JPH0653968U - pH / chlorine ion continuous automatic measuring device - Google Patents
pH / chlorine ion continuous automatic measuring deviceInfo
- Publication number
- JPH0653968U JPH0653968U JP4062691U JP4062691U JPH0653968U JP H0653968 U JPH0653968 U JP H0653968U JP 4062691 U JP4062691 U JP 4062691U JP 4062691 U JP4062691 U JP 4062691U JP H0653968 U JPH0653968 U JP H0653968U
- Authority
- JP
- Japan
- Prior art keywords
- ion
- chlorine
- pure water
- container
- storage container
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 51
- IQDRAVRWQIIASA-VZPOTTSCSA-N phlorin Chemical compound C/1=C(N2)\C=C\C2=C\C(N2)=CC=C2CC(N2)=CC=C2\C=C2\C=CC\1=N2 IQDRAVRWQIIASA-VZPOTTSCSA-N 0.000 title claims description 25
- 239000000460 chlorine Substances 0.000 claims abstract description 125
- 150000002500 ions Chemical class 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000002904 solvent Substances 0.000 claims abstract description 47
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 33
- 239000003960 organic solvent Substances 0.000 claims abstract description 31
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims description 75
- 238000004140 cleaning Methods 0.000 claims description 17
- 239000012088 reference solution Substances 0.000 claims description 16
- 239000008351 acetate buffer Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 239000007853 buffer solution Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 2
- 230000006866 deterioration Effects 0.000 abstract description 13
- 238000001816 cooling Methods 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 36
- 239000002699 waste material Substances 0.000 description 30
- 238000005259 measurement Methods 0.000 description 27
- 239000012086 standard solution Substances 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 6
- -1 hydrogen ions Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000001139 pH measurement Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012482 calibration solution Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000004457 water analysis Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
(57)【要約】
【目的】 溶剤洗浄器に付設された塩素系有機溶剤のｐ
Ｈ・塩素イオン連続自動測定装置を提供することにあ
る。
【構成】 溶剤洗浄器からサンブリングした塩素系有機
溶剤に一定量の純水を添加して室温に冷却した後、ｐＨ
・Ｃｌイオンを自動的に連続測定し、溶剤の劣化を監視
することのできる装置である。
(57) [Abstract] [Purpose] p of chlorine-based organic solvent attached to the solvent cleaner
It is to provide a continuous H / chlorine ion automatic measuring device. [Constitution] After adding a certain amount of pure water to the chlorine-based organic solvent sampled from the solvent washer and cooling to room temperature,
・ It is a device that can monitor Cl ion automatically and continuously to monitor the deterioration of the solvent.
Description
【０００１】[0001]
本考案は、塩素系有機溶剤を用いた溶剤洗浄機に付設されるｐＨ・塩素イオン 連続自動測定装置に関する。 また、本考案の装置は、実験室などにおいて単独で使用することもできる。 The present invention relates to a continuous pH / chlorine ion automatic measuring device attached to a solvent washer using a chlorine-based organic solvent. Further, the device of the present invention can be used alone in a laboratory or the like.
【０００２】[0002]
従来、塩素系有機溶剤を使用する洗浄機などの装置では、溶剤回収が十分に行 われていないため、溶剤のロスに応じて多量の溶剤を補給しており、溶剤が劣化 するおそれがほとんどなく、溶剤の劣化を頻繁に測定・監視する必要がなかった 。 しかし、塩素性有機溶剤を使用する装置においては、環境保全の観点から、溶 剤ロスを少なくするために、溶剤回収を十分行う傾向がある。このような傾向の 下では、塩素系有機溶剤が装置内で劣化することが問題となる。 塩素系有機溶剤は洗浄に用いられると、油脂、異物などの不純物が次第に増加 して汚染され溶剤の温度履歴、相変化などの因子とあいまって、徐々に分解、劣 化する。この結果、塩素系有機溶剤は洗浄作用を失うばかりでなく、劣化により 塩酸を発生する。 Conventionally, in devices such as washing machines that use chlorine-based organic solvents, solvent recovery has not been sufficiently performed, so a large amount of solvent is replenished according to solvent loss, and there is almost no risk of solvent deterioration. It was not necessary to frequently measure and monitor the deterioration of the solvent. However, in an apparatus using a chlorinated organic solvent, there is a tendency to sufficiently recover the solvent in order to reduce solvent loss from the viewpoint of environmental protection. Under such a tendency, there is a problem that the chlorine-based organic solvent deteriorates in the apparatus. When chlorine-based organic solvents are used for cleaning, impurities such as fats and oils and foreign substances gradually increase and become contaminated, and due to factors such as solvent temperature history and phase change, they gradually decompose and deteriorate. As a result, the chlorine-based organic solvent not only loses its cleaning action, but also produces hydrochloric acid due to deterioration.
【０００３】 塩素系有機溶剤の分解により塩酸が発生する反応としては以下のものが知られ ている。 （１）メチレンクロライドの分解反応 ＣＨ2 Ｃｌ2 → Ｃ＋２ＨＣｌ ＣＨ2 Ｃｌ2 ＋Ｈ2 Ｏ → ＨＣＨＯ＋２ＨＣｌ （２）トリクロロエチレンの分解反応 ＣＨＣｌ＝ＣＣｌ2 ＋Ｏ→ＣＨＣｌ2 ＣＯＣｌ＋Ｈ2 Ｏ→ＣＨＣｌ2 ＣＯＯＨ ＋ＨＣｌ ＣＨＣｌ＝ＣＣｌ2 ＋Ｏ2 ＋ＣＨＣｌ2 ＣＯＯＣｌ＋Ｈ2 Ｏ→ＨＣｌ＋ＣＯ＋ ＣＯＣｌ2 ＣＨＣｌ＝ＣＣｌ2 ＋ＣＨＣｌ＝ＣＣｌ2 →ＣＣｌ3 ＝ＣＣｌ＝ＣＨＣｌ＋Ｈ Ｃｌ （この反応はＡｌＣｌ3 の存在で分解する） ＣＣｌ2 ＝ＣＣｌ−Ｃ＝ＣＨＣｌ＋ＣＣｌ2 ＝ＣＣｌ−Ｃ＝ＣＨＣｌ→分子間 脱塩化水素縮合物 （３）１．１．１．−トリクロロエタンの分解反応 ＣＣｌ3 ＣＨ3 → ＣＣｌ2 ＝ＣＨ2 ＋ＨＣｌ （この反応はＡｌＣｌ3 の存在で分解する） ＣＣｌ3 ＣＨ3 ＋Ｈ2 Ｏ → ＣＨ3 ＣＯＣｌ＋２ＨＣｌ ＣＨ3 ＣＯＣｌ＋Ｈ2 Ｏ → ＣＨ3 ＣＯＯＨ＋ＨＣｌThe following reactions are known to generate hydrochloric acid by decomposing a chlorine-based organic solvent. (1) Decomposition reaction of methylene chloride CH 2 Cl 2 → C + 2HCl CH 2 Cl 2 + H 2 O → HCHO + 2HCl (2) Decomposition reaction of trichloroethylene CHCl = CCl 2 + O → CHCl 2 COCl + H 2 O → CHCl 2 COOH + HCl CHCl = CCl 2 + O 2 + CHCl 2 COOCl + H 2 O → HCl + CO + COCl 2 CHCl = CCl 2 + CHCl = CCl 2 → CCl 3 = CCl = CHCl + H Cl (This reaction decomposes in the presence of AlCl 3 ) CCl 2 = CCl-C = CHCl + CCl 2 = CCl -C = CHCl-> intermolecular dehydrochlorination condensate (3) 1.1.1. - decomposition reaction CCl trichloroethane 3 CH 3 → CCl 2 = CH 2 + HCl ( the reaction is decomposed in the presence of AlCl 3) CCl 3 CH 3 + H 2 O → CH 3 COCl + 2HCl CH 3 COCl + H 2 O → CH 3 COOH + HCl
【０００４】 塩素系有機溶剤の劣化により塩酸が発生すると、装置の腐食を招いたり、被洗 物（ワーク）に悪影響を与える。塩酸中の塩素イオンは、溶剤中の安定剤と反応 して、中性、アルカリ性になっても液性に関係なく洗浄機の構成材（鉄、アルミ ニウム、銅など）および被洗物（金属部品）を腐食するおそれがある。 従来は、塩素系有機溶剤の劣化の指標として通常ｐＨが採用され、補給のため の一定の判断基準が採用されていたが、腐食を予防する上ではｐＨだけでは正確 に判断することができない。したがって、より正確に腐食を防止するためにｐＨ 測定に加えて塩素イオンを測定する必要がある。When hydrochloric acid is generated due to the deterioration of the chlorine-based organic solvent, it causes corrosion of the apparatus and adversely affects the work (work) to be washed. Chloride ion in hydrochloric acid reacts with the stabilizer in the solvent and becomes neutral or alkaline, regardless of the liquidity, and is a component of the washing machine (iron, aluminium, copper, etc.) and the object to be washed (metal). Parts) may be corroded. Conventionally, pH is usually used as an index of the deterioration of chlorine-based organic solvents, and a certain criterion for replenishment has been adopted, but in order to prevent corrosion, it is not possible to make an accurate determination by pH alone. Therefore, it is necessary to measure chloride ion in addition to pH measurement in order to prevent corrosion more accurately.
