JP2008058025A - Residual chlorine concentration meter - Google Patents
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Abstract
Description
この発明は、プール水等の残留塩素濃度を測定する残留塩素濃度計に関するものである。 The present invention relates to a residual chlorine concentration meter for measuring residual chlorine concentration in pool water or the like.
従来、残留塩素濃度をポーラログラフィーによって検出するため次のような残留塩素測定装置の提案があった（特許文献１）。
すなわち、生活用水、プール水等では、それらの滅菌のために塩素が注入される。塩素注入量は、検水に含まれる遊離残留塩素濃度を測定することにより管理されている。遊離残留塩素濃度を測定する無試薬測定方法としては、主としてポーラログラフ法が使用されている。
ポーラログラフ法は、検水に浸漬した２つの電極（対電極と作用電極）の間に電圧を印加したときに２電極間に流れる酸化・還元電流を測定することにより、特定の化学種のイオン濃度を測定する方法である。
さらに、図２に示すように、対電極11及び作用電極12の他に 比較電極(参照電極)13を増設した３電極型も知られている。この３電極型では、絶対電位の不明な作用電極12の電位を特定するため、比較電極13に基準電位を与えるようにしている。この３電極法によれば、電導度変化に強いという利点がある。
ところで、電極と接触する検水の流量が変化すると酸化・還元電流値も変化するため、電極を流量一定の検水に浸漬するためのフローセルと呼ばれる測定槽(図示せず)を使用する。そして、作用電極12の表面は汚れてくるため測定槽にセラミックビーズ(図示せず)を収納し、水流によりセラミックビーズに電極表面を衝突させて電極表面を洗浄することがなされている。
しかし、前記セラミックビーズでは電極表面清掃効果が殆ど期待できず(セラミックビーズでは酸化皮膜は切除できない)、作用電極に酸化皮膜が形成され (この酸化皮膜に次第に油脂分等が吸着されていくせいか)測定精度が経時的に不安定になっていく傾向があるという問題があった。
That is, in domestic water, pool water, etc., chlorine is injected for sterilization thereof. The amount of chlorine injected is controlled by measuring the concentration of free residual chlorine contained in the sample water. As a reagent-free measuring method for measuring the free residual chlorine concentration, a polarographic method is mainly used.
The polarographic method measures the ion concentration of a specific chemical species by measuring the oxidation / reduction current that flows between two electrodes when a voltage is applied between the two electrodes (counter electrode and working electrode) immersed in the test water. Is a method of measuring.
Further, as shown in FIG. 2, a three-electrode type in which a reference electrode (reference electrode) 13 is added in addition to the counter electrode 11 and the working electrode 12 is also known. In this three-electrode type, a reference potential is applied to the comparison electrode 13 in order to specify the potential of the working electrode 12 whose absolute potential is unknown. This three-electrode method has the advantage of being resistant to changes in conductivity.
By the way, since the oxidation / reduction current value changes when the flow rate of the sample water in contact with the electrode changes, a measurement tank called a flow cell (not shown) for immersing the electrode in the sample water with a constant flow rate is used. Since the surface of the working electrode 12 becomes dirty, ceramic beads (not shown) are accommodated in a measurement tank, and the electrode surface is made to collide with the ceramic beads by a water flow to clean the electrode surface.
However, with the ceramic beads, the electrode surface cleaning effect can hardly be expected (the ceramic beads cannot remove the oxide film), and an oxide film is formed on the working electrode (whether the oil or fat is gradually adsorbed on the oxide film). There was a problem that the measurement accuracy tends to become unstable over time.
そこでこの発明は、測定精度が従来よりも経時的に不安定となっていき難い残留塩素濃度計を提供しようとするものである。 Therefore, the present invention is intended to provide a residual chlorine concentration meter whose measurement accuracy is less likely to become unstable over time than in the past.
