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WO2022264563A1 - Water quality measurement device - Google Patents

Water quality measurement device Download PDF

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Publication number
WO2022264563A1
WO2022264563A1 PCT/JP2022/010883 JP2022010883W WO2022264563A1 WO 2022264563 A1 WO2022264563 A1 WO 2022264563A1 JP 2022010883 W JP2022010883 W JP 2022010883W WO 2022264563 A1 WO2022264563 A1 WO 2022264563A1
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WO
WIPO (PCT)
Prior art keywords
water
water quality
pipe
measuring device
quality measuring
Prior art date
Application number
PCT/JP2022/010883
Other languages
French (fr)
Japanese (ja)
Inventor
伸説 新井
裕二 深和
和 赤崎
Original Assignee
栗田工業株式会社
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Publication of WO2022264563A1 publication Critical patent/WO2022264563A1/en

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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/02Devices for withdrawing samples
    • G01N1/10Devices for withdrawing samples in the liquid or fluent state
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18Water

Definitions

  • the present invention relates to a water quality measuring device for measuring the quality of pure water, ultrapure water, etc., and more particularly to a water quality measuring device for measuring the quality of water sampled from multiple water sampling points with a single water quality measuring device.
  • the present invention particularly relates to a water quality measuring apparatus suitable for measuring the number of fine particles contained in pure water or ultrapure water.
  • the ultrapure water used for cleaning semiconductors is produced by an ultrapure water production system consisting of a pretreatment system, a primary pure water production system, and a subsystem (secondary pure water production system). , well water, etc.).
  • the subsystem includes a sub-tank, pump, heat exchanger, low-pressure ultraviolet oxidation device (UV device), ion exchange device and ultrafiltration membrane (UF membrane) separation device.
  • UV device low-pressure ultraviolet oxidation device
  • ion exchange device ion exchange device
  • UF membrane ultrafiltration membrane
  • TOC is decomposed into organic acids and further CO 2 by ultraviolet rays of 185 nm emitted from a low-pressure ultraviolet lamp.
  • Organic matter and CO 2 produced by the decomposition are removed in the subsequent ion exchange unit.
  • the ultrafiltration membrane separation device removes fine particles and also removes effluent particles from the ion exchange resin. The ultrapure water thus produced is delivered to the point of use.
  • Ultrapure water are used as cleaning and rinsing water in the process of manufacturing electronic components such as semiconductors. With the miniaturization of semiconductor integrated circuits, ultrapure water is required to further reduce the amount (concentration) of impurities in water and to manage water quality more strictly.
  • the number of fine particles is one of the water quality control items for ultrapure water, and it is required to manage fine particles with a particle size of several tens of nanometers on the order of ⁇ 1/mL.
  • microparticles with a particle size of several tens of nanometers can be removed at a high removal rate.
  • Special UF membranes are used that are manufactured with care to prevent contamination and elution.
  • UF membranes currently used in this field are generally capable of processing about 10 m 3 /h per module (one piece). That is, in a facility that requires 100 m 3 /h of ultrapure water, parallel processing is performed around the above-described 10 UF membrane modules.
  • An advantage of parallel processing with a plurality of modules is that normal water quality can be maintained by disconnecting the module when a problem occurs in one module. For example, when producing 100 m 3 /h of ultrapure water, 11 UF membrane modules capable of producing 10 m 3 /h of treated water are installed in parallel, and even if one UF membrane module is separated, 100 m 3 /h is sufficient. If it is configured to be able to supply, even if a problem occurs in one UF membrane module (for example, the hollow fiber membrane breaks and the number of fine particles in the treated water increases, etc.), by separating this one UF membrane module, The water quality of ultrapure water can be maintained, and a treated water flow rate of 100 m 3 /h can also be maintained.
  • Another advantage of parallel processing with multiple modules is that it is possible to minimize deterioration of ultrapure water quality caused by initial elution components after module replacement. That is, if some of the modules installed in parallel are not replaced at the same time, but some of the modules are replaced, the deterioration of the ultrapure water quality caused by the initial elution can be reduced.
  • the water quality is measured by introducing water flowing through multiple lines into a common measuring device via a preparative valve.
  • a preparative valve For example, in Patent Document 1, ultrapure water from an ultrapure water line and concentrated water obtained by concentrating this ultrapure water with a reverse osmosis membrane separation device are switched by a valve and introduced into a common measurement device for analysis. is stated.
  • analysis items include metal ion concentration, resistivity, number of fine particles, TOC concentration, silica concentration, and dissolved oxygen concentration (paragraph 0049).
  • Patent Document 2 describes a method of maintaining measurement accuracy by providing a blow line and constantly blowing to avoid stagnation of target water.
  • the present invention avoids deterioration in measurement accuracy due to retention of target water, prevents deterioration in ultrapure water production efficiency due to an increase in the amount of blow water, and also avoids complication around the measurement device.
  • An object of the present invention is to provide a water quality measuring device capable of
  • the water quality measuring device of the present invention is a water quality measuring device for measuring the water quality by introducing water to be measured for water quality sampled from a plurality of water sampling points via water sampling pipes into a common water quality measuring device, wherein each water sampling pipe a loop-shaped flow channel in which the downstream end of and a water sampling valve provided in each water sampling pipe.
  • the water quality measuring instrument is a fine particle counting instrument.
  • n water sampling pipes (n is an integer of 2 or more) are provided, and the downstream ends of the first to n-th water sampling pipes are connected in this order to the loop-shaped flow path,
  • the distance from the connection point of the first water sampling pipe to the loop-shaped channel to the connection point of the supply pipe, and the distance from the connection point of the n-th water sampling pipe to the loop-shaped channel to the connection point of the supply pipe is substantially the same as the distance of
  • a discharge pipe through which the outflow water from the water quality measuring instrument flows is provided, and the discharge pipe is provided with a flow control valve.
  • An aspect of the present invention includes control means for controlling the water sampling valves to be opened in a predetermined order for a predetermined period of time.
  • the membrane filtration system of the present invention comprises membrane modules installed in parallel, supply means for supplying water to be treated to each membrane module through a common water supply pipe and branch pipes branched from it, and treated water from each membrane module.
  • a membrane filtration system having a confluence pipe is provided with the water quality measuring device of the present invention, and the water quality measuring device is installed so as to measure at least the treated water of each membrane module.
  • the water quality measuring device is further installed so as to measure the water to be treated flowing through the common water supply pipe and the combined treated water flowing through the combined pipe.
  • the flow path from the water sampling point to the water sampling valve contains sampled water except during water quality measurement (when the water sampling valve is open and water is flowing through the water quality measuring instrument).
  • water in the common flow path from the water sampling valve to the downstream water quality measuring instrument, water always flows in both directions in the looped flow path, so water does not stagnate and the previous measurement It is possible to minimize the influence of residual target water and mixing of target water, and to obtain highly accurate water quality measurement values.
  • the amount of water discharged to the outside of the system is the amount of one point during water quality measurement, which is small.
  • the effect of reducing the amount of discharged water and piping around the measuring device is very large.
  • FIG.1 shows the structure of a filtration part
  • FIG.1(b) has shown the structure of a water-quality measurement part.
  • 4 is a configuration diagram of a subsystem
  • FIG. 1 is a configuration diagram of a water quality measuring device according to an embodiment
  • FIG. 1 is a configuration diagram of a water quality measuring device according to an embodiment
  • FIG. It is a graph which shows an experimental result. It is a graph which shows an experimental result.
  • FIG. 1 is a configuration diagram of a membrane filtration system equipped with a water quality measuring device according to an embodiment, FIG. 1(a) showing the configuration of the filtering section, and FIG. 1(b) showing the configuration of the water quality measuring section.
  • UF membrane (ultrafiltration membrane) modules 4a, 4b, and 4c are installed in the filtration unit, but it may be two or four or more.
  • the water to be treated such as ion exchanger effluent of the subsystem (secondary pure water device), can be sent from a pipe 1 having a pump 2 to each UF module 4a to 4c via branch pipes 3a, 3b, and 3c. It is Filtrated water that has passed through the UF membranes of the UF membrane modules 4a to 4c flows from the filtered water pipes 5a, 5b, and 5c to the combined pipe 6 and is taken out as filtered water.
  • ion exchanger effluent of the subsystem secondary pure water device
  • Water sampling points are set in the pipe 1 on the downstream side of the pump 2, the filtered water pipes 5a, 5b, 5c, and the confluence pipe 6, respectively. Intake) water sampling pipes 10 to 14 are branched.
  • each of the water sampling pipes 10 to 14 are connected to a looped pipe 20.
  • Valves 10V, 11V, 12V, 13V, and 14V consisting of on-off valves are provided as water sampling valves in the middle of each of the water sampling pipes 10-14.
  • the loop-shaped pipe 20 has a substantially annular shape, and ends of the water sampling pipes 10 to 14 are connected to one half of the circle with the center of the circle interposed therebetween.
  • Connection points of the water sampling pipes 10 to 14 to the looped pipe 20 are preferably equidistant in the circumferential direction of the circle.
  • the distance from the connection point of the water sampling pipe 10 on the one end side in the winding direction to the connection point of the water sampling pipe 14 on the other end side is 10 to 80%, especially 20%, of the total length of the looped pipe 20 in the winding direction. It is preferably about 50%.
  • a measurement pipe 21 is connected on the opposite side across the center of the circle. Water flowing through the looped pipe 20 is introduced into the water quality measuring instrument 22 through the measuring pipe 21, and the water quality is measured. The measured waste water is discharged outside the system through a discharge pipe 23 having a flow control valve 24 .
  • a particle meter is used as the water quality measuring instrument 22 in this embodiment, various online water quality instruments such as a TOC meter and a sodium meter can also be used.
  • each valve 10V to 14V is automatically performed by the controller.
  • the distance between the water sampling pipe 14 and the loop-shaped pipe 20 is 100%.
  • the distance from the connection point to the connection point of the measurement pipe 21 is preferably 10 to 45%, particularly 25 to 40%, but is not limited to this.
  • the water to be treated is branched from the pipe 1 to the pipes 3a to 3c, membrane-filtered by each of the UF membrane modules 4a to 4c, and passed through the filtered water pipes 5a to 5c to join the pipes. It merges at 6, is taken out as filtered water, and is sent to the next process or point of use.
  • each pipe 1, 5a, 5b, 5c, 6 The water flowing through each pipe 1, 5a, 5b, 5c, 6 is sampled in order or in a specific order, and the water quality is measured.