【０００５】 現在、ｐＨおよび塩素イオンは、以下のような手法により、手分析で測定され ている。すなわち、ｐＨ・塩素イオン測定容器に被検液を一定量分取し、これに 純水を等量加え、手または攪はん器で攪はんして、被検液中の水素イオンおよび 塩素イオンを純水によって抽出する。数分間静置して溶剤相と水相とを分離させ 、上相の水相部に先ずｐＨ電極を挿入してｐＨ値を読み取り、つぎにこの水相部 に酢酸緩衝液（ｐＨ＝５）を加え、手または攪はん器で攪はんして、数分間静置 して溶剤相と水相とを分離させ、上相の水相部に塩素イオン電極を挿入して塩素 イオン濃度値を読み取る。そして容器内の液を廃液として捨てる。次の測定に供 えるため測定後のｐＨ電極および塩素イオン電極、ｐＨ・塩素イオン測定容器に 純水を注入してｐＨ電極、塩素イオン電極を浸せきする。また、ｐＨ測定器、塩 素イオン測定器の校正も、ｐＨ基準液、塩素イオン基準液を用いて手で行われて いる。 この方法は、塩素イオン測定時のｐＨを５に限定して測定しているため、抽出 液が酸性の場合には、水酸化ナトリウム溶液（４ｗ／ｖ％）、アルカリ性の場合 には酢酸（１＋１０）で、あらかじめ抽出液をｐＨ５に調節する手間が生じる。At present, pH and chloride ions are measured by manual analysis by the following methods. That is, a certain amount of the test liquid is dispensed into a pH / chlorine ion measuring container, an equal amount of pure water is added to the container, and the mixture is stirred with a hand or a stirrer to remove hydrogen ions and chlorine in the test liquid. Ions are extracted with pure water. Let stand for several minutes to separate the solvent phase from the aqueous phase. Insert the pH electrode into the upper aqueous phase to read the pH value, and then add the acetate buffer (pH = 5) to this aqueous phase. Then, stir with a hand or a stirrer and let it stand for a few minutes to separate the solvent phase from the water phase. To read. Then, the liquid in the container is discarded as waste liquid. To prepare for the next measurement, pour pure water into the pH electrode, chloride ion electrode and pH / chlorine ion measuring container after measurement to immerse the pH electrode and chloride ion electrode. Further, the calibration of the pH measuring instrument and the chloride ion measuring instrument is also performed by hand using the pH standard solution and the chlorine ion standard solution. In this method, the pH of chlorine ions is limited to 5 when measuring, so if the extract is acidic, sodium hydroxide solution (4 w / v%) is used. If the extract is alkaline, acetic acid (1 + 10%) is used. ), It takes time to adjust the pH of the extract to 5 in advance.
【０００６】[0006]
しかし、前記のように手分析を行う場合、以下のような問題がある。（ａ）測 定に時間がかかるため、測定が不行き届きになりやすく、溶剤劣化の監視が不十 分となる。（ｂ）手分析では被検液中の水素イオン、塩素イオンを水に抽出する 操作を一定にすることが不十分な場合もあり、測定値にバラツキが生じる。 したがって、溶剤の劣化を監視するには、ｐＨ、塩素イオンを自動的に連続測 定することが要請される。 周知のように、水溶液を試料としたｐＨ自動測定装置は数多く考案されている が、前回の測定液と次回の測定液との置換と、ｐＨ電極、塩素イオン電極及びｐ Ｈ・塩素イオン測定容器に洗浄液まで自動化したｐＨ・塩素イオン連続自動測定 装置はない。まして、塩素系有機溶剤を試料とするｐＨ・塩素イオン連続自動測 定装置は全く考案されてない。 本考案は、前記問題点を解決するためになされたものであり、ｐＨ・塩素イオ ンを自動的に連続測定する装置を提供することを目的とする。 However, the manual analysis as described above has the following problems. (A) Since it takes a long time to perform the measurement, the measurement tends to be poor, and monitoring of solvent deterioration becomes insufficient. (B) In manual analysis, there are cases where it is not sufficient to make the operation of extracting hydrogen ions and chlorine ions in the test liquid into water constant, resulting in variations in measured values. Therefore, in order to monitor the deterioration of the solvent, it is required to automatically measure the pH and chlorine ion continuously. As is well known, a number of automatic pH measuring devices using aqueous solutions as samples have been devised, but replacement of the previous measuring liquid with the next measuring liquid, pH electrode, chlorine ion electrode, and pH / chlorine ion measuring container There is no continuous automatic pH / chlorine ion measuring device for cleaning solutions. Furthermore, no continuous pH / chlorine ion automatic measuring device using a chlorine-based organic solvent as a sample has been devised. The present invention has been made to solve the above problems, and an object of the present invention is to provide an apparatus for automatically and continuously measuring pH and chlorine ions.
【０００７】[0007]
本考案は、塩素系有機溶剤洗浄器に付設されるｐＨ・塩素イオン連続自動測定 装置において制御器と、ｐＨ・塩素イオン測定容器と、ｐＨ基準液貯蔵容器と、 塩素イオン基準液貯蔵容器と、酢酸緩衝液貯蔵容器と、純水貯蔵容器と、前記ｐ Ｈ基準液貯蔵容器内の基準液、塩素イオン基準液貯蔵容器内の基準液、酢酸緩衝 液、及び貯蔵容器内の緩衝液をそれぞれ前記ｐＨ・塩素イオン測定容器に供給す る手段と、溶剤洗浄機の洗浄槽から一定量の有機溶剤を前記ｐＨ・塩素イオン測 定容器に供給する手段と、前記純水貯蔵容器から一定量の純水を前記ｐＨ・塩素 イオン測定容器に供給する手段と、前記ｐＨ・塩素イオン測定容器の液を攪はん する手段と、前記ｐＨ・塩素イオン測定容器の液のｐＨ・塩素イオンを測定する 手段と、前記ｐＨ・塩素イオン測定容器内の液を排出する手段とを具備したこと を特徴とするｐＨ・塩素イオン連続自動測定装置である。 The present invention provides a controller, a pH / chlorine ion measuring container, a pH reference liquid storage container, and a chlorine ion reference liquid storage container in a pH / chlorine ion continuous automatic measuring device attached to a chlorine-based organic solvent washer. The acetic acid buffer storage container, the pure water storage container, the reference solution in the pH standard solution storage container, the reference solution in the chloride ion standard solution storage container, the acetic acid buffer solution, and the buffer solution in the storage container are respectively described above. A means for supplying a pH / chlorine ion measuring container, a means for supplying a certain amount of an organic solvent from the cleaning tank of the solvent washing machine to the pH / chlorine ion measuring container, and a certain amount of pure water from the pure water storage container. Means for supplying water to the pH / chlorine ion measuring container, means for stirring the liquid in the pH / chlorine ion measuring container, and means for measuring pH / chlorine ion in the liquid in the pH / chlorine ion measuring container And the p - a pH-chloride automatic continuous measuring apparatus characterized by comprising a means for discharging the chloride ion liquid in the measurement container.
