JP5801153B2 - BF4-measurement post-processing method and BF4-measurement method - Google Patents
BF4-measurement post-processing method and BF4-measurement method Download PDFInfo
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- 238000005259 measurement Methods 0.000 title claims description 142
- 238000000034 method Methods 0.000 title claims description 30
- 238000012805 post-processing Methods 0.000 title claims description 13
- 238000000691 measurement method Methods 0.000 title claims description 11
- 239000012085 test solution Substances 0.000 claims description 85
- 239000007788 liquid Substances 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 30
- 230000002452 interceptive effect Effects 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 6
- 238000006477 desulfuration reaction Methods 0.000 description 34
- 230000023556 desulfurization Effects 0.000 description 34
- 239000002351 wastewater Substances 0.000 description 33
- 238000010790 dilution Methods 0.000 description 19
- 239000012895 dilution Substances 0.000 description 19
- 239000012528 membrane Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 12
- 239000012488 sample solution Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000005416 organic matter Substances 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- -1 tetrafluoroborate ions Chemical class 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000004673 fluoride salts Chemical class 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Description
本発明は、ＢＦ４ −計測の後処理方法及びＢＦ４ −計測方法に関する。さらに詳述すると、本発明は、石炭火力発電所から排出される脱硫排水等の被検溶液に含まれるＢＦ４ −濃度を、液体膜型ＢＦ４ −電極を利用してフロー方式で計測するのに好適なＢＦ４ −計測の後処理方法及びＢＦ４ −計測方法に関する。 The present invention, BF 4 - post-processing method for measuring and BF 4 - related measurement method. In more detail, the present invention is, BF 4 contained in a test solution of the desulfurization waste water discharged from coal fired power plants - to measure by using the electrode flow method - the concentration, liquid film-type BF 4 preferably a BF 4 - regarding measurement method - post-processing method and BF 4 measurements.
石炭火力発電所から排出される脱硫排水中のホウ素は、主にホウ酸（Ｈ３ＢＯ３）やテトラフルオロホウ酸イオン（ＢＦ４ −）の形態で存在している。ＢＦ４ −はホウ素原子とフッ素原子により構成されるイオンであることから、排水中のホウ素濃度のみならず、フッ素濃度をも上昇させる要因となる。 Boron in the desulfurization effluent discharged from a coal-fired power plant exists mainly in the form of boric acid (H 3 BO 3 ) or tetrafluoroborate ions (BF 4 − ). Since BF 4 − is an ion composed of a boron atom and a fluorine atom, it increases not only the boron concentration in the wastewater but also the fluorine concentration.
フッ素の排水基準は、海域の公共用水域に放流される排水については１５ｍｇ／Ｌに設定され、海域以外の公共用水域（陸水域）に放流される排水については８ｍｇ／Ｌに設定されている。そこで、これらの排水基準を遵守すべく、排水中に含まれるＢＦ４ −を専用分解槽にてホウ酸とフッ化物イオン（Ｆ−）に分解し、Ｆ−をフッ化物塩として排水から分離・除去し、排水中のフッ素濃度を低減する手法が提案されている（非特許文献１）。 Fluorine drainage standards are set at 15 mg / L for wastewater discharged into public waters in the sea, and 8 mg / L for wastewater discharged into public waters (land waters) other than the sea. . Therefore, in order to comply with these effluent standards, BF 4 contained in the waste water - decompose, F - boric acid at only decomposition vessel fluoride ions (F) - a-separated from the waste water as the fluoride salt A technique for removing and reducing the fluorine concentration in the waste water has been proposed (Non-Patent Document 1).
ここで、ＢＦ４ −の分解を効率よく行い、Ｆ−をフッ化物塩として排水から効率よく分離・除去するためには、ＢＦ４ −の分解条件やＦ−をフッ化物塩とするために最適な薬剤の量を、排水中のＢＦ４ −とＦ−を計測して決定することが重要となる。 Here, in order to efficiently decompose BF 4 − and efficiently separate and remove F − as a fluoride salt from waste water, it is optimal for the decomposition conditions of BF 4 − and F − as a fluoride salt. It is important to determine the amount of an appropriate drug by measuring BF 4 − and F − in the waste water.
