TWI380954B - Process for supplying ozone water and apparatus for supplying ozone water - Google Patents

Description

Ozone water supply method and ozone water supply device

The present invention relates to an ozone water supply method and an ozone water supply device. More specifically, the present invention relates to an ozone water supply method and an ozone water supply device capable of stably supplying a specified ozone concentration to a point of use in a wet cleaning step, a surface treatment step, and the like of an electronic material such as a semiconductor or a liquid crystal. .

Removal of organic matter, metals, and the like from the surface of an electronic material such as a semiconductor substrate for a semiconductor, a glass substrate for a liquid crystal, or a quartz substrate for a photomask is extremely important in order to ensure product quality and yield. Ozone water in which ozone is dissolved in pure water is used to reduce the concentration of dissolved ozone to a low concentration of several mg/L, and exerts an extremely strong oxidizing power to remove impurities such as organic substances and metals adhering to the surface of electronic materials. The step of contaminating, or the step of uniformly oxidizing the surface of the ruthenium substrate to form an oxide film layer. In this case, the concentration of the supplied ozone water affects the control of the surface cleaning power and the oxide film thickness, and the concentration management is very important.

The ozone dissolved in water has a problem that the decomposition itself is intense and the dissolved ozone concentration in the ozone water is easily lowered. Here, as an ozone water supply device that supplies a certain concentration of ozone water to a use point even if ozone water is transported over a long distance, the concentration of ozone in the transfer is small, it is proposed to dissolve ozone in pure water to generate Ozone water supply device for ozone water, and ozone water supply device for supplying ozone water supply pipe for generating ozone water, which is an ozone water supply provided by adding means for dissolving carbonic acid gas or organic compound in pure water or ozone water Device (Patent Document 1). As an apparatus for supplying ozone-dissolved water having the same effect, an ozone dissolving device that dissolves ozone in dissolved water, a water supply pipe that supplies dissolved water to the dissolving device, and an ozone that delivers ozone dissolving water from the dissolving device are proposed. a supply device for dissolving water, which is selected from the group consisting of nitrous acid, nitrite, carbonic acid, carbonate, bicarbonate, sulfurous acid, sulfite, bisulfite and hydrazine; An ozone-dissolved water supply device in which the ozone-decomposing inhibitor of 2 or more is added to the drug supply device at any position from the water supply pipe to the delivery pipe (Patent Document 2).

In addition, when the ozone water is supplied to the use site, the ozone water concentration adjustment method capable of easily supplying the ozone water of a desired concentration is proposed, and the ozone water concentration adjustment method for excessively dissolving ozone is proposed, which is based on the length of the water passage. A method of adjusting ozone water concentration by adjusting the concentration of ozone water by temperature, ultrasonic wave, ultraviolet ray or turbulence to promote decomposition of ozone (Patent Document 3). An ozone concentration adjustment method for supplying ozone-containing water having a desired dissolved ozone concentration to a point of use, and an ozone concentration adjustment method for bringing ozone-containing water into contact with glass to form a desired concentration of ozone-containing water (Patent Document 4) .

However, in the conventional ozone water supply method and the ozone water supply device, it is extremely difficult to supply ozone water having a stable concentration and to control the concentration of dissolved ozone at the use point.

JP-A-2000-37695 (P. 2) (Patent Document 2) Japanese Laid-Open Patent Publication No. JP-A No. 2000-180433 (Patent Document 3) (JP-A-2000-180433) (p. 2-3) (Patent Document 1) Japanese Patent Laid-Open Publication No. 2000-334468 (page 2)

An object of the present invention is to provide an ozone water supply method and ozone water capable of stably supplying ozone water having a specified ozone concentration to a point of use in a wet cleaning step, a surface treatment step, or the like of an electronic material such as a semiconductor or a liquid crystal. Supply device.

In order to solve the above problems, the inventors of the present invention have found that high-concentration ozone water in which an ozonolysis inhibitor is present is transported to a point of use by a concentration test, and is reduced to a specified ozone concentration by a concentration adjustment means at a point of use. The ozone water of a specified concentration can be stably supplied to the point of use, and the present invention has been completed based on the findings.

That is, the present invention provides the following methods and apparatus.

(1) A method for supplying ozone water, which is characterized in that ozone water in which an ozonolysis inhibitor is present is transported to a point of use, and is reduced to a predetermined ozone concentration by a concentration adjusting means in the vicinity of a point of use.

(2) The method of supplying ozone water according to the above (1), wherein the ozonolysis inhibitor is one or more selected from the group consisting of a water-soluble organic compound, an inorganic acid or a salt thereof, and a hydrazine.

(3) The ozone water supply method according to (2), wherein the inorganic acid or a salt thereof is hydrochloric acid, sulfuric acid, carbonic acid, carbonate, hydrogencarbonate, nitrous acid, nitrite, sulfurous acid, sulfite or sulfurous acid. Hydrogen salt.

(4) The ozone water supply method according to (1), wherein the concentration adjusting means dissolves ozone.

(5) The ozone water supply method according to (4), wherein the one selected from the group consisting of ultrasonic irradiation, ultraviolet irradiation, turbulent flow generation, stirring, heating, addition of a base, and addition of hydrogen peroxide Or two or more means for decomposing dissolved ozone.

(6) The ozone water supply method according to (1), wherein the concentration adjustment means is dilution of ozone water.

(7) The ozone water supply method according to any one of (1) to (6), wherein the ozone water is transported to the use point in a gas-liquid mixed state in which the ozone water and the ozone gas coexist.