【０００８】[0008]
本考案のｐＨ・塩素イオン連続自動測定装置では、全ての構成要素は制御器か ら送られる信号により自動的に一定の時間間隔でＯＮ−ＯＦＦするように作動す る。したがって、ｐＨ・塩素イオン測定容器への一定量の有機溶剤及び純水の供 給、ｐＨ・塩素イオン測定容器内の液の攪はん、ｐＨ・塩素イオンの測定、測定 後の測定液の排出、ｐＨ・塩素イオン測定容器及びｐＨ電極、塩素イオン電極の 洗浄を自動的に連続して行える。また、ｐＨ・塩素イオン連続自動測定装置の校 正も自動的に行える。 本考案において、純水は中性水が好ましい。また、ｐＨ基準液としては、中性 及びアルカリ性のｐＨ基準液を用いてｐＨを測定する機器を校正する場合でも、 アルカリ性領域だけでなく、酸性領域まで正確に測定することができる。また、 ｐＨ・塩素イオン測定容器を高形にすれば、測定に供する有機溶剤及び純水の量 を少なくすることができる。 本考案においては、ｐＨ値、塩素イオン値を表示する印刷機などの表示手段や 、ｐＨ値が一定値以下になったときや、塩素イオン値が一定値以上になったとき に警報音や警報ランプを作動させる警報手段を設けることもできる。 In the pH / chlorine ion continuous automatic measuring device of the present invention, all the components operate so as to be automatically turned on and off at a fixed time interval by a signal sent from the controller. Therefore, supply a fixed amount of organic solvent and pure water to the pH / chlorine ion measuring container, stir the liquid in the pH / chlorine ion measuring container, measure pH / chlorine ion, and discharge the measured liquid after the measurement. Cleaning of pH / chlorine ion measuring container, pH electrode, and chlorine ion electrode can be performed automatically and continuously. In addition, the pH / chlorine ion continuous automatic measuring device can be calibrated automatically. In the present invention, the pure water is preferably neutral water. Further, even when a device for measuring pH is calibrated using a neutral and alkaline pH standard solution as the pH standard solution, not only the alkaline range but also the acidic range can be accurately measured. Further, if the pH / chlorine ion measuring container is made high-profile, the amount of organic solvent and pure water to be used for the measurement can be reduced. In the present invention, the display means such as a printing machine for displaying the pH value and the chlorine ion value, and the alarm sound and the alarm when the pH value is below a certain value or when the chlorine ion value is above a certain value It is also possible to provide alarm means for operating the lamp.
【０００９】[0009]
以下、本考案の実施例を図面を参照して説明する。第１図は本考案に係るｐＨ ・Ｃｌイオン連続自動測定装置の構成図である。 この装置による塩素系有機溶剤のｐＨ及びＣｌイオン測定は以下のようにして 行われる。 制御器（１０）の電源をＯＮにすると、ｐＨ・Ｃｌイオン連続自動測定器（１ １）及び印刷機（１９）に電源が入力され、安定化する。 ｐＨ・Ｃｌイオンを測定するに先立ち、制御器（１０）からの信号により廃液 用電磁弁（８ａ）が作動し、ｐＨ・Ｃｌイオン測定容器（１４）の電極安定用純 水が排出管（２４）を通って廃液貯蔵容器（１７）に排出される。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a block diagram of a pH / Cl ion continuous automatic measuring device according to the present invention. The pH and Cl ion of the chlorine-based organic solvent are measured by this device as follows. When the power of the controller (10) is turned on, the power is input to the pH / Cl ion continuous automatic measuring device (11) and the printing machine (19) to be stabilized. Before measuring pH / Cl ions, the waste liquid solenoid valve (8a) is activated by a signal from the controller (10), and pure water for electrode stabilization of the pH / Cl ion measuring container (14) is discharged from the discharge pipe (24). ) And discharged to the waste liquid storage container (17).
【００１０】 制御器（１０）からの信号により溶剤ポンプ（８）と純水ポンプ（９）とが同 時に作動し、溶剤洗浄機の洗浄槽（図示せず）中の溶剤が溶剤供給管（２０）を 通って溶剤定量容器（４）へ供給され、純水貯蔵容器（１８）中の純水が純水供 給管（２２）を通って純水定量容器（５）へ供給される。溶剤定量容器（４）及 び純水定量容器（５）には、同一の液量が収容されるようにレベル管（２６）、 （２６）′が取り付られ、過剰の溶剤及び純水はレベル管（２６）、（２６）′ を通ってそれぞれ洗浄槽及び純水貯蔵容器（１８）に戻される。また、溶剤定量 容器（４）及び純水定量容器（５）には、通気口（２５）、（２５）′が設けら れ、内部圧力の上昇を防止している。The solvent pump (8) and the pure water pump (9) are simultaneously operated by a signal from the controller (10), and the solvent in the cleaning tank (not shown) of the solvent cleaning machine is supplied to the solvent supply pipe ( 20) to be supplied to the solvent quantitative container (4), and pure water in the pure water storage container (18) is supplied to the pure water quantitative container (5) through the pure water supply pipe (22). The level pipes (26) and (26) 'are attached to the solvent quantitative container (4) and the pure water quantitative container (5) so that the same amount of liquid can be stored. It is returned to the cleaning tank and the pure water storage container (18) through the level pipes (26) and (26) ', respectively. Further, the solvent quantitative container (4) and the pure water quantitative container (5) are provided with vent holes (25) and (25) 'to prevent the internal pressure from rising.
【００１１】 制御器（１０）からの信号により溶剤用電磁弁（４ａ）と純水用電磁弁（５ａ ）とが同時に作用し、溶剤定量容器（４）中の溶剤及び純水定量容器（５）の純 水が、それぞれ溶剤注入管（２１）及び純水注入管（２３）を通ってｐＨ・Ｃｌ イオン測定容器（１４）に注入される。 制御器（１０）からの信号により攪はん装置（１５）が作動し、回転子（１６ ）の回転により溶剤と純水とが混合される。この結果、溶剤中の水素イオンと塩 素イオンが純水中に抽出される。制御器（１０）からの信号により攪はんが停止 され、数分間静置した後、溶剤相と水相とを形成させる。 制御器（１０）からの信号によりｐＨ・Ｃｌイオン測定容器（１４）中のｐＨ 電極（１２）がはじめに作動し、水相中に挿入されているｐＨ電極（１２）によ り検知される水素イオン濃度がｐＨ・Ｃｌイオン連続自動測定器（１１）により 測定され、同時に制御器（１０）からの信号により自動印刷機（１９）が作動し 、ｐＨ値が印字される。The solenoid valve for solvent (4a) and the solenoid valve for pure water (5a) act simultaneously by the signal from the controller (10), and the solvent and pure water quantitative container (5) in the solvent quantitative container (4) is Pure water) is injected into the pH / Cl 2 ion measuring container (14) through the solvent injection pipe (21) and the pure water injection pipe (23), respectively. The stirrer (15) is activated by a signal from the controller (10), and the solvent and pure water are mixed by the rotation of the rotor (16). As a result, hydrogen ions and chloride ions in the solvent are extracted into pure water. Stirring is stopped by a signal from the controller (10), and after standing for several minutes, a solvent phase and an aqueous phase are formed. The pH electrode (12) in the pH / Cl ion measuring container (14) is first activated by the signal from the controller (10), and hydrogen is detected by the pH electrode (12) inserted in the aqueous phase. The ion concentration is measured by the pH / Cl ion continuous automatic measuring device (11), and at the same time, the automatic printer (19) is operated by the signal from the controller (10) to print the pH value.
