JPH09127081A - Continuous reproducing column for cation electrical conductivity measurement - Google Patents
Continuous reproducing column for cation electrical conductivity measurementInfo
- Publication number
- JPH09127081A JPH09127081A JP8187397A JP18739796A JPH09127081A JP H09127081 A JPH09127081 A JP H09127081A JP 8187397 A JP8187397 A JP 8187397A JP 18739796 A JP18739796 A JP 18739796A JP H09127081 A JPH09127081 A JP H09127081A
- Authority
- JP
- Japan
- Prior art keywords
- cation
- column
- continuous regeneration
- regeneration column
- conductivity measurement
- 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.)
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は溶液の陽イオン電導
度測定用連続再生カラムに関し、特に、陽イオン交換特
性を有するイオン交換膜と電極を用いてカラムに充電さ
れた陽イオン交換樹脂が連続的に再生されるようにし
て、連続的に用いられ得るようにした陽イオン電導度測
定用連続再生カラムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a continuous regeneration column for measuring the cation conductivity of a solution, and more particularly to a continuous cation exchange resin charged in the column using an ion exchange membrane having cation exchange characteristics and an electrode. The present invention relates to a continuous regeneration column for measuring cation conductivity, which can be continuously used by being regenerated.
【０００２】[0002]
【従来の技術】周知のように、高純度の水が循環されて
いる循環系統において、外部からの不純物の流入を積極
的に抑制するためには、水質を連続的に監視することが
非常に重要である。As is well known, in a circulation system in which high-purity water is circulated, it is very important to continuously monitor the water quality in order to positively suppress the inflow of impurities from the outside. is important.
【０００３】現在、系統循環水の水質を監視するため
に、最も広く用いられている方法は陽イオン電導度測定
法である。Currently, the most widely used method for monitoring the water quality of system circulating water is the cation conductivity measuring method.
【０００４】この場合、陽イオン電導度は陽イオン樹脂
が充電されたカラムを通過した水の電気的な抵抗を測定
して逆数で表わした値であって、単位としてはｍｈｏが
用いられる。In this case, the cation conductivity is a value represented by the reciprocal of the electrical resistance of water which has passed through the column charged with the cation resin, and is represented by mho.
【０００５】一般に、多量の不純物が含まれている水は
電気的な抵抗が小さく、少量の不純物が含まれている水
は電気的な抵抗が大きく表わされる。すなわち、水中に
不純物が大きい場合には電気電導度が大きく、不純物が
小さい場合には電気電導度が少なく表わされる。In general, water containing a large amount of impurities has a low electric resistance, and water containing a small amount of impurities has a large electric resistance. That is, when the impurities in water are large, the electric conductivity is high, and when the impurities are small, the electric conductivity is low.
【０００６】しかし、大部分の場合、水循環系統には材
質の腐食やスケール付着を防止するためにアンモニア水
などのような種々の薬品を注入しているが、このような
注入薬品は水の電導度を高める原因となるため、循環水
の電導度を直接測定する場合、注入薬品による影響と外
部の不純物の流入による影響とを区別しにくくなり、か
つ不純物が微量で流入される場合には測定感度が低くて
感知が困難になるという問題点を有している。In most cases, however, various chemicals such as ammonia water are injected into the water circulation system in order to prevent corrosion of materials and scale adhesion. When measuring the conductivity of circulating water directly, it is difficult to distinguish the effect of injected chemicals from the effect of inflow of external impurities, and it is necessary to measure if the impurities flow in in trace amounts. There is a problem that the sensitivity is low and it becomes difficult to detect.
【０００７】よって、陽イオン電導度に対する測定感度
を高め、注入される薬品による影響を排除するために、
まず測定水を測定水中の陽イオンを吸着し得る陽イオン
交換樹脂が充電されたカラムを通過させた後、陽イオン
電導度を測定する方法が広く用いられている。Therefore, in order to enhance the measurement sensitivity to the cation conductivity and eliminate the influence of the injected chemicals,
A method is widely used in which measurement water is first passed through a column charged with a cation exchange resin capable of adsorbing cations in the measurement water, and then the cation conductivity is measured.
【０００８】このような方法によれば、測定水が陽イオ
ンカラムを通過する場合、測定水中の注入薬品により表
される電導度は抑制される反面、不純物による電導度は
増幅されて、陽イオン電導度を容易に測定し得ることに
なる。According to such a method, when the measurement water passes through the cation column, the conductivity represented by the injection chemical in the measurement water is suppressed, but the conductivity due to impurities is amplified and the cation is The electric conductivity can be easily measured.
【０００９】一般に、水の電気電導度は主に水中に存在
する陽イオンおよび陰イオンの種類および濃度によって
変わる。下記の表１は水中に存在する代表的なイオンの
電気電導度を表わしたものである。In general, the electric conductivity of water mainly depends on the types and concentrations of cations and anions present in water. Table 1 below shows the electric conductivity of typical ions existing in water.
【００１０】[0010]
【表１】 [Table 1]
【００１１】また、図１は、従来技術による陽イオン電
導度測定用連続再生カラムの作動原理を示した概念図で
あって、測定水１が陽イオン交換樹脂３が充電されたカ
ラム２を通過することになると、測定水１中の注入薬品
の１つの種類であるアンモニア水のアンモニウムイオン
が陽イオン交換樹脂３と置換反応を起こして、陽イオン
交換樹脂３に吸着されて水素イオンが流出される。上記
した過程のとおり流出された水素イオンアンモニア水の
中に残っている水酸化イオンと反応して水となる。FIG. 1 is a conceptual diagram showing the operating principle of a conventional continuous regeneration column for measuring cation conductivity, in which water for measurement 1 passes through a column 2 charged with a cation exchange resin 3. In doing so, ammonium ions of ammonia water, which is one type of injection chemical in the measurement water 1, undergoes a substitution reaction with the cation exchange resin 3 and is adsorbed by the cation exchange resin 3 to release hydrogen ions. It As described above, the hydrogen ions react with the hydroxide ions remaining in the hydrogen ion ammonia water to become water.