  • the valve 10V is opened for a predetermined period of time, and the water sampled from the pipe 1 on the downstream side of the pump 2 is allowed to flow into the water quality measuring instrument 22 through the pipe 10, the loop 20, and the pipe 21, Take water quality measurements.
  • the valve 10V is closed and the valve 11V is opened for a predetermined time.
  • part of the filtered water from the UF membrane module 4a is separated from the filtered water pipe 5a, flows into the water quality measuring instrument 22 via the pipe 11, the looped pipe 20, and the pipe 21, and is filtered by the UF membrane module 4a. Water quality is measured.
  • the valve 11V is closed, the valve 12V is opened for a predetermined time, and the water quality of the filtered water from the UF membrane module 4b is measured. Thereafter, the water quality measurement of the filtered water of the UF membrane module 4c and the water quality measurement of the combined filtered water are performed in the same manner.
  • the quality of the water to be treated, the filtered water from each UF membrane module, and the combined filtered water are sequentially measured.
  • the order of measurement is not limited to this, and may be changed as appropriate, or the frequency of measurement at a specific water sampling point may be increased as described later.
  • the water flowing into the loop-shaped pipe 20 from any of the water sampling pipes 10 to 14 flows in one direction (clockwise direction in FIG. 1(b)) and It flows in both the other direction (counterclockwise direction in FIG. 1( b )), reaches the measurement pipe 21 , and is introduced into the water quality measuring instrument 22 .
  • the water flowing into the looped pipe 20 from one water sampling pipe flows in both directions through the looped pipe 20, the water remaining in the looped pipe 20 at the time of the previous measurement ( In this case, the entire amount of the water from the water sampling pipe 11 is quickly pushed out to the pipe 23, and the water quality of the water sampled this time, which is not mixed with the previous water sample, can be measured. Moreover, the time required for measurement can be shortened.
  • the sampling pipe 12 When the water quality measurement of the water sampled from one water sampling pipe (for example, the water sampling pipe 12) is completed and the water quality measurement of the next water sampling (in this case, the water sampling from the water sampling pipe 13) is switched to, the sampling is started. Water remains in the water pipe 12, but water does not stay in the looped pipe 20, so the mixing in the next water sample is eliminated in a short time after switching.
  • the amount of water quality measurement wastewater is only the amount of water sampled from one water sampling pipe that is measuring water quality, and is a small amount.
  • the loop-shaped flow path 20 is designed to pass liquid so as not to flow in one direction due to the influence of the distance, and to quickly push out the water to be measured at the time of the previous measurement. It is preferable to design in consideration of the flow rate and the channel differential pressure generated under the flow rate conditions. More specifically, in the case of using a common smooth-surface flow path pipe, it is preferable to configure the flow path pipe so that the linear velocity is about 0.3 to 2.0 m/sec.
  • the water quality measuring method using the water quality measuring device of the present invention it is preferable to discard the data of the water quality measuring device 22 for a predetermined period of time after switching the valves 10V to 14V. This is because when the valve is switched, dust generation and elution may occur due to the operation of the valve. Since changes in water quality due to these influences are not changes in water quality that should be monitored, the accuracy of water quality measurement results can be improved by rejecting data for a predetermined period of time after switching the valve.
  • the water quality to be monitored is the number of fine particles and the water quality measuring device is a laser light scattering type fine particle meter, it is preferable to turn off the laser and suspend the water quality measurement for the above-mentioned predetermined time. By suspending water quality measurement, it is possible to extend the apparent life of the expensive laser light source (period of use including the period of suspension of measurement) and reduce maintenance costs.
  • the water quality measurement method using the water quality measurement device of the present invention it is preferable to average the obtained water quality measurement results. That is, as described above, in order to avoid the influence of water quality fluctuations caused by the opening and closing operation of the valve, even if the data for the predetermined time after the valve switching is discarded, the influence time is not necessarily clear, so the predetermined time has passed. It is possible that there are still repercussions. Therefore, by averaging and handling a plurality of data obtained after a predetermined period of time until the next switching, this influence can be leveled or minimized, and the reliability of the measurement result is improved.
  • the function of judging whether the water quality measurement result is good or bad and the function of switching the flow path using an automatic valve or the like are used together, and based on the water quality measurement result If it is determined that the water treatment equipment is
  • the number of fine particles in the filtered water of a plurality of UF membrane modules is measured by an online fine particle monitor, and when the number of fine particles exceeds a predetermined number, the corresponding UF membrane module All or any of the automatic valves installed in the water supply, treated water, and concentrated water pipes are closed to avoid deterioration of the ultrapure water quality.
  • a pressure gauge, a flow meter (not shown), and a flow control valve 24 are provided downstream of the water quality measuring instrument 22. It is preferable to dispose and appropriately adjust the pressure and flow rate. By installing these devices on the downstream side of the water quality measuring instrument, it is possible to adjust the flow rate and pressure to a predetermined level, and the influence of dust generation due to the operation of the flow control valve 24 and the inside of the pressure gauge and flow meter can avoid the influence of the stagnant part.
  • the opening of the flow control valve 24 installed downstream of the water quality measuring instrument may be throttled to apply back pressure to the water quality measuring instrument.
  • one online particle monitor can be used to monitor the treated water of a plurality of water treatment equipment. can be monitored as well as confluence water can be monitored as before.
  • changes in the number of particles in the water supply can be immediately confirmed, so the time required to narrow down the cause of the increase in the number of particles can be shortened.
  • the water quality measuring device of the present invention if there are a large number of water treatment devices such as UF membrane modules, there is a concern that the interval between measurements of combined water will become excessively long. In such a case, it can be improved by increasing the number of times the combined water is measured.
  • 10 UF membrane modules A to J are installed in parallel, and when measuring a total of 11 types of water quality of filtered water W1 to W10 of each module and combined water WM, each filtered water W1 to W10 Measurement of the merged water WM may be interposed between the measurements. That is, the order of water to be measured is W1 ⁇ WM ⁇ W2 ⁇ WM ⁇ W3 ⁇ WM ⁇ .
  • the W1 to W10 measurements may be divided into a plurality of groups, and the WM measurement may be interposed between each group. For example, in the case of two groups, the order of W1->W2->W3->W4->W5->WA->W6->W7->W8->W9->W10->WM is repeated as one cycle.
  • the measurement frequency of some target water can be made higher than other target water.
  • Example 1 The apparatus of the present invention was incorporated into an ultrapure water production subsystem having three UF membrane modules installed in parallel, and the number of fine particles in the UF membrane module feed water, each UF membrane module filtered water, and combined filtered water was measured.
  • the overall configuration of this subsystem is subtank ⁇ subpump ⁇ ultraviolet oxidizer (UV) ⁇ [non-regenerative ion exchange device filled with anion exchange resin] ⁇ degassing membrane ⁇ [cation exchange resin and Non-regenerative ion exchange device mixed and filled with anion exchange resin] ⁇ UF membrane modules ( three units in parallel) ⁇ point of use.
  • UV ultraviolet oxidizer
  • an air-driven 5-station manifold type branch valve (CKD's air operated valve for chemical liquids GAMDZ3R-6UR-Z05W) was used.
  • this air operated valve 30 is provided with five inlets and two outlets. Two outlets are located at opposite ends of the valve body. Each inlet faces a water channel 31 connecting two outlets via open/close valves V1 to V5.
  • Each inflow port was connected to water sampling points S1 to S5 by a tube.
  • the tip of the tube 32 was connected to one outlet of the water channel 31, and the tip of the tube 33 was connected to the other outlet.
  • the rear end of tube 32 was connected to first inlet 34 a of T-shaped connector 34
  • the rear end of tube 33 was connected to second inlet 34 b of T-shaped connector 34 .
  • An on-line particle counter 36 was connected via a tube 35 to the outlet 34c of the T-shaped connector.
  • a loop-like structure composed of the water passage 31, the tube 32, the T-shaped connector 34, and the tube 33 inside the air operated valve 30 is formed.
  • a flow path was constructed.
  • the length of the tubes 32, 33 was 300 mm, and the total length of the loop-shaped channel was about 800 mm.
  • K-LAMIC-KS2 manufactured by Kurita Water Industries was used.
  • a flow control valve (4601-F4P, manufactured by Flowell) 37 was installed on the outlet side of the particle counter 36 to adjust the flow rate to about 1 L/min.
  • a PFA tube with an inner diameter of 4 mm was used as each of the above tubes.
  • 60 series (flare joint) manufactured by Flowell was used as a connector.
  • Air-operated valves, PFA tubes, and connectors were chemically cleaned (passed with 40 mg/L choline hydroxide solution for 2 hours) and rinsed (passed with ultrapure water for 2 hours) in advance.
  • the order of measurement of the number of fine particles is as follows: first UF membrane-treated water (S1) ⁇ second UF membrane-treated water (S2) ⁇ third UF membrane-treated water (S3) ⁇ use point feed (S4) ⁇ sub-pump outlet ( The order of S5) was repeated, and the measurement was repeated.
  • the valves V1 to V5 of the air operated valve 30 were switched at intervals of 2 hours, and the number of particles measured by the on-line particle counter 36 was continuously and repeatedly measured at intervals of 20 minutes.
  • Fig. 5 shows the measurement results.
  • the solid line shows the results of measuring the number of fine particles (>0.05 ⁇ m fine particles) every 20 minutes. indicated by .
  • the number of fine particles was >100 cells/mL were repeatedly confirmed.
  • the water quality measuring device of the present invention even when there are water sampling points where the number of fine particles differs by a factor of 100 or more, the measurement results at other water sampling points are not affected. It was observed that levels of ⁇ 1 particle/mL of particles less than 0.05 ⁇ m could be monitored.
  • Example 2 Twenty UF membrane modules were installed in parallel, four air operated valves (five manifold type switching valves) 30 were connected in series as shown in FIG. 4, and each of the twenty UF membrane modules The same method as in Example 1 was performed except that water sampling points S1 to S20 were provided in the outflow part and the filtered water of each UF membrane module was connected to the four air operated valves 30 so that the water was measured. A fine particle count was performed.
  • the number of fine particles in the filtered water from S1 to S20 was measured sequentially to make one cycle, and the number of fine particles was measured for 6 cycles. The results are shown in FIG.
  • the bar graph shows the average value of the measurement results of 1 to 6 cycles
  • the upper end of the error bar shows the maximum value of the measurement results of 1 to 6 cycles
  • the lower end shows the minimum value
  • the measurement result of each cycle was taken as the average value after the number of fine particles was measured six times for 20 minutes during the two-hour switching interval of the water sampling points, and the maximum value was discarded.