(8) An ozone water supply device comprising: an ozone dissolving device that dissolves ozone gas in pure water to prepare ozone water; a means for supplying an ozonolysis suppressing substance to pure water or ozone water; The prepared ozone water is sent to the ozone water transport pipe at the use point; and the concentration adjustment means is provided near the use point and the ozone water transported by the ozone water transfer pipe is lowered to the specified ozone concentration.

(9) The ozone water supply device according to the above (8), wherein the ozonolysis inhibitor is one or more selected from the group consisting of a water-soluble organic compound, an inorganic acid or a salt thereof, and a hydrazine.

(10) The ozone water supply device according to (9), wherein the inorganic acid or a salt thereof is hydrochloric acid, sulfuric acid, carbonic acid, carbonate, hydrogencarbonate, nitrous acid, nitrite, sulfurous acid, sulfite or sulfurous acid. Hydrogen salt.

(11) The ozone water supply device according to (8), wherein the concentration adjusting means dissolves ozone.

(12) The ozone water supply device according to (11), wherein the ozone water supply device is selected from the group consisting of ultrasonic irradiation, ultraviolet irradiation, turbulent flow generation, stirring, heating, addition of a base, and addition of hydrogen peroxide. Or two or more means for decomposing dissolved ozone.

(13) The ozone water supply device according to (8), wherein the concentration adjusting means is dilution of ozone water.

The ozone water supply device according to any one of (8) to (13), wherein the ozone water is supplied to the use point in a gas-liquid mixed state in which the ozone water and the ozone gas coexist.

According to the method of the present invention, the ozone water in which the ozonolysis inhibitory substance is present is transported to the point of use while maintaining the high dissolved ozone concentration, and is lowered to the designated ozone concentration by the concentration adjusting means in the vicinity of the use point, thereby being stable Ozone water having a certain dissolved ozone concentration is supplied to the point of use.

In the ozone water supply method of the present invention, the ozone water in which the ozonolysis inhibitor is present is transported to the point of use, and is lowered to a predetermined ozone concentration by a concentration adjusting means in the vicinity of the point of use. The ozone water supply device of the present invention comprises: an ozone dissolving device that dissolves ozone gas in pure water to prepare ozone water; a means for supplying an ozonolysis suppressing substance to pure water or ozone water; and ozone to be prepared by an ozone dissolving device The ozone water transfer pipe that is transported to the use point by the water; and the concentration adjustment means that is disposed near the use point and that reduces the ozone water transported by the ozone water transfer pipe to the specified ozone concentration.

Fig. 1 is a system diagram showing the steps of an aspect of the ozone water supply device of the present invention. The oxygen gas and the nitrogen gas container 2 are supplied from the oxygen container 1 and the nitrogen gas container 2 to the ozone generator 3 of the silent discharge mode to produce an ozone-containing gas. In the ozone dissolving device 4, it is preferable to dissolve the ozone in the purely degassed gas. Ozone water is produced in water. The apparatus shown in the figure includes means 5 for supplying an ozone decomposition inhibitor to pure water or ozone water, ozone water supplied from an ozone dissolving device to an ozone water delivery pipe 6 at a point of use, and a vicinity of the use point 7; Further, the ozone water transported by the ozone water transport pipe is lowered to the concentration adjusting means 8 for specifying the dissolved ozone concentration. In the apparatus of the present aspect, the ozone water which is not used at the point of use is recovered by the ozone decomposing tower 9 filled with activated carbon or the like as water containing no ozone.

In the present invention, by allowing the ozonolysis inhibitor to be present in the ozone water, the dissolved ozone concentration of the ozone water produced by the ozone dissolving device can be greatly reduced, and the ozone water can be transported to the point of use, so that even if it is borrowed near the point of use The ozone concentration is lowered by the concentration adjustment means, and the desired dissolved ozone concentration can still be maintained at the point of use. In the present invention, ozone can be formed by dissolving ozone in pure water after adding an ozonolysis inhibitor, or by adding an ozone decomposition inhibitor to ozone water. Ozone water in which an ozone decomposition inhibiting substance is present may be formed. The dissolved ozone concentration of the ozone water in which the ozonolysis inhibitor is present is preferably 1 to 100 mg/L higher than the specified ozone concentration at the point of use.

In the present invention, the amount of the ozonolysis inhibitor in the ozone water is preferably 0.1 to 500 mg/L, more preferably 1 to 400 mg/L, still more preferably 10 to 300 mg/L. When the amount of the ozonolysis inhibitor is less than 0.1 mg/L, the ozonolysis inhibitory effect is not sufficiently observed, and there is a fear that the ozone in the ozone water is rapidly decomposed during the transportation to the point of use. When the amount of the ozonolysis inhibitor is more than 500 mg/L, there is a concern that the ozonolysis inhibitor is used as an impurity to adversely affect the object to be washed. The detailed mechanism for suppressing decomposition of ozone by adding an ozonolysis inhibitor is not clear, but it can be estimated that the ozonolysis inhibitor reacts with a hydroxyl group which promotes decomposition of ozone to stop the chain reaction of ozone decomposition.