前記課題を解決するためこの発明では次のような技術的手段を講じている。
(１)この発明の残留塩素濃度計は、残留塩素濃度測定用の作用極と対電極とを有し、前記作用極に対面させて対向電極を配設し、作用極に付着した酸化皮膜のクリーニング時には前記作用極が負に対向電極が正になるように印加すると共に、前記作用極の表面に形成された酸化皮膜の酸素と被検液中の水素イオンとにより水を生成させるように電流を流して電気分解するようにしたことを特徴とする。
この発明では、作用極に付着した酸化皮膜のクリーニング時には前記作用極が負に、対向電極が正になるように印加するようにしたので、作用極(負)と対向電極(正)との両電極間で、被検液中の水素イオン(Ｈ＋)は還元雰囲気の作用極(負)に惹き付けられることとなる。そして、作用極の表面に形成された酸化皮膜の酸素と被検液中の水素イオンとにより水を生成させるように電流を流して電気分解するようにしたので、前記酸化皮膜の酸素と被検液中の水素イオンとにより水を生成させることができ、これにより作用極表面の酸化皮膜を水として好適に除去することができる。こうして、作用極の電極表面がクリーニングされ、適正化された状態で残留塩素濃度測定を再開することができる。
前記残留塩素濃度の測定は例えば公知のポーラログラフィー方式で行うことができ、比較電極も配設することができる。また、前記作用極と対電極の材質として白金や金を用いることができ、前記比較電極として銀−塩化銀電極を用いることができる。前記酸化皮膜のクリーニングは、残留塩素濃度測定の合間に行うとよい。
ところで、前記ポーラログラフィー方式での対電極は例えば線状で輪状の電極であり非常に面積が小さくてまた作用極から距離的にも離れているものであり、作用極と対電極との間で酸化皮膜の処理をするのには無理である。また、対電極に対して作用極に電圧値を印加していたが、この電圧値では酸化皮膜は除去できないものであった。
一方、本発明のように構成して作用極に対して対向電極を新設すると、作用極に近接して且つある程度面積が大きな電極として構成することができる。また、電圧値を酸化皮膜の酸素と被検液中の水素イオンとにより水を生成させるように電流を流して電気分解することにより、測定レベルではなく電気分解レベルの電流を流して酸化皮膜を還元除去することができる。
In order to solve the above problems, the present invention takes the following technical means.
(1) A residual chlorine concentration meter according to the present invention has a working electrode for measuring the residual chlorine concentration and a counter electrode. A counter electrode is disposed facing the working electrode, and an oxide film attached to the working electrode is formed. At the time of cleaning, the working electrode is applied so that the counter electrode is negative and the current is generated so that water is generated by oxygen of the oxide film formed on the surface of the working electrode and hydrogen ions in the test solution. It is characterized in that it is electrolyzed by flowing.
In the present invention, when the oxide film adhered to the working electrode is cleaned, the working electrode is applied so that the working electrode is negative and the counter electrode is positive. Therefore, both the working electrode (negative) and the counter electrode (positive) are applied. Between the electrodes, the hydrogen ions (H + ) in the test solution are attracted to the working electrode (negative) of the reducing atmosphere. Since the oxygen is formed on the surface of the working electrode and the hydrogen ions in the test solution generate water, an electric current is passed to cause electrolysis. Water can be generated by the hydrogen ions in the liquid, whereby the oxide film on the surface of the working electrode can be suitably removed as water. Thus, the residual chlorine concentration measurement can be resumed in a state where the electrode surface of the working electrode is cleaned and optimized.
The measurement of the residual chlorine concentration can be performed by, for example, a known polarography method, and a comparative electrode can also be provided. Moreover, platinum and gold can be used as the material of the working electrode and the counter electrode, and a silver-silver chloride electrode can be used as the comparative electrode. The oxide film may be cleaned between residual chlorine concentration measurements.
By the way, the counter electrode in the polarography method is, for example, a linear and ring-shaped electrode, which has a very small area and is distant from the working electrode, and is located between the working electrode and the counter electrode. It is impossible to treat the oxide film. Further, although a voltage value was applied to the working electrode with respect to the counter electrode, the oxide film could not be removed with this voltage value.
