JP2000193656A - Automatic drainage analyzer - Google Patents
Automatic drainage analyzerInfo
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- JP2000193656A JP2000193656A JP10367758A JP36775898A JP2000193656A JP 2000193656 A JP2000193656 A JP 2000193656A JP 10367758 A JP10367758 A JP 10367758A JP 36775898 A JP36775898 A JP 36775898A JP 2000193656 A JP2000193656 A JP 2000193656A
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- Prior art keywords
- sample
- gas
- liquid
- sample liquid
- processing container
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- Automatic Analysis And Handling Materials Therefor (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、排水の分析装置で
あり、特に、プロセス排水、地下水、井戸水等に含有す
るハロゲン化炭化水素を自動分析する装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for analyzing wastewater, and more particularly to an apparatus for automatically analyzing halogenated hydrocarbons contained in process wastewater, groundwater, well water and the like.
【０００２】[0002]
【従来の技術】従来、プロセス排水等に含有のハロゲン
化炭化水素（ジクロロメタン、トリクロロエチレン、テ
トラクロロエチレン等）は、ＪＩＳＫ０１２５によるヘ
ッドスペース・ガスクロマトグラフ法がある。この方法
は採取した試料液をバイアル瓶で、２５℃で気液平衡状
態にした後、ガス部をガスクロマトグラフで分析する方
法である。又、試料液中に空気や窒素を吹き込むバブリ
ング法は、含有のハロゲン化炭化水素を前記空気で追い
出して、そのガスを分析する方法である。又、試薬とハ
ロゲン化炭化水素を反応させ、生成する蛍光縮合物を測
定する方法がある。2. Description of the Related Art Conventionally, there is a headspace gas chromatography method according to JIS K0125 for halogenated hydrocarbons (dichloromethane, trichloroethylene, tetrachloroethylene, etc.) contained in process wastewater and the like. This method is a method in which a collected sample solution is brought into a gas-liquid equilibrium state at 25 ° C. in a vial bottle, and then the gas portion is analyzed by gas chromatography. The bubbling method in which air or nitrogen is blown into a sample solution is a method in which halogenated hydrocarbons contained are expelled by the air and the gas is analyzed. There is also a method in which a reagent is reacted with a halogenated hydrocarbon to measure a fluorescent condensate produced.
【０００３】[0003]
【発明が解決しようとする課題】前記分析方法は、いず
れも試料液を採取したり、気液平衡状態まで昇温したり
等の作業は、人手で行っている。また、前記ヘッドスペ
ース・ガスクロマトグラフ法は、気液平衡状態になるま
で、約３０分以上かかり、試料採取から分析終了まで約
２時間を要する。バブリング法は、試料液に空気や窒素
ガスを吹き込むために、ハロゲン化炭化水素濃度が希釈
され、正確な濃度分析を得ることができない。蛍光縮合
物を測定する方法は、試薬と反応させるために、反応可
能な物質はハロゲン化炭化水素に限定され、その他の物
質の測定には不適である。以上のように、従来の分析方
法は、何れも、短時間に且つ精度よく分析することが困
難である。そこで、本発明は、かかる課題を解消する自
動排水分析装置を提供するものである。In each of the above-mentioned analysis methods, operations such as collecting a sample liquid and raising the temperature to a gas-liquid equilibrium state are performed manually. In addition, the headspace gas chromatograph method requires about 30 minutes or more to reach a gas-liquid equilibrium state, and requires about 2 hours from sampling to completion of analysis. In the bubbling method, since air or nitrogen gas is blown into a sample solution, the concentration of the halogenated hydrocarbon is diluted, and accurate concentration analysis cannot be obtained. In the method of measuring a fluorescent condensate, a reactable substance is limited to a halogenated hydrocarbon because it reacts with a reagent, and is not suitable for measurement of other substances. As described above, it is difficult to analyze all of the conventional analysis methods in a short time and with high accuracy. Therefore, the present invention provides an automatic drainage analyzer that solves such a problem.
【０００４】[0004]
【課題を解決するための手段】請求項１の自動排水分析
装置は、制御装置を介して、サンプリング工程から順
次、試料液の供給工程、試料液の処理工程、試料ガスの
送気工程、分析工程の処理をする自動化を図るものであ
り、時間的、労力面において経済性に富む。請求項２の
自動排水分析装置は、制御装置によって試料液のサンプ
リング工程、試料液の供給工程、試料液の処理工程、試
料ガスの送気工程、分析工程を実施し、試料液の供給工
程の前段階において、試料処理容器を試料液により洗浄
することによって、前回の試料液と混ざることなく、新
たな試料液の受入れができる。請求項３の自動排水分析
装置は、試料ガスの送気工程において、試料液、水道水
又は洗浄水等を用いて、試料処理容器のガス槽の試料ガ
スを分析機器に送気することによって、簡便に、試料ガ
スを送り込むことができる。According to the first aspect of the present invention, there is provided an automatic drainage analyzer, wherein a sample liquid supply step, a sample liquid treatment step, a sample gas supply step, and an analysis step are sequentially performed from a sampling step through a control unit. It is intended to automate the processing of the process, and is economical in terms of time and labor. The automatic drainage analyzer according to claim 2 performs a sample liquid sampling step, a sample liquid supply step, a sample liquid processing step, a sample gas supply step, and an analysis step by the control device, and performs the sample liquid supply step. By washing the sample processing container with the sample liquid in the previous stage, a new sample liquid can be received without being mixed with the previous sample liquid. The automatic drainage analyzer according to claim 3, in the gas supply step of the sample gas, by using a sample liquid, tap water, or washing water, etc., by sending the sample gas in the gas tank of the sample processing container to the analysis device, The sample gas can be easily sent.
