WO2005096359A1

WO2005096359A1 - Method of ozone water supply and ozone water supply apparatus

Info

Publication number: WO2005096359A1
Application number: PCT/JP2005/005632
Authority: WO
Inventors: Takeo Fukui; Junichi Ida; Hiroshi Morita
Original assignee: Kurita Water Industries Ltd.
Priority date: 2004-03-31
Filing date: 2005-03-18
Publication date: 2005-10-13
Also published as: TWI380954B; CN1938829A; TW200533608A; JP2005294377A; JP4513122B2

Abstract

A method of ozone water supply, characterized in that ozone water wherein an ozonolysis inhibiting substance is present is transferred to use point (7) and that the ozone concentration is lowered to a given level by concentration regulation means in the vicinity of the use point. Further, there is provided an ozone water supply apparatus characterized by including ozone dissolution unit (4) for dissolving ozone gas in pure water to thereby prepare ozone water; means for feeding an ozonolysis inhibiting substance into the pure water or ozone water; ozone water transfer piping (6) for transferring the ozone water prepared by the ozone dissolution unit to a use point; and disposed in the vicinity of the use point, concentration regulation means (8) for lowering the ozone concentration of ozone water having been transferred through the ozone water transfer piping to a given level. In the use of this apparatus, the ozone water of given ozone concentration can be stably supplied to the use point so as to be available in, for example, the wet cleaning and surface treatment steps for electronic materials, such as semiconductors and liquid crystals.

Description

Description ozone water supply;

Sickle field

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 solution capable of stably supplying ozone water having a predetermined ozone concentration to a use point in an etching process, a surface treatment process, or the like of an electronic material such as a body or a liquid crystal. Water supply and ozone water supply. Background scythe

It is very important to remove objects and conditions from the surface of electronic neo-materials such as silicon substrates for semiconductors, glass for liquid crystal, and photomasks for securing product quality and yield. Ozone water with ozone dissolved in fek exhibits extremely strong and oxidizing power even though the amount of fertilizer is a few mg / L, and impurities such as organic substances and metals attached to the electronic material surface The process has been shifted to the process of removing contamination due to oxidization and the process of uniformly oxidizing the surface of silicon II to form an oxidized surface. Since the concentration of the supplied ozone water affects the m-plane »power and the control of acidity, it is very important to control the concentration.

There is a problem that ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^^^^^^^^^^^^ 自己が。i 自己 In to all. Even if the ozone water is sent for a long time, the ozone water drops little during the transfer and can supply the ozone water at a certain concentration to the point of use. An ozone water dissolving device that dissolves ozone to generate ozone water, and an ozone water supply device that transports the generated ozone water. There has been proposed an ozone water supply device provided with an admission means for dissolving a gas or an arrested compound (Patent Document 1). The same effect can be achieved by using an ozone dissolving device that dissolves ozone in the water to be dissolved, a water supply pipe that supplies the water to be dissolved to the dissolving device, and a fast-acting device. In the water supply device having a delivery pipe for delivering water, a water supply pipe is provided at an arbitrary position from the yarn ^ K pipe to the delivery pipe, asatsu, asia M ^, carbonic acid, charcoal, 赚, One or more ozone components selected from the group consisting of sulfurous acid, sulfurous acid, and hydrazine: an ozone-dissolved water supply device provided with a supply device that excites the inhibitor (Patent Document 2).

In addition, when supplying ozone water to a shelf location, the concentration of ozone water in which ozone is dissolved in ii ^ is used as the concentration of ozone water that can easily provide the required concentration of ozone water. ^ Kffi length, calorie temperature, ultrasonic wave, ultraviolet light or turbulence promotes ozone decomposition, and the ozone water concentration adjustment method to haze ozone water concentration is $ ^ Patent Document 3) As a control of ozone that can easily supply ozone-containing water having a desired ozone concentration to a point of use, ozone-containing water is woven with glass, and the ozone-containing water having a desired concentration is mixed with ozone-containing water. The fS & ^ method of the degree of oscillosis has been tested (Patent Document 4).

However, with the conventional ozone water supply method and the ozone water supply weaving apparatus, it is difficult to supply a stable concentration of ozone water, and it is also very difficult to control the ozone concentration to a predetermined level at the point of use. was there.

[Memorial Document 1] Japanese Patent Application Laid-Open No. 2000-370695 (page 2)

Reference 2] Column 2 0 0 2-1 8 4 5 4 Publication (page 2)

[Patent Document 3] Japanese Patent Application Laid-Open No. 2000-1808043 (pages 2-3)

[Patent Document 4] Japanese Patent Application Laid-Open No. 2000-330334 (page 2)

The present invention provides an ozone water supply system that can stably supply ozone water having a predetermined ozone concentration to a use point in an ejection process and a surface treatment process of an electronic material such as a liquid crystal and a liquid crystal. The purpose is to remove and supply ozone water. Disclosure of the invention

The inventors of the present invention have made intensive efforts to solve the above, and as a result, transferred highly concentrated ozone water in which an ozone suppressing substance was present to a use point, and returned to the use point by a concentration adjusting means. The present inventors have found that by reducing the ozone concentration to a predetermined value, it is possible to stably supply ozone water of a predetermined ozone level to a youth bottle, and based on this finding, completed the present invention.