In the present invention, one or two or more selected from the group consisting of a water-soluble organic compound, an inorganic acid or a salt thereof and a hydrazine are preferred. The water-soluble organic compound used in the present invention may, for example, be an alcohol such as methanol, ethanol, propanol or isopropanol; a ketone such as acetone, methyl ethyl ketone or methyl isopropanone; ethylene glycol or propylene glycol; Ethylene glycols; alkanolamines such as monoethanolamine and diethanolamine; fatty acids such as acetic acid and propionic acid; aromatic compounds such as benzyl alcohol, phenol, hydroquinone, benzoic acid, and isoacid. In this case, an alcohol such as isopropyl alcohol is used for washing a glass substrate or the like on a ruthenium wafer, and there is no fear that the affected object may be affected. Therefore, it is suitable for use. The water-soluble organic compound acts as a scavenger for trapping a hydroxyl group which promotes ozonolysis, and can suppress the self-decomposition of ozone and prevent a rapid decrease in the ozone concentration.

The inorganic acid or a salt thereof used in the present invention may, for example, be hydrochloric acid, sulfuric acid, carbonic acid, carbonate, hydrogencarbonate, nitrous acid, nitrite, sulfurous acid, sulfite, hydrogensulfite or hydrofluoric acid. . In this case, carbonic acid can be volatilized by carbonic acid gas after the use of ozone water, so it is suitable for use. The inorganic acid or a salt thereof may be added as an aqueous solution to pure water or ozone water, or may be added as a gas such as carbonic acid gas or sulfurous acid gas, or may be added by passing an aqueous solution of HCO ₃ -type anion exchange resin. By adding an acid to a pH of 2 to 6, the amount of the hydroxyl group which promotes ozonolysis is reduced, and the decomposition of ozone itself can be suppressed, and the rapid decrease of the ozone concentration can be prevented. Further, an anion such as a carbonate ion or a nitrite ion which forms a salt also has a function of reducing a hydroxyl group and prevents a sudden decrease in the ozone concentration.

In the present invention, the ozone concentration adjusting means is a decomposition of dissolved ozone in ozone water, and examples thereof include dilution of ozone water. The means for dissolving ozone in the ozone water is not particularly limited, and examples thereof include ultrasonic irradiation, ultraviolet irradiation, turbulent flow generation, stirring, heating, addition of a base, and addition of hydrogen peroxide. The dissolved ozone concentration of the ozone water adjusted by the concentration adjusting means is preferably 5 mg/L or more than 5 mg/L. When the dissolved ozone concentration is less than 5 mg/L, there is a concern that the ozone water has a insufficient washing effect and surface treatment effect when used in a point of use.

In the present invention, the ultrasonic wave is irradiated with ozone water by, for example, mechanically connecting the ultrasonic oscillator to the water passage of the ozone water. Ultrasonic cavitation is generated in ozone water by irradiating ultrasonic waves into ozone water to generate hydroxyl groups to promote decomposition of ozone. The frequency of the irradiated ultrasonic wave is preferably 10 kHz to 3 MHz. Since there is a fear that particles or the like are generated by the oscillation portion of the ultrasonic wave, it is preferable to use it in combination with a filter. By selecting the amplitude, frequency, output, etc. of the ultrasonic wave, it is possible to adjust to the specified ozone concentration.

In the present invention, by irradiating ozone water with ultraviolet rays, for example, an ultraviolet irradiation device is provided in the water passage of the ozone water, and ultraviolet rays can be irradiated to the ozone water. The light source used for the irradiation of ultraviolet rays is not particularly limited, and examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a deuterium lamp, and a halogenated metal lamp. The wavelength of the irradiated ultraviolet light can be changed by changing the type of the lamp. Among these, a low-pressure mercury lamp having a high ultraviolet irradiation efficiency having a dominant wavelength of 253.7 nm is preferably used. By providing a unit made of a material such as ultraviolet ray transparent material such as quartz glass or polytetrafluoroethylene in the piping of the ultraviolet ray irradiation portion of the water passage, ultraviolet rays can be efficiently irradiated to the ozone water. The amount of ultraviolet radiation can be controlled by adjusting the output of the lamp or by shielding the surface of the lamp. By irradiating ultraviolet rays to generate hydroxyl groups, the self-decomposition of ozone is promoted. Ultraviolet irradiation is easy to use as a concentration adjustment means and does not cause ozone water contamination, so it is suitable for use.

In the present invention, the output adjustment of the ultraviolet lamp can be performed by adjusting the lamp primary side voltage value, the primary side current value, the secondary side voltage value, and the secondary side current value. In the case of using a low-pressure mercury lamp as a lamp for irradiating ultraviolet rays, the secondary side power consumption of the lamp is preferably 0.5 to 15 W. In the range of 0.5 to 15 W of power consumption on the secondary side of the low-pressure mercury lamp, the curve relationship between the power consumption of the secondary side of the lamp and the amount of ozone decomposed is good and stable, and the ozone water can be easily adjusted to the specified ozone concentration. In the case of using a high-pressure mercury lamp as a lamp for irradiating ultraviolet rays, the secondary side power consumption of the lamp is preferably 5 to 1500 W. In the range of 5 to 1500 W of power consumption on the secondary side of the high-pressure mercury lamp, the curve of the regenerability and smoothness is satisfied between the power consumption of the secondary side of the lamp and the amount of ozone decomposition, and the ozone water can be easily adjusted to the specified ozone concentration. An inverse number of the residence time in the ozone water is irradiated with ultraviolet rays lamp vessel, i.e. a space velocity (SV), to 100 ~ 5000h ^{- 1} is preferred.