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Abstract

The present invention addresses the problem of providing a water quality measurement device which makes it possible to avoid a decline in measurement accuracy due to the target water being still, to prevent a decline in ultrapure water production efficiency caused by an increase in the blow water amount, and to avoid complicating the periphery of the measurement device. A valve 10V is opened for a prescribed time period, collected water from a pipe 1 downstream from a pump 2 flows into a water quality measurement apparatus via a pipe 10, a loop-shaped pipe 20, and a measurement pipe 21, and the water quality of the water to be treated is measured. Thereafter, the valve 10V is closed, the valve 11V is opened for a prescribed time period, and the water quality of filtered water which has passed through a UF membrane module 4b is measured. The valves 12V, 13V, 14V are sequentially opened for a prescribed time period, and the water quality of the filtered water from the UF membrane filter 4c, the combined filtered water and the water to be treated is measured. The steps described above constitute one cycle, which is repeated.

Description

水質測定装置Water quality measuring device
 本発明は、純水、超純水などの水質を測定する水質測定装置に関し、特に複数の採水点から採水した水を1台の水質測定器で水質測定する水質測定装置に関する。本発明は、特に、純水、超純水中に極少量含まれる微粒子数を測定する場合に好適な水質測定装置に関する。 The present invention relates to a water quality measuring device for measuring the quality of pure water, ultrapure water, etc., and more particularly to a water quality measuring device for measuring the quality of water sampled from multiple water sampling points with a single water quality measuring device. The present invention particularly relates to a water quality measuring apparatus suitable for measuring the number of fine particles contained in pure water or ultrapure water.
 半導体洗浄用水として用いられている超純水は、前処理システム、一次純水製造装置、サブシステム(二次純水製造装置)から構成される超純水製造装置で原水(工業用水、市水、井水等)を処理することにより製造される。 The ultrapure water used for cleaning semiconductors is produced by an ultrapure water production system consisting of a pretreatment system, a primary pure water production system, and a subsystem (secondary pure water production system). , well water, etc.).
 サブシステムは、サブタンク、ポンプ、熱交換器、低圧紫外線酸化装置(UV装置)、イオン交換装置及び限外濾過膜(UF膜)分離装置等を備えている。 The subsystem includes a sub-tank, pump, heat exchanger, low-pressure ultraviolet oxidation device (UV device), ion exchange device and ultrafiltration membrane (UF membrane) separation device.
 低圧紫外線酸化装置では、低圧紫外線ランプより出される185nmの紫外線によりTOCを有機酸、さらにはCOまで分解する。分解により生成した有機物及びCOは後段のイオン交換装置で除去される。限外濾過膜分離装置では、微粒子が除去され、イオン交換樹脂からの流出粒子も除去される。このようにして製造された超純水がユースポイントに送水される。 In the low-pressure ultraviolet oxidizer, TOC is decomposed into organic acids and further CO 2 by ultraviolet rays of 185 nm emitted from a low-pressure ultraviolet lamp. Organic matter and CO 2 produced by the decomposition are removed in the subsequent ion exchange unit. The ultrafiltration membrane separation device removes fine particles and also removes effluent particles from the ion exchange resin. The ultrapure water thus produced is delivered to the point of use.
 純水、超純水は、半導体などの電子部品を製造する工程において、洗浄水やリンス水として使用されている。半導体集積回路の微細化に伴い、超純水に対しては、水中の不純物量(濃度)の更なる低減や、より厳密な水質管理が求められている。 Pure water and ultrapure water are used as cleaning and rinsing water in the process of manufacturing electronic components such as semiconductors. With the miniaturization of semiconductor integrated circuits, ultrapure water is required to further reduce the amount (concentration) of impurities in water and to manage water quality more strictly.
 微粒子数は超純水の水質管理項目の1つで、粒径数十nmの微粒子を<1個/mLのオーダーで管理することが求められている。 The number of fine particles is one of the water quality control items for ultrapure water, and it is required to manage fine particles with a particle size of several tens of nanometers on the order of <1/mL.
 上記の通り、超純水製造装置では、超純水中の微粒子数を低減するために、粒径数十nmの微粒子を高い除去率で除去することができ、また膜自体からの微粒子発塵や溶出がないように留意して製造された特別なUF膜が用いられる。 As described above, in the ultrapure water production equipment, in order to reduce the number of microparticles in the ultrapure water, microparticles with a particle size of several tens of nanometers can be removed at a high removal rate. Special UF membranes are used that are manufactured with care to prevent contamination and elution.
 現在この分野で使用されているUF膜は、1モジュール(1本)当たり、10m/h程度を処理できるものが一般的である。すなわち、100m/hの超純水を必要とする設備では、上述のUF膜モジュール10モジュール前後で並列処理することとなる。 UF membranes currently used in this field are generally capable of processing about 10 m 3 /h per module (one piece). That is, in a facility that requires 100 m 3 /h of ultrapure water, parallel processing is performed around the above-described 10 UF membrane modules.
 複数のモジュールで並列処理する際のメリットとしては、1つのモジュールで問題が発生したときに当該モジュールを切り離すことで正常な水質を維持できることが挙げられる。例えば、100m/hの超純水を製造するに際し、10m/hの処理水を製造できるUF膜モジュールを11モジュール並設し、1つのUF膜モジュールを切り離しても100m/hを十分供給できる構成としておけば、1つのUF膜モジュールで問題(例えば中空糸膜が破断し処理水の微粒子数が増加する等)が発生した場合にも、この1つのUF膜モジュールを切り離すことで、超純水の水質を維持し、100m/hの処理水流量も維持できる。 An advantage of parallel processing with a plurality of modules is that normal water quality can be maintained by disconnecting the module when a problem occurs in one module. For example, when producing 100 m 3 /h of ultrapure water, 11 UF membrane modules capable of producing 10 m 3 /h of treated water are installed in parallel, and even if one UF membrane module is separated, 100 m 3 /h is sufficient. If it is configured to be able to supply, even if a problem occurs in one UF membrane module (for example, the hollow fiber membrane breaks and the number of fine particles in the treated water increases, etc.), by separating this one UF membrane module, The water quality of ultrapure water can be maintained, and a treated water flow rate of 100 m 3 /h can also be maintained.
 また、複数のモジュールで並列処理する際のメリットとして、モジュール交換後の初期の溶出成分に起因した超純水の水質悪化を最小化できることも挙げられる。即ち、並列設置された複数のモジュールのすべてを同時に交換するのではなく、一部のモジュールを交換する場合には、初期溶出に起因した超純水水質の悪化の程度を小さくすることができる。 Another advantage of parallel processing with multiple modules is that it is possible to minimize deterioration of ultrapure water quality caused by initial elution components after module replacement. That is, if some of the modules installed in parallel are not replaced at the same time, but some of the modules are replaced, the deterioration of the ultrapure water quality caused by the initial elution can be reduced.
 複数のUF膜モジュールで並列処理する濾過システムにおいて、あるUF膜モジュールにおいて中空糸膜の破断などの問題が発生し、濾過水中の微粒子数が増加した場合、どのモジュールで問題が発生しているか特定するために、それぞれのUF膜モジュールに微粒子モニタを設置し常時監視するのでは、微粒子モニタの数が多くなり、コストが嵩む。 In a filtration system that performs parallel processing with multiple UF membrane modules, if a problem such as hollow fiber membrane breakage occurs in a certain UF membrane module and the number of fine particles in the filtered water increases, identify which module is causing the problem. Therefore, if a particle monitor is installed in each UF membrane module for constant monitoring, the number of particle monitors increases and the cost increases.
 複数のラインを流れる水を分取用のバルブを介して共通の測定装置に導入して水質を測定することは従来より行われている。例えば、特許文献1では、超純水ラインからの超純水と、この超純水を逆浸透膜分離装置で濃縮した濃縮水とを、バルブで切り替えて共通の測定装置に導入して分析することが記載されている。分析項目としては、金属イオン濃度、抵抗率、微粒子数、TOC濃度、シリカ濃度、溶存酸素濃度が例示されている(0049段落)。  Conventionally, the water quality is measured by introducing water flowing through multiple lines into a common measuring device via a preparative valve. For example, in Patent Document 1, ultrapure water from an ultrapure water line and concentrated water obtained by concentrating this ultrapure water with a reverse osmosis membrane separation device are switched by a valve and introduced into a common measurement device for analysis. is stated. Examples of analysis items include metal ion concentration, resistivity, number of fine particles, TOC concentration, silica concentration, and dissolved oxygen concentration (paragraph 0049).
 複数箇所の対象水を切換弁で流路を切り換え、共通の測定装置に順次導入して水質を測定する場合、流路に滞留していた水が混入すると測定精度の低下が懸念される。 When measuring the water quality by switching the flow path of the target water at multiple locations with a switching valve and sequentially introducing it into a common measurement device, there is a concern that the measurement accuracy will decrease if water that has accumulated in the flow path is mixed.
 特許文献2には、ブローラインを設け、常時ブローを行うことで対象水の滞留を避け、測定精度を保つ方法が記載されている。 Patent Document 2 describes a method of maintaining measurement accuracy by providing a blow line and constantly blowing to avoid stagnation of target water.