That is, the present invention

(1) Ozone water supplied with ozone-suppressed substances is transported to youth bottles, placed near the youth bottles, and ii. ,

(2) Ozone The anti-drought substance is derived from a water-soluble arizide compound, maleic acid or its: ^ ¾ ぴ hydrazine The ozone water supply method according to (1), wherein the ozone water supply method is one or more kinds selected from the group consisting of: o) Fiber ^ X is a salt of carbon dioxide, charcoal, carbon salt, nitrite,

, ¾ «, Oranj 叙 is ozone water supply according to (2),

(4) The ozone water supply according to (1), wherein the concentration means is a yuzozon;

(5) The amount of dissolved ozone is selected from the group consisting of ultrasonic irradiation, ultraviolet irradiation, tongue generation, «≥, warming, alkali addition, and peroxygen b ^ element addition. (4) Ozone water supply method of 5¾,

(6) The ozone water supply method according to (1), wherein the concentrated β¾ means is ozone water ^

(7) The transfer of the water to the point of use is carried out in a gas-liquid mixture of ozone water and ozone gas. (1) to (6)

(8) Ozone dissolving device for dissolving ozone gas in yarn fcR to prepare ozone water, means for supplying an ozone dissolution inhibiting substance to ttft¾¾7_k or tiff self-ozone water, ozone water prepared using a self-contained zon dissolution device Ozone water transfer pipe for sending the ozone water to the point of use, and a concentration concession means for reducing the ozone water transferred by the ozone 7pipe suitable pipe to a predetermined ozone concentration. Ozone water supply device,

(9) The ozone water supply system according to (8), wherein the ozone-suppressing substance is selected from the group consisting of water-soluble soluble thiol, oxalic acid and ぴ hydrazine, and 1 ¾X is two or more.

do) ^ «x is a salt of, sulfuric acid, carbonic acid, charcoal«, charcoal ^^ salt, zinc, mm salt, β-acid, is a sulfurous acid ^ / salt (9) ^ Place,

(11) The ozone water supply apparatus according to (8), wherein the concentration haze means is free ozone.

(12) Dissolved ozone is selected from the group consisting of ultrasonic irradiation, ultraviolet irradiation, tongue generation, m heating, heating, and peroxidation. Ozone water supply weaving device according to (11),

(13) Ozone water supply arrangement according to (8), wherein the concentration adjusting means is ozone water, and (14) transfer of the ozone water to the point of use is performed by gas-liquid mixing of ozone water and ozone gas. Ozone water supply according to any one of (8) to (13)

It is what you do. Brief Description of Drawings

FIG. 1 is a process flow diagram of one embodiment of the ozone water supply apparatus of the present invention, and FIG. 2 is low | ¾K silver. Fig. 3 is a graph showing the relationship between ififfik silver lamp output and ozone concentration, Fig. 4 is a diagram showing concentration means with a lifetime and cool-off time. FIG. 5 is a graph showing the relationship between the silver lamp output and the fertilizer yield. In the figure, reference numeral 1 denotes an oxygen gas container, 2 denotes a nitrogen gas container, 3 denotes a leaching generator, 4 denotes a leaching device, 5 denotes an ozone-reducing substance and a co-joining means, and 6 denotes ozone water transfer. Self-management, 7 is use point, 8 is means, 9 is ozone angle angle? t water, 10 is ballast with dimming function, 11 is 7k cell, 12 is dissolved ozone meter, 13 is dissolved ozone meter Kahen, 14 represents. BEST MODE FOR CARRYING OUT THE INVENTION

In the ozone water supply method of the present invention, the ozone water covered with the ozone-suppressing substance is transferred to a use point through a use point, and is lowered to a predetermined ozone concentration by a concentration adjusting means near the use point. The ozone water supply device of the present invention is an ozone dissolving device for preparing ozone water by dissolving ozone gas in IfeK, a means for supplying an ozone-suppressing substance to tfif self-fek or unfavorable ozone water. The ozone water transfer pipe for transferring the ozone water prepared by the self-disciplined zoning apparatus to the use point, and the ozone water transfer pipe installed in the vicinity of the use point, and the ozone water transferred by the three ozone water transfer pipes are used for the specified ozone. It has a density adjusting means for reducing the temperature.

FIG. 1 is a process diagram of one fiber of the ozone water supply / separation device of the present invention. Oxygen gas 1 and nitrogen gas container 2 The ozone generator 3 with no power is supplied with a mixed gas of gas and a small amount of nitrogen gas to produce ozone-containing gas. In 4, the ozone water is produced preferably by dissolving ozone in the previously degassed fibrils. The device shown in this figure is a means for supplying an ozone decomposition inhibiting substance to the pure water or flit self-ozone water 5, an ozone water transfer device for transferring ozone water produced by an ozone dissolution device to a use point, a self-management pipe 6, a use device. There is provided a concentration haze means 8 provided near the point 7 for reducing the ozone water transferred by the ozone feed pipe to a predetermined ozone concentration. In the device of the present fiber, ozone water not used at the point of use is converted into ozone ^ 9 filled with active acid and the like, and is recovered as ozone-free water.