【００１２】一方、水に代表的な不純物の微量の塩分が
流入される場合には、測定水は陽イオンカラム２を通過
しながら塩分中のナトリウムイオンの陽イオン交換樹脂
３に吸着され、水素イオンは流出されて、残留する陰イ
オンの塩素イオンとともにカラム２から排出される。こ
の際、カラム２の出口側にはカラム２から排出される測
定水１の電気電導度を測定するための電導度測定器４が
連結される。On the other hand, when a small amount of salt, which is a typical impurity, flows into water, the measurement water is adsorbed on the cation exchange resin 3 of sodium ions in the salt while passing through the cation column 2 to generate hydrogen. The ions flow out and are discharged from the column 2 together with the remaining anion chloride ions. At this time, the outlet side of the column 2 is connected with an electric conductivity measuring device 4 for measuring the electric conductivity of the measurement water 1 discharged from the column 2.
【００１３】さらに詳述すれば、循環水のｐＨを高める
ために、代表的な注入薬品のアンモニア水（ＮＨ4 + Ｏ
Ｈ）（約０．３ｐｐｍ）を用いる系統において、測定水
１が図１に示されたカラム２を通過することになると、
注入された薬品は陽イオン交換樹脂３により除去され
て、循環水の電導度に影響を及ぼさなくなるが、外部か
ら流入された代表的な不純物の塩分（ＮａＣｌ）中の陽
イオンは陽イオン交換樹脂３により電気電導度が大きい
水素イオン（Ｈ+ ）に置換されて、測定感度が代表的に
増加される。すなわち、測定水１の中のアンモニウムイ
オンは陽イオン交換樹脂３と置換反応を起こして陽イオ
ン交換樹脂３に吸着除去され、水素イオンのみ流出され
ることになる。しかし、このように流出された水素イオ
ンは、下記の式（１）に表示されたように、残っている
水酸化イオン（ＯＨ- ）と反応して水になるが、純粋な
水は電気電導度が極めて低いため、電気電導度に影響を
及ぼさなくなって、バックグラウンドが低くなる。More specifically, in order to raise the pH of the circulating water, ammonia water (NH 4 + O), which is a typical injection chemical, is used.
H) (about 0.3 ppm), when the measured water 1 passes through the column 2 shown in FIG. 1,
The injected chemicals are removed by the cation exchange resin 3 and do not affect the conductivity of the circulating water, but the cations in the salt (NaCl) of the typical impurities introduced from the outside are cation exchange resin. 3 is replaced with hydrogen ions (H + ) having high electric conductivity, and the measurement sensitivity is typically increased. That is, ammonium ions in the measurement water 1 undergo a substitution reaction with the cation exchange resin 3 to be adsorbed and removed by the cation exchange resin 3, and only hydrogen ions are flown out. However, as shown in the following formula (1), the hydrogen ions thus discharged react with the remaining hydroxide ions (OH − ) to become water, but pure water is an electrically conductive material. The extremely low degree does not affect the electric conductivity and the background is low.
【００１４】 ＮＨ4 + ＋ＯＨ- ＋Ｒ−Ｈ→Ｒ−ＮＨ4 ＋Ｈ+ ＋ＯＨ- （１） ２．５μｍｈｏ／ｃｍ（通過前） ０．３μｍｈｏ／ｃｍ（通過後） （ここで、上記式（１）でＲ−Ｈは陽イオン交換樹脂） 一方、不純物として微量の塩分（ＮａＣｌ，０．１ｐｐ
ｍ ａｓ Ｃｌ）を含んでいる海水が流入される場合に
は、測定水１が陽イオンカラム２を通過するとともに下
記の式（２）に表わされた反応が生じて、塩分中のナト
リウムイオン（Ｎａ+ ）は陽イオン交換樹脂３に吸着さ
れるが、陽イオン交換樹脂３からイオン電導度が大きい
水素イオン（Ｈ+ ）が流出されて、陰イオンの塩素イオ
ンとともにカラム２の外部へ流出される。NH 4 + + OH − + R−H → R—NH 4 + H + + OH − (1) 2.5 μmho / cm (before passing) 0.3 μmho / cm (after passing) (where, the above formula (1) RH is a cation exchange resin. On the other hand, a small amount of salt (NaCl, 0.1 pp) as an impurity.
(m as Cl) containing inflowing seawater, the measurement water 1 passes through the cation column 2 and the reaction represented by the following formula (2) occurs to generate sodium ions in the salt. Although (Na + ) is adsorbed by the cation exchange resin 3, hydrogen ions (H + ) having a high ionic conductivity flow out from the cation exchange resin 3 and flow out to the outside of the column 2 together with anion chloride ions. To be done.
【００１５】 ＮＨ+ ＋Ｃｌ- ＋Ｒ−Ｈ→Ｒ−Ｎａ＋Ｈ+ ＋Ｃｌ- （２） ２．９３５μｍｈｏ／ｃｍ（通過前） １．６２９μｍｈｏ／ｃｍ（通過後） 上記の反応式（１）および（２）からわかるように、陽
イオンカラム２を用いない場合には、塩分流入前後の電
導度の変化は、２．５μｍｈｏ／ｃｍ〜２．９３５μｍ
ｈｏ／ｃｍで、増加幅は０．４３５μｍｈｏ／ｃｍにな
る。しかし、陽イオンカラム２を通過する場合、電導度
の変化は０．３μｍｈｏ／ｃｍ〜１．６２９μｍｈｏ／
ｃｍで、増加幅は１．３２９μｍｈｏ／ｃｍで大幅に増
加する。NH + + Cl − + RH −R−Na + H + + Cl − (2) 2.935 μmho / cm (before passage) 1.629 μmho / cm (after passage) From the above reaction formulas (1) and (2) As can be seen, when the cation column 2 is not used, the change in conductivity before and after the salt inflow is 2.5 μmho / cm to 2.935 μm.