【００１２】 制御器（１０）からの信号により印刷機（１９）の印字が停止すると、制御器 （１０）からの信号により酢酸緩衝液（ｐＨ＝５）用電磁弁（３ａ）が作用し、 酢酸緩衝液（ｐＨ＝５）の一定量が酢酸緩衝液（ｐＨ＝５）注入管（２９）を通 ってｐＨ・Ｃｌイオン測定容器（１４）に注入される。 制御器（１０）からの信号により攪はん装置（１５）が作動し、回転子（１６ ）の回転により溶剤と酢酸緩衝液（ｐＨ＝５）と純水とが混合される。 制御器（１０）からの信号によりｐＨ・Ｃｌイオン測定容器（１４）中のＣｌ イオン電極（１３）が続いて作動し、水相中に挿入されているＣｌイオン電極（ １３）により検知されるＣｌイオン濃度がｐＨ・Ｃｌイオン連続自動測定器（１ １）により測定され、同時に制御器（１０）からの信号により自動印刷機（１９ ）が作動し、Ｃｌイオン値が印字される。When the printing of the printing press (19) is stopped by the signal from the controller (10), the acetic acid buffer solution (pH = 5) solenoid valve (3a) is actuated by the signal from the controller (10), A fixed amount of acetate buffer (pH = 5) is injected into the pH / Cl ion measuring container (14) through an acetate buffer (pH = 5) injection pipe (29). The stirrer (15) is activated by a signal from the controller (10), and the solvent, acetate buffer (pH = 5) and pure water are mixed by the rotation of the rotor (16). The Cl ion electrode (13) in the pH / Cl ion measuring container (14) is subsequently operated by a signal from the controller (10), and is detected by the Cl ion electrode (13) inserted in the aqueous phase. The Cl ion concentration is measured by the pH / Cl ion continuous automatic measuring device (11), and at the same time, the automatic printer (19) is operated by the signal from the controller (10) to print the Cl ion value.
【００１３】 制御器（１０）からの信号により自動印刷機（１９）の印字が停止すると、制 御器（１０）からの信号により廃液用電磁弁（８ａ）が作動し、ｐＨ・Ｃｌイオ ン測定容器（１４）中の液が排出管（２４）を通って流下し廃液貯蔵容器（１７ ）に排出される。 制御器（１０）からの信号により純水ポンプ（９）と純水用電磁弁（５ａ）と が同時に作動し、純水貯蔵容器（１８）から一定量の純水が純水供給管（２２） を通ってｐＨ・Ｃｌイオン測定容器（１４）に供給される。制御器（１０）から の信号により攪はん装置（１５）が作動し、回転子（１６）により純水を回転攪 はんしてｐＨ電極（１２）及びＣｌイオン電極（１３）の表面とｐＨ・Ｃｌイオ ン測定容器（１４）内壁を洗浄する。制御器（１０）からの信号により攪はんが 停止すると廃液用電磁弁（８ａ）が作動し、ｐＨ・Ｃｌイオン測定容器（１４） 中の測定液が排出管（２４）を通って流下し廃液貯蔵容器（１７）に排出される 。洗浄は、制御器（１０）で自動的に任意の回数繰り返しができるが、通常３回 の繰り返し洗浄で十分であった。When the printing of the automatic printing machine (19) is stopped by the signal from the controller (10), the waste liquid solenoid valve (8a) is activated by the signal from the controller (10), and the pH / Cl ion is discharged. The liquid in the measurement container (14) flows down through the discharge pipe (24) and is discharged into the waste liquid storage container (17). The pure water pump (9) and the pure water solenoid valve (5a) are simultaneously operated by a signal from the controller (10), and a certain amount of pure water is supplied from the pure water storage container (18) to the pure water supply pipe (22). ) Is supplied to the pH / Cl ion measuring container (14). The stirrer (15) is actuated by a signal from the controller (10), and pure water is rotatively stirred by the rotor (16) so that the surface of the pH electrode (12) and the Cl ion electrode (13) is The inner wall of the pH / Cl ion measuring container (14) is washed. When the stirring is stopped by the signal from the controller (10), the waste liquid solenoid valve (8a) is activated, and the measurement liquid in the pH / Cl ion measuring container (14) flows down through the discharge pipe (24). It is discharged to the waste liquid storage container (17). The washing can be automatically repeated by the controller (10) any number of times, but usually three times repeated washing was sufficient.
【００１４】 制御器（１０）からの信号により廃液用電磁弁（８ａ）が停止すると純水ポン プ（９）と純水用電磁弁（５ａ）が作動し、ｐＨ・Ｃｌイオン測定容器（１４） 中に純水が貯水される。制御器（１０）からの信号により純水ポンプ（９）と純 水用電磁弁（５ａ）が停止する。貯水された純水はｐＨ電極（１２）とＣｌイオ ン電極（１３）を安定化させる作用を有する。この操作により装置は最初の状態 に復帰する。When the waste liquid solenoid valve (8a) is stopped by a signal from the controller (10), the pure water pump (9) and the pure water solenoid valve (5a) are activated, and the pH / Cl ion measuring container (14) ) Is filled with pure water. The pure water pump (9) and the pure water solenoid valve (5a) are stopped by a signal from the controller (10). The stored pure water has a function of stabilizing the pH electrode (12) and the Cl ion electrode (13). This operation returns the device to the initial state.
【００１５】 次回測定は、洗浄と並行して、制御器（１０）からの信号により溶剤ポンプ（ ８）が作動し、測定溶剤により溶剤ポンプ（８）、溶剤供給管（２０）、溶剤定 量容器（４）内に前回の測定で残留している溶剤を置換する。測定溶剤による洗 浄量は、２０〜５０ｍｌ程度で十分であった。洗浄用に使用した測定溶剤は通常 洗浄槽へ戻すが、廃液槽（１７）に戻すことも考えられる。 なお、ｐＨ・Ｃｌイオン連続自動測定器（１１）により測定されるｐＨ値が一 定値以下になったときや、Ｃｌイオンが一定値以上になったときに、警報器や警 報ランプを作動させるようにしてもよい。 また、廃液量を減らす観点から、次の方法を採用することも考えられる。（１ ）排出管（２４）からの排液は全量洗浄槽へ戻す。（２）又はこの排液を水相と 溶剤相に静置分離後、水相部の水を排液とし、溶剤相は洗浄槽へ戻す。なお、通 常の純水は完全な中性水でないため、より正確にｐＨを測定する必要がある場合 には、純水を０．０１規定の水酸化ナトリウム溶液でｐＨ７．０に調整して使用 することが好ましい。In the next measurement, the solvent pump (8) is operated by a signal from the controller (10) in parallel with the cleaning, and the solvent pump (8), the solvent supply pipe (20), and the solvent constant amount are measured by the measured solvent. The solvent remaining in the previous measurement in the container (4) is replaced. A washing amount of about 20 to 50 ml was sufficient for the measurement solvent. The measurement solvent used for cleaning is usually returned to the cleaning tank, but it may be returned to the waste liquid tank (17). In addition, when the pH value measured by the pH / Cl ion continuous automatic measuring device (11) falls below a certain value or when the Cl ion exceeds a certain value, an alarm device or a warning lamp is activated. You may do it. Further, from the viewpoint of reducing the amount of waste liquid, it is possible to adopt the following method. (1) Return all the drainage from the drain pipe (24) to the washing tank. (2) Or, after the waste liquid is statically separated into a water phase and a solvent phase, the water in the water phase is used as the waste liquid, and the solvent phase is returned to the washing tank. Since normal pure water is not completely neutral water, if it is necessary to measure the pH more accurately, adjust the pure water to pH 7.0 with 0.01N sodium hydroxide solution. It is preferable to use.
【００１６】 この装置における、ｐＨ・Ｃｌイオン連続自動測定器の校正は以下のようにし て行われる。先ず、ｐＨの校正からはじめる。ｐＨの測定に先立ち、ｐＨ７基準 液貯蔵容器（６）にｐＨ７基準液を、ｐＨ９基準液貯蔵容器（７）にｐＨ９基準 液を入れておく。 制御器（１０）からの信号によりｐＨ７基準液用電磁弁（６ａ）が作用し、ｐ Ｈ７基準液貯蔵容器（６）中のｐＨ７基準液が電磁弁（６ａ）とｐＨ７基準液注 入管（２７）を通ってｐＨ・Ｃｌイオン測定容器（１４）に一定量注入される。 制御器（１０）からの信号によりｐＨ・Ｃｌイオン連続自動測定器（１１）が作 動し、自動的にｐＨ７に調整される。The calibration of the pH / Cl ion continuous automatic measuring device in this apparatus is performed as follows. First, start with the pH calibration. Prior to the pH measurement, the pH 7 standard solution is stored in the pH 7 standard solution storage container (6) and the pH 9 standard solution is stored in the pH 9 standard solution storage container (7). The electromagnetic valve (6a) for pH7 reference solution is actuated by a signal from the controller (10), and the pH7 reference solution in the pH7 reference solution storage container (6) is supplied to the electromagnetic valve (6a) and the pH7 reference solution injection pipe (27). A) and a fixed amount is injected into the pH / Cl ion measuring container (14). The signal from the controller (10) activates the pH / Cl ion continuous automatic measuring device (11) to automatically adjust the pH to 7.
