WO2020203122A1 - Dissolved-gas concentration measurement apparatus and measurement method - Google Patents

Dissolved-gas concentration measurement apparatus and measurement method Download PDF

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Publication number
WO2020203122A1
WO2020203122A1 PCT/JP2020/010546 JP2020010546W WO2020203122A1 WO 2020203122 A1 WO2020203122 A1 WO 2020203122A1 JP 2020010546 W JP2020010546 W JP 2020010546W WO 2020203122 A1 WO2020203122 A1 WO 2020203122A1
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gas
phase chamber
liquid
dissolved
permeable membrane
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PCT/JP2020/010546
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French (fr)
Japanese (ja)
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森田　博志
忠行 岡村
博美 木村
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栗田工業株式会社
クリタ分析センター株式会社
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Publication of WO2020203122A1 publication Critical patent/WO2020203122A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N7/00—Analysing materials by measuring the pressure or volume of a gas or vapour
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N7/00—Analysing materials by measuring the pressure or volume of a gas or vapour
    • G01N7/14—Analysing materials by measuring the pressure or volume of a gas or vapour by allowing the material to emit a gas or vapour, e.g. water vapour, and measuring a pressure or volume difference

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  • the present invention relates to a liquid flow type dissolved gas concentration measuring device and a measuring method capable of measuring the concentration of gas dissolved in a liquid easily and accurately.
  • Ultrasonic cleaning is widely applied in the precision cleaning process of electronic parts.
  • the concentration of dissolved gas in the cleaning water used affects the cleaning effect. That is, it is desirable that the concentration of the dissolved gas in the cleaning water used for ultrasonic cleaning is near the saturation concentration in terms of both a high cleaning effect and suppression of damage to the object to be cleaned. Therefore, it is necessary to measure the dissolved gas concentrations of the washing water and the rinsing water used for ultrasonic cleaning and control them to desired concentrations.
  • a gas permeable membrane is provided in a closed container, one side is divided into a liquid phase chamber and the other side is divided into a gas phase chamber, and a pressure gauge for measuring the degree of vacuum in the chamber is provided in the gas phase chamber.
  • a gas permeable membrane module provided with the above is described.
  • the dissolved gas concentration of the test solution is measured by flowing the test solution through the liquid phase chamber and measuring the degree of vacuum of the gas phase in equilibrium with the liquid phase.
  • FIG. 3 is a system diagram showing the dissolved gas concentration measuring device of Patent Document 1.
  • the main pipe 10 through which the test liquid to be measured for the dissolved gas concentration flows has a flow rate adjusting valve 10V.
  • the inside of the closed container 2 of the gas permeable membrane module 1 is divided into a liquid phase chamber 4 and a gas phase chamber 5 by the gas permeable membrane 3.
  • the liquid phase chamber 4 includes a water sampling pipe 11 that separates a part of the test liquid from the main pipe 10 as sample water and introduces it into the liquid phase chamber 4, and a discharge pipe 12 that discharges water from the liquid phase chamber 4. Are concatenated. Opening / closing valves 11V and 12V are provided in these pipes 11 and 12, respectively.
  • the gas phase chamber 5 is provided with a gas pressure gauge 6 for measuring the gas pressure in the gas phase chamber 5 via a gas pipe 13 having an on-off valve 13V.
  • the gas in the gas phase chamber 5 When completely degassed water is passed through the gas phase chamber 4 of this dissolved gas concentration measuring device, the gas in the gas phase chamber 5 is sucked into the degassed water through the gas permeation film 3 in the closed container 2, and the gas phase.
  • the pressure in the chamber 5 approaches the vacuum pressure (gauge pressure -101.3 kPa).
  • the pressure in the gas phase chamber 5 stabilizes at atmospheric pressure (gauge pressure ⁇ 0 kPa).
  • a gas phase pressure of -101.3 kPa corresponds to 0% saturation of the test solution.
  • the gas phase pressure of 0 kPa corresponds to 100% saturation.
  • the saturation of the dissolved gas in the test solution can be obtained by proportional calculation from the measured value of the gas phase pressure. By multiplying the determined saturation (%) by the saturation concentration of the dissolved gas in the test solution under atmospheric pressure, the dissolved gas concentration of the test solution can be obtained.
  • the measuring device of Patent Document 1 has a simple and inexpensive configuration. It is possible to accurately measure the dissolved gas concentration of many types of gas.
  • the present invention solves the above-mentioned problems of the prior art, divides the inside of the closed container into a liquid phase chamber and a gas phase chamber by a gas permeable film, flows a test solution into the liquid phase chamber, and measures the pressure in the gas phase chamber. Therefore, in the device for measuring the dissolved gas concentration of the test solution, it is possible to prevent the increase of water in the gas phase chamber and the hydrophilicity of the membrane, and to always accurately measure the dissolved gas concentration even in continuous use for a long period of time.
  • An object of the present invention is to provide a dissolved gas concentration measuring device and a measuring method capable of this.
  • the present inventor has provided a ventilation means for aerating dry gas in the gas phase chamber, and the test solution is passed through the liquid phase chamber to measure the dissolved gas concentration. It has been found that the above-mentioned problems can be solved by alternately performing the measurement step of performing the above and the regeneration step of stopping the flow of the test solution and aerating the dry gas into the gas phase chamber. That is, the gist of the present invention is as follows.
  • a gas permeable membrane module in which the inside of a closed container is divided into a liquid phase chamber and a gas phase chamber by a gas permeable membrane, a liquid introduction pipe for introducing a test liquid into the liquid phase chamber, and a test from the liquid phase chamber. It has a liquid discharge pipe for discharging the liquid and a pressure gauge for measuring the pressure in the gas phase chamber, and the measured value of the pressure in the gas phase chamber when the test liquid is passed through the liquid phase chamber.
  • a gas introduction pipe for introducing dry gas into the gas phase chamber and a gas discharge pipe for discharging dry gas from the gas phase chamber were provided.
  • a characteristic dissolved gas concentration measuring device In the dissolved gas concentration measuring device.
  • a dissolved gas concentration measuring device characterized by providing means.
  • the liquid introduction pipe and the liquid discharge pipe and the gas introduction pipe and the gas discharge pipe are each provided with an on-off valve, and the switching means is provided by opening and closing these on-off valves.
  • Dissolved gas concentration measurement characterized by switching between water flow of the test liquid to the liquid phase chamber, non-water flow of the test liquid to the liquid phase chamber, and ventilation of dry gas to the gas phase chamber. apparatus.
  • [5] Measure the pressure in the gas phase chamber when the test solution is passed through the liquid phase chamber of the gas permeable membrane module in which the inside of the closed container is divided into a liquid phase chamber and a gas phase chamber by a gas permeable membrane.
  • the measurement step of passing the test solution through the liquid phase chamber and the flow of the test solution through the liquid phase chamber are stopped.
  • a method for measuring the concentration of dissolved gas which comprises alternately performing a regeneration step of ventilating the dry gas into the gas phase chamber.
  • the inside of the closed container is divided into a liquid phase chamber and a gas phase chamber by a gas permeable film, the test liquid is passed through the liquid phase chamber, and the pressure in the gas phase chamber is measured to measure the pressure of the test liquid.
  • the measurement step of passing the test solution through the liquid phase chamber to measure the dissolved gas concentration and stopping the passage of the test solution to ventilate the dry gas into the gas phase chamber.
  • the dissolved gas concentration measuring device and measuring method of the present invention are useful for controlling the quality of ultrapure water and washing water used in the washing process of precision processed parts such as silicon wafers for semiconductors.
  • the regeneration process of ventilating is repeated alternately.
  • the switching timing can be applied to simple timer control, control to switch when water accumulated in the gas phase chamber is detected, and the like.
  • the main factors are the characteristics of the gas permeable membrane itself, the measurement environment temperature, the dissolved gas concentration of the test solution, and the like.
  • a porous membrane made of a hydrophobic polymer material such as polypropylene is desirable, and one that is generally used for deaeration is preferable.
  • a gas permeable membrane is oxidized (deteriorated) due to long-term water flow or contact with an oxidizing fluid, the original hydrophobicity is lowered.
  • water tends to move from the liquid phase chamber to the gas phase chamber. Further, when the measurement environment temperature is low, water vapor in the gas phase chamber is likely to condense.
  • the gas on the gas phase chamber side is sucked into the liquid phase chamber side through the gas permeable membrane, so that the air pressure in the gas phase chamber drops. Along with this, the amount of water vapor moving from the liquid phase chamber to the gas phase chamber side increases.
  • the membrane becomes hydrophilic and the amount of condensed water on the gas phase chamber side increases.
  • the dew condensation water on the gas phase chamber side is discharged to the outside of the gas phase chamber by aerating the dry gas to the gas phase chamber, and in addition, the surface of the gas permeable film on the gas phase chamber side is sufficiently dried.
  • the hydrophobicity of the gas permeable film can be restored. Therefore, by inserting the regeneration step by aeration of dry gas, the surface of the gas permeable membrane is not hydrophilic, so to speak, a state close to a new one is maintained, and a correct measured value can be easily obtained.
  • the purpose of the regeneration step is to discharge the dew condensation water and make the gas permeable membrane hydrophobic as described above, but it is sufficient if it is a drying gas aeration step that can achieve it, and the conditions are not unconditionally defined. It is desirable to strengthen the conditions of the regeneration process when the measurement process of passing the test liquid is lengthened and the regeneration process is started after a certain amount of condensed water has accumulated. That is, the flow rate of the dry gas is increased and the ventilation time is lengthened. On the contrary, if the regeneration process is started at a minor stage where the amount of condensed water does not affect the measurement, the conditions of the regeneration process are also light (that is, the flow rate of the dry gas is small and the ventilation time is short). Can achieve the desired purpose.
  • the respective times of the measurement step and the regeneration step in the present invention differ depending on the water quality of the test solution, the characteristics of the gas permeable film, the measurement environment temperature, the surrounding environmental conditions, etc., and are generally defined. Although it cannot be done, for example, a time schedule in which a regeneration process of 1 to 30 hours is performed for each measurement process of 10 to 100 hours can be mentioned.