そこで、本願発明者等は、ＢＦ４ −とＦ−を計測するための既存技術であるイオンクロマトグラフ法や吸光光度法よりも簡易に、しかもＢＦ４ −とＦ−を同時に計測できる手法を特許文献１において提案している。具体的には、被検溶液を流通路に送液し、この流通路内を流通する被検溶液に液体膜型ＢＦ４ −電極を接触させてＢＦ４ −の計測を行うと共に、固体膜型Ｆ−電極を接触させてＦ−の計測を行うことにより、ＢＦ４ −とＦ−を同時に且つ簡易に計測可能としている。この計測方法を実施するための計測システム１０１の一例を図１２に示す。図１２に示すＢＦ４ −とＦ−の同時計測システム１０１は、被検溶液を貯留する容器１０２と、第一のフローセル１０３ａと、第二のフローセル１０３ｂと、第一のフローセル１０３ａに備えられる液体膜型ＢＦ４ −電極１０６と、第二のフローセル１０３ｂに備えられる固体膜型Ｆ−電極１０７と、液体膜型ＢＦ４ −電極１０６及び固体膜型Ｆ−電極１０７と接続されてＢＦ４ −とＦ−を計測する計測装置１０８とを備え、容器１０２から第一のフローセル１０３ａ及び第二のフローセル１０３ｂのそれぞれに被検溶液を同時に送液する送液手段４ａ、４ｂを備えて、第一のフローセル１０３ａ内を流通する被検溶液に液体膜型ＢＦ４ −電極１０６を接触させると共に、第二のフローセル１０３ｂ内を流通する被検溶液に固体膜型Ｆ−電極１０７を接触させるものとしている。図１２中、符号１１０はデータ収録用のコンピュータである。また、符号１０６’は比較電極である。 Therefore, the inventors of the present application have patented a method that can measure BF 4 − and F − simultaneously more easily than the existing techniques for measuring BF 4 − and F − , such as ion chromatography and absorptiometry. Proposed in Document 1. Specifically, it was fed to the flow path the sample solution, a liquid film-type BF 4 in the sample solution flowing through the flow passage - by contacting electrode BF 4 - performs the measurement, the solid membrane By measuring F − with the F − electrode in contact, BF 4 − and F − can be measured simultaneously and easily. An example of the measurement system 101 for implementing this measurement method is shown in FIG. The simultaneous measurement system 101 for BF 4 − and F − shown in FIG. 12 includes a container 102 for storing a test solution, a first flow cell 103a, a second flow cell 103b, and a liquid provided in the first flow cell 103a. film type BF 4 - and the electrode 106, the second solid film type F is provided to the flow cell 103b - an electrode 107, a liquid film-type BF 4 - is connected to the electrode 107 BF 4 - - electrode 106 and the solid film-type F and A measuring device 108 for measuring F − , and provided with liquid feeding means 4a and 4b for simultaneously feeding a test solution from the container 102 to each of the first flow cell 103a and the second flow cell 103b. liquid membrane in the sample solution flowing in the flow cell 103a BF 4 - with contacting the electrode 106, a solid film on the sample solution flowing in the second flow cell 103b F - it is assumed that contacting the electrode 107. In FIG. 12, reference numeral 110 denotes a data recording computer. Reference numeral 106 'denotes a reference electrode.
しかしながら、特許文献１に記載の計測システムを利用したＢＦ４ −及びＦ−の同時計測について、石炭火力発電所から排出される脱硫排水を用いて本願発明者等が検討を行ったところ、２回以上連続して計測を実施すると、ＢＦ４ −の計測値に正誤差が生じることが明らかとなった。 However, the inventors of the present application have examined the simultaneous measurement of BF 4 − and F − using the measurement system described in Patent Document 1 using desulfurization effluent discharged from a coal-fired power plant. When the measurement was continuously performed as described above, it became clear that a positive error occurred in the measurement value of BF 4 − .