【００１７】 制御器（１０）からの信号により廃液用電磁弁（８ａ）が作動し、ｐＨ・Ｃｌ イオン測定容器（１１）の液が排出管（２４）を通って流下し廃液貯蔵容器（１ ７）に排出される。制御器（１０）からの信号により純水ポンプ（９）と純水用 電磁弁（５ａ）とが同時に作動し、純水貯蔵容器（１８）から一定量の純水が純 水供給管（２２）を通ってｐＨ・Ｃｌイオン測定容器（１４）に供給される。制 御器（１０）からの信号により攪はん装置（１５）が作動し、回転子（１６）に より純水を回転攪はんしてｐＨ電極（１２）及びＣｌイオン電極（１３）の表面 とｐＨ・Ｃｌイオン測定容器（１４）内壁を洗浄する。制御器（１０）からの信 号により攪はんが停止すると廃液用電磁弁（８ａ）が作動し、ｐＨ・Ｃｌイオン 測定容器（１４）中の液が排出管（２４）を通って流下し廃液貯蔵容器（１７） に排出される。この洗浄は、制御器（１０）で自動的に任意の回数繰り返しがで きるように設定できる。The waste liquid solenoid valve (8a) is activated by a signal from the controller (10), the liquid of the pH / Cl ion measuring container (11) flows down through the discharge pipe (24), and the waste liquid storage container (1) is discharged. It is discharged to 7). The pure water pump (9) and the pure water solenoid valve (5a) are simultaneously actuated by a signal from the controller (10), and a certain amount of pure water is supplied from the pure water storage container (18) to the pure water supply pipe (22). ) And is supplied to the pH / Cl ion measuring container (14). The stirrer (15) is activated by the signal from the controller (10), and the pure water is rotatably stirred by the rotor (16) so that the pH electrode (12) and the Cl ion electrode (13) The surface and the inner wall of the pH / Cl ion measuring container (14) are washed. When the stirring is stopped by the signal from the controller (10), the waste liquid solenoid valve (8a) is activated, and the liquid in the pH / Cl ion measuring container (14) flows down through the discharge pipe (24). It is discharged to the waste liquid storage container (17). This cleaning can be set by the controller (10) so that it can be automatically repeated any number of times.
【００１８】 制御器（１０）からの信号によりｐＨ９基準液用電磁弁（７ａ）が作動し、ｐ Ｈ９基準液貯蔵容器（７）中のｐＨ９基準液が電磁弁（７ａ）とｐＨ９基準液注 入管（２８）を通ってｐＨ・Ｃｌイオン測定容器（１４）に一定量注入される。 制御器（１０）からの信号によりｐＨ・Ｃｌイオン連続自動測定器（１１）が作 動し、自動的にｐＨ９に調整される。 制御器（１０）からの信号により廃液用電磁弁（８ａ）が作動し、ｐＨ・Ｃｌ イオン測定容器（１４）の液が排出管（２４）を通って流下し廃液貯蔵容器（１ ７）に排出される。制御器（１０）からの信号により純水ポンプ（９）と純水電 磁弁（５ａ）とが同時に作動し、純水貯蔵容器（１８）から一定量の純水が純水 供給管（２２）を通ってｐＨ・Ｃｌイオン測定容器（１４）に供給される。制御 器（１０）からの信号により攪はん装置（１５）が作動し、回転子（１６）によ り純水を回転攪はんしてｐＨ電極（１２）及びＣｌイオン電極（１３）の表面と ｐＨ・Ｃｌイオン測定容器（１４）内壁を洗浄する。制御器（１０）からの信号 により攪はんが停止すると廃液用電磁弁（８ａ）が作動し、ｐＨ・Ｃｌイオン測 定容器（１４）中の液が排出管（２４）を通って流下し廃液貯蔵容器（１７）に 排出される。この洗浄は、制御器（１０）で自動的に任意の回数繰り返しができ るように設定する。The electromagnetic valve (7a) for pH9 reference solution is activated by a signal from the controller (10), and the pH9 reference solution in the pH9 reference solution storage container (7) is injected with the electromagnetic valve (7a) and the pH9 reference solution. A certain amount is injected into the pH / Cl ion measuring container (14) through the inlet pipe (28). A pH / Cl ion continuous automatic measuring device (11) is activated by a signal from the controller (10), and the pH is automatically adjusted to 9. The signal from the controller (10) actuates the waste liquid solenoid valve (8a), and the liquid in the pH / Cl ion measuring container (14) flows down through the discharge pipe (24) into the waste liquid storage container (17). Is discharged. The pure water pump (9) and the pure water electromagnetic valve (5a) are simultaneously operated by a signal from the controller (10), and a certain amount of pure water is supplied from the pure water storage container (18) to the pure water supply pipe (22). And is supplied to the pH / Cl ion measuring container (14). The stirrer (15) is activated by a signal from the controller (10), and the pure water is rotatably stirred by the rotor (16) to rotate the pH electrode (12) and the Cl ion electrode (13). The surface and the inner wall of the pH / Cl ion measuring container (14) are washed. When the stirring is stopped by the signal from the controller (10), the waste liquid solenoid valve (8a) is activated, and the liquid in the pH / Cl ion measuring container (14) flows down through the discharge pipe (24). It is discharged to the waste liquid storage container (17). This cleaning is set by the controller (10) so that it can be automatically repeated any number of times.
【００１９】 つぎに、ｐＨ・Ｃｌイオン連続自動測定器（１１）によるＣｌイオンの校正は 以下のようにして行われる。Ｃｌイオンの測定に先立ち、Ｃｌイオン基準液（５ ｍｇ／ｌ）貯蔵容器（２）にＣｌイオン基準液（５ｍｇ／ｌ）を、Ｃｌイオン基 準液（１０ｍｇ／ｌ）貯蔵容器（１）にＣｌイオン基準液（１０ｍｇ／ｌ）を、 酢酸緩衝液（ｐＨ＝５）貯蔵容器（３）に酢酸緩衝液（ｐＨ＝５）を入れておく 。 制御器（１０）からの信号によりＣｌイオン基準液（５ｍｇ／ｌ）用電磁弁（ ２ａ）が作動し、Ｃｌイオン基準液（５ｍｇ／ｌ）貯蔵容器（２）中のＣｌイオ ン基準液（５ｍｇ／ｌ）が電磁弁（２ａ）とＣｌイオン基準液（５ｍｇ／ｌ）注 入管（３０）を通ってｐＨ・Ｃｌイオン測定容器（１４）に１００ｍｌ注入され る。制御器（１０）からの信号により酢酸緩衝液（ｐＨ＝５）貯蔵容器用電磁弁 （３ａ）が作動し、酢酸緩衝液（ｐＨ＝５）貯蔵容器（３）中の酢酸緩衝液（ｐ Ｈ＝５）１０ｍｌが電磁弁（３ａ）と酢酸緩衝液（ｐＨ＝５）注入管（２９）を 通ってｐＨ・Ｃｌイオン測定容器（１４）に注入される。制御器（１０）からの 信号により攪はん装置（１５）が作動し、回転子（１６）の回転によりＣｌイオ ン基準液と酢酸緩衝液（ｐＨ＝５）とが混合される。制御器（１０）からの信号 によりｐＨ・Ｃｌイオン連続自動測定器（１１）が作動しＣｌイオン電極（１３ ）により検知され、自動的にＣｌイオン濃度（５ｍｇ／ｌ）に調整される。Next, the calibration of Cl ions by the pH / Cl ion continuous automatic measuring device (11) is performed as follows. Prior to the Cl ion measurement, the Cl ion reference solution (5 mg / l) was stored in the Cl ion reference solution (5 mg / l) storage container (2) and the Cl ion reference solution (10 mg / l) was stored in the storage container (1). The Cl ion standard solution (10 mg / l) is put into the acetate buffer (pH = 5) storage container (3), and the acetate buffer (pH = 5) is put therein. The solenoid valve (2a) for the Cl ion reference liquid (5 mg / l) is activated by a signal from the controller (10), and the Cl ion reference liquid (5 mg / l) Cl ion reference liquid (5 mg / l) in the storage container (2) ( 100 mg of 5 mg / l) is injected into the pH / Cl ion measuring container (14) through the solenoid valve (2a) and the Cl ion reference liquid (5 mg / l) injection pipe (30). The solenoid valve (3a) for the acetic acid buffer (pH = 5) storage container is activated by a signal from the controller (10), and the acetic acid buffer (pH) in the acetic acid buffer (pH = 5) storage container (3) = 5) 10 ml is injected into the pH / Cl ion measuring container (14) through the solenoid valve (3a) and the acetate buffer (pH = 5) injection pipe (29). The stirrer (15) is activated by the signal from the controller (10), and the Cl ion standard solution and the acetate buffer solution (pH = 5) are mixed by the rotation of the rotor (16). The pH / Cl ion continuous automatic measuring device (11) is activated by a signal from the controller (10), is detected by the Cl ion electrode (13), and is automatically adjusted to the Cl ion concentration (5 mg / l).
