JP2019150760A - Ozone-dissolved water manufacturing apparatus and ozone-dissolved water manufacturing method - Google Patents

Abstract

To provide an apparatus and a method for manufacturing ozone-dissolved water capable of manufacturing ozone-dissolved water in which ozone gas is dissolved in a liquid such as ultrapure water with high dissolution efficiency.SOLUTION: The present invention provides an apparatus and a method for manufacturing ozone-dissolved water, including a gas-dissolved membrane module 1 in which a gas-phase chamber 12 and a liquid-phase chamber 13 are partitioned by a gas-dissolved membrane 11, a gas supply line L1 that communicates with the gas-phase chamber 12 and can supply an ozone-containing gas G; a gas discharge line L2 that communicates with the gas-phase chamber 12 and can discharge the treated surplus gas G, a liquid supply line L3 that communicates with the liquid phase chamber 13 and can supply the treated water W, a liquid discharge line L4 that communicates with the liquid phase chamber 13 and can discharge the treated ozone-dissolved water W, a first pressure gauge 2 connected to the liquid discharge line L4, a second pressure gauge 3 connected to the gas discharge line L2, a pressure control mechanism 5 that controls the pressure of the gas in the gas phase chamber 12, and a moisture removal mechanism 4 that removes moisture contained in the surplus gas G.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an apparatus for producing ozone-dissolved water capable of producing ozone-dissolved water having a high ozone concentration and containing no bubbles, and a method for producing ozone-dissolved water using the same.

  In the manufacturing process of electronic components such as semiconductors, liquid crystals, organic EL, etc., cleaning to remove particles and organic substances attached to silicon wafers and glass substrates for flat panel displays, which are the materials for semiconductor substrates, is extremely important. is there. As cleaning methods for silicon wafers, etc., conventionally, a mixed solution of hydrogen peroxide solution and sulfuric acid, a mixed solution of hydrogen peroxide solution, hydrochloric acid and water, a mixed solution of hydrogen peroxide solution, ammonia water and water, etc. A cleaning method using a high-concentration chemical solution based on hydrogen peroxide water, a so-called RCA cleaning method, is common. However, since the RCA cleaning method uses a large amount of chemical solution, a large amount of ultrapure water for rinsing, etc., there are concerns about an increase in cost in the cleaning process and an increase in burden on the environment. Various cleaning methods aimed at reducing costs and reducing the burden on the environment have been invented and have achieved results. A typical cleaning method is a method of cleaning a silicon wafer or the like using gas-dissolved water obtained by dissolving a specific gas such as ozone gas or hydrogen in a liquid such as ultrapure water.

  Among the gas-dissolved water used in the cleaning method as described above, ozone-dissolved water in which ozone gas is dissolved has a high cleaning effect due to its oxidizing power. It is used for the modification of the substrate (hydrophilization of the substrate surface).

  The ozone-dissolved water is usually produced by dissolving high-purity ozone gas in ultrapure water. As a method for dissolving ozone gas in ultrapure water, a method in which ozone gas is directly blown into ultrapure water by bubbling, or a gas dissolution membrane module in which a gas phase chamber and a liquid phase chamber are partitioned by a gas dissolution film A method of dissolving by bringing gas-liquid contact through the pores of the gas dissolution film by supplying ultrapure water to the liquid phase chamber and supplying ozone-containing gas to the liquid phase chamber has been put into practical use. . Among these, the ozone gas dissolving method using the gas dissolving membrane module is suitably used for the production of ozone-dissolved water because the dissolved ozone concentration is relatively stable.

  Here, the oxidizing power of ozone-dissolved water is expressed as the ozone concentration increases. Therefore, in order to produce ozone-dissolved water having a high ozone concentration by a method using a gas-dissolving membrane module, it is necessary to improve the dissolution efficiency of ozone gas. The dissolution efficiency is a value indicating the ratio of the amount of ozone dissolved in the liquid to the amount of ozone contained in the supplied ozone gas.

  One method for improving the dissolution efficiency of ozone gas is to bring the pressure in the gas phase chamber of the gas dissolution membrane module as close as possible to the pressure in the liquid phase chamber. In general, since dissolution of a gas in a liquid follows Henry's law, the higher the gas pressure, the greater the solubility in the liquid. However, on the other hand, if the pressure in the gas phase chamber is increased too much to increase the ozone gas dissolution efficiency and the pressure in the gas phase chamber becomes equal to or higher than the pressure in the liquid phase chamber, the ozone gas in the gas phase chamber becomes pores of the gas dissolution film. The bubbles are generated in the liquid in the liquid phase chamber (hereinafter, also referred to as “bubbling phenomenon”), and the produced ozone-dissolved water contains bubbles. Ozone-dissolved water containing bubbles is not preferable because it may cause poor cleaning in a cleaning device as a use point or damage to a nozzle used for cleaning.

  Therefore, recently, in the apparatus for producing ozone-dissolved water using the gas-dissolving membrane module as described above, in order to control the pressure in the gas phase chamber according to the pressure in the liquid phase chamber, that is, the occurrence of the bubbling phenomenon. In order to prevent this, an attempt has been made to control the flow rate of ozone gas by providing a gas precise control mechanism such as a mass flow controller (hereinafter also referred to as “MFC”) on the surplus gas discharge side of the gas dissolution membrane module. . However, the conventional precision control mechanism for gas such as MFC is generally vulnerable to moisture, and the excess gas discharged from the gas-dissolving membrane module also contains moisture. If the precise control mechanism for gas such as this is used as it is, there is a problem that the flow path is blocked by moisture contained in the surplus gas, and the pressure in the gas phase chamber in the gas dissolution membrane module is precisely controlled. There is a problem that it is difficult.