In the present invention, the ozone water is allowed to contain an ozone-suppressing substance, so that the ozone water can be removed without drastically reducing the agrochemical level of the ozone water Mt produced by the ozone M digester. Since it can be transferred to the use point, even if the concentration is reduced by the concentration adjusting means near the use point, it is still required at the use point. The concentration can be i¾. According to the present invention, ffck is added with an ozone-suppressing substance, and then is allowed to generate an ozone-water containing ozone-suppressing substance. Ozonated water containing ozone-suppressing substances can be produced by exciting willow materials. It is preferable that the free agriculture of the aquatic water having the inhibitory substance be present is 1 to L 0 mg / L higher than the predetermined ozone in the youth bottle.

In the present invention, the presence of ozone decomposition inhibiting agent of the ozone water, it forces S preferably _{0. 1~ 5 0 0 m g /} / L, more preferably 1~4 0 Om gZL, 1 0 More preferably, it is 〜300 mg / L. If the amount of the ozone-suppressing substance is less than 0.1 lm gZL, the ozone-suppressing effect is fully exhibited.¾-f, ozone in the ozone water may be advanced during transfer to the point of use. There is. If the amount of the ozone-suppressing substance exceeds 50 O mg / L, the ozone-suppressing substance may have an adverse effect on the substance as an impurity. The details of the ozone-suppressing substance が, which suppresses the premature ozone generation, are not obvious. However, the ozone-suppressing substance reacts with hydroxyl radical, which promotes the ^^- It is presumed to stop the ozone ^ 军 run.

In the present invention, the ozone decomposition inhibitor is preferably at least two kinds of 1SX selected from the group consisting of zk-soluble anionic compounds, inorganic acids or salts thereof, and hydrazine. Examples of the water-soluble aridani used in the present invention include alcohols such as methanol, ethanol, propanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and methyl isopropyl / leketone, and ethylene. Glycols such as glycol and propylene glycol, alcohols such as monoethanolamine and diethanolamine, fatty acids such as acetic acid and propionic acid, benzyl alcohol, phenol, hydroquinone, benzoic acid, isophthalic acid, etc. Aromatic rudder compounds and the like can be mentioned. Of these, alcohols such as isopyl pill alcohol can be suitably used because they do not have a possibility of adversely affecting the coating upon jfe ^ such as silicon-a-chamber glass anticoagulation. . 7 Solubility (The conjugate works as a scavenger to withdraw the hydroxyl radical that promotes ozone ^^, suppresses ozone self-depletion, and can prevent a sharp decrease in agricultural yield.

Examples of the salt used in the present invention as X include, for example, hydrochloric acid, sulfuric acid, carbonic acid, carbonic acid, hydrogencarbonate, nitrous acid, sulfuric acid, β », ffi« 7, hydrofluoric acid and the like. Can do. Among them, carbonic acid can be suitably used because it can be volatilized as carbon dioxide gas after using ozone water. Inorganic te: ha salt can be added to fck or ozone water as an intense night of water, and can be pumped in gaseous form such as carbon dioxide gas, sub-gas, etc.

HC 0 ₃ - be cowpea to Rohm Anion交麵fat forms can be added. The amount of hydroxyl radical that promotes ozone ^^ is reduced by suppressing the pH to 2 to 6 by exciting the acid, and the ozone self ^^ is suppressed. Can be prevented. Also, anions such as carbonate ions and nitrite ions that form salts have a function of reducing hydroxyl radicals, thereby preventing a sharp decrease in the concentration of dilute zon.

In the present invention, examples of the Ozofuji Jtfi adjusting means include a ^^^ of ozone water, ozone water, and the like. There is no particular limitation on the means of ozone: ^ 军, for example, ultrasonic irradiation, ultraviolet irradiation, tongue generation, 辦, warming, alkali addition, exothermic toK element outlet, etc. it can. The concentration of the ozone water obtained by the concentration adjusting means is preferably 5 mg / L or more. If the concentration of free ozone is less than 5 mg / L, the effect of ozone water and surface treatment may be insufficient at the point of use.

In the present invention, the irradiation of the ultrasonic wave to the ozone water can be performed by, for example, irradiating the ultrasonic wave to the ozone water with ultrasonic waves. By irradiating the ozone water with ultrasonic waves, ultrasonic cavitation is generated in the ozone, and hydroxyl radicals are generated. The frequency of the ultrasonic waves to be illuminated is preferably 10 kHz to 3 MHz. It is preferable to use the filter in combination with a filter because there is a possibility that fine particles may be generated in the ultrasonic wave | 5. By selecting the ultrasonic amplitude, frequency, output, etc., it is possible to achieve a predetermined ozone concentration.

In the present invention, the ultraviolet irradiation of the water can be performed by, for example, providing an ultraviolet irradiation device at the ifek of the ozone water and irradiating the ozone water with the ultraviolet light. There is no particular limitation on the type of lamp, for example, ίδΕτΚ silver lamp, medium ffi_K silver lamp, high ffik silver lamp, xenon lamp, elemental lamp, metal / ride lamp, etc. The wavelength of the ultraviolet light to be illuminated can be changed, and among them, a high-mercury lamp with a high ultraviolet irradiation efficiency having a main wavelength of 253.7 nm can be used for S7k «ultraviolet irradiation. In the piping of the section, a cell made of an ultraviolet! ^! Material such as quartz glass, transparent polytetrafluoroethylene etc. The line can be effectively illuminated tf ". Ultraviolet illumination can be controlled by blurring the lamp output, and some lasers can be controlled by blocking the lamp surface. UV irradiation generates hydroxyl radicals and promotes ozone self-radiation UV irradiation can be used favorably because it is easy to handle as a concentration adjusting means and does not cause ozone water contamination.