【０００５】請求項４の自動排水分析装置は、試料液を
採取するサンプル保管槽とサンプル保管槽の試料液を試
料処理容器に供給するに当たって汚物除去をするフィル
タを洗浄水を介して洗浄可能に構成してあることによっ
て、異物を含まない試料液での分析が可能であると共
に、連続自動分析を可能にする。請求項５の自動排水分
析装置は、試料ガスの送気工程が終了後に、送気管内に
置換ガスを送気することによって、送気管内を乾燥させ
ることができ、水分除去によって試料ガスの吸収が防止
でき、正確な分析を可能にする。According to a fourth aspect of the present invention, there is provided an automatic drainage analyzer, wherein a sample storage tank for collecting a sample liquid and a filter for removing dirt when supplying the sample liquid in the sample storage tank to the sample processing container can be washed through the washing water. With this configuration, it is possible to perform analysis using a sample liquid containing no foreign matter, and to enable continuous automatic analysis. The automatic drainage analyzer according to claim 5 can dry the inside of the air supply pipe by feeding the replacement gas into the air supply pipe after the gas supply step of the sample gas is completed, and can absorb the sample gas by removing water. Can be prevented and accurate analysis can be performed.
【０００６】[0006]
【発明の実施の態様】本発明の実施の形態を図を参照し
て説明する。図１はプロセス排水等に含有のハロゲン化
炭化水素（ジクロロメタン、トリクロロエチレン、テト
ラクロロエチレン等）の自動排水分析装置の全体図であ
り、サンプリング部、試料液処理部、分析部及び制御部
で構成する。先ず、サンプリング部について説明する
と、サンプル保管槽２は試料液を貯留するものであり、
底部２ａが尖塔状で排出したとき残液が残らない形状の
筒体である。又、プロセス排水等から試料液ポンプ１等
を介して、前記サンプル保管槽２に試料液を送液する入
口管１ａが、サンプル保管槽２の上部に接続してある。Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is an overall view of an automatic drainage analyzer for halogenated hydrocarbons (e.g., dichloromethane, trichloroethylene, tetrachloroethylene, etc.) contained in process wastewater and the like, and includes a sampling unit, a sample liquid treatment unit, an analysis unit, and a control unit. First, the sampling section will be described. The sample storage tank 2 stores a sample liquid.
The bottom 2a is a cylinder having a shape in which no residual liquid remains when discharged in a spire shape. An inlet pipe 1a for sending a sample solution from the process wastewater or the like to the sample storage tank 2 via a sample liquid pump 1 or the like is connected to an upper portion of the sample storage tank 2.
【０００７】前記サンプル保管槽２の底部には、逆Ｕ字
状の循環排出管３が設置してあり、この頂部３ａがサン
プル保管槽の液位となる。又、サンプル保管槽２の底部
にはドレン電磁弁Ａを介して排出管４が設けてある。
尚、サンプル保管槽２には、常時多量の試料液を流し、
循環排出管３よりオーバーフローさせており、サンプル
保管槽２の滞留時間を短くしているので、試料液の入れ
替えが早くでき、試料処理容器１０にはいつも新しい試
料液の供給可能である。又、前記サンプル保管槽２の液
位のほぼ中央となる位置には、異物を除去するフィルタ
５が取り付けてあり、試料液電磁弁Ｂを介して、試料処
理容器１０に、ヘッド差で供給可能な供給管７が設けて
ある。尚、前記フィルタ５の下流側（試料液電磁弁Ｂの
上流側）には、洗浄水電磁弁Ｃを介して洗浄管６が接続
してあり、この洗浄液によって、前記フィルタ５の洗浄
を可能にする。又、フィルタ５の下流側の供給管７に
は、必ずしも必要でない、試料ガスの送気に使用する水
道管１８が、水道水電磁弁Ｇを介して接続してある。At the bottom of the sample storage tank 2, an inverted U-shaped circulation discharge pipe 3 is installed, and the top 3a is the liquid level of the sample storage tank. A discharge pipe 4 is provided at the bottom of the sample storage tank 2 via a drain solenoid valve A.
It should be noted that a large amount of the sample liquid is always flowed into the sample storage tank 2,
Since the sample is overflowed from the circulation discharge pipe 3 and the residence time of the sample storage tank 2 is shortened, the replacement of the sample liquid can be performed quickly, and a new sample liquid can always be supplied to the sample processing container 10. A filter 5 for removing foreign matter is attached at a position substantially at the center of the liquid level of the sample storage tank 2, and can be supplied to the sample processing container 10 via the sample liquid solenoid valve B with a head difference. Supply pipe 7 is provided. A washing pipe 6 is connected to the downstream side of the filter 5 (upstream of the sample liquid solenoid valve B) via a washing water solenoid valve C, and the washing liquid enables the filter 5 to be washed. I do. Further, a water supply pipe 18 which is not always necessary and is used for feeding the sample gas is connected to the supply pipe 7 on the downstream side of the filter 5 via a tap water solenoid valve G.
【０００８】次に、試料液処理部の構成について説明す
ると、前記試料処理容器１０は５０〜２０００ｍｌの容
量であり、後述する分析機器（ガスクロマトグラフ）２
０に到る送気管１５の置換が十分に行え、且つ、試料ガ
スが得られることと、気液平衡状態になるまでに要する
時間を考慮すると共に、試料液は試料処理容器１０の４
０〜６０％に充填すること等を考慮して選定する。Next, the configuration of the sample liquid processing section will be described. The sample processing container 10 has a capacity of 50 to 2000 ml, and has an analytical instrument (gas chromatograph) 2 described later.