On the other hand, when the counter electrode is newly provided with respect to the working electrode configured as in the present invention, it can be configured as an electrode that is close to the working electrode and has a large area to some extent. In addition, the voltage value is electrolyzed by flowing current so that water is generated by oxygen of the oxide film and hydrogen ions in the test solution, so that the current of the electrolysis level is passed instead of the measurement level. It can be reduced and removed.
(２) 前記作用極に付着した酸化皮膜のクリーニング後、作用極と対向電極の極性を入れ替えることによりクリーニング時に作用極に付着してきたスケール成分を除去するようにしたこととしてもよい。
このように構成すると、作用極を負に帯電させて電気分解するクリーニング中に該作用極に引き寄せられ付着したスケール成分(炭酸カルシウム、シリカ、マグネシウム、有機物など)を除去することができ、作用極の電極表面がより適正化された状態で残留塩素濃度測定を再開することができる。
(３) 前記作用極と対向電極により被検液の導電率を測定できるように設定したこととしてもよい。このように構成すると、対向電極をクリーニング用としてのみならず導電率の測定用にも利用することができ、例えばプール水などの被検液について残留塩素濃度だけではなくその導電率をも同じセンサーで把握することができ、センサーとしての利便性が非常に高いものとなる。ここで、被検液の導電率の測定時は作用極と対向電極との間に交流電流を流すことにより公知の方法で測定することができる。
(2) After cleaning the oxide film adhering to the working electrode, the scale components adhering to the working electrode during cleaning may be removed by switching the polarities of the working electrode and the counter electrode.
With this configuration, it is possible to remove scale components (calcium carbonate, silica, magnesium, organic matter, etc.) attracted to and adhered to the working electrode during cleaning that is electrolyzed by negatively charging the working electrode. Residual chlorine concentration measurement can be resumed in a state where the electrode surface is more optimized.
(3) It is good also as setting so that the electrical conductivity of a test liquid can be measured with the said working electrode and a counter electrode. When configured in this way, the counter electrode can be used not only for cleaning but also for measuring conductivity. For example, for the test liquid such as pool water, not only the residual chlorine concentration but also the conductivity is the same sensor. This makes it very convenient for the sensor. Here, when measuring the conductivity of the test solution, it can be measured by a known method by passing an alternating current between the working electrode and the counter electrode.
この発明は上述のような構成であり、次の効果を有する。
作用電極の酸化皮膜がクリーニングされ適正化された状態で残留塩素濃度測定を行うことができる構造であるので、測定精度が従来よりも経時的に不安定となっていき難い残留塩素濃度計を提供することができる。
The present invention is configured as described above and has the following effects.
Since the residual chlorine concentration can be measured with the oxide film on the working electrode cleaned and optimized, a residual chlorine concentration meter is provided in which the measurement accuracy is less likely to become unstable over time. can do.
以下、この発明の実施の形態を図面を参照して説明する。
図１に示すように、この実施形態の残留塩素濃度計は、残留塩素濃度測定用の作用極１と対電極２とを有する。前記残留塩素濃度の測定は公知のポーラログラフィー方式で行うことができ、比較電極(参照電極)３も配設している。
そして、前記作用極１に対面させて対向電極４を配設し、作用極１に付着した酸化皮膜のクリーニング時には前記作用極１が負に対向電極４が正になるように印加すると共に、前記作用極１の表面に形成された酸化皮膜の酸素と被検液中の水素イオンとにより水を生成させるように電流(例えば１〜５Ａ程度)を流して電気分解するようにしている。
前記対向電極４の材質として、フェライト製のものとすると難腐食性の点で好ましい。なお、ポーラログラフィー方式では一定値の電圧を印加した際に流れる電流値を測定し、この測定値から液中の残留塩素濃度を評価する。すなわち、一定値の電圧を印加すると次亜塩素酸が還元されてイオン化され、溶液中を流れる電流値が増加することなどを利用している。
前記作用極１と対電極４の材質として白金や金を用いることができ、前記比較電極３として銀−塩化銀電極を用いることができる。前記酸化皮膜のクリーニングは、残留塩素濃度測定の合間に行うとよい。５は対向電極４からの引き出し配線である。
Embodiments of the present invention will be described below with reference to the drawings.