In the present invention, the output of the ultraviolet lamp can be adjusted by adjusting the lamp primary side mm value, primary side separation value, secondary side ΔE value, secondary side temporary value, and the like. When using a ZR silver lamp as a lamp for irradiating ultraviolet rays, the power consumption on the secondary side of the lamp is preferably 0.5 to 15 W. When the secondary consumption of the ffi mercury lamp is in the range of 0.5 to 15 w, the reproducible gradual force between the secondary consumption of the lamp and the amount of ozone ^^ The zoning water can be easily reduced to the specified azo level. When a high-pressure mercury lamp is used as a lamp for irradiating ultraviolet rays, it is preferable that the secondary consumption of the lamp is 5 to 1,500 W. When the power consumption on the secondary side of the high-pressure mercury lamp is in the range of 5 to 1,500 W, the relationship between the secondary consumption of the lamp and the ozone ^^ It can be easily made to ozone water at a given ozone it degree. The reciprocal of the residence time of the ozone water in the lamp irradiating ultraviolet rays, that is, the space velocity (SV) is preferably 100 to 5,000 h- ¹ .

In the present invention, turbulence can be generated, for example, by providing a turbulent flow generating device in ifek ^ of ozone water and oxidizing ozone water. There are no particular restrictions on the location of the turbulent flow generator 4 on the shelf, and examples thereof include, for example, a static mixer without an image portion, an ultrasonic device that emits fine fibers, and a pipeline mixer that incorporates a turbine and a stator. be able to. Among these, the static mixer is easy to control, and there is no risk of contaminating ozone water due to foreign matter, so that it can be used appropriately. By tongue the flow of water

The energy of the dissolved ozone is changed to St, and the drought of ozone is increased.

In the present invention, for example, ozone water can be drained by providing a ^^ step on a crane. Examples of the means for passing water fibers include stirring blades such as paddle blades, discta single bin blades, curved blades, and the like, a magnetic stirrer, and a stationary machine. Among these, the static mixer can be used for females because there is no risk of polluting the ozone water by dust generation. By using ozone water, energy is dissipated in the dissolved ozone, and the ozone is promoted. In the present invention, the ozone water can be heated by, for example, providing heat exchange to the ozone water ¾k ^^. The heat exchange woman provided in the above can use the foreign matter force and contaminate the ozone water, so that it can be suitably used. Heating the ozone water gives energy to the dissolved ozone, which promotes o ozone water whose free ozone has been reduced to a predetermined concentration by heating. It is important to cool the product to the specified temperature required for youth points by using a heater. Heating and cooling of the ozone water can use the recovered heat to increase the leakage rate. According to the present invention, the ozone can be promoted by adding the calorie to the fresh water. There is no particular limitation on the alkali to be pumped into the ozone water, and examples thereof include ammonia, zk sodium oxide, lithium hydroxide, and calcium hydroxide. Among them, ammonia can be suitably used because it does not volatilize to leave foreign substances. When the pH rises and the ozone water becomes individual, the ozone power becomes unstable, and the speed increases.

In this effort, by adding oxyperoxide to ozone water, it is possible to increase the age of the child. Peroxygen generates hydroxyl radicals in water, and hydroxyl radicals decompose ozone.

In the present invention, the irradiation amount of the ultraviolet ray to the ozone water, the irradiation amount of the ultrasonic wave, the intensity of the generated tongue, the intensity of the tongue, the intensity and the time, the upper skirt by the temperature of the caro, Since a clear quantitative relationship is established with good alertness between the amount of guidance and the decrease in the amount of free ozone W ozone due to ^^, it is necessary to determine the quantitative relationship in advance. The ozone concentration of ozone water can be set to a predetermined value. ,

In the present invention, ozone water can be used as a means for concentrating ozone water near the use point. Ozone water may be used for the production of ozone water, or may have the same qualities as ffek. In order to prevent the concentration of ozone from dropping due to the drought, you can also work with acid [· raw ffok, or fifek, which has organic acid, especially organic acid. By using the ozone water to form ozone water having a predetermined ozone concentration, ozone dissolved in the ozone water transferred to the use point can be completely and completely removed without waste.