In addition to taking into account that the gas supply pipe 15 can be sufficiently replaced with zero and that the sample gas is obtained and that the time required for the gas-liquid equilibrium state is achieved,
It is selected in consideration of filling to 0 to 60%.
【０００９】そして、この試料処理容器１０は、水を媒
体の恒温槽１１に入れられ、この恒温槽１１はヒータで
所定温に保持されると共に、撹拌棒（スターラー）を介
して撹拌可能になっている。尚、この撹拌操作は、早期
に気液平衡状態にするので望ましいが、必ずしも必要で
ない。また、ハロゲン化炭化水素の分析における気液平
衡温度は、３０〜７０℃で、望ましくは３５〜６０℃で
あり、試料処理容器１０内の試料液量及び昇温時間等を
考慮してヒータ前記容量を選定する。即ち、この気液平
衡温度を３０℃以下にすると、気液平衡状態になるまで
に多くの時間を要する一方、７０℃以上では水蒸気の発
生が多くなり分析精度の低下を招来するし、後記の送気
管１５内において、水蒸気が結露してハロゲン化炭化水
素を吸収して分析精度の低下となる。そのため、気液平
衡温度を３５〜６０℃に設定すると、各成分の蒸気圧
（分圧）が高くなり、ハロゲン化炭化水素の分析感度の
向上となって、２ｐｐｂの微量まで測定可能となる。The sample processing vessel 10 is filled with water in a constant temperature bath 11 of a medium. The constant temperature bath 11 is maintained at a predetermined temperature by a heater and can be stirred through a stirrer (stirrer). ing. Note that this stirring operation is desirable because it brings the gas-liquid equilibrium state at an early stage, but is not always necessary. The vapor-liquid equilibrium temperature in the analysis of the halogenated hydrocarbon is 30 to 70 ° C., preferably 35 to 60 ° C., and the temperature of the heater is determined in consideration of the amount of the sample liquid in the sample processing container 10 and the heating time. Select the capacity. That is, if the gas-liquid equilibrium temperature is set to 30 ° C. or lower, it takes a lot of time to reach the gas-liquid equilibrium state. In the air supply pipe 15, water vapor is condensed and absorbs halogenated hydrocarbons, thereby lowering the analysis accuracy. Therefore, when the vapor-liquid equilibrium temperature is set to 35 to 60 ° C., the vapor pressure (partial pressure) of each component is increased, the analysis sensitivity of the halogenated hydrocarbon is improved, and a trace amount of 2 ppb can be measured.
【００１０】又、前記気液平衡状態に到るまでの所要時
間は、８〜３０分でよく、１２〜２５分が望ましい。こ
の所要時間を短時間（例えば８分以下）で行うと、気液
平衡状態にならない状態での分析となって、分析精度の
低下となるし、３０分以上となると、気液平衡状態は変
わらず、時間の浪費であると共に、分解する物質が生ず
る。The time required to reach the gas-liquid equilibrium state may be 8 to 30 minutes, preferably 12 to 25 minutes. If this required time is performed in a short time (for example, 8 minutes or less), the analysis will be performed in a state where the gas-liquid equilibrium is not attained, and the analysis accuracy will be reduced. Time consuming and decomposes substances.
【００１１】又、試料処理容器１０内の試料液の全量を
抜くために、液抜き管１３が底部近くに挿入してあり、
液抜電磁弁Ｄを介してアスピレータ（図示略）等で排出
可能になっている。一方、試料処理容器１０の上部に
は、試料ガスを送気する送気管１５が施設してあり、そ
の途中には、置換電磁弁（３方電磁弁）Ｅと切換電磁弁
（６方電磁弁）Ｆが直列に装着してある。そして、前記
置換電磁弁Ｅには、置換ガス（窒素ガスや空気等）を送
り込む置換管１４が接続してあり、送気管１５等の置換
を行う。又、前記切換電磁弁Ｆは、図３（Ａ）（Ｂ）に
示すように６方弁であり、(1)は送気ガス（窒素ガス
等）に、(3)は送気管１５に、(2)と(5)は定量管（テフ
ロンチューブで形成の容量２ｍｌ）１６に接続してあ
り、(4)は排気管１７に、(6)は分析機器（ガスクロマト
グラフ）２０に接続してある。そして、この切換電磁弁
Ｆは、常時は、(1)と(6)、(2)と(3)、(4)と(5)が導通の
排気側であり、試料ガスを採取するときには、(1)と
(2)、(3)と(4)、(5)と(6)を導通の採取側にして行われ
る。ガスクロマトグラフ２０はよく知られた分析計であ
り、分析結果はデータ処理機２１を介して分析結果を出
力する。A drain pipe 13 is inserted near the bottom in order to drain the entire amount of the sample liquid in the sample processing container 10,
The liquid can be discharged by an aspirator (not shown) or the like via a liquid draining electromagnetic valve D. On the other hand, an air supply pipe 15 for supplying a sample gas is provided at the upper part of the sample processing container 10, and a replacement solenoid valve (3-way solenoid valve) E and a switching solenoid valve (6-way solenoid valve) are provided in the middle thereof. ) F is mounted in series. The replacement solenoid valve E is connected to a replacement pipe 14 for sending a replacement gas (nitrogen gas, air, or the like), and replaces the air supply pipe 15 and the like. The switching solenoid valve F is a six-way valve as shown in FIGS. 3A and 3B. (1) is for an air supply gas (such as nitrogen gas), (3) is for an air supply pipe 15, (2) and (5) are connected to a quantitative tube (volume of 2 ml formed with a Teflon tube) 16, (4) is connected to an exhaust pipe 17, and (6) is connected to an analytical instrument (gas chromatograph) 20. is there. The switching solenoid valve F is normally on the exhaust side where (1) and (6), (2) and (3), and (4) and (5) are conducting, and when the sample gas is collected, (1) and
(2), (3) and (4), and (5) and (6), with the conducting side being the sampling side. The gas chromatograph 20 is a well-known analyzer, and the analysis result is output via a data processor 21.