  • the dry gas used in the present invention is not particularly limited, but inert nitrogen gas, clean dry air, etc. are suitable.
  • the present invention by alternately repeating the measurement step and the regeneration step, it is possible to stably obtain a correct measured value for a long period of time.
  • the measurement will be stopped during the regeneration process, so the measurement will be intermittent.
  • Two gas permeable membrane modules may be provided in parallel and used alternately, or three or more gas permeable membrane modules may be provided in parallel and each module may be sequentially used for measurement.
  • the measurement process and the regeneration process can be performed simultaneously for the entire device, so that continuous measurement can be performed without interrupting the measurement.
  • gas-dissolved water in which a single gas is dissolved in sufficiently degassed ultrapure water is widely used.
  • the saturation concentration of the gas at room temperature and atmospheric pressure hydrogen is about 1.6 mg / L, oxygen is about 40 mg / L, nitrogen is about
  • the dissolved gas concentration can be determined by multiplying 18 mg / L) by the saturation degree (%).
  • the dissolved gas concentration of the test solution can be easily obtained from the measured gas phase pressure.
  • the saturation of the dissolved gas can be obtained with higher accuracy by subtracting the water vapor pressure according to the water temperature of the sample water from the gas phase pressure.
  • accurate calculation is possible by considering the temperature dependence of the saturation concentration.
  • the dissolved gas measured by the dissolved gas concentration measuring apparatus and the measuring method of the present invention is not particularly limited, and examples thereof include nitrogen, oxygen, hydrogen, argon, and the like, and the present invention includes semiconductors and electronic displays (liquid crystal, plasma display, etc.). It is useful for measuring the dissolved gas concentration of gas-dissolved water used in the cleaning process of electronic materials such as organic EL).
  • FIGS. 2A, 2B, 2C and 2D are system diagrams showing other examples.
  • members having the same functions as the members shown in FIG. 3 are designated by the same reference numerals.
  • 10V indicates a flow rate adjustment valve
  • 11V, 12V, 13V, 14V, 15V, 11aV, 11bV, 12aV, 12bV, 13aV, 13bV, 14aV, 14bV, 15aV, 15bV indicate an on-off valve.
  • the white valve indicates the valve that is open
  • the black valve indicates the valve that is closed.
  • the pipe shown by the solid line indicates the liquid flow path
  • the pipe shown by the dotted line indicates the gas flow path.
  • the measurement step of passing the test liquid through the liquid phase chamber 4 and the gas phase by stopping the water flow of the test liquid into the liquid phase chamber 4 are stopped.
  • the regeneration step of ventilating the dry gas into the chamber 5 is alternately performed.
  • the water accumulated in the gas phase chamber 5 in the measurement step is discharged from the gas phase chamber 5 and the gas permeable membrane 3 is dried to restore the hydrophobicity.
  • the gas phase chamber 5 of the gas permeation film module 20 is provided with a gas introduction pipe 14 for introducing a dry gas and a gas discharge pipe 15 for discharging the introduced dry gas from the gas phase chamber 5.
  • .. 14V and 15V are on-off valves provided in the respective pipes 14 and 15.
  • the on-off valves 11V, 12V, 13V are opened, and the on-off valves 14V, 15V are opened. Close.
  • the sample water collected in the pipe 11 is passed through the liquid phase chamber 4, and the pressure in the gas phase chamber 5 at this time is measured by the gas pressure gauge 6.
  • the dissolved gas concentration of the sample water is obtained from the measured gas phase pressure by the above principle.
  • the sample water from the pipe 12 may be discharged to the outside of the system, or may be returned to the main pipe 10 of the test liquid by the return pipe indicated by the alternate long and short dash line.
  • the regeneration step is performed by switching the on-off valve as shown in FIG. 1B.
  • the on-off valves 14V and 15V are opened, the on-off valves 11V, 12V and 13V are closed, the sampling of sample water is stopped, the water flow to the liquid phase chamber 4 is stopped, and instead, the gas introduction pipe 14 is used.
  • the dry gas is ventilated into the gas phase chamber 5 and discharged from the gas discharge pipe 15.
  • the gas permeable membrane 3 is hydrophobized by draining the water in the gas phase chamber 5 and drying the gas permeable membrane 3 on the gas phase chamber side.
  • the opening / closing operation of the opening / closing valve 11V to 15V can be automatically performed by timer control.
  • the dissolved gas concentration measuring device shown in FIGS. 2A to 2D has two gas permeable membrane modules 20A and 20B. Continuous measurement is performed by alternately switching between the gas permeable membrane module for measurement and the gas permeable membrane module for regeneration.
  • 20A is the first gas permeable membrane module, and the inside of the closed container 2a is divided into a liquid phase chamber 4a and a gas phase chamber 5a by the gas permeable membrane 3a.
  • the liquid phase chamber 4a is provided with a pipe 11a and a discharge pipe 12a branched from the water sampling pipe 11 of the test liquid, and the discharge pipe 12a is connected to the pipe 12.
  • a gas pressure gauge 6a is provided in the gas phase chamber 5a via a pipe 13a, and a pipe 14a branched into a dry gas introduction pipe 14 and a discharge pipe 15a are provided.
  • Reference numeral 20B is a second gas permeable membrane module, and the inside of the closed container 2b is divided into a liquid phase chamber 4b and a gas phase chamber 5b by the gas permeable membrane 3b.
  • the liquid phase chamber 4b is provided with a pipe 11b and a discharge pipe 12b branched from the water sampling pipe 11 of the test liquid, and the discharge pipe 12b is connected to the pipe 12.
  • a gas pressure gauge 6b is provided in the gas phase chamber 5b via a pipe 13b, and a pipe 14b and a discharge pipe 15b branched into a dry gas introduction pipe 14 are provided.
  • the on-off valves 11bV, 12bV, 13bV, the on-off valves 14aV, 15aV are opened, and the other on-off valves are closed, and the sample is sampled.
  • the water supply destination is switched to the second gas permeable membrane module 20B, and the measurement is performed in the same manner with the second gas permeable membrane module 20B.
  • dry gas is aerated in the gas phase chamber 5a to discharge water and dry the gas permeable membrane 3a (regeneration step of the first gas permeable membrane module 20A, second. Measurement step of the gas permeable membrane module 20B).
  • the on-off valves 14aV and 15aV are closed, only the on-off valves 11bV, 12bV and 13bV are opened, and the second gas permeable membrane module is opened.
  • Water flow and ventilation of the first gas permeable membrane module 20A are all stopped (pause step of the first gas permeable membrane module 20A, measurement step of the second gas permeable membrane module 20B).
  • the on-off valves 11aV, 12aV, 13aV and the on-off valves 14bV, 15bV are opened, and the other on-off valves are closed, as shown in FIG. 2D.
  • the feed destination of the sample water is switched to the first gas permeable film module 20A, the measurement in the first gas permeable film module 20A is restarted, and the regeneration step of the second gas permeable film module 20B is performed. (Measuring step of the first gas permeable membrane module 20A, regeneration step of the second gas permeable membrane module 20B).
  • regeneration is performed by the second gas permeable membrane module 20B while the measurement is performed by the first gas permeable membrane module 20A, and the first gas permeation is performed.
  • the membrane module 20A is regenerated, the second gas permeable membrane module 20B is used for measurement, so that the dissolved gas concentration of the test solution can be continuously measured.
  • valves of 11aV, 12aV, 11bV, and 12bV are all open, and are the same for both modules.
  • the sample water discharged from the liquid phase chambers 4a and 4b may be discharged to the outside of the system or returned to the main pipe 10 of the test liquid. May be good.
  • a gas permeable membrane module a gas permeable membrane (0.5 ⁇ 1 micromodule manufactured by Hoechst Celanese) is provided in a closed container, and a gas phase chamber (capacity: about 0.5 mL) and a liquid are provided. The one partitioned into a shared room (volume 3.5 mL) was used.
  • a "GC67 digital pressure gauge” manufactured by Nagano Keiki Co., Ltd. was used.
  • degassed treated water and gas-dissolved water having a saturation of 90% are used in advance, and a calibration line of the dissolved gas concentration and the gas phase pressure with respect to the dissolved gas saturation of the test solution is prepared. It was made possible to obtain the dissolved gas concentration from the gas phase pressure.
  • the drying gas was used water concentration of 0% high-purity N 2 gas.
  • the measurement error with respect to the dissolved gas concentration of the test solution was calculated by the following formula.
  • Example 1 Measurement of dissolved gas concentration of degassed treated water
  • two units were used as the test solution using ultrapure water whose dissolved N 2 gas concentration was less than 1 mg / L (value measured by the Orbisfair liquid phase N 2 meter) by the degassing treatment.
  • the dissolved gas concentration was measured by continuous water flow by alternately performing the measurement step and the regeneration step using the gas permeable membrane modules 20A and 20B of the above.
  • the regeneration step in each of the gas permeable membrane modules 20A and 20B was performed for 24 hours for each measurement step of 24 hours.
  • the flow rate of the test solution in the measurement step was 30 mL / min, and the aeration flow rate of the dry gas in the regeneration step was 200 mL / min.
  • the measurement error in the continuous measurement for 30 days was calculated, and the results are shown in Table 1.
  • Example 2 Measurement of dissolved gas concentration of 90% saturation gas dissolved water
  • the results are shown in Table 1 It was.
  • Example 1 Measurement of dissolved gas concentration in degassed water
  • the dissolved gas concentration was measured by the conventional dissolved gas concentration measuring device shown in FIG. 3 using the same degassed treated water as in Example 1 as the test solution.
  • the gas permeable membrane module used here has the same configuration as the gas permeable membrane module used in the examples except that there is no means for venting dry gas, and is continuous for 30 days without performing a regeneration step. Measurements were made. The measurement error at this time was obtained, and the results are shown in Table 1.
  • Comparative Example 2 Measurement of Dissolved Gas Concentration of 90% Saturation Gas Dissolved Water
  • the measurement error in the continuous measurement for 30 days was obtained in the same manner as in Comparative Example 1 except that the N 2 gas-dissolved water having a saturation of 90% was used as the test solution as in Example 2, and the results are shown in Table 1. It was.