In the present invention, the transfer of the ozone water to the use point can be performed in a gas-liquid mixed state in which ozone_k and ozone gas coexist. Ozone water and ozone gas »gas-liquid mixed state For example, the shape can be changed by injecting k into the ejector, blowing out the injected feK to the center of the bench lily nozzle, and sucking and ozone-containing gas by E generated around the nozzle. The ozone contained in the ozone-containing gas absorbed into the ejector dissolves to form ozone water, and the ozone-containing gas [!] Becomes a gas-liquid mixture of ozone water and natural gas, «Expansion The pressure increases as the flow velocity decreases in the section, and is discharged to the ozone tube X. The ozone water in a gas-liquid mixed state with ozone gas contains ozone while it is transferred through the ozone water supply line. The ozone water and ozone gas at the outlet of the ejector can be used to compensate for the ozone lost by ^^ and ozone loss. ^ The power S is preferably higher than ^, and the pressure is more preferably 200 kPa or more.The pressure of the gas-liquid mixed fluid of ozone water and ozone gas is increased by more than In particular, the effect of suppressing the rapid decrease in ozone concentration due to the ozone-suppressing substances and the use of ozone water and ozone gas to maintain the ozone concentration. According to the preferred embodiment of the present invention, the ozone water and the ozone gas are sent to the use point in a gas-liquid mixed state to the use point immediately before the use point. Since it is possible to mist to a predetermined concentration by using the ozone water device, it is possible to freely supply the ozone water having a required concentration to each of many use points from one ozone water device. Age of transfer in a mixed state, youth boin It is preferable to reduce the ozone concentration by the concentration adjusting means in the next step, excluding the excess gas in the immediately preceding air and nighttime β. The gas-liquid separator can be provided after the concentration haze means, that is, the gas-liquid separator can be provided before, after, or both before and after the ozone concentration adjusting means.

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

In the examples and comparative examples, Fig. 1 shows the process diagram of the ozone generator [Sumitomo Seimitsu Kogyo Co., Ltd., silent ^ Ozone generator SG-01 CHU] 3, ozone Solver [Janongo-Tex Co., Ltd., Ozo ^! ^ A pilot with 8 means The plant was used. For the ozone generation, high oxygen gas and high nitrogen gas were supplied from the oxygen gas container 1 and the nitrogen gas container 2, respectively. ^ J's Sai Zong water was decomposed after passing water through an ozone decomposition tower 9 filled with live [Kurita Kogyo Co., Ltd., Clicor WG 160]. To the ozone generator, supply 1 L of oxygen gas (standard condition) Zmin and 4 mL of nitrogen gas (standard condition J / min, and set the ozone generator current to 0.6 A, and the ozone yield 200 g / m An ozone-containing gas of ³ (standard state) was produced.7_R was supplied at 20 L / min to the ozone dissolving apparatus 4, and the ozone gas was dissolved and supplied to a concentration adjusting means 8 of 10 m2.

Example 1

As a means for adjusting ozone concentration, an S≡¾k silver lamp with a dominant stabilizer 10 with a dominant wavelength of 253.7 nm as shown in Fig. 2 [Chiyoda Sales Co., Ltd., GL-4, GL-10 and GL The test was carried out using a water flow cell 11 equipped with The dissolved ozone concentration of the ozone water at the outlet of the flow cell was measured using an ozone meter 12.

Supplying fireman's standard ifek pie port Ttopuranto, from carbon dioxide gas cylinder as carbon dioxide勵Ro means, so that the C0 ₂ concentration 3 mg / L, and添Ro dissolved carbon dioxide in the super-fek, carbonate O zone Yokai device Ozone was dissolved in gas-dissolved ultrapure water to prepare ozone water with a ^ ozone concentration of 25.9 mg / L. When this water was applied to the cell without firing the {gffi * silver lamp, the ozone concentration of ozone water was 25.9 mgZL at both the cell inlet and cell outlet. Next, when the ffizk silver lamp was turned on with an output of 1.5 W, the zo ^ I degree at the cell outlet was 20. lmg / L. When the output of the ffi mercury lamp is increased sequentially, the relationship between the output and the dissolved azo fertility at the cell outlet is 18.0 mg ZL at 2 W, 13.7 mg / L at 3.5 WO, 11.6 mg ZL at 5 W, 11.6 mg ZL, 1 OW At that time, it was 8. Omg / L and at 15W it was 5.7 mgZL.

Comparative Example 1

The same operation as in Example 1 was performed, except that ozone water having a synthetic ozone concentration of 25.9 mg / L was prepared without dissolving carbon dioxide in the ¾¾zK supplied to the pit mouth plant.

When ozone water was applied to the cell without turning on the ίδΕτΚ silver lamp, the dissolved ozone concentration of the ozone water was 8.2 mg / L at both the cell inlet and cell outlet. Next, the silver lamp was turned on with an output of 1.5 W, and the cell outlet had a zonal temperature of 5.9 mg / L. ί © ¾Κ The output of the silver lamp? When ifc ± rises, the relationship between the output and the yield at the senore outlet is 5. Omg / L at 2 W, 4. lmg / L at 3.5 W, 2.1 mg L at 5 W At 1 OW, it was 2.6 mg gZL.

• The results of Male Example 1 and Comparative Example 1 are shown in Table 1 and FIG.