【００１２】次に、制御部の制御装置２５は、前記構成
の分析装置の各機器を制御し、この自動分析の制御過程
について、図２（Ａ）（Ｂ）を参照して説明する。尚、
各工程は、電磁弁等の操作終了によったり、タイマー
（制御装置内蔵）によるタイムアップによって制御す
る。Next, the control unit 25 of the control unit controls each device of the analyzer having the above-described configuration, and a control process of the automatic analysis will be described with reference to FIGS. still,
Each step is controlled by terminating the operation of a solenoid valve or the like or by time-up by a timer (built-in control device).
【００１３】（１）試料液のサンプリング工程 ドレン電磁弁Ａと試料液電磁弁Ｂを閉にし、試料液ポン
プ１を起動すると、試料液は入口管１ａ、サンプル保管
槽２、循環排出管３を介して循環し、サンプル保管槽２
には新たな試料液が貯留される。(1) Sample Liquid Sampling Step When the drain electromagnetic valve A and the sample liquid electromagnetic valve B are closed and the sample liquid pump 1 is started, the sample liquid passes through the inlet pipe 1a, the sample storage tank 2, and the circulation discharge pipe 3. Circulates through the sample storage tank 2
, A new sample liquid is stored.
【００１４】（２）試料処理容器の前処理工程 この処理において、試料処理容器１０は、置換ガスが送
気管１５に送気可能側に置換電磁弁Ｅを切換えてある
（後記の（７）で処理済）と共に、試料液電磁弁Ｂが閉
状態で、閉鎖状態であり、撹拌棒（スターラー）を停止
する。そして、液抜電磁弁Ｄを開にした後に、アスピレ
ータ等を介して試料処理容器１０内の試料液を抜いた後
に、試料液電磁弁Ｂを開にして、サンプル保管槽２から
試料液をフィルタ５を介して、試料処理容器の８０〜１
００％になるまで充填する。そして、再度、液抜電磁弁
Ｄを開にした後に、アスピレータ等を介して、試料処理
容器１０内の試料液を抜くと、試料処理容器１０内は新
たな試料液で洗浄されて空になる。そのため、前回の試
料液と交ざることなく、新たな試料液の受入れができ
る。(2) Pretreatment Step of Sample Processing Vessel In this process, the sample processing vessel 10 switches the replacement solenoid valve E to the side where the replacement gas can be supplied to the air supply pipe 15 (see (7) described later). The sample liquid solenoid valve B is in a closed state with the sample liquid solenoid valve B closed, and the stirring rod (stirrer) is stopped. Then, after opening the liquid draining electromagnetic valve D, the sample liquid in the sample processing container 10 is drained through an aspirator or the like, and then the sample liquid electromagnetic valve B is opened to filter the sample liquid from the sample storage tank 2. 5 through 80-1 of the sample processing container
Fill to 00%. Then, after opening the liquid draining electromagnetic valve D again, when the sample liquid in the sample processing container 10 is drained via an aspirator or the like, the inside of the sample processing container 10 is washed with a new sample liquid and becomes empty. . Therefore, a new sample liquid can be received without intersecting with the previous sample liquid.
【００１５】（３）試料液の供給工程 次に、前記（２）の工程で、試料液で洗浄された試料処
理容器１０に、試料液を供給するために試料液電磁弁Ｂ
を開にすると、サンプル保管槽２の試料液はフィルタ５
を介して試料処理容器１０に供給される。そして、試料
処理容器の４０〜６０％なったとき、試料液電磁弁Ｂを
閉にして供給を停止する。(3) Step of Supplying Sample Liquid Next, in the step (2), the sample liquid solenoid valve B is used to supply the sample liquid to the sample processing container 10 which has been washed with the sample liquid.
Is opened, the sample liquid in the sample storage tank 2 is
Is supplied to the sample processing container 10 through the. When the amount of the sample processing container reaches 40 to 60%, the sample liquid solenoid valve B is closed to stop the supply.
【００１６】（４）試料液の処理工程 そして、試料処理容器１０内の試料液を撹拌棒等で撹拌
すると共に、恒温槽１１を介して試料処理容器１０が気
液平衡温度まで昇温すると共に維持する。尚、この気液
平衡温度は５０℃で、所要時間は約２０分で行う。(4) Sample Liquid Processing Step The sample liquid in the sample processing container 10 is agitated with a stirring rod or the like, and the temperature of the sample processing container 10 is raised to the gas-liquid equilibrium temperature via the thermostat 11. maintain. The vapor-liquid equilibrium temperature is 50 ° C. and the required time is about 20 minutes.