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Abstract

A dissolved-gas concentration measurement apparatus for determining the dissolved gas concentration of a test liquid by measuring the pressure of a gas-phase chamber 5 of a gas-permeable-membrane module 20, in which the inside of a sealed container 2 is divided into a liquid-phase chamber 4 and a gas-phase chamber 5 by a gas-permeable membrane 3, when the test liquid is passed through the liquid-phase chamber 4, wherein dry gas ventilation means 14, 15 are provided to the gas-phase chamber 5, and a measurement step for passing the test liquid through the liquid-phase chamber 4, and a regeneration step for stopping the passage of the test liquid to the liquid-phase chamber 4 and passing the dry gas through the gas-phase chamber 5 are alternately performed.

Description

溶存ガス濃度測定装置及び測定方法Dissolved gas concentration measuring device and measuring method
　本発明は、液体中に溶存するガスの濃度を簡便にかつ精度良く測定することができる液流通式の溶存ガス濃度測定装置及び測定方法に関する。 The present invention relates to a liquid flow type dissolved gas concentration measuring device and a measuring method capable of measuring the concentration of gas dissolved in a liquid easily and accurately.
　電子部品などの精密洗浄工程では、超音波洗浄が広く適用されている。超音波洗浄では、用いる洗浄水の溶存ガス濃度が洗浄効果に影響する。即ち、超音波洗浄に用いる洗浄水の溶存ガス濃度は飽和濃度付近であることが、高い洗浄効果と被洗浄物へのダメージ抑制の両面から望ましい。このため、超音波洗浄に用いる洗浄水およびリンス水の溶存ガス濃度を測定して所望の濃度に制御することが必要となる。 Ultrasonic cleaning is widely applied in the precision cleaning process of electronic parts. In ultrasonic cleaning, the concentration of dissolved gas in the cleaning water used affects the cleaning effect. That is, it is desirable that the concentration of the dissolved gas in the cleaning water used for ultrasonic cleaning is near the saturation concentration in terms of both a high cleaning effect and suppression of damage to the object to be cleaned. Therefore, it is necessary to measure the dissolved gas concentrations of the washing water and the rinsing water used for ultrasonic cleaning and control them to desired concentrations.
　特許文献１には、密閉容器内に気体透過膜を設けて、一方の側を液相室、他方の側を気相室に区画し、該気相室に室内の真空度を測定する圧力計を設けた気体透過膜モジュールが記載されている。該液相室に被検液を流し、液相と平衡状態にある気相の真空度を測定することで、被検液の溶存ガス濃度が測定される。 In Patent Document 1, a gas permeable membrane is provided in a closed container, one side is divided into a liquid phase chamber and the other side is divided into a gas phase chamber, and a pressure gauge for measuring the degree of vacuum in the chamber is provided in the gas phase chamber. A gas permeable membrane module provided with the above is described. The dissolved gas concentration of the test solution is measured by flowing the test solution through the liquid phase chamber and measuring the degree of vacuum of the gas phase in equilibrium with the liquid phase.
　図３は、特許文献１の溶存ガス濃度測定装置を示す系統図である。溶存ガス濃度の測定対象となる被検液が流れる主配管１０は、流量調整バルブ１０Ｖを有する。気体透過膜モジュール１の密閉容器２内が気体透過膜３によって液相室４と気相室５とに区画されている。液相室４には、主配管１０から被検液の一部を試料水として分取して液相室４に導入する採水配管１１と、液相室４から水を排出する排出配管１２が連結されている。これらの配管１１，１２にはそれぞれ開閉バルブ１１Ｖ，１２Ｖが設けられている。気相室５には、気相室５内のガス圧力を測定するガス圧力計６が、開閉バルブ１３Ｖを有するガス配管１３を介して設けられている。 FIG. 3 is a system diagram showing the dissolved gas concentration measuring device of Patent Document 1. The main pipe 10 through which the test liquid to be measured for the dissolved gas concentration flows has a flow rate adjusting valve 10V. The inside of the closed container 2 of the gas permeable membrane module 1 is divided into a liquid phase chamber 4 and a gas phase chamber 5 by the gas permeable membrane 3. The liquid phase chamber 4 includes a water sampling pipe 11 that separates a part of the test liquid from the main pipe 10 as sample water and introduces it into the liquid phase chamber 4, and a discharge pipe 12 that discharges water from the liquid phase chamber 4. Are concatenated. Opening / closing valves 11V and 12V are provided in these pipes 11 and 12, respectively. The gas phase chamber 5 is provided with a gas pressure gauge 6 for measuring the gas pressure in the gas phase chamber 5 via a gas pipe 13 having an on-off valve 13V.
　この溶存ガス濃度測定装置の気相室４に完全脱気水を通水すると、密閉容器２内で気相室５内のガスが気体透過膜３を介して脱気水に吸引され、気相室５内の圧力は真空圧（ゲージ圧－１０１．３ｋＰａ）に近づく。逆に、大気圧下での飽和濃度に相当するガスを溶解した被検液を液相室４に通水すると、気相室５内の圧力は大気圧（ゲージ圧±０ｋＰａ）で安定する。 When completely degassed water is passed through the gas phase chamber 4 of this dissolved gas concentration measuring device, the gas in the gas phase chamber 5 is sucked into the degassed water through the gas permeation film 3 in the closed container 2, and the gas phase. The pressure in the chamber 5 approaches the vacuum pressure (gauge pressure -101.3 kPa). On the contrary, when the test solution in which the gas corresponding to the saturation concentration under atmospheric pressure is dissolved is passed through the liquid phase chamber 4, the pressure in the gas phase chamber 5 stabilizes at atmospheric pressure (gauge pressure ± 0 kPa).
　－１０１．３ｋＰａの気相圧力が、被検液の飽和度０％に相当する。０ｋＰａの気相圧力が飽和度１００％に相当する。気相圧力の測定値から比例計算で被検液の溶存ガスの飽和度が求められる。求めた飽和度（％）に、被検液中の溶存ガスの大気圧下での飽和濃度に乗じることで、当該被検液の溶存ガス濃度が求められる。特許文献１の測定装置は、簡易で安価な構成を有する。多種類のガスの溶存ガス濃度を精度良く測定することができる。 A gas phase pressure of -101.3 kPa corresponds to 0% saturation of the test solution. The gas phase pressure of 0 kPa corresponds to 100% saturation. The saturation of the dissolved gas in the test solution can be obtained by proportional calculation from the measured value of the gas phase pressure. By multiplying the determined saturation (%) by the saturation concentration of the dissolved gas in the test solution under atmospheric pressure, the dissolved gas concentration of the test solution can be obtained. The measuring device of Patent Document 1 has a simple and inexpensive configuration. It is possible to accurately measure the dissolved gas concentration of many types of gas.
特開２０００－６５７１０号公報Japanese Unexamined Patent Publication No. 2000-65710
　特許文献１の装置によって、長期間連続して測定を行った場合、測定値に誤差が生じるようになり、測定精度の安定性が低下する。
　即ち、特許文献１の測定装置では、長期間連続して測定を行った場合、液相室から膜を介して気相室側に移動した水蒸気が気相室内で結露して溜まっていく。同時に膜表面の疎水性が失われていく。これらが原因となって、膜を介したガスの移動を妨げ、正確な濃度測定が阻害される。 When the measurement is continuously performed for a long period of time by the apparatus of Patent Document 1, an error occurs in the measured value, and the stability of the measurement accuracy is lowered.
That is, in the measuring device of Patent Document 1, when the measurement is continuously performed for a long period of time, the water vapor that has moved from the liquid phase chamber to the gas phase chamber side via the membrane condenses and accumulates in the gas phase chamber. At the same time, the hydrophobicity of the film surface is lost. Due to these factors, the movement of gas through the membrane is hindered and accurate concentration measurement is hindered.
　本発明は上記従来技術の問題を解決し、密閉容器内を気体透過膜で液相室と気相室とに区画し、液相室に被検液を流し、気相室の圧力を測定することで被検液の溶存ガス濃度を測定する装置において、気相室内の水の増加、膜の親水化を防止して、長期間連続使用においても、溶存ガス濃度を常時正確に測定することができる溶存ガス濃度測定装置及び測定方法を提供することを課題とする。 The present invention solves the above-mentioned problems of the prior art, divides the inside of the closed container into a liquid phase chamber and a gas phase chamber by a gas permeable film, flows a test solution into the liquid phase chamber, and measures the pressure in the gas phase chamber. Therefore, in the device for measuring the dissolved gas concentration of the test solution, it is possible to prevent the increase of water in the gas phase chamber and the hydrophilicity of the membrane, and to always accurately measure the dissolved gas concentration even in continuous use for a long period of time. An object of the present invention is to provide a dissolved gas concentration measuring device and a measuring method capable of this.
　本発明者は、上記の課題を解決すべく鋭意検討を重ねた結果、気相室に乾燥ガスを通気する通気手段を設け、液相室に被検液を通水して溶存ガス濃度の測定を行う測定工程と、被検液の通水を停止して気相室に乾燥ガスを通気する再生工程とを交互に行うことにより、上記課題を解決することができることを見出した。
　即ち、本発明は以下を要旨とする。 As a result of diligent studies to solve the above problems, the present inventor has provided a ventilation means for aerating dry gas in the gas phase chamber, and the test solution is passed through the liquid phase chamber to measure the dissolved gas concentration. It has been found that the above-mentioned problems can be solved by alternately performing the measurement step of performing the above and the regeneration step of stopping the flow of the test solution and aerating the dry gas into the gas phase chamber.
That is, the gist of the present invention is as follows.