Table 1

As can be seen in Table 1 and Fi.g.3, in Example 1 in which carbonic acid was present as an ozone- ^ ¹ control substance in super fcK, the ozone concentration prepared by the ozone dissolving apparatus was 25. 9 mg ZL of ozone water poison concentration S is transferred to youth point without lowering. In addition, when the output of the silver lamp of the water passage cell is increased, ozone is drastically reduced. The ozone concentration power S decreases, and the relationship between the output and the free ozone concentration becomes a gentle curve, so ί © ϊτΚ By controlling the output of the silver lamp, it can be seen that the desired water can be obtained in a stable manner. On the other hand, in Comparative Example 1, where ^ fcK is not carbonized as ozone ^^ = a control substance, the free water of ozone water transferred to the use point> t is up to 8.2 mg / L. There is a great deal of variation in the relationship between the output of the iS k silver lamp and the azo crop. Row 2 As an ozone t ^ i means, a test was performed using the mouth 13 shown in FIG. The Yu O zo ^? Concentration of ozone water cold Sahima outlet of in the same manner as in Example 1 was measured using a O zone 2, Ji 0 ₂ concentration 31118 _/ /, ozone concentration 25, 9 mg / L O A zonal water was prepared. This ozone water was heated to 25 ° C with calo, and it was allowed to flow out at 25 ° C for | 去 | The ozone concentration of ozone water at the outlet of the cooler was 14. lmgZL. Heating with a heater at 30 ° C, 40 ° C, and 50 ° C, and when cooling to 25 ° C in the cool-off period, the free fertilizer at the outlet of the cooler is 12.8 mg /: L each. 10. Omg / L and 6.4 mg / L.

Comparative Example 2

The same operation as in Difficult Example 2 was performed, except that ozone water having a concentration of 25.9 mg ZL was prepared without dissolving carbon dioxide gas into the ^ fok supplied to the pilot plant.

When ozone water is heated to 25 ° C with calo and discharged at 25 ° C for ί ^ separation,!? The concentration of ozone was 6.0 mgZL. When the caloric heat due to caro is 30 ° C, 40 ° C, and 50 ° C, and the air is cooled to 25 ° C during the cool-off period, the free ozone concentration of the ozone water at the outlet is 2.Omg / L and 0.6mgZL, respectively. Table 2 shows the results of m 2, which was 0.6 mg / L, and Comparative Example 2.

As can be seen in Table 2, a male example of carbonation of super hot fck as ozone willow substance W

In (2), when the calorie heat due to the power is increased, ozone is released and the ozone is reduced, and the M system of the power P heat release and the 農ォ f f is a smooth curve. By controlling the calorie due to the rise in calories, it is possible to stably obtain ozone water of a desired degree. In contrast, in Comparative Example 2, the carbon dioxide as the ozone-suppressing substance was not allowed to be applied to ¾K, and the ozone-water concentration power S sharply decreased by heating with caro β.

Row 3

As a means of adjusting ozone concentration, it has a dimmer chamber with a dominant wavelength of 253.7 nm as shown in Fig. 2. © ¾k silver lamp [Chiyoda Corporation, GL-4, GL-10 and GL-40] The test was performed using an ifek cell with! /.

Prepare ozone water with a concentration of C ォ_{2 of} 3 mg / L and a free ozone concentration of 25.9 mg / L in the same manner as in Male Example 1, and let the water flow through the cell with a space (SV) of 2,000 h- ^1. The output of the silver lamp was changed from 1.6 W to 40 W. ί © Ϊ7_Κ The output of the silver lamp and the ozone water at the outlet of the cell ^ # years old; The relationship between the agricultural degree is 20. Omg / L at 1.6W, 13.9mgZL at 3.6W, 11. lmg at 5.6W It was 8.1 mg / L at / L, 9.9W, 7.7mgZL at 15.0W, 3.8mgZL at 20.OW, 3.4mg / L at 31.8W, and 2.7mgZL at 40.0W.

Table 3 shows the results of Example 3.

As shown in Table 3, ¾ * fek is carbonated as an ozone-suppressing substance

In Fig. 3, when the output of the teffiTk silver lamp in the ¾k cell is increased, ozone is reduced and the ozone concentration is reduced, and the relationship between the output and the free fertility is a smooth curve. By controlling the output of the silver lamp, it is possible to stably obtain ozone water of a desired level. In particular, the lamp output and the age of less than 20 W are stable in the lamp output and the concentration of free ozone.

"table

Difficult case 4

As an ozone concentration adjusting means, an iS¾K silver lamp with a dimming function at the main wavelength of 253.7 nm as shown in Fig. 2 [Chiyoda Sales, GL-4, GL-10 and GL-40] With

Using the k-cell, we made fiber.

In Bruno I port Ttopuranto supplying super operator J, the carbon dioxide gas cylinder as carbon dioxide添口means, so that the C0 ₂ concentration 3mg Bruno L, and勸Ro dissolved carbon dioxide in the super L¾j, O zo Yokai device Dissolve ozone in water to prepare ozone water with an ozone concentration of 36.5 mg / L, and pass water through the water flow cell at a space velocity (SV) of 6,000 h— ^1. £ mercury lamp output It was changed from 1.5W to 17.OW. © The relationship between the output of the silver lamp and the dissolving capacity of ozone water at the cell outlet is 20. Omg / L at 1.5W, 13.9mg / L at 3.6W, 10.9mg / L at 5.5W, 9.8 togi 8.3mg / L, 17.0 "W, 5.0mgZL.

Comparative Example 3

Carbon dioxide is supplied to ultra ffek supplied to the pilot plant- The same operation as in Example 4 was performed, except that the prepared ozone water having the ozone concentration of 36.5 mg ZL was prepared. f © ± The relationship between the output of the mercury lamp and the ozone water ozone concentration at the cell outlet is 31.8 mg / L at 1.5 W, 25.7 mg / L at 3.6 W, 18.8 mg / L at 5.5 W, 9.8 W At that time, it was 14. lmgZL, and at OW, it was 10. OmgZL.