In the present invention, turbulent flow occurs, and if a turbulent flow generating device is provided in the water passage path of the ozone water, the flow of the ozone water can be formed into a turbulent flow. The turbulence generating device to be used is not particularly limited, and examples thereof include a static mixer having no driving portion, a mechanical oscillating ultrasonic wave, a line mixer incorporating a turbine and a vane, and the like. Among these, the static type mixer is easy to maintain and manage, and there is no fear of contaminating ozone water due to foreign matter being mixed therein, so it is suitable for use. The flow of ozone water is formed into a turbulent flow, and energy is transferred to the dissolved ozone water to promote the decomposition of ozone.

In the present invention, stirring, for example, by providing a stirring means through the water passage, the ozone water can be stirred. Examples of the stirring means of the water passage include a stirring blade such as a blade, a disk turbine blade, and a curved blade, or a magnetic stirring type magnetic stirrer or a static mixer. Among these, the static mixer has no fear of polluting ozone water due to dusting, and thus is suitable for use. By stirring the ozone water, energy is transferred to the dissolved ozone water to promote the decomposition of ozone.

In the present invention, the ozone water is heated, and the ozone water can be heated by providing a heat exchanger or the like by the water passage of the ozone water. The heat exchanger provided in the water passage is more suitable for use because it does not contain foreign matter and contaminates the ozone water. By heating the ozone water, the energy is transferred to the dissolved ozone water to promote the decomposition of ozone. The ozone water whose concentration of dissolved ozone is lowered to a predetermined concentration by heating is preferably cooled to a predetermined temperature required at the point of use by a cooler or the like provided in the water passage. As for the warming and cooling of ozone water, a recovery heat exchanger can be used to increase the thermal efficiency.

In the present invention, ozone decomposition can be promoted by adding a base to ozone water. The base to be added to the ozone water is not particularly limited, and examples thereof include ammonia, sodium hydroxide, potassium hydroxide, and calcium hydroxide. Among these, since ammonia is volatilized and no foreign matter remains, it is suitable for use. By adding a base, when the Ph value is increased and the ozone water becomes alkaline, the ozone becomes unstable, thereby promoting the decomposition of ozone.

In the present invention, ozone decomposition can be promoted by adding hydrogen peroxide to ozone water. Hydrogen peroxide forms hydroxyl groups in water, while hydroxyl groups decompose ozone.

In the present invention, the amount of ultraviolet light to be irradiated with ozone water, the amount of irradiation of ultrasonic waves, the intensity of turbulence generated, the stirring strength and time, the rising temperature of the heating, the amount of alkali added, or the amount of hydrogen peroxide added, and decomposition Between the amount of decrease in the dissolved ozone concentration of the ozone water, the reproducibility satisfies a well-defined relationship. Therefore, by adjusting the relationship of the amount in advance, the dissolved ozone concentration of the ozone water can be adjusted to a specified value. .

In the present invention, as the concentration adjustment means of the ozone water in the vicinity of the use point, the ozone water can be diluted. The dilution of the ozone water is preferably carried out using pure water for producing the ozone water and pure water having the same degree of purity. In order to prevent a decrease in concentration due to ozonolysis, it may be diluted with acidic pure water or pure water to which an organic compound, particularly an organic acid, is added. By diluting ozone water to form ozone water having a specified dissolved ozone concentration, ozone dissolved in ozone water delivered to the point of use can be completely utilized without waste.

In the present invention, the ozone water can be transported to the point of use in a gas-liquid mixed state in which ozone water and ozone gas coexist. a gas-liquid mixed state in which ozone water and ozone gas coexist, for example, pressurizing pure water into an ejector, and injecting pure water from a center of a venturi nozzle, and inhaling an ozone-containing gas by a negative pressure generated at the periphery thereof, that is, Can be formed. The ozone in the ozone-containing gas sucked into the ejector is dissolved in pure water to generate ozone, and the remaining ozone-containing gas is formed into a gas-liquid mixed state of ozone water and ozone gas, and is increased while decreasing the flow velocity in the enlarged portion of the flow path. Large pressure is discharged from the ozone water delivery piping. During the transportation by the ozone water transfer pipe, ozone is dissolved in the ozone water in which the ozone gas is mixed with the ozone gas, thereby compensating for the ozone lost by the decomposition, thereby preventing the decrease in the dissolved ozone concentration. The pressure of the gas-liquid mixed fluid of the ozone water and the ozone gas at the outlet of the ejector is preferably a high pressure, particularly preferably 200 kPa or more. The long-distance transport of ozone water can be performed by setting the pressure of the gas-liquid mixed fluid of ozone water and ozone gas to a relatively high gas pressure. In particular, the ozone concentration-suppressing action by the presence of the ozonolysis suppressing substance and the ozone concentration maintaining action by the coexistence state of the ozone water and the ozone gas can be transported while maintaining the high ozone concentration. Therefore, it is better.

According to the method and the device of the present invention, the ozone water and the ozone gas coexist in the gas-liquid mixed state, and are transported to the use point for a long distance, and can be adjusted to a specified concentration just before reaching the use point, so that the ozone water production device can be used. The required concentration of ozone water is freely supplied to a large number of points of use, respectively. In the case of conveying in the gas-liquid mixed state, the residual gas is removed by the gas-liquid separator in front of the use point, and then it is preferable to reduce the ozone concentration by the concentration adjusting means. In the case where the oxygen generated by the decomposition of ozone at the time of concentration adjustment becomes a supersaturated state, a gas-liquid separator can be provided after the concentration adjustment means. That is, the gas-liquid separator may be provided in the front stage, the rear stage, or both the front stage and the rear stage of the ozone concentration adjustment means.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited to the examples.