特開2010-44022号公報JP 2010-44022 A 特開2014-185904号公報JP 2014-185904 A
 特許文献2のように常時ブローする場合、対象の箇所が多くなればなるほどブローラインの数が多くなって測定装置周りが煩雑となるだけでなく、ブロー水量(系外に排出される水量)も多くなることから、超純水製造効率の低下に繋がる。全体のブロー水量を少なくするために個々のブロー水量を小さくすれば効率の低下は抑えられるが、測定装置周りの煩雑さの改善には繋がらない。 In the case of constant blowing as in Patent Document 2, the more parts to be measured, the greater the number of blow lines and the more complicated the surroundings of the measuring device. This increases the efficiency of ultrapure water production. If individual blow water amounts are reduced in order to reduce the overall blow water amount, the decrease in efficiency can be suppressed, but this does not lead to improvement in complexity around the measuring device.
 本発明は、対象水の滞留に起因する測定精度の低下を回避し、またブロー水量の増大による超純水製造効率の低下が防止されるとともに、測定装置周りが煩雑となることも回避することができる水質測定装置を提供することを課題とする。 The present invention avoids deterioration in measurement accuracy due to retention of target water, prevents deterioration in ultrapure water production efficiency due to an increase in the amount of blow water, and also avoids complication around the measurement device. An object of the present invention is to provide a water quality measuring device capable of
 本発明の水質測定装置は、複数の採水点から採水配管を介して採水した水質測定対象水を共通の水質測定器に導入して水質を測定する水質測定装置において、各採水配管の下流端が連なるループ状流路と、該ループ状流路と前記水質測定器とを接続する測定配管と、
各採水配管に設けられた採水弁とを有することを特徴とする。
The water quality measuring device of the present invention is a water quality measuring device for measuring the water quality by introducing water to be measured for water quality sampled from a plurality of water sampling points via water sampling pipes into a common water quality measuring device, wherein each water sampling pipe a loop-shaped flow channel in which the downstream end of
and a water sampling valve provided in each water sampling pipe.
 本発明の一態様では、前記水質測定器は微粒子数測定器である。 In one aspect of the present invention, the water quality measuring instrument is a fine particle counting instrument.
 本発明の一態様では、前記採水配管がn個(nは2以上の整数)設けられ、第1ないし第nの採水配管の下流端がこの順に前記ループ状流路に連なっており、第1の採水配管のループ状流路への接続点から前記供給配管の接続点までの距離と、第nの採水配管のループ状流路への接続点から前記供給配管の接続点までの距離とが略同一である。 In one aspect of the present invention, n water sampling pipes (n is an integer of 2 or more) are provided, and the downstream ends of the first to n-th water sampling pipes are connected in this order to the loop-shaped flow path, The distance from the connection point of the first water sampling pipe to the loop-shaped channel to the connection point of the supply pipe, and the distance from the connection point of the n-th water sampling pipe to the loop-shaped channel to the connection point of the supply pipe is substantially the same as the distance of
 本発明の一態様では、前記水質測定器からの流出水が流れる排出配管が設けられており、該排出配管に流量調整弁が設けられている。 In one aspect of the present invention, a discharge pipe through which the outflow water from the water quality measuring instrument flows is provided, and the discharge pipe is provided with a flow control valve.
 本発明の一態様では、前記採水弁を所定の順番で所定時間開とするよう制御する制御手段を有する。 An aspect of the present invention includes control means for controlling the water sampling valves to be opened in a predetermined order for a predetermined period of time.
 本発明の膜濾過システムは、並列設置された膜モジュールと、共通の給水配管及びそれから分岐した分岐配管を介して各膜モジュールに被処理水を供給する供給手段と、各膜モジュールの処理水が合流する合流配管とを有する膜濾過システムにおいて、本発明の水質測定装置を備えており、該水質測定装置は、少なくとも各膜モジュールの処理水を測定対象とするように設置されている。 The membrane filtration system of the present invention comprises membrane modules installed in parallel, supply means for supplying water to be treated to each membrane module through a common water supply pipe and branch pipes branched from it, and treated water from each membrane module. A membrane filtration system having a confluence pipe is provided with the water quality measuring device of the present invention, and the water quality measuring device is installed so as to measure at least the treated water of each membrane module.
 本発明の膜濾過システムの一態様では、前記水質測定装置は、さらに前記共通の給水配管を流れる被処理水と、前記合流配管を流れる合流処理水を測定対象とするように設置されている。 In one aspect of the membrane filtration system of the present invention, the water quality measuring device is further installed so as to measure the water to be treated flowing through the common water supply pipe and the combined treated water flowing through the combined pipe.
 本発明の水質測定装置によれば、採水点から採水弁までの流路には、水質測定時(採水弁が開き水質測定器に通水しているとき)以外は採取した水が滞留することとなるが、採水弁から下流の水質測定器に至る共用の流路においては、ループ状流路に双方向に常に水が流れるため、水が滞留することがなく、前回の測定対象水の残留や、測定対象水の混和の影響を最小限とすることができ、精度の高い水質測定値を得ることができる。 According to the water quality measuring device of the present invention, the flow path from the water sampling point to the water sampling valve contains sampled water except during water quality measurement (when the water sampling valve is open and water is flowing through the water quality measuring instrument). However, in the common flow path from the water sampling valve to the downstream water quality measuring instrument, water always flows in both directions in the looped flow path, so water does not stagnate and the previous measurement It is possible to minimize the influence of residual target water and mixing of target water, and to obtain highly accurate water quality measurement values.
 本発明の水質測定装置によれば、系外に排出される水量は水質測定中の1箇所分であり、少ない。また、測定装置周りの配管類も少ない。採水点が多数(例えば20以上)となる場合、この排出水量と測定装置周り配管の削減効果は非常に大きい。 According to the water quality measuring device of the present invention, the amount of water discharged to the outside of the system is the amount of one point during water quality measurement, which is small. In addition, there are few pipes around the measuring device. When there are many water sampling points (for example, 20 or more), the effect of reducing the amount of discharged water and piping around the measuring device is very large.
実施の形態に係る水質測定装置を備えた膜濾過システムの構成図であり、図1(a)は濾過部の構成を示し、図1(b)は水質測定部の構成を示している。BRIEF DESCRIPTION OF THE DRAWINGS It is a block diagram of the membrane filtration system provided with the water-quality-measurement apparatus which concerns on embodiment, Fig.1 (a) shows the structure of a filtration part, FIG.1(b) has shown the structure of a water-quality measurement part. サブシステムの構成図である。4 is a configuration diagram of a subsystem; FIG. 実施の形態に係る水質測定装置の構成図である。1 is a configuration diagram of a water quality measuring device according to an embodiment; FIG. 実施の形態に係る水質測定装置の構成図である。1 is a configuration diagram of a water quality measuring device according to an embodiment; FIG. 実験結果を示すグラフである。It is a graph which shows an experimental result. 実験結果を示すグラフである。It is a graph which shows an experimental result.
 以下、図1を参照して実施の形態について説明する。図1は実施の形態に係る水質測定装置を備えた膜濾過システムの構成図であり、図1(a)は濾過部の構成を示し、図1(b)は水質測定部の構成を示している。 An embodiment will be described below with reference to FIG. FIG. 1 is a configuration diagram of a membrane filtration system equipped with a water quality measuring device according to an embodiment, FIG. 1(a) showing the configuration of the filtering section, and FIG. 1(b) showing the configuration of the water quality measuring section. there is
 この実施の形態では、濾過部に3台のUF膜(限外濾過膜)モジュール4a,4b,4cが設置されているが、2台又は4台以上であってもよい。 In this embodiment, three UF membrane (ultrafiltration membrane) modules 4a, 4b, and 4c are installed in the filtration unit, but it may be two or four or more.
 サブシステム(2次純水装置)のイオン交換器流出水などよりなる被処理水は、ポンプ2を有する配管1から分岐配管3a,3b,3cを介して各UFモジュール4a~4cに送水可能とされている。UF膜モジュール4a~4cのUF膜を透過した濾過水は、濾過水配管5a,5b,5cから合流配管6に流れ、濾過水として取り出される。 The water to be treated, such as ion exchanger effluent of the subsystem (secondary pure water device), can be sent from a pipe 1 having a pump 2 to each UF module 4a to 4c via branch pipes 3a, 3b, and 3c. It is Filtrated water that has passed through the UF membranes of the UF membrane modules 4a to 4c flows from the filtered water pipes 5a, 5b, and 5c to the combined pipe 6 and is taken out as filtered water.
 ポンプ2の下流側の配管1、各濾過水配管5a,5b,5c及び合流配管6にそれぞれ採水点が設定されており、これらの5か所の採水点からそれぞれ採水用(試料水分取用)の採水配管10~14が分岐している。 Water sampling points are set in the pipe 1 on the downstream side of the pump 2, the filtered water pipes 5a, 5b, 5c, and the confluence pipe 6, respectively. Intake) water sampling pipes 10 to 14 are branched.
 図1(b)の通り、各採水配管10~14の末端はループ状配管20に接続されている。各採水配管10~14の途中に採水弁として開閉弁よりなるバルブ10V,11V,12V,13V,14Vが設けられている。 As shown in FIG. 1(b), the ends of each of the water sampling pipes 10 to 14 are connected to a looped pipe 20. Valves 10V, 11V, 12V, 13V, and 14V consisting of on-off valves are provided as water sampling valves in the middle of each of the water sampling pipes 10-14.
 ループ状配管20は、この実施の形態では略円環形であり、円の中心を挟んで一半側に採水配管10~14の末端が接続されている。採水配管10~14のループ状配管20への接続点は、円の周回方向に等間隔であることが好ましい。周回方向一端側の採水配管10のループ状配管20への接続点から他端側採水配管14の接続点までの距離は、ループ状配管20の周回方向の全長の10~80%特に20~50%程度であることが好ましい。 In this embodiment, the loop-shaped pipe 20 has a substantially annular shape, and ends of the water sampling pipes 10 to 14 are connected to one half of the circle with the center of the circle interposed therebetween. Connection points of the water sampling pipes 10 to 14 to the looped pipe 20 are preferably equidistant in the circumferential direction of the circle. The distance from the connection point of the water sampling pipe 10 on the one end side in the winding direction to the connection point of the water sampling pipe 14 on the other end side is 10 to 80%, especially 20%, of the total length of the looped pipe 20 in the winding direction. It is preferably about 50%.
 周回方向一端側の採水配管10末端の接続点と周回方向他端側の採水配管14末端の接続点との周回方向の中間(この実施の形態では採水配管12末端の接続点)と円の中心を挟んで反対側に測定配管21が接続されている。ループ状配管20を流れる水は、この測定配管21を通って水質測定器22に導入され、水質測定される。測定排水は、流量調整弁24を有する排出配管23を介して系外に排出される。 midway in the circulation direction between the connection point at the end of the water sampling pipe 10 on the one end side in the rotation direction and the connection point at the end of the water sampling pipe 14 on the other end side in the rotation direction (in this embodiment, the connection point at the end of the water sampling pipe 12); A measurement pipe 21 is connected on the opposite side across the center of the circle. Water flowing through the looped pipe 20 is introduced into the water quality measuring instrument 22 through the measuring pipe 21, and the water quality is measured. The measured waste water is discharged outside the system through a discharge pipe 23 having a flow control valve 24 .
 水質測定器22として、この実施の形態では微粒子計が用いられているが、TOC計やナトリウム計等の各種オンライン水質計器を用いることもできる。 Although a particle meter is used as the water quality measuring instrument 22 in this embodiment, various online water quality instruments such as a TOC meter and a sodium meter can also be used.
 各バルブ10V~14Vの開閉は、制御器によって自動的に行われる。  The opening and closing of each valve 10V to 14V is automatically performed by the controller.
 採水配管10とループ状配管20との接続点から測定配管21の接続点までの距離(周回方向の短い方の距離)を100%とした場合、採水配管14とループ状配管20との接続点から測定配管21の接続点までの距離(周回方向の短い方の距離)は10~45%特に25~40%であることが好ましいが、これに限定されない。 When the distance from the connection point between the water sampling pipe 10 and the loop-shaped pipe 20 to the connection point of the measurement pipe 21 (shorter distance in the winding direction) is 100%, the distance between the water sampling pipe 14 and the loop-shaped pipe 20 is 100%. The distance from the connection point to the connection point of the measurement pipe 21 (shorter distance in the winding direction) is preferably 10 to 45%, particularly 25 to 40%, but is not limited to this.
 このように構成された膜濾過システムにおいて、被処理水は、配管1から配管3a~3cに分流し、各UF膜モジュール4a~4cで膜濾過され、濾過水配管5a~5cを通って合流配管6にて合流し、濾過水として取り出され、次工程やユースポイントに送水される。 In the membrane filtration system configured as described above, the water to be treated is branched from the pipe 1 to the pipes 3a to 3c, membrane-filtered by each of the UF membrane modules 4a to 4c, and passed through the filtered water pipes 5a to 5c to join the pipes. It merges at 6, is taken out as filtered water, and is sent to the next process or point of use.
 各配管1,5a,5b,5c,6を流れる水を順番に又は特定順序で採水し、水質測定を行う。 The water flowing through each pipe 1, 5a, 5b, 5c, 6 is sampled in order or in a specific order, and the water quality is measured.
 この実施の形態の一例では、まず、バルブ10Vを所定時間開とし、ポンプ2の下流側の配管1からの採水を配管10、ループ状20、配管21を経て水質測定器22に流入させ、水質測定を行う。その後、バルブ10Vを閉とし、バルブ11Vを所定時間開とする。これにより、濾過水配管5aからUF膜モジュール4aの濾過水の一部が分取され、配管11、ループ状配管20、配管21を介して水質測定器22に流入し、UF膜モジュール4aの濾過水の水質が測定される。 In one example of this embodiment, first, the valve 10V is opened for a predetermined period of time, and the water sampled from the pipe 1 on the downstream side of the pump 2 is allowed to flow into the water quality measuring instrument 22 through the pipe 10, the loop 20, and the pipe 21, Take water quality measurements. After that, the valve 10V is closed and the valve 11V is opened for a predetermined time. As a result, part of the filtered water from the UF membrane module 4a is separated from the filtered water pipe 5a, flows into the water quality measuring instrument 22 via the pipe 11, the looped pipe 20, and the pipe 21, and is filtered by the UF membrane module 4a. Water quality is measured.
 その後、バルブ11Vを閉とし、バルブ12Vを所定時間開とし、UF膜モジュール4bの濾過水の水質測定を行う。以下、同様にしてUF膜モジュール4cの濾過水の水質測定及び合流濾過水の水質測定を行う。以上を1サイクルとし、これを繰り返すことにより、被処理水、各UF膜モジュール濾過水及び合流濾過水の水質測定を順番に行う。なお、測定の順番はこれに限定されるものではなく、適宜入れ替えてもよく、後述のように特定の採水点の測定頻度を多くするようにしてもよい。 After that, the valve 11V is closed, the valve 12V is opened for a predetermined time, and the water quality of the filtered water from the UF membrane module 4b is measured. Thereafter, the water quality measurement of the filtered water of the UF membrane module 4c and the water quality measurement of the combined filtered water are performed in the same manner. By repeating the above process as one cycle, the quality of the water to be treated, the filtered water from each UF membrane module, and the combined filtered water are sequentially measured. The order of measurement is not limited to this, and may be changed as appropriate, or the frequency of measurement at a specific water sampling point may be increased as described later.
 この水質測定装置を用いた水質測定方法によると、採水配管10~14のいずれかからループ状配管20に流入した水は、周回方向の一方向(図1(b)の時計回り方向)と他方向(図1(b)の反時計回り方向)との双方向に流れて測定配管21に到達し、水質測定器22に導入される。 According to the water quality measuring method using this water quality measuring device, the water flowing into the loop-shaped pipe 20 from any of the water sampling pipes 10 to 14 flows in one direction (clockwise direction in FIG. 1(b)) and It flows in both the other direction (counterclockwise direction in FIG. 1( b )), reaches the measurement pipe 21 , and is introduced into the water quality measuring instrument 22 .
 1つの採水配管(例えば採水配管12)からループ状配管20に流入した水がループ状配管20を双方向に流れるので、ループ状配管20内に残っていた前番の測定時の水(この場合、採水配管11からの水)は速やかに全量が配管23へ押し出され、前番の採水が混和していない今回採水の水質測定を行うことができるので、測定精度が高くなり、しかも測定に要する時間を短縮することができる。 Since the water flowing into the looped pipe 20 from one water sampling pipe (for example, the water sampling pipe 12) flows in both directions through the looped pipe 20, the water remaining in the looped pipe 20 at the time of the previous measurement ( In this case, the entire amount of the water from the water sampling pipe 11 is quickly pushed out to the pipe 23, and the water quality of the water sampled this time, which is not mixed with the previous water sample, can be measured. Moreover, the time required for measurement can be shortened.
 1つの採水配管(例えば採水配管12)からの採水の水質測定が終了し、次番の採水(この場合、採水配管13からの採水)の水質測定に切り替えられると、採水配管12内には、採水が滞留するが、ループ状配管20には水が滞留しないので、次番採水への混和は切り換え後、短時間で解消する。 When the water quality measurement of the water sampled from one water sampling pipe (for example, the water sampling pipe 12) is completed and the water quality measurement of the next water sampling (in this case, the water sampling from the water sampling pipe 13) is switched to, the sampling is started. Water remains in the water pipe 12, but water does not stay in the looped pipe 20, so the mixing in the next water sample is eliminated in a short time after switching.
 この水質測定装置では、水質測定排水量は、水質測定している1つの採水配管からの採水量のみであり、少量である。 With this water quality measurement device, the amount of water quality measurement wastewater is only the amount of water sampled from one water sampling pipe that is measuring water quality, and is a small amount.
 本発明の水質測定装置では、ループ状流路20は、距離の影響で片流れしたりすることのない様に、また1つ前の測定時の測定対象水を速やかに押し出すために、通液したい流量とその流量条件で発生する流路差圧とを考慮し設計することが好ましい。より具体的には、一般的な平滑表面の流路配管を用いる場合、線速度として0.3~2.0m/秒程度となる流路配管の構成とすることが好ましい。 In the water quality measuring apparatus of the present invention, the loop-shaped flow path 20 is designed to pass liquid so as not to flow in one direction due to the influence of the distance, and to quickly push out the water to be measured at the time of the previous measurement. It is preferable to design in consideration of the flow rate and the channel differential pressure generated under the flow rate conditions. More specifically, in the case of using a common smooth-surface flow path pipe, it is preferable to configure the flow path pipe so that the linear velocity is about 0.3 to 2.0 m/sec.