そこで、本発明は、被検溶液を流通路に流通させて、流通路に設置された液体膜型ＢＦ４ −電極にて被検溶液のＢＦ４ −濃度を計測する方法において、２回以上連続してＢＦ４ −濃度を計測する際に生じる計測値の正誤差を抑える方法を提供することを目的とする。 The present invention, by circulating the test solution into the flow passage, the liquid membrane was installed in the flow path BF 4 - BF 4 of the test solution at the electrode - a method for measuring the concentration, two or more times in succession and to provide a method of suppressing the positive error of the measured value caused when measuring the concentration - BF 4 in.
かかる課題を解決するため、本願発明者等が鋭意検討を行った結果、被検溶液の計測終了後にＢＦ４ −溶液を流通路に流通させることで、次回のＢＦ４ −濃度の計測の際に計測値に正誤差が発生するのを抑えることができることを知見し、この知見に基づいてさらに種々検討を重ねて、本願発明を完成するに至った。 To solve such a problem, a result of the present inventors have conducted extensive studies, after the end measurement of the test solution BF 4 - solution be to the flow in the flow path, next BF 4 - in the measurement of the concentration The inventors have found that it is possible to suppress the occurrence of a positive error in the measured value, and have made further studies based on this finding, thereby completing the present invention.
即ち、本発明のＢＦ４ −計測の後処理方法は、被検溶液を流通路に流通させて、流通路に設置された液体膜型ＢＦ４ −電極にて被検溶液のＢＦ４ −濃度を計測するに際し、被検溶液の計測終了後の後処理として流通路にＢＦ４ −溶液を流通させて、液体膜型ＢＦ ４ − 電極にて被検溶液のＢＦ ４ − 濃度を計測した際に液体膜型ＢＦ ４ − 電極の電極感応膜に付着した計測妨害成分を除去するようにしている。 That, BF 4 of the present invention - post-processing method of measurement, by circulating the test solution into the flow passage, the installed liquid film type BF 4 the flow path - the concentration - BF 4 of the test solution at electrode upon measuring, BF to passage as post-processing after completion measurement of the test solution 4 - liquid upon measuring the concentration - solution was circulated, the liquid film type BF 4 - BF 4 of the test solution at electrode are in so that to remove the measuring disturbance component adhering to the electrode sensitive membrane electrode - membrane BF 4.
被検溶液の計測終了後の後処理として流通路にＢＦ４ −溶液を流通させることで、被検溶液の計測により液体膜型ＢＦ４ −電極の電極感応膜に付着した計測妨害成分が除去される。これにより、次回のＢＦ４ −濃度の計測の際に計測値に正誤差が発生するのを抑えることができる。 BF in flow passage as post-processing after completion of measurement of the test solution 4 - solution by circulating the liquid film type BF 4 by the measurement of the test solution - measuring interference component adhering to the electrode the electrode sensitive film is removed The Thus, next BF 4 - may be prevented from positive error occurs in the measurement value during the measurement of the concentration.
次に、本発明のＢＦ４ −計測方法は、被検溶液を流通路に流通させて、流通路に設置された液体膜型ＢＦ４ −電極にて被検溶液のＢＦ４ −濃度を計測する方法において、被検溶液の計測終了後の後処理として流通路にＢＦ４ −溶液を流通させて、液体膜型ＢＦ ４ − 電極にて被検溶液のＢＦ ４ − 濃度を計測した際に液体膜型ＢＦ ４ − 電極の電極感応膜に付着した計測妨害成分を除去した後、新たな被検溶液の計測を実施するようにしている。 Next, BF 4 of the present invention - measurement method, by circulating the test solution into the flow passage, the flow liquid membrane installed in the passage BF 4 - measuring the concentration - BF 4 of the test solution at electrode in the method, BF 4 the flow path as a post-treatment after completion measurement of the test solution - solution was circulated, the liquid film type BF 4 - at the electrodes of the test solution BF 4 - liquid film upon measuring the concentration type BF 4 - after removing the measured interference components attached to the electrode sensitive membrane electrode, and so as to implement the measurement of a new test solution.