  The present invention has been made based on the above circumstances, and in manufacturing ozone-dissolved water using a gas-dissolving membrane module, the pressure in the gas phase chamber is precisely controlled according to the pressure in the liquid phase chamber. Accordingly, an object of the present invention is to provide an apparatus for producing ozone-dissolved water capable of producing ozone-dissolved water having a high ozone concentration and no bubbles, and a method for producing ozone-dissolved water using the same.

  In order to solve the above-described problems, first, the present invention includes a gas-dissolved membrane module in which a gas-phase chamber and a liquid-phase chamber are defined by a gas-dissolving membrane; A gas supply line capable of supplying, a gas discharge line communicating with the gas phase chamber and capable of discharging surplus gas after processing, a liquid supply line communicating with the liquid phase chamber and capable of supplying water to be treated; A liquid discharge line communicating with the liquid phase chamber and capable of discharging treated ozone-dissolved water, a first pressure gauge connected to the liquid discharge line and measuring an outlet pressure of the liquid phase chamber, and the gas discharge A second pressure gauge connected to a line and measuring the outlet pressure of the gas phase chamber; and provided on the downstream side of the second pressure gauge of the gas discharge line, the measured value of the first pressure gauge and the second pressure gauge Pressure for controlling the pressure of the gas in the gas phase chamber based on the measured value of the pressure gauge A control mechanism, provided upstream of the pressure control mechanism of the gas discharge line, to provide an apparatus for producing ozone-dissolved water and a moisture removing mechanism for removing moisture contained in the excess gas (Invention 1).

  According to this invention (Invention 1), the pressure control mechanism provided in the gas discharge line controls the pressure in the gas phase chamber based on the measurement value of the first pressure gauge and the measurement value of the second pressure gauge. By controlling according to the pressure, the occurrence of the bubbling phenomenon can be prevented, and the moisture contained in the excess gas flowing into the pressure control mechanism is removed in advance by the moisture removal mechanism provided on the upstream side of the pressure control mechanism. Therefore, it is possible to precisely control the pressure in the gas-phase chamber of the gas-dissolving membrane module by the pressure control mechanism, so that ozone-dissolved water having a high ozone concentration and containing no bubbles can be produced.

  In the said invention (invention 1), it is preferable that the said moisture removal mechanism is provided in the downstream of said 2nd pressure gauge (invention 2).

  According to this invention (Invention 2), the pressure in the gas phase chamber can be accurately measured by the second pressure gauge even if the pressure loss of the water removal mechanism is not small enough to be ignored. The mechanism enables more precise control of the pressure in the gas phase chamber of the gas dissolution membrane module.

  In the said invention (invention 1 and 2), it is preferable that the said moisture removal mechanism has a gas decomposition | disassembly means (invention 3).

In the process in which the gas decomposition means decomposes excess ozone gas into oxygen gas, heat of decomposition is generated according to the following formula (1). And when ambient temperature rises by this decomposition heat, the water | moisture content contained in excess gas turns into water vapor | steam, and it lose | disappears.
2O ₃ → 3O ₂ (1)
Therefore, according to this invention (invention 3), not only the removal of moisture contained in the surplus gas, but also the detoxification of the surplus gas can be performed.

  In the said invention (invention 3), it is preferable that the said gas decomposition | disassembly means is a gas decomposition catalyst (invention 4).

  According to this invention (invention 4), by using a gas decomposition catalyst having high contact efficiency with surplus gas as the gas decomposition means, decomposition of surplus gas into oxygen is promoted, so that moisture contained in the surplus gas Can be efficiently removed.

  Secondly, the present invention is a method for producing ozone-dissolved water using an apparatus for producing ozone-dissolved water comprising a gas-dissolved membrane module in which a gas-phase chamber and a liquid-phase chamber are partitioned by a gas-dissolved membrane, A gas supply step for supplying ozone-containing gas to the gas phase chamber; a liquid supply step for supplying water to be treated to the liquid phase chamber; and the ozone-containing gas is dissolved in the water to be treated through the gas dissolving film. A gas dissolving step, a first pressure measuring step for measuring an outlet pressure of the liquid phase chamber, a second pressure measuring step for measuring an outlet pressure of the gas phase chamber, and an excess gas discharged from the gas phase chamber. A moisture removal step for removing moisture contained therein, and a pressure control step for controlling the pressure of the gas in the gas phase chamber based on the measurement value obtained by the first pressure measurement step and the measurement value obtained by the second pressure measurement step. The pressure after the moisture removal step To provide a production method of the ozone dissolved water that performs control step (Invention 5).

  According to this invention (invention 5), in the pressure control step, the pressure in the gas phase chamber is set according to the pressure in the liquid phase chamber based on the measurement value in the first pressure measurement step and the measurement value in the second pressure measurement step. By controlling, it is possible to prevent the bubbling phenomenon from occurring, and in the moisture removal process performed before the pressure control process, it is possible to remove the moisture contained in the surplus gas in advance, so that the gas dissolution in the pressure control process It is possible to precisely control the pressure in the gas phase chamber of the membrane module, so that ozone-dissolved water having a high ozone concentration and no bubbles can be produced.