【００１７】（５）試料ガスの送気工程 試料処理容器１０のガス槽の試料ガスをガスクロマトグ
ラフ２０に送気するために、試料処理容器１０内に媒体
（試料液、水道水、洗浄水等）を注水することによっ
て、ガス槽の試料ガスの排出ができる。そこで、先ず、
切換電磁弁Ｆを排気側（図３（Ａ））を維持する一方、
置換電磁弁Ｅは、置換ガスが送気管１５に送気不可側に
切り換えて、置換ガスの送気管１５への送気を停止す
る。(5) Sample Gas Supply Step In order to send the sample gas in the gas tank of the sample processing container 10 to the gas chromatograph 20, a medium (sample liquid, tap water, washing water, etc.) is placed in the sample processing container 10. ), The sample gas in the gas tank can be discharged. So, first,
While maintaining the switching solenoid valve F on the exhaust side (FIG. 3A),
The replacement solenoid valve E switches the replacement gas to the side where the supply of the replacement gas to the air supply pipe 15 is impossible, and stops the supply of the replacement gas to the air supply pipe 15.
【００１８】（イ）そして、試料液電磁弁Ｂを開にし
て、試料液を試料処理容器１０に供給すると、試料ガス
は送気管１５から切換電磁弁Ｆの(3)に入り、(2)(5)の
定量管１６を経て(4)の排気管１７から排気される。こ
の処置によって、前記経路は試料ガスによって置換され
る。一方、送気ガス（窒素ガス）は切換電磁弁Ｆの(1)
から入り、(6)から分析機器２０に流入し、この経路は
窒素ガスで置換される。(A) Then, when the sample liquid solenoid valve B is opened and the sample liquid is supplied to the sample processing container 10, the sample gas enters (3) of the switching solenoid valve F from the air supply pipe 15 and (2) The gas is exhausted from the exhaust pipe 17 of (4) through the quantitative pipe 16 of (5). By this measure, the path is replaced by the sample gas. On the other hand, the supply gas (nitrogen gas) is supplied by the switching solenoid valve F (1)
, And flows into the analyzer 20 from (6), and this path is replaced with nitrogen gas.
【００１９】その後、切換電磁弁Ｆを採取側（図３
（Ｂ））に切り換えると、送気ガスは切換電磁弁Ｆの
(1)から入り、(2)(5)の定量管１６を経て、(6)から分析
機器２０に流入し、前記定量管１６内の試料ガスは分析
機器２０に送り込まれて定量のサンプル採取が可能であ
る。一方、試料ガスは送気管１５から切換電磁弁Ｆの
(3)に入り、(4)の排気管１７から排気される。Thereafter, the switching solenoid valve F is moved to the sampling side (FIG. 3).
(B)), the supply gas is supplied to the switching solenoid valve F.
It enters from (1), passes through the quantitative tube 16 of (2) and (5), flows into the analytical device 20 from (6), and the sample gas in the quantitative tube 16 is sent to the analytical device 20 to collect a quantitative sample. Is possible. On the other hand, the sample gas is supplied from the air supply pipe 15 to the switching solenoid valve F.
After entering (3), the air is exhausted from the exhaust pipe 17 of (4).
【００２０】（ロ）又、他の方法について説明すると、
水道水電磁弁Ｇを開にして、水道水を水道水管１８を介
して試料処理容器１０に送る。これによって、試料処理
容器１０内の試料ガスは、送気管１５に送られるので、
前記（イ）と同様の操作によって、試料ガスをガスクロ
マトグラフ２０に送気可能になる。(B) Another method will be described.
The tap water solenoid valve G is opened, and tap water is sent to the sample processing container 10 through the tap water pipe 18. Thereby, the sample gas in the sample processing container 10 is sent to the air supply pipe 15,
The sample gas can be sent to the gas chromatograph 20 by the same operation as the above (a).
【００２１】（ハ）又、後記で詳述するフィルタ５等の
洗浄をする「洗浄水」を使用するときには、フィルタ５
の下流に電磁弁（図示略）を設置して、洗浄水がフィル
タ５側に流れないようにする。そして、洗浄水電磁弁Ｃ
を開にして、洗浄水を試料処理容器１０に送ることによ
って、試料処理容器１０内の試料ガスは、送気管１５に
送られ、前記（イ）と同様の操作によって、試料ガスを
ガスクロマトグラフ２０に送気可能になる。尚、この洗
浄水の使用は、フィルタ５等の洗浄にために設置の施設
（洗浄水配管６、洗浄水電磁弁Ｃ）を使用することがで
きるので、設備の簡素化を図ることができる。(C) When using "wash water" for washing the filter 5 and the like described in detail below, the filter 5
An electromagnetic valve (not shown) is provided downstream of the filter to prevent the washing water from flowing to the filter 5 side. And the washing water solenoid valve C
Is opened, and the cleaning water is sent to the sample processing container 10, whereby the sample gas in the sample processing container 10 is sent to the air supply pipe 15, and the sample gas is transferred to the gas chromatograph 20 by the same operation as in (a). It becomes possible to send air. The use of this washing water can use the installed facilities (washing water piping 6, washing water solenoid valve C) for washing the filter 5 and the like, so that the equipment can be simplified.
【００２２】以上のように、試料処理容器１０内に試料
液等を供給することによって、簡便に、試料ガスは送気
管１５に送られ、送気管１５内の置換を行った後に、ガ
スクロマトグラフ２０に送気するので、ガスクロマトグ
ラフ２０には試料ガスのみが送られる。As described above, by supplying the sample liquid or the like into the sample processing container 10, the sample gas is easily sent to the gas supply pipe 15, and after the gas supply pipe 15 is replaced, the gas chromatograph 20 , Only the sample gas is sent to the gas chromatograph 20.
【００２３】（６）分析工程 ガスクロマトフラフ２０に送られた試料ガスは分析され
て、分析結果はデータ処理機２１を介して分析結果を出
力する。(6) Analysis Step The sample gas sent to the gas chromatograph 20 is analyzed, and the analysis result is output via the data processor 21.