被検溶液の計測終了後の後処理として流通路にＢＦ４ −溶液を流通させることで、被検溶液の計測により液体膜型ＢＦ４ −電極の電極感応膜に付着した計測妨害成分が除去される。したがって、新たな被検溶液の計測の際に計測値に正誤差が発生するのを抑えることができる。 BF in flow passage as post-processing after completion of measurement of the test solution 4 - solution by circulating the liquid film type BF 4 by the measurement of the test solution - measuring interference component adhering to the electrode the electrode sensitive film is removed The Therefore, it is possible to suppress the occurrence of a positive error in the measurement value when measuring a new test solution.
ここで、本発明のＢＦ４ −計測方法において、新たな被検溶液を希釈して計測に供することが好ましい。これにより、計測妨害成分が計測中に計測値に与える影響を低減することができる。 Here, the present invention BF 4 - in the measuring method, it is advantageous to subject the measurement by diluting a new test solution. Thereby, the influence which a measurement disturbance component has on a measured value during measurement can be reduced.
本発明のＢＦ４ −計測の後処理方法によれば、被検溶液を流通路に流通させて、流通路に設置された液体膜型ＢＦ４ −電極にて被検溶液のＢＦ４ −濃度を計測する際に電極感応膜に付着した計測妨害成分を除去することができる。したがって、次回の計測の際に、計測値に正誤差が発生するのを抑えて、信頼性の高い計測値を得ることが可能となる。 Of the present invention BF 4 - According to the post-processing method of measurement, by circulating the test solution into the flow passage, the installed liquid film type BF 4 the flow path - the concentration - BF 4 of the test solution at electrode Measurement interference components adhering to the electrode sensitive film during measurement can be removed. Therefore, in the next measurement, it is possible to obtain a highly reliable measurement value by suppressing the occurrence of a positive error in the measurement value.
また、本発明のＢＦ４ −計測方法によれば、被検溶液を流通路に流通させて、流通路に設置された液体膜型ＢＦ４ −電極にて被検溶液のＢＦ４ −濃度を計測する方法において、２回以上連続してＢＦ４ −濃度を計測する際に生じる計測値の正誤差を抑えることができる。したがって、新たな被検溶液の計測について、計測妨害成分による計測値の正誤差の発生を抑えることができ、信頼性の高い計測値を得ることが可能となる。 Further, BF 4 of the present invention - according to the measurement method, by circulating the test solution into the flow passage, the flow liquid membrane installed in the passage BF 4 - measuring the concentration - BF 4 of the test solution at electrode a method of more than two consecutive BF 4 - can be suppressed positive error of the measured value caused when measuring the concentration. Therefore, regarding the measurement of a new test solution, it is possible to suppress the occurrence of a positive error in the measurement value due to the measurement interference component, and it is possible to obtain a highly reliable measurement value.
以下、本発明を実施するための形態について、図面に基づいて詳細に説明する。 Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings.
本発明のＢＦ４ −計測方法は、被検溶液を流通路に流通させて、流通路に設置された液体膜型ＢＦ４ −電極にて被検溶液のＢＦ４ −濃度を計測する方法において、被検溶液の計測終了後の後処理として流通路にＢＦ４ −溶液を流通させた後、新たな被検溶液の計測を実施するようにしている。つまり、被検溶液の計測終了後における流通路へのＢＦ４ −溶液の流通が本発明における後処理に該当する。尚、本発明のＢＦ４ −計測の後処理方法及びＢＦ４ −計測方法は、上述の特許文献１において提案されているＢＦ４ −とＦ−の同時計測法に適用できることは勿論のこと、被検溶液のＢＦ４ −濃度のみを計測する方法にも当然に適用できることは言うまでもない。 BF 4 of the present invention - measurement method, by circulating the test solution into the flow passage, the liquid membrane was installed in the flow path BF 4 - A method for measuring the concentration, - BF 4 of the test solution at electrode BF 4 the flow path as post-processing after completion of measurement of the test solution - after flowing the solution, so that to implement the measurement of a new test solution. That, BF 4 to passage after completion measurement of the test solution - distribution of the solution corresponds to the post-processing of the present invention. Incidentally, BF 4 of the present invention - post-processing method and BF 4 measurement - measurement method, BF 4 proposed in Patent Document 1 described above - and F - of course it can be applied to the simultaneous measurement method, the of test solution BF 4 - it goes without saying that only can also naturally applicable to a method for measuring the concentration.