［１］　密閉容器内を気体透過膜で液相室と気相室とに区画した気体透過膜モジュールと、該液相室に被検液を導入する液導入配管及び該液相室から被検液を排出する液排出配管と、該気相室内の圧力を測定する圧力計とを有し、該液相室に被検液が通水されているときの該気相室内の圧力の測定値から該被検液の溶存ガス濃度を求める溶存ガス濃度測定装置において、該気相室に乾燥ガスを導入するガス導入配管及び該気相室から乾燥ガスを排出するガス排出配管を設けたことを特徴とする溶存ガス濃度測定装置。 [1] A gas permeable membrane module in which the inside of a closed container is divided into a liquid phase chamber and a gas phase chamber by a gas permeable membrane, a liquid introduction pipe for introducing a test liquid into the liquid phase chamber, and a test from the liquid phase chamber. It has a liquid discharge pipe for discharging the liquid and a pressure gauge for measuring the pressure in the gas phase chamber, and the measured value of the pressure in the gas phase chamber when the test liquid is passed through the liquid phase chamber. In the dissolved gas concentration measuring device for determining the dissolved gas concentration of the test solution, a gas introduction pipe for introducing dry gas into the gas phase chamber and a gas discharge pipe for discharging dry gas from the gas phase chamber were provided. A characteristic dissolved gas concentration measuring device.
［２］　［１］において、前記液相室への被検液の通水と、該液相室への被検液の非通水及び前記気相室への乾燥ガスの通気とを切り換える切り換え手段を設けたことを特徴とする溶存ガス濃度測定装置。 [2] In [1], switching between passing the test liquid through the liquid phase chamber, non-passing the test liquid through the liquid phase chamber, and ventilating the dry gas into the gas phase chamber. A dissolved gas concentration measuring device characterized by providing means.
［３］　［２］において、前記液導入配管及び液排出配管と、前記ガス導入配管及びガス排出配管にはそれぞれ開閉バルブが設けられており、前記切り換え手段は、これらの開閉バルブの開閉により、前記液相室への被検液の通水と、該液相室への被検液の非通水及び前記気相室への乾燥ガスの通気とを切り換えることを特徴とする溶存ガス濃度測定装置。 [3] In [2], the liquid introduction pipe and the liquid discharge pipe and the gas introduction pipe and the gas discharge pipe are each provided with an on-off valve, and the switching means is provided by opening and closing these on-off valves. Dissolved gas concentration measurement characterized by switching between water flow of the test liquid to the liquid phase chamber, non-water flow of the test liquid to the liquid phase chamber, and ventilation of dry gas to the gas phase chamber. apparatus.
［４］　［１］ないし［３］のいずれかにおいて、前記気体透過膜モジュールを２台以上並列に設け、前記被検液を通水する気体透過膜モジュールを切り換える切り換え手段を設けたことを特徴とする溶存ガス濃度測定装置。 [4] In any of [1] to [3], two or more gas permeable membrane modules are provided in parallel, and a switching means for switching the gas permeable membrane module through which the test solution is passed is provided. Dissolved gas concentration measuring device.
［５］　密閉容器内を気体透過膜で液相室と気相室とに区画した気体透過膜モジュールの該液相室に被検液を通水したときの該気相室の圧力を測定することにより、該被検液の溶存ガス濃度を求める溶存ガス濃度測定方法において、該液相室に被検液を通水する測定工程と、該液相室への被検液の通水を停止して該気相室に乾燥ガスを通気する再生工程とを交互に行うことを特徴とする溶存ガス濃度測定方法。 [5] Measure the pressure in the gas phase chamber when the test solution is passed through the liquid phase chamber of the gas permeable membrane module in which the inside of the closed container is divided into a liquid phase chamber and a gas phase chamber by a gas permeable membrane. As a result, in the dissolved gas concentration measuring method for determining the dissolved gas concentration of the test solution, the measurement step of passing the test solution through the liquid phase chamber and the flow of the test solution through the liquid phase chamber are stopped. A method for measuring the concentration of dissolved gas, which comprises alternately performing a regeneration step of ventilating the dry gas into the gas phase chamber.
［６］　［５］において、前記測定工程の時間と再生工程の時間との比が１：０．１～１であることを特徴とする溶存ガス濃度測定方法。 [6] The method for measuring a dissolved gas concentration according to [5], wherein the ratio of the time of the measurement step to the time of the regeneration step is 1: 0.1 to 1.
　本発明によれば、密閉容器内を気体透過膜で液相室と気相室とに区画し、液相室に被検液を流し、気相室の圧力を測定することで被検液の溶存ガス濃度を測定する装置において、液相室に被検液を通水して溶存ガス濃度の測定を行う測定工程と、被検液の通水を停止して気相室に乾燥ガスを通気する再生工程とを交互に行うことにより、気相室内の水の増加、気体透過膜の親水化を防止して、長期間連続使用においても、被検液の溶存ガス濃度を常時正確に測定することが可能となる。 According to the present invention, the inside of the closed container is divided into a liquid phase chamber and a gas phase chamber by a gas permeable film, the test liquid is passed through the liquid phase chamber, and the pressure in the gas phase chamber is measured to measure the pressure of the test liquid. In the device for measuring the dissolved gas concentration, the measurement step of passing the test solution through the liquid phase chamber to measure the dissolved gas concentration, and stopping the passage of the test solution to ventilate the dry gas into the gas phase chamber. By alternately performing the regeneration process, the increase in water in the gas phase chamber and the hydrophilicity of the gas permeable membrane are prevented, and the dissolved gas concentration of the test solution is always accurately measured even during continuous use for a long period of time. It becomes possible.
　本発明の溶存ガス濃度測定装置及び測定方法は、半導体用シリコンウェハなどの精密加工部品の洗浄工程で使用される超純水や洗浄水の水質管理などに有用である。 The dissolved gas concentration measuring device and measuring method of the present invention are useful for controlling the quality of ultrapure water and washing water used in the washing process of precision processed parts such as silicon wafers for semiconductors.
本発明の溶存ガス濃度測定装置の実施の形態の一例を示す系統図であり、測定工程のバルブ開閉を示す。It is a system diagram which shows an example of embodiment of the dissolved gas concentration measuring apparatus of this invention, and shows valve opening and closing of a measuring process. 本発明の溶存ガス濃度測定装置の実施の形態の一例を示す系統図であり、再生工程のバルブ開閉を示す。It is a system diagram which shows an example of embodiment of the dissolved gas concentration measuring apparatus of this invention, and shows valve opening and closing of a regeneration process. 本発明の溶存ガス濃度測定装置の実施の形態の他の例を示す系統図であり、第１の気体透過膜モジュールの測定工程と第２の気体透過膜モジュールの休止工程のバルブ開閉を示す。It is a system diagram which shows another example of embodiment of the dissolved gas concentration measuring apparatus of this invention, and shows the valve opening and closing of the measurement process of the 1st gas permeable membrane module, and the resting process of the 2nd gas permeable membrane module. 本発明の溶存ガス濃度測定装置の実施の形態の他の例を示す系統図であり、第１の気体透過膜モジュールの再生工程と第２の気体透過膜モジュールの測定工程のバルブ開閉を示す。It is a system diagram which shows another example of embodiment of the dissolved gas concentration measuring apparatus of this invention, and shows the valve opening and closing of the regeneration process of the 1st gas permeable membrane module, and the measurement step of a 2nd gas permeable membrane module. 本発明の溶存ガス濃度測定装置の実施の形態の他の例を示す系統図であり、第１の気体透過膜モジュールの休止工程と第２の気体透過膜モジュールの測定工程のバルブ開閉を示す。It is a system diagram which shows another example of the Embodiment of the dissolved gas concentration measuring apparatus of this invention, and shows the valve opening and closing of the resting process of the 1st gas permeable membrane module and the measuring step of a 2nd gas permeable membrane module. 本発明の溶存ガス濃度測定装置の実施の形態の他の例を示す系統図であり、第１の気体透過膜モジュールの測定工程と第２の気体透過膜モジュールの再生工程のバルブ開閉を示す。It is a system diagram which shows another example of embodiment of the dissolved gas concentration measuring apparatus of this invention, and shows the valve opening and closing of the measurement process of the 1st gas permeable film module and the regeneration process of the 2nd gas permeable film module. 従来の溶存ガス濃度測定装置を示す系統図である。It is a system diagram which shows the conventional dissolved gas concentration measuring apparatus.
　以下に本発明の溶存ガス濃度測定装置及び測定方法の実施の形態を詳細に説明する。 Hereinafter, embodiments of the dissolved gas concentration measuring apparatus and measuring method of the present invention will be described in detail.
　本発明では、液相室に被検液を通水して気相室のガス圧力を測定する測定工程と、液相室への被検液の通水を停止して気相室に乾燥ガスを通気する再生工程とを交互に繰り返す。その切り換えタイミングは、単純なタイマー制御、気相室内に溜まる水を検知したときに切り換える制御などが適用できる。 In the present invention, the measurement step of passing the test liquid through the liquid phase chamber to measure the gas pressure in the gas phase chamber and the drying gas in the gas phase chamber by stopping the passage of the test liquid into the liquid phase chamber. The regeneration process of ventilating is repeated alternately. The switching timing can be applied to simple timer control, control to switch when water accumulated in the gas phase chamber is detected, and the like.
　気体透過膜の親水化、気相室側に移動した水蒸気の結露には、様々な要因が関与する。
　主な要因は気体透過膜自体の特性、測定環境温度、被検液の溶存ガス濃度などである。 Various factors are involved in the hydrophilization of the gas permeable membrane and the dew condensation of water vapor that has moved to the gas phase chamber side.
The main factors are the characteristics of the gas permeable membrane itself, the measurement environment temperature, the dissolved gas concentration of the test solution, and the like.
