, well water, seawater, pure water, and ultrapure water as raw water,
The ozone water generation method according to claim 2, wherein the ozone water is generated.

The invention according to claim 4
The raw water is at least tap water, well water, seawater, pure water, ultrapure water, and a solution obtained by adding at least one of sulfuric acid, hydrochloric acid, acetic acid, and hydrogen peroxide as raw water,
The ozone water generation method according to claim 2, wherein the ozone aqueous solution is generated.

The invention described in claim 5
The ozone gas is arbitrarily mixed or contained with at least one of oxygen, hydrogen, nitrogen, helium, and ammonia, and it is sucked and introduced into the water of claim 3 or the liquid of claim 4 for gas-liquid mixing. And
The ozone water generation method according to claim 2, wherein the ozone water or the ozone aqueous solution is generated.

The invention described in claim 6
Using the ozone water generation method according to claim 2,
The raw water is ozone water, characterized in that water containing at least any one of tap water, well water, seawater, pure water, and ultrapure water is not produced as raw water.

The invention described in claim 7
Using the ozone water generation method according to claim 2,
The raw water is produced as a raw water by adding at least any one of sulfuric acid, hydrochloric acid, acetic acid, and hydrogen peroxide to tap water, well water, seawater, pure water, and ultrapure water. It is an ozone aqueous solution.

The invention according to claim 8 provides:
Using the ozone water generation method according to claim 2,
The ozone gas is arbitrarily mixed or contained with at least one of oxygen, hydrogen, nitrogen, helium, and ammonia, and it is sucked and introduced into the water of claim 3 or the liquid of claim 4 for gas-liquid mixing. It is ozone water characterized by being produced.

The invention according to claim 9 is:
Using the ozone water generation method according to claim 2,
The ozone gas is arbitrarily mixed or contained with at least one of oxygen, hydrogen, nitrogen, helium, and ammonia, and it is sucked and introduced into the water of claim 3 or the liquid of claim 4 for gas-liquid mixing. It is ozone water or ozone aqueous solution characterized by producing | generating.

With the above configuration, the present invention has the following effects.

  According to the present invention, it is possible to generate ozone water or an ozone aqueous solution with extremely high efficiency by gas cooling with extremely high heat exchange efficiency rather than liquid cooling that requires a large amount of energy.

  Therefore, it is possible to reduce the size of the ozone water generating device, and to reduce the device manufacturing cost due to high efficiency. Therefore, it is possible to expand the application and widely spread.

  Hereinafter, embodiments of an ozone water generating device, an ozone water generating method, ozone water, an ozone aqueous solution, and ozone water or an ozone aqueous solution according to the present invention will be described. The embodiment of the present invention shows the most preferable mode of the present invention, and the present invention is not limited to this.

  Ozone is more stable and less self-decomposing at lower temperatures, and has the property of decomposing and returning to oxygen at a faster rate when exposed to high temperatures. In order to efficiently generate ozone water and consequently generate high-concentration ozone water, a method of cooling the raw material gas upstream of the discharge for generating ozone until now, on the other hand, water and aqueous solution mixed with ozone gas, Methods have been proposed and put into practical use for holding down cooling and suppressing decomposition. However, ozone gas cooling is returned to a constant high temperature again by electric discharge, so that it is difficult to mix while cooling. Regarding cooling of water and aqueous solution, it was impossible to cool to a lower water temperature up to around 0 ° C., and a sufficient ozone stabilizing effect could not be achieved.

  In the system in which ozone gas is dissolved in water using the ejector or injector 1 shown in FIG. 1, the water fed by pressurized water is squeezed from the inflow water channel 1a on the ejector of the ejector or injector 1 in a reverse radial manner. It receives a high pressurizing action and becomes a water flow that passes through the orifice portion 16, reaches an extremely high flow velocity at the orifice portion 16, passes through the orifice portion 16 instantaneously in a pressurized state, and then toward the downstream drainage channel 1 b. The cavitation is caused by exposure to a strong vacuum through the flow and then the radially open channels.

  At the same time, ozone gas is adjusted to an appropriate amount from the gas suction introduction pipe 20 provided in the vicinity of the orifice section 16 by a vacuum action, and is passed through the orifice section 16 or the gas suction introduction pipe 4 connecting portion. In the above process, the following phenomenon is expected to occur. That is, a continuous two-stage crushing action or sonoluminescence action. This effect is shown in FIG.