Further, in the examples and the comparative examples, the ozone generator (Sumitomo Precision Industries Co., Ltd., silent discharge type ozone generator SG-01CHU) 3, ozone dissolving device [Japan Coa] Dykes (Ozone), Ozone Dissolved Membrane Module 4, Carbonic Acid Adding Means 5, Ozone Water Delivery Pipe 6, Branch Pipes for Use Point 7, and Test Equipment with Ozone Concentration Adjustment Device 8. High-purity oxygen and high-purity nitrogen gas are supplied to the ozone generating device by the oxygen container 1 and the nitrogen container 2, respectively. The remaining ozone water is discharged through ozone decomposing tower 9 filled with activated carbon [Kurita Industrial Co., Ltd., Kuli WG WG160] after decomposing ozone. Oxygen gas 1 L (standard state) / min and nitrogen gas 4 L (standard state) / min were supplied to the ozone generator to make the ozone generator current 0.6 A, and an ozone-containing gas having an ozone concentration of 200 g/m ³ (standard state) was produced. The pure water was supplied to the ozone dissolving device 4 at a flow rate of 20 L/min, and the ozone gas was dissolved and supplied to the concentration adjusting means 8 leaving 10 m.

(Example 1)

As the ozone concentration adjusting means, a low-pressure mercury lamp (Chiyoda dealer (share), GL-4, GL-10, and GL-40) having a main wavelength of 253.7 nm and having a dimming function stabilizer 10 as shown in Fig. 2 is used. The water passing unit 11 is tested. The dissolved ozone concentration of the ozone water at the outlet of the water passing unit was measured using a dissolved ozone meter 12.

The ultrapure water is supplied to the test apparatus, and the carbon dioxide gas is added and dissolved in the ultrapure water so that the CO ₂ concentration is 3 mg/L from the carbon dioxide gas cylinder as the carbonic acid gas supply means, and the ozone is dissolved by the ozone dissolving device. Dissolved in carbon dioxide gas to dissolve ultrapure water, and prepared to obtain ozone water having a dissolved ozone concentration of 25.9 mg/L. When the ozone water was passed through the unit without lighting the low-pressure mercury lamp, the dissolved ozone concentration of the ozone water was 25.9 mg/L at both the unit inlet and the unit outlet. Next, when the low-pressure mercury lamp was lighted at an output of 1.5 W, the dissolved ozone concentration at the unit outlet was 20.1 mg/L. When the output of the low-pressure mercury lamp is gradually increased, the relationship between the output and the dissolved ozone concentration at the cell outlet is 18.0 mg/L at 2 W, 13.7 mg/L at 3.5 W, and 11.6 mg/L at 5 W. It was 8.0 mg/L at 10 W and 5.7 mg/L at 15 W.

(Comparative Example 1)

The operation was carried out in the same manner as in Example 1 except that the carbon dioxide gas was not dissolved in the ultrapure water supplied to the test apparatus, and ozone water having a dissolved ozone concentration of 25.9 mg/L was prepared.

When the low-pressure mercury lamp was not turned on and the ozone water was passed through the unit, the dissolved ozone concentration of the ozone water was 8.2 mg/L at both the unit inlet and the unit outlet. Next, when the low-pressure mercury lamp was lighted at an output of 1.5 W, the dissolved ozone concentration at the unit outlet became 5.9 mg/L. When the output of the low-pressure mercury lamp is gradually increased, the relationship between the output and the dissolved ozone concentration at the unit outlet is 5.0 mg/L at 2 W, 4.1 mg/L at 3.5 W, and 2.1 mg/L at 5 W. At 10W, it was 2.6mg/L.

Tables 1 and 3 show the results of Example 1 and Comparative Example 1.

In the first example and the third figure, in the first embodiment, in the ultrapure water, the dissolved ozone concentration of 25.9 mg/L prepared by the ozone dissolving device is dissolved in ozone water. The ozone concentration did not drop and was sent to the point of use. In addition, when the output of the low-pressure mercury lamp of the water-passing unit rises, the ozone decomposes to lower the dissolved ozone concentration, and the relationship between the output and the dissolved ozone concentration becomes a smooth curve. Therefore, by controlling the output of the low-pressure mercury lamp, the desired dissolution can be stably obtained. Ozone water with ozone concentration. On the other hand, in Comparative Example 1 in which carbonic acid as an ozonolysis inhibitor was not present in ultrapure water, the dissolved ozone concentration of ozone water delivered to the point of use was decreased to 8.2 mg/L, and the output of the low pressure mercury lamp was dissolved and dissolved. The concentration relationship has a large deviation.

(Example 2)

As the ozone concentration adjusting means, the test was performed using the heater 13 and the cooler 14 shown in Fig. 4. The dissolved ozone concentration of the ozone water at the outlet of the cooler was measured using a dissolved ozone meter 12.

In the same manner as in Example 1, ozone water having a CO ₂ concentration of 3 mg/L and a dissolved ozone concentration of 25.9 mg/L was prepared. The ozone water was heated to 25 ° C by a heater and discharged while maintaining a temperature of 25 ° C in a cooler. The dissolved ozone concentration of the ozone water at the cooler outlet was 14.1 mg/L. When the heating temperature of the heater is set to 30 ° C, 40 ° C, 50 ° C, and is cooled by a cooler to 25 ° C, the dissolved ozone concentration of the ozone water at the outlet of the cooler is 12.8 mg / L, 10.0 mg / L, 6.4, respectively. Mg/L.