　水は通さないがガスを透過できる気体透過膜としては、ポリプロピレン等の疎水性の高分子材料の多孔性膜が望ましく、一般的に脱気目的で使われているものが好適である。このような気体透過膜が、長期通水や酸化性流体との接触などで表面の酸化（劣化）が進むと、本来の疎水性が低下してくる。疎水性の低下した気体透過膜では、液相室から気相室への水の移動が起こり易い。
　また、測定環境温度が低い場合、気相室内の水蒸気が結露し易くなる。
　被検液の溶存ガス濃度が低い場合は、気相室側のガスが気体透過膜を介して液相室側へ吸引されることで気相室の気圧が下がる。これに伴い液相室から気相室側に移動する水蒸気量が増える。 As the gas permeable membrane that does not allow water to pass through but allows gas to pass through, a porous membrane made of a hydrophobic polymer material such as polypropylene is desirable, and one that is generally used for deaeration is preferable. When the surface of such a gas permeable membrane is oxidized (deteriorated) due to long-term water flow or contact with an oxidizing fluid, the original hydrophobicity is lowered. In a gas permeable membrane with reduced hydrophobicity, water tends to move from the liquid phase chamber to the gas phase chamber.
Further, when the measurement environment temperature is low, water vapor in the gas phase chamber is likely to condense.
When the dissolved gas concentration of the test solution is low, the gas on the gas phase chamber side is sucked into the liquid phase chamber side through the gas permeable membrane, so that the air pressure in the gas phase chamber drops. Along with this, the amount of water vapor moving from the liquid phase chamber to the gas phase chamber side increases.
　これらの条件が組み合わさって、膜の親水化と気相室側の結露水増加が進む。 By combining these conditions, the membrane becomes hydrophilic and the amount of condensed water on the gas phase chamber side increases.
　どのような条件にも無駄なく対応するには、気相室側の結露水が所定量溜まったことを何らかの手段で検知して乾燥ガスを通気する再生工程に移行する切り換えが考えられる。しかし、通水条件が小刻みに変わるようなことがなければ、その条件での結露水の増加傾向を見定めて、それが正しい測定に影響を及ぼさないうちに再生工程に切り換える単純なタイマー制御で十分に目的を達することができる。 In order to deal with any conditions without waste, it is conceivable to switch to a regeneration process in which a predetermined amount of condensed water on the gas phase chamber side is detected by some means and the dry gas is aerated. However, if the water flow conditions do not change little by little, a simple timer control that determines the increasing tendency of condensed water under those conditions and switches to the regeneration process before it affects the correct measurement is sufficient. Can reach the purpose.
　本発明によれば、気相室への乾燥ガスの通気により気相室側の結露水を気相室外へ排出すると共に、それに加えて気体透過膜の気相室側表面を十分乾燥させることで気体透過膜の疎水性を回復させることができる。このため、乾燥ガス通気による再生工程を挿入することで、気体透過膜の表面が親水化していない、いわば新品に近い状態が維持され、正しい測定値を容易に得ることができるようになる。 According to the present invention, the dew condensation water on the gas phase chamber side is discharged to the outside of the gas phase chamber by aerating the dry gas to the gas phase chamber, and in addition, the surface of the gas permeable film on the gas phase chamber side is sufficiently dried. The hydrophobicity of the gas permeable film can be restored. Therefore, by inserting the regeneration step by aeration of dry gas, the surface of the gas permeable membrane is not hydrophilic, so to speak, a state close to a new one is maintained, and a correct measured value can be easily obtained.
　再生工程は、上記のように結露水の排出と気体透過膜の疎水化が目的となるが、それが達成できる乾燥ガスの通気工程であればよく、条件は一概に定められない。被検液を通水する測定工程を長くとり、ある程度の結露水が溜まってから再生工程に移る場合には、再生工程の条件を強くすることが望ましい。即ち、乾燥ガスの流量を多めに、通気時間を長めにする。
　逆に、結露水の量が測定に影響を与えるほどでもない軽微な段階で再生工程に移行する場合は、再生工程の条件も軽め（即ち、乾燥ガスの流量は少なめ、通気時間は短め）で所望の目的を達することができる。 The purpose of the regeneration step is to discharge the dew condensation water and make the gas permeable membrane hydrophobic as described above, but it is sufficient if it is a drying gas aeration step that can achieve it, and the conditions are not unconditionally defined. It is desirable to strengthen the conditions of the regeneration process when the measurement process of passing the test liquid is lengthened and the regeneration process is started after a certain amount of condensed water has accumulated. That is, the flow rate of the dry gas is increased and the ventilation time is lengthened.
On the contrary, if the regeneration process is started at a minor stage where the amount of condensed water does not affect the measurement, the conditions of the regeneration process are also light (that is, the flow rate of the dry gas is small and the ventilation time is short). Can achieve the desired purpose.
　このようなことから、本発明における測定工程と再生工程のそれぞれの時間については、被検液の水質、気体透過膜の特性、測定環境温度等、周囲の環境条件等により異なり、一概に規定することはできないが、一例として、例えば１０～１００時間の測定工程毎に１～３０時間の再生工程を行うタイムスケジュールが挙げられる。 Therefore, the respective times of the measurement step and the regeneration step in the present invention differ depending on the water quality of the test solution, the characteristics of the gas permeable film, the measurement environment temperature, the surrounding environmental conditions, etc., and are generally defined. Although it cannot be done, for example, a time schedule in which a regeneration process of 1 to 30 hours is performed for each measurement process of 10 to 100 hours can be mentioned.
　なお、本発明で用いる乾燥ガスに特に制限はないが、不活性な窒素ガス、クリーンドライエアなどが好適である。 The dry gas used in the present invention is not particularly limited, but inert nitrogen gas, clean dry air, etc. are suitable.
　以上のように、本発明では、測定工程と再生工程を交互に繰り返すことで、長期に亘り正しい測定値を安定的に得ることできる。 As described above, in the present invention, by alternately repeating the measurement step and the regeneration step, it is possible to stably obtain a correct measured value for a long period of time.
　気体透過膜モジュールが一つだけの場合は、再生工程中は測定停止状態となるので断続的な測定となる。２つの気体透過膜モジュールを並列配置で設け、これらを交互に使用するか、又は３つ以上の気体透過膜モジュールを並列配置で設け、各モジュールを順次に測定に使用してもよい。これにより、装置全体として測定工程と再生工程を同時に行えるので、測定を中断することなく連続的な測定が可能となる。 If there is only one gas permeable membrane module, the measurement will be stopped during the regeneration process, so the measurement will be intermittent. Two gas permeable membrane modules may be provided in parallel and used alternately, or three or more gas permeable membrane modules may be provided in parallel and each module may be sequentially used for measurement. As a result, the measurement process and the regeneration process can be performed simultaneously for the entire device, so that continuous measurement can be performed without interrupting the measurement.
　複数の気体透過膜モジュールを並列で設けた場合には、通水気体透過膜モジュールへの通気（再生）と、再生済気体透過膜モジュールの通水（測定）との切り替えは、同時に行う必要はない。通気から通水に移る切替を先行して、２以上の気体透過膜モジュールに同じ試料水を同時に通水するオーバーラップ時間を設け、あとから通水したモジュールの気相圧力が先行していたモジュールのそれと同等になった後に、先行通水気体透過膜モジュールの通水を通気に切り替えるようにしてもよい。これにより、切り替え時の気相圧力の変動を回避して安定な連続測定が可能となる。 When a plurality of gas permeable membrane modules are provided in parallel, it is necessary to switch between ventilation (regeneration) to the water vapor permeable membrane module and water flow (measurement) of the regenerated gas permeable membrane module at the same time. Absent. Prior to switching from aeration to water flow, an overlap time was provided for two or more gas permeable membrane modules to pass the same sample water at the same time, and the gas phase pressure of the module that passed water later preceded the module. After it becomes equivalent to that of the above, the water flow of the preceding water vapor permeable membrane module may be switched to ventilation. As a result, stable continuous measurement is possible by avoiding fluctuations in the gas phase pressure at the time of switching.
　電子部品などの精密洗浄工程では、十分に脱気処理された超純水に単一ガスを溶解させたガス溶解水が汎用されている。このように実質的に被検液中の溶存ガスが一種類の場合、そのガスの常温大気圧下での飽和濃度（水素は約１．６ｍｇ／Ｌ、酸素は約４０ｍｇ／Ｌ、窒素は約１８ｍｇ／Ｌ）に飽和度（％）を乗じることで溶存ガス濃度を求めることができる。 In the precision cleaning process of electronic parts, gas-dissolved water in which a single gas is dissolved in sufficiently degassed ultrapure water is widely used. In this way, when there is substantially one type of dissolved gas in the test solution, the saturation concentration of the gas at room temperature and atmospheric pressure (hydrogen is about 1.6 mg / L, oxygen is about 40 mg / L, nitrogen is about The dissolved gas concentration can be determined by multiplying 18 mg / L) by the saturation degree (%).
　予め本発明の溶存ガス濃度測定装置で測定された気相圧力と被検液の溶存ガス飽和度又はこの溶存ガス飽和度から算出される溶存ガス濃度との検量線を作成しておくことで、測定された気相圧力から容易に被検液の溶存ガス濃度を求めることができる。 By creating a calibration line in advance between the gas phase pressure measured by the dissolved gas concentration measuring device of the present invention and the dissolved gas saturation of the test solution or the dissolved gas concentration calculated from this dissolved gas saturation, The dissolved gas concentration of the test solution can be easily obtained from the measured gas phase pressure.
　この際、試料水の水温に応じた水蒸気圧を気相圧力から差し引くことで、より精度高く溶存ガスの飽和度を求めることができる。特定ガスの飽和度から溶存濃度を算出する場合、飽和濃度の温度依存性を考慮することで、正確な算出が可能となる。 At this time, the saturation of the dissolved gas can be obtained with higher accuracy by subtracting the water vapor pressure according to the water temperature of the sample water from the gas phase pressure. When calculating the dissolved concentration from the saturation of a specific gas, accurate calculation is possible by considering the temperature dependence of the saturation concentration.
　本発明の溶存ガス濃度測定装置及び測定方法で測定される溶存ガスについては特に制限はなく、窒素、酸素、水素、アルゴン等が挙げられ、本発明は、半導体や電子ディスプレイ（液晶、プラズマディスプレイ、有機ＥＬなど）といった電子材料の洗浄工程等で使用されるガス溶解水の溶存ガス濃度の測定に有用である。 The dissolved gas measured by the dissolved gas concentration measuring apparatus and the measuring method of the present invention is not particularly limited, and examples thereof include nitrogen, oxygen, hydrogen, argon, and the like, and the present invention includes semiconductors and electronic displays (liquid crystal, plasma display, etc.). It is useful for measuring the dissolved gas concentration of gas-dissolved water used in the cleaning process of electronic materials such as organic EL).