  According to the ozone dissolved water manufacturing apparatus and the ozone dissolved water manufacturing method using the same according to the present invention, the measured value of the first pressure gauge and the measured value of the second pressure gauge are measured by the pressure control mechanism provided in the gas discharge line. Based on the above, by controlling the pressure in the gas phase chamber according to the pressure in the liquid phase chamber, the occurrence of the bubbling phenomenon can be prevented, and the pressure control can be performed by the moisture removing mechanism provided upstream of the pressure control mechanism. Since the moisture contained in the surplus gas flowing into the mechanism can be removed in advance, the pressure control mechanism can precisely control the pressure in the gas phase chamber of the gas dissolution membrane module, and the ozone concentration is high, and Ozone-dissolved water that does not contain bubbles can be produced.

It is typical explanatory drawing which shows the manufacturing apparatus of ozone dissolution water by one Embodiment of this invention.

  Hereinafter, an embodiment of an apparatus for producing ozone-dissolved water and a method for producing ozone-dissolved water using the same will be described with reference to the drawings as appropriate. The embodiment described below is for facilitating the understanding of the present invention, and does not limit the present invention.

[Production equipment for ozone-dissolved water]
FIG. 1 is a schematic explanatory diagram showing an apparatus for producing ozone-dissolved water 10 according to an embodiment of the present invention. The ozone-dissolved water production apparatus 10 shown in FIG. 1 includes a gas-dissolved membrane module 1, a first pressure gauge 2, a second pressure gauge 3, a moisture removal mechanism 4, a pressure control mechanism 5, and a gas supply line L1. And a gas discharge line L2, a liquid supply line L3, and a liquid discharge line L4.

In the gas dissolution membrane module 1, a gas phase chamber 12 and a liquid phase chamber 13 are partitioned by a gas dissolution membrane 11. The gas supply line L1 communicates with the gas phase chamber 12 so that the ozone-containing gas G can be supplied. Gas exhaust line L2 is in communication with the gas phase chamber 12 so that it can discharge the excess gas G _R after treatment. The liquid supply line L3 communicates with the liquid phase chamber 13 so that the water to be treated W can be supplied. Liquid discharge line L4 is in communication with the liquid phase chamber 13 so that it can discharge the ozone-dissolved water W _O after treatment. The first pressure gauge 2 measures the outlet pressure of the liquid phase chamber 13, and is connected to the liquid discharge line L4. The second pressure gauge 3 measures the outlet pressure of the gas phase chamber 12, and is connected to the gas discharge line L2. The pressure control mechanism 5 controls the pressure of the gas in the gas phase chamber 12 based on the measurement value of the first pressure gauge 2 and the measurement value of the second pressure gauge 3, and the second pressure control mechanism 5 in the gas discharge line L 2. It is provided on the downstream side of the pressure gauge 3. The moisture removal mechanism 4 is provided on the upstream side of the pressure control mechanism 5 in the gas discharge line L2.

  In the present embodiment, the gas supply line L1 is provided with the gas flow rate adjusting mechanism 6 and the ozonizer 7 in this order from the upstream side toward the downstream side. In the liquid supply line L3, a to-be-treated water flow rate adjusting mechanism 8 and a flow meter 9 are provided in this order from the upstream side toward the downstream side. Hereinafter, the measurement value of the first pressure gauge 2 may be referred to as P1, and the measurement value of the second pressure gauge 3 may be referred to as P2.

(Ozone-containing gas)
The ozone-containing gas G means a mixed gas of ozone gas and oxygen gas. As the ozone-containing gas G, for example, a mixed gas generated by an ozonizer using electrolysis of water or silent discharge in air or oxygen gas can be used, but is not limited thereto. In the present embodiment, the ozone-containing gas G is generated by supplying oxygen gas to the ozonizer 7. The ozone gas concentration of the generated ozone-containing gas G is preferably about 200 g / Nm ³ . Such an ozone-containing gas G often contains 10-20 wt% ozone gas and 80-90 wt% oxygen gas.

(Treated water)
In addition to the water quality suitable for cleaning, the water to be treated W has a pH of neutral or lower and a hydrogen peroxide concentration in order to maintain the ozone gas concentration of the ozone-dissolved water W 2 _O to be produced. Is sufficiently low (preferably 10 ppb or less). For example, ultrapure water or pure water from which impurities are removed to the limit is suitably used. In the present embodiment, ultrapure water is used as the water to be treated W, but the present invention is not limited to this. For example, carbonated water in which carbon dioxide gas is dissolved in ultrapure water may be used.

[Gas dissolved membrane module]
In the gas dissolution membrane module 1, a gas phase chamber 12 and a liquid phase chamber 13 are partitioned by a gas dissolution membrane 11. When the ozone-containing gas G supplied to the gas phase chamber 12 of the gas-dissolved membrane module 1 and the water to be treated W supplied to the liquid-phase chamber 13 come into gas-liquid contact via the gas-dissolved membrane 11, an ozone-containing gas is obtained. G is dissolved in the water to be treated W, ozone-dissolved water W _O is produced. The gas dissolution membrane module 1 undissolved ozone-containing gas not dissolved in G, i.e. excess gas G _R, after being removed moisture by moisture removal mechanism 4, through the gas exhaust line L2, finally external Is discharged.

  As the material of the gas dissolution membrane 11 constituting the gas dissolution membrane module 1, a fluororesin membrane such as polytetrafluoroethylene that is hydrophobic and excellent in ozone resistance can be suitably used. Moreover, there is no restriction | limiting in particular in the shape of the gas dissolution film | membrane 11, For example, hollow fiber membrane shape, spiral winding shape, etc. other than the flat membrane shape as shown in FIG. 1 can be used. In addition, since ozone resistance is requested | required also as a material of the gas dissolution membrane module 1, it is preferable to use fluorine resin materials, such as a polytetrafluoroethylene.