As shown in FIG. 1, the residual chlorine concentration meter of this embodiment has a working electrode 1 and a counter electrode 2 for measuring the residual chlorine concentration. The residual chlorine concentration can be measured by a known polarography method, and a reference electrode (reference electrode) 3 is also provided.
Then, the counter electrode 4 is disposed so as to face the working electrode 1, and when the oxide film adhering to the working electrode 1 is cleaned, the working electrode 1 is applied so that the counter electrode 4 becomes negative and the counter electrode 4 becomes positive. Electrolysis is performed by passing an electric current (for example, about 1 to 5 A) so that water is generated by oxygen of the oxide film formed on the surface of the working electrode 1 and hydrogen ions in the test solution.
The material of the counter electrode 4 is preferably made of ferrite from the viewpoint of hardly corroding. In the polarography method, a current value that flows when a constant voltage is applied is measured, and the residual chlorine concentration in the liquid is evaluated from the measured value. That is, when a constant voltage is applied, hypochlorous acid is reduced and ionized to increase the value of current flowing in the solution.
Platinum or gold can be used as the material of the working electrode 1 and the counter electrode 4, and a silver-silver chloride electrode can be used as the comparative electrode 3. The oxide film may be cleaned between residual chlorine concentration measurements. Reference numeral 5 denotes a lead wiring from the counter electrode 4.
また、前記作用極１に付着した酸化皮膜のクリーニング後、作用極１と対向電極４の極性を入れ替えることによりクリーニング時に作用極１に付着してきたスケール成分を除去するようにしている。さらに、前記作用極１と対向電極４により被検液の導電率を測定できるように設定している。被検液の導電率の測定時は、作用極１と対向電極４との間に交流電流を流すことにより公知の方法で測定することができる。 Further, after cleaning the oxide film adhering to the working electrode 1, the scale components adhering to the working electrode 1 during cleaning are removed by switching the polarities of the working electrode 1 and the counter electrode 4. Furthermore, the working electrode 1 and the counter electrode 4 are set so that the conductivity of the test solution can be measured. When measuring the conductivity of the test solution, it can be measured by a known method by passing an alternating current between the working electrode 1 and the counter electrode 4.
次に、この実施形態の残留塩素濃度計の使用状態を説明する。
この実施形態では、作用極１に付着した酸化皮膜のクリーニング時には前記作用極１が負に、対向電極４が正になるように印加するようにしたので、作用極１(負)と対向電極４(正)との両電極間で、被検液中の水素イオン(Ｈ＋)は還元雰囲気の作用極(負)に惹き付けられることとなる。そして、作用極１の表面に形成された酸化皮膜の酸素と被検液中の水素イオンとにより水を生成させるように電流を流して電気分解するようにしたので、前記酸化皮膜の酸素と被検液中の水素イオンとにより水を生成させることができ、これにより作用極表面の酸化皮膜を水として好適に除去することができる。こうして、作用極１の電極表面がクリーニングされ、適正化された状態で残留塩素濃度測定を再開することができ、測定精度が従来よりも経時的に不安定となっていき難いという利点がある。
Next, the usage state of the residual chlorine concentration meter of this embodiment will be described.
In this embodiment, when the oxide film adhered to the working electrode 1 is cleaned, the working electrode 1 is applied so that the working electrode 1 is negative and the counter electrode 4 is positive. Therefore, the working electrode 1 (negative) and the counter electrode 4 are applied. Between the positive and negative electrodes, the hydrogen ions (H + ) in the test solution are attracted to the working electrode (negative) of the reducing atmosphere. Then, since the current is made to electrolyze so that water is generated by the oxygen of the oxide film formed on the surface of the working electrode 1 and the hydrogen ions in the test solution, the oxygen of the oxide film Water can be generated by the hydrogen ions in the test solution, whereby the oxide film on the surface of the working electrode can be suitably removed as water. Thus, the residual chlorine concentration measurement can be restarted in a state where the electrode surface of the working electrode 1 is cleaned and optimized, and there is an advantage that the measurement accuracy is less likely to become unstable over time than in the past.