The results of Example 4 and Comparative Example 3 are shown in Table 4 and FIG.

Table 4

As can be seen in Table 4 and Fig. 5, «j contains ozone 炭酸 and carbonic acid as a suppressor ^ ¾ In Example 4, the space velocity (SV) is 6,000 h- ^1. Residence time in water cell Even if it is short, when the output of the iz © ΕτΚ silver lamp of the iizk cell is increased, ozone is ^^ and the ozone concentration is reduced, and the relationship between output and free ozone is a smooth curve, so iS¾k silver By controlling the output of the lamp, it is possible to stably obtain ozone water having a desired level of water. In contrast, in Comparative Example 3 Ultra ffeR not cause a carbonate as ozone ^军抑system material, residence time in the water flow cell as a space velocity (SV) 6, 0001T ¹ and the short Rere, Yuo zone The degree of decline in the agricultural level is small and the relationship between the output of the teffiTk silver lamp and the ozone concentration is large.

Row 5

The test was performed using a cell equipped with an ultrasonic generator β [セル 005 JIA] manufactured by Pretec Co., Ltd. as a means of ozone concentration haze.

1 in the same manner as was C 0 ₂ concentration 3 mg / L, the O zone down water ozone concentration 25. 9 mg / L was prepared. This ozone water was made into a cell, and ultrasonic waves with a frequency of 39 kHz were oscillated at an output of 30 W, 40 W, and 50 W: ¾60 W, and illuminated with the ozone water.

オゾン The ozone concentration at the cell outlet was 19mg / L at 30W output, 17mgZL at 4OW, 15mgZL at 5OW, and 14mgZL at 6OW. Comparative Example 4

Without dissolving carbon dioxide gas into the ¾7 supplied to the Neulot plant, without? The same operation as in Example 5 was performed except that ozone water having a concentration of 25.9 mg / L was prepared.

The ozone concentration of ozone water at the outlet of the flow cell was 5 mg / L at an output of 3 OW, 40 W (6 mgZL at 5 OW, 6 mgZL at 5 OW, and 3 mg / L at 6 OW).

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

Table 5

As shown in Table 5, an example of carbon dioxide as an ozone willow substance in the vein In Fig. 5, when the output of the ultrasonic oblique device in the ¾k cell is increased, the ozone intensity is reduced and the fertilizer power is decreased, and the relationship between the output and the free zig becomes a gentle curve. Therefore, by controlling the output of ultrasonic dew, it is possible to stably obtain ozone water of the desired ozone level.

. On the other hand, in the specific tree sequence 4 that does not cause carbon dioxide as a suppressive ozone ^^ inhibitory substance, there is no fixed ^^ between the output of ultrasonic wave β and? The decrease in free ozone concentration was significant.

Bell column 6

As a means of farming, fiber was turned on using a glass cell with a turntable for magnetic stirrer [Az-One Co., Ltd., HS-3B].

In the same manner as flame Example 1 was C 0 ₂ concentration 3 mg ZL, the O zone down water Yu ozone concentration 25. 9m g / L was prepared. The ozone water was applied to a glass cell, and was applied at 100 rpm, 500 rpm, 1,000 rpm or 1,500 rpm each time.

The dissolved ozone concentration of the ozone water at the glass cell outlet is determined by the rotation of the rotor! ¾Female 100 rpm, 500 rpm, l, 000 rpm, 1,500 rpm, 19 mgZL, 15 mg / L, respectively , 13 mg ZL and 1 Smg / L.

Comparative Example 5

The same operation as in Example 6 was carried out, except that ozone water having a free ozone concentration of 25.9 mg / L was prepared without dissolving carbon dioxide in the ¾ifek supplied to the neurot plant.

Ozone water at the outlet of the glass cell At 100 rpm, 500 rpm, l, 000 rpm, and 1,500 rpm, the rotation was 5 mgZL, 7 mg / L, 4 mgZL, and 5 mg / L, respectively.

Table 6 shows the results of Example 6 and comparative tree sequence 5.

Table 6

Maleozone concentration (mg / L)

Round car (rpm)

Example 6 Comparative Example 5

100 19 5

500 15 7

1000 13 4

1500 12 5 As can be seen in Table 6, in Difficult Example 6, where carbon dioxide was applied as an ozone-suppressing substance to super ¾7, when the number of rotations was increased, ozone was released and the ozone concentration decreased, and the rotation speed was reduced. Since the relationship between と and 游ゾ農農農農農農度度 f 農農度ととだらなだらなだら曲線、、、、、、 Obtainable. On the other hand, in Comparative Example 4 in which carbon dioxide as an ozone-suppressing substance was not added to the super-R, there was no fixed relationship between the repetition time and the ozone concentration, and the ozone concentration was low. The large decrease in the amount of poly-dissolved ozone is large.

麵 row

As a means of ozone concentration, a test was conducted with peroxyperoxide.