被検溶液に含まれ得るＢＦ４ −以外の成分には、計測の際に液体膜型ＢＦ４ −電極の電極感応膜に付着（吸着）して、次回の被検溶液の計測の際に計測を妨害して、計測値に正誤差を生じさせ得るものがある。本発明では、被検溶液の計測終了後における流通路へのＢＦ４ −溶液の流通によって、液体膜型ＢＦ４ −電極の電極感応膜に付着している計測妨害成分を除去し、次回のＢＦ４ −計測における計測値の正誤差の発生を抑えるようにしている。例えば、石炭火力発電所から排出される脱硫排水には有機物が含まれており、この有機物がＢＦ４ −計測の計測妨害成分となり得る。本発明では、被検溶液の計測終了後における流通路へのＢＦ４ −溶液の流通によって、液体膜型ＢＦ４ −電極の電極感応膜に付着している有機物を除去し、次回のＢＦ４ −計測における計測値の正誤差の発生を抑えることができる。 Components other than BF 4 − that can be contained in the test solution adhere (adsorb) to the electrode sensitive film of the liquid film type BF 4 − electrode during measurement, and are measured during the next measurement of the test solution. Some may cause a positive error in the measured value. In the present invention, BF 4 to passage after completion measurement of the test solution - by distribution of the solution, the liquid film type BF 4 - to remove the measuring disturbance component which is attached to the electrode sensitive membrane electrode, next BF 4 - thereby suppressing the occurrence of a positive error of the measured value in the measurement. For example, the desulfurization wastewater discharged from coal-fired power plants contains organic matter, the organic matter is BF 4 - may be measured interference components of the measurement. In the present invention, BF 4 to passage after completion measurement of the test solution - by distribution of the solution, the liquid film type BF 4 - to remove organic substances adhering to the electrode sensitive membrane electrode, next BF 4 - It is possible to suppress the occurrence of positive errors in measurement values in measurement.
尚、ＢＦ４ −溶液とは、計測妨害成分を実質的に含まないＢＦ４ −溶液、例えば蒸留水や純水等に水溶性のＢＦ４ −含有化合物（例えばテトラフルオロホウ酸ナトリウム等）を添加した溶液である。 Incidentally, BF 4 - A solution, BF 4 containing no measuring interfering components substantially - additives containing compound (e.g., sodium tetrafluoroborate, etc.) - a solution, for example distilled water or pure water soluble BF 4 Solution.
計測終了後に流通路に流通させるＢＦ４ −溶液の濃度は、特に限定されるものではないが、高濃度とする程、液体膜型ＢＦ４ −電極の電極感応膜に付着している計測妨害成分を短時間で除去することができ、好適である。具体的には、１０ｍｇ／Ｌ以上とすることが好適であり、５０ｍｇ／Ｌ以上とすることがより好適であり、１００ｍｇ／Ｌ以上とすることがさらに好適である。 BF 4 to be circulated in the flow path after the measurement - concentration of the solution, is not particularly limited, as a high density, the liquid film type BF 4 - Measurement adhering to the electrode sensitive membrane electrode interfering components Can be removed in a short time, which is preferable. Specifically, it is preferably 10 mg / L or more, more preferably 50 mg / L or more, and further preferably 100 mg / L or more.