　以下に、図面を参照して本発明の溶存ガス濃度測定装置の実施の形態をより具体的に説明する。 Hereinafter, embodiments of the dissolved gas concentration measuring apparatus of the present invention will be described in more detail with reference to the drawings.
　図１Ａ，１Ｂは本発明の溶存ガス濃度測定装置の実施の形態の一例を示す系統図であり、図２Ａ，２Ｂ，２Ｃ，２Ｄは他の例を示す系統図である。これらの図において、図３に示す部材と同一機能を奏する部材には同一符号を付してある。
　１０Ｖは流量調整バルブ、１１Ｖ，１２Ｖ，１３Ｖ，１４Ｖ，１５Ｖ，１１ａＶ，１１ｂＶ，１２ａＶ，１２ｂＶ，１３ａＶ，１３ｂＶ，１４ａＶ，１４ｂＶ，１５ａＶ，１５ｂＶは開閉バルブを示す。図中、白ぬきのバルブは開とされているバルブを示し、黒塗りのバルブは閉とされているバルブを示す。また、実線で示す配管は液体流路を示し、点線で示す配管は気体流路を示す。 1A and 1B are system diagrams showing an example of an embodiment of the dissolved gas concentration measuring apparatus of the present invention, and FIGS. 2A, 2B, 2C and 2D are system diagrams showing other examples. In these figures, members having the same functions as the members shown in FIG. 3 are designated by the same reference numerals.
10V indicates a flow rate adjustment valve, and 11V, 12V, 13V, 14V, 15V, 11aV, 11bV, 12aV, 12bV, 13aV, 13bV, 14aV, 14bV, 15aV, 15bV indicate an on-off valve. In the figure, the white valve indicates the valve that is open, and the black valve indicates the valve that is closed. The pipe shown by the solid line indicates the liquid flow path, and the pipe shown by the dotted line indicates the gas flow path.
　図１Ａ，１Ｂでは、１台の気体透過膜モジュール２０において、液相室４に被検液を通水する測定工程と、液相室４への被検液の通水を停止して気相室５に乾燥ガスを通気する再生工程とを交互に行う。測定工程で気相室５内に溜まった水を気相室５から排出すると共に気体透過膜３を乾燥させて疎水性を回復させる。気体透過膜モジュール２０の気相室５には、乾燥ガスを導入するためのガス導入配管１４と、導入された乾燥ガスを気相室５から排出するためのガス排出配管１５が設けられている。１４Ｖ，１５Ｖは各々の配管１４，１５に設けられた開閉バルブである。 In FIGS. 1A and 1B, in one gas permeable membrane module 20, the measurement step of passing the test liquid through the liquid phase chamber 4 and the gas phase by stopping the water flow of the test liquid into the liquid phase chamber 4 are stopped. The regeneration step of ventilating the dry gas into the chamber 5 is alternately performed. The water accumulated in the gas phase chamber 5 in the measurement step is discharged from the gas phase chamber 5 and the gas permeable membrane 3 is dried to restore the hydrophobicity. The gas phase chamber 5 of the gas permeation film module 20 is provided with a gas introduction pipe 14 for introducing a dry gas and a gas discharge pipe 15 for discharging the introduced dry gas from the gas phase chamber 5. .. 14V and 15V are on-off valves provided in the respective pipes 14 and 15.
　このように構成された気体透過膜モジュール２０により被検液の溶存ガス濃度を測定するには、まず、図１Ａに示すように、開閉バルブ１１Ｖ，１２Ｖ，１３Ｖを開、開閉バルブ１４Ｖ，１５Ｖを閉とする。配管１１で採取した試料水を液相室４に通水し、このときの気相室５内の圧力をガス圧力計６で測定する。測定された気相圧力から前述の原理で試料水の溶存ガス濃度を求める。
　配管１２からの試料水は、系外へ排出してもよいし、一点鎖線で示す戻り配管により、被検液の主配管１０に戻してもよい。 In order to measure the dissolved gas concentration of the test solution by the gas permeable membrane module 20 configured in this way, first, as shown in FIG. 1A, the on-off valves 11V, 12V, 13V are opened, and the on-off valves 14V, 15V are opened. Close. The sample water collected in the pipe 11 is passed through the liquid phase chamber 4, and the pressure in the gas phase chamber 5 at this time is measured by the gas pressure gauge 6. The dissolved gas concentration of the sample water is obtained from the measured gas phase pressure by the above principle.
The sample water from the pipe 12 may be discharged to the outside of the system, or may be returned to the main pipe 10 of the test liquid by the return pipe indicated by the alternate long and short dash line.
　所定時間の測定を行った後、或いは測定誤差が大きくなってきたことが検出されたときには、開閉バルブの切り換えで図１Ｂに示す通り、再生工程を行う。
　再生工程では、開閉バルブ１４Ｖ，１５Ｖを開、開閉バルブ１１Ｖ，１２Ｖ，１３Ｖを閉として、試料水の採水を停止して液相室４への通水を止め、代りにガス導入配管１４から乾燥ガスを気相室５内に通気してガス排出配管１５から排出する。気相室５内の水を排出すると共に気体透過膜３の気相室側を乾燥させることより、気体透過膜３が疎水化される。 After the measurement for a predetermined time is performed, or when it is detected that the measurement error has become large, the regeneration step is performed by switching the on-off valve as shown in FIG. 1B.
In the regeneration process, the on-off valves 14V and 15V are opened, the on-off valves 11V, 12V and 13V are closed, the sampling of sample water is stopped, the water flow to the liquid phase chamber 4 is stopped, and instead, the gas introduction pipe 14 is used. The dry gas is ventilated into the gas phase chamber 5 and discharged from the gas discharge pipe 15. The gas permeable membrane 3 is hydrophobized by draining the water in the gas phase chamber 5 and drying the gas permeable membrane 3 on the gas phase chamber side.
　この再生工程を経た後は、再び、図１Ａに示すように通水工程に切り換え、以降再生工程と通水工程を交互に行う。 After passing through this regeneration process, the process is switched to the water flow process again as shown in FIG. 1A, and thereafter, the regeneration process and the water flow process are alternately performed.
　この開閉バルブ１１Ｖ～１５Ｖの開閉操作はタイマー制御にて自動的に行うことができる。 The opening / closing operation of the opening / closing valve 11V to 15V can be automatically performed by timer control.
　図２Ａ～２Ｄに示す溶存ガス濃度測定装置では、２台の気体透過膜モジュール２０Ａ，２０Ｂを有する。測定を行う気体透過膜モジュールと再生を行う気体透過膜モジュールとを交互に切り換えることで連続的な測定を行う。 The dissolved gas concentration measuring device shown in FIGS. 2A to 2D has two gas permeable membrane modules 20A and 20B. Continuous measurement is performed by alternately switching between the gas permeable membrane module for measurement and the gas permeable membrane module for regeneration.
　図２Ａ～２Ｄにおいて、２０Ａは第１の気体透過膜モジュールであり、密閉容器２ａ内が気体透過膜３ａにより液相室４ａと気相室５ａとに区画されている。液相室４ａに被検液の採水配管１１から分岐した配管１１ａと排出配管１２ａが設けられ、排出配管１２ａは配管１２に連結されている。気相室５ａにはガス圧力計６ａが配管１３ａを介して設けられると共に、乾燥ガスの導入配管１４に分岐した配管１４ａと排出配管１５ａが設けられている。
　２０Ｂは第２の気体透過膜モジュールであり、密閉容器２ｂ内が気体透過膜３ｂにより液相室４ｂと気相室５ｂとに区画されている。液相室４ｂに被検液の採水配管１１から分岐した配管１１ｂと排出配管１２ｂが設けられ、排出配管１２ｂは配管１２に連結されている。気相室５ｂにはガス圧力計６ｂが配管１３ｂを介して設けられると共に、乾燥ガスの導入配管１４に分岐した配管１４ｂと排出配管１５ｂが設けられている。 In FIGS. 2A to 2D, 20A is the first gas permeable membrane module, and the inside of the closed container 2a is divided into a liquid phase chamber 4a and a gas phase chamber 5a by the gas permeable membrane 3a. The liquid phase chamber 4a is provided with a pipe 11a and a discharge pipe 12a branched from the water sampling pipe 11 of the test liquid, and the discharge pipe 12a is connected to the pipe 12. A gas pressure gauge 6a is provided in the gas phase chamber 5a via a pipe 13a, and a pipe 14a branched into a dry gas introduction pipe 14 and a discharge pipe 15a are provided.
Reference numeral 20B is a second gas permeable membrane module, and the inside of the closed container 2b is divided into a liquid phase chamber 4b and a gas phase chamber 5b by the gas permeable membrane 3b. The liquid phase chamber 4b is provided with a pipe 11b and a discharge pipe 12b branched from the water sampling pipe 11 of the test liquid, and the discharge pipe 12b is connected to the pipe 12. A gas pressure gauge 6b is provided in the gas phase chamber 5b via a pipe 13b, and a pipe 14b and a discharge pipe 15b branched into a dry gas introduction pipe 14 are provided.
　この溶存ガス濃度測定装置により、被検液の連続測定を行うには、まず、図２Ａの通り、開閉バルブ１１ａＶ，１２ａＶ，１３ａＶを開、その他の開閉バルブを閉として、配管１１で採水した試料水を配管１１ａを介して液相室４ａに通水し、このときの気相室５ａ内の圧力をガス圧力計６ａで測定する（第１の気体透過膜モジュール２０Ａの測定工程、第２の気体透過膜モジュール２０Ｂの休止工程）。 In order to continuously measure the test solution with this dissolved gas concentration measuring device, first, as shown in FIG. 2A, the on-off valves 11aV, 12aV, 13aV were opened, the other on-off valves were closed, and water was sampled through the pipe 11. The sample water is passed through the liquid phase chamber 4a via the pipe 11a, and the pressure in the gas phase chamber 5a at this time is measured by the gas pressure gauge 6a (measurement step of the first gas permeable membrane module 20A, the second Step of resting the gas permeable membrane module 20B).
