JPH1010102A - Water-quality analyzing device - Google Patents
Water-quality analyzing deviceInfo
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- JPH1010102A JPH1010102A JP18122396A JP18122396A JPH1010102A JP H1010102 A JPH1010102 A JP H1010102A JP 18122396 A JP18122396 A JP 18122396A JP 18122396 A JP18122396 A JP 18122396A JP H1010102 A JPH1010102 A JP H1010102A
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- sample
- section
- unit
- gas
- carrier gas
- Prior art date
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は水道水源や水道水中
の有機化合物、例えば揮発性有機化合物を分析する装置
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for analyzing organic compounds, such as volatile organic compounds, in tap water sources and tap water.
【０００２】[0002]
【従来の技術】水道水源や水道水中には各種の揮発性有
機化合物が含まれている。例えばトリクロロエチレンや
その他のクロロエタンなどのハイテク汚染物質、塩素消
毒での副生成物であるトリハロメタン、又はジメチルイ
ソボルネオ−ルやジオスミンなどのかび臭い成分等があ
り、これらの有機化合物は我々の健康で快適な生活に影
響を及ぼす。そのため、それらの化合物の濃度をつねに
知ることが必要となりつつある。それらの化合物は一般
に、パ−ジ／トラップ付きＧＣ（ガスクロマトグラフ）
やパ−ジ／トラップ付きＧＣ／ＭＳ（ガスクロマトグラ
フ／質量分析計）で測定されている。2. Description of the Related Art Tap water sources and tap water contain various volatile organic compounds. For example, there are high-tech pollutants such as trichlorethylene and other chloroethanes, trihalomethane which is a by-product of chlorination, and musty components such as dimethyl isoborneol and diosmin. Affects life. Therefore, it is becoming necessary to always know the concentrations of those compounds. These compounds are generally GC / GC with purge / trap.
And GC / MS (gas chromatograph / mass spectrometer) with purge / trap.
【０００３】[0003]
【発明が解決しようとする課題】パ−ジ／トラップ付き
のＧＣやＧＣ／ＭＳは、測定に数十分という長時間を要
するため、頻度の高いモニターは難しい。そのため、異
常水質の検知や対応策の遅れを生じる可能性がある。例
えばトリハロメタンを例にとれば、その測定に数十分を
要していたのでは、その間のトリハロメタンの急激な濃
度変化を見過ごす可能性がある。そこで、本発明は水溶
液試料中の有機化合物をモニタできるとともに、必要に
応じて成分分析もできるようにすることを目的とするも
のである。A GC or a GC / MS with a purge / trap takes a long time of several tens of minutes to measure, so that frequent monitoring is difficult. Therefore, detection of abnormal water quality and delay of countermeasures may occur. For example, in the case of trihalomethane, if it takes tens of minutes for the measurement, a rapid change in the concentration of trihalomethane during that time may be overlooked. Accordingly, it is an object of the present invention to monitor an organic compound in an aqueous solution sample and to perform component analysis as necessary.
【０００４】[0004]
【課題を解決するための手段】ＧＣやＧＣ／ＭＳによる
成分分析は長時間を要するので、それらの対象成分の成
分濃度と相関関係のある全有機体炭素（ＴＯＣ）、揮発
性有機体炭素（ＰＯＣ）、揮発性有機体ハロゲン（ＰＯ
Ｘ）、揮発性有機体イオウ（ＰＯＳ）のような迅速に測
定できる総括指標を常時測定し、総括指標があらかじめ
定めたレベルを越えたときに成分分析に切り換えるよう
にする。Means for Solving the Problems Since component analysis by GC or GC / MS takes a long time, total organic carbon (TOC) and volatile organic carbon (TOC) which have a correlation with the component concentration of the target component are used. POC), volatile organic halogen (PO
X) A general index that can be measured quickly, such as volatile organic sulfur (POS), is always measured, and when the general index exceeds a predetermined level, the analysis is switched to component analysis.
【０００５】そのため、本発明の第１の局面は、水溶液
試料を採取する試料採取部と、試料中のＴＯＣ又はＰＯ
Ｃを測定する測定部と、試料中の有機成分を分析する成
分分析部と、試料採取部で採取された試料を測定部と成
分分析部のいずれかに切り換えて供給する試料分配部と
を備えている。[0005] Therefore, a first aspect of the present invention is to provide a sampling section for collecting an aqueous solution sample, and a TOC or POC in the sample.
A measuring section for measuring C, a component analyzing section for analyzing organic components in the sample, and a sample distributing section for switching and supplying the sample collected by the sample collecting section to either the measuring section or the component analyzing section. ing.
【０００６】本発明の第２の局面は、水溶液試料を採取
する試料採取部と、試料採取部に採取された試料を以後
の測定に支障のないガスで通気処理する通気処理部と、
通気処理に用いたガスに含まれる揮発性有機化合物を保
持するとともに、保持した揮発性有機化合物を脱離させ
てキャリアガスとともに送出する保持・脱離部と、保持
・脱離部から送出されたキャリアガス中の総炭素濃度を
測定する炭素測定部と、保持・脱離部から送出されたキ
ャリアガス中の有機成分を分析する成分分析部と、保持
・脱離部から送出されたキャリアガスを炭素測定部と成
分分析部のいずれかに切り換えて供給するガス分配部と
を備えている。[0006] A second aspect of the present invention provides a sampling section for collecting an aqueous solution sample, a ventilation section for aerating a sample collected by the sample collection section with a gas that does not hinder subsequent measurement,
A holding / desorption unit that holds the volatile organic compound contained in the gas used for the aeration treatment, desorbs the held volatile organic compound, and sends out the carrier gas together with the carrier gas, and is sent from the holding / desorption unit. A carbon measuring unit for measuring the total carbon concentration in the carrier gas, a component analyzing unit for analyzing organic components in the carrier gas sent from the holding / desorbing unit, and a carrier gas sent from the holding / desorbing unit. A gas distribution unit is provided for switching to and supplying any of the carbon measurement unit and the component analysis unit.
