JP6717625B2 - System and method for parallel and automatic determination of fluoride ion and mercury concentrations in water - Google Patents
System and method for parallel and automatic determination of fluoride ion and mercury concentrations in water Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 158
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims description 69
- 229910052753 mercury Inorganic materials 0.000 title claims description 67
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims description 55
- 238000000034 method Methods 0.000 title claims description 14
- 239000000523 sample Substances 0.000 claims description 74
- 238000005070 sampling Methods 0.000 claims description 71
- 238000010790 dilution Methods 0.000 claims description 25
- 239000012895 dilution Substances 0.000 claims description 25
- 238000005259 measurement Methods 0.000 claims description 25
- 238000007865 diluting Methods 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 13
- -1 fluoride ions Chemical class 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012470 diluted sample Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 5
- 238000004891 communication Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000003306 harvesting Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002731 mercury compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229960002523 mercuric chloride Drugs 0.000 description 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 2
- 229940008718 metallic mercury Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SPIUPAOJDZNUJH-UHFFFAOYSA-N diethylmercury Chemical compound CC[Hg]CC SPIUPAOJDZNUJH-UHFFFAOYSA-N 0.000 description 1
- ATZBPOVXVPIOMR-UHFFFAOYSA-N dimethylmercury Chemical compound C[Hg]C ATZBPOVXVPIOMR-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N hydroxylamine hydrochloride Substances Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- WCYJQVALWQMJGE-UHFFFAOYSA-M hydroxylammonium chloride Chemical compound [Cl-].O[NH3+] WCYJQVALWQMJGE-UHFFFAOYSA-M 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000013450 outlier detection Methods 0.000 description 1
- XEBWQGVWTUSTLN-UHFFFAOYSA-M phenylmercury acetate Chemical compound CC(=O)O[Hg]C1=CC=CC=C1 XEBWQGVWTUSTLN-UHFFFAOYSA-M 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 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
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- VMOXILJFUFEZJL-UHFFFAOYSA-M sodium;ethylmercury;2-sulfanylbenzoate Chemical compound [Na+].CC[Hg].[O-]C(=O)C1=CC=CC=C1S VMOXILJFUFEZJL-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Description
本発明は、水中の弗化物イオンおよび水銀の濃度を並列に自動測定するためのシステムまたは方法に関する。 The present invention relates to a system or method for automatically measuring fluoride ion and mercury concentrations in water in parallel.
工場においては、冷却に用いる水や洗浄に用いる工業用の水等が大量に用いられている。これらの工業用の水の多くは、冷却部分や洗浄部分と貯水槽（循環槽）との配管によって循環させて用いられる。そこで、これらの循環用水には、環境排水基準に規定される物質が少なからず含まれており、操業の状況によって急激に濃度が高くなったり、循環することにより徐々に高くなったりしていくものもある。このため、値が高くなった循環用水等は、ブリードオフしては廃水処理設備にて環境排水基準値以下に処理することによって、工場外に排出される。このようなことから、貯水槽（循環槽）の水質を常時モニタリングすることは肝要となる。 In factories, a large amount of water used for cooling, industrial water used for washing, and the like are used. Most of these industrial waters are circulated and used by piping between a cooling part or a cleaning part and a water storage tank (circulation tank). Therefore, these circulating waters contain a considerable amount of substances specified in the environmental wastewater standards, and the concentration may increase rapidly depending on the operating conditions, or may gradually increase due to circulation. There is also. For this reason, the circulating water or the like having a high value is discharged outside the factory by bleeding off the wastewater and treating it with the wastewater treatment facility to the environmental wastewater standard value or less. For this reason, it is essential to constantly monitor the water quality of the water storage tank (circulation tank).
環境排水基準に規定される物質として弗化物イオン（F-）と水銀（Hg）がある。例えば我が国の水質汚濁防止法と排水基準を定める省令が定める一律の排水基準としては、2015年現在の基準値（許容限度）であるが「水銀及びアルキル水銀その他の水銀化合物」が0.005 mg Hg/L以下、「ふっ素及びその化合物」は8 mg F/L以下（海域以外の公共用水域に排出されるもの）または15 mg F/L（海域に排出されるもの）とされている。また、工場の所在地によってはこれよりも厳しい基準値が条例等で別途定められている場合もある。そこで、弗化物イオン（F-）と水銀（Hg）についても、同様に、貯水槽（循環槽）の水質をモニタリングする必要がある。 Fluoride ions (F - ) and mercury (Hg) are substances specified in the environmental wastewater standards. For example, as a uniform drainage standard established by the Ministry of Water Pollution Control Law and drainage standards in Japan, the standard value (allowable limit) as of 2015 is "mercury and alkylmercury and other mercury compounds" 0.005 mg Hg/ Below L, "fluorine and its compounds" are defined as 8 mg F/L or less (emitted to public water bodies other than the sea area) or 15 mg F/L (emitted to the sea area). Further, depending on the location of the factory, there are cases where stricter standard values are specified separately by ordinances. Therefore, it is necessary to monitor the water quality in the water storage tank (circulation tank) for fluoride ion (F - ) and mercury (Hg) as well.
一方、工場では、一般に発生した貴金属スクラップ（弗素系樹脂を含む）、リチウムイオン電池、または電子基板に含まれる水銀リレーといった廃電子部品屑を炉（定置炉やキルン炉など）で焼却処理しているが、その処理量が増加傾向にある。このため、排ガス洗浄設備等からの冷却用水や洗浄用水に含まれる弗化物イオンと水銀の濃度が高くなりつつあり、これまで以上に貯水槽（循環槽）の水質をモニタリングする頻度が必要となってきた。また、人力によるサンプリングに伴う作業負担も問題となってきた。 On the other hand, in the factory, waste electronic components such as scraps of precious metals (including fluorine resin), lithium ion batteries, and mercury relays contained in electronic substrates that are generally generated are incinerated in a furnace (stationary furnace, kiln furnace, etc.). However, the amount of processing is increasing. For this reason, the concentration of fluoride ions and mercury contained in cooling water and cleaning water from exhaust gas cleaning equipment, etc. is increasing, and it is necessary to monitor the water quality of the water storage tank (circulation tank) more frequently than ever. Came. In addition, the work load associated with manual sampling has become a problem.
このような排水中の金属濃度分析のための自動化については、例えば特許文献1に記載の手法が提案されている。 For automation of such metal concentration analysis in wastewater, for example, the method described in Patent Document 1 has been proposed.
しかしながら特許文献1に記載されている従来技術は、１又は２以上の試料液採取箇所に対して１種類の金属濃度分析を自動で行う装置及びシステムであり、弗化物イオンと水銀のように別々の測定機器で各々の測定用試料液を調製して、分析を行う装置及びシステムではない。このため、測定用試料液の作製には、試料液採取箇所に対して計量、希釈などといった煩雑な作業が前処理として要求され、自動運転を謳っている従来技術に係る分析装置であっても、２つの測定を並列かつ自動で行うためには改善の余地があった。 However, the prior art described in Patent Document 1 is an apparatus and system for automatically performing one kind of metal concentration analysis on one or more sample liquid sampling points, and separates such as fluoride ion and mercury. This is not an apparatus and system that prepares and analyzes each sample liquid for measurement with the measuring instrument of. For this reason, in the preparation of the sample liquid for measurement, complicated work such as weighing and dilution is required as a pretreatment for the sample liquid sampling point, and even the analyzer according to the conventional technique which claims automatic operation. There was room for improvement in order to perform two measurements in parallel and automatically.
上記事情に鑑み、弗化物イオンと水銀の水中濃度を並行かつ自動で測定し、異常値を監視でき、人力によるサンプリング等の頻度からの作業負担を要求しない手法が課せられた。 In view of the above circumstances, there has been imposed a method capable of automatically measuring the concentrations of fluoride ion and mercury in water in parallel and monitoring abnormal values, and not requiring a work load due to the frequency of manual sampling and the like.
本発明の一つの実施形態においては、水中の弗化物イオンおよび水銀の濃度を自動測定するためのシステムであって、
前記システムは、
弗化物イオンの水中濃度を測定するように構成される弗化物イオン濃度測定手段、および
水銀の水中濃度を測定するように構成される水銀濃度測定手段
に接続するように構成されるものであり、
前記システムは、
弗化物イオンまたは水銀の水源に接続して、測定対象となる試料原水を蓄積し循環させるように構成される、循環水系と、
前記試料原水を、前記循環水系が接続する採取容器から採取し、受取容器に排出するように構成される、第一採取手段と、
前記受取容器から、第一の量の前記試料原水を採取し、前記弗化物イオン濃度測定手段の試料受入容器に渡し、所定の希釈率に希釈するように構成される、第二採取手段と、
前記受取容器から、第二の量の前記試料原水を採取し、所定の希釈率に希釈し、第三の量の前記希釈した試料液を採取し、前記水銀濃度測定手段に渡すように構成される、第三採取手段と
を含むシステムが提供される。
In one embodiment of the invention, a system for automatically measuring the concentration of fluoride ions and mercury in water, comprising:
The system is
A fluoride ion concentration measuring means configured to measure the concentration of fluoride ion in water, and a mercury concentration measuring means configured to measure the concentration of mercury in water.
The system is
A circulating water system configured to connect to a fluoride ion or mercury water source and accumulate and circulate sample raw water to be measured,
First sampling means configured to collect the sample raw water from a sampling container to which the circulating water system is connected, and discharge the raw water into a receiving container,
From the receiving container, a first amount of the sample raw water is collected, passed to the sample receiving container of the fluoride ion concentration measuring means, and configured to be diluted to a predetermined dilution rate, second collecting means,
A second amount of the sample raw water is collected from the receiving container, diluted to a predetermined dilution rate, and a third amount of the diluted sample liquid is collected and passed to the mercury concentration measuring means. A third collection means is provided.
また当該実施形態は、水中の弗化物イオンおよび水銀の濃度を自動測定するための方法であって、
弗化物イオンの源または水銀の源に接続して測定対象となる試料原水を蓄積し循環させるように構成される循環水系から、前記試料原水を採取し、受取容器に格納するステップと、
前記受取容器から、第一の量の前記試料原水を採取し、弗化物イオン濃度測定手段に渡し、所定の希釈率に希釈して、前記弗化物イオン濃度測定手段が試料原水中の弗化物イオン濃度を算出するステップと、
前記受取容器から、第二の量の前記試料原水を採取し、所定の希釈率に希釈し、第三の量の前記希釈した試料液を採取し、前記水銀濃度測定手段が試料原水中の水銀濃度を算出するステップと
を含む方法も提供する。
The embodiment is also a method for automatically measuring the concentrations of fluoride ions and mercury in water,
Collecting the sample raw water from a circulating water system configured to accumulate and circulate the sample raw water to be measured by connecting to a source of fluoride ions or a source of mercury, and storing the sample raw water in a receiving container;
A first amount of the sample raw water is collected from the receiving container, passed to a fluoride ion concentration measuring means, diluted to a predetermined dilution ratio, and the fluoride ion concentration measuring means measures the fluoride ion in the sample raw water. Calculating the concentration,
A second amount of the sample raw water is collected from the receiving container, diluted to a predetermined dilution rate, and a third amount of the diluted sample liquid is collected, and the mercury concentration measuring means is used to measure the mercury in the sample raw water. And a step of calculating the concentration.
本発明に係るシステムまたは方法を用いることによって、弗化物イオンと水銀の水中濃度を並行かつ自動で測定ができ、貯水槽（循環槽）の水質の監視や異常値の管理をすることが可能で、かつ人力による作業負担も軽減され、継続的に機能するという効果を図ったものである。 By using the system or method according to the present invention, the concentrations of fluoride ion and mercury in water can be measured in parallel and automatically, and it is possible to monitor the water quality of the water tank (circulation tank) and manage abnormal values. Moreover, the work load due to human power is reduced, and the effect of continuous functioning is achieved.
以下、本発明の実施形態を図面に基づいて詳細に説明するが、これは本発明を何ら限定するものではない。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings, but the present invention is not limited thereto.
本明細書においては、「約」または「およそ」なる表現は、特段の断わりが無いかぎりはその修飾する数値の±10%の範囲を包摂する。 In this specification, the expression “about” or “approximately” includes a range of ±10% of the modifying numerical value, unless otherwise specified.
本明細書においては、水中濃度に関する文脈における「弗化物イオン」、「フッ化物イオン」、「フッ素」または「ふっ素」などの表記は、特段の断わりが無いかぎりは環境基準（排水基準）における「ふっ素及びその化合物」すなわち水中の弗化物イオンおよびその前駆体化合物を含有する。なお混乱を避けるため、本明細書の記載においては原則としては「弗化物イオン」表記で統一している。またその濃度については、上述したように従来技術に基づいて弗化物イオン換算量として計算することができる。 In the present specification, the notation such as “fluoride ion”, “fluoride ion”, “fluorine” or “fluorine” in the context of the concentration in water means “in the environmental standard (drainage standard)” unless otherwise specified. Fluorine and its compounds", ie fluoride ions in water and their precursor compounds. In order to avoid confusion, in the description of the present specification, as a general rule, the expression "fluoride ion" is used. The concentration can be calculated as a fluoride ion conversion amount based on the conventional technique as described above.
本明細書においては、「水銀」または「Hg」なる表現は、特段の断わりが無いかぎりは金属水銀、無機水銀（硫化水銀、酸化水銀、塩化第一水銀、塩化第二水銀など）、アルキル水銀その他の水銀化合物（メチル水銀、ジメチル水銀、エチル水銀チオサリチル酸ナトリウム、ジエチル水銀、酢酸フェニル水銀など）を包含する。なおその濃度については、上述したように従来技術に基づいて金属水銀換算量として計算することができる。 In this specification, the expression "mercury" or "Hg" means, unless otherwise specified, metallic mercury, inorganic mercury (mercury sulfide, mercury oxide, mercuric chloride, mercuric chloride, etc.), alkylmercury. Other mercury compounds (methyl mercury, dimethyl mercury, ethyl mercury sodium thiosalicylate, diethyl mercury, phenyl mercury acetate, etc.) are included. The concentration can be calculated as a metallic mercury conversion amount based on the conventional technique as described above.
本明細書においては、弗化物イオンおよび水銀（アルキル水銀その他の水銀化合物を含む）の濃度定量方法に関しては環境基準（排水基準）に合った任意の手法を選択することができる。具体的には、弗化物イオンの測定には当該環境庁告示に示されるJIS K 0102:2013の第34節「ふっ素化合物」の項に掲げられる測定方法を使用できる。また具体的には、水銀の測定には当該環境庁告示に示される昭和46年環境庁告示第59号付表1に掲げられる測定方法を使用できる。 In the present specification, as a method for quantifying the concentration of fluoride ions and mercury (including alkylmercury and other mercury compounds), any method that meets environmental standards (wastewater standards) can be selected. Specifically, for the measurement of fluoride ions, the measurement method described in JIS K 0102:2013, Section 34, "Fluorine compounds", which is indicated in the notification of the relevant environment agency, can be used. In addition, specifically, the measurement methods listed in Appendix 1 of the Environmental Agency Notification No. 59 of 1972, which is indicated in the Environmental Agency Notification, can be used to measure mercury.
本発明に係る実施形態については、図1を参照しつつ以下に説明する。 Embodiments according to the present invention will be described below with reference to FIG.
実施形態に係るシステム 100 は、弗化物イオン濃度測定手段 89 および水銀濃度測定手段 99 （それぞれ各成分の自動測定を行う）に接続し、システム全体として自動化された二種の測定を並行かつ継続的に実現できるように構成されている。概要として、システム 100 は測定用試料水を水源としての循環水系 102 から採取し、当該二種の濃度測定手段と協働して自動かつ並列に弗化物イオン濃度と水銀濃度を測定することを可能とするものである。なお、図1中の実線矢印は水の流れならびに当該水に添加される希釈用水もしくは試薬の流れの概要を示すものである。また一点鎖線矢印はデータ通信の流れの概要を示すものである。別の実施形態においてはこれらの矢印以外の流れがあってもよい。なお、弗化物イオン濃度測定手段 89 および水銀濃度測定手段 99 はシステム 100 に含まれていないことに留意されたい。 The system 100 according to the embodiment is connected to a fluoride ion concentration measuring means 89 and a mercury concentration measuring means 99 (which each perform automatic measurement of each component) to perform two types of automated measurements in parallel and continuously as a whole system. It is configured so that it can be realized. As an outline, the system 100 is capable of collecting the sample water for measurement from the circulating water system 102 as a water source and measuring the fluoride ion concentration and the mercury concentration automatically and in parallel in cooperation with the two concentration measuring means. It is what The solid-line arrows in FIG. 1 show the outline of the flow of water and the flow of dilution water or reagents added to the water. The one-dot chain line arrow shows the outline of the flow of data communication. In other embodiments, there may be flows other than these arrows. It should be noted that the fluoride ion concentration measuring means 89 and the mercury concentration measuring means 99 are not included in the system 100.
弗化物イオン濃度測定手段 89 は市販の任意の分析装置であってよく、例えば好ましくはイオン電極式分析計または吸光光度計であってよい。 The fluoride ion concentration measuring means 89 may be any commercially available analyzer, for example, preferably an ion electrode type analyzer or an absorptiometer.
弗化物イオン濃度測定手段 89 としてのイオン電極式分析計は、例えばF-72（堀場製作所製）やMM-60R（東亞DKK株式会社製）などが市販されており、これらを使うことが可能である。 As the ion electrode type analyzer as the fluoride ion concentration measuring means 89, for example, F-72 (manufactured by Horiba Ltd.) and MM-60R (manufactured by Toago DKK Co., Ltd.) are commercially available, and these can be used. is there.
水銀濃度測定手段 99 も市販の任意の分析装置であってよく、例えば好ましくは安全性と共存元素の妨害の少なさという観点から原子吸光装置、ICP発光分析装置（ICP/OES）、ICP質量分析装置（ICP/MS）または水銀測定装置であってよい。 The mercury concentration measuring means 99 may also be any commercially available analyzer, and for example, preferably from the viewpoint of safety and less interference of coexisting elements, atomic absorption spectrometer, ICP emission spectrometer (ICP/OES), ICP mass spectrometer. It may be an instrument (ICP/MS) or a mercury measuring instrument.
水銀濃度測定手段 99 は、水銀濃度専用測定装置として、例えばRA-5、RA-3A、RA-3110（日本インスツルメンツ株式会社製）やHG-400（平沼産業株式会社製）などが市販されており、これらを使うことが可能である。 As the mercury concentration measuring means 99, for example, RA-5, RA-3A, RA-3110 (manufactured by Nippon Instruments Co., Ltd.) and HG-400 (manufactured by Hiranuma Sangyo Co., Ltd.) are commercially available as mercury concentration measuring devices. , It is possible to use these.
循環水系 102 は、システム 100 外の工場敷地内の貯水槽（以下、試料原水採取箇所） 79 とシステム 100 と配管で接続し、試料原水採取箇所 79 の試料原水を循環する循環水系である。循環水系 102 には、第一採取手段 104 のために、測定室内に採取容器 104a を設け、試料原水が試料原水採取箇所 79 からその採取容器 104a を経由して試料原水採取箇所 79 にふたたび循環するようになっている。具体的には、行きの試料原水を採取容器 104a の下から入れ、採取容器 104a の上部から戻りの試料原水を排出する機構によって循環できる。なお、循環水系 102 は、試料原水採取箇所ごとに設けられる。 The circulating water system 102 is a circulating water system that circulates the sample raw water at the sample raw water sampling point 79 by connecting the water tank (hereinafter referred to as sample raw water sampling point) 79 on the factory premises outside the system 100 to the system 100 by piping. In the circulating water system 102, a sampling container 104a is provided in the measurement chamber for the first sampling means 104, and the sample raw water is circulated again from the sample raw water sampling point 79 to the sample raw water sampling point 79 via the sampling container 104a. It is like this. Specifically, it can be circulated by a mechanism in which the raw sample water is put under the sampling container 104a and the returning sample raw water is discharged from the upper part of the sampling container 104a. The circulating water system 102 is provided at each sampling point of raw water.
第一採取手段 104 は、循環水系 102 の中に設置された採取容器 104a から試料原水を採取（サンプリング）し、受取容器 104b に排出するように機能する手段である。 The first sampling means 104 is a means that functions to collect (sample) the raw water sample from the sampling container 104a installed in the circulating water system 102 and discharge it to the receiving container 104b.
第一採取手段 104 が採取する試料原水の量は特に限定されず、測定目的や計器の検出限界や循環水系の容量などに応じた任意の量を採取することができるものであってもよい。 The amount of raw water sampled by the first sampling means 104 is not particularly limited, and may be any amount that can be sampled according to the purpose of measurement, the detection limit of the instrument, the volume of the circulating water system, and the like.
また第一採取手段 104 は、水を自動で採取するためなどの各種装置・手段を含むことができる。第一採取手段 104 が含みうるものとしては例えば、採取ノズル管、当該採取ノズル管を水源に対して移動させる手段（モーター等）、当該採取ノズル管を洗浄する手段（洗浄用水供給装置等）、ピストンビュレット、減圧ポンプ、採取した水を一時的に蓄えておく手段（バッファータンクなど）、ドレーン、フィルター、およびそれらの組み合わせなどが挙げられるが、これらに限定はされない。上記フィルターの使用については例えば、水源の水が汚泥、スラリー、砕石や塵芥などを含んで懸濁しておりそのままでは水質検査に適さないような場合に、好ましい。上記フィルターとしては例えば、濾紙、濾過膜、濾過カラム、ガラスボールフィルターなどが含まれるが、これらに限定はされない。 Further, the first sampling means 104 can include various devices/means for automatically collecting water. The first sampling means 104 may include, for example, a sampling nozzle tube, means for moving the sampling nozzle tube with respect to a water source (motor, etc.), means for cleaning the sampling nozzle tube (cleaning water supply device, etc.), Examples include, but are not limited to, a piston buret, a vacuum pump, a means for temporarily storing the collected water (such as a buffer tank), a drain, a filter, and a combination thereof. The use of the above filter is preferable, for example, when the water of the water source is suspended with sludge, slurry, crushed stone, dust, etc., and is not suitable for water quality inspection as it is. Examples of the filter include, but are not limited to, filter paper, filter membrane, filter column, and glass ball filter.
また第一採取手段 104 は、後述する制御手段 114 とデータ通信するための手段を含むことが可能で、例えば有線もしくは無線の受信機または送信機やLAN（ローカルエリアネットワーク）への接続手段などを使うことができる。これにより、制御手段 114 からの第一採取手段 104 の実施開始指示及び第一採取手段 104 の制御手段 114 への終了報告による第二採取手段 108 もしくは第三採取手段 110 の実施開始指示が可能となる。 The first sampling means 104 may include means for data communication with the control means 114, which will be described later. For example, a wired or wireless receiver or transmitter, a LAN (local area network) connection means, or the like may be included. Can be used. As a result, it is possible to instruct the control means 114 to start the execution of the first sampling means 104 and to instruct the control means 114 of the first sampling means 104 to start the execution of the second sampling means 108 or the third sampling means 110. Become.
また第一採取手段 104 は、正確な定量や汚染防止の観点などから、洗浄手段を含んでもよい。例えば洗浄手段は、洗浄水タンクに収めた洗浄用水（蒸留水、脱イオン水、もしくは水道水など）を使って第一採取手段 104 を洗浄するものであってよい。 The first sampling means 104 may also include a cleaning means from the viewpoint of accurate quantification and prevention of contamination. For example, the cleaning means may be one that cleans the first sampling means 104 using cleaning water stored in a cleaning water tank (distilled water, deionized water, tap water, or the like).
第二採取手段 108 は、第一採取手段 104 の受取容器 104b から、第一の量の試料原水を採取して弗化物イオン濃度測定手段 89 、具体的には、弗化物イオン濃度測定手段 89 の測定用容器 89a に渡し、弗化物イオン濃度の値を得させるように機能するものである。当該第一の量は特に限定されないが、弗化物イオン濃度測定手段 89 の仕様（計量管の容量や要請される希釈率や添加試薬量など）に基づいて定まる量であってよく、例えば第一の量を約100 mL以下の量とすることができる。 The second sampling means 108 collects a first amount of sample raw water from the receiving container 104b of the first sampling means 104 to measure the fluoride ion concentration measuring means 89, specifically, the fluoride ion concentration measuring means 89. It passes to the measuring container 89a and functions to obtain the value of the fluoride ion concentration. The first amount is not particularly limited, but may be an amount determined based on the specifications of the fluoride ion concentration measuring means 89 (volume of measuring tube, required dilution rate, amount of added reagent, etc.), for example, the first amount. Can be up to about 100 mL.
なお第二採取手段 108 には希釈手段 122 が含まれ、弗化物イオン濃度測定手段 89 の試料受入容器 89a に渡す試料原水を、所定の希釈率に希釈するように構成される。例えば希釈手段 122 は、試料原水を弗化物イオン濃度測定手段 89 に渡した後に希釈用水で希釈するように機能するものであってよい。 The second sampling means 108 includes a diluting means 122 and is configured to dilute the raw water sample to be passed to the sample receiving container 89a of the fluoride ion concentration measuring means 89 to a predetermined dilution rate. For example, the diluting means 122 may function so as to dilute the sample raw water to the fluoride ion concentration measuring means 89 and then dilute it with diluting water.
第二採取手段 108 は、第一採取手段 104 と同様に、弗化物イオン濃度測定手段 89 や、後述する制御手段 114 とデータ通信するための手段を含んでいてもよい。 Like the first sampling means 104, the second sampling means 108 may include means for data communication with the fluoride ion concentration measuring means 89 and the control means 114 described later.
なお、弗化物イオン濃度測定手段 89 が稼働中に常に溶液を通しておく必要がある装置である場合（イオン電極式分析装置など）には、第二採取手段 108 が分析実行時以外には弗化物イオン濃度測定手段 89 の測定用容器 89a を洗浄用水で満たしておくような構成にしておくことが望ましい。なお、試料液受入の際には、直前に洗浄用水を排出するような構成となっている。 If the fluoride ion concentration measuring means 89 is a device that needs to constantly pass the solution during operation (such as an ion electrode type analyzer), the second sampling means 108 should be used only when the analysis is performed. It is desirable that the measuring container 89a of the concentration measuring means 89 is filled with cleaning water. When receiving the sample liquid, the cleaning water is discharged immediately before.
第三採取手段 110 は、第一採取手段 104 の受取用容器 104b から、採取した試料原水を希釈し、第三の量の試料原水を採取して水銀濃度測定手段 99 、具体的にはその測定用容器 99a に渡し、水銀濃度の値を得させるように機能するものである。第二の量は特に限定されないが、水銀濃度測定手段 99 の仕様（計量管の容量や要請される希釈率や添加試薬量など）に基づいて定まる量であってよく、例えば第二の量は約5 mL程度の量とすることができる。 The third sampling means 110 dilutes the sample raw water collected from the receiving container 104b of the first sampling means 104 and collects a third amount of the sample raw water to measure the mercury concentration measuring means 99, specifically the measurement. It passes to the container 99a for use and functions to obtain the value of the mercury concentration. The second amount is not particularly limited, but may be an amount determined based on the specifications of the mercury concentration measuring means 99 (volume of measuring tube, required dilution ratio, amount of added reagent, etc.). For example, the second amount is The volume can be about 5 mL.
なお、第三採取手段 110 には希釈手段 124 が含まれてもよく、受取容器 104b から採取された試料原水を、所定の希釈率に希釈してから水銀濃度測定手段 99 に渡すように構成される。希釈手段 124 は、水銀濃度測定手段 99 に試料原水を渡すに先立って試料原水を希釈用水で希釈するように機能してもよい。 The third sampling means 110 may include a diluting means 124, which is configured to dilute the raw water sample collected from the receiving container 104b to a predetermined dilution ratio and then deliver it to the mercury concentration measuring means 99. It The diluting means 124 may function to dilute the sample raw water with the diluting water prior to passing the sample raw water to the mercury concentration measuring means 99.
本発明では、水銀濃度測定手段 99 は市販の装置である。そのため、当該装置に付属している測定用容器には容量の制約があり（5mL程度）、第三採取手段 110 においては受取容器 104b から装置付属の測定用容器 99a に水を受けても直接希釈できない場合がある。そのため別の態様では、第三採取手段 110が、第一採取手段 104 の受取容器 104b から第一の量の試料原水が採取された後に受取容器 104b の残りの試料原水を排出して、さらにその後に第二の量の試料原水を受取容器 104b に採取してから、その第二の量の試料原水を希釈手段 124 が所定の希釈倍率に希釈してから、その希釈されたうちから第三の量を水銀濃度測定手段 99 （の測定用容器 99a ）に渡すように機能することができる。 In the present invention, the mercury concentration measuring means 99 is a commercially available device. Therefore, there is a limit to the capacity of the measuring container attached to the device (about 5 mL), and in the third sampling means 110, even if water is received from the receiving container 104b into the measuring container 99a attached to the device, it is diluted directly. Sometimes you can't. Therefore, in another embodiment, the third sampling means 110 discharges the remaining raw sample water in the receiving container 104b after the first amount of raw sample water is collected from the receiving container 104b of the first collecting means 104, and further thereafter. First, the second amount of the sample raw water is collected in the receiving container 104b, the second amount of the sample raw water is diluted to a predetermined dilution ratio by the diluting means 124, and then the third amount is diluted. It can function to deliver the quantity to (the measuring vessel 99a of) the mercury concentration measuring means 99.
なおさらに別の態様では、希釈用容器を設置し、当該第二の量の試料原水を希釈用容器に排出し、所定の希釈倍率に希釈した後、第二の量を採取して水銀濃度測定手段 99 に渡すことも可能である。 In still another aspect, a diluting container is installed, the second amount of raw water sample is discharged into the diluting container, diluted to a predetermined dilution ratio, and then the second amount is collected to measure the mercury concentration. It is also possible to pass it to the means 99.
また第三採取手段 110 は、上述した第一採取手段 104 または第二採取手段 108 と同様の特徴や手段を含むものであってもよい。 Further, the third sampling means 110 may include the same features and means as the above-mentioned first sampling means 104 or second sampling means 108.
本実施形態に係る第二採取手段 108 と第三採取手段 110 の行う操作は、並行して自動で行うものである。或る態様においては、第二採取手段 108 と第三採取手段 110 とは協働する別個の装置であってよい。別の態様では、第二採取手段 108 と第三採取手段 110 とが単一の装置に含まれていてもよい。 The operations performed by the second sampling means 108 and the third sampling means 110 according to this embodiment are automatically performed in parallel. In some embodiments, the second harvesting means 108 and the third harvesting means 110 may be separate cooperating devices. Alternatively, the second harvesting means 108 and the third harvesting means 110 may be contained in a single device.
記録手段 112 は、第二採取手段 108 が渡した第一の量の試料原水に基づいて弗化物イオン濃度測定手段 89 が定量した弗化物イオン濃度をデータとして格納するように機能する。また記録手段 112 は、第三採取手段 110 が渡した第二の量の試料原水に基づいて水銀濃度測定手段 99 が定量した水銀濃度をデータとして格納するようにも機能する。或る態様においては当該データが、後述する計時手段 118 が定める測定時刻と紐付されていてもよい。なお記録手段 112 は複数の記録媒体（例えば電磁記録媒体）から構成されるものであってもよく、例えば物理的には別箇の記録媒体に別箇の濃度データをそれぞれ格納するようにしてもよい。 The recording means 112 functions to store, as data, the fluoride ion concentration quantified by the fluoride ion concentration measuring means 89 based on the first amount of sample raw water passed by the second sampling means 108. The recording means 112 also functions to store the mercury concentration quantified by the mercury concentration measuring means 99 based on the second amount of sample raw water passed by the third sampling means 110 as data. In one aspect, the data may be associated with the measurement time set by the timekeeping means 118 described later. Note that the recording means 112 may be composed of a plurality of recording media (for example, electromagnetic recording media), and may physically store different density data in different recording media. Good.
ある態様では、システム 100 が異常値検出手段を含んでもよい。異常値検出手段は、記録手段 112 が格納する記録に基づき弗化物イオンまたは水銀の濃度の値が所定の閾値を超えたかどうかの判断を行うように構成される手段である。当該閾値は環境基準や気温その他の一時的な条件等に基づき適切に定めることができる。当該閾値が記録手段 112 に格納され異常値検出手段が随時参照する構成となっていてもよいし、異常値検出手段自身が当該閾値を格納していてもよい。ある実施形態においては、弗化物イオン濃度測定手段 89 が算出した弗化物イオンの水中濃度の値が所定の弗化物イオン濃度閾値を超えているとき、または、水銀濃度測定手段 99 が算出した水銀の水中濃度の値が所定の水銀濃度閾値を超えているときに、警報（例えば警告灯の点灯など）を出すようにすることができる。 In some embodiments, system 100 may include outlier detection means. The abnormal value detecting means is a means configured to judge whether the value of the concentration of fluoride ion or mercury exceeds a predetermined threshold value based on the record stored in the recording means 112. The threshold can be appropriately set based on environmental standards, temperature, and other temporary conditions. The threshold value may be stored in the recording means 112 and referred to by the abnormal value detecting means at any time, or the abnormal value detecting means itself may store the threshold value. In one embodiment, when the value of the fluoride ion concentration in water calculated by the fluoride ion concentration measuring means 89 exceeds a predetermined fluoride ion concentration threshold value, or when the value of the mercury concentration calculated by the mercury concentration measuring means 99 is When the value of the concentration in water exceeds a predetermined mercury concentration threshold value, an alarm (for example, lighting of a warning light) can be issued.
計時手段 118 は、測定が行なわれる時刻を特定するために、測定地点の時刻を定める機能を有する手段である。計時手段 118 は例えば電波時計等の装置であってもよいし、NTPサーバと同期するソフトウェアを含んでもよい。測定を行う時刻は任意に定めることができ、決まった日の定刻（例えば本システムを設置する工場等の施設の営業日の始業時と終業時や、あるいは0時、6時、12時、18時のうちの一回以上など）に行うようにしてもよいし、任意の時間おき（例えば約10分間おき、約30分間おき、もしくは約1時間おきなど）に測定を行ってもよい。計時手段 118 は、コンピュータ（図示せず）によって制御されるものであってよい。また当該コンピュータは計時手段 118 以外の他の構成要素を制御してもよい（他の実施形態でも同様である）。またそれら他の構成要素が別箇の時計を含むことも可能であり、それら複数の時計同士を同期するように制御することも可能である。 The time measuring means 118 is a means having a function of determining the time at the measurement point in order to specify the time at which the measurement is performed. The clock means 118 may be a device such as a radio clock, or may include software that synchronizes with an NTP server. The time to perform the measurement can be set arbitrarily and can be set on a fixed day (for example, at the beginning and end of the business day of the facility such as the factory where the system is installed, or at 0:00, 6:00, 12:00, 18 The measurement may be performed once or more times, or at any time (for example, about 10 minutes, about 30 minutes, or about 1 hour). The timing means 118 may be controlled by a computer (not shown). Further, the computer may control other components than the timing means 118 (similarly in other embodiments). Further, the other components may include separate clocks, and the plurality of clocks may be controlled to be synchronized with each other.
本実施形態では、計時手段 118 より測定時間の情報を得て、第一採取手段 104 の実施指示が行われる。その終了の報告を受けてから、第二採取手段 108 もしくは第三採取手段 110 の実施指示、各々の測定手段の終了を受けての記録手段 112 の実施指示を出すプログラムを有する制御手段 114 を有する。好ましい態様では、制御手段 114 の動作として、第一採取手段 104 の実施指示の後に、第二採取手段 108 の実施指示が行われ、さらにその後に、第三採取手段 110 の実施指示が行われてから、記録手段 112 の実施指示が行われる。換言すれば、計時手段 118 は一連の実施のトリガーとして機能できるものである。 In this embodiment, the information of the measurement time is obtained from the time measuring means 118, and the execution instruction of the first collecting means 104 is given. It has a control means 114 having a program for, after receiving the report of the end, instructing execution of the second sampling means 108 or the third sampling means 110, and instructing execution of the recording means 112 in response to the end of each measuring means. .. In a preferred mode, as an operation of the control means 114, an execution instruction of the second sampling means 108 is given after an execution instruction of the first sampling means 104, and further, an execution instruction of the third sampling means 110 is given thereafter. Then, the execution instruction of the recording means 112 is given. In other words, the timing means 118 can function as a trigger for a series of implementations.
制御手段 114 は、計時手段 118 、第一採取手段 104 、第二採取手段 108 、第三採取手段 110 とデータ通信するための手段を含むことが可能で、例えば有線もしくは無線の受信機または送信機やLAN（ローカルエリアネットワーク）への接続手段などを使うことができる。 The control means 114 can include means for data communication with the timing means 118, the first sampling means 104, the second sampling means 108, the third sampling means 110, for example a wired or wireless receiver or transmitter. Or LAN (local area network) connection means can be used.
希釈手段 122 は、第二採取手段 108 が試料原水を弗化物イオン濃度測定手段 89 に渡すに際し、適切な濃度分析を行うために希釈用の水を注入し、試料原水を所定の希釈率を以って希釈するように機能するものである。当該希釈用の水としては測定精度に実質的に影響しない範囲で任意のものを使用でき、例えば蒸留水、脱イオン水、もしくは水道水などを用いてよい。 When the second sampling means 108 passes the sample raw water to the fluoride ion concentration measuring means 89, the diluting means 122 injects dilution water to perform an appropriate concentration analysis, and dilutes the sample raw water to a predetermined dilution ratio or less. It functions as a dilution. As the water for dilution, any water can be used as long as it does not substantially affect the measurement accuracy, and for example, distilled water, deionized water, or tap water may be used.
希釈手段 124 は、第三採取手段 110 が試料原水を水銀イオン濃度測定手段 99 に渡すに際しても、希釈手段 122 と同様に希釈用の水を注入できる。 Similarly to the diluting means 122, the diluting means 124 can inject the water for dilution when the third sampling means 110 passes the sample raw water to the mercury ion concentration measuring means 99.
希釈手段 122, 124 が対象の水を希釈する際の希釈率は、試料原水の濃度、用いる測定手段が安定して測定できる濃度範囲によって決まる。すなわち、原水を用いる測定手段が安定して測定できる濃度範囲まで、希釈して、測定を実施する。たとえば、本発明では、フッ素濃度では、原水が2 ppm〜200 ppmの範囲にあることが想定され、用いる装置の測定範囲は、0.05 ppm〜10,000 ppmであるために、希釈率は、本システムの仕様から10倍とすることができる。同様に、水銀の濃度についても原水が0.1 ppb〜200 ppbの範囲にあることが想定され、用いる装置の測定範囲は、0.005 ppb〜400 ppbであるために、希釈率は、本システムの仕様から10倍とすることができる。 The dilution rate when the diluting means 122, 124 dilutes the target water depends on the concentration of the raw water sample and the concentration range in which the measuring means used can stably measure. That is, the measurement is carried out by diluting to a concentration range where the measuring means using raw water can stably measure. For example, in the present invention, it is assumed that the raw water is in the range of 2 ppm to 200 ppm in terms of the fluorine concentration, and the measuring range of the device used is 0.05 ppm to 10,000 ppm. It can be multiplied by 10 from the specifications. Similarly, regarding the concentration of mercury, it is assumed that the raw water is in the range of 0.1 ppb to 200 ppb, and the measuring range of the equipment used is 0.005 ppb to 400 ppb. It can be 10 times.
上述したシステム 100 を用いることにより、所定の工程を含んだ水中の弗化物イオンおよび水銀の濃度を自動かつ並列に測定するための方法を実現することができる。この方法は、制御手段 114 によってハードウェア資産およびソフトウェア資産を用いて実行することが可能となる。制御手段 114 は例えば自動制御盤であり、計時手段 118 からの時間の情報を受けて動作可能である。 By using the system 100 described above, it is possible to realize a method for automatically and in parallel measuring the concentrations of fluoride ions and mercury in water, including predetermined steps. The method allows the control means 114 to be implemented with hardware and software assets. The control means 114 is, for example, an automatic control panel, and is operable by receiving time information from the timekeeping means 118.
本出願人の金属精錬工場の貯水槽（循環槽）からの試料用原水を対象として、本発明に係る自動システムおよび方法を使用して自動測定の検証を行った。態様としては上述した実施形態に対応するものを使用し、水源として、本出願人の工場内に在る定置炉、新定置炉、キルンの３基のガス冷却用循環水の貯水槽（循環槽）およびシックナーからの廃水槽の４基から配管を接続し、測定室内に採取容器４基を設置し、各々の配管に接続し、４基の試料原水採取箇所から試料原水を循環できるようにした。 For the sample raw water from the water tank (circulation tank) of the applicant's metal smelting factory, the automatic measurement was verified using the automatic system and method according to the present invention. As an aspect, the one corresponding to the above-described embodiment is used, and as a water source, a stationary water tank, a new stationary furnace, and a kiln in the applicant's factory, three tanks for circulating water for gas cooling (circulation tank). ) And a wastewater tank from Thickener were connected to 4 pipes, 4 collection containers were installed in the measurement chamber, and each pipe was connected to enable circulation of sample raw water from 4 sample raw water sampling points. ..
弗化物イオン濃度測定手段として、マルチ水質計MM-60R（東亞DKK株式会社製）を使用した。当該水質計の試料採取量は5 mLとし、緩衝液の量は5 mLまたは50 mLとした。弗化物イオン単能電極にはF-125（東亞DKK株式会社製）を、比較電極にはHS-305DP（東亞DKK株式会社製）を使用した。 As a fluoride ion concentration measuring means, a multi water quality meter MM-60R (manufactured by Toago DKK Co., Ltd.) was used. The sampling amount of the water quality meter was 5 mL, and the amount of the buffer solution was 5 mL or 50 mL. F-125 (manufactured by Toago DKK Co., Ltd.) was used for the fluoride ion unipotential electrode, and HS-305DP (manufactured by Toago DKK Co., Ltd.) was used for the reference electrode.
水銀濃度測定手段として、還元気化水銀測定装置RA-3A（日本インスツルメンツ株式会社製）を使用した。当該測定装置の試料採取量は5 mLとした。分析試薬として、硫酸(1+1)を0.7 mL、硝酸を0.2 mL、2.5% KMnO4を0.7 mL、0.8% 塩化ヒドロキシルアンモニウムを3 mL、10% 塩化スズを0.3 mLをそれぞれ添加して用いた。 As a mercury concentration measuring means, a reduced vaporized mercury measuring device RA-3A (manufactured by Japan Instruments Co., Ltd.) was used. The sampling amount of the measuring device was 5 mL. As analytical reagents, 0.7 mL of sulfuric acid (1+1), 0.2 mL of nitric acid, 0.7 mL of 2.5% KMnO 4 , 3 mL of 0.8% hydroxylammonium chloride, and 0.3 mL of 10% tin chloride were used. ..
各測定手段間のデータ通信はLAN経由で行った。 Data communication between each measuring means was performed via LAN.
測定は、１から３日間にわたり連続して行った。測定間隔は、1時間ごと1回とした。 The measurement was continuously performed for 1 to 3 days. The measurement interval was once every hour.
上記実施の結果、人力負担を要することなく、自動濃度測定運転を行うことが可能であることが実証された。 As a result of the above implementation, it was demonstrated that it is possible to perform the automatic concentration measurement operation without requiring human labor.
79 試料原水採取箇所
89 弗化物イオン濃度測定手段
89a 弗化物イオン濃度測定手段の用いる測定用容器
99 水銀濃度測定手段
99a 水銀濃度測定手段の用いる測定用容器
100 本発明の実施形態に係るシステム
102 循環水系
104 第一採取手段
104a 第一採取手段が試料原水を採取する先の採取容器
104b 第一採取手段が試料原水を収める受取容器
108 第二採取手段
110 第三採取手段
112 記録手段
114 制御手段
118 計時手段
122 第二採取手段が含む希釈手段
124 第三採取手段が含む希釈手段
79 Sample raw water sampling point
89 Fluoride ion concentration measuring means
89a Measuring container for measuring fluoride ion concentration
99 Mercury measuring means
99a Measuring container used for mercury concentration measuring means
100 System according to an embodiment of the present invention
102 Circulating water system
104 First sampling means
104a Collection container to which the first collection means collects sample raw water
104b Receiving container in which the first sampling means stores the raw water sample
108 Second collection means
110 Third collection method
112 recording means
114 control means
118 Timekeeping means
122 Dilution means included in the second collection means
124 Dilution means included in the third collection means
Claims (10)
前記システムは、
弗化物イオンの水中濃度を測定するように構成される弗化物イオン濃度測定手段、および
水銀の水中濃度を測定するように構成される水銀濃度測定手段
に接続するように構成されるものであり、
前記システムは、
弗化物イオンまたは水銀の水源に接続して、測定対象となる試料原水を蓄積し循環させるように構成される、循環水系と、
前記試料原水を、前記循環水系が接続する採取容器から採取し、受取容器に排出するように構成される、第一採取手段と、
前記受取容器から、第一の量の前記試料原水を採取し、前記弗化物イオン濃度測定手段の試料受入容器に渡し、所定の希釈率に希釈するように構成される、第二採取手段と、
前記受取容器から、第二の量の前記試料原水を採取し、所定の希釈率に希釈し、第三の量の前記希釈した試料液を採取し、前記水銀濃度測定手段に渡すように構成される、第三採取手段と
を含む
ことを特徴とする、システム。 A system for automatically measuring the concentration of fluoride ions and mercury in water, comprising:
The system is
A fluoride ion concentration measuring means configured to measure the concentration of fluoride ion in water, and a mercury concentration measuring means configured to measure the concentration of mercury in water.
The system is
A circulating water system configured to connect to a fluoride ion or mercury water source and accumulate and circulate sample raw water to be measured,
First sampling means configured to collect the sample raw water from a sampling container to which the circulating water system is connected, and discharge the raw water into a receiving container,
From the receiving container, a first amount of the sample raw water is collected, passed to the sample receiving container of the fluoride ion concentration measuring means, and configured to be diluted to a predetermined dilution rate, second collecting means,
A second amount of the sample raw water is collected from the receiving container, diluted to a predetermined dilution rate, and a third amount of the diluted sample liquid is collected and passed to the mercury concentration measuring means. And a third collection means.
前記第一採取手段、前記第二採取手段、および前記第三採取手段のうちの少なくとも一つの手段を洗浄するように構成される、洗浄手段
をさらに含む
ことを特徴とする、請求項1に記載のシステム。 The system is
2. The cleaning device according to claim 1, further comprising a cleaning unit configured to clean at least one of the first collecting unit, the second collecting unit, and the third collecting unit. System.
前記第二採取手段から渡された前記第一の量の前記試料原水に基づいて前記弗化物イオン濃度測定手段が算出する弗化物イオンの水中濃度についてのデータ、および、前記第三採取手段から渡された前記第二の量の前記試料原水に基づいて前記水銀濃度測定手段が算出する水銀の水中濃度についてのデータを格納するように構成される、記録手段
をさらに含む
ことをさらに特徴とする、請求項1または2に記載のシステム。 The system is
Data on the concentration of fluoride ion in water calculated by the fluoride ion concentration measuring means based on the first amount of the sample raw water passed from the second collecting means, and from the third collecting means. Further comprising a recording means configured to store data about the concentration of mercury in water calculated by the mercury concentration measuring means based on the second amount of the raw water sample. The system according to claim 1 or 2.
時刻を定めるための計時手段と、
前記計時手段より測定時間の情報を得て、前記第一採取手段の実施指示、その終了の報告を受けて前記第二採取手段もしくは前記第三採取手段の実施指示、各々の測定手段の終了を受けての記録手段の実施指示を出すように構成される、制御手段と
をさらに含む、請求項1〜3のいずれか一項に記載のシステム。 The system is
Timekeeping means for setting the time,
Obtaining information on the measurement time from the time measuring means, instructing execution of the first sampling means, receiving a report of the end thereof, instructing execution of the second sampling means or the third sampling means, and terminating each measuring means. 4. The system according to any one of claims 1 to 3, further comprising a control means configured to issue an instruction to perform the receiving recording means.
または、
前記第三採取手段が含む希釈手段が、前記水銀濃度測定手段の測定用容器に試料原水を渡すに先立って試料原水を希釈用水で希釈するように機能する、
請求項1〜4のいずれか一項に記載のシステム。 Whether the diluting means included in the second collecting means functions to dilute the raw water sample with the diluting water after passing it to the measuring container of the fluoride ion concentration measuring means,
Or
The diluting means included in the third sampling means functions so as to dilute the sample raw water with the diluting water prior to passing the sample raw water to the measurement container of the mercury concentration measuring means.
The system according to any one of claims 1 to 4.
弗化物イオンの源または水銀の源に接続して測定対象となる試料原水を蓄積し循環させるように構成される循環水系から、前記試料原水を採取し、受取容器に格納するステップと、
前記受取容器から、第一の量の前記試料原水を採取し、弗化物イオン濃度測定手段に渡し、所定の希釈率に希釈して、前記弗化物イオン濃度測定手段が試料原水中の弗化物イオン濃度を算出するステップと、
前記受取容器から、第二の量の前記試料原水を採取し、所定の希釈率に希釈し、第三の量の前記希釈した試料液を採取し、水銀濃度測定手段に渡し、前記水銀濃度測定手段が試料原水中の水銀濃度を算出するステップと
を含む、方法。 A method for automatically measuring the concentration of fluoride ions and mercury in water, comprising:
Collecting the sample raw water from a circulating water system configured to accumulate and circulate the sample raw water to be measured by connecting to a source of fluoride ions or a source of mercury, and storing the sample raw water in a receiving container;
A first amount of the sample raw water is collected from the receiving container, passed to a fluoride ion concentration measuring means, diluted to a predetermined dilution ratio, and the fluoride ion concentration measuring means measures the fluoride ion in the sample raw water. Calculating the concentration,
From the receiving container, a second amount of the sample raw water is sampled, diluted to a predetermined dilution rate, and a third amount of the diluted sample liquid is sampled and passed to a mercury concentration measuring means to measure the mercury concentration. The step of calculating the mercury concentration in the sample raw water.
をさらに含む、請求項9に記載の方法。 When the value of the fluoride ion concentration in water calculated by the fluoride ion concentration measuring means exceeds a predetermined fluoride ion concentration threshold value, or the value of the mercury concentration in water calculated by the mercury concentration measuring means is predetermined. 10. The method of claim 9, further comprising issuing an alarm when the mercury concentration threshold of is exceeded.
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