ところで、前記ポーラログラフィー方式での対電極２は例えば線状で輪状の電極であり非常に面積が小さくてまた作用極１から距離的にも離れているものであり、作用極１と対電極２との間で酸化皮膜の処理をするのには無理である。また、対電極２に対して作用極１に電圧値として−数百ｍｍＶを印加していたが、この電圧値では酸化皮膜は除去できないものであった。
一方、上記のように構成して作用極１に対して対向電極４を新設すると、作用極１に近接して且つある程度面積が大きな電極として構成することができる。また、電圧値を酸化皮膜の酸素と被検液中の水素イオンとにより水を生成させるように電流を流して電気分解することにより、測定レベルではなく電気分解レベルの電流を流して酸化皮膜を還元除去することができる。
By the way, the counter electrode 2 in the polarography system is, for example, a linear and ring-shaped electrode, which has a very small area and is separated from the working electrode 1 by distance. It is impossible to treat the oxide film between the two. Further, although −100 mmV was applied as a voltage value to the working electrode 1 with respect to the counter electrode 2, the oxide film could not be removed at this voltage value.
On the other hand, when the counter electrode 4 is newly provided with respect to the working electrode 1 configured as described above, it can be configured as an electrode that is close to the working electrode 1 and has a large area to some extent. In addition, the voltage value is electrolyzed by flowing current so that water is generated by oxygen of the oxide film and hydrogen ions in the test solution, so that the current of the electrolysis level is passed instead of the measurement level. It can be reduced and removed.
また、前記作用極１に付着した酸化皮膜のクリーニング後、作用極１と対向電極４の極性を入れ替えることによりクリーニング時に作用極１に付着してきたスケール成分を除去するようにしており、作用極１を負に帯電させて電気分解するクリーニング中に該作用極１に引き寄せられ付着したスケール成分(炭酸カルシウム、シリカ、マグネシウム、有機物など)を除去することができ、作用極１の電極表面がより適正化された状態で残留塩素濃度測定を再開することができるという利点がある。 Further, after cleaning the oxide film adhering to the working electrode 1, the polarity of the working electrode 1 and the counter electrode 4 is switched to remove scale components adhering to the working electrode 1 during cleaning. It is possible to remove scale components (calcium carbonate, silica, magnesium, organic substances, etc.) attracted to and adhered to the working electrode 1 during cleaning that is negatively charged and electrolyzed, and the electrode surface of the working electrode 1 is more appropriate. There is an advantage that the residual chlorine concentration measurement can be resumed in a converted state.
さらに、前記作用極１と対向電極４により被検液の導電率を測定できるように設定しており、対向電極４をクリーニング用としてのみならず導電率の測定用にも利用することができ、例えばプール水などの被検液について残留塩素濃度だけではなくその導電率をも同じセンサーで把握することができ、センサーとしての利便性が非常に高いものとなる。ここで、被検液の導電率の測定時は作用極と対向電極との間に交流電流を流すことにより公知の方法で測定することができるという利点がある。 Further, the working electrode 1 and the counter electrode 4 are set so that the conductivity of the test liquid can be measured, and the counter electrode 4 can be used not only for cleaning but also for measuring the conductivity, For example, not only the residual chlorine concentration but also the conductivity of a test solution such as pool water can be grasped by the same sensor, and the convenience as a sensor becomes very high. Here, when measuring the conductivity of the test liquid, there is an advantage that it can be measured by a known method by passing an alternating current between the working electrode and the counter electrode.