ＢＦ４ −溶液の流通路への流通時間は、ＢＦ４ −溶液の濃度、液体膜型ＢＦ４ −電極の電極感応膜に付着している計測妨害成分量に応じて適宜設定される。即ち、ＢＦ４ −溶液の濃度が高い程、流通時間を短時間とできる。逆に、ＢＦ４ −溶液の濃度が低い程、流通時間を長時間とする必要がある。また、液体膜型ＢＦ４ −電極の電極感応膜に付着している計測妨害成分量が少ない程、流通時間を短時間とできる。逆に、液体膜型ＢＦ４ −電極の電極感応膜に付着している計測妨害成分量が多い程、流通時間を長時間とする必要がある。尚、ＢＦ４ −溶液の流速については、液体膜型ＢＦ４ −電極の電極感応膜へのＢＦ４ −溶液の接触絶対量を高めて短時間で計測妨害成分を除去する上では、大きいほど好適であるが、一旦除去された計測妨害成分が液体膜型ＢＦ４ −電極の電極感応膜に再付着することがない流速を確保すれば十分である。例えば、流速を５ｍＬ／ｍｉｎ以上とすれば、一旦除去された計測妨害成分が液体膜型ＢＦ４ −電極の電極感応膜に再付着することはないと考えられる。 BF 4 - Flow time for passage of the solution, BF 4 - concentration of the solution, the liquid film type BF 4 - is appropriately set in accordance with the measured interference component amount adhered to the electrode sensitive membrane electrode. That, BF 4 - higher concentration of the solution can be a distribution time and a short period of time. Conversely, BF 4 - the lower the concentration of the solution, it is necessary to set long the flow time. The liquid film-type BF 4 - as measured interfering component amount adhered to the electrode sensitive film of the electrode is small, can the flow time and short time. Conversely, the liquid film type BF 4 - The more measurement disturbing quantities of ingredients adhering to the electrodes of the electrode sensitive film, it is necessary to make long the flow time. Incidentally, BF 4 - For flow rate of the solution, the liquid film type BF 4 - BF 4 to the electrodes of the electrode sensitive film - in removing short time measurement interfering components to increase the contact absolute amount of the solution is preferably larger although, once removed measured interference component liquid film type BF 4 - is sufficient to ensure a flow rate not be re-attached to the electrode sensitive membrane electrode. For example, if the flow rate of 5 mL / min or more, once removed measured interference component liquid film type BF 4 - It is considered that no re-attached to the electrode of the electrode sensitive film.
以上、被検溶液の計測終了後における流通路へのＢＦ４ −溶液の流通によって、被検溶液の計測の際に液体膜型ＢＦ４ −電極の電極感応膜に付着した計測妨害成分が除去される。これにより、次回の被検溶液の計測の際に、前回の被検溶液の計測の際に液体膜型ＢＦ４ −電極の電極感応膜に付着した計測妨害成分による計測の妨害、即ち計測値の正誤差の発生が抑えられる。これにより、信頼性の高い分析を連続して実施することが可能になる。 Above, BF 4 to passage after completion measurement of the test solution - by distribution of the solution, the liquid film type BF 4 during measurement of the test solution - measuring interference component adhering to the electrode sensitive film electrode is removed The Thus, during the measurement of the next sample solution, a liquid film-type BF 4 during the measurement of the previous test solution - interference measurement by the measuring disturbance component adhering to the electrode the electrode sensitive film, i.e. the measured value Generation of positive errors can be suppressed. This makes it possible to continuously perform highly reliable analysis.
ここで、本発明のＢＦ４ −計測方法において、上記新たな被検溶液は、希釈することが好ましい。これにより、計測中における液体膜型ＢＦ４ −電極の電極感応膜への計測妨害成分の付着を低減して、より正確な計測値を得ることが可能となる。また、次回の計測を考慮した場合に、液体膜型ＢＦ４ −電極の電極感応膜への計測妨害成分の付着量が被検溶液を希釈しない場合と比較して低下するので、被検溶液を希釈しない場合と比較して、計測終了後のＢＦ４ −溶液の流通路への流通による付着計測妨害成分の除去を短時間で達成することができる。即ち、計測終了後のＢＦ４ −溶液の流通路への流通時間を短時間とできるという利点が得られる。尚、ここでいう希釈とは、計測妨害成分を実質的に含まない水（例えば純水や蒸留水等）で被検溶液を希釈することを意味している。 Here, BF 4 of the present invention - in the measuring method, the new test solution, it is preferable to dilute. Thus, the liquid film type BF 4 in the measurement - by reducing the adhesion of the measuring disturbance component to the electrodes of the electrode sensitive film, it is possible to obtain a more accurate measurement. Also, when considering the next measurement, the liquid film type BF 4 - since the amount of deposition of the measuring disturbance component to the electrodes of the electrode sensitive film is reduced compared with the case of not diluting the test solution, the test solution compared with no dilution, measured after completion of the BF 4 - the removal of adhesion measured interference components due to the flow of the flow path of the solution can be achieved in a short time. That, BF 4 after the end of the measurement - the advantage that flow time to passage of the solution can and short is obtained. In addition, dilution here means diluting a test solution with the water (for example, pure water, distilled water, etc.) which does not contain a measurement interference component substantially.