【００２０】 制御器（１０）からの信号により廃液用電磁弁（８ａ）が作動し、ｐＨ・Ｃｌ イオン測定容器（１４）の液が排出管（２４）を通って流下し廃液貯蔵容器（１ ７）に排出される。制御器（１０）からの信号により純水ポンプ（９）と純水電 磁弁（５ａ）とが同時に作動し、純水貯蔵容器（１８）から一定量の純水が純水 供給管（２２）を通ってｐＨ・Ｃｌイオン測定容器（１４）に供給される。制御 器（１０）からの信号により攪はん装置（１５）が作動し、回転子（１６）によ り純水を回転攪はんしてｐＨ電極（１２）及びＣｌイオン電極（１３）の表面と ｐＨ・Ｃｌイオン測定容器（１４）内壁を洗浄する。制御器（１０）からの信号 により攪はんが停止すると廃液用電磁弁（８ａ）が作動し、ｐＨ・Ｃｌイオン測 定容器（１４）中の液が排出管（２４）を通って流下し廃液貯蔵容器（１７）に 排出される。この洗浄は、制御器（１０）で自動的に任意の回数繰り返しができ るように設定する。The signal from the controller (10) activates the waste liquid solenoid valve (8a), the liquid in the pH / Cl ion measuring container (14) flows down through the discharge pipe (24), and the waste liquid storage container (1) is discharged. It is discharged to 7). The pure water pump (9) and the pure water electromagnetic valve (5a) are simultaneously operated by a signal from the controller (10), and a certain amount of pure water is supplied from the pure water storage container (18) to the pure water supply pipe (22). And is supplied to the pH / Cl ion measuring container (14). The stirrer (15) is activated by a signal from the controller (10), and the pure water is rotatably stirred by the rotor (16) to rotate the pH electrode (12) and the Cl ion electrode (13). The surface and the inner wall of the pH / Cl ion measuring container (14) are washed. When the stirring is stopped by the signal from the controller (10), the waste liquid solenoid valve (8a) is activated, and the liquid in the pH / Cl ion measuring container (14) flows down through the discharge pipe (24). It is discharged to the waste liquid storage container (17). This cleaning is set by the controller (10) so that it can be automatically repeated any number of times.
【００２１】 制御器（１０）からの信号によりＣｌイオン基準液（１０ｍｇ／ｌ）用電磁弁 （１ａ）が作動し、Ｃｌイオン基準液（１０ｍｇ／ｌ）貯蔵容器（１）中のＣｌ イオン基準液（１０ｍｇ／ｌ）が電磁弁（１ａ）とＣｌイオン基準液（１０ｍｇ ／ｌ）注入管（３１）を通ってｐＨ・Ｃｌイオン測定容器（１４）に１００ｍｌ 注入される。制御器（１０）からの信号により酢酸緩衝液（ｐＨ＝５）貯蔵容器 用電磁弁（３ａ）が作動し、酢酸緩衝液（ｐＨ＝５）貯蔵容器（３）中の酢酸緩 衝液（ｐＨ＝５）１０ｍｌが電磁弁（３ａ）と酢酸緩衝液（ｐＨ＝５）注入管（ ２９）を通ってｐＨ・Ｃｌイオン測定容器（１４）に注入される。制御器（１０ ）からの信号により攪はん装置（１５）が作動し、回転子（１６）の回転により Ｃｌイオン基準液と酢酸緩衝液（ｐＨ＝５）とが混合される。制御器（１０）か らの信号によりｐＨ・Ｃｌイオン連続自動測定器（１１）が作動し、基準液はＣ ｌイオン電極（１３）により検知され、自動的にＣｌイオン濃度（１０ｍｇ／ｌ ）に調整される。The solenoid valve (1a) for the Cl ion reference liquid (10 mg / l) is activated by a signal from the controller (10), and the Cl ion reference liquid (10 mg / l) storage container (1) stores the Cl ion reference liquid. 100 ml of the liquid (10 mg / l) is injected into the pH / Cl ion measuring container (14) through the solenoid valve (1a) and the Cl ion reference liquid (10 mg / l) injection pipe (31). The solenoid valve (3a) for the acetic acid buffer solution (pH = 5) storage container is activated by a signal from the controller (10), and the acetic acid buffer solution (pH = 5) in the acetic acid buffer solution (pH = 5) storage container (3) is activated. 5) 10 ml is injected into the pH / Cl ion measuring container (14) through the solenoid valve (3a) and the acetate buffer (pH = 5) injection pipe (29). The stirrer (15) is activated by the signal from the controller (10), and the Cl ion reference solution and the acetate buffer solution (pH = 5) are mixed by the rotation of the rotor (16). The pH / Cl ion continuous automatic measuring device (11) is activated by the signal from the controller (10), the reference liquid is detected by the Cl ion electrode (13), and the Cl ion concentration (10 mg / l) is automatically detected. Adjusted to.
【００２２】 制御器（１０）からの信号により廃液用電磁弁（８ａ）が作動し、ｐＨ・Ｃｌ イオン測定容器（１４）の液が排出管（２４）を通って流下し廃液貯蔵容器（１ ７）に排出される。制御器（１０）からの信号により純水ポンプ（９）と純水電 磁弁（５ａ）とが同時に作動し、純水貯蔵容器（１８）から一定量の純水が純水 供給管（２２）を通ってｐＨ・Ｃｌイオン測定容器（１４）に供給される。制御 器（１０）からの信号により攪はん装置（１５）が作動し、回転子（１６）によ り純水を回転攪はんしてｐＨ電極（１２）及びＣｌイオン電極（１３）の表面と ｐＨ・Ｃｌイオン測定容器（１４）内壁を洗浄する。制御器（１０）からの信号 により攪はんが停止すると廃液用電磁弁（８ａ）が作動し、ｐＨ・Ｃｌイオン測 定容器（１４）中の液が排出管（２４）を通って流下し廃液貯蔵容器（１７）に 排出される。この洗浄は、制御器で自動的に任意の回数繰り返しができるように 設定する。The signal from the controller (10) activates the waste liquid solenoid valve (8a), the liquid in the pH / Cl ion measuring container (14) flows down through the discharge pipe (24), and the waste liquid storage container (1) is discharged. It is discharged to 7). The pure water pump (9) and the pure water electromagnetic valve (5a) are simultaneously operated by a signal from the controller (10), and a certain amount of pure water is supplied from the pure water storage container (18) to the pure water supply pipe (22). And is supplied to the pH / Cl ion measuring container (14). The stirrer (15) is activated by a signal from the controller (10), and the pure water is rotatably stirred by the rotor (16) to rotate the pH electrode (12) and the Cl ion electrode (13). The surface and the inner wall of the pH / Cl ion measuring container (14) are washed. When the stirring is stopped by the signal from the controller (10), the waste liquid solenoid valve (8a) is activated, and the liquid in the pH / Cl ion measuring container (14) flows down through the discharge pipe (24). It is discharged to the waste liquid storage container (17). This cleaning is set so that the controller can automatically repeat any number of times.
【００２３】 本考案の装置では、被測定液である塩素系有機溶剤と純水とを１：１の割合で 混合して抽出を行っているが、何かの要因でこの割合がずれた場合、ｐＨ値がず れる可能性も考えられる。これを確認するために、塩素系有機溶剤と純水との混 合割合を種々変化させてｐＨを測定した。In the device of the present invention, the chlorine-based organic solvent as the liquid to be measured and pure water are mixed at a ratio of 1: 1 for extraction. It is possible that the pH value may shift. In order to confirm this, the mixing ratio of the chlorine-based organic solvent and pure water was variously changed and the pH was measured.