作用電極の酸化皮膜がクリーニングされ適正化された状態で残留塩素濃度測定を行うことができる構造であり、ビーズを使用しなくても測定精度が従来よりも経時的に不安定となっていき難いことによって、種々の残留塩素濃度計の用途に適用することができる。
そしてこの水質測定システムは、飲料用水、工業用水、電気洗濯機用洗濯用水、業務用殺菌洗浄水、食品加工用殺菌洗浄水、梅などの食品加工排水、スクラバー用循環殺菌水、クーリングタワー循環殺菌水、金属切削用クーラントエマルジョン殺菌水、温泉水循環殺菌水、浴場用循環殺菌水、噴水用循環水、殺菌管理用センサー、水質浄化管理センサー、藻類発生防止用の水その他の残留塩素濃度を好適に測定することができる。
It is a structure that can measure the residual chlorine concentration with the oxide film on the working electrode cleaned and optimized, and the measurement accuracy is less likely to become unstable over time without using beads. Thus, it can be applied to various uses of the residual chlorine concentration meter.
And this water quality measuring system is used for drinking water, industrial water, washing water for electric washing machines, industrial sterilization washing water, sterilization washing water for food processing, food processing wastewater such as plum, circulation sterilization water for scrubber, cooling tower circulation sterilization water Coolant emulsion sterilized water for metal cutting, hot spring water sterilized water, bath sterilized water, fountain circulated water, sterilization control sensor, water purification control sensor, algae generation prevention water and other residual chlorine concentration can do.
１ 作用極
２ 対電極
４ 対向電極
1 Working electrode 2 Counter electrode 4 Counter electrode
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2006232440A JP2008058025A (en) | 2006-08-29 | 2006-08-29 | Residual chlorine concentration meter |
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| JP2006232440A JP2008058025A (en) | 2006-08-29 | 2006-08-29 | Residual chlorine concentration meter |
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| JP2008058025A true JP2008058025A (en) | 2008-03-13 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011027584A (en) * | 2009-07-27 | 2011-02-10 | Horiba Advanced Techno Co Ltd | Water quality measuring device |
| JP2015087234A (en) * | 2013-10-30 | 2015-05-07 | ダイハツ工業株式会社 | Hydrazine concentration detector |
| JP2017053746A (en) * | 2015-09-10 | 2017-03-16 | 東亜ディーケーケー株式会社 | Residual chlorine measurement device and residual chlorine measurement method |
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| JPH0972879A (en) * | 1995-09-05 | 1997-03-18 | Kubota Corp | Electrode type sensor |
| JPH1082761A (en) * | 1996-09-05 | 1998-03-31 | Merusu Giken:Kk | Method and apparatus for measuring residual chlorine, and probe for detecting residual chlorine |
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| JPH11333460A (en) * | 1998-05-26 | 1999-12-07 | Tacmina Corp | Washing of residual chlorine meter |
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| JPS628050A (en) * | 1985-07-05 | 1987-01-16 | Nippon Fuirukon Kk | Method and apparatus for measuring concentration of oxidizable substance in liquid to be inspected |
| JPH0972879A (en) * | 1995-09-05 | 1997-03-18 | Kubota Corp | Electrode type sensor |
| JPH1082761A (en) * | 1996-09-05 | 1998-03-31 | Merusu Giken:Kk | Method and apparatus for measuring residual chlorine, and probe for detecting residual chlorine |
| JPH10296242A (en) * | 1997-04-23 | 1998-11-10 | Matsushita Electric Works Ltd | Water purifier |
| JPH11333460A (en) * | 1998-05-26 | 1999-12-07 | Tacmina Corp | Washing of residual chlorine meter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011027584A (en) * | 2009-07-27 | 2011-02-10 | Horiba Advanced Techno Co Ltd | Water quality measuring device |
| JP2015087234A (en) * | 2013-10-30 | 2015-05-07 | ダイハツ工業株式会社 | Hydrazine concentration detector |
| JP2017053746A (en) * | 2015-09-10 | 2017-03-16 | 東亜ディーケーケー株式会社 | Residual chlorine measurement device and residual chlorine measurement method |
| US10473618B2 (en) | 2015-09-10 | 2019-11-12 | Kurita Water Industries Ltd. | Residual chlorine measuring apparatus and method of measuring residual chlorine |
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