　第１の気体透過膜モジュール２０Ａにおける測定工程を所定時間行った後は、図２Ｂの通り、開閉バルブ１１ｂＶ，１２ｂＶ，１３ｂＶと、開閉バルブ１４ａＶ，１５ａＶを開、その他の開閉バルブを閉として、試料水の送給先を第２の気体透過膜モジュール２０Ｂに切り換え、第２の気体透過膜モジュール２０Ｂで同様に測定を行う。この間、第１の気体透過膜モジュール２０Ａでは、気相室５ａに乾燥ガスを通気して水の排出、気体透過膜３ａの乾燥を行う（第１の気体透過膜モジュール２０Ａの再生工程、第２の気体透過膜モジュール２０Ｂの測定工程）。 After performing the measurement step in the first gas permeable membrane module 20A for a predetermined time, as shown in FIG. 2B, the on-off valves 11bV, 12bV, 13bV, the on-off valves 14aV, 15aV are opened, and the other on-off valves are closed, and the sample is sampled. The water supply destination is switched to the second gas permeable membrane module 20B, and the measurement is performed in the same manner with the second gas permeable membrane module 20B. During this period, in the first gas permeable membrane module 20A, dry gas is aerated in the gas phase chamber 5a to discharge water and dry the gas permeable membrane 3a (regeneration step of the first gas permeable membrane module 20A, second. Measurement step of the gas permeable membrane module 20B).
　第１の気体透過膜モジュール２０Ａの再生工程を所定時間行った後は、図２Ｃの通り、開閉バルブ１４ａＶ，１５ａＶを閉じ、開閉バルブ１１ｂＶ，１２ｂＶ，１３ｂＶのみ開とし、第２の気体透過膜モジュール２０Ｂによる測定を継続する。第１の気体透過膜モジュール２０Ａについては通水、通気をすべて停止する（第１の気体透過膜モジュール２０Ａの休止工程、第２の気体透過膜モジュール２０Ｂの測定工程）。 After the regeneration step of the first gas permeable membrane module 20A is performed for a predetermined time, as shown in FIG. 2C, the on-off valves 14aV and 15aV are closed, only the on-off valves 11bV, 12bV and 13bV are opened, and the second gas permeable membrane module is opened. Continue the measurement with 20B. Water flow and ventilation of the first gas permeable membrane module 20A are all stopped (pause step of the first gas permeable membrane module 20A, measurement step of the second gas permeable membrane module 20B).
　第２の気体透過膜モジュール２０Ｂにおける測定工程を所定時間行った後は、図２Ｄの通り、開閉バルブ１１ａＶ，１２ａＶ，１３ａＶと、開閉バルブ１４ｂＶ，１５ｂＶを開、その他の開閉バルブを閉とする。これにより、試料水の送給先を第１の気体透過膜モジュール２０Ａに切り換え、第１の気体透過膜モジュール２０Ａでの測定を再開すると共に、第２の気体透過膜モジュール２０Ｂの再生工程を行う（第１の気体透過膜モジュール２０Ａの測定工程、第２の気体透過膜モジュール２０Ｂの再生工程）。 After performing the measurement step in the second gas permeable membrane module 20B for a predetermined time, the on-off valves 11aV, 12aV, 13aV and the on-off valves 14bV, 15bV are opened, and the other on-off valves are closed, as shown in FIG. 2D. As a result, the feed destination of the sample water is switched to the first gas permeable film module 20A, the measurement in the first gas permeable film module 20A is restarted, and the regeneration step of the second gas permeable film module 20B is performed. (Measuring step of the first gas permeable membrane module 20A, regeneration step of the second gas permeable membrane module 20B).
　これ以降、図２Ａ～２Ｄを同様に順次行うことで、第１の気体透過膜モジュール２０Ａで測定を行っている間に、第２の気体透過膜モジュール２０Ｂで再生を行い、第１の気体透過膜モジュール２０Ａの再生時には第２の気体透過膜モジュール２０Ｂで測定を行うようにすることで、被検液の溶存ガス濃度の測定を連続的に行うことが可能となる。 After that, by sequentially performing FIGS. 2A to 2D, regeneration is performed by the second gas permeable membrane module 20B while the measurement is performed by the first gas permeable membrane module 20A, and the first gas permeation is performed. When the membrane module 20A is regenerated, the second gas permeable membrane module 20B is used for measurement, so that the dissolved gas concentration of the test solution can be continuously measured.
　図２Ａ～２Ｄに示す実施の形態においては、図２Ａから図２Ｂへ、図２Ｃから図２Ｄへの切替に際しては、１１ａＶ、１２ａＶ、１１ｂＶ、１２ｂＶのバルブがいずれも開で、両方のモジュールに同じ試料水が通水されるオーバーラップ時間を設けることで、より安定な連続測定を可能とすることができる。 In the embodiment shown in FIGS. 2A to 2D, when switching from FIG. 2A to FIG. 2B and from FIG. 2C to FIG. 2D, the valves of 11aV, 12aV, 11bV, and 12bV are all open, and are the same for both modules. By providing an overlap time during which the sample water is passed, more stable continuous measurement can be made possible.
　図２Ａ～２Ｄにおいても、図１Ａ，１Ｂにおけると同様に、液相室４ａ，４ｂから排出された試料水は、系外へ排出してもよいし、被検液の主配管１０に戻してもよい。 In FIGS. 2A to 2D, as in FIGS. 1A and 1B, the sample water discharged from the liquid phase chambers 4a and 4b may be discharged to the outside of the system or returned to the main pipe 10 of the test liquid. May be good.
　以下に実施例及び比較例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
　以下の実施例及び比較例では、気体透過膜モジュールとして、密閉容器に気体透過膜（ヘキスト・セラニーズ社製　０．５×１マイクロモジュール）を設けて気相室（容量約０．５ｍＬ）と液相室（容量３．５ｍＬ）とに区画したものを用いた。
　ガス圧力計としては、長野計器（株）製「ＧＣ６７デジタル圧力計」を用いた。
　この気体透過膜モジュールについては、予め脱気処理水と飽和度９０％のガス溶解水とを用い、被検液の溶存ガス飽和度に対する溶存ガス濃度と気相圧力との検量線を作成しておき、気相圧力から溶存ガス濃度を求めることができるようにした。
　乾燥ガスとしては、水分濃度０％の高純度Ｎ２ガスを用いた。 In the following examples and comparative examples, as a gas permeable membrane module, a gas permeable membrane (0.5 × 1 micromodule manufactured by Hoechst Celanese) is provided in a closed container, and a gas phase chamber (capacity: about 0.5 mL) and a liquid are provided. The one partitioned into a shared room (volume 3.5 mL) was used.
As the gas pressure gauge, a "GC67 digital pressure gauge" manufactured by Nagano Keiki Co., Ltd. was used.
For this gas permeable membrane module, degassed treated water and gas-dissolved water having a saturation of 90% are used in advance, and a calibration line of the dissolved gas concentration and the gas phase pressure with respect to the dissolved gas saturation of the test solution is prepared. It was made possible to obtain the dissolved gas concentration from the gas phase pressure.
The drying gas was used water concentration of 0% high-purity N 2 gas.
　被検液の溶存ガス濃度に対する測定誤差は、下記式で算出した。 The measurement error with respect to the dissolved gas concentration of the test solution was calculated by the following formula.
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
［実施例１：脱気処理水の溶存ガス濃度測定］
　脱気処理により溶存Ｎ２ガス濃度が１ｍｇ／Ｌ未満（オービスフェア液相Ｎ２計により測定した値）とされた超純水を被検液として、図２Ａ～図２Ｄに示す通り、２台の気体透過膜モジュール２０Ａ，２０Ｂを用いて測定工程と再生工程を交互に行うことで、連続通水にて溶存ガス濃度の測定を行った。
　各気体透過膜モジュール２０Ａ，２０Ｂにおける再生工程は、２４時間の測定工程毎に２４時間行った。
　測定工程における被検液の通水流量は３０ｍＬ／分とし、再生工程における乾燥ガスの通気流量は２００ｍＬ／分とした。
　３０日間の連続測定における測定誤差を求め、結果を表１に示した。 [Example 1: Measurement of dissolved gas concentration of degassed treated water]
As shown in FIGS. 2A to 2D, two units were used as the test solution using ultrapure water whose dissolved N 2 gas concentration was less than 1 mg / L (value measured by the Orbisfair liquid phase N 2 meter) by the degassing treatment. The dissolved gas concentration was measured by continuous water flow by alternately performing the measurement step and the regeneration step using the gas permeable membrane modules 20A and 20B of the above.
The regeneration step in each of the gas permeable membrane modules 20A and 20B was performed for 24 hours for each measurement step of 24 hours.
The flow rate of the test solution in the measurement step was 30 mL / min, and the aeration flow rate of the dry gas in the regeneration step was 200 mL / min.
The measurement error in the continuous measurement for 30 days was calculated, and the results are shown in Table 1.
［実施例２：飽和度９０％ガス溶解水の溶存ガス濃度測定］
　実施例１で用いた脱気処理水に気体透過膜モジュールとＮ２ガス供給手段を用いた溶解処理を施し、超純水にＮ２ガスを飽和度９０％濃度（１５．８ｍｇ／Ｌ：オービスフェア液相Ｎ２計による測定値）に溶解させたガス溶解水を被検液としたこと以外は、実施例１と同様に３０日間の連続測定における測定誤差を求め、結果を表１に示した。 [Example 2: Measurement of dissolved gas concentration of 90% saturation gas dissolved water]
Subjected to dissolution treatment using a gas permeable membrane module and the N 2 gas supply means to the deaerated water used in Example 1, saturation 90% concentration of N 2 gas in ultrapure water (15.8 mg / L: Orvis except that fair liquid phase N 2 meter gas dissolved water dissolved in the measured value) according to the test liquid and obtains the measurement error in the continuous measurement of likewise 30 days as in example 1. the results are shown in Table 1 It was.