[First pressure gauge]
The first pressure gauge 2 measures the outlet pressure of the liquid phase chamber 13, that is, the water pressure of the ozone-dissolved water W 2 _O. The first pressure gauge 2 is not particularly limited as long as it has ozone resistance and can measure the water pressure of the ozone-dissolved water W 2 _O. For example, a commercially available liquid pressure gauge can be used. . Further, since the pressure control mechanism 5 described later controls the pressure of the gas in the gas phase chamber 12 based on the measured value of the first pressure gauge 2 and the measured value of the second pressure gauge 3, the first pressure gauge 2 As shown in FIG. 1, it is preferable to have first transmission output means T1 for outputting the measurement value as data to the pressure control mechanism 5. Since the first pressure gauge 2 has the first transmission output means T1, even when the outlet pressure of the liquid phase chamber 13 fluctuates due to the use situation at the use point P of the ozone-dissolved water W 2 _O , the pressure Follow-up control can be easily performed by the control mechanism 5.

[Second pressure gauge]
The second pressure gauge 3, the outlet pressure of the gas phase chamber 12, that is, to measure the pressure of the excess gas G _R. The second pressure gauge 3, there is resistance to ozone, if it is possible to measure the pressure of the excess gas G _R, the configuration is not particularly limited, for example, may be a commercially available gas pressure gauge. Further, since the pressure control mechanism 5 described later controls the pressure of the gas in the gas phase chamber 12 based on the measured value of the first pressure gauge 2 and the measured value of the second pressure gauge 3, the second pressure gauge 3 As shown in FIG. 1, it is preferable to have the second transmission output means T2 for outputting the measurement value as data to the pressure control mechanism 5. By the second pressure gauge 3 with the second transmission output unit T2, even if the variation in outlet pressure of the liquid phase chamber 13 due to the operating conditions of the use point P of the ozone dissolved water W _O occurs, the pressure Follow-up control can be easily performed by the control mechanism 5.

[Moisture removal mechanism]
Water removal mechanism 4 is for preliminarily removing moisture contained in the excess gas G _R flowing into the pressure control mechanism 5. The moisture removal mechanism 4, if it is possible to remove the moisture contained in the excess gas G _R, the configuration is not particularly limited, for example, the gas decomposition means and water having a suction removable hygroscopic agent Although it is possible to use not only the removal of the water contained in the excess gas G _R, in that it can also be carried out detoxification of excess gas G _R, having a gas decomposition means of the combustion and catalytic combustion Those are preferred.

In the process in which the combustion type or catalytic combustion type gas decomposition means decomposes excess ozone gas into oxygen gas, heat of decomposition is generated according to the following equation (1). And when ambient temperature rises by this decomposition heat, the water | moisture content contained in excess gas turns into water vapor | steam, and it lose | disappears.
2O ₃ → 3O ₂ (1)

Further, as the gas decomposition means as described above, a catalytic combustion type is particularly preferably used because it is compact and advantageous in running cost. In the present embodiment, the moisture removing mechanism 4 has a gas decomposition catalyst as a gas decomposition means. By contact efficiency with excess gas G _R uses a high gas decomposition catalyst, the decomposition into oxygen gas excess gas G _R is accelerated, by performing the removal of moisture contained in the excess gas G _R efficiently Is possible.

  Next, in consideration of the above-described effects of the moisture removal mechanism 4, the position where the moisture removal mechanism 4 is installed is upstream of the second pressure gauge 3 as long as it is upstream of the pressure control mechanism 5 described later. In order to accurately measure the outlet pressure of the gas phase chamber 12 even when there is a pressure loss in the moisture removing mechanism 4 itself, as shown in FIG. It is preferable to be upstream of the mechanism 5 and downstream of the second pressure gauge 3. Thus, by providing the moisture removal mechanism 4 between the second pressure gauge 3 and the pressure control mechanism 5, even if the pressure loss of the moisture removal mechanism 4 is not small enough to be ignored, the second pressure The total 3 makes it possible to accurately measure the outlet pressure of the gas phase chamber 12.

  In the present embodiment, the second pressure gauge 3 and the water removal mechanism 4 are installed as separate devices. However, a catalyst device or the like that is small enough that the pressure loss of the water removal mechanism 4 can be ignored is used. Then, you may install the 2nd pressure gauge 3 and the water | moisture-content removal mechanism 4 as an integrated apparatus.

[Pressure control mechanism]
Pressure control mechanism 5 on the basis of the measured value of the first pressure gauge 2 and the second pressure gauge 3 measurements, by controlling the flow rate of the excess gas G _R, controls the pressure of the gas in the gas phase chamber 12 To do. Specifically, the pressure control mechanism 5 may control so that the difference between the measured value P1 of the first pressure gauge 2 and the measured value P2 of the second pressure gauge 3 satisfies the following formula (2). It is more preferable that the measured value P2 is controlled to be 0.02 MPa smaller than the measured value P1.
P1> P2 (2)
By accurately controlling the pressure in the gas phase chamber 12 according to the pressure in the liquid phase chamber 13 by the pressure control mechanism 5, the occurrence of a bubbling phenomenon can be prevented.

