JP6031795B2 - Ion exchange device breakthrough detection method and operation method - Google Patents
Ion exchange device breakthrough detection method and operation method Download PDFInfo
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- JP6031795B2 JP6031795B2 JP2012080582A JP2012080582A JP6031795B2 JP 6031795 B2 JP6031795 B2 JP 6031795B2 JP 2012080582 A JP2012080582 A JP 2012080582A JP 2012080582 A JP2012080582 A JP 2012080582A JP 6031795 B2 JP6031795 B2 JP 6031795B2
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- ion exchange
- exchange device
- carbon dioxide
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- carbonic acid
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- 238000005342 ion exchange Methods 0.000 title claims description 45
- 238000001514 detection method Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 24
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- Treatment Of Water By Ion Exchange (AREA)
- Physical Water Treatments (AREA)
Description
本発明はイオン交換装置の破過検知方法に係り、特にイオン交換装置からのアニオンリークを早期に検知することができるイオン交換装置の破過検知方法に関する。また、本発明は、このイオン交換装置の破過検知方法に基づいて、イオン交換装置の運転方法に関する。 The present invention relates to an ion exchange apparatus breakthrough detection method, and more particularly to an ion exchange apparatus breakthrough detection method capable of early detection of anion leakage from an ion exchange apparatus. Moreover, this invention relates to the operating method of an ion exchange apparatus based on the breakthrough detection method of this ion exchange apparatus.
イオン交換装置の後段に設けた導電率計又は比抵抗計によりイオン交換装置からのイオンリークを検知する方法が行われている（例えば特許文献１）。特許文献１には、導電率計又は比抵抗計を用いてシリカブレークを検出する方法が開示されている。 A method of detecting an ion leak from an ion exchange device using a conductivity meter or a specific resistance meter provided at a subsequent stage of the ion exchange device is performed (for example, Patent Document 1). Patent Document 1 discloses a method for detecting a silica break using a conductivity meter or a resistivity meter.
特許文献１は、微増する塩素に起因する導電率の上昇又は比抵抗値の低下を検知するものであるが、塩素の微増リークはシリカブレークよりも遅いため、イオン交換装置からの流出水中のシリカ濃度が高くなってから塩素の微増リークが検知されることとなる。 Patent Document 1 detects an increase in conductivity or a decrease in specific resistance value caused by slightly increasing chlorine. However, since the slightly increasing leak of chlorine is slower than the silica break, silica in the effluent water from the ion exchange device is disclosed. A slight increase in chlorine leakage is detected after the concentration is increased.
本発明では、塩素の微増リークよりも早期に発生する炭酸の微増リークを直接的に炭酸濃度計により測定することにより、導電率の上昇又は比抵抗値の低下が生じる前にブレークを検知可能なイオン交換装置の破過検知方法と、この方法に基づいたイオン交換装置の運転方法を提供することを目的とする。 In the present invention, a slight increase leak of carbonic acid that occurs earlier than a slight increase leak of chlorine is directly measured by a carbon dioxide concentration meter, so that a break can be detected before an increase in conductivity or a decrease in specific resistance value occurs. It is an object of the present invention to provide an ion exchange apparatus breakthrough detection method and an ion exchange apparatus operation method based on this method.
本発明のイオン交換装置の破過検知方法は、アニオン交換体を備えたイオン交換装置の破過を検知する方法において、該イオン交換装置の後段に炭酸濃度測定器を設置して、導電率の上昇または非抵抗値の低下が検知される前に該イオン交換装置からリークする微量の炭酸イオンを検知し、該イオン交換装置の処理水中の炭酸濃度が１０μｇ−Ｃ／Ｌ以下に設定された閾値を超えた場合に該イオン交換装置が破過したものと判断することを特徴とするものである。 Breakthrough detection method of the ion exchanger of the present invention is a method for detecting the breakthrough of the ion exchange device having an anion exchanger, subsequent to set up a carbon concentration measuring instrument of the ion exchanger, the conductivity increase or decrease of non-resistance senses the carbonate ion traces of leaks from the ion exchange device before being detected, carbonate concentration in the treated water of the ion exchange device is set below 10 [mu] g-C / L threshold It is determined that the ion exchange device has been broken through when the value exceeds.
前記閾値は５μｇ−Ｃ／Ｌ以下例えば０．１〜５μｇ−Ｃ／Ｌに設定されることが好ましい。 The threshold value is preferably set to 5 μg-C / L or less, for example, 0.1 to 5 μg-C / L.
前記イオン交換装置の処理水中の炭酸濃度が１０μｇ−Ｃ／Ｌ以下に設定された閾値を超えた場合で、かつ、前記イオン交換装置の処理水中の炭酸濃度の単位時間当たりの増加量が所定値を上回った場合に前記イオン交換装置が破過したものと判断してもよい。 When the carbonic acid concentration in the treated water of the ion exchange device exceeds the threshold value set to 10 μg-C / L or less, and the increase amount per unit time of the carbonic acid concentration in the treated water of the ion exchange device is a predetermined value It may be determined that the ion exchange device has been broken through.
前記炭酸濃度測定器は、前記処理水に酸性薬剤を添加して、溶解している炭酸を炭酸ガスとした後、ガス透過膜を通して脱イオン水に炭酸ガスを溶解させた液の導電率を測定することにより前記処理水中の炭酸濃度を測定するものであることが好ましい。 The carbonic acid concentration measuring device measures the electrical conductivity of a solution in which carbon dioxide dissolved in deionized water is added through a gas permeable membrane after an acidic chemical is added to the treated water to convert the dissolved carbon dioxide into carbon dioxide. It is preferable to measure the carbonic acid concentration in the treated water.
本発明のイオン交換装置の運転方法は、かかる本発明の破過検知方法により、前記イオン交換装置が破過したと判断されたときに、該イオン交換装置への通水を停止し、前記アニオン交換体を再生又は交換することを特徴とするものである。 The operation method of the ion exchange apparatus of the present invention is such that when it is determined by the breakthrough detection method of the present invention that the ion exchange apparatus has broken through, water flow to the ion exchange apparatus is stopped, and the anion The exchanger is regenerated or exchanged.
本発明によれば、導電率の上昇または比抵抗値の低下が検知される前にリークする微量の炭酸イオンを検知することにより、導電率又は比抵抗値がブレークする前に確実にアニオン交換体のブレークを感知することが可能となる。 According to the present invention, by detecting a small amount of carbonate ion that leaks before an increase in conductivity or a decrease in specific resistance value is detected, the anion exchanger can be reliably manufactured before the electric conductivity or specific resistance value breaks. It becomes possible to detect a break.
本発明のイオン交換装置の破過検知方法では、アニオン交換体を備えたイオン交換装置の後段に炭酸濃度測定器を設置し、該イオン交換装置の処理水中の炭酸濃度が１０μｇ−Ｃ／Ｌ以下、好ましくは５μｇ−Ｃ／Ｌ以下、例えば０．１〜５μｇ−Ｃ／Ｌに設定された閾値を超えた場合に該イオン交換装置が破過したものと判断する。アニオン交換体としては、アニオン交換樹脂が好適である。 In the breakthrough detection method of the ion exchange apparatus of the present invention, a carbonic acid concentration measuring device is installed at the subsequent stage of the ion exchange apparatus provided with the anion exchanger, and the carbonic acid concentration in the treated water of the ion exchange apparatus is 10 μg-C / L or less. The ion exchange apparatus is judged to have broken through when the threshold value set to 5 μg-C / L or less, for example, 0.1 to 5 μg-C / L is exceeded. As the anion exchanger, an anion exchange resin is suitable.
本発明に用いる炭酸濃度測定器は、イオン交換装置からの処理水に酸性薬剤を添加して、溶解している炭酸を炭酸ガスとした後、ガス透過膜を通して脱イオン水に炭酸ガスを溶解させた液の導電率を測定するガス透過膜式の炭酸濃度測定方式によるものが好ましい。例えば、米国特許番号４，２０９，２９９に開示の測定技術を採用可能である。 The carbonic acid concentration measuring instrument used in the present invention adds an acidic agent to the treated water from the ion exchange device to convert the dissolved carbon dioxide into carbon dioxide gas, and then dissolves the carbon dioxide gas in deionized water through a gas permeable membrane. It is preferable to use a gas permeable membrane type carbonic acid concentration measuring method for measuring the electrical conductivity of the liquid. For example, the measurement technique disclosed in US Pat. No. 4,209,299 can be employed.
当該方式による炭酸濃度の測定における定量下限値は３０μｇ−Ｃ／Ｌ程度であるが、アニオン交換体のブレークによる炭酸濃度の上昇を検知する際には、炭酸濃度の絶対値が最小で０．０１〜１０μｇ−Ｃ／Ｌ程度の極微量の炭酸濃度域において、０．１〜２μｇ−Ｃ／Ｌ程度の炭酸濃度の上昇を検知することが可能である。 The lower limit of quantification in the measurement of carbonic acid concentration by this method is about 30 μg-C / L, but when detecting an increase in carbonic acid concentration due to an anion exchanger break, the absolute value of the carbonic acid concentration is 0.01 It is possible to detect an increase in carbonic acid concentration of about 0.1 to 2 μg-C / L in a very small amount of carbonic acid concentration range of about 10 μg-C / L.
上記のような炭酸濃度域における炭酸濃度の微量な上昇を導電率又は比抵抗値により検知することは難しく、特に超純水製造工程における一次純水系のように処理水質が１５ＭΩ・ｃｍ以下のレベルの処理においては、処理水の導電率又は比抵抗値の変動により、いっそう検知が困難となる。 It is difficult to detect a slight increase in the carbonic acid concentration in the carbonic acid concentration region as described above based on the conductivity or specific resistance value. Particularly, the treated water quality is at a level of 15 MΩ · cm or less like the primary pure water system in the ultrapure water production process. In this process, detection becomes more difficult due to fluctuations in the conductivity or specific resistance value of the treated water.
イオン交換装置の処理水中の炭酸濃度の単位時間当たりの増加量が所定値を上回った場合に前記イオン交換装置が破過したものと判断してもよい。
本発明方法によってイオン交換装置のブレークが検知されたときには、該イオン交換装置への通水を停止し、アニオン交換体を再生又は交換する。
You may judge that the said ion exchange apparatus broke through when the increase amount per unit time of the carbonic acid density | concentration in the treated water of an ion exchange apparatus exceeds predetermined value.
When a break of the ion exchange device is detected by the method of the present invention, water flow to the ion exchange device is stopped and the anion exchanger is regenerated or exchanged.
内径４０ｍｍのカラムにゲル型アニオン交換樹脂（三菱化学（株）製、完全再生形（ＯＨ形）ＳＡ１０ＡＯＨ）を層高４００ｍｍとなるように充填したイオン交換装置に下記水質の被処理水を１．１Ｌ／ｈで下向流にて通水した。イオン交換装置の処理水の炭酸濃度をＴＯＣ分析装置（Ｓｉｅｖｅｒｓ９００ポータブル型）を用いて測定した。測定の際には、６Ｍ正リン酸溶液を１．０μＬ／ｍｉｎの割合で該処理水に添加して炭酸イオンをガス化させた。また、ＴＯＣの分解による無機炭酸濃度の測定値に誤差が生じないように、ＴＯＣ測定用の酸化剤の流量を０として測定を行った。 To an ion exchange apparatus in which a gel type anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd., fully regenerated (OH type) SA10AOH) is packed in a column having an inner diameter of 40 mm so as to have a layer height of 400 mm, 1. Water was passed in a downward flow at 1 L / h. The carbonic acid concentration of the treated water of the ion exchanger was measured using a TOC analyzer (Sievers 900 portable type). At the time of measurement, a 6M orthophosphoric acid solution was added to the treated water at a rate of 1.0 μL / min to gasify carbonate ions. In addition, the measurement was performed with the flow rate of the oxidizing agent for TOC measurement being 0 so that an error does not occur in the measured value of the inorganic carbonic acid concentration due to the decomposition of TOC.
処理水の導電率及び炭酸濃度の破過曲線を図１に示す。図１より、導電率が上昇し始める２時間程度前には、微量炭酸イオンのリークが見られることがわかる。例えば、破過濃度を３μｇ−Ｃ／Ｌと設定した場合には、通水時間１０時間で通水を停止し、イオン交換装置の再生又は樹脂交換を行うことにより、導電率ブレークが起こることなく、安定した採水を行えることがわかる。 A breakthrough curve of the conductivity and carbonic acid concentration of the treated water is shown in FIG. From FIG. 1, it can be seen that a leak of a small amount of carbonate ions is observed about 2 hours before the start of the increase in conductivity. For example, when the breakthrough concentration is set to 3 μg-C / L, the water flow is stopped after 10 hours and the ion exchange device is regenerated or the resin is exchanged, so that the conductivity break does not occur. It can be seen that stable sampling can be performed.
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