(Comparative Example 2)

The operation was carried out in the same manner as in Example 2 except that the carbon dioxide gas was not dissolved in the ultrapure water supplied to the test apparatus, and ozone water having a dissolved ozone concentration of 25.9 mg/L was prepared.

When the ozone water was heated to 25 ° C by a heater and kept in a state of 25 ° C in a cooler, the dissolved ozone concentration of the ozone water at the outlet of the cooler was 6.0 mg / L. When the heating temperature of the heater is set to 30 ° C, 40 ° C, 50 ° C, and is cooled by a cooler to 25 ° C, the dissolved ozone concentration of the ozone water at the outlet of the cooler is 2.0 mg / L, 0.6 mg / L, 0.6, respectively. Mg/L.

The second table shows the results of Example 2 and Comparative Example 2.

As is clear from the second table, in Example 2 in which carbon dioxide as an ozonolysis suppressing substance is present in ultrapure water, when the heating temperature of the heater rises, the ozone decomposes to lower the dissolved ozone concentration, and the heating temperature and the dissolved ozone concentration are lowered. The relationship becomes a smooth curve, so by controlling the heating temperature of the heater, the ozone water of the desired dissolved ozone concentration can be stably obtained. On the other hand, in Comparative Example 2 in which carbonic acid as an ozonolysis inhibitor was not present in ultrapure water, the ozone concentration of ozone water was rapidly lowered by heating by the heater.

(Example 3)

As a means for adjusting the ozone concentration, a water-passing unit having a low-pressure mercury lamp (Chiyoda dealer (share), GL-4, GL-10, and GL-40) having a main wavelength of 253.7 nm and having a dimming function as shown in Fig. 2 is used. experimenting.

In the same manner as in Example 1, ozone water having a CO ₂ concentration of 3 mg/L and a dissolved ozone concentration of 25.9 mg/L was prepared. At a space velocity (SV) 2000h ^{- 1} pass through the flow cell, so that the output from the low-pressure mercury lamp 1.6W changes to 40W. The relationship between the output of the low-pressure mercury lamp and the dissolved ozone concentration of the ozone water at the outlet of the unit is 20.0 mg/L at 1.6 W, 13.9 mg/L at 3.6 W, and 11.1 mg/L at 5.6 W, at 9.9 W. The ratio was 8.1 mg/L, 7.7 mg/L at 15.0 W, 3.8 mg/L at 20.0 W, 3.4 mg/L at 31.8 W, and 2.7 mg/L at 40.0 W.

Table 3 shows the results of Example 3.

As is clear from the third table, in Example 3 in which carbonic acid as an ozone decomposition inhibitor is present in ultrapure water, ozone is decomposed to lower the dissolved ozone concentration, and the relationship between the output and the dissolved ozone concentration is stable. By controlling the output of the low-pressure mercury lamp, it is possible to stably obtain the ozone water of the desired dissolved ozone concentration. In particular, when the lamp output is 20 W or less, the relationship between the lamp output and the dissolved ozone concentration is stable.

(Example 4)

As a means for adjusting the ozone concentration, a water-passing unit having a low-pressure mercury lamp (Chiyoda dealer (share), GL-4, GL-10, and GL-40) having a main wavelength of 253.7 nm and having a dimming function as shown in Fig. 2 is used. experimenting.

The ultrapure water is supplied to the test apparatus, and the carbon dioxide gas is added and dissolved in the ultrapure water so that the CO ₂ concentration is 3 mg/L from the carbon dioxide gas cylinder as the carbonic acid gas supply means, and the ozone is dissolved by the ozone dissolving device. dissolved carbonic acid gas is dissolved in ultrapure water to prepare a concentration of dissolved ozone to give 36.5mg / L of ozone water, and at a space velocity (SV) 6000h ^{- 1} pass through the flow cell, so that the output from the low-pressure mercury lamp to change 1.5W 17.0 W. The relationship between the output of the low-pressure mercury lamp and the dissolved ozone concentration of the ozone water at the outlet of the unit is 20.0 mg/L at 1.5 W, 13.9 mg/L at 3.6 W, and 10.9 mg/L at 5.5 W, at 9.8 W. The time was 8.3 mg/L, and at 17.0 W, it was 5.0 mg/L.

(Comparative Example 3)

The same operation as in Example 4 was carried out except that the carbon dioxide gas was not added to the ultrapure water supplied to the test apparatus, and ozone water having a dissolved ozone concentration of 36.5 mg/L was prepared. The relationship between the output of the low-pressure mercury lamp and the dissolved ozone concentration of the ozone water at the outlet of the unit is 31.8 mg/L at 1.5 W, 25.7 mg/L at 3.6 W, and 18.8 mg/L at 5.5 W, at 9.8 W. The time was 14.1 mg/L, and at 17.0 W, it was 10.0 mg/L.

Tables 4 and 5 show the results of Example 4 and Comparative Example 3.

Seen from Table 4 and FIG.5, the presence of ozone in ultra pure water serving as an embodiment carbonate decomposition inhibiting substance 4, even if, as the space velocity (SV) 6000h ^{- 1} In general the residence time of water through the unit, when When the output of the low-pressure mercury lamp of the water-passing unit is still rising, the ozone is decomposed to lower the dissolved ozone concentration, and the relationship between the output and the dissolved ozone concentration becomes a stable curve. Therefore, by controlling the output of the low-pressure mercury lamp, the desired dissolved ozone can be stably obtained. Concentration of ozone water. In contrast, in the absence of ultra pure water as in Comparative Example carbonate ozonolysis inhibiting substance 3, when such a space velocity (SV) 6000h ^{- 1} In general the residence time of the water passing means short, dissolved ozone concentration The decrease is small, and the relationship between the output of the low-pressure mercury lamp and the dissolved ozone concentration is large.