As long as the pressure control mechanism 5 can control the pressure of the gas in the gas phase chamber 12 based on the measurement value of the first pressure gauge 2 and the measurement value of the second pressure gauge 3, the configuration thereof is not particularly limited. There, the pressure control mechanism 5 in the present embodiment receives a transmission instruction and transmission instruction of the second transmission output unit T2 of the first transmission output unit T1, by controlling the flow rate of the excess gas G _R, the gas phase chamber The pressure of the gas in 12 is controlled. Further, the pressure control mechanism 5 from the oxygen gas after excess gas G _R is decomposed by water removal mechanism 4 provided on the upstream side flows, it is preferably used for the oxygen. As such a pressure control mechanism 5, a motor valve, MFC, etc. can be used conveniently, for example.

In the present embodiment, as described above, own pressure control mechanism 5 that received the transmission instruction of the transmission instruction and a second transmission output unit T2 of the first transmission output unit T1 may control the flow of excess gas G _R Thus, the pressure of the gas in the gas phase chamber 12 is controlled, but the pressure control mechanism 5 receiving the transmission instruction of the first transmission output means T1 and the transmission instruction of the second transmission output means T2 supplies the gas. A transmission instruction is sent to the gas flow rate adjusting mechanism 6 provided in the line L1 or a gas flow rate adjusting mechanism separately provided on the downstream side of the ozonizer 7, and the gas flow rate adjusting mechanism receiving the transmission instruction controls the flow rate of the gas. Thus, the gas pressure in the gas phase chamber 12 may be controlled.

[Gas supply line, gas discharge line]
Gas supply line L1, the ozone-containing gas G is communicated with the gas phase chamber 12 so as to be supplied to the gas phase chamber 12, the gas exhaust line L2, is capable discharging excess gas G _R after treatment Thus, the gas phase chamber 12 is communicated. As the material for the gas supply line L1 and the gas discharge line L2, it is preferable to use a fluororesin material having ozone resistance such as perfluoroalkoxyalkane or polytetrafluoroethylene.

  In the present embodiment, a gas supply port for supplying oxygen gas as a raw material gas is provided on one end side of the gas supply line L1 and upstream of the gas dissolution membrane module 1, and the gas supply line L1 Is connected to the gas phase chamber 12 of the gas dissolving membrane module 1. The gas supply line L1 is provided with a gas flow rate adjusting mechanism 6 and an ozonizer 7 in this order from the upstream side toward the downstream side. In the present embodiment, a gas discharge port for discharging oxygen gas as the final surplus gas is provided on one end side of the gas discharge line L2 and on the downstream side of the gas dissolving membrane module 1, The other end side of the discharge line L2 communicates with the gas phase chamber 12 of the gas dissolution membrane module 1. The gas discharge line L2 is provided with a second pressure gauge 3, a moisture removal mechanism 4, and a pressure control mechanism 5 in this order from the upstream side toward the downstream side.

  The gas flow rate adjusting mechanism 6 adjusts the flow rate of oxygen gas supplied from the gas supply port of the gas supply line L1. The oxygen gas whose flow rate has been adjusted is supplied to the ozonizer 7. The ozonizer 7 generates an ozone-containing gas G that is a mixed gas of ozone gas and oxygen from the supplied oxygen gas. As long as the ozonizer 7 can generate the ozone-containing gas G, there is no particular limitation on the configuration thereof, and for example, a UV irradiation type or a discharge type can be used. Are preferably used. The generated ozone-containing gas G is supplied to the gas phase chamber 12 of the gas dissolution membrane module 1.

[Liquid supply line, liquid discharge line]
Liquid supply line L3 communicates with the liquid chamber 13 so that it can supply the water to be treated W to the liquid phase chamber 13, the liquid discharge line L4 is capable discharging ozone dissolved water W _O after treatment It communicates with the liquid phase chamber 13 as if there is. The material of the liquid supply line L3 is not particularly limited as long as it is a material that is not corroded by the liquid to be contacted. For example, a fluororesin-based piping material such as polyvinylidene fluoride (PVDF) is suitable, but in a low concentration range. If present, vinyl chloride (PVC) or the like can also be used. As the material for the liquid discharge line L4, a fluororesin material having ozone resistance such as perfluoroalkoxyalkane or polytetrafluoroethylene is preferably used.

In the present embodiment, a liquid supply port for supplying water to be treated W such as ultrapure water is provided on one end side of the liquid supply line L3 and upstream of the gas dissolution membrane module 1. The other end side of the supply line L3 communicates with the liquid phase chamber 13 of the gas dissolution membrane module 1. Moreover, the to-be-processed water flow volume adjusting mechanism 8 and the flowmeter 9 are provided in this order from the upstream to the downstream in the liquid supply line L3. In the present embodiment, a one end of the liquid discharge line L4 on the downstream side of the gas dissolving membrane module 1 is the liquid discharge port is provided for supplying ozone-dissolved water W _O produced in use point P The other end side of the liquid discharge line L4 communicates with the liquid phase chamber 13 of the gas dissolution membrane module 1. Further, the first pressure gauge 2 is provided in the liquid discharge line L4.

  The to-be-processed water flow rate adjusting mechanism 8 adjusts the flow rate of the to-be-processed water W supplied from the liquid supply port of the liquid supply line L3. The water W to be treated whose flow rate is adjusted is measured by the flow meter 9 and then supplied to the liquid phase chamber 13 of the gas dissolution membrane module 1.