Attach a peroxygen solution ¾λ port to the inlet side of the glass cell of the same device as m6, and turn the rotor with a magnetic stirrer! It rotated at ¾ woman 100 rpm and », 1 weight ^_0/0 by injecting peracid ffek oxygen water, a hydrogen peroxide concentration of the ozone water 5m gZL, 7mgZL, 15mgZL, 22mgZL , and 32mgZ, 5 Omg / L And

The ozone concentration of ozone water at the glass cell outlet is 18 mgZ when the hydrogen peroxide concentration in the ozone water is 5 mg / L, 7 mg / L, 15 mg / L, 22 mg / L _s 32 mg / L, and 50 mgZL. Re: 16mg / L, 8mg / L, 6mg / L, 5mg / L, 4mgZL.

Comparative Example 6

The same operation as in Example 7 was performed except that ozone water with an ozone concentration of 25.9 mg / L was prepared without introducing carbon dioxide into the pilot plant [7] without injecting carbon dioxide.

Dissolved ozone concentration of ozone water glass cell outlet, can the Kasani匕水iodine concentration of ozone in water 5m g / L 7mg / L, 15mg / L, 22mg / L, 32mg / / L, and was SOMG / L The results were 5 mg / L, 4 mgZL, 5 mgZL, 3 mg / L, 4 mgZL, and 3 mgZ, respectively.

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

As can be seen in Table 7, a male example of carbonation of オゾン k with ozone ^ 卬

In Figure 7, when the amount of peroxygen to be stimulated is increased, ozone is released and the concentration of free ozone is reduced, and the relationship between the amount of added peroxygen and the free ozone concentration is rather poor. Since the curve becomes a curve, it is possible to stably obtain ozone water having a desired degree of agriculture by controlling the amount of added silicon peroxide. On the other hand, in Comparative Example 6 in which ¾ feK did not emit carbonic acid as an ozone-suppressing substance, there was no fixed relationship between the amount of hydrogen peroxide added and the ^^ ozone concentration. , And the @g of the decline in Yuzo W farming is large.

Bell column 8

The test was performed using isopropyl alcohol (hereinafter referred to as IPA) as an ozone-suppressing substance.

出力 The output of the ffiffiTk silver lamp was changed in the same manner as in Wei Example 1, except that the IPA concentration was increased to 50 μg / L in place of the carbon dioxide gas in column 1, except that the IPA was melted. I did fiber.

As a result, the Yuzo f agriculture at the cell outlet was as shown in Table 8. Table 8

From these results, it can be seen that even when IPA is used as the ozone-suppressing substance, the ozone fertility can be adjusted according to the lamp (ultraviolet) output. Industrial applicability

ADVANTAGE OF THE INVENTION According to the ozone water supply method and apparatus of this invention, decomposition | decomposition of ozone is suppressed, ozone agriculture is high, ozone water is transported to a use point, and the ozone agriculture is arranged near a use point. Ozone water of a predetermined concentration can be stably supplied to the use point by lowering the ozone concentration to a predetermined value by using means.

Claims

Shi — the scope of the request

1. The ozone water containing the ozone-suppressed substance is transferred to the use point, and is brought close to the use point to reduce the concentration to a predetermined level by a fiber means. The water zone is gone.

2. The ozone supply method according to claim 1, wherein the ozone-suppressing substance is selected from the group consisting of a water-soluble conjugate, and hydrazine.

3. The salt solution according to claim 2, wherein the salt is hydrochloric acid, «, carbonic acid, charcoal ^^, charcoal ^ K salt, nitrous acid, nitrous acid, sulfuric acid, sulfurous acid, is a salt. ; ^ Leave.

4. The method for supplying ozone water according to claim 1, wherein the concentration means is a decomposition of genzo.

5. The 率 ozone ratio is determined by ultrasonic irradiation, ultraviolet irradiation, tongue generation, m-calo temperature, alkali addition Π and peroxy acid! The ozone water supply described in claim 4.

6. Supply of ozone water according to claim 1, wherein the concentration adjusting means is a rare ozone water;

7. The supply of ozone water according to any one of claims 1 to 6, wherein the transfer of the ozone water to the use point is performed in a gas-liquid mixture of the ozone water and the ozone gas.

8. An ozone dissolving device that dissolves ozone gas in pure water to prepare ozone water, tiit¾feK or a means for supplying an ozone decomposition inhibitor to the above-mentioned genius zonal water, Ozone water transfer evacuation pipe for transferring to the point of use, provided near the point of use, and a means for concentrating and regulating the ozone water transferred by the ozone 7 transmission pipe to a predetermined ozone concentration. Ozone water supply to be laid ^ ^

9. The ozone water supply apparatus according to claim 8, wherein the ozone-suppressing substance is a water-soluble arid compound, and X is selected from the group consisting of hydrazine.

10 0. The salt is «,, carbonic acid, charcoal ^^, charcoal salt, nitrous acid, nitrous acid, nitrous acid, nitrous acid,

1 1. The ozone water supply according to claim 8, wherein the concentrated JP adjusting means is ^^ of ozone.

1 2. Ultrasonic irradiation and ultraviolet irradiation of ozone ^ 军! The ozone water according to claim 11, wherein 1 @ X selected from the group consisting of 射 ^ radiation, turbulent flow generation, m-caloric temperature, alkali Service

13. The ozone water supply device according to claim 8, wherein the concentration means is ozone water dilution.

1 4. The transfer of ozone water to the point of use is performed in a gas-liquid mixture of ozone water and ozone gas.