(Example 5)

As a means for adjusting the ozone concentration, a test was carried out using a water-passing unit equipped with an ultrasonic oscillator [Preitix Co., Ltd., PT005JIA].

In the same manner as in Example 1, ozone water having a CO ₂ concentration of 3 mg/L and a dissolved ozone concentration of 25.9 mg/L was prepared. The ozone water was passed through the unit, and was irradiated with ozone water by outputting an ultrasonic wave having an oscillation frequency of 39 kHz of 30 W, 40 W, 50 W or 60 W.

The dissolved ozone concentration of the ozone water at the outlet of the water passing unit was 19 mg/L at the output of 30 W, 17 mg/L at the output of 40 W, 15 mg/L at the output of 50 W, and 14 mg/L at the output of 60 W.

(Comparative Example 4)

The operation was carried out in the same manner as in Example 5 except that the carbon dioxide gas was not dissolved in the ultrapure water supplied to the test apparatus, and ozone water having a dissolved ozone concentration of 25.9 mg/L was prepared.

The dissolved ozone concentration of the ozone water at the outlet of the water-passing unit was 5 mg/L at the output of 30 W, 6 mg/L at the output of 40 W, 6 mg/L at the output of 50 W, and 3 mg/L at the output of 60 W.

Table 5 shows the results of Example 5 and Comparative Example 4.

As is clear from the fifth table, in the fifth embodiment in which carbonic acid as an ozone decomposition inhibiting substance is present in the ultrapure water, when the output of the ultrasonic oscillator of the water passing unit rises, the ozone is decomposed to lower the dissolved ozone concentration, and the output is lowered. The relationship with the dissolved ozone concentration becomes a smooth curve, so by controlling the output of the ultrasonic oscillator, it is possible to stably obtain the ozone water of the desired dissolved ozone concentration. On the other hand, in Comparative Example 4 in which no carbonic acid as an ozonolysis inhibitor was present in ultrapure water, there was no relationship between the output of the ultrasonic oscillator and the dissolved ozone concentration, and the decomposition of ozone was large, and the dissolved ozone concentration was The degree of reduction is large.

(Example 6)

As a means for adjusting the ozone concentration, a glass unit in which a rotating fin that was stirred by a magnetic stirrer [Aduwan (stock), HS-3B] was placed was tested.

In the same manner as in Example 1, ozone water having a CO ₂ concentration of 3 mg/L and a dissolved ozone concentration of 25.9 mg/L was prepared. The ozone water was passed through a glass unit and stirred at a number of revolutions of the rotary fins of 100 rpm, 500 rpm, 1000 rpm or 1500 rpm.

The dissolved ozone concentration of the ozone water at the outlet of the glass unit was 19 mg/L, 15 mg/L, 13 mg/L, and 12 mg/L at a rotation number of the rotary fin of 100 rpm, 500 rpm, 1000 rpm, or 1500 rpm, respectively.

(Comparative Example 5)

The same operation as in Example 6 was carried out except that the carbon dioxide gas was not added to the ultrapure water supplied to the test apparatus, and ozone water having a dissolved ozone concentration of 25.9 mg/L was prepared.

The dissolved ozone concentration of the ozone water at the outlet of the glass unit was 5 mg/L, 7 mg/L, 4 mg/L, and 5 mg/L at a rotation number of the rotary fin of 100 rpm, 500 rpm, 1000 rpm, or 1500 rpm, respectively.

Table 6 shows the results of Example 6 and Comparative Example 5.

As is clear from the sixth table, in Example 6 in which carbonic acid as an ozonolysis suppressing substance is present in ultrapure water, when the number of rotations of the rotating fin increases, ozone decomposes to lower the dissolved ozone concentration, and the number of rotations and dissolved ozone The relationship of the concentration becomes a smooth curve, and therefore the ozone water of the desired dissolved ozone concentration can be stably obtained by controlling the intensity of the stirring by the number of rotations of the rotating fins. On the other hand, in Comparative Example 5 in which no carbonic acid as an ozonolysis suppressing substance was present in ultrapure water, there was no relationship between the number of rotations of the rotating fins and the dissolved ozone concentration, and the decomposition of ozone was large, and the dissolved ozone concentration was The degree of reduction is large.

(Example 7)

As a means for adjusting the ozone concentration, hydrogen peroxide was added for the test.

A hydrogen peroxide water injection port was attached to the inlet side of the glass unit of the apparatus similar to that of Example 6, and the rotary vane was rotated and stirred by a magnetic stirrer at a number of revolutions of 100 rpm, and one type of hydrogen peroxide water was injected. The concentration of hydrogen peroxide in the ozone water was 5 mg/L, 7 mg/L, 15 mg/L, 22 mg/L, 32 mg/L, and 50 mg/L.

The dissolved ozone concentration of ozone water at the outlet of the glass unit is 18 mg/L when the hydrogen peroxide concentration in the ozone water is 5 mg/L, 7 mg/L, 15 mg/L, 22 mg/L, 32 mg/L, and 50 mg/L, respectively. , 16mg / L, 8mg / L, 6mg / L, 5mg / L, 4mg / L.

(Comparative Example 6)

The operation was carried out in the same manner as in Example 7 except that the carbon dioxide gas was not dissolved in the ultrapure water supplied to the test apparatus, and ozone water having a dissolved ozone concentration of 25.9 mg/L was prepared.