[Production method of ozone-dissolved water]
Next, a method for producing ozone-dissolved water using the ozone-dissolved water producing apparatus 10 of the present embodiment as described above will be described in detail with reference to FIG.

The ozone-dissolved water production method using the ozone-dissolved water production apparatus 10 includes a gas supply step of supplying the ozone-containing gas G to the gas phase chamber 12 of the gas-dissolved membrane module 1, and a liquid-phase chamber 13 of the gas-dissolved membrane module 1. A liquid supply step for supplying the water to be treated W, an ozone gas dissolving step for dissolving the ozone-containing gas G in the water to be treated W via the gas dissolving membrane 11 in the gas dissolving membrane module 1, and a liquid phase chamber of the gas dissolving membrane module 1 13 outlet pressure, i.e. the first pressure measurement step of measuring the pressure of the ozone-dissolved water W _O, the outlet pressure of the gas phase chamber 12 of the gas dissolving membrane module 1, i.e. the second pressure measurement for measuring the pressure of excess gas G _R step, the water removal step of removing the moisture contained in the excess gas G _R which is discharged from the gas-phase chamber 12, the gas phase on the basis of the measurements by the measurement value and the second pressure measurement process according to the first pressure measuring step Mainly comprising a pressure control step of controlling the pressure of the gas in the 12. The pressure control process is performed after the moisture removal process.

[Gas supply process]
In the gas supply process, the ozone-containing gas G is supplied to the gas phase chamber 12 of the gas dissolution membrane module 1. In the present embodiment, a gas flow rate adjusting step for adjusting the flow rate of oxygen gas supplied from the gas supply port of the gas supply line L1 by the gas flow rate adjusting mechanism 6 and a gas flow rate adjusting step before the gas supplying step. The ozone-containing gas generation step of supplying the oxygen gas whose flow rate has been adjusted to the ozonizer 7 to generate the ozone-containing gas G is performed in this order. By providing the gas flow rate adjusting step, the pressure of the oxygen gas supplied to the gas supply line L1 can be adjusted, so that the ozone-containing gas generating step in the ozonizer 7 can be performed with a suitable pressure. .

[Liquid supply process]
In the liquid supply step, the water to be treated W is supplied to the liquid phase chamber 13 of the gas dissolution membrane module 1. In the present embodiment, the to-be-treated water flow rate adjusting step of adjusting the flow rate of the to-be-treated water W supplied from the liquid supply port of the liquid supply line L3 by the to-be-treated water flow rate adjusting mechanism 8 before the liquid supplying step. And the to-be-processed water flow rate measurement process which measures the flow volume of the to-be-processed water W by which the flow volume was adjusted by the to-be-processed water flow rate adjustment process with the flowmeter 9 is performed in this order. Since the pressure of the to-be-processed water W supplied to the liquid supply line L3 can be adjusted by providing the to-be-processed water flow rate adjustment process, the gas dissolution process in the gas dissolution membrane module 1 is performed with a suitable pressure. It becomes possible.

[Ozone gas dissolution process]
In the ozone gas dissolving step, the ozone-containing gas G supplied to the gas phase chamber 12 of the gas dissolving membrane module 1 and the treated water W supplied to the liquid phase chamber 13 are in gas-liquid contact via the gas dissolving membrane 11. Thus, the ozone-containing gas G is dissolved in the water to be treated W, and the ozone-dissolved water W 2 _O is produced. In the present embodiment, the gas dissolution membrane 11 is a flat membrane as shown in FIG. 1, but is not limited to this, for example, a hollow fiber membrane or spiral winding Can be used.

[First pressure measurement process]
In the first pressure measurement step, the outlet pressure of the liquid phase chamber 13 of the gas dissolution membrane module 1 is measured by the first pressure gauge 2. In the pressure control process described later, the pressure of the gas in the gas phase chamber 12 is controlled by the pressure control mechanism 5 based on the measurement value obtained by the first pressure measurement process and the measurement value obtained by the second pressure measurement process. The first pressure measurement step preferably includes a first transmission output step for outputting the obtained measurement value as data to the pressure control mechanism 5. By the first pressure measuring step has a first transmission output step, even if the variation in outlet pressure of the liquid phase chamber 13 due to the operating conditions of the use point P of the ozone dissolved water W _O occurs, pressure control Follow-up control can be easily performed in the process.

[Second pressure measurement process]
In the second pressure measurement step, the outlet pressure of the gas phase chamber 12 of the gas dissolution membrane module 1 is measured by the second pressure gauge 3. In the pressure control process described later, the pressure of the gas in the gas phase chamber 12 is controlled by the pressure control mechanism 5 based on the measurement value obtained by the first pressure measurement process and the measurement value obtained by the second pressure measurement process. The second pressure measurement step preferably includes a second transmission output step of outputting the obtained measurement value as data to the pressure control mechanism 5. By the second pressure measuring step has a second transmission output step, even if the variation in outlet pressure of the liquid phase chamber 13 due to the operating conditions of the use point P of the ozone dissolved water W _O occurs, pressure control Follow-up control can be easily performed in the process.

[Moisture removal process]
In the water removal step, the water contained in the excess gas G _R after the second pressure measuring step is removed by the moisture removal mechanism 4. Water removal step, the moisture removing mechanism 4, if it is possible to remove the moisture contained in the excess gas G _R, although its structure is not particularly limited, only the removal of moisture contained in the excess gas G _R is rather, in that it can also be carried out detoxification of excess gas G _R, it is preferably performed by water removing mechanism 4 having a gas decomposition means of the combustion and catalytic combustion.