ここで、希釈率が高い程、計測妨害成分の濃度が低くなり好適ではあるが、希釈率が高すぎるとＢＦ４ −の濃度が液体膜型ＢＦ４ −電極による計測下限値よりも低くなる虞があるので、液体膜型ＢＦ４ −電極による計測下限値以上の濃度とする必要がある。例えば、石炭火力発電所から排出される脱硫排水については、概ね１０倍程度に希釈することが好適であるが、この希釈率に限定されるものではなく、計測対象となる排水等に含まれ得るＢＦ４ −濃度に応じて、液体膜型ＢＦ４ −電極による計測下限値との兼ね合いから、希釈率を適宜設定し得る。 Here, the higher the dilution, although it is preferred the lower the concentration of the measurement interfering components, the dilution ratio is too high BF 4 - concentration liquid film type BF 4 - it is lower than the measurement lower limit value by the electrode fear since there is a liquid film-type BF 4 - it is required to be a concentration of more than the measurement lower limit value by the electrode. For example, desulfurization effluent discharged from a coal-fired power plant is preferably diluted approximately 10 times, but is not limited to this dilution rate and may be included in effluent to be measured. BF 4 - depending on the concentration, the liquid film type BF 4 - from consideration of the measurement lower limit value by the electrode, may set the dilution rate appropriate.
上述の形態は本発明の好適な形態の一例ではあるがこれに限定されるものではなく本発明の要旨を逸脱しない範囲において種々変形実施可能である。例えば、上述の実施形態では、上記新たな被検溶液を希釈するようにしていたが、上記被検溶液（即ち、ＢＦ４ −溶液の流通路への流通する前の計測において供される被検溶液）を希釈するようにしてもよい。この場合にも、計測中における液体膜型ＢＦ４ −電極の電極感応膜への計測妨害成分の付着を低減して、より正確な計測値を得ることが可能となる。また、次回の計測（新たな被検溶液の計測）を考慮した場合に、液体膜型ＢＦ４ −電極の電極感応膜への計測妨害成分の付着量が被検溶液を希釈しない場合と比較して低下するので、被検溶液を希釈しない場合と比較して、計測終了後のＢＦ４ −溶液の流通路への流通による付着計測妨害成分の除去を短時間で達成することができる。即ち、計測終了後のＢＦ４ −溶液の流通路への流通時間を短時間とできるという利点が得られる。 The above-described embodiment is an example of a preferred embodiment of the present invention, but is not limited thereto, and various modifications can be made without departing from the gist of the present invention. For example, in the embodiment described above has been to dilute the fresh test solution, the test solution (i.e., BF 4 - test to be subjected in the measurement before flowing into the solution circulation passage The solution may be diluted. In this case, the liquid film type BF 4 in the measurement - by reducing the adhesion of the measuring disturbance component to the electrodes of the electrode sensitive film, it is possible to obtain a more accurate measurement. Also, when considering the next measurement (measurement of a new test solution), a liquid film-type BF 4 - adhesion amount measuring disturbance component to the electrode sensitive film electrode in comparison with the case of not diluting the test solution since reduced Te, as compared with the case of not diluting the test solution, BF 4 after the end of the measurement - can be achieved in a short time to remove the adhesion measured interference components due to the flow of the flow path of the solution. That, BF 4 after the end of the measurement - the advantage that flow time to passage of the solution can and short is obtained.