 本発明の水質測定装置を用いた水質測定方法においては、バルブ10V~14Vの切り換え後、所定時間の間は水質測定器22のデータを棄却することが好ましい。これは、バルブが切り替わる際には、バルブが動作することに起因した発塵や溶出が起こることがあるためである。これらの影響による水質の変化は、本来監視したい水質の変化ではないため、バルブの切り換え後の所定時間のデータを棄却することにより、水質測定結果の精度を向上させることができる。 In the water quality measuring method using the water quality measuring device of the present invention, it is preferable to discard the data of the water quality measuring device 22 for a predetermined period of time after switching the valves 10V to 14V. This is because when the valve is switched, dust generation and elution may occur due to the operation of the valve. Since changes in water quality due to these influences are not changes in water quality that should be monitored, the accuracy of water quality measurement results can be improved by rejecting data for a predetermined period of time after switching the valve.
 また、監視対象の水質が微粒子数であり、水質測定器がレーザー光散乱方式の微粒子計である場合には、上述の所定時間、レーザーを消灯し水質測定を休止することが好ましい。水質測定を休止することで、高価なレーザー光源の見かけ寿命(測定休止期間を含む使用期間)を延ばすことができ、メンテナンスコストを低減できる。 In addition, when the water quality to be monitored is the number of fine particles and the water quality measuring device is a laser light scattering type fine particle meter, it is preferable to turn off the laser and suspend the water quality measurement for the above-mentioned predetermined time. By suspending water quality measurement, it is possible to extend the apparent life of the expensive laser light source (period of use including the period of suspension of measurement) and reduce maintenance costs.
 本発明の水質測定装置を用いた水質測定方法においては、得られる水質測定結果を平均化して取り扱うことが好ましい。即ち、上述の通り、バルブの開閉動作に起因した水質変動の影響を避けるために、バルブ切替後の所定時間のデータを棄却しても、影響する時間は必ずしも明確ではないため、所定時間を経過後も影響が残っている可能性はある。そこで、所定時間後から次の切り換え時までに得られた複数のデータを平均化して取り扱うことで、この影響を平準化又は最小化することができ、測定結果の信頼度が向上する。 In the water quality measurement method using the water quality measurement device of the present invention, it is preferable to average the obtained water quality measurement results. That is, as described above, in order to avoid the influence of water quality fluctuations caused by the opening and closing operation of the valve, even if the data for the predetermined time after the valve switching is discarded, the influence time is not necessarily clear, so the predetermined time has passed. It is possible that there are still repercussions. Therefore, by averaging and handling a plurality of data obtained after a predetermined period of time until the next switching, this influence can be leveled or minimized, and the reliability of the measurement result is improved.
 本発明の水質測定装置にあっては、水質測定結果の良否を判断する機能と自動弁などを利用して流路を切り換える機能とを併用して、水質測定結果に基づき(水質測定結果が不良と判断された場合)該当する水処理機器を自動的に切り離す機構を付帯してもよい。 In the water quality measuring device of the present invention, the function of judging whether the water quality measurement result is good or bad and the function of switching the flow path using an automatic valve or the like are used together, and based on the water quality measurement result If it is determined that the water treatment equipment is
 このような機構の具体的な構成としては、複数のUF膜モジュールの濾過水中の微粒子数を、オンライン微粒子モニタにて測定し、あらかじめ規定した微粒子数を超過した場合には、該当するUF膜モジュールの給水、処理水、濃縮水配管に設置された全て、またはいずれかの自動弁を閉止し、超純水の水質悪化を回避する構成が挙げられる。 As a specific configuration of such a mechanism, the number of fine particles in the filtered water of a plurality of UF membrane modules is measured by an online fine particle monitor, and when the number of fine particles exceeds a predetermined number, the corresponding UF membrane module All or any of the automatic valves installed in the water supply, treated water, and concentrated water pipes are closed to avoid deterioration of the ultrapure water quality.
 本発明の水質測定装置を用いた水質測定方法において、流量や系内の圧力を調整したい場合には、水質測定器22の下流側に圧力計や流量計(図示なし)、流量調整弁24を配置し、圧力や流量を適宜調整することが好ましい。水質測定器の下流側にこれら機器を設置することで、所定の流量や圧力への調整が可能になるとともに、流量調整弁24の操作に起因する発塵の影響や、圧力計や流量計内部の滞留部の影響を回避することができる。 In the water quality measuring method using the water quality measuring device of the present invention, if it is desired to adjust the flow rate or the pressure in the system, a pressure gauge, a flow meter (not shown), and a flow control valve 24 are provided downstream of the water quality measuring instrument 22. It is preferable to dispose and appropriately adjust the pressure and flow rate. By installing these devices on the downstream side of the water quality measuring instrument, it is possible to adjust the flow rate and pressure to a predetermined level, and the influence of dust generation due to the operation of the flow control valve 24 and the inside of the pressure gauge and flow meter can avoid the influence of the stagnant part.
 また、水質測定器の下流に設置した流量調整弁24の開度を絞り、水質測定器に背圧がかかる条件としてもよい。これにより、溶存ガス成分が減圧されたときに気泡化して微粒子として誤検知されることを回避でき、測定精度の向上に繋がる。 Alternatively, the opening of the flow control valve 24 installed downstream of the water quality measuring instrument may be throttled to apply back pressure to the water quality measuring instrument. As a result, when the dissolved gas component is decompressed, it can be prevented from forming bubbles and being erroneously detected as fine particles, leading to an improvement in measurement accuracy.
 本実施の形態では、複数のUF膜モジュールの処理水だけでなく、合流水や、給水の水質を併せて測定している。そのため、例えば、従来は1台のオンライン微粒子モニタで合流水のみを監視していた設備において、本発明の構成を採用することにより、1台のオンライン微粒子モニタで、複数の水処理機器の処理水を監視するとともに、従来通りの合流水の監視もできる。また、給水の監視も行うことにより、微粒子数が増加する様な有事の際に、給水の微粒子数の変化も即時確認できるので、微粒子数増加原因の絞り込みに要する時間を短縮できる。 In this embodiment, not only the treated water from multiple UF membrane modules, but also the combined water and water quality of the feed water are measured. Therefore, for example, in a facility that conventionally monitors only combined water with one online particle monitor, by adopting the configuration of the present invention, one online particle monitor can be used to monitor the treated water of a plurality of water treatment equipment. can be monitored as well as confluence water can be monitored as before. In addition, by monitoring the water supply, in the event of an emergency such as an increase in the number of particles, changes in the number of particles in the water supply can be immediately confirmed, so the time required to narrow down the cause of the increase in the number of particles can be shortened.
 本発明の水質測定装置では、UF膜モジュール等の水処理機器の個数が多数の場合、合流水の測定間隔が過度に長くなる懸念がある。この様な場合には、合流水の測定回数を増やす構成とすることで改善できる。例えば、10台のUF膜モジュールA~Jが並列設置されており、各モジュールの濾過水W1~W10と合流水WMの合計11種の水質を測定する場合には、各濾過水W1~W10の測定の間にそれぞれ合流水WMの測定を介在させるようにしてもよい。即ち、測定対象とする水の順番をW1→WM→W2→WM→W3→WM→…→W9→WM→W10→WMの順番を1サイクルとし、これらを繰り返す。 With the water quality measuring device of the present invention, if there are a large number of water treatment devices such as UF membrane modules, there is a concern that the interval between measurements of combined water will become excessively long. In such a case, it can be improved by increasing the number of times the combined water is measured. For example, 10 UF membrane modules A to J are installed in parallel, and when measuring a total of 11 types of water quality of filtered water W1 to W10 of each module and combined water WM, each filtered water W1 to W10 Measurement of the merged water WM may be interposed between the measurements. That is, the order of water to be measured is W1→WM→W2→WM→W3→WM→ .
 W1~W10の測定を複数のグループに分け、各グループの間にWMの測定を介在させるようにしてもよい。例えば、2グループの場合であれば、W1→W2→W3→W4→W5→WA→W6→W7→W8→W9→W10→WMの順番を1サイクルとし、これを繰り返す。 The W1 to W10 measurements may be divided into a plurality of groups, and the WM measurement may be interposed between each group. For example, in the case of two groups, the order of W1->W2->W3->W4->W5->WA->W6->W7->W8->W9->W10->WM is repeated as one cycle.
 このようにして、一部の測定対象水の測定頻度を他の対象水よりも高くすることができる。 In this way, the measurement frequency of some target water can be made higher than other target water.
[実施例1]
 並列設置された3台のUF膜モジュールを備えた超純水製造用サブシステムに本発明装置を組み込み、UF膜モジュール給水、各UF膜モジュール濾過水及び合流濾過水の微粒子数を測定した。
[Example 1]
The apparatus of the present invention was incorporated into an ultrapure water production subsystem having three UF membrane modules installed in parallel, and the number of fine particles in the UF membrane module feed water, each UF membrane module filtered water, and combined filtered water was measured.
 このサブシステムの全体構成は、図2の通り、サブタンク→サブポンプ→紫外線酸化器(UV)→[アニオン交換樹脂が充填された非再生式のイオン交換装置]→脱気膜→[カチオン交換樹脂とアニオン交換樹脂とが混合充填された非再生式のイオン交換装置]→UF膜モジュール(並列に3台)→ユースポイントの構成であり、UF膜処理水量は約20m/hである。 As shown in Fig. 2, the overall configuration of this subsystem is subtank → subpump → ultraviolet oxidizer (UV) → [non-regenerative ion exchange device filled with anion exchange resin] → degassing membrane → [cation exchange resin and Non-regenerative ion exchange device mixed and filled with anion exchange resin]→UF membrane modules ( three units in parallel)→point of use.