In the process in which the combustion type or catalytic combustion type gas decomposition means decomposes excess ozone gas into oxygen gas, heat of decomposition is generated according to the following equation (1). And when ambient temperature rises by this decomposition heat, the water | moisture content contained in excess gas turns into water vapor | steam, and it lose | disappears.
2O ₃ → 3O ₂ (1)

Further, as the above-described gas decomposition means used in the water removal step, a catalytic combustion type is particularly preferably used because it is compact and advantageous in running cost. In this embodiment, the water removal mechanism 4 used in the water removal step has a gas decomposition catalyst as a gas decomposition means. By contact efficiency with excess gas G _R uses a high gas decomposition catalyst, the decomposition into oxygen gas excess gas G _R is accelerated, by performing the removal of moisture contained in the excess gas G _R efficiently Is possible.

  In this embodiment, the water removal step is performed after the second pressure measurement step. However, when the pressure loss of the water removal mechanism 4 is small enough to be ignored, the water removal mechanism 4 is set to the second pressure. By providing on the upstream side of the total 3, the moisture removal step may be performed after the second pressure measurement step, or by providing the second pressure gauge 3 and the moisture removal mechanism 4 as an integrated device. You may perform a pressure measurement process and a water | moisture-content removal process simultaneously.

[Pressure control process]
The pressure control process is performed after the moisture removal process. In the pressure control process, based on the measurement value of the first pressure gauge 2 obtained in the first pressure measurement process and the measurement value of the second pressure gauge 3 obtained in the second pressure measurement process, the pressure control mechanism 5 The pressure of the gas in the gas phase chamber 12 is controlled. Pressure control step In the present embodiment, by a pressure control mechanism 5 that received the transmission instruction by the transmission instruction and the second pressure measurement process according to the first pressure measurement step is, for controlling the flow rate of excess gas G _R, the gas phase chamber The pressure of the gas in 12 is controlled.

Note that the pressure control step in the present embodiment, as described above, the pressure control mechanism 5 that received the transmission instruction by the transmission instruction and the second pressure measurement process according to the first pressure measurement step, the flow rate of the excess gas G _R By controlling, the pressure of the gas in the gas phase chamber 12 is controlled. The pressure control mechanism 5 that receives the transmission instruction by the first pressure measurement process and the transmission instruction by the second pressure measurement process is supplied with the gas. A transmission instruction is sent to the gas flow rate adjusting mechanism 6 provided in the line L1 or a gas flow rate adjusting mechanism separately provided on the downstream side of the ozonizer 7, and the gas flow rate adjusting mechanism that receives this transmission instruction controls the gas flow rate. Alternatively, the gas pressure in the gas phase chamber 12 may be controlled.

  As described above, according to the ozone dissolved water manufacturing apparatus and the ozone dissolved water manufacturing method using the same according to the present invention, the measured value of the first pressure gauge and the second value are measured by the pressure control mechanism provided in the gas discharge line. By controlling the pressure in the gas phase chamber according to the pressure in the liquid phase chamber based on the measured value of the pressure gauge, it is possible to prevent the bubbling phenomenon from occurring and to remove moisture provided upstream of the pressure control mechanism. Since the mechanism allows the moisture contained in the excess gas flowing into the pressure control mechanism to be decomposed and removed in advance, the pressure control mechanism can precisely control the pressure in the gas phase chamber of the gas dissolution membrane module. Ozone-dissolved water having a high ozone concentration and no bubbles can be produced.

  The present invention has been described above with reference to the drawings. However, the present invention is not limited to the above-described embodiment, and various modifications can be made. For example, in FIG. 1, the flow direction of the gas flowing through the gas phase chamber 12 of the gas dissolution membrane module 1 and the flow direction of the liquid flowing through the liquid phase chamber 13 of the gas dissolution membrane module 1 are the same direction. The gas flow direction and the liquid flow direction may be opposite.

  EXAMPLES Hereinafter, although this invention is further explained in full detail based on an Example, this invention is not limited to a following example.

[Example 1]
The ozone-dissolved water was manufactured using the ozone-dissolved water manufacturing apparatus 10 shown in FIG. The conditions are as follows.
Gas-dissolved membrane: GNH-01R (manufactured by Japan Gore-Tex)
Ozonizer: GR-RB (manufactured by Sumitomo Precision Industries)
Moisture removal mechanism: Ozone decomposition catalyst KMS-200 (manufactured by Wako System Control)
Pressure control mechanism: MFC MC-3000L (manufactured by Lintec)

As treated water to be supplied, pure water having a water temperature of 25 ° C. was used. The pure water was supplied to the liquid phase chamber of the gas dissolution membrane module after adjusting the supply flow rate to 20 L / min. As a gas to be supplied, oxygen gas was used as a source gas. The oxygen gas was adjusted so that the supply flow rate to the ozonizer was 4 L / min, and then supplied to the ozonizer. A mixed gas of ozone and oxygen was generated by an ozonizer, and this ozone-containing gas was supplied to the gas phase chamber of the gas dissolution membrane module. The ozone gas concentration of the ozone-containing gas was 200 g / Nm ³ .

〔Example〕
When the pressure control mechanism controls the flow rate of excess gas so that the outlet pressure of the gas phase chamber is 0.02 MPa lower than the outlet pressure of the liquid phase chamber, and when the outlet pressure of the liquid phase chamber changes The difference was tracked and controlled.