  In the ejector inlet channel, the water pressure rapidly increases and is vigorously mixed with the ozone gas sucked and introduced at the orifice portion 16 which is the highest pressure point. At this moment, a very strong pressure shock wave is generated and acts on the water and the bubbles, but the phenomenon of bubble compression called collapse is caused by the pressure shock wave. The fine bubbles compressed by crushing are compressed to an internal pressure of several hundred atmospheres or more, and further reduced in size to a fine bubble diameter while increasing the intermolecular density.

  Next, due to the strong vacuum acting on the crushing action portion, that is, the pressure shock wave region and acting on the downstream side, the bubbles are exposed to the strong vacuum immediately downstream of the orifice portion 16 to generate cavitation. Due to the impact of the cavitation action, the bubbles are deformed and deformed into a strain rather than a true sphere. Bubbles that have already been crushed and reduced in size are subject to extremely high water pressures, but due to deformation caused by cavitation, an imbalance occurs in the pressure distribution on the surface of the bubbles, and additional high pressure is locally applied to the weakest part of the internal pressure. The bubbles break up. Further, the divided fine bubbles are subjected to a stronger pressure shock wave and act on the inside of the bubbles to be repeatedly miniaturized and dissolved at a high concentration. A refinement model of mechanical bubble shearing is shown in FIG. 2, and a fragmentation model of bubbles by crushing and cavitation is shown in (FIG. 3).

    However, what is important here is thermal energy. After 1993, for example, when fine bubbles are forcibly contracted by irradiating ultrasonic waves of 20 kHz to 1 MHz, spherical shock waves are generated in the contracting bubbles, and the temperature in the bubbles is changed from 7,000 K to 20,000 K. It has been reported that even a phenomenon in which bubbles are emitted due to the gasification of the gas is observed.

    This phenomenon is called sonoluminescence, but the duration of high temperature and high pressure inside the contracted bubble is said to be nanoseconds or less. Although the principle of contracting bubbles is different from that of ultrasonic waves, the pressure shock wave generated in the upstream portion immediately adjacent to the orifice portion 16 is comparable to crushing, and further, a large amount of vacuum is generated in a radial path immediately downstream from the orifice portion 16 by vacuum. It seems that the second stage of crushing action is continuously generated after the cavitation occurs and the bubbles are divided. Sonoluminescence is applied to a large number of fine bubbles by applying a pressure shock wave that causes crushing and a shock wave of cavitation by vacuum in a short gap where water and bubbles pass through the orifice portion 16 at high speed. If the action is applied, although the heat is exchanged instantaneously with water in the orifice part 16 and its downstream where it is generated, extremely high heat energy is generated in the bubbles so that it is converted into plasma and emits light, It was expected that ozone was decomposed in large quantities.

    Therefore, the inventors rapidly cooled the ozone gas immediately before introducing it into the orifice part 16 and cooled it to 0 ° C. or less, more preferably minus tens of degrees C. or less, and kept it at a low temperature to supply it to the ejector suction introducing part. We thought it was important to reduce the damage of ozone decomposition caused by sonoluminescence and plasma emission, and found that the efficiency of ozone water generation could be improved.

    That is, as shown in FIG. 4, a gas cooling device 2 is provided for cooling ozone gas to a low temperature of 0 ° C. or lower and introducing it into the ejector in the gas suction introduction pipe path from the ozonizer 3 to the ejector 1. .

    It is desirable that the gas cooling device 2 is directly connected to the gas suction introducing portion of the ejector, but the gas cooling device 2 is connected to the gas cooling device 2 by a gas introduction path upstream from the suction introducing portion, and sufficient heat insulation is provided between them. It is also possible to have a form in which the material is coated and insulated with an effective material.

    In the embodiment, the Peltier type is used for the gas cooling device 2. However, the device type is not limited as long as sufficient ozone gas cooling is possible. In addition, the structure of the mixing mechanism such as the ejector or injector 1 as a mixing device is not limited to the structure, but can be applied to any mixing device as long as gas-liquid mixing is performed with a cavitation action. It is. FIG. 4 is a flow chart of an ozone water generating apparatus by the gas cooling and mixing method of the present invention.

  Moreover, ozone water can be produced | generated when raw | natural water uses as raw water the water which does not contain at least any one of tap water, well water, seawater, pure water, and ultrapure water.

  In addition, the raw water can be converted into raw water by using at least tap water, well water, seawater, pure water, ultrapure water and at least one additive of sulfuric acid, hydrochloric acid, acetic acid, or hydrogen peroxide as raw water. An aqueous solution can be produced.

  In addition, at least any gas of oxygen, hydrogen, nitrogen, helium, and ammonia is arbitrarily mixed or contained in ozone gas, and it is sucked and introduced into the above-mentioned water or the above-mentioned liquid, and gas-liquid mixed. Ozone water or an aqueous ozone solution can be produced.

  About an Example, embodiment and its effect are demonstrated in detail based on the verification test machine flowchart shown in FIG. The demonstration test machine was operated under the same conditions as shown below to generate ozone water. The water used was tap water (in Setagaya-ku, Tokyo). First, water is supplied to a full tank of tank 5 having an actual capacity of 55 liters, pressurized and fed by a cascade circulation pump 6 of 0.4 kw / h, and 10 liters per minute is passed through an ejector 1 having an orifice diameter of 2.5φ to adjust pressure. The valve 15 was circulated in the circulation path under the condition of 0.45 MPa.

In order to make the water pressure in the ejector 1 appropriate, it was adjusted while confirming with the pressure gauge 11. The path returning to the tank 5 downstream from the pressure adjustment valve 15 is atmospheric pressure. From the upper part of the tank, an undissolved ozone gas discharge path was provided, and it was discharged out of the machine through an exhaust ozone decomposition device. On the other hand, oxygen gas adjusted to an oxygen concentration of 95% was supplied to the ozonizer 3 at 4 liters per minute, discharged, and sucked into the ejector 1 as ozone gas. The ozone gas concentration at this time was 4.8 g / Nm ³ .

  The path through which the ozone gas was introduced into the ejector 1 was a Teflon tube. However, the tube was directly cooled, and the Peltier-type gas cooling device 2 was arranged so as to adjust the ozone gas temperature to about minus 10 ° C. Although the dissolved ozone concentration increases with the circulation, a path through which the sampling solution can be collected from the path from the circulation pump 6 to the ejector 1 is provided, and the concentration is continuously measured using the dissolved ozone concentration meter 12 by the ultraviolet absorption type. . The water temperature of the target water (and ozone water) was maintained at a constant plus 15 ° C. by automatically adjusting the temperature of two chillers 7 of 400 w.

  Under these operating conditions, first, the rise in dissolved ozone concentration was compared between the case where ozone gas cooled to minus 10 ° C by gas cooling was introduced and the case where gas introduction was performed at plus 35 ° C without gas cooling. . As shown in Table 1 of FIG. 8, according to the comparison in which only the ozone gas temperature introduced and introduced is different, a significant increase in concentration by 30% was observed when cooled ozone was used. From this result, it can be seen that when ozone gas is cooled upstream of the gas-liquid mixing section, a large amount of ozone that is lost by self-decomposition due to thermal energy remains suppressed.

  Subsequent to the test related to the concentration increase, the supply of ozone gas was stopped after the apparatus was stopped, the transition of concentration decrease was measured, and a comparative test regarding the concentration decrease rate was performed. The apparatus stops the ozone supply line, closes the solenoid valve 13 in the circulation path, reduces the output of the circulation pump 6 to 10% or less by the inverter 14, and can only supply the sample solution to the dissolved ozone concentration meter 12. Maintained in a state. Also during the concentration reduction rate test, the water temperature was 15 ° C., and the pressure in the tank 5 was atmospheric pressure. An exhaust ozone decomposing apparatus 10 is connected to the tank 5.

  As a result, as shown in Table 2 of FIG. 9, when ozone gas was cooled and mixed, an extremely stable ozone concentration was maintained even after 5 hours, which was significantly different from the case of not cooling. From this result, in addition to the fact that ozone decomposition was suppressed by gas cooling, microbubbles that are hard to rise due to the effect of crushing and sonoluminescence were strongly affected, so that high-concentration Was expected to be met. The gas cooling mixing method was confirmed to be extremely effective as a technique for increasing the concentration of ozone and at the same time as a stabilization technique, and the invention was completed.

  The present invention is applicable to an ozone water generating apparatus and an ozone water generating method in which ozone gas is introduced into raw water and gas-liquid mixed to generate ozone water or an aqueous ozone solution. The ozone gas is dissolved in water or an aqueous solution, Cooling the ozone-containing gas sucked and introduced into the ejector with the aim of suppressing the self-decomposition of ozone molecules in the bubbles by the thermal energy generated by the sonoluminescence action during mixing and increasing the dissolution efficiency and the concentration reached. In addition, a gas cooling device capable of maintaining a low temperature is provided, and the ozone water generating device can be downsized and highly effective ozone water can be generated.

It is the figure which showed the effect | action in an ejector. It is a model figure of bubble refinement | miniaturization by mechanical shearing. It is a model figure of bubble refinement | miniaturization by crushing and a cavitation action. It is an ozone water generating apparatus flow chart by a gas cooling mixing method (technique of the present invention). It is a flowchart of a conventional / water-cooled ozone water generator. It is a flowchart of a conventional / raw material gas cooled ozone water generator. FIG. 7 is a flow chart of the verification test machine. It is dissolved ozone concentration rise rate measurement data. It is dissolved ozone concentration reduction rate measurement data.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Ejector or injector 2 Gas cooling device 3 Ozonizer 4 Gas suction introduction pipe 5 Tank 6 Circulation pump 7 Chiller 8 Water cooling pump 9 Raw material gas cooling device 10 Exhaust ozone decomposition device 11 Pressure gauge 12 Dissolved ozone concentration meter 13 Solenoid valve 14 Inverter 15 Pressure adjustment valve 16 Orifice

Claims (9)

From the inflow water channel on the ejector to the downstream drainage channel through the orifice part or the gas suction introduction pipe connection part, the ozone gas is caused to flow from the suction introduction pipe connected in the vicinity of the orifice part to the passing water or raw liquid water, An ozone water generator that generates ozone water or an aqueous ozone solution by gas-liquid mixing.
An ozone water generating device comprising a gas cooling device for cooling ozone gas to a low temperature of 0 ° C. or lower and introducing it into the ejector in a gas suction introduction pipe path from the ozonizer to the ejector. From the inflow water channel on the ejector to the downstream drainage channel through the orifice part or the gas suction introduction pipe connection part, the ozone gas is caused to flow from the suction introduction pipe connected in the vicinity of the orifice part to the passing water or raw liquid water, It is an ozone water generation method that generates ozone water or an ozone aqueous solution by gas-liquid mixing.
A method for generating ozone water, comprising a gas cooling device, wherein ozone gas is cooled to a low temperature of 0 ° C. or less in a gas suction introduction pipe path from an ozonizer to an ejector and introduced into the ejector. The raw water is water that does not contain at least one of tap water, well water, seawater, pure water, and ultrapure water as raw water,
The ozone water generation method according to claim 2, wherein the ozone water is generated. The raw water is at least tap water, well water, seawater, pure water, ultrapure water, and a solution obtained by adding at least one of sulfuric acid, hydrochloric acid, acetic acid, and hydrogen peroxide as raw water,
The ozone water generation method according to claim 2, wherein the ozone aqueous solution is generated. The ozone gas is arbitrarily mixed or contained with at least one of oxygen, hydrogen, nitrogen, helium, and ammonia, and it is sucked and introduced into the water of claim 3 or the liquid of claim 4 for gas-liquid mixing. And
The ozone water generation method according to claim 2, wherein the ozone water or the ozone aqueous solution is generated. Using the ozone water generation method according to claim 2,
Ozone water characterized in that the raw water is produced as raw water containing at least tap water, well water, seawater, pure water, or ultrapure water. Using the ozone water generation method according to claim 2,
The raw water is produced as a raw water by adding at least any one of sulfuric acid, hydrochloric acid, acetic acid, and hydrogen peroxide to tap water, well water, seawater, pure water, and ultrapure water. Aqueous ozone solution. Using the ozone water generation method according to claim 2,
The ozone gas is arbitrarily mixed or contained with at least one of oxygen, hydrogen, nitrogen, helium, and ammonia, and it is sucked and introduced into the water of claim 3 or the liquid of claim 4 for gas-liquid mixing. Ozone water characterized by being produced as a result. Using the ozone water generation method according to claim 2,
The ozone gas is arbitrarily mixed or contained with at least one of oxygen, hydrogen, nitrogen, helium, and ammonia, and it is sucked and introduced into the water of claim 3 or the liquid of claim 4 for gas-liquid mixing. Ozone water or an aqueous ozone solution produced by

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