【０００７】本発明の第３の局面は、水溶液試料を採取
する試料採取部と、試料採取部に採取された試料を以後
の測定に支障のないガスで通気処理する通気処理部と、
通気処理に用いたガスに含まれる揮発性有機化合物を保
持するとともに、保持した揮発性有機化合物を脱離させ
てキャリアガスとともに送出する保持・脱離部と、保持
・脱離部から送出されたキャリアガス中のハロゲン濃度
を測定するハロゲン測定部と、保持・脱離部から送出さ
れたキャリアガス中のハロゲン化合物を分析する成分分
析部と、保持・脱離部から送出されたキャリアガスをハ
ロゲン測定部と成分分析部のいずれかに切り換えて供給
するガス分配部とを備えている。[0007] A third aspect of the present invention provides a sampling section for collecting an aqueous solution sample, a ventilation section for aerating the sample collected by the sampling section with a gas that does not hinder subsequent measurement,
A holding / desorption unit that holds the volatile organic compound contained in the gas used for the aeration treatment, desorbs the held volatile organic compound, and sends out the carrier gas together with the carrier gas, and is sent from the holding / desorption unit. A halogen measuring section for measuring the halogen concentration in the carrier gas, a component analyzing section for analyzing a halogen compound in the carrier gas sent from the holding / desorbing section, and a halogen analyzing section for analyzing the carrier gas sent from the holding / desorbing section. A gas distribution unit is provided for switching between the measurement unit and the component analysis unit.
【０００８】本発明の第４の局面は、水溶液試料を採取
する試料採取部と、試料採取部に採取された試料を以後
の測定に支障のないガスで通気処理する通気処理部と、
通気処理に用いたガスに含まれる揮発性有機化合物を保
持するとともに、保持した揮発性有機化合物を脱離させ
てキャリアガスとともに送出する保持・脱離部と、保持
・脱離部から送出されたキャリアガス中のイオウ濃度を
測定するイオウ測定部と、保持・脱離部から送出された
キャリアガス中のイオウ化合物を分析する成分分析部
と、保持・脱離部から送出されたキャリアガスをイオウ
測定部と成分分析部のいずれかに切り換えて供給するガ
ス分配部とを備えている。[0008] A fourth aspect of the present invention comprises a sampling section for collecting an aqueous solution sample, a ventilation section for aerating the sample collected by the sampling section with a gas that does not hinder subsequent measurement,
A holding / desorption unit that holds the volatile organic compound contained in the gas used for the aeration treatment, desorbs the held volatile organic compound, and sends out the carrier gas together with the carrier gas, and is sent from the holding / desorption unit. A sulfur measurement section for measuring the sulfur concentration in the carrier gas, a component analysis section for analyzing the sulfur compounds in the carrier gas sent from the holding / desorption section, and a sulfur analysis section for measuring the sulfur concentration in the carrier gas sent from the holding / desorption section. A gas distribution unit is provided for switching between the measurement unit and the component analysis unit.
【０００９】[0009]
【発明の実施の形態】試料採取部は１つの共通ポートと
複数の分配ポートを有するマルチポート型切換えバルブ
と、その共通ポートに接続されプランジャの駆動手段を
備えたシリンジと、前記切換えバルブの異なる分配ポー
トのそれぞれに接続された試料採水チューブ及び排出チ
ューブとを備えており、通気処理部は試料採取部のシリ
ンジとそれに接続された通気ガス供給口とからなり、保
持・脱離部はガス中の特定成分を吸着し脱離することの
できる吸着カラムと、その吸着カラムの一端を前記排出
チューブとガス分配部のいずれかに切り換えて接続する
切換えバルブと、吸着カラムの他端からキャリアガスを
供給するキャリアガス供給部とを備えている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A sampling section is a multi-port type switching valve having one common port and a plurality of distribution ports, a syringe connected to the common port and provided with a driving means for a plunger, and the switching valve is different. It has a sample sampling tube and a discharge tube connected to each of the distribution ports, the ventilation section comprises a syringe of the sampling section and a ventilation gas supply port connected to it, and the holding / desorption section has a gas supply port. An adsorption column capable of adsorbing and desorbing specific components therein, a switching valve for switching one end of the adsorption column to one of the discharge tube and the gas distribution section, and a carrier gas from the other end of the adsorption column. And a carrier gas supply unit for supplying the carrier gas.
【００１０】ＰＯＣ、ＰＯＸ又はＰＯＳの測定では、シ
リンジ内で試料を通気処理できるように通気ガス供給口
を備えたシリンジを複数の分配ポートをもつ切換えバル
ブを経由して試料供給チューブおよび試料中の有機成分
を吸着・脱着させる吸着カラムと接続可能とし、この吸
着カラムをＰＯＣ、ＰＯＸ又はＰＯＳの測定部と有機成
分分析部（ＧＣ又はＧＣ／ＭＳ）のいずれにも接続可能
な構造とし、通常は迅速に測定できるＰＯＣ、ＰＯＸ又
はＰＯＳの測定を行なっておき、ＰＯＣ値、ＰＯＸ値又
はＰＯＳ値があらかじめ定められた濃度を越えると有機
成分分析に切り換えるようにする。In the measurement of POC, POX, or POS, a syringe provided with a vent gas supply port is connected to a sample supply tube and a sample supply tube through a switching valve having a plurality of distribution ports so that the sample can be ventilated in the syringe. It can be connected to an adsorption column that adsorbs and desorbs organic components, and this adsorption column has a structure that can be connected to both the POC, POX or POS measurement unit and the organic component analysis unit (GC or GC / MS). Measurement of POC, POX or POS which can be measured quickly is performed, and when the POC value, POX value or POS value exceeds a predetermined concentration, the analysis is switched to the organic component analysis.
【００１１】例えばＰＯＣ値をモニタする場合には、シ
リンジポンプに一定量採取した試料にパージガスを通気
して揮発性有機物を気化させ、吸着カラムに導いて吸着
させる。この吸着成分を脱着させて全ての有機成分をＣ
Ｏ2に酸化した後、ＣＯ2を測定することによりＰＯＣを
測定する。問題となる揮発性有機成分の濃度とＰＯＣと
の相関関係をあらかじめ求めておき、試料中のＰＯＣが
あるレベルを越えると吸着カラムの吸着物の成分分析に
切り換える。For example, when monitoring the POC value, a purge gas is passed through a sample taken in a fixed amount through a syringe pump to vaporize volatile organic substances, and the volatile organic substances are led to an adsorption column for adsorption. By desorbing this adsorbed component, all organic components are converted to C
After oxidation to O 2 , the POC is measured by measuring CO 2 . The correlation between the concentration of the volatile organic component, which is a problem, and the POC is determined in advance, and when the POC in the sample exceeds a certain level, the analysis is switched to the component analysis of the adsorbed substance in the adsorption column.