At ho / cm, the increment is 0.435 μmho / cm. However, when passing through the cation column 2, the change in conductivity is 0.3 μmho / cm to 1.629 μmho /
In cm, the increase width is significantly increased at 1.329 μmho / cm.
【００１６】上記したように、一定量の不純物が流入さ
れるとき、陽イオンカラム２を用いない場合には、不純
物流入前後の電導度比は１．１７（＝２．９３５／２．
５）であるが、陽イオンカラム２を用いる場合には、電
導度比は５．４３（＝１．６２９／０．３）であって、
陽イオンカラム２を用いない場合に比べ感度が５倍（＝
５．４３／１．１７）程度大幅に増加するので、外部か
ら微量の不純物が流入される場合にも容易に感知し得る
ことになる。As described above, when a certain amount of impurities are introduced, the conductivity ratio before and after the inflow of impurities is 1.17 (= 2.935 / 2.
5) but when using the cation column 2, the conductivity ratio is 5.43 (= 1.629 / 0.3),
The sensitivity is 5 times (=
Since it greatly increases by about 5.43 / 1.17), it can be easily detected even when a trace amount of impurities is introduced from the outside.
【００１７】しかし、上記した従来の陽イオン電導度測
定用カラム２は使用回数が増加するにつれて、カラム２
内に陽イオン樹脂が飽和されて、陽イオン交換性能を失
うことになるので、カラム２を解体して陽イオン交換樹
脂２を取出して再生した後、樹脂を再充電し、組立をし
なければならなかった。陽イオン交換樹脂３を再生する
ためには、飽和された陽イオン交換樹脂３を取出して薄
い塩酸溶液に浸すと、下記式（３）および（４）に表わ
された反応によって陽イオン交換樹脂（３）に吸着され
た陽イオンは離れて水素イオンと結合して、元のイオン
交換性能を回復することになる。この場合、上記したイ
オン交換樹脂３から離脱された陽イオンは水で洗って除
去する。However, the above-mentioned conventional cation conductivity measuring column 2 is used as the number of times of use increases.
The cation resin will be saturated inside and the cation exchange performance will be lost. Therefore, after disassembling the column 2 and taking out and regenerating the cation exchange resin 2, the resin must be recharged and assembled. did not become. In order to regenerate the cation exchange resin 3, the saturated cation exchange resin 3 is taken out and immersed in a dilute hydrochloric acid solution, and the cation exchange resin 3 is subjected to the reactions represented by the following formulas (3) and (4). The cations adsorbed in (3) are separated and combine with hydrogen ions to restore the original ion exchange performance. In this case, the cations released from the ion exchange resin 3 are washed with water and removed.
【００１８】 Ｒ−ＮＨ4 ＋Ｈ+ ＋Ｃｌ- →Ｒ−Ｈ＋ＮＨ4 + ＋Ｃｌ- （３） Ｒ−Ｎａ＋Ｈ+ ＋Ｃｌ- →Ｒ−Ｈ＋Ｎａ+ ＋Ｃｌ- （４） [0018] R-NH 4 + H + + Cl - → R-H + NH 4 + + Cl - (3) R-Na + H + + Cl - → R-H + Na + + Cl - (4)
【００１９】[0019]
【発明が解決しようとする課題】このように、上記した
従来の陽イオン電導度測定用カラム２においては、前述
したようなイオン交換樹脂３の再生過程を月１〜２回程
度一定期間ごとに繰返して行なわなければならないた
め、これによる入力、時間および再生に用いられる薬品
費が多量に必要であるのみならず、再生の作業時、薬品
の取扱いに危険が伴うことは勿論、カラム２内の陽イオ
ン交換樹脂３の交替期間には電導度の測定が不可能であ
るという問題点あった。As described above, in the conventional cation conductivity measuring column 2 described above, the regeneration process of the ion exchange resin 3 as described above is performed once or twice a month at regular intervals. Since this must be repeated, not only is the input, time, and the cost of the chemicals used for regeneration large, but there is a danger in handling the chemicals during the regeneration work, and of course, the column 2 There was a problem that the conductivity could not be measured during the replacement period of the cation exchange resin 3.
【００２０】したがって、本発明の主な目的は、系統循
環水の水質を監視するための測定水の電導度測定過程
中、カラム内に充電された陽イオン交換樹脂が自動的に
再生されるようにして、連続的な使用が可能であるよう
にした陽イオン電導度測定用連続再生カラムを提供する
ことである。Therefore, the main object of the present invention is to automatically regenerate the cation exchange resin charged in the column during the process of measuring the electric conductivity of the measured water for monitoring the water quality of the system circulating water. Another object of the present invention is to provide a continuous regeneration column for measuring positive ion conductivity which enables continuous use.
【００２１】[0021]
【課題を解決するための手段】上記の目的を達成するた
めに、本発明の陽イオン電導度測定用連続再生カラム
は、測定用連続再生カラムが、一対の陽イオン交換膜
と、上記した一対の陽イオン交換膜の間に配置され、陽
イオン交換樹脂を支える支持スペーサと、上記した支持
スペーサ内に充電（充填）された陽イオン交換樹脂と、
上記した陽イオン交換膜を通過した陽イオンを運搬する
ための洗浄水が流れる空間を提供する一対の洗浄スペー
サと、一対の電極と、この電極に直流電源を供給する直
流電源供給部とを含んでいる。In order to achieve the above object, in the continuous regeneration column for cation conductivity measurement of the present invention, the continuous regeneration column for measurement comprises a pair of cation exchange membranes and a pair of cation exchange membranes as described above. A supporting spacer that is disposed between the cation-exchange membranes and supports the cation-exchange resin, and a cation-exchange resin charged (filled) in the supporting spacer described above.
It includes a pair of cleaning spacers for providing a space in which cleaning water for transporting cations passing through the cation exchange membrane flows, a pair of electrodes, and a DC power supply unit for supplying DC power to the electrodes. I'm out.
【００２２】[0022]
【発明の実施の形態】以下、本発明の陽イオン電導度測
定用連続再生カラムに対する好ましい実施の形態を図面
を参照しながらより詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the continuous regeneration column for measuring cation conductivity according to the present invention will be described below in more detail with reference to the drawings.
【００２３】図２は、本発明の陽イオン電導度測定用連
続再生カラムの作動原理を示す概念図であって、測定水
１が連続再生陽イオンカラムへ流入されれば、上記式
（１）および（２）に表わされた反応によって、陽イオ
ンは陽イオン交換樹脂３の水素イオンと置換されて吸着
され、水素イオンが流出される。一方、陰イオンはすぐ
カラムを通過して、カラムを通過した水には水素イオン
と陰イオンのみ存在するため、電導度測定強度が大幅に
増加することになる。FIG. 2 is a conceptual diagram showing the operating principle of the continuously regenerating cation column for cation conductivity measurement of the present invention. If the measurement water 1 flows into the continuously regenerating cation column, the above formula (1) is obtained. By the reactions shown in (2) and (2), the cations are replaced with the hydrogen ions of the cation exchange resin 3 and adsorbed, and the hydrogen ions flow out. On the other hand, anions immediately pass through the column, and only hydrogen ions and anions exist in the water that has passed through the column, so that the conductivity measurement intensity is significantly increased.
【００２４】一方、直流電源供給部（図示せず）により
直流電圧が印加される２つの電極６、７のうち、陽電極
６では下記式（５）で表わされる反応が生じて水素イオ
ンと酸素ガスとが発生することになる。On the other hand, of the two electrodes 6, 7 to which a direct current voltage is applied by a direct current power supply (not shown), the positive electrode 6 causes a reaction represented by the following formula (5) to generate hydrogen ions and oxygen. Gas and will be generated.
【００２５】２Ｈ2 Ｏ→４Ｈ+ ＋Ｏ2 （５） この場合、発生した水素イオンは陽極７の方向へ引か
れ、陽イオンのみを通過させて、陰イオンは通過させな
い陽イオン交換膜５を通過して、陽イオン交換樹脂３に
吸着されている陽イオン（ＮＨ4 + 、Ｎａ+ ）との置換
反応によって、下記の式（６）および（７）に表わされ
たように、水素イオンは陽イオン交換樹脂３に吸着され
て陽イオン交換樹脂が再生される反面、以前に吸着され
ていた陽イオンは流出される。2H 2 O → 4H + + O 2 (5) In this case, the generated hydrogen ions are drawn toward the anode 7 and pass through the cation exchange membrane 5 which allows only cations to pass but not anions. Then, by the substitution reaction with the cations (NH 4 + , Na + ) adsorbed on the cation exchange resin 3, as shown in the following formulas (6) and (7), While the cation exchange resin is regenerated by being adsorbed by the cation exchange resin 3, the cations that were previously adsorbed are discharged.
【００２６】 Ｒ−ＮＨ4 ＋Ｈ+ →Ｒ−Ｈ＋ＮＨ4 + （６） Ｒ−Ｎａ＋Ｈ+ →Ｒ−Ｈ＋Ｎａ+ （７） その後、陽イオン交換樹脂３から流出された陽イオン
は、電位差によって陰極７側へ引かれて、水素イオンが
通過した反対側の陽イオン交換膜５を通過してカラムの
外部へ抜け出る。R-NH 4 + H + → RH-NH + NH 4 + (6) R-Na + H + → RH-Na + (7) After that, the cations flowing out from the cation-exchange resin 3 are discharged to the cathode 7 side due to the potential difference. To the outside of the column through the cation exchange membrane 5 on the opposite side to which the hydrogen ions have passed.
【００２７】一方、陰極７においては、下記式（８）で
表わされる反応が生じて、水酸化イオンと水素ガスが発
生し、水酸化イオンは陽イオン交換膜５を抜け出た陽イ
オンと反応して、下記の式（９）および（１０）に表わ
されたように、アンモニア水と苛性ソーダに変換され、
陽イオン交換膜と電極との間を流れる洗浄水により運搬
されて外部へ排出される。On the other hand, in the cathode 7, a reaction represented by the following formula (8) occurs to generate hydroxide ions and hydrogen gas, and the hydroxide ions react with the cations that have passed through the cation exchange membrane 5. Then, as represented by the following formulas (9) and (10), the ammonia water and the caustic soda are converted into
It is carried by the wash water flowing between the cation exchange membrane and the electrode and discharged to the outside.
【００２８】２Ｈ2 Ｏ→２Ｈ2 ＋ＯＨ- （８） ＮＨ4 + ＋ＯＨ- →ＮＨ4 ＯＨ （９） Ｎａ+ ＋ＯＨ- →ＮａＯＨ （１０） 一方、陽極６から発生して、陽イオンと置換が行なわれ
なかった水素イオンは陽イオン交換膜を通過して、陰極
７に到達した後、下記の式（１１）に表されたように、
陰極から発生した水酸化イオン（ＯＨ- ）と結合して水
となるため、電気電導度にはいかなる影響も及ぼさな
い。2H 2 O → 2H 2 + OH − (8) NH 4 + + OH − → NH 4 OH (9) Na + + OH − → NaOH (10) On the other hand, the cations generated by the anode 6 are replaced. The unreacted hydrogen ions pass through the cation exchange membrane, reach the cathode 7, and then, as represented by the following formula (11),
Since it combines with hydroxide ions (OH − ) generated from the cathode to form water, it has no influence on the electric conductivity.
【００２９】Ｈ4 + ＋ＯＨ- →Ｈ2 Ｏ （１１） 図３は、本発明の陽イオン電導度測定用連続再生カラム
の概略的な構成図であって、本発明の陽イオン電導度測
定用連続再生カラムは、図３に示されたように、一対の
陽イオン交換膜５と、上記した一対の陽イオン交換膜５
の間に陽イオン交換樹脂３を支える支持スペーサ１２
と、上記した支持スペーサ１２内に充電（充填）された
陽イオン交換樹脂３と、上記した陽イオン交換膜５を通
過した陽イオンを運搬するための洗浄水が流れる空間を
設ける一対の洗浄スペーサ１４と、陽極６と陰極７とか
ら構成される一対の電極６、７および上記した電極６、
７に直流電源を供給する直流電源供給部（図示せず）か
ら構成される。H 4 + + OH − → H 2 O (11) FIG. 3 is a schematic diagram of the continuous regeneration column for cation conductivity measurement according to the present invention, which is for cation conductivity measurement according to the present invention. As shown in FIG. 3, the continuous regeneration column includes a pair of cation exchange membranes 5 and a pair of cation exchange membranes 5 described above.
Support spacer 12 for supporting the cation exchange resin 3 between
And a pair of cleaning spacers provided with a space for flowing the cleaning water for transporting the cations that have passed through the cation exchange membrane 5 and the cation exchange resin 3 charged (filled) in the support spacer 12 described above. 14, a pair of electrodes 6, 7 composed of an anode 6 and a cathode 7 and the above-mentioned electrode 6,
7, a DC power supply unit (not shown) for supplying DC power.
【００３０】この場合、上記した電極のうち、陽極６の
上端には洗浄水入口８と測定水の入口９とが備えられ、
陽極６の下端には、洗浄水出口１１と測定水の出口１０
とが備えられる。In this case, of the above-mentioned electrodes, a cleaning water inlet 8 and a measurement water inlet 9 are provided at the upper end of the anode 6.
At the lower end of the anode 6, a wash water outlet 11 and a measurement water outlet 10 are provided.
And are provided.
【００３１】また、実際的な陽イオン電導度測定用連続
再生カラムは、電導度測定に要する十分な量の測定水が
通過し得るように、図３に示されたような１つまたは２
つ以上の陽イオンカラムを並列または直列に配置して構
成し得る。すなわち、一対の電極６、７の間に、一対の
陽イオン交換膜５と支持スペーサ１２および一対の洗浄
スペーサ１４を交互に配置して構成する。Further, the practical continuous regeneration column for cation conductivity measurement has one or two as shown in FIG. 3 so that a sufficient amount of water for measurement of conductivity can pass through.
One or more cation columns may be arranged in parallel or in series. That is, the pair of cation exchange membranes 5, the support spacers 12 and the pair of cleaning spacers 14 are alternately arranged between the pair of electrodes 6 and 7.
【００３２】このとき、支持スペーサ１２は一対の陽イ
オン交換膜５を固定し、その間の空間に陽イオン交換樹
脂３が充電されるように構成し、測定水が陽イオン交換
樹脂３の内部を流れる間、イオンの交換が行なわれ得る
ようにする。At this time, the supporting spacers 12 are constructed such that a pair of cation exchange membranes 5 are fixed and the space between them is charged with the cation exchange resin 3, and the measurement water is charged inside the cation exchange resin 3. Allow the exchange of ions to take place during the flow.
【００３３】また、洗浄スペーサ１４は一対の陽イオン
交換膜５と電極６、７との間に測定水の一部が流れる
か、または純水が流れるようにして、陽イオン交換膜５
を抜け出た陽イオンを運搬除去するのに役立つ。In the cleaning spacer 14, a part of the measurement water or pure water flows between the pair of cation exchange membranes 5 and the electrodes 6 and 7 so that pure water flows.
Helps to transport and remove the cations that escaped.
【００３４】また、一対の電極６、７は電位差を与えて
陽イオンは陰極側へ移動し得るようにし陽極６で水素イ
オンを発生させて陽イオン交換樹脂３および吸着された
陽イオンとの置換により陽イオン交換樹脂３の再生が行
なわれるようにし、陰極７では水酸化イオン（ＯＨ- ）
が発生するようにして、陽イオン交換膜５を通過した陽
イオンと反応が行なわれるようにする。Further, the pair of electrodes 6, 7 gives a potential difference so that cations can move to the cathode side and hydrogen ions are generated at the anode 6 to replace the cation exchange resin 3 and the adsorbed cations. So that the cation exchange resin 3 is regenerated. At the cathode 7, hydroxide ions (OH − )
Are generated so that the reaction is performed with the cations that have passed through the cation exchange membrane 5.
【００３５】一方、測定水は２つの部分に分かれて、一
部は陽イオンカラムを通過して電導度の測定用として用
いられ、残りは洗浄スペーサ１４の間を流れながら陽イ
オン交換膜５を通過した陽イオンを運搬および除去す
る。On the other hand, the water to be measured is divided into two parts, a part of which passes through the cation column and is used for measuring the electric conductivity, and the other part of which flows between the washing spacers 14 to form the cation exchange membrane 5. Transports and removes cations that have passed through.
【００３６】このとき、上記電極６、７は一対または複
数の対の陽極６および陰極７の電極が交替に配置される
ように構成し得、上記支持スペーサ１２および洗浄スペ
ーサ１４は１つまたは複数が直列または並列に配置され
るように構成し得る。At this time, the electrodes 6 and 7 may be configured such that the electrodes of the anodes 6 and the cathodes 7 of one pair or a plurality of pairs are alternately arranged, and the number of the supporting spacers 12 and the cleaning spacers 14 is one or more. Can be arranged in series or in parallel.
【００３７】また、上記した本発明の陽イオンの電導度
測定用カラムに対するカラムの構造は、測定水が均一に
陽イオン交換樹脂スペーサ１２の間に分配されるように
する構造から形成され、上記したカラムの構造は測定水
の一部または洗浄水が電極６、７と陽イオン交換膜５と
の間を流れるように形成する。The column structure for the above-described cation conductivity measuring column of the present invention is formed so that the measurement water is uniformly distributed between the cation exchange resin spacers 12. The structure of the column is formed so that a part of the measurement water or the washing water flows between the electrodes 6 and 7 and the cation exchange membrane 5.
【００３８】そして、上記した本発明の陽イオン電導度
測定用連続再生カラムは、過電圧／過電流を遮断する回
路を追加的に含むように構成することが好ましい。The continuous regeneration column for cation conductivity measurement of the present invention described above is preferably constructed to additionally include a circuit for interrupting overvoltage / overcurrent.
【００３９】また、上記した本発明の陽イオン電導度測
定用連続再生カラムは、流量を調節し得る流量調節手段
を追加的に含むように構成することが好ましく、洗浄水
が洗浄スペーサ１４の間を均一に流れるようにカラムの
構造を形成することが好ましい。The above-mentioned continuous regeneration column for cation conductivity measurement of the present invention is preferably constructed so as to additionally include a flow rate adjusting means capable of adjusting the flow rate, and the washing water is added between the washing spacers 14. It is preferable to form the column structure so as to uniformly flow through the column.
【００４０】また、上記した本発明の陽イオン電導度測
定用連続再生カラムは、全体的に円筒形または六面体の
形状を有するように構成することが好ましい。The continuous regeneration column for cation conductivity measurement of the present invention described above is preferably constructed so as to have an overall cylindrical or hexahedral shape.
【００４１】そして、本発明の陽イオン電導度測定用連
続再生カラムは、溶液の電導度測定用計測器で必要とす
る測定水の量に応じて、平行に配置されたカラムの数字
を加減し得る。In the continuous regeneration column for measuring cation conductivity of the present invention, the numbers of the columns arranged in parallel are adjusted according to the amount of water to be measured required by the measuring instrument for measuring the conductivity of the solution. obtain.
【００４２】本発明の陽イオン電導度測定用連続再生カ
ラムで用いられる陽イオン交換膜５は、高選択性、高電
導度、適当な充電膨張性および優れた機械的強度が要求
され、均質膜と非均質膜とに関係なく、このような条件
を満たすものであればいずれも用いられ得る。The cation exchange membrane 5 used in the continuous regeneration column for cation conductivity measurement of the present invention is required to have high selectivity, high conductivity, appropriate charge expansion property and excellent mechanical strength, and is a homogeneous membrane. And any non-homogeneous film can be used as long as these conditions are satisfied.
【００４３】また、本発明の陽イオン電導度測定用連続
再生カラムに対する電極６、７の材質としては、陽極６
の場合にはチタニウム板に白金属や貴金属を鍍金するか
酸化物を被覆したものを用い、陰極７の場合にはチタニ
ウム板、ステンレス鋼板またはその他の合金鋼を用い
る。The material of the electrodes 6, 7 for the continuous regeneration column for cation conductivity measurement of the present invention is anode 6
In the case of, a titanium plate plated with a white metal or a noble metal or coated with an oxide is used, and in the case of the cathode 7, a titanium plate, a stainless steel plate or another alloy steel is used.
【００４４】また、本発明の陽イオン電導度測定用連続
再生カラムにおいて、イオン交換樹脂３としては、粒度
が均一で交換容量が大きい強酸性陽イオン交換樹脂を用
いることが好ましく、支持スペーサ１２および洗浄スペ
ーサ１４はポリプロピレンまたはポリエチレンを用いる
ことが好ましい。In the continuous regeneration column for cation conductivity measurement of the present invention, as the ion exchange resin 3, it is preferable to use a strongly acidic cation exchange resin having a uniform particle size and a large exchange capacity, and the supporting spacer 12 and It is preferable to use polypropylene or polyethylene for the cleaning spacer 14.
【００４５】上記した本発明の陽イオン電導度測定用連
続再生カラムは、電位差によるイオンの移動性を用い
て、カラム内に含まれた陽イオン交換樹脂を連続再生す
ると同時に、陽イオン電導度の測定を行なうことにな
る。The continuous regeneration column for cation conductivity measurement of the present invention described above uses the mobility of ions due to the potential difference to continuously regenerate the cation exchange resin contained in the column, and at the same time, to change the cation conductivity. The measurement will be performed.
【００４６】図４は、本発明の連続再生陽イオンカラム
の性能に対する測定試験結果を示したグラフであって、
本発明の陽イオン電導度の測定用連続再生カラムに純水
を注入した場合、アンモニアを測定水に添加した場合、
および塩分を測定水に添加した場合に対して、カラムを
通過した測定水を電導度測定器を用いて電気電導度を測
定した試験結果を表わしたものである。FIG. 4 is a graph showing the measurement test results for the performance of the continuously regenerated cation column of the present invention.
When pure water is injected into the continuous regeneration column for measuring the cation conductivity of the present invention, when ammonia is added to the measurement water,
2 shows the test results obtained by measuring the electric conductivity of the measurement water that has passed through the column using an electric conductivity measuring device, in the case where the salt content is added to the measurement water.
【００４７】図４のグラフからわかるように、測定水に
不純物として塩分が含まれる場合、カラムを通過する前
に比べ、本発明の陽イオン電導度測定用連続再生カラム
を通過した後には、電気電導度が大幅に増幅されたこと
がわかる。As can be seen from the graph of FIG. 4, when the measurement water contains salt as an impurity, it is more likely that the water after passing through the continuous regeneration column for cation conductivity measurement of the present invention is more electric than that before passing through the column. It can be seen that the conductivity was greatly amplified.
【００４８】以上に詳細に説明したように、本発明の陽
イオン電導度測定用連続再生カラムは系統循環水の水質
を監視するための測定水の電導度測定過程中、カラム内
に充電された陽イオン交換樹脂を自動的に再生し得るた
め、陽イオン交換樹脂を交替することなく溶液に対する
陽イオン電導度を連続的に測定し得ることが確認され
た。As described in detail above, the continuous regeneration column for cation conductivity measurement according to the present invention was charged in the column during the measurement process of the conductivity of the measured water for monitoring the water quality of the system circulating water. Since the cation exchange resin can be automatically regenerated, it was confirmed that the cation conductivity with respect to the solution can be continuously measured without changing the cation exchange resin.
【００４９】上記において、本発明の特定の実施の形態
について説明したが、本明細書に記載した特許請求の範
囲を逸脱することなく、当業者は種々の変更を加えるこ
とは勿論である。Although the specific embodiments of the present invention have been described above, those skilled in the art can of course make various changes without departing from the scope of the claims described in the specification.
【００５０】[0050]
【発明の効果】したがって、本発明によれば、系統循環
水の水質を監視するための測定水の電導度測定過程中、
カラム内に充電された陽イオン交換樹脂が自動的に再生
されるようにして連続的に使用することができる。Therefore, according to the present invention, during the process of measuring the electric conductivity of the measured water for monitoring the water quality of the system circulating water,
The cation exchange resin charged in the column is automatically regenerated and can be continuously used.
【図１】従来技術による陽イオン電導度測定用連続再生
カラムの作動原理を示す概念図である。FIG. 1 is a conceptual diagram showing an operating principle of a continuous regeneration column for measuring cation conductivity according to a conventional technique.
【図２】本発明の陽イオン電導度測定用連続再生カラム
の作動原理を示す概念図である。FIG. 2 is a conceptual diagram showing the operating principle of the continuous regeneration column for cation conductivity measurement of the present invention.
【図３】本発明の陽イオン電導度測定用連続再生カラム
の概略図である。FIG. 3 is a schematic view of a continuous regeneration column for measuring positive ion conductivity according to the present invention.
【図４】本発明の連続再生陽イオンカラムの性能に対す
る測定試験結果を示すグラフである。FIG. 4 is a graph showing the measurement test results for the performance of the continuously regenerated cation column of the present invention.
１：測定水 ２：カラム ３：陽イオン交換樹脂 ４：電導度測定器 ５：陽イオン交換膜 ６：陽極 ７：陰極 ８：洗浄水の入口 ９：測定水の入口 １０：測定水の出口 １１：洗浄水の出口 １２：支持スペーサ １３：洗浄スペーサ 1: Measurement water 2: Column 3: Cation exchange resin 4: Conductivity measuring instrument 5: Cation exchange membrane 6: Anode 7: Cathode 8: Wash water inlet 9: Measurement water inlet 10: Measurement water outlet 11 : Wash water outlet 12: Support spacer 13: Wash spacer
Claims (12)
換樹脂を支える支持スペーサと、 前記支持スペーサ内に充電された前記陽イオン交換樹脂
と、 前記陽イオン交換膜を通過した陽イオンを運搬するため
の洗浄水が流れる空間を提供する一対の洗浄スペーサ
と、 一対の電極と、前記電極に直流電源を供給する直流電源
供給部とを含むことを特徴とする、陽イオン電導度測定
用連続再生カラム。1. A pair of cation exchange membranes, a support spacer disposed between the pair of cation exchange membranes and supporting a cation exchange resin, and the cation exchange resin charged in the support spacers. A pair of washing spacers for providing a space for washing water for transporting cations passing through the cation exchange membrane, a pair of electrodes, and a DC power supply unit for supplying DC power to the electrodes A continuous regeneration column for measuring cation conductivity, which is characterized in that
ることを特徴とする、請求項１に記載の陽イオン電導度
測定用連続再生カラム。2. The continuous regeneration column for cation conductivity measurement according to claim 1, wherein the ion exchange membrane is a cation exchange membrane.
交互に配置されて構成されることを特徴とする、請求項
１に記載の陽イオン電導度測定用連続再生カラム。3. The continuous regeneration column for cation conductivity measurement according to claim 1, wherein the electrode is formed by alternately arranging a pair of anodes and cathodes.
は、１つ以上が直列または並列に配置されて構成された
ことを特徴とする、請求項１に記載の陽イオン電導度測
定用連続再生カラム。4. The continuous regeneration column for cation conductivity measurement according to claim 1, wherein one or more of the support spacer and the cleaning spacer are arranged in series or in parallel.
るカラムの構造は、測定水が均一に交換樹脂スペーサの
間に分配されるようにする構造から形成されたことを特
徴とする、請求項１に記載の陽イオン電導度測定用連続
再生カラム。5. The structure of the column for the cation conductivity measuring column is formed so as to uniformly distribute the measuring water between the exchange resin spacers. The continuous regeneration column for measuring the cation conductivity described in.
ムの構造は、測定水の一部または洗浄水が電極とイオン
の交換膜との間を流れるように形成されたことを特徴と
する、請求項１に記載の陽イオン電導度測定用連続再生
カラム。6. The structure of the continuous regeneration column for cation conductivity measurement is characterized in that part of the measurement water or wash water is formed so as to flow between the electrode and the ion exchange membrane. The continuous regeneration column for cation conductivity measurement according to claim 1.
ムは、過電圧／過電流を遮断する回路をさらに含むこと
を特徴とする、請求項１に記載の陽イオン電導度測定用
連続再生カラム。7. The continuous regeneration column for cation conductivity measurement according to claim 1, further comprising a circuit for blocking overvoltage / overcurrent.
ムは、流量を調節し得る流量調節手段をさらに含むこと
を特徴とする、請求項１に記載の陽イオン電導度測定用
連続再生カラム。8. The continuous regeneration column for cation conductivity measurement according to claim 1, wherein the continuous regeneration column for cation conductivity measurement further comprises flow rate adjusting means capable of adjusting a flow rate.
ムに対するカラムの構造は、洗浄水が洗浄スペーサの間
を均一に流れるように形成されたことを特徴とする、請
求項１に記載の陽イオン電導度測定用連続再生カラム。9. The positive electrode according to claim 1, wherein the structure of the column for the continuous regeneration column for measuring the cation conductivity is formed so that washing water uniformly flows between the washing spacers. Continuous regeneration column for ion conductivity measurement.
ラムは、電位差によるイオンの移動性を用いてカラム内
に含まれた陽イオン交換樹脂を連続再生すると同時に、
陽イオン電導度の測定を行なうことを特徴とする、請求
項１に記載の陽イオン電導度測定用連続再生カラム。10. The continuous regeneration column for cation conductivity measurement continuously regenerates the cation exchange resin contained in the column by using the mobility of ions due to a potential difference, and at the same time,
The continuous regeneration column for cation conductivity measurement according to claim 1, wherein the cation conductivity is measured.
ラムは、円筒形または六面体の形状を有するように構成
されたことを特徴とする、請求項１に記載の陽イオン電
導度測定用連続再生カラム。11. The continuous regeneration column for cation conductivity measurement according to claim 1, wherein the continuous regeneration column for cation conductivity measurement is configured to have a cylindrical shape or a hexahedral shape. column.
としては、ポリプロピレンまたはポリエチレンを用いる
ことを特徴とする、請求項１に記載の陽イオン電導度測
定用連続再生カラム。12. The continuous regeneration column for cation conductivity measurement according to claim 1, wherein polypropylene or polyethylene is used as the supporting spacer and the washing spacer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR95P34520 | 1995-10-09 | ||
| KR1019950034520A KR0180627B1 (en) | 1995-10-09 | 1995-10-09 | Continuous regenerative column for measuring cationic conductance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09127081A true JPH09127081A (en) | 1997-05-16 |
Family
ID=19429598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8187397A Pending JPH09127081A (en) | 1995-10-09 | 1996-07-17 | Continuous reproducing column for cation electrical conductivity measurement |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH09127081A (en) |
| KR (1) | KR0180627B1 (en) |
| FR (1) | FR2739693B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113109399A (en) * | 2021-05-08 | 2021-07-13 | 浙江西热利华智能传感技术有限公司 | Method and system for detecting organic matter content of water vapor sample of steam power equipment |
| CN114477385A (en) * | 2021-12-16 | 2022-05-13 | 华能南京燃机发电有限公司 | Method and device for removing cations in steam water of power station |
| KR102623982B1 (en) * | 2023-02-01 | 2024-01-11 | 주식회사 에모닉 | Tear conductivity sensor and method for manufacturing thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014140993A1 (en) * | 2013-03-15 | 2014-09-18 | Koninklijke Philips N.V. | Sensing a characteristic of aqueous solution |
| CN113960118A (en) * | 2021-11-23 | 2022-01-21 | 中国神华能源股份有限公司惠州热电分公司 | Electric regeneration type system for measuring water vapor hydrogen conductivity |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801551A (en) * | 1986-10-06 | 1989-01-31 | Westinghouse Electric Corp. | Rugged dissolved carbon dioxide monitor for high purity water |
| DE3808043A1 (en) * | 1988-03-11 | 1989-09-21 | Cillit Wassertechnik | METHOD AND DEVICE FOR PARTIAL OR FULL DESALINATION OF WATER |
| US5061638A (en) * | 1989-08-18 | 1991-10-29 | Boyle Engineering Corporation | Nitrate analyzer |
| CA2087481C (en) * | 1992-02-10 | 2001-09-04 | John R. Stillian | Ion chromatography system using electrochemical suppression and detector effluent recycle |
| FR2693383B1 (en) * | 1992-06-24 | 1995-06-23 | Flork Michel | NEW PROCESS FOR THE REGENERATION OR ELUTION OF ABSORBENTS, AND DEVICES FOR IMPLEMENTING SAME. |
| US5306399A (en) * | 1992-10-23 | 1994-04-26 | Electric Power Research Institute | Electrochemical exchange anions in decontamination solutions |
-
1995
- 1995-10-09 KR KR1019950034520A patent/KR0180627B1/en not_active IP Right Cessation
-
1996
- 1996-07-17 JP JP8187397A patent/JPH09127081A/en active Pending
- 1996-07-19 FR FR9609081A patent/FR2739693B1/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113109399A (en) * | 2021-05-08 | 2021-07-13 | 浙江西热利华智能传感技术有限公司 | Method and system for detecting organic matter content of water vapor sample of steam power equipment |
| CN113109399B (en) * | 2021-05-08 | 2024-03-22 | 浙江西热利华智能传感技术有限公司 | Method and system for detecting organic matter content of steam sample of steam power equipment |
| CN114477385A (en) * | 2021-12-16 | 2022-05-13 | 华能南京燃机发电有限公司 | Method and device for removing cations in steam water of power station |
| KR102623982B1 (en) * | 2023-02-01 | 2024-01-11 | 주식회사 에모닉 | Tear conductivity sensor and method for manufacturing thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2739693B1 (en) | 1999-03-05 |
| FR2739693A1 (en) | 1997-04-11 |
| KR970022309A (en) | 1997-05-28 |
| KR0180627B1 (en) | 1999-05-15 |
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