 採水点は、各UF膜モジュール出口S1,S2,S3、ユースポイント送り(UF膜処理水の合流水)S4及びポンプ出口S5の5箇所とした。 There are five water sampling points: UF membrane module outlets S1, S2, and S3, point-of-use feeding (merged water of UF membrane-treated water) S4, and pump outlet S5.
 水質測定システムの採水バルブとして、エア駆動方式の5連マニホールド型の分岐弁(CKD社製の薬液用エアオペレイトバルブGAMDZ3R-6UR-Z05W)を使用した。 As the water sampling valve for the water quality measurement system, an air-driven 5-station manifold type branch valve (CKD's air operated valve for chemical liquids GAMDZ3R-6UR-Z05W) was used.
 図3に模式的に示すように、このエアオペレイトバルブ30は、5個の流入口と2個の流出口とが設けられている。2個の流出口はバルブボディーの両端側に位置している。2個の流出口を結ぶ水路31に対し、各流入口がそれぞれ開閉式のバルブV1~V5を介して臨んでいる。 As schematically shown in FIG. 3, this air operated valve 30 is provided with five inlets and two outlets. Two outlets are located at opposite ends of the valve body. Each inlet faces a water channel 31 connecting two outlets via open/close valves V1 to V5.
 各流入口を採水点S1~S5とチューブによって接続した。水路31の一方の流出口にチューブ32の先端を接続し、他方の流出口にチューブ33の先端を接続した。チューブ32の後端をT字コネクタ34の第1流入口34aに接続し、チューブ33の後端をT字コネクタ34の第2流入口34bに接続した。T字コネクタの流出口34cには、チューブ35を介してオンライン微粒子計36を接続した。 Each inflow port was connected to water sampling points S1 to S5 by a tube. The tip of the tube 32 was connected to one outlet of the water channel 31, and the tip of the tube 33 was connected to the other outlet. The rear end of tube 32 was connected to first inlet 34 a of T-shaped connector 34 , and the rear end of tube 33 was connected to second inlet 34 b of T-shaped connector 34 . An on-line particle counter 36 was connected via a tube 35 to the outlet 34c of the T-shaped connector.
 エアオペレイトバルブ30、チューブ32,33、及びT字コネクタ34を上述のように接続することにより、エアオペレイトバルブ30内部の水路31、チューブ32、T字コネクタ34及びチューブ33よりなるループ状の流路を構成した。チューブ32,33の長さは300mmであり、ループ状流路の全長は約800mmとなった。 By connecting the air operated valve 30, the tubes 32, 33, and the T-shaped connector 34 as described above, a loop-like structure composed of the water passage 31, the tube 32, the T-shaped connector 34, and the tube 33 inside the air operated valve 30 is formed. A flow path was constructed. The length of the tubes 32, 33 was 300 mm, and the total length of the loop-shaped channel was about 800 mm.
 オンライン微粒子計36としては、栗田工業製、K-LAMIC-KS2を用いた。 As the online particle counter 36, K-LAMIC-KS2 manufactured by Kurita Water Industries was used.
 微粒子計36の出口側には流量調整弁(フロウエル社製、4601-F4P)37を設置して、約1L/minで流れるように調整した。 A flow control valve (4601-F4P, manufactured by Flowell) 37 was installed on the outlet side of the particle counter 36 to adjust the flow rate to about 1 L/min.
 上記の各チューブとしてはPFA製、内径4mmのチューブを使用した。コネクタとしてはフロウエル社製60シリーズ(フレア継手)を使用した。 A PFA tube with an inner diameter of 4 mm was used as each of the above tubes. As a connector, 60 series (flare joint) manufactured by Flowell was used.
 エアオペレイトバルブ、PFAチューブ、コネクタは、事前に薬液洗浄(水酸化コリン40mg/L溶液を2時間通液)とリンス(超純水を2時間通液)を行った。 Air-operated valves, PFA tubes, and connectors were chemically cleaned (passed with 40 mg/L choline hydroxide solution for 2 hours) and rinsed (passed with ultrapure water for 2 hours) in advance.
 微粒子数の測定順番は、1本目のUF膜処理水(S1)→2本目のUF膜処理水(S2)→3本目のUF膜処理水(S3)→ユースポイント送り(S4)→サブポンプ出口(S5)の順番とし、繰り返し測定した。エアオペレイトバルブ30のバルブV1~V5の切り換えは2時間間隔とし、オンライン微粒子計36での微粒子数の測定は20分間隔で連続繰り返し測定とした。 The order of measurement of the number of fine particles is as follows: first UF membrane-treated water (S1) → second UF membrane-treated water (S2) → third UF membrane-treated water (S3) → use point feed (S4) → sub-pump outlet ( The order of S5) was repeated, and the measurement was repeated. The valves V1 to V5 of the air operated valve 30 were switched at intervals of 2 hours, and the number of particles measured by the on-line particle counter 36 was continuously and repeatedly measured at intervals of 20 minutes.
 切換間隔2時間(120分)の間に20分毎の微粒子数測定結果6つを取得し、切換時の発塵影響がある1つの結果(最大値の結果)を棄却して、残りの5つの結果の平均値を求め、対象水の微粒子数として取り扱うこととした。 During the switching interval of 2 hours (120 minutes), 6 fine particle count measurement results were acquired every 20 minutes. The average value of the two results was calculated and treated as the number of fine particles in the target water.
 測定結果を図5に示す。20分毎の微粒子数測定結果(>0.05μm微粒子数)を実線で示し、2時間分の測定結果である20分×6つの結果から最大値を棄却して平均値を求めた結果を破線で示す。 Fig. 5 shows the measurement results. The solid line shows the results of measuring the number of fine particles (>0.05 μm fine particles) every 20 minutes. indicated by .
 図5の通り、サブポンプ出口の採水点S5からの採水水質を測定していた8~10時間、18~20時間、28~30時間、38~40時間、48~50時間において、微粒子数>100個/mLが繰り返し確認された。 As shown in FIG. 5, the number of fine particles was >100 cells/mL were repeatedly confirmed.
 また、各UF膜処理水S1~S3とユースポイント送り水S4の水質を測定していた時間には、微粒子数<10個/mLが繰り返し確認された。 In addition, during the time when the water quality of each UF membrane-treated water S1 to S3 and the point-of-use feed water S4 was being measured, the number of fine particles <10/mL was repeatedly confirmed.
 エアオペレイトバルブ30の切り換えタイミングと、微粒子数測定の間隔とが微妙にずれてしまった10~28時間の区間では、20分測定2回分が微粒子数高めの結果となってしまい、最大値1点棄却後の平均値がバラついてしまったが、タイミングを修正した後の30時間以降においては、<1個/mLの安定した結果が繰り返し確認された。 In the interval of 10 to 28 hours when the switching timing of the air operated valve 30 and the interval of fine particle count measurement are slightly different, two 20 minute measurements result in a high fine particle count, and the maximum value is 1. Although the average value after point rejection varied, a stable result of <1 cell/mL was repeatedly confirmed after 30 hours after the timing was corrected.
 以上の結果から、本発明の水質測定装置によれば、微粒子数が100倍以上異なる採水点が含まれる様な場合においても、他の採水点の測定結果に影響することはなく、0.05μm未満の微粒子数<1個/mLのレベルで監視できることが認められた。 From the above results, according to the water quality measuring device of the present invention, even when there are water sampling points where the number of fine particles differs by a factor of 100 or more, the measurement results at other water sampling points are not affected. It was observed that levels of <1 particle/mL of particles less than 0.05 μm could be monitored.
[実施例2]
 20台のUF膜モジュールを並列に設置したこと、図4の通り4台のエアオペレイトバルブ(5連マニホールド型の切換弁)30を直列に接続したこと、及び20個の各UF膜モジュールの流出部に採水点S1~S20を設け、各UF膜モジュールの濾過水を測定対象水とするように4台のエアオペレイトバルブ30に接続したこと以外は、実施例1と同様の方法で微粒子数の測定を行った。
[Example 2]
Twenty UF membrane modules were installed in parallel, four air operated valves (five manifold type switching valves) 30 were connected in series as shown in FIG. 4, and each of the twenty UF membrane modules The same method as in Example 1 was performed except that water sampling points S1 to S20 were provided in the outflow part and the filtered water of each UF membrane module was connected to the four air operated valves 30 so that the water was measured. A fine particle count was performed.
 S1~S20の濾過水を順次に微粒子数測定して1サイクルとし、6サイクルの微粒子数測定を行った。結果を図6示す。 The number of fine particles in the filtered water from S1 to S20 was measured sequentially to make one cycle, and the number of fine particles was measured for 6 cycles. The results are shown in FIG.
 棒グラフは、1~6サイクルの測定結果の平均値を示し、エラーバーの上端は1~6サイクルの測定結果の最大値、下端は最小値を示す。 The bar graph shows the average value of the measurement results of 1 to 6 cycles, the upper end of the error bar shows the maximum value of the measurement results of 1 to 6 cycles, and the lower end shows the minimum value.
 なお、各サイクルの測定結果は、採水点の切り換え間隔である2時間の間に20分間の微粒子数測定を6回行い、最大値を棄却した後の平均値とした。 In addition, the measurement result of each cycle was taken as the average value after the number of fine particles was measured six times for 20 minutes during the two-hour switching interval of the water sampling points, and the maximum value was discarded.
 以上の結果から、採水点が20点となって、各点の水質測定間隔が38時間となる様な条件においても、約0.2個/mL程度のバラツキの範囲で、再現性のある微粒子数測定ができることが確認された。
 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、2021年6月18日付で出願された日本特許出願2021-101691に基づいており、その全体が引用により援用される。
From the above results, even under conditions where there are 20 water sampling points and the water quality measurement interval at each point is 38 hours, reproducibility is achieved within a range of variation of about 0.2 / mL. It was confirmed that the number of fine particles can be measured.
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 spirit and scope of the invention.
This application is based on Japanese Patent Application No. 2021-101691 filed on June 18, 2021, which is incorporated by reference in its entirety.
 4a,4b,4c UF膜モジュール
 10~14 採水配管
 20 ループ状流路
 22 水質測定器
 30 エアオペレイトバルブ
 34 T字コネクタ
 36 オンライン微粒子計

 
4a, 4b, 4c UF membrane module 10-14 Water sampling pipe 20 Loop-shaped channel 22 Water quality measuring instrument 30 Air operated valve 34 T-shaped connector 36 Online particle counter

Claims (7)

  1.  複数の採水点から採水配管を介して採水した水質測定対象水を共通の水質測定器に導入して水質を測定する水質測定装置において、
     各採水配管の下流端が連なるループ状流路と、
     該ループ状流路と前記水質測定器とを接続する測定配管と、
     各採水配管に設けられた採水弁と
    を有することを特徴とする水質測定装置。
    In a water quality measuring device for measuring water quality by introducing water to be measured for water quality sampled from a plurality of water sampling points through water sampling pipes into a common water quality measuring device,
    A loop-shaped channel in which the downstream ends of the water sampling pipes are connected,
    a measurement pipe that connects the loop-shaped channel and the water quality measuring instrument;
    and a water sampling valve provided in each water sampling pipe.
  2.  前記水質測定器は微粒子数測定器であることを特徴とする請求項1の水質測定装置。 The water quality measuring device according to claim 1, wherein the water quality measuring device is a fine particle number measuring device.
  3.  前記採水配管がn個(nは2以上の整数)設けられ、第1ないし第nの採水配管の下流端がこの順に前記ループ状流路に連なっており、
     第1の採水配管のループ状流路への接続点から前記供給配管の接続点までの距離と、第nの採水配管のループ状流路への接続点から前記供給配管の接続点までの距離とが略同一である請求項1又は2の水質測定装置。
    The water sampling pipe is provided with n pieces (n is an integer of 2 or more), and the downstream ends of the first to n-th water sampling pipes are connected to the loop-shaped flow path in this order,
    The distance from the connection point of the first water sampling pipe to the loop-shaped channel to the connection point of the supply pipe, and the distance from the connection point of the n-th water sampling pipe to the loop-shaped channel to the connection point of the supply pipe 3. The water quality measuring device according to claim 1 or 2, wherein the distances between and are substantially the same.
  4.  前記水質測定器からの流出水が流れる排出配管が設けられており、該排出配管に流量調整弁が設けられている請求項1~3のいずれかの水質測定装置。 The water quality measuring device according to any one of claims 1 to 3, wherein a discharge pipe is provided through which the outflow water from the water quality measuring device flows, and the discharge pipe is provided with a flow control valve.
  5.  前記採水弁を所定の順番で所定時間開とするよう制御する制御手段を有する請求項1~4のいずれかの水質測定装置。 The water quality measuring device according to any one of claims 1 to 4, comprising control means for controlling the water sampling valves to be opened in a predetermined order for a predetermined time.
  6.  並列設置された膜モジュールと、
     共通の給水配管及びそれから分岐した分岐配管を介して各膜モジュールに被処理水を供給する供給手段と、
     各膜モジュールの処理水が合流する合流配管と
    を有する膜濾過システムにおいて、
     請求項1~5のいずれかの水質測定装置を備えており、
     該水質測定装置は、少なくとも各膜モジュールの処理水を測定対象とするように設置されている膜濾過システム。
    Membrane modules installed in parallel;
    supply means for supplying water to be treated to each membrane module through a common water supply pipe and branch pipes branched from the common water supply pipe;
    In a membrane filtration system having a confluence pipe where treated water from each membrane module merges,
    Equipped with the water quality measuring device according to any one of claims 1 to 5,
    The water quality measuring device is a membrane filtration system installed so as to measure at least the treated water of each membrane module.
  7.  前記水質測定装置は、さらに前記共通の給水配管を流れる被処理水と、前記合流配管を流れる合流処理水を測定対象とするように設置されている請求項6の膜濾過システム。

     
    7. The membrane filtration system according to claim 6, wherein the water quality measuring device is installed so as to measure the water to be treated flowing through the common water supply pipe and the combined treated water flowing through the combined pipe.

PCT/JP2022/010883 2021-06-18 2022-03-11 Water quality measurement device WO2022264563A1 (en)

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JP2002282850A (en) * 2001-03-26 2002-10-02 Mitsubishi Electric Corp Ultrapure water producing equipment
JP2004077299A (en) * 2002-08-19 2004-03-11 Kurita Water Ind Ltd Device and method for concentrating test water
JP2005017098A (en) * 2003-06-26 2005-01-20 Hitachi Ltd Water quality measuring method and water quality measuring system
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