[Comparative Example]
The outlet pressure of the liquid phase chamber, that is, the water pressure of the ozone-dissolved water varies depending on the use state at the use point of the ozone-dissolved water, for example, the use state in the cleaning apparatus. In this embodiment, when the use timings of a plurality of cleaning devices connected to the use point overlap, the water pressure of the ozone-dissolved water may drop instantaneously or within a certain time from 0.2 MPa to 0.15 MPa or less. there were. Therefore, in the comparative example, safety measures were taken so that the outlet pressure of the gas phase chamber, that is, the pressure of the surplus gas was controlled to be about 0.12 MPa.

〔result〕
In the examples, no bubbling phenomenon occurred in the liquid phase chamber of the gas-dissolving membrane module, and ozone-dissolved water containing no bubbles of about 30 ppm could be stably produced. On the other hand, in the comparative example, the dissolved ozone concentration is lower by about 1 to 2 ppm on average than in the examples, and the ozone dissolved water increases in the cleaning device connected to the use point. When the water pressure of the dissolved water is lowered, bubbles may be generated in the ozone-dissolved water very momentarily. As described above, in the comparative example, the water pressure of the ozone-dissolved water was irregularly decreased from 0.12 MPa. Therefore, it was necessary to further reduce the pressure of the surplus gas from 0.12 MPa.

  As described above, according to the ozone dissolved water manufacturing apparatus of the present invention and the ozone dissolved water manufacturing method using the same, the pressure control mechanism provided in the gas discharge line allows the first pressure gauge measurement value and the first By controlling the pressure in the gas phase chamber in accordance with the pressure in the liquid phase chamber based on the measured value of the two pressure gauges, it is possible to prevent the bubbling phenomenon from occurring and to provide moisture provided upstream of the pressure control mechanism. Since the moisture contained in the excess gas flowing into the pressure control mechanism can be removed in advance by the removal mechanism, the pressure in the gas phase chamber of the gas dissolution membrane module can be precisely controlled by the pressure control mechanism. Ozone-dissolved water having a high ozone concentration and no bubbles can be produced.

  The present invention is for cleaning to remove particles or organic substances adhering to a silicon wafer or a glass substrate for a flat panel display as a material of a semiconductor substrate in a manufacturing process of an electronic component such as a semiconductor, a liquid crystal, and an organic EL. This is useful as an ozone-dissolved water production apparatus and a method for producing ozone-dissolved water using the same.

DESCRIPTION OF SYMBOLS 10 Ozone dissolved water production apparatus 1 Gas dissolution membrane module 11 Gas dissolution membrane 12 Gas phase chamber 13 Liquid phase chamber 2 First pressure gauge 3 Second pressure gauge 4 Moisture removal mechanism 5 Pressure control mechanism 6 Gas flow rate adjustment mechanism 7 Ozonizer 8 treated water flow adjustment mechanism 9 flowmeter L1 gas supply line L2 gas discharge line L3 liquid supply line L4 liquid discharge line T1 first transmission output unit T2 second transmission output unit P POU G ozone-containing gas _{G R} excess gas W to be Treated water W _O ozone dissolved water

Claims (5)

A gas dissolution membrane module in which a gas phase chamber and a liquid phase chamber are partitioned by a gas dissolution membrane;
A gas supply line communicating with the gas phase chamber and capable of supplying an ozone-containing gas;
A gas discharge line communicating with the gas phase chamber and capable of discharging surplus gas after treatment;
A liquid supply line communicating with the liquid phase chamber and capable of supplying water to be treated;
A liquid discharge line communicating with the liquid phase chamber and capable of discharging the treated ozone-dissolved water;
A first pressure gauge connected to the liquid discharge line and measuring an outlet pressure of the liquid phase chamber;
A second pressure gauge connected to the gas discharge line and measuring an outlet pressure of the gas phase chamber;
Pressure control that is provided downstream of the second pressure gauge in the gas discharge line and controls the pressure of the gas in the gas phase chamber based on the measured value of the first pressure gauge and the measured value of the second pressure gauge Mechanism,
An apparatus for producing ozone-dissolved water, comprising a water removal mechanism that is provided on the upstream side of the pressure control mechanism of the gas discharge line and removes water contained in the surplus gas.   The apparatus for producing ozone-dissolved water according to claim 1, wherein the moisture removing mechanism is provided downstream of the second pressure gauge.   The apparatus for producing ozone-dissolved water according to claim 1 or 2, wherein the moisture removing mechanism has gas decomposition means.   The apparatus for producing ozone-dissolved water according to claim 3, wherein the gas decomposition means is a gas decomposition catalyst. A method for producing ozone-dissolved water using an apparatus for producing ozone-dissolved water comprising a gas-dissolved membrane module in which a gas-phase chamber and a liquid-phase chamber are partitioned by a gas-dissolved membrane,
A gas supply step of supplying an ozone-containing gas to the gas phase chamber;
A liquid supply step of supplying water to be treated to the liquid phase chamber;
A gas dissolving step for dissolving the ozone-containing gas in the water to be treated through the gas dissolving film;
A first pressure measuring step for measuring an outlet pressure of the liquid phase chamber;
A second pressure measuring step for measuring an outlet pressure of the gas phase chamber;
A moisture removal step of removing moisture contained in surplus gas discharged from the gas phase chamber;
A pressure control step of controlling the pressure of the gas in the gas phase chamber based on the measurement value by the first pressure measurement step and the measurement value by the second pressure measurement step;
A method for producing ozone-dissolved water, wherein the pressure control step is performed after the moisture removal step.

Images