以下に本発明の実施例を説明するが、本発明はこれら実施例に限られるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
尚、本実施例における「標準添加」とは、テトラフルオロホウ酸ナトリウムを添加することにより、所定量のＢＦ４ −を添加することを意味している。 The “standard addition” in this example means that a predetermined amount of BF 4 − is added by adding sodium tetrafluoroborate.
（１）計測システム
図１２に示すＢＦ４ −とＦ−の同時計測システム１０１に基づき、ＢＦ４ −の計測に特化したＢＦ４ −計測システムを構築して実験を行った（図１３）。図１３に示すＢＦ４ −計測システム１は、被検溶液を貯留する容器２と、フローセル３と、液体膜型ＢＦ４ −電極６と、送液手段４と、計測装置８と、コンピュータ１０とから構成されるものとした。
(1) Measurement System Figure 12 shows BF 4 - on the basis of the simultaneous measurement system 101, BF 4 - - and F BF 4 specialized in the measurement - Experiments were performed to construct a measurement system (FIG. 13). BF 4 13 - measurement system 1 includes a container 2 for storing a sample solution, a flow cell 3, a liquid film-type BF 4 - and the electrode 6, the liquid supply means 4, the measuring device 8, a computer 10 It shall consist of.
送液手段４としてペリスタポンプ（アズワン（株）製 チュービングポンプＴＰ−１０ＳＡ）を用い、ペリスタポンプに付属しているチューブにより、ペリスタポンプを介して容器２とフローセル３の液体流入部とを接続した。これにより、フローセル３内における被検溶液の流速を制御可能とした。尚、フローセル３の液体排出部から排出される計測済み溶液は、廃液として回収した。 A peristaltic pump (Tubing Pump TP-10SA manufactured by As One Co., Ltd.) was used as the liquid feeding means 4, and the container 2 and the liquid inflow portion of the flow cell 3 were connected via a peristaltic pump by a tube attached to the peristaltic pump. Thereby, the flow rate of the test solution in the flow cell 3 can be controlled. In addition, the measured solution discharged | emitted from the liquid discharge part of the flow cell 3 was collect | recovered as a waste liquid.
フローセル３は、東亜ディーケーケー製のＦＬＣ−１２型とし、これに液体膜型ＢＦ４ −電極６を装着した。液体膜型ＢＦ４ −電極６は、東亜ディーケーケー製の７４６１Ｌとした。また、フローセル３には、比較電極６’（東亜ディーケーケー製 ４４０１Ｌ）を装着した。これにより、フローセル３内を流通する被検溶液が液体膜型ＢＦ４ −電極６と比較電極６’に接触可能とした。 Flow cell 3, and the FLC-12 type manufactured by DKK-TOA, liquid film-type BF 4 thereto - wearing the electrode 6. Liquid membrane type BF 4 - electrode 6 was manufactured by DKK-TOA-made 7461L. The flow cell 3 was equipped with a reference electrode 6 ′ (4401L manufactured by Toa DKK). Thus, the sample solution flowing in the flow cell 3 is liquid film type BF 4 - was contactable to the comparison electrode 6 'and the electrode 6.
計測装置８は、東亜ディーケーケー製のマルチ水質計ＭＭ−６０Ｒとし、液体膜型ＢＦ４ −電極６による計測データの表示と収録を行い、収録したデータを専用ソフトでコンピュータ１０へ転送した。 Measuring device 8, a multi water quality meter MM-60R manufactured by DKK-TOA, liquid film-type BF 4 - by the electrode 6 performs recording and display of measurement data, and transfers the recording data to the computer 10 by a dedicated software.
（２）プロセス排水のＢＦ４ −計測における正誤差の検討
プロセス排水（脱硫排水）を、図１３に示すＢＦ４ −計測システム１によって計測した際に生じるＢＦ４ −の計測値の正誤差について検討した。被検溶液の流速は５ｍＬ／ｍｉｎとした。
(2) Process wastewater BF 4 - examined positive error of the measured value - review process wastewater positive error in the measurement of (desulfurization effluent), BF 4 shown in FