KR0173368B1 - Apparatus and method for producing ionic water and system and method for producing electrolytic ionic water - Google Patents

Abstract

An object of the present invention is to provide an ionized water production apparatus capable of producing reproducibly ionized water containing a low concentration of electrolyte. Moreover, it aims at providing the electrolytic ion water manufacturing apparatus which can obtain stable electrolytic ion water.

At least one gas-liquid mixing means for mixing the raw water and gas, and an ultrasonic excitation means for generating ions by applying ultrasonic waves to the gas-liquid mixture obtained by the gas-liquid mixing means.

And gas-liquid mixing means for mixing raw water and a gas dissolved in water to generate ions, and the gas-liquid mixing means separates the gas and the raw water through a gas permeable membrane through which only gas passes. Permeate the gas to the raw water side, characterized in that mixed with the raw water.

Description

Ionized water production apparatus and ionized water production method, electrolytic ion water production system and electrolytic ion water production method

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ionized water production apparatus, an ionized water production method, an electrolytic ion water production system, and an electrolytic ion water production method, and more particularly, to a method and an apparatus for producing ionized water supplied to an electrolytic ion water production apparatus used for cleaning a highly clean surface. .

In recent years, the washing | cleaning using electrolytic ionized water is examined for the purpose of more clean washing | cleaning. An example of the electrolytic ion water production method is shown in FIG.

The electrolysis device 400 has an anode chamber 403 in which an anode electrode 401 is disposed and a cathode chamber 404 in which an anode electrode 402 is disposed, and both chambers are separated by an ion exchange membrane 405. .

Introductory piping systems 406 and 407 for introducing raw water into the anode chamber 403 and the cathode chamber 404 of the electrolytic apparatus 400, and discharge piping systems 408 and 409 for discharging the electrolytic treatment solution therefrom. have.

Electrolyte addition devices 410 and 411 are connected to the inlet pipes 406 and 407, and continuous injection of HCl, NH ₄ OH and the like into raw water, for example, is performed by energizing the current directly to the electrodes 401 and 402. Electrolysis reaction can be performed, and electrolytic anode water and electrolytic cathode water of desired pH can be obtained continuously.

The electrolyte is added for efficient electrolysis and for pH control. However, in the system of FIG. 4, the electrolyte needs to be diluted and added to the required concentration, and it takes time. This causes a problem that the water supply to the electrolytic device is not constant, and electrolysis conditions change, making it difficult to produce stable electrolytic ion water. In this method, it is difficult to add the electrolyte accurately and reproducibly at low concentration (100 ppm or less). In addition, a high concentration of liquid agglomerates occur, and there is a problem in the management of fine particles and the like.

In view of such a phenomenon, an object of the present invention is to provide an ionized water production apparatus and an ionized water production method capable of producing reproducibly ionized water containing a low concentration of electrolyte. Moreover, it aims at providing the electrolytic ion water manufacturing apparatus and electrolytic ion water manufacturing method which can obtain stable electrolytic ion water.

1 is a conceptual diagram showing an example of the electrolytic ion water production system of the present invention,

2 is a graph showing the relationship between gas partial pressure and ion concentration,

3 is a conceptual diagram showing an example of the electrolytic ion water production system of the present invention,

4 is a conceptual diagram showing another example of the electrolytic ion water production system of the present invention,

5 is a graph showing the relationship between the ion concentration and the gas pressure at the outlet of the ultrasonic wave excitation device,

6 is a conceptual diagram showing a conventional electrolytic ion water production system.

* Explanation of symbols for main parts of the drawings

1, 1 ': gas-liquid mixing means 2, 2': gas introduction pipe

3, 3 ': gas discharge pipe 4, 4': raw water introduction pipe

5, 5 ': permeable membrane 6, 6': valve

7, 7 ': Pipe 8, 400: Electrolyzer

9, 401: anode electrode 10, 402: cathode electrode

11, 403: anode chamber 12, 404: cathode chamber

13, 405: ion exchange membrane 406, 407: introduction piping

408, 409: exhaust piping system 410, 411: electrolyte addition device

The ionized water production apparatus of the present invention has gas-liquid mixing means for mixing raw water and a gas dissolved in water to generate ions.

According to the ionized water production apparatus, the ion concentration can be controlled by the partial pressure of the gas, the ion concentration can be precisely controlled even at a low concentration, and the ion water can be easily produced with high reproducibility.

The electrolytic ion water production system of the present invention includes a gas-liquid mixing means for mixing raw water and a gas which is dissolved in water to generate ions, and a pipe for supplying ionized water containing ions obtained by the gas-liquid mixing means to the electrolysis device; Electrolysis of the ionized water consists of an electrolysis device for producing electrolytic ionized water.

Therefore, by combining the ion production apparatus of the present invention with an electrolysis apparatus, the ion concentration of the supplied ion water can be precisely controlled, so that electrolytic ion water of stable characteristics can be obtained.

Preferably, the gas-liquid mixing means separates the gas and the raw water through a gas permeable membrane that transmits only gas from the viewpoint of controllability or handling of ion concentration, and mixes the gas into the raw water by passing the gas through the raw water side. . In addition, the gas contains NH ₃ , HCl, Cl ₂ or SO ₂ gas.

In the electrolytic ion water discharge relationship of the electrolysis device, it is preferable that a chromium oxide passivation film is formed on the inner surface. This chromium oxide passivation film has high corrosion resistance and extremely low elution of impurities, and does not contaminate electrolytic ion water, and is suitable for ultra-clean cleaning.

Another ionized water production apparatus of the present invention includes at least an gas-liquid mixing means for mixing raw water and gas, and at least an ultrasonic-exciting means for generating ions by applying ultrasonic waves to the gas-liquid mixture obtained by the gas-liquid mixing means.

In addition, according to the ionized water production apparatus, the ion concentration can be accurately controlled even at low concentration, and the ion water can be easily produced with high reproducibility.

It is preferable that this gas-liquid mixing means also separates gas and raw water through the above-mentioned gas permeable membrane, and permeates the gas to the raw water side to mix the raw water.

The gas is a gas obtained by diluting N ₂ , N ₂ and H ₂ or N ₂ and O ₂ or these with argon (Ar), krypton (Kr) or xenon (Xe).

Moreover, it is preferable to have two or more said gas-liquid mixing means, and to divide and mix the said gas which consists of multiple types into two or more gas-liquid mixing means. In addition, it is preferable that one of the two or more gas-liquid mixing means mixes any one of Ar, Kr or Xe with raw water.

The ionized water production method of the present invention is characterized in that the gas is reacted to generate ions by dissolving a gas in raw water and applying ultrasonic waves thereto.

According to this method, ionized water can be manufactured easily.

The gas is characterized in that N ₂ , N ₂ and O ₂ or N ₂ and H ₂ gas. Moreover, it is preferable to dissolve at least 1 sort (s) of Ar, Kr, and Xe in the said raw water.

Moreover, it is preferable to change the density | concentration of the said ion by the frequency and / or output of the said ultrasonic wave.

Another electrolytic ion water production system of the present invention is characterized in that the ionized water production apparatus is disposed on the electrolyte supply side of the electrolytic apparatus.

Therefore, according to this system, electrolytic ionized water having stable characteristics can be obtained by combining the ionized water producing apparatus with an electrolytic apparatus.

The method for producing electrolytic ion water of the present invention is characterized by producing electrolytic ion water by electrolyzing the ion water produced by the method for producing ionized water.

According to this method, electrolytic ionized water of stable characteristics can be obtained.

One embodiment of the ionized water production apparatus and the electrolytic ion water production system of the present invention will be described with reference to FIG.

In Fig. 1, 1 and 1 'are gas-liquid mixing means for mixing gas and raw water. 2. 2 'is gas introduction pipe, 3' and 3 'is gas discharge pipe, 4 and 4' is raw water introduction pipe, 5 and 5 'are permeable membranes for gas only, 6 and 6' are valves, and 7 'is This pipe supplies ionized water to the electrolysis device.

8 is an electrolysis device, and is divided into an anode chamber 11 in which the anode electrode 9 is arranged and a cathode chamber 12 in which the cathode electrode 10 is arranged by the ion exchange membrane 13. The ionized water discharged from the ion production apparatus is introduced into the anode chamber 11 and the cathode chamber 12, respectively, and a DC voltage is applied from the electrodes 9 and 10 to be electrolyzed.

The electrolyzed ionized water that has been electrolyzed is sent to each use point via the electrolytic cathode ionized water discharge pipe 14 and the electrolytic cathode ionized water discharge pipe 15, and is used for washing the gas, respectively. As the discharge pipe of the electrolytic ion water, a stainless pipe having a chromium oxide passivation film formed on its inner surface is used.

The production method of ionized water and electrolytic ionized water using the apparatus of FIG. 1 is demonstrated.

The gas-liquid mixing means 1 sends HCl gas (or inert gas such as Ar, gas diluted with N ₂ and H ₂ , etc.) from the gas introduction pipe 2 to the gas-liquid mixing means 1, and the pure water degassed through the raw water supply pipe 4. When supplied, HCl gas penetrates through the gas permeable membrane 5, enters pure water, dissolves and dissociates to generate ions. Ionized water is sent to the anode chamber 11 via the pipe 7.

On the other hand, the ionized water sent to the cathode chamber 12 is similarly treated. That is, NH ₃ gas (or inert gas such as Ar, N ₂ or H _2, etc.) is sent from the gas introduction pipe 2 'to the gas-liquid mixing means 1', and the raw water supply pipe 4 ' When the pure water degassed through is supplied, NH ₃ gas penetrates through the gas-permeable membrane 5 ', enters the pure water, dissolves, and dissociates to generate ions. Ionized water is sent to the cathode chamber 12 via the pipe 7 '.

Since the ion concentration in the ionized water produced in this way can be controlled by the pressure of the gas introduced into the gas-liquid mixing means, the ionized water having a low ion concentration can be obtained accurately and stably.

The ionized water introduced into the anode chamber 11 and the cathode chamber 12 is electrolyzed by applying a predetermined voltage between the electrodes (about 5 to 10V when the distance between the electrodes is 20 mm), and an electrolytic anode water having a desired pH, Electrolytic cathode water is produced.

The characteristics such as pH, specific resistance, redox potential, and the like of the electrolytic ion water produced as described above are extremely stable because the ion concentration of the supplied ion water is precisely controlled.

In the example of FIG. 1, although HCl was introduced into the gas-liquid mixing means 1 in the process of producing the ionized water supplied to the anode chamber 11, Cl ₂ , SO ₂ , and the like may also be used.

In addition, the shape of the gas permeable membrane of the gas-liquid mixing means of FIG. 1 may be any shape such as a flat plate type or a hollow fiber type. In addition to the method of using a permeable membrane, for example, a method of dissolving gas by bubbling or an ejector method may be used. However, it is preferable to use a gas permeable membrane from the viewpoint of controllability or handling of ion concentration. .

The ion concentration of the ionized water supplied to the electrolysis device is preferably about 1 to 400 ppm on the cathode side and about 1 to 40 ppm on the anode side. When the surface of a member such as a semiconductor element is cleaned using an electrolytic cathode water or an electrolytic cathode water obtained in this range, the surface of the member can be more excellent in the removal property against metal contamination, the metal removal property, the particle removal property and the organic matter removal property.

As for the electrolytic ion water discharge pipe of the present invention, it is preferable to use the inner surface of which formed a chromium oxide passivation film as described above. This chromium oxide passivation film has extremely high corrosion resistance and little elution of impurities, and does not contaminate electrolytic ion water, and is suitable for ultra-clean cleaning.

Moreover, in this invention, it is more preferable to form a chromium oxide passivation film not only in the discharge pipe of electrolytic ion water but also in the inner surface of gas piping mixing means, a gas introduction pipe, and other piping systems.

A chromium oxide passivation film can be formed as follows, for example.

The surface of the stainless material (SUS316L) was polished by electrolytic compound polishing, followed by baking in an inert gas to remove moisture, followed by inert gas such as N ₂ or Ar, and 500 ppb to ₂ % H ₂ O gas. The passivation film of chromium oxide is formed by heat-processing at the temperature of 450-600 degreeC in the mixed gas of.

Ion water was prepared and electrolyzed under various conditions using the apparatus of FIG. 1 to investigate the relationship between the ion concentration and the partial pressure of HCl and NH ₃ gas and the characteristics of electrolytic ion water. The results are shown in FIG. 2 and Table 1.

As shown in FIG. 2, ion concentrations such as Cl ⁻ and NH 4 ⁺ obtained by dissolving HCl and NH ₃ gas can be obtained in proportion to the partial pressure. However, the contact time between water and gas is kept constant.

In addition, the results of FIG. 2 and Table 1 show that the ion concentration is in the range of ± 10% even if repeated three times, and the pH and redox potential of the electrolytic ion water are also highly reproducible.

L: liter

Next, another embodiment of the ionized water production apparatus and the electrolytic ion water production system of the present invention will be described with reference to FIG.

In Fig. 3, 101, 101 ', 101' ', 101' '' are gas-liquid mixing means for mixing gas and raw water. 102, 102 ', 102' ', 102' '' are gas introduction pipes, 103, 103 ', 103' ', 103' '' are gas discharge pipes, 104, 104 ', 104' ', 104' '' Water inlet pipe, 105, 105 ', 105' ', 105' '' is a permeable membrane for gas only transmission, 106, 106 ', 106' ', 107, 107' is an ultrasonic excitation device for applying ultrasonic wave to gas-liquid mixture The gas-liquid mixed water has a sealed structure so as not to contact the atmosphere.

108 is an electrolysis device, and is divided into an anode chamber 111 in which the anode electrode 109 is disposed and an anode chamber 112 in which the cathode electrode 110 is arranged by the ion exchange membrane 113. The ionized water discharged from the ultrasonic wave excitation apparatuses 107 and 107 'is introduced into the anode chamber 111 and the cathode chamber 112, respectively, and a DC voltage is applied from the electrodes 109 and 110 to be electrolyzed.

The electrolyzed ionized water that has been electrolyzed is sent to each use point through the anode ion water discharge pipe 114 and the cathode ion water discharge pipe 115, and is used for washing the gas.

The production method of ionized water and electrolytic ionized water using the apparatus of FIG. 3 is demonstrated.

The gas-liquid mixing means 101 sends a mixed gas of N ₂ gas and O ₂ gas (for example, 2: 3) from the gas introduction pipe 102 at a pressure of 0.5 atm, and degassed through the raw water supply pipe 104. When pure water is supplied at 1 L / min (L: liter), the N ₂ and O ₂ gases pass through the gas permeable membrane 105 and are dissolved about 4 mg / L and 13 mg / L in pure water, respectively.

The pure water in which N ₂ and O ₂ gas is dissolved is sent to the gas-liquid mixing means 101 'of the next step via the pipe 104', and similarly, Ar gas is dissolved at about 6 mg / L, for example, at 0.1 atmosphere.

The raw water in which N ₂ , O _2, and Ar gas are dissolved is subjected to ultrasonic waves in the ultrasonic excitation device 107, whereby dissolved N ₂ and O ₂ react to generate about 16 mg / L of NO ₃ ⁻ . Here, 10 kHz to 3 MHz is suitably used as the frequency of the ultrasonic waves to be applied, and the concentration of the generated NO ₃ ⁻ ions can be controlled by the frequency or output of the ultrasonic waves to be applied. In other words, by applying an appropriate frequency and output frequency, various ion concentrations can be set accurately and reproducibly.

Moreover, by mixing Ar gas, the ion concentration in pure water can be produced more efficiently. Although the details of this reason are not clear at present, it is thought that the presence of Ar in water promotes the production of OH radicals by applying ultrasonic waves and has a catalytic action of the reaction of N ₂ and O ₂ . The same effect is confirmed for Kr and Xe gases.

Ionized water containing NO ₃ ⁻ is sent to the anode chamber 111.

On the other hand, the ionized water sent to the cathode chamber 112 is similarly processed. Here, N ₂ , H ₂ gas (eg, 1: 3) is used in the first gas-liquid mixing means 101 '', and Ar gas is dissolved in the next gas-liquid mixing means 101 '''. The device (107 ') with ultrasound to the N ₂ and H ₂ gas react to generate the NH ₄ ^+. The generated ion concentration may be changed by the frequency and / or output of the ultrasonic waves as described above.

The ionized water introduced into the anode chamber 111 and the cathode chamber 112 is electrolyzed by applying a predetermined voltage between the electrodes (about 0 to 10 V in the case of an inter-electrode distance of 20 mm), and an electrolytic anode water having a desired pH, Electrolytic cathode water can be produced.

The characteristics such as pH, specific resistance, redox potential, and the like of the electrolytic ion water produced as described above are extremely stable because the ion concentration of the supplied ion water is precisely controlled.

In the example of FIG. 3, in the manufacturing process of the ionized water supplied to the anode chamber 111, the gas-liquid mixing means 101 of the first step is a mixed gas of N ₂ , O ₂ , and the gas mixing mechanism 101 ′ of the next stage. Although Ar gas was introduced, a gas-liquid mixing means may be used as one step, and a mixed gas of N ₂ , O _2, and Ar gas may be introduced therein. The same applies to the cathode side.

In addition, as shown in FIG. 4, each gas dissolved in pure water may be introduced into a separate gas-liquid mixing means to dissolve.

As the base, N ₂ or N ₂ , O _2, or the like is used on the anode side. On the cathode side, N ₂ , H _2, and the like are used. Moreover, although Ar, Kr, and Xe gas are not used, the effect of this invention is acquired, but since these gases have a catalysis, it is preferable to dissolve in raw water.

The pressure of the gas is appropriately determined by the concentration dissolved in the raw water, but is about 1 × 10 ⁴ to 6 × 10 ⁵ Pa.

The ratio of the dissolved concentration of the gas is preferably in the stoichiometric ratio required to form the desired ions.

In the example of FIG. 3, a gas permeable membrane is used as the gas-liquid mixing means, but the shape of the gas permeable membrane may be any shape such as a flat plate or a hollow fiber type. In addition to the method of using a permeable membrane, for example, a method of dissolving the gas by bubbling the gas or a method using an ejector may be used.

The ion concentration of the ionized water supplied to the electrolysis device is preferably about 1 to 400 mg / L on the cathode side and 1 to 40 mg / L on the anode side. When the member such as a semiconductor element is cleaned by using the cathode water or the anode water obtained in this range, the surface contamination removal property (metal removal property, fine particle removal property and organic matter removal property) is further excellent.

The ion concentration changes depending on the concentration of dissolved gas (that is, the pressure of the gas in the gas mixing mechanism), the power of the ultrasonic wave applied to the ultrasonic wave excitation device, the frequency, and the like.

Using the apparatus of FIG. 4, N ₂ , O ₂ and Ar gases were dissolved in pure water on the anode side and N ₂ , H ₂ and Ar gases on the cathode side, and ultrasonic water was applied to prepare ionized water.

5 shows the relationship between the ion concentrations (NO ₃ ⁻ , NH ₄ ⁺ ) of the prepared ionized water and the respective gas pressures. The temperature and flow rate of pure water are 20 ° C and 1 L / min on both the anode side and the cathode side, and the ultrasonic wave excitation apparatus uses a tank having a volume of 11 liters, and the frequency and the output are 0.95 MHz and 1200 W, respectively. It was set as.

As shown in FIG. 5, it can be seen that the ion concentration generated by the pressure of the gas can be controlled, and the ion generation can be efficiently performed by dissolving Ar gas.

In addition, even if the result of FIG. 5 is repeated 10 times, it turned out that ion concentration exists in the range of +/- 5%, and reproducibility is high.

The pressures of N ₂ , O ₂ , and Ar gas on the anode side are 1 × 10 ⁵ , 1.5 × 10 ⁵ , 1 × 10 ⁴ Pa, respectively, and the pressures of N2, H2, Ar gas on the cathode side are 0.5 × 10 ⁵ , respectively. , 2 × 10 ⁵ , 1 × 10 ⁴ Pa, and the other conditions were prepared as in the above example, and ionized water was produced, and the prepared ionized water was sent to the anode chamber and the cathode chamber, respectively, and subjected to electrolysis under the conditions shown in Table 2, and electrolytically Anode water and electrolytic cathode water were prepared. The characteristics of the prepared electrolytic ion water are also shown in Table 2.

According to the present invention, there is provided an ionized water production apparatus and ionized water production method capable of producing ionized water containing a low concentration of electrolyte with high reproducibility, and an electrolytic ion water production apparatus and an electrolytic ion water production method capable of obtaining stable electrolytic ionized water. Can provide.

Claims (18)

Ionized water production apparatus characterized in that it has a gas-liquid mixing means for mixing the raw water and a gas that is dissolved in water and generates ions. The ionized water production apparatus according to claim 1, wherein the gas-liquid mixing means separates the gas and the raw water through a gas permeable membrane through which only gas passes, and mixes the gas with the raw water by passing the gas through the raw water side. . The device of claim 1, wherein the gas contains NH ₃ , HCl, CL _2, or SO ₂ gas. A gas-liquid mixing means for mixing raw water and a gas dissolved in water to generate ions, a pipe for supplying ionized water containing ions obtained by the gas-liquid mixing means to an electrolysis device, and electrolytic ion water by electrolyzing the ionized water. Electrolytic ionized water production system comprising an electrolysis device to manufacture. The electrolytic ion water production method according to claim 4, wherein the gas-liquid mixing means separates the gas and the raw water through a gas permeable membrane through which only gas passes, and mixes the gas with the raw water by passing the gas through the raw water side. system. The system of claim 4, wherein the gas is NH ₃ , HCl, Cl _2, or SO ₂ gas. 5. The electrolytic ion water production system according to claim 4, wherein a chromium oxide passivation film is formed on the inner surface of the electrolytic ion water discharge distribution system of the electrolysis device. And at least an ultrasonic vibrating means for generating ions by applying ultrasonic waves to the gas-liquid mixture obtained by the gas-liquid mixing means. 9. The ionized water production apparatus according to claim 8, wherein the gas-liquid mixing means separates the gas and the raw water through a gas permeable membrane through which only gas passes, and mixes the gas with the raw water by passing the gas through the raw water side. . The ionized water production apparatus according to claim 8, wherein the gas is N ₂ , N ₂ and H ₂ or N ₂ and O ₂ , or a gas diluted with argon, krypton or xenon. 9. An ionized water production apparatus according to claim 8, wherein said gas-liquid mixing means has two or more, and said gas composed of plural kinds is divided and mixed into said two or more gas-liquid mixing means. 12. The ionized water production apparatus according to claim 11, wherein one of the two or more gas-liquid mixing means mixes any one of argon, krypton or xenon with raw water. A method of producing ionized water, characterized in that a gas is dissolved in raw water and ultrasonic waves are applied to the gas to cause ions to react. The method of claim 13, wherein the gas is N ₂ , N ₂ and O _2, or N ₂ and H ₂ gases. The method of claim 13, wherein at least one of argon, krypton, and xenon is dissolved in the raw water. The method of claim 13, wherein the concentration of the ion is changed by the frequency and / or output of the ultrasonic wave. A method for producing electrolytic ion water, wherein the ionized water produced by the method for producing ionized water according to claim 13 is electrolyzed to produce electrolytic ion water. An ionized water production system according to claim 8, wherein the ionized water production apparatus is disposed on the electrolyte supply side of the electrolytic apparatus.