【００１２】[0012]
【実施例】図１は第１の実施例を概略的に表わしたもの
である。２は水溶液試料を採取する試料採取部、４は試
料水中のＴＯＣ又はＰＯＣを測定する測定部、８は試料
中の有機成分を分析する成分分析部、１０は試料採取部
２で採取された試料を測定部４と成分分析部８のいずれ
かに切り換えて供給する試料分配部である。試料分配部
１０から供給された試料水中の揮発性有機化合物を成分
分析部８で測定するために、供給された試料を以後の測
定に支障のないガスで通気処理する通気処理部と、通気
処理に用いたガスに含まれる揮発性有機化合物を保持す
るとともに、保持した揮発性有機化合物を脱離させてキ
ャリアガスとともに送出するパージ／トラップ部６を備
えている。成分分析部８は例えばＧＣ／ＭＳである。FIG. 1 schematically shows a first embodiment. Reference numeral 2 denotes a sample collecting unit for collecting an aqueous solution sample, 4 denotes a measuring unit for measuring TOC or POC in sample water, 8 denotes a component analyzer for analyzing organic components in the sample, and 10 denotes a sample collected by the sample collecting unit 2. Is a sample distributing unit that switches and supplies to either the measuring unit 4 or the component analyzing unit 8. In order to measure the volatile organic compounds in the sample water supplied from the sample distribution unit 10 by the component analysis unit 8, a ventilation unit for aerating the supplied sample with a gas that does not hinder the subsequent measurement; And a purge / trap section 6 for holding the volatile organic compound contained in the gas used for the above and for releasing the held volatile organic compound and sending it out together with the carrier gas. The component analyzer 8 is, for example, a GC / MS.
【００１３】また、測定部４で測定した値があらかじめ
設定した値を越えたときにその測定値を示した試料を成
分分析部８で測定できるように、測定部４での測定に供
給した試料と同じ試料を一時保存しておく試料保存部１
２も設けられている。試料保存部１２に保存される試料
は測定試料が変わるごとに新しいものに更新される。Further, when the value measured by the measuring section 4 exceeds a preset value, the sample showing the measured value can be measured by the component analyzing section 8 so that the sample supplied to the measurement by the measuring section 4 can be measured. Sample storage unit 1 for temporarily storing the same sample as
2 is also provided. The sample stored in the sample storage unit 12 is updated each time the measurement sample changes.
【００１４】この実施例では３通りの測定方法がある。
第１の測定方法は、試料保存部１２を使用しない方法で
あり、試料採取部２に試料を吸引し、その試料中のＴＯ
Ｃ又はＰＯＣを測定部４で分析する動作を繰り返してお
き、測定部４での測定値が設定値を越えたときに、試料
分配部１０をＧＣ／ＭＳ８側に切り換えて試料の成分分
析を行なう。In this embodiment, there are three measurement methods.
The first measurement method is a method that does not use the sample storage unit 12, in which a sample is sucked into the sample collection unit 2 and the TO
The operation of analyzing C or POC by the measurement unit 4 is repeated, and when the measurement value in the measurement unit 4 exceeds the set value, the sample distribution unit 10 is switched to the GC / MS 8 to perform the component analysis of the sample. .
【００１５】第２の測定方法は、試料採取部２で採取
し、試料分配部１０から測定部４に供給した試料と同一
の試料を試料保存部１２に保存した状態で、測定部４で
の測定を行なう。測定部４での測定値が設定値を越えな
ければ、試料保存部１２に保存する試料を新しいものに
更新し、新しい試料を測定部４で測定する動作を繰り返
す。測定部４での測定値が設定値を越えたら、試料分配
部１０を切り換えて試料保存部１２に保存しておいた試
料をＧＣ／ＭＳ８で成分分析する。In the second measuring method, the same sample as the sample collected by the sample collecting unit 2 and supplied from the sample distributing unit 10 to the measuring unit 4 is stored in the sample storing unit 12 and Perform a measurement. If the measured value in the measuring section 4 does not exceed the set value, the sample stored in the sample storing section 12 is updated to a new one, and the operation of measuring the new sample in the measuring section 4 is repeated. When the measured value in the measuring section 4 exceeds the set value, the sample distributing section 10 is switched and the sample stored in the sample storing section 12 is subjected to component analysis by the GC / MS 8.
【００１６】第３の測定方法は、ＧＣ／ＭＳ８による測
定をある時間間隔で行ないつつ、その間にＰＯＣ、ＰＯ
Ｘ又はＰＯＳを測定部４で測定する。測定部４での測定
値が予め定められたレベルを越えると試料採取部２又は
試料分配部１０に残されていた試料を試料保存部１２に
移して保存し、その試料を用いてＧＣ／ＭＳ８での測定
を行なう。In the third measuring method, the measurement by the GC / MS 8 is performed at a certain time interval, while the POC and the PO
X or POS is measured by the measuring unit 4. When the value measured by the measuring section 4 exceeds a predetermined level, the sample left in the sample collecting section 2 or the sample distributing section 10 is transferred to and stored in the sample storing section 12, and the GC / MS 8 is used by using the sample. Perform measurements at
【００１７】図２はＰＯＣをモニタとする第２の実施例
を概略的に表わしたものである。試料採取部２に採取さ
れた試料を以後の測定に支障のないガスで通気処理する
ために通気処理（パージ）部１４が設けられている）。
通気処理に用いたガスに含まれる揮発性有機化合物を保
持するとともに、保持した揮発性有機化合物を脱離させ
てキャリアガスとともに送出する保持・脱離部１６が設
けられており、保持・脱離部１６にはキャリアガスを供
給するキャリアガス供給部２０が接続されている。４ａ
は保持・脱離部１６から送出されたキャリアガス中の総
炭素濃度を測定する炭素測定部であり、この場合はＰＯ
Ｃ測定部である。８ａは保持・脱離部１６から送出され
たキャリアガス中の有機成分を分析する成分分析部であ
り、例えばＧＣ／ＭＳである。保持・脱離部１６から送
出されたキャリアガスを炭素測定部４ａと成分分析部８
ａのいずれかに切り換えて供給するためにガス分配部１
８として切換えバルブが設けられている。図２の実施例
において、ＰＯＣに代えてＰＯＸ又はＰＯＳをモニタと
する場合は、炭素測定部４ａをハロゲン又はイオウの測
定部とすればよい。FIG. 2 schematically shows a second embodiment using a POC as a monitor. An aeration (purge) unit 14 is provided to aerate the sample collected by the sample collection unit 2 with a gas that does not interfere with subsequent measurements.
A holding / desorption unit 16 is provided for holding the volatile organic compound contained in the gas used for the aeration treatment and desorbing the held volatile organic compound and sending out the carrier gas together with the carrier gas. The section 16 is connected to a carrier gas supply section 20 for supplying a carrier gas. 4a
Is a carbon measuring unit for measuring the total carbon concentration in the carrier gas delivered from the holding / desorbing unit 16, and in this case, PO
It is a C measuring unit. Reference numeral 8a denotes a component analyzer for analyzing organic components in the carrier gas sent from the holding / desorbing unit 16, and is, for example, a GC / MS. The carrier gas delivered from the holding / desorption unit 16 is supplied to the carbon measurement unit 4a and the component analysis unit 8
a gas distribution unit 1 for switching to any one of
As 8, a switching valve is provided. In the embodiment shown in FIG. 2, when POX or POS is used as a monitor instead of POC, the carbon measuring unit 4a may be a halogen or sulfur measuring unit.
【００１８】図３は図２の実施例を具体的に示したもの
である。５ポートバルブ２２の共通ポートにはシリンジ
２４が接続され、シリンジ２４はプランジャ２６とそれ
を駆動するモータ２８を備え、プランジャ２６の後退と
前進により試料の吸引と排出を行なう。シリンジ２４に
は切換えバルブ３０を介してスパージガス供給部３２が
接続されており、そのスパージガスによりシリンジ２４
内の試料を通気処理し、試料中の揮発性有機化合物をそ
のスパージガスにより送り出すようになっている。FIG. 3 specifically shows the embodiment of FIG. A syringe 24 is connected to a common port of the five-port valve 22. The syringe 24 includes a plunger 26 and a motor 28 for driving the plunger 26. The plunger 26 retracts and advances to suck and discharge a sample. A sparge gas supply unit 32 is connected to the syringe 24 via a switching valve 30.
The inside sample is aerated, and volatile organic compounds in the sample are sent out by the sparge gas.
【００１９】５ポートバルブ２２の１つの分配ポートに
は試料をオンラインで供給する試料採水チューブ３４が
接続され、他の１つの分配ポートには通気処理して揮発
性有機化合物を含んだスパージガスを排出する排出チュ
ーブ３６が接続され、更に他の１つの分配ポートにはＴ
ＯＣ、ＰＯＣ、ＰＯＸ又はＰＯＳを測定部５０で測定中
にその試料を一時保存する試料保存部３８の容器が接続
され、更に他の１つ分配ポートには校正用の標準液３９
を供給するチューブが接続されている。更に他の１つの
分配ポートはシリンジ内の試料を排水するのに用いられ
る。A sample sampling tube 34 for supplying a sample on-line is connected to one distribution port of the 5-port valve 22, and a sparger gas containing a volatile organic compound is ventilated to the other distribution port. A discharge tube 36 for discharging is connected, and the other distribution port has a T port.
While the OC, POC, POX, or POS is being measured by the measuring unit 50, a container of a sample storage unit 38 for temporarily storing the sample is connected, and another distribution port is connected to a standard solution 39 for calibration.
The tube that supplies is connected. Still another distribution port is used to drain the sample in the syringe.
【００２０】保守・脱離部１６は吸着剤が充填された吸
着カラム４０を備え、吸着カラム４０の一端は切換えバ
ルブ４２を介して５ポートバルブに接続された排出チュ
ーブ３６と切換えバルブ４４に接続されている。吸着カ
ラム４０の他端には切換えバルブ４８を介してキャリア
ーガス供給部４９が接続されてキャリアーガスが供給さ
れるとともに、その切換えバルブ４８により排出チュー
ブ３６から供給されたスパージガスを排出できるように
なっている。吸着カラム４０の周囲には加熱装置４６が
設けられ、吸着カラム４０に吸着した揮発性有機化合物
を加熱して脱着させるようになっている。The maintenance / desorption section 16 includes an adsorption column 40 filled with an adsorbent, and one end of the adsorption column 40 is connected via a switching valve 42 to a discharge tube 36 connected to a 5-port valve and a switching valve 44. Have been. A carrier gas supply unit 49 is connected to the other end of the adsorption column 40 via a switching valve 48 to supply the carrier gas, and the switching valve 48 allows the sparge gas supplied from the discharge tube 36 to be discharged. ing. A heating device 46 is provided around the adsorption column 40 so that the volatile organic compounds adsorbed on the adsorption column 40 are heated and desorbed.
【００２１】吸着カラム４０は例えばテナックスやテナ
ックス・シリカゲルが吸着剤として充填されたものであ
り、加熱装置４６は吸着剤を２００℃に加熱して吸着成
分を脱着させる。キャリアガスとしてはヘリウム又は酸
素の入ったヘリウムを用いることができる。The adsorption column 40 is filled with, for example, Tenax or Tenax silica gel as an adsorbent, and a heating device 46 heats the adsorbent to 200 ° C. to desorb adsorbed components. Helium or helium containing oxygen can be used as the carrier gas.
【００２２】切換えバルブ４４はガス分配部１８に該当
するものであり、測定部５０と分析部８のＧＣ／ＭＳが
切換え可能に接続されている。測定部５０には測定装置
５６と、その上流でキャリアガスとともに送られてきた
揮発性有機化合物を酸化する加熱分解炉が設けられてい
る。加熱分解炉は白金や酸化銅などの酸化触媒が充填さ
れたカラム５２と、その酸化触媒を６００〜１０００℃
に加熱する加熱炉５４を含んでいる。その加熱分解炉で
は、有機化合物が酸化されてＣＯ2が発生するととも
に、その揮発性有機化合物が有機ハロゲン化合物である
場合にはハロゲン化水素が発生し、その揮発性有機化合
物が有機イオウ化合物である場合にはＳＯ2が発生す
る。The switching valve 44 corresponds to the gas distribution unit 18, and the measurement unit 50 and the GC / MS of the analysis unit 8 are switchably connected. The measuring section 50 is provided with a measuring device 56 and a pyrolysis furnace for oxidizing volatile organic compounds sent with the carrier gas upstream of the measuring device 56. The pyrolysis furnace is a column 52 filled with an oxidation catalyst such as platinum or copper oxide, and the oxidation catalyst is heated to 600 to 1000 ° C.
And a heating furnace 54 for heating. In the pyrolysis furnace, the organic compound is oxidized to generate CO 2 , and when the volatile organic compound is an organic halogen compound, hydrogen halide is generated, and the volatile organic compound is an organic sulfur compound. In some cases, SO 2 is generated.
【００２３】測定装置５６はＣＯ2を測定する場合には
ＮＤＩＲ（非分散型赤外線ガス分析計）であり、ハロゲ
ン化水素やＳＯ2を測定する場合にはクーロメータであ
る。ＮＤＩＲによるＣＯ2の測定はよく知られたもので
ある。クーロメータによるハロゲン化水素やＳＯ2の測
定は次の反応で行なわれる。The measuring device 56 is an NDIR (non-dispersive infrared gas analyzer) when measuring CO 2 , and is a coulometer when measuring hydrogen halide or SO 2 . Measurement of CO 2 by the NDIR are those well known. The measurement of hydrogen halide and SO 2 by a coulometer is performed by the following reaction.
【００２４】（有機ハロゲン化合物の測定の場合）クー
ロメータでは ＨＸ＋Ａｇ+ → ＡｇＸ＋Ｈ+ の反応が起こり、アノードとカソードでは次の反応とな
って電流が流れる。 アノード： Ａｇ → Ａｇ+＋ｅ カソード（Ｐｔ）： Ｈ+＋ｅ → 1/2 Ｈ2 (In the case of measuring an organic halogen compound) In the coulometer, a reaction of HX + Ag + → AgX + H + occurs, and the following reaction occurs between the anode and the cathode, and current flows. Anode: Ag → Ag + + e Cathode (Pt): H + + e → 1/2 H 2
【００２５】（有機イオウ化合物の測定の場合）クーロ
メータではＳＯ2によって塩素酸イオンＣｌＯ3-が塩素
イオンＣｌ-に還元され、そのＣｌ-がＡｇ+と反応す
る。 ＣｌＯ3 - → Ｃｌ- Ａｇ+＋Ｃｌ-→ ＡｇＣｌ その結果としてアノードとカソードでは上と同じ反応が
起こって電流が流れる。(Measurement of Organic Sulfur Compound) In a coulometer, chlorate ion ClO 3 − is reduced to chlorine ion Cl − by SO 2 , and the Cl − reacts with Ag +. ClO 3 − → Cl − Ag + + Cl − → AgCl As a result, the same reaction as described above occurs at the anode and the cathode, and a current flows.
【００２６】図３の実施例の動作について説明する。一
定量の試料水をシリンジ２４内に吸引した後、５ポート
バルブ２２を共通ポートが排出チューブ３６を経て吸着
カラム４０につながる分配ポートに接続し、シリンジ２
４内の試料水にスパージガスを供給して試料水を通気処
理し、試料水中の揮発性成分を吸着カラム４０に導入し
て吸着させる。次に、吸着カラム４０を測定部５０又は
成分分析部８のＧＣ／ＭＳに接続した状態で、キャリア
ガス供給部４９からキャリアガスを流しつつ、吸着カラ
ム４０の温度を上昇させて吸着成分をカラム４０から脱
離させ、試料中のＰＯＣ、ＰＯＸ又はＰＯＳを測定部５
０又は成分分析部８に導き分析を行なう。シリンジ内の
測定が終わった試料は、５ポートバルブ２２から排水出
口へ排出される。The operation of the embodiment shown in FIG. 3 will be described. After a certain amount of sample water has been sucked into the syringe 24, the 5-port valve 22 is connected to the distribution port whose common port is connected to the adsorption column 40 via the discharge tube 36, and the syringe 2
A sparge gas is supplied to the sample water in 4 to aerate the sample water, and volatile components in the sample water are introduced into the adsorption column 40 and adsorbed. Next, in a state where the adsorption column 40 is connected to the GC / MS of the measurement unit 50 or the component analysis unit 8, while the carrier gas is supplied from the carrier gas supply unit 49, the temperature of the adsorption column 40 is increased, and the adsorption component is removed. 40, and the POC, POX or POS in the sample is measured by the measuring unit 5
0 or to the component analyzer 8 for analysis. The sample after the measurement in the syringe is discharged from the 5-port valve 22 to the drain outlet.
【００２７】この実施例では３通りの測定方法がある。
第１の測定方法は、シリンジ２４に試料を吸引し、その
試料中のＰＯＣ、ＰＯＸ又はＰＯＳを測定部５０で分析
する動作を繰り返しておき、測定部５０での測定値が設
定値を越えたときに、切換えバルブ４４を成分分析部８
側に切り換え、シリンジ２４に吸引した試料の成分分析
を行なう。In this embodiment, there are three measurement methods.
In the first measurement method, the operation of sucking the sample into the syringe 24 and analyzing the POC, POX, or POS in the sample by the measuring unit 50 is repeated, and the measured value of the measuring unit 50 exceeds the set value. At this time, the switching valve 44 is connected to the component analyzer 8.
Side, and the components of the sample sucked into the syringe 24 are analyzed.
【００２８】第２の測定方法は、シリンジ２４に吸引す
る試料と同一の試料をシリンジ２４を介して試料保存部
３８に保存しておき、シリンジ２４に吸引した試料を測
定部５０で分析する。測定部５０での測定値が設定値を
越えなければ、試料保存部３８に保存する試料を新しい
ものに更新し、新しい試料をシリンジ２４に吸引して測
定部５０での測定を繰り返す。測定部５０での測定値が
設定値を越えたら、試料保存部３８に保存しておいた試
料をシリンジ２４に吸引し、切換えバルブ４４を成分分
析部８側に切り換えて成分分析を行なう。In the second measuring method, the same sample as the sample to be sucked into the syringe 24 is stored in the sample storage section 38 via the syringe 24, and the sample sucked into the syringe 24 is analyzed by the measuring section 50. If the measured value in the measuring section 50 does not exceed the set value, the sample stored in the sample storing section 38 is updated to a new one, the new sample is sucked into the syringe 24, and the measurement in the measuring section 50 is repeated. When the value measured by the measuring section 50 exceeds the set value, the sample stored in the sample storing section 38 is sucked into the syringe 24, and the switching valve 44 is switched to the component analyzing section 8 to perform component analysis.
【００２９】第３の測定方法は、成分分析部８による測
定をある時間間隔で行ないつつ、その間にＰＯＣ、ＰＯ
Ｘ又はＰＯＳを測定部５０で測定する。測定部５０での
測定値が予め定められたレベルを越えると試料採取部又
は試料分配部に残されていた試料を試料保存部３８に移
して保存し、その試料を用いて成分分析部８での測定を
行なう。In the third measuring method, while the measurement by the component analyzing section 8 is performed at a certain time interval, the POC, PO
X or POS is measured by the measuring unit 50. When the measured value in the measuring section 50 exceeds a predetermined level, the sample left in the sample collecting section or the sample distributing section is transferred to the sample storing section 38 and stored, and the sample is used in the component analyzing section 8. Is measured.
【００３０】図４は保持・脱離部として１６Ａと１６Ｂ
で示されるように２組を備え、一方の吸着カラムの吸着
成分を測定中に、他方の吸着カラムにはシリンジ２４内
に採取した同一試料中の揮発性成分を吸着させて保存し
ておき、一方の吸着カラムの吸着成分の測定部５０によ
る測定値があらかじめ定められた濃度を越えたときに他
方の吸着カラムの吸着成分を成分分析部８に供給して成
分分析を行なうようにした実施例である。そのため、２
組の保持・脱離部１６Ａと１６Ｂがマルチポートバルブ
２２ａのそれぞれの分配ポートに切換えバルブ４２Ａ，
４２Ｂを介してそれぞれ接続されている。各吸着カラム
４０Ａ，４０Ｂには共通のキャリアーガス供給部４９か
ら切換えバルブ５１を介してキャリアーガスが切り換え
て供給されるようになっており、両方の吸着カラム４０
Ａ，４０Ｂからキャリアーガスとともに送り出される吸
着成分を切り換えて測定部５０又は成分分析部８に供給
するために切換えバルブ４２Ａ，４２Ｂ、４３、４４が
設けられている。この場合には、試料保存部３８は不要
である。FIG. 4 shows 16A and 16B as holding and detaching portions.
As shown in the above, two sets are provided, while measuring the adsorption component of one adsorption column, the other adsorption column adsorbs and stores the volatile component in the same sample collected in the syringe 24, Embodiment in which when the measured value of the adsorbed component of one adsorption column by the measuring unit 50 exceeds a predetermined concentration, the adsorbed component of the other adsorption column is supplied to the component analyzing unit 8 to perform the component analysis. It is. Therefore, 2
A pair of holding / disengaging portions 16A and 16B are switched to respective distribution ports of the multi-port valve 22a, and the switching valves 42A,
Each is connected via 42B. A carrier gas is selectively supplied to each of the adsorption columns 40A and 40B from a common carrier gas supply unit 49 via a switching valve 51.
Switching valves 42A, 42B, 43, 44 are provided for switching the adsorbed components sent out together with the carrier gas from A, 40B and supplying the adsorbed components to the measuring section 50 or the component analyzing section 8. In this case, the sample storage section 38 is unnecessary.
【００３１】試料分配部１０や切換えバルブ１８，４４
を測定部４，４ａ，５０から成分分析部８，８ａに切り
換えるために、ＰＯＣ、ＰＯＸ又はＰＯＳと有機成分濃
度との相関関係を表わす数式を予め測定して記憶してお
く必要がある。その相関関係を表わす数式は、測定部
４，４ａ，５０での測定値と、切換えバルブ１８，４４
で切り換えて成分分析部８で測定を行なった同一試料に
よる成分濃度値とを用いて常に修正するようにすれば、
試料測定と同時に校正を行なうことができ、好都合であ
る。The sample distribution unit 10 and the switching valves 18 and 44
In order to switch from the measurement units 4, 4a, 50 to the component analysis units 8, 8a, it is necessary to measure and store in advance a mathematical expression representing the correlation between the POC, POX, or POS and the organic component concentration. A mathematical expression representing the correlation is obtained by measuring values in the measuring units 4, 4a, 50 and switching valves 18, 44.
If the correction is always made using the component concentration values of the same sample measured by the component analysis unit 8 by switching in
Calibration can be performed simultaneously with sample measurement, which is convenient.
【００３２】[0032]
【発明の効果】本発明では、常時は迅速、かつ容易に測
定できるＴＯＣ、ＰＯＣ、ＰＯＸ、ＰＯＳなど、総括的
な水質指標をモニタしておき、その測定値が予め定めた
レベルを越えると測定待機状態にあったＧＣやＧＣ／Ｍ
Ｓなどの成分分析装置で目的成分を測定するようにした
ので、目的成分を見過ごすことなく測定することができ
る。また、浄水場の場合、総括的指標で以上を検知した
段階で、まず取水を停止させ、成分分析で異常が確認さ
れてから対応する適切な処置、例えば活性炭による処置
など、を行なえば、水質異常に遅れをとることなく、効
率のよい水処理を行なうことができる。According to the present invention, a comprehensive water quality index such as TOC, POC, POX, POS, etc., which can be measured quickly and easily at all times, is monitored, and when the measured value exceeds a predetermined level, it is measured. GC or GC / M in standby state
Since the target component is measured by a component analyzer such as S, the target component can be measured without overlooking it. In the case of a water treatment plant, at the stage where the above is detected by the comprehensive index, water intake is first stopped, and after an abnormality is confirmed by component analysis, appropriate measures, such as treatment with activated carbon, are taken. Efficient water treatment can be performed without an abnormal delay.
【図１】第１の実施例を概略的に示すブロック図であ
る。FIG. 1 is a block diagram schematically showing a first embodiment.
【図２】第２の実施例を概略的に示すブロック図であ
る。FIG. 2 is a block diagram schematically showing a second embodiment.
【図３】図２の実施例を具体的に示す流路図である。FIG. 3 is a flow chart specifically showing the embodiment of FIG. 2;
【図４】保持・脱離部を２組備えた実施例を示す要部流
路図である。FIG. 4 is a main part flow path diagram showing an embodiment including two sets of holding / separating parts.
２ 試料採取部 ４，４ａ，５０ 測定部 ６ パージ／トラップ部 ８，８ａ 成分分析部 １０ 試料分配部 １２，３８ 試料保存部 １４ 通気処理部 １６ 保持・脱離部 １８ ガス分配部 ２２ ５ポートバルブ ２４ シリンジ ３２ スパージガス供給部 ４０，４０Ａ，４０Ｂ 吸着カラム ４４ 切換えバルブ ５６ 測定装置 2 Sampling unit 4, 4a, 50 Measuring unit 6 Purge / trap unit 8, 8a Component analysis unit 10 Sample distribution unit 12, 38 Sample storage unit 14 Ventilation processing unit 16 Holding / desorption unit 18 Gas distribution unit 22 5-port valve 24 syringe 32 sparge gas supply unit 40, 40A, 40B adsorption column 44 switching valve 56 measuring device
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０１Ｎ 30/88 Ｇ０１Ｎ 30/88 Ｃ 33/18 33/18 Ｂ １０６ １０６Ｚ // Ｇ０１Ｎ 31/00 31/00 Ｄ Ｑ Ｐ ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location G01N 30/88 G01N 30/88 C 33/18 33/18 B 106 106Z // G01N 31/00 31 / 00 D Q P
Claims (7)
測定部と、 試料中の有機成分を分析する成分分析部と、 試料採取部で採取された試料を前記測定部と前記成分分
析部のいずれかに切り換えて供給する試料分配部と、を
備えたことを特徴とする水質分析装置。A sampler for collecting an aqueous solution sample; a measuring unit for measuring total organic carbon or volatile organic carbon in the sample; a component analyzer for analyzing organic components in the sample; A water quality analyzer, comprising: a sample distribution unit that switches and supplies a sample collected by the unit to one of the measurement unit and the component analysis unit.
ガスで通気処理する通気処理部と、 通気処理に用いたガスに含まれる揮発性有機化合物を保
持するとともに、保持した揮発性有機化合物を脱離させ
てキャリアガスとともに送出する保持・脱離部と、 保持・脱離部から送出されたキャリアガス中の総炭素濃
度を測定する炭素測定部と、 保持・脱離部から送出されたキャリアガス中の有機成分
を分析する成分分析部と、 保持・脱離部から送出されたキャリアガスを炭素測定部
と成分分析部のいずれかに切り換えて供給するガス分配
部と、を備えたことを特徴とする水質分析装置。2. A sampling section for collecting an aqueous solution sample, a ventilation section for aerating the sample collected by the sampling section with a gas that does not interfere with subsequent measurements, and a gas contained in the gas used for the aeration processing. Holds and desorbs the volatile organic compound and releases the volatile organic compound and sends it out together with the carrier gas.Measures the total carbon concentration in the carrier gas sent from the holding and desorbing section A carbon analyzer that analyzes the organic components in the carrier gas sent from the holding and desorbing unit, and a carbon measuring unit and a component analyzer that analyzes the carrier gas sent from the holding and desorbing unit A water quality analyzer, comprising: a gas distribution unit configured to switch and supply a crab.
ガスで通気処理する通気処理部と、 通気処理に用いたガスに含まれる揮発性有機化合物を保
持するとともに、保持した揮発性有機化合物を脱離させ
てキャリアガスとともに送出する保持・脱離部と、 保持・脱離部から送出されたキャリアガス中のハロゲン
濃度を測定するハロゲン測定部と、 保持・脱離部から送出されたキャリアガス中のハロゲン
化合物を分析する成分分析部と、 保持・脱離部から送出されたキャリアガスをハロゲン測
定部と成分分析部のいずれかに切り換えて供給するガス
分配部と、を備えたことを特徴とする水質分析装置。3. A sampling section for collecting an aqueous solution sample, a ventilation section for aerating the sample collected in the sample section with a gas that does not hinder subsequent measurement, and a gas contained in the gas used for the aeration processing. Holds and removes volatile organic compounds and releases the volatile organic compounds together with the carrier gas, and measures the concentration of halogen in the carrier gas delivered from the hold and release unit. A halogen analyzer, a component analyzer for analyzing a halogen compound in the carrier gas sent from the holding / desorbing unit, and a carrier gas sent from the holding / desorbing unit for the halogen measuring unit or the component analyzer. And a gas distribution unit that switches and supplies the water to the water quality analyzer.
ガスで通気処理する通気処理部と、 通気処理に用いたガスに含まれる揮発性有機化合物を保
持するとともに、保持した揮発性有機化合物を脱離させ
てキャリアガスとともに送出する保持・脱離部と、 保持・脱離部から送出されたキャリアガス中のイオウ濃
度を測定するイオウ測定部と、 保持・脱離部から送出されたキャリアガス中のイオウ化
合物を分析する成分分析部と、 保持・脱離部から送出されたキャリアガスをイオウ測定
部と成分分析部のいずれかに切り換えて供給するガス分
配部と、を備えたことを特徴とする水質分析装置。4. A sampling section for collecting an aqueous solution sample, a ventilation section for aerating a sample collected by the sampling section with a gas that does not hinder subsequent measurement, and a gas included in the gas used for the aeration processing. Holds and removes the volatile organic compound and sends it out together with the carrier gas while holding the volatile organic compound, and measures the sulfur concentration in the carrier gas sent from the holding and desorption section Sulfur measurement section, component analysis section for analyzing sulfur compounds in carrier gas sent from holding / desorption section, and carrier gas sent from holding / desorption section to either sulfur measurement section or component analysis section And a gas distribution unit that switches and supplies the water to the water quality analyzer.
分配ポートを有するマルチポート型切換えバルブと、そ
の共通ポートに接続されプランジャの駆動手段を備えた
シリンジと、前記切換えバルブの異なる分配ポートのそ
れぞれに接続された試料採水チューブ及び排出チューブ
とを備えており、 通気処理部は前記シリンジとそれに接続された通気ガス
供給口とからなり、 保持・脱離部はガス中の特定成分を吸着し脱離すること
のできる吸着カラムと、その吸着カラムの一端を前記排
出チューブとガス分配部のいずれかに切り換えて接続す
る切換えバルブと、吸着カラムの他端からキャリアガス
を供給するキャリアガス供給部とを備えている請求項
２，３又は４に記載の水質分析装置。5. A sampling unit comprising: a multi-port switching valve having one common port and a plurality of distribution ports; a syringe connected to the common port and having a driving means for a plunger; and a different distribution port of the switching valve. A sample sampling tube and a discharge tube connected to each of the above, wherein the ventilation section comprises the syringe and a ventilation gas supply port connected thereto, and the holding / desorption section removes a specific component in the gas. An adsorption column capable of being adsorbed and desorbed, a switching valve for switching one end of the adsorption column to one of the discharge tube and the gas distribution unit and a carrier gas for supplying a carrier gas from the other end of the adsorption column The water quality analyzer according to claim 2, further comprising a supply unit.
る試料保存部をさらに設けた請求項２，３，４又は５に
記載の水質分析装置。6. The water quality analyzer according to claim 2, further comprising a sample storage unit capable of storing the same sample water as the sample water under measurement.
一方の保持・脱離部の吸着成分を測定中に、他方の保持
・脱離部には試料採取部に採取した同一試料中の揮発性
成分を吸着させて保存できるようにした請求項２，３，
４又は５に記載の水質分析装置。7. Two sets of holding / detachable parts are switchable,
The method according to claim 2, wherein during the measurement of the adsorbed component of one of the holding and desorbing sections, the other holding and desorbing section is capable of adsorbing and storing volatile components in the same sample collected by the sample collecting section. 3,
The water quality analyzer according to 4 or 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18122396A JP3539080B2 (en) | 1996-06-20 | 1996-06-20 | Water quality analyzer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18122396A JP3539080B2 (en) | 1996-06-20 | 1996-06-20 | Water quality analyzer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1010102A true JPH1010102A (en) | 1998-01-16 |
| JP3539080B2 JP3539080B2 (en) | 2004-06-14 |
Family
ID=16096973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18122396A Expired - Fee Related JP3539080B2 (en) | 1996-06-20 | 1996-06-20 | Water quality analyzer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3539080B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1019862A (en) * | 1996-07-08 | 1998-01-23 | Shimadzu Corp | Odor detector |
| JP2000193656A (en) * | 1998-12-24 | 2000-07-14 | Toagosei Co Ltd | Automatic drainage analyzer |
| JP2011232300A (en) * | 2010-04-30 | 2011-11-17 | Shimizu Corp | Monitoring system and monitoring method |
| KR101275700B1 (en) * | 2012-10-22 | 2013-06-17 | 유형조 | Realtime analizing equipment for taste and odor matters(geosmin, 2-mib) in water using sparger |
| WO2014156694A1 (en) * | 2013-03-28 | 2014-10-02 | 栗田工業株式会社 | Particulate-measuring method, particulate-measuring system, and system for manufacturing ultrapure water |
| JP2015094641A (en) * | 2013-11-11 | 2015-05-18 | 新コスモス電機株式会社 | Environment monitoring system |
| JP2017122661A (en) * | 2016-01-07 | 2017-07-13 | 紀本電子工業株式会社 | Volatile organic compound measuring device and volatile organic compound measuring method |
| JP2017223583A (en) * | 2016-06-16 | 2017-12-21 | 株式会社島津製作所 | Water Quality Analyzer |
| JP2018009931A (en) * | 2016-07-15 | 2018-01-18 | 日本電子株式会社 | Gas chromatography pretreatment device and gas collecting tube |
| KR20190107411A (en) * | 2018-03-12 | 2019-09-20 | 주식회사 과학기술분석센타 | Continuous measuring device for odorous susbstances and method thereof |
| WO2020022413A1 (en) * | 2018-07-25 | 2020-01-30 | ダイキン工業株式会社 | Gas concentration prediction method |
-
1996
- 1996-06-20 JP JP18122396A patent/JP3539080B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1019862A (en) * | 1996-07-08 | 1998-01-23 | Shimadzu Corp | Odor detector |
| JP2000193656A (en) * | 1998-12-24 | 2000-07-14 | Toagosei Co Ltd | Automatic drainage analyzer |
| JP2011232300A (en) * | 2010-04-30 | 2011-11-17 | Shimizu Corp | Monitoring system and monitoring method |
| KR101275700B1 (en) * | 2012-10-22 | 2013-06-17 | 유형조 | Realtime analizing equipment for taste and odor matters(geosmin, 2-mib) in water using sparger |
| WO2014156694A1 (en) * | 2013-03-28 | 2014-10-02 | 栗田工業株式会社 | Particulate-measuring method, particulate-measuring system, and system for manufacturing ultrapure water |
| JP2015094641A (en) * | 2013-11-11 | 2015-05-18 | 新コスモス電機株式会社 | Environment monitoring system |
| JP2017122661A (en) * | 2016-01-07 | 2017-07-13 | 紀本電子工業株式会社 | Volatile organic compound measuring device and volatile organic compound measuring method |
| JP2017223583A (en) * | 2016-06-16 | 2017-12-21 | 株式会社島津製作所 | Water Quality Analyzer |
| JP2018009931A (en) * | 2016-07-15 | 2018-01-18 | 日本電子株式会社 | Gas chromatography pretreatment device and gas collecting tube |
| KR20190107411A (en) * | 2018-03-12 | 2019-09-20 | 주식회사 과학기술분석센타 | Continuous measuring device for odorous susbstances and method thereof |
| WO2020022413A1 (en) * | 2018-07-25 | 2020-01-30 | ダイキン工業株式会社 | Gas concentration prediction method |
| JPWO2020022413A1 (en) * | 2018-07-25 | 2021-03-25 | ダイキン工業株式会社 | Gas concentration prediction method |
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| Publication number | Publication date |
|---|---|
| JP3539080B2 (en) | 2004-06-14 |
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