［比較例１：脱気処理水の溶存ガス濃度測定］
　実施例１におけると同様の脱気処理水を被検液として、図３に示す従来の溶存ガス濃度測定装置により、溶存ガス濃度の測定を行った。ここで用いた気体透過膜モジュールは、乾燥ガスの通気手段がないこと以外は、実施例で用いた気体透過膜モジュールと同様の構成とされており、再生工程を行うことなく、３０日間の連続測定を行った。このときの測定誤差を求め、結果を表１に示した。 [Comparative Example 1: Measurement of dissolved gas concentration in degassed water]
The dissolved gas concentration was measured by the conventional dissolved gas concentration measuring device shown in FIG. 3 using the same degassed treated water as in Example 1 as the test solution. The gas permeable membrane module used here has the same configuration as the gas permeable membrane module used in the examples except that there is no means for venting dry gas, and is continuous for 30 days without performing a regeneration step. Measurements were made. The measurement error at this time was obtained, and the results are shown in Table 1.
［比較例２：飽和度９０％ガス溶解水の溶存ガス濃度測定］
　実施例２におけると同様の飽和度９０％のＮ２ガス溶解水を被検液としたこと以外は、比較例１と同様に３０日間の連続測定における測定誤差を求め、結果を表１に示した。 [Comparative Example 2: Measurement of Dissolved Gas Concentration of 90% Saturation Gas Dissolved Water]
The measurement error in the continuous measurement for 30 days was obtained in the same manner as in Comparative Example 1 except that the N 2 gas-dissolved water having a saturation of 90% was used as the test solution as in Example 2, and the results are shown in Table 1. It was.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１より明らかなように、乾燥ガス通気による再生工程を行わない比較例１では、連続測定を行うと、測定精度が低下して測定誤差が大きくなる。特に、被検液が脱気処理水の場合は、前述の通り、気相室のガスが気体透過膜を介して液相室に吸引されることで、気相室内の気圧が下がり、この結果液相室側から気相室側へ移動する水蒸気が増えるため、再生工程のない比較例１では気相室に水が溜まり易く、この結果、測定誤差が大きくなる。
　これに対して、気相室への乾燥ガスの通気手段を設け、測定工程と再生工程とを交互に行った実施例１では、３０日間の連続測定でも、測定誤差は全くなく、精度よく測定することができる。 As is clear from Table 1, in Comparative Example 1 in which the regeneration step by aeration of dry gas is not performed, continuous measurement lowers the measurement accuracy and increases the measurement error. In particular, when the test liquid is degassed treated water, as described above, the gas in the gas phase chamber is sucked into the liquid phase chamber through the gas permeable membrane, so that the pressure in the gas phase chamber drops, and as a result, Since the amount of water vapor moving from the liquid phase chamber side to the gas phase chamber side increases, water tends to accumulate in the gas phase chamber in Comparative Example 1 without the regeneration step, and as a result, the measurement error becomes large.
On the other hand, in Example 1 in which a means for venting dry gas to the gas phase chamber was provided and the measurement step and the regeneration step were alternately performed, there was no measurement error even in continuous measurement for 30 days, and the measurement was accurate. can do.
　本発明を特定の態様を用いて詳細に説明したが、本発明の意図と範囲を離れることなく様々な変更が可能であることは当業者に明らかである。
　本出願は、２０１９年３月２９日付で出願された日本特許出願２０１９－０６６９０５に基づいており、その全体が引用により援用される。 Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the intent and scope of the invention.
This application is based on Japanese Patent Application No. 2019-066905 filed on March 29, 2019, which is incorporated by reference in its entirety.
　２，２ａ，２ｂ　密閉容器
　３，３ａ，３ｂ　気体透過膜
　４，４ａ，４ｂ　液相室
　５，５ａ，５ｂ　気相室
　６，６ａ，６ｂ　ガス圧力計
　２０，２０Ａ，２０Ｂ　気体透過膜モジュール 2,2a, 2b Airtight container 3,3a, 3b Gas permeable membrane 4,4a, 4b Liquid phase chamber 5,5a, 5b Gas phase chamber 6,6a, 6b Gas pressure gauge 20, 20A, 20B Gas permeable membrane module

Claims (6)

  1. 　密閉容器内を気体透過膜で液相室と気相室とに区画した気体透過膜モジュールと、
    　該液相室に被検液を導入する液導入配管及び該液相室から被検液を排出する液排出配管と、
    　該気相室内の圧力を測定する圧力計とを有し、
    　該液相室に被検液が通水されているときの該気相室内の圧力の測定値から該被検液の溶存ガス濃度を求める溶存ガス濃度測定装置において、
    　該気相室に乾燥ガスを導入するガス導入配管及び該気相室から乾燥ガスを排出するガス排出配管を設けたことを特徴とする溶存ガス濃度測定装置。     A gas permeable membrane module in which the inside of the closed container is divided into a liquid phase chamber and a gas phase chamber by a gas permeable membrane,
    A liquid introduction pipe for introducing the test liquid into the liquid phase chamber, a liquid discharge pipe for discharging the test liquid from the liquid phase chamber, and a liquid discharge pipe.
    It has a pressure gauge to measure the pressure in the gas phase chamber.
    In a dissolved gas concentration measuring device for obtaining the dissolved gas concentration of the test liquid from the measured value of the pressure in the gas phase chamber when the test liquid is passed through the liquid phase chamber.
    A dissolved gas concentration measuring device characterized in that a gas introduction pipe for introducing dry gas into the gas phase chamber and a gas discharge pipe for discharging dry gas from the gas phase chamber are provided.
  2. 　請求項１において、前記液相室への被検液の通水と、該液相室への被検液の非通水及び前記気相室への乾燥ガスの通気とを切り換える切り換え手段を設けたことを特徴とする溶存ガス濃度測定装置。 In claim 1, a switching means for switching between passing the test liquid through the liquid phase chamber, non-passing the test liquid through the liquid phase chamber, and ventilating the dry gas into the gas phase chamber is provided. A dissolved gas concentration measuring device characterized in that.
  3. 　請求項２において、前記液導入配管及び液排出配管と、前記ガス導入配管及びガス排出配管にはそれぞれ開閉バルブが設けられており、前記切り換え手段は、これらの開閉バルブの開閉により、前記液相室への被検液の通水と、該液相室への被検液の非通水及び前記気相室への乾燥ガスの通気とを切り換えることを特徴とする溶存ガス濃度測定装置。 In claim 2, the liquid introduction pipe and the liquid discharge pipe and the gas introduction pipe and the gas discharge pipe are each provided with an on-off valve, and the switching means is the liquid phase by opening and closing these on-off valves. A dissolved gas concentration measuring device characterized by switching between passing the test liquid through the chamber, non-passing the test liquid through the liquid phase chamber, and ventilating the dry gas into the gas phase chamber.
  4. 　請求項１ないし３のいずれか１項において、前記気体透過膜モジュールを２台以上並列に設け、前記被検液を通水する気体透過膜モジュールを切り換える切り換え手段を設けたことを特徴とする溶存ガス濃度測定装置。 The dissolution according to any one of claims 1 to 3, wherein two or more gas permeable membrane modules are provided in parallel, and a switching means for switching the gas permeable membrane module through which the test solution is passed is provided. Gas concentration measuring device.
  5. 　密閉容器内を気体透過膜で液相室と気相室とに区画した気体透過膜モジュールの該液相室に被検液を通水したときの該気相室の圧力を測定することにより、該被検液の溶存ガス濃度を求める溶存ガス濃度測定方法において、
    　該液相室に被検液を通水する測定工程と、該液相室への被検液の通水を停止して該気相室に乾燥ガスを通気する再生工程とを交互に行うことを特徴とする溶存ガス濃度測定方法。     By measuring the pressure in the gas phase chamber when the test solution is passed through the liquid phase chamber of the gas permeable membrane module in which the inside of the closed container is divided into a liquid phase chamber and a gas phase chamber by a gas permeable membrane. In the dissolved gas concentration measuring method for determining the dissolved gas concentration of the test solution,
    The measurement step of passing the test liquid through the liquid phase chamber and the regeneration step of stopping the passage of the test liquid through the liquid phase chamber and ventilating the dry gas into the gas phase chamber are alternately performed. A method for measuring a dissolved gas concentration.
  6. 　請求項５において、前記測定工程の時間と再生工程の時間との比が１：０．１～１であることを特徴とする溶存ガス濃度測定方法。 The dissolved gas concentration measuring method according to claim 5, wherein the ratio of the time of the measuring step to the time of the regenerating step is 1: 0.1 to 1.
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JPH11290659A (en) * 1998-04-13 1999-10-26 Nitto Denko Corp Operation of membrane module
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JP2006071340A (en) * 2004-08-31 2006-03-16 Kurita Water Ind Ltd Method of measuring concentration of dissolved gas in liquid, measuring device, and manufacture device of nitrogen gas-dissolved water
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JP2009095778A (en) * 2007-10-17 2009-05-07 Kurita Water Ind Ltd Production unit, production apparatus, and production method of gas dissolved water
JP2015180500A (en) * 2015-05-29 2015-10-15 栗田工業株式会社 Gas dissolved water supply device and manufacturing method of gas dissolved water
JP2019200061A (en) * 2018-05-14 2019-11-21 栗田工業株式会社 Measuring apparatus and measuring method of dissolved gas concentration

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11290659A (en) * 1998-04-13 1999-10-26 Nitto Denko Corp Operation of membrane module
JP2000051606A (en) * 1998-08-07 2000-02-22 Japan Organo Co Ltd Gas permeation membrane apparatus
JP2006071340A (en) * 2004-08-31 2006-03-16 Kurita Water Ind Ltd Method of measuring concentration of dissolved gas in liquid, measuring device, and manufacture device of nitrogen gas-dissolved water
JP2007225439A (en) * 2006-02-23 2007-09-06 Kurita Water Ind Ltd Concentration measuring instrument of dissolved gas and concentration measuring method of dissolved gas
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