【００２４】（７）送気管１５の乾燥工程 この工程は、特に、試料ガスにハロゲン化炭化水素を含
む場合に備えるものであり、前記（５）の試料ガスの送
気工程が終了した後には、置換ガスが送気管１５に送気
可能側に置換電磁弁Ｅを切換えると共に、切換電磁弁Ｆ
を排気側（図３（Ａ））に切り換えて、排気管１７を介
して排出可能にする。置換ガスは、送気管１５、定量管
１６内の試料ガスの放出を行い、それらの経路内の水分
除去を行うと共に乾燥させる。そのため、水分による試
料ガスの吸収が防止でき、正確な分析が可能となる。
尚、この工程は、ハロゲン化炭化水素以外の物質の場合
には、必ずしも必要でない。(7) Step of drying the gas supply pipe 15 This step is provided especially when the sample gas contains a halogenated hydrocarbon. After the step (5), the sample gas supply step is completed. , The switching solenoid valve E is switched to a side where the replacement gas can be supplied to the air supply pipe 15 and the switching solenoid valve F
Is switched to the exhaust side (FIG. 3 (A)) so that exhaust can be performed via the exhaust pipe 17. The replacement gas releases the sample gas in the air supply pipe 15 and the fixed quantity pipe 16, removes water in those paths, and is dried. Therefore, absorption of the sample gas by moisture can be prevented, and accurate analysis can be performed.
This step is not always necessary for substances other than halogenated hydrocarbons.
【００２５】（８）フィルタ５の洗浄工程 プロセス排水等の試料液に含有のゴミ等は、フィルタ５
で除去されるので、フィルタ５の洗浄を要すると共に、
サンプル保管槽２の底部に溜る汚物等を除去する必要が
ある。そこで、これらフィルタ５、サンプル保管槽２の
洗浄を行うには、前記（５）の試料ガスの送気に使用す
る媒体によって、下記の時に行うが、毎回行う必要はな
い。(8) Filter 5 Cleaning Step Dust and the like contained in the sample liquid such as process wastewater are removed by the filter 5.
So that the filter 5 needs to be washed and
It is necessary to remove dirt and the like accumulated at the bottom of the sample storage tank 2. Therefore, the filter 5 and the sample storage tank 2 are cleaned at the following times, depending on the medium used for supplying the sample gas in the above (5), but need not be performed every time.
【００２６】（イ）媒体に「試料液」を使用するときに
は、この試料液は、試料処理容器１０内のガスを送気管
１５からガスクロマトフラフ２０に送気するのに使用す
るために、この処理の終了後において実施する（図２
（Ａ））。そして、試料液ポンプ１を停止すると共に試
料液電磁弁Ｂを閉にし、ドレン電磁弁Ａを開にして、サ
ンプル保管槽２内の試料液を抜きながら、洗浄水電磁弁
Ｃを開にする。そして、洗浄水を洗浄管６から流すと、
洗浄水はフィルタ５からサンプル保管槽２に流れ込み、
フィルタ５とサンプル保管槽２を洗浄した後、ドレン電
磁弁Ａを介して排出管４から排出される。(A) When a “sample liquid” is used as a medium, this sample liquid is used for sending gas in the sample processing container 10 from the air supply pipe 15 to the gas chromatograph 20. This is performed after the processing is completed (FIG. 2
(A)). Then, the sample solution pump 1 is stopped, the sample solution solenoid valve B is closed, the drain solenoid valve A is opened, and the washing water solenoid valve C is opened while draining the sample solution in the sample storage tank 2. Then, when the washing water flows from the washing pipe 6,
The washing water flows from the filter 5 into the sample storage tank 2,
After the filter 5 and the sample storage tank 2 have been washed, they are discharged from the discharge pipe 4 via the drain solenoid valve A.
【００２７】（ロ）一方、媒体に「水道水」を使用する
場合には、試料液が試料液電磁弁Ｂを開にしてサンプル
保管槽２から試料処理容器１０に供給された後、即ち、
前記「（３）試料液の供給」の終了以降に行うことがで
きるので（図２（Ｂ））、前記（イ）の時期に実施して
もよい。この処理は、前記（イ）と同様に、試料液ポン
プ１を停止、試料液電磁弁Ｂを閉、ドレン電磁弁Ａを
開、洗浄水電磁弁Ｃを開にした後に、洗浄水を洗浄管６
から流すと、フィルタ５とサンプル保管槽２が共に洗浄
される。(B) On the other hand, when “tap water” is used as the medium, the sample liquid is supplied from the sample storage tank 2 to the sample processing vessel 10 by opening the sample liquid solenoid valve B, ie,
Since it can be performed after the end of “(3) Supply of sample liquid” (FIG. 2B), it may be performed at the time of (A). In this process, the sample liquid pump 1 is stopped, the sample liquid solenoid valve B is closed, the drain solenoid valve A is opened, the washing water solenoid valve C is opened, and then the washing water is flushed. 6
, The filter 5 and the sample storage tank 2 are both washed.
【００２８】この様に、フィルタ５、サンプル保管槽２
の洗浄を同時に自動的に行うことによって、連続自動分
析を可能にする。尚、前記（イ）又は（ロ）のフィルタ
等の洗浄が終了したときには、前記「（１）試料のサン
プリング」工程に戻る。As described above, the filter 5 and the sample storage tank 2
By automatically performing the washing of the sample simultaneously, continuous automatic analysis is enabled. When the washing of the filter (a) or (b) is completed, the process returns to the "(1) sample sampling" step.