【００２４】 図２は塩素系有機溶剤としてメチレンクロライド（Ａ：劣化前、Ｂ：劣化後） の一定量（２０ｍｌ）に対して純水１５〜３０ｍｌを添加したときのｐＨ値を示 す。横軸は純水の添加量、縦軸はｐＨ値を示す。図３は純水の一定量（２０ｍｌ ）に対しメチレンクロライド（Ａ：劣化前、Ｂ：劣化後）１５ｍｌ〜３０ｍｌを 添加したときの添加量をｐＨ値で示す。横軸はメチレンクロライドの添加量、縦 軸はｐＨ値を示す。図２、図３とも、ｐＨ値にはほとんど変化は認められないこ とから、塩素系有機溶剤と純水との混合割合がずれても影響がないと考えられる 。FIG. 2 shows pH values when 15 to 30 ml of pure water was added to a fixed amount (20 ml) of methylene chloride (A: before deterioration, B: after deterioration) as a chlorine-based organic solvent. The horizontal axis represents the amount of pure water added, and the vertical axis represents the pH value. FIG. 3 shows the addition amount as a pH value when 15 ml to 30 ml of methylene chloride (A: before deterioration, B: after deterioration) was added to a fixed amount of pure water (20 ml). The horizontal axis shows the amount of methylene chloride added, and the vertical axis shows the pH value. Since there is almost no change in the pH value in both FIGS. 2 and 3, it is considered that there is no effect even if the mixing ratio of the chlorine-based organic solvent and pure water deviates.
【００２５】 また、通常、ｐＨ測定器の校正に関しては、酸性側でｐＨを測定しようとする 場合には酸性ｐＨ基準液を用いて校正が行われ、アルカリ側でｐＨを測定しよう とする場合にはアルカリ性のｐＨ基準液を用いて校正が行われる。本考案の装置 でも前記のようにして校正を行うと、操作が煩雑になる。そこで、アルカリ性ｐ Ｈ基準液を用いて校正した場合と、酸性ｐＨ基準液を用いて校正した場合とで、 酸性の被測定液のｐＨ値にどの程度の差が生じるかを調べた。図４は、ｐＨ６〜 １の被測定液について、横軸を酸性ｐＨ基準液を用いて校正した場合のｐＨ値と し、縦軸をアルカリ性ｐＨ基準液を用いて校正した場合のｐＨ値として、プロッ トした図である。図４から、いずれの基準値を用いて校正しても、ｐＨ値にはほ とんど変化のないことがわかる。このことから、前記実施例のように、ｐＨ測定 器をアルカリ性ｐＨ基準液を用いて校正し、アルカリ性から酸性までの全領域に わたってｐＨを測定しても問題は生じない。[0025] Usually, with respect to the calibration of the pH measuring device, when the pH is to be measured on the acidic side, the calibration is performed using an acidic pH standard solution, and when the pH is to be measured on the alkaline side. Is calibrated using an alkaline pH reference solution. Even if the apparatus of the present invention is calibrated as described above, the operation becomes complicated. Therefore, it was examined how much the pH value of the acidic solution to be measured differs between the case where the calibration is performed using the alkaline pH standard solution and the case where the calibration is performed using the acidic pH standard solution. FIG. 4 shows the pH value when the horizontal axis is the pH value when calibrated using an acidic pH standard solution, and the vertical axis is the pH value when the alkaline pH standard solution is calibrated for the measured solution of pH 6 to 1. This is a plot. It can be seen from FIG. 4 that the pH value hardly changes even if calibration is performed using any of the reference values. From this, no problem will occur even if the pH meter is calibrated using the alkaline pH standard solution and the pH is measured over the entire range from alkaline to acidic as in the above-mentioned Example.
【００２６】 また、本考案の装置においては、測定に供される塩素系有機溶剤の量を少なく し、ｐＨ測定後の廃液量を少なくすることが好ましい。そこで、ｐＨ測定容器の 形状を図７に示すように断面積を小さく縦長の高形とし、塩素系有機溶剤の量を ３〜８ｍｌの範囲で変化させ、等量の純水を添加して、ｐＨを測定することが好 ましい。 その結果を図５に示す。図５からわかるように、塩素系有機溶剤の量が５ｍｌ 以上であれば、ｐＨ値は変化しない。したがって、図６に示す定量容器の容量が ５ｍｌとなるように、液面レベル管を取り付けたことにより、廃液量を少なくす ることができた。Further, in the device of the present invention, it is preferable to reduce the amount of the chlorine-based organic solvent used for the measurement and reduce the amount of the waste liquid after the pH measurement. Therefore, as shown in Fig. 7, the shape of the pH measuring container has a small cross-sectional area and a vertically long and high shape, the amount of the chlorine-based organic solvent is changed in the range of 3 to 8 ml, and an equal amount of pure water is added, It is preferable to measure the pH. The result is shown in FIG. As can be seen from FIG. 5, if the amount of chlorine-based organic solvent is 5 ml or more, the pH value does not change. Therefore, the amount of waste liquid could be reduced by attaching the liquid level tube so that the volume of the quantitative container shown in FIG. 6 would be 5 ml.
【００２７】 また、一般にイオン電極は、広範囲のｐＨで使用可能であるが、高濃度の酸、 アルカリではｐＨの影響が生じてくる場合がある。これを確認するために、１０ -4 ｍｏｌ／ｌ〜１０-1ｍｏｌ／ｌのＣｌイオン濃度液で、ｐＨを０〜１４と変化 させてｐＨを測定した。その結果を図８に示す。図８からわかるように、ｐＨ１ 〜１１の範囲以内ならば、全く影響しないことが分かった。ＪＩＳＫ０１０１工 業用水分析方法によれば、Ｃｌイオンの測定時のｐＨは５．０に限定され、試料 が酸性の場合には、水酸化ナトリウム溶液（４ｗ／ｖ％）、アルカリ性の場合に は酢酸（１＋１００）で、あらかじめｐＨ約５に調節することが規定されている 。しかし、図８の結果を確認するために、安定剤でｐＨ１１にしてある塩素系有 機溶剤を水で抽出し、この液１０に対し酢酸緩衝液を１の割合で添加して、電位 を測定したところ電位に変動がなく一定であった。本考案はこのようにＪＩＳ通 りに行わなくてもよい。In general, the ion electrode can be used in a wide range of pH, but a high concentration of acid or alkali may cause the influence of pH. To confirm this, 10 -Four mol / l-10-1The pH was measured by changing the pH from 0 to 14 with a mol / l Cl ion concentration solution. The result is shown in FIG. As can be seen from FIG. 8, it was found that there was no effect if the pH was within the range of 1-11. According to the JISK0101 industrial water analysis method, the pH during Cl ion measurement is limited to 5.0. Sodium hydroxide solution (4 w / v%) is used when the sample is acidic, and acetic acid is used when the sample is alkaline. (1 + 100) regulates the pH to about 5 beforehand. However, in order to confirm the results in FIG. 8, a chlorine-based organic solvent adjusted to pH 11 with a stabilizer was extracted with water, and an acetate buffer solution was added to this solution 10 at a ratio of 1 to measure the potential. After that, the potential was constant without change. The present invention does not have to be carried out according to JIS in this way.
【００２８】 また、イオン電極に生じる起電力はイオン活量の対数に比例し、活量は活量係 数で除することにより濃度に変換される。そして、活量係数はイオン強度の影響 を受けて変化し測定誤差の原因になる。したがって、Ｃｌイオンの測定誤差をな くすために、測定液量に対し酢酸緩衝液の添加量を１０：１の割合で加え、校正 液と被検液のイオン強度を一定にしたところ、測定可能となった。Further, the electromotive force generated in the ion electrode is proportional to the logarithm of the ion activity, and the activity is converted into the concentration by dividing by the activity coefficient. Then, the activity coefficient changes under the influence of ionic strength and causes a measurement error. Therefore, in order to eliminate the measurement error of Cl ion, the addition amount of acetate buffer is added at a ratio of 10: 1 to the amount of the measurement solution, and the ionic strength of the calibration solution and the test solution is kept constant. Became.
【００２９】[0029]
以上詳述したように、本考案のｐＨ・Ｃｌイオン連続測定装置を用いれば、溶 剤洗浄機のベーパー洗浄槽よりサンプリングし、溶剤供給管で室温に冷却するこ とにより塩素系有機溶剤をｐＨ及びＣｌイオンを自動的に連続測定することがで き、測定者が測定に煩わされることがなくなり、しかもｐＨ及びＣｌイオン測定 値のバラツキがなくなる。したがって、塩素系有機溶剤の劣化を確実に監視する ことができ、装置の長寿命化、被洗物（ワーク）への悪影響の防止を図りつつ、 溶剤消費量の低減を達成することができる。 As described above in detail, when the pH / Cl ion continuous measuring device of the present invention is used, the chlorine-based organic solvent is adjusted to pH by sampling from the vapor cleaning tank of the solvent washer and cooling to room temperature with the solvent supply pipe. Since Cl and Cl ions can be continuously measured automatically, the operator is not bothered by the measurement, and variations in pH and Cl ion measurement values are eliminated. Therefore, it is possible to reliably monitor the deterioration of the chlorine-based organic solvent, prolong the life of the apparatus, and prevent the adverse effect on the object to be washed (workpiece), while achieving the reduction of solvent consumption.
【００３０】 また、この装置の最も大きな特徴は、Ｃｌイオンの自動測定にあたって、ＪＩ Ｓ法の手分析をそのまま踏襲して自動化すれば、Ｃｌイオン測定時の液性をｐＨ ５に厳守する必要があるが、安定剤でｐＨ１１に調整されているほとんどの塩素 系有機溶剤は、水抽出後、酢酸（１＋１００）でｐＨ５に調整する必要があり、 これを自動化することは、ｐＨとの連続測定を考慮した場合、かなり複雑な装置 となる。しかし、本考案の装置では、全くＪＩＳ法にしたがわずにＣｌイオンが 測定できたため、装置を複雑にすることなく容易にｐＨとの連続測定が可能にな った。In addition, the most important feature of this device is that in the automatic measurement of Cl ions, if the JIS method is automated by directly following the manual analysis, it is necessary to strictly maintain the liquidity at the time of Cl ion measurement to pH 5. However, most chlorine-based organic solvents that have been adjusted to pH 11 with stabilizers need to be adjusted to pH 5 with acetic acid (1 + 100) after water extraction, and automating this requires continuous measurement with pH. Considered, it is a fairly complex device. However, with the device of the present invention, Cl ions can be measured without using the JIS method at all, so that continuous measurement with pH has become possible without complicating the device.
【図面の簡単な説明】[Brief description of drawings]
【図１】本考案に係るｐＨ・Ｃｌイオン連続自動測定装
置の構成図である。FIG. 1 is a configuration diagram of a pH / Cl ion continuous automatic measuring device according to the present invention.
【図２】一定量のメチレンクロライドに対して純水の量
を変化させて添加した場合のｐＨの測定結果を示す図で
ある。FIG. 2 is a diagram showing pH measurement results when a pure water amount was changed and added to a fixed amount of methylene chloride.
【図３】一定量の純水に対してメチレンクロライドの量
を変化させて添加した場合のｐＨの測定結果を示す図で
ある。FIG. 3 is a diagram showing the measurement results of pH when varying the amount of methylene chloride was added to a fixed amount of pure water.
【図４】ｐＨ７基準液とアルカリ性基準液又は酸性基準
液とを用校正されたｐＨ・Ｃｌイオン連続自動測定装置
によるｐＨの測定結果を示す図である。FIG. 4 is a diagram showing a pH measurement result by a pH / Cl ion continuous automatic measuring device calibrated using a pH 7 standard solution and an alkaline standard solution or an acidic standard solution.
【図５】測定に供される塩素系有機溶剤の量とｐＨとの
関係を示す図である。FIG. 5 is a diagram showing the relationship between the amount of a chlorine-based organic solvent used for measurement and pH.
【図６】液面レベル管を有する定量容器の断面図であ
る。FIG. 6 is a sectional view of a metering container having a liquid level tube.
【図７】高形ｐＨ・Ｃｌイオン測定容器の断面図であ
る。FIG. 7 is a cross-sectional view of a high pH / Cl ion measuring container.
【図８】Ｃｌイオン電極のｐＨ特性図である。FIG. 8 is a pH characteristic diagram of a Cl ion electrode.
Claims (1)
・塩素イオン連続自動測定装置において制御器と、ｐＨ
・塩素イオン測定容器と、ｐＨ基準液貯蔵容器と、塩素
イオン基準液貯蔵容器と、酢酸緩衝液貯蔵容器と、純水
貯蔵容器と、前記ｐＨ基準液貯蔵容器内の基準液、塩素
イオン基準液貯蔵容器内の基準液、酢酸緩衝液、及び貯
蔵容器内の緩衝液をそれぞれ前記ｐＨ・塩素イオン測定
容器に供給する手段と、溶剤洗浄機の洗浄槽から一定量
の有機溶剤を前記ｐＨ・塩素イオン測定容器に供給する
手段と、前記純水貯蔵容器から一定量の純水を前記ｐＨ
・塩素イオン測定容器に供給する手段と、前記ｐＨ・塩
素イオン測定容器の液を攪はんする手段と、前記ｐＨ・
塩素イオン測定容器の液のｐＨ・塩素イオンを測定する
手段と、前記ｐＨ・塩素イオン測定容器内の液を排出す
る手段とを具備したことを特徴とするｐＨ・塩素イオン
連続自動測定装置。1. A pH attached to a chlorine-based organic solvent cleaner
・ Controller and pH in continuous chlorine ion automatic measuring device
・ Chlorine ion measuring container, pH reference liquid storage container, chlorine ion reference liquid storage container, acetate buffer storage container, pure water storage container, reference liquid in the pH reference liquid storage container, chlorine ion reference liquid Means for supplying the reference solution in the storage container, the acetate buffer solution, and the buffer solution in the storage container to the pH / chlorine ion measuring container, respectively, and a certain amount of organic solvent from the cleaning tank of the solvent washer to the pH / chlorine Means for supplying to the ion measuring container and a certain amount of pure water from the pure water storage container
・ Means for supplying to the chloride ion measuring container, means for agitating the liquid of the above-mentioned chloride ion chloride container,
A continuous automatic pH / chlorine ion measuring device comprising means for measuring pH / chlorine ion of a liquid in a chlorine ion measuring container and means for discharging the liquid in the pH / chlorine ion measuring container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4062691U JPH0653968U (en) | 1991-05-31 | 1991-05-31 | pH / chlorine ion continuous automatic measuring device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4062691U JPH0653968U (en) | 1991-05-31 | 1991-05-31 | pH / chlorine ion continuous automatic measuring device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0653968U true JPH0653968U (en) | 1994-07-22 |
Family
ID=12585755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4062691U Withdrawn JPH0653968U (en) | 1991-05-31 | 1991-05-31 | pH / chlorine ion continuous automatic measuring device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653968U (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106556671A (en) * | 2015-09-24 | 2017-04-05 | 赛默飞世尔（上海）仪器有限公司 | Deposit minimizing technology and device in online water analysis instrument |
| CN114544266A (en) * | 2020-11-20 | 2022-05-27 | 中国兵器工业第五九研究所 | Real-time monitoring device for chloride ion in atmospheric environment |
| CN120741878A (en) * | 2025-08-22 | 2025-10-03 | 湖南大学 | Full-automatic polymer material free chloride ion content detection device and method |
-
1991
- 1991-05-31 JP JP4062691U patent/JPH0653968U/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106556671A (en) * | 2015-09-24 | 2017-04-05 | 赛默飞世尔（上海）仪器有限公司 | Deposit minimizing technology and device in online water analysis instrument |
| CN114544266A (en) * | 2020-11-20 | 2022-05-27 | 中国兵器工业第五九研究所 | Real-time monitoring device for chloride ion in atmospheric environment |
| CN114544266B (en) * | 2020-11-20 | 2023-12-22 | 中国兵器工业第五九研究所 | Chloride ion real-time monitoring device used in atmosphere environment |
| CN120741878A (en) * | 2025-08-22 | 2025-10-03 | 湖南大学 | Full-automatic polymer material free chloride ion content detection device and method |
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