The dissolved ozone concentration of ozone water at the outlet of the glass unit is 5 mg/L when the concentration of hydrogen peroxide in the ozone water is 5 mg/L, 7 mg/L, 15 mg/L, 22 mg/L, 32 mg/L, and 50 mg/L, respectively. , 14mg / L, 5mg / L, 3mg / L, 4mg / L, 3mg / L.

Table 7 shows the results of Example 7 and Comparative Example 6.

As is clear from the seventh table, in Example 7 in which carbonic acid as an ozonolysis suppressing substance is present in ultrapure water, when the amount of hydrogen peroxide added is increased, the ozone is decomposed to lower the dissolved ozone concentration, and hydrogen peroxide is reduced. The relationship between the amount of addition and the concentration of dissolved ozone becomes a stable curve, and therefore, by controlling the amount of addition of hydrogen peroxide, it is possible to stably obtain ozone water having a desired dissolved ozone concentration. On the other hand, in Comparative Example 6 in which carbonic acid as an ozonolysis inhibitor was not present in ultrapure water, there was no relationship between the amount of hydrogen peroxide added and the dissolved ozone concentration, and the decomposition of ozone was large, and the dissolved ozone concentration was The degree of reduction is large.

(industrial availability)

According to the ozone water supply method and apparatus of the present invention, the ozone water having a high ozone concentration is suppressed from being transported to the use point by the decomposition of ozone, and the concentration is adjusted to a predetermined ozone concentration in the vicinity of the use point, and the ozone water of the specified concentration can be stably stabilized. Supply point of use.

1. . . Oxygen container

2. . . Nitrogen container

3. . . Ozone generator

4. . . Ozone dissolving device

5. . . Ozone decomposition inhibiting substance supply means

6. . . Ozone water delivery piping

7. . . Use point

8. . . Concentration adjustment means

9. . . Ozone decomposition tower

10. . . With dimming function stabilizer

11. . . Water unit

12. . . Dissolved ozone meter

13. . . Heater

14. . . Cooler

Fig. 1 is a system diagram showing the steps of an aspect of the ozone water supply device of the present invention.

Fig. 2 is an explanatory view of a concentration adjusting means provided with a low-pressure mercury lamp.

Figure 3 is a graph showing the relationship between the output of the low pressure mercury lamp and the dissolved ozone concentration.

Fig. 4 is an explanatory view of a concentration adjusting means including a heater and a cooler.

Figure 5 is a graph showing the relationship between the output of the low pressure mercury lamp and the dissolved ozone concentration.

1. . . Oxygen container

2. . . Nitrogen container

3. . . Ozone generator

4. . . Ozone dissolving device

5. . . Ozone decomposition inhibiting substance supply means

6. . . Ozone water delivery piping

7. . . Use point

8. . . Concentration adjustment means

9. . . Ozone decomposition tower

Claims (10)

An ozone water supply method characterized in that ozone water in which an ozonolysis inhibitor is present is transported to a use point, and is reduced to a specified ozone concentration by a concentration adjustment means in the vicinity of a use point, and the concentration adjustment means decomposes dissolved ozone or ozone Dilution of water. The ozone water supply method according to the first aspect of the invention, wherein the ozonolysis inhibitory substance is one or more selected from the group consisting of a water-soluble organic compound, an inorganic acid or a salt thereof and a hydrazine. An ozone water supply method according to claim 2, wherein the inorganic acid or a salt thereof is hydrochloric acid, sulfuric acid, carbonic acid, carbonate, hydrogencarbonate, nitrous acid, nitrite, sulfurous acid, sulfite or hydrogensulfite. salt. An ozone water supply method according to the first aspect of the patent application, which is selected from the group consisting of ultrasonic irradiation, ultraviolet irradiation, turbulent flow generation, stirring, heating, addition of a base, and addition of hydrogen peroxide. Or two or more means for decomposing dissolved ozone. The ozone water supply method according to any one of claims 1 to 4, wherein the ozone water is supplied to the use point in a gas-liquid mixed state in which ozone water and ozone gas coexist. An ozone water supply device characterized by comprising: an ozone dissolving device for dissolving ozone gas in pure water to prepare ozone water; a means for supplying an ozonolysis suppressing substance to pure water or ozone water; and ozone to be prepared by an ozone dissolving device Water is transported to the ozone water transfer piping at the point of use; A concentration adjustment means for reducing ozone water conveyed by the ozone water delivery pipe to a specified ozone concentration, which is a dilution of dissolved ozone or ozone water, is used in the vicinity of the point of use. The ozone water supply device according to the sixth aspect of the invention, wherein the ozonolysis inhibitory substance is one or more selected from the group consisting of a water-soluble organic compound, an inorganic acid or a salt thereof and a hydrazine. An ozone water supply device according to claim 7 wherein the inorganic acid or a salt thereof is hydrochloric acid, sulfuric acid, carbonic acid, carbonate, hydrogencarbonate, nitrous acid, nitrite, sulfurous acid, sulfite or hydrogen sulfite. salt. An ozone water supply device according to claim 6, wherein one selected from the group consisting of ultrasonic irradiation, ultraviolet irradiation, turbulent flow generation, stirring, heating, addition of a base, and addition of hydrogen peroxide or Two or more means are used to decompose dissolved ozone. The ozone water supply device according to any one of claims 6 to 9, wherein the ozone water is supplied to the use point in a gas-liquid mixed state in which ozone water and ozone gas coexist.