【００２９】以上のように、制御装置２５を介して、
（１）試料液のサンプリング工程、（２）試料処理容器
の前処理工程、（３）試料液の供給工程、（４）試料液
の処理工程、（５）試料ガスの送気工程、（６）分析工
程、（７）送気管の乾燥工程、（８）フィルタの洗浄工
程の一連の操作を実施することによって、人手を介さず
に、且つ、短時間で連続自動分析をすることができる。
尚、前記自動排水分析装置は、ハロゲン化炭化水素の沸
点が−２０〜２００℃の物質に適用する例を示したが、
気液平衡による分析を用いる他の物質に適用できること
はいうまでもないし、高沸点物における気液平衡温度を
下げるために、試料処理容器１０に凝縮器と真空ポンプ
を介して、減圧化で気液平衡状態にして、試料ガスを採
取する構成であってもよい。As described above, through the control device 25,
(1) sample liquid sampling step, (2) sample processing container pretreatment step, (3) sample liquid supply step, (4) sample liquid processing step, (5) sample gas feeding step, (6) By performing a series of operations of the analysis step, (7) drying step of the air supply pipe, and (8) washing step of the filter, continuous automatic analysis can be performed in a short time without manual operation.
In addition, although the said automatic drainage analyzer showed the example applied to the substance whose boiling point of a halogenated hydrocarbon is -20-200 degreeC,
It goes without saying that the analysis by gas-liquid equilibrium can be applied to other substances. In order to lower the gas-liquid equilibrium temperature of high-boiling substances, the sample processing vessel 10 is evacuated through a condenser and a vacuum pump. A configuration in which the sample gas is collected in a liquid equilibrium state may be employed.
【００３０】[0030]
【発明の効果】請求項１の自動排水分析装置は、制御装
置を介して、サンプリング工程から順次、試料液の供給
工程、処理工程、送気工程、分析工程の処理をする自動
化を図るものであり、時間的、労力面において経済性に
富む。請求項２の自動排水分析装置は、試料液の供給工
程の前段階において、試料処理容器を試料液を介して洗
浄することによって、前回の試料液と交ざることなく、
新たな試料液での分析ができる。請求項３の自動排水分
析装置は、試料ガスの送気工程において、試料液、水道
水又は洗浄水等を用いて、試料処理容器のガス槽の試料
ガスを分析機器に送気することによって、簡便に、試料
ガスを送り込むことができる。請求項４の自動排水分析
装置は、試料液を採取するサンプル保管槽とサンプル保
管槽の試料液を試料処理容器に供給するに当たって汚物
除去をするフィルタを洗浄水を介して洗浄可能に構成し
てあることによって、異物を含まない試料液での分析が
可能であると共に、連続自動分析を可能にする。請求項
５の自動排水分析装置は、試料ガスの送気工程が終了後
に、送気管内に置換ガスを送気することによって、送気
管内を乾燥させることができ、水分除去によって試料ガ
スの吸収が防止でき、正確な分析を可能にする。According to the first aspect of the present invention, there is provided an automatic drainage analyzer which automates processing of a sample liquid supply step, a processing step, an air supply step, and an analysis step from a sampling step through a control device. Yes, economical in terms of time and labor. The automatic drainage analyzer according to claim 2 cleans the sample processing container via the sample liquid at a stage prior to the sample liquid supply step, so that the sample processing container does not intersect with the previous sample liquid.
Analysis with a new sample solution is possible. The automatic drainage analyzer according to claim 3, in the gas supply step of the sample gas, by using a sample liquid, tap water, or washing water, etc., by sending the sample gas in the gas tank of the sample processing container to the analysis device, The sample gas can be easily sent. The automatic drainage analyzer according to claim 4 is configured such that a sample storage tank for collecting the sample liquid and a filter for removing dirt when supplying the sample liquid in the sample storage tank to the sample processing container can be washed through the washing water. This makes it possible to perform analysis using a sample liquid that does not contain foreign matter, and also enables continuous automatic analysis. The automatic drainage analyzer according to claim 5 can dry the inside of the air supply pipe by feeding the replacement gas into the air supply pipe after the gas supply step of the sample gas is completed, and can absorb the sample gas by removing water. Can be prevented and accurate analysis can be performed.
【図１】自動排水装置の全体図である。FIG. 1 is an overall view of an automatic drainage device.
【図２】（Ａ）（Ｂ）は、制御工程を示す図である。FIGS. 2A and 2B are diagrams showing a control process.
【図３】（Ａ）（Ｂ）は切換電磁弁Ｆの導通状態の概念
を示す図である。FIGS. 3A and 3B are diagrams showing a concept of a conductive state of a switching solenoid valve F. FIGS.
１ 試料液ポンプ ２ サンプル保管槽 ３ 循環排出管 ５ フィルタ １０ 試料処理容器 １５ 送気管 １６ 定量管 １７ 排気管 ２０ 分析機器（ガスクロマトグラフ） ２５ 制御装置 Ａ ドレン電磁弁 Ｂ 試料液電磁弁 Ｃ 洗浄水電磁弁 Ｄ 液抜電磁弁 Ｅ 置換電磁弁（３方電磁弁） Ｆ 切換電磁弁（６方電磁弁） Ｇ 水道水電磁弁 DESCRIPTION OF SYMBOLS 1 Sample liquid pump 2 Sample storage tank 3 Circulation discharge pipe 5 Filter 10 Sample processing container 15 Air supply pipe 16 Quantitative pipe 17 Exhaust pipe 20 Analytical equipment (gas chromatograph) 25 Controller A Drain solenoid valve B Sample liquid solenoid valve C Wash water electromagnetic Valve D Drainage solenoid valve E Replacement solenoid valve (3-way solenoid valve) F Switching solenoid valve (6-way solenoid valve) G Tap water solenoid valve
───────────────────────────────────────────────────── フロントページの続き (72)発明者 太田 茂行 徳島県徳島市川内町中島575−１ 東亞合 成株式会社徳島工場内 (72)発明者 川村 篤 徳島県徳島市川内町中島575−１ 東亞合 成株式会社徳島工場内 (72)発明者 吉田 豊文 徳島県徳島市川内町中島575−１ 東亞合 成株式会社徳島工場内 Ｆターム(参考） 2G058 AA01 AA03 BA07 BA08 BB06 BB10 DA09 EA17 EC05 FB01 FB12 GA14 GE01 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigeyuki Ota 575-1 Nakajima, Kawauchi-cho, Tokushima City, Tokushima Prefecture Toa Gosei Securities Co., Ltd. (72) Inventor Atsushi Kawamura 575-1, Nakajima, Kawauchi-cho, Tokushima City, Tokushima In the Tokushima Plant of Gosei Co., Ltd. (72) Inventor Toyofumi Yoshida 575-1 Nakajima, Kawauchi-cho, Tokushima City, Tokushima Prefecture GE01
Claims (5)
プリング工程、前記サンプル保管槽から試料を試料処理
容器に供給する試料液の供給工程、試料液を気液平衡状
態にする試料液の処理工程、平衡状態の試料ガスを分析
機器に送る試料ガスの送気工程、分析機器で分析を行う
分析工程で構成し、 前記サンプリング工程から順次、試料液の供給工程、処
理工程、送気工程、分析工程を制御装置を介して制御す
ることを特徴とする自動排水分析装置。1. A sampling step of collecting a sample liquid into a sample storage tank, a step of supplying a sample liquid to supply a sample from the sample storage tank to a sample processing container, and a step of processing the sample liquid to bring the sample liquid into a gas-liquid equilibrium state , A sample gas sending step for sending a sample gas in an equilibrium state to an analytical instrument, and an analyzing step for performing analysis with an analytical instrument. The sample liquid supplying step, the processing step, the gas sending step, and the analysis are sequentially performed from the sampling step. An automatic drainage analyzer, wherein the process is controlled via a control device.
料処理容器を試料液により洗浄することを特徴とする請
求項１の自動排水分析装置。2. The automatic drainage analyzer according to claim 1, wherein the sample processing container is washed with the sample liquid before the step of supplying the sample liquid.
水道水又は洗浄水等を用いて、試料処理容器のガス槽の
試料ガスを分析機器に送気することを特徴とする請求項
１又は請求項２の自動排水分析装置。3. The method according to claim 1, wherein in the step of feeding the sample gas, a sample liquid,
3. The automatic drainage analyzer according to claim 1, wherein the sample gas in the gas tank of the sample processing container is supplied to the analyzer using tap water or washing water.
プル保管槽の試料液を試料処理容器に供給するにあたっ
て汚物除去をするフィルタを洗浄水を介して洗浄可能に
構成してあることを特徴とする請求項１、請求項２又は
請求項３の自動排水分析装置。4. A sample storage tank for collecting a sample liquid and a filter for removing contaminants when supplying the sample liquid in the sample storage tank to the sample processing container are configured to be washable through washing water. 4. The automatic drainage analyzer according to claim 1, 2 or 3, wherein:
内に置換ガスを送気することを特徴とする請求項１、請
求項２、請求項３又は請求項４の自動排水分析装置。5. The automatic drainage analyzer according to claim 1, wherein the replacement gas is supplied into the gas supply pipe after the sample gas supply step is completed. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36775898A JP3656441B2 (en) | 1998-12-24 | 1998-12-24 | Automatic drainage analyzer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36775898A JP3656441B2 (en) | 1998-12-24 | 1998-12-24 | Automatic drainage analyzer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000193656A true JP2000193656A (en) | 2000-07-14 |
| JP3656441B2 JP3656441B2 (en) | 2005-06-08 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36775898A Expired - Lifetime JP3656441B2 (en) | 1998-12-24 | 1998-12-24 | Automatic drainage analyzer |
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| Country | Link |
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| JP (1) | JP3656441B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109459275A (en) * | 2018-10-15 | 2019-03-12 | 浙江省海洋水产研究所 | A kind of petrochemical industry garden water body matter characteristic contamination collector |
| WO2020022413A1 (en) * | 2018-07-25 | 2020-01-30 | ダイキン工業株式会社 | Gas concentration prediction method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0968485A (en) * | 1995-08-30 | 1997-03-11 | Mitsubishi Chem Corp | Sample feeder in sucker for analyzing total organic halogen |
| JPH1010102A (en) * | 1996-06-20 | 1998-01-16 | Shimadzu Corp | Water-quality analyzing device |
-
1998
- 1998-12-24 JP JP36775898A patent/JP3656441B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0968485A (en) * | 1995-08-30 | 1997-03-11 | Mitsubishi Chem Corp | Sample feeder in sucker for analyzing total organic halogen |
| JPH1010102A (en) * | 1996-06-20 | 1998-01-16 | Shimadzu Corp | Water-quality analyzing device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109459275A (en) * | 2018-10-15 | 2019-03-12 | 浙江省海洋水产研究所 | A kind of petrochemical industry garden water body matter characteristic contamination collector |
| CN109459275B (en) * | 2018-10-15 | 2021-01-05 | 浙江省海洋水产研究所 | Collector for characteristic pollutants of water quality in petrochemical park |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3656441B2 (en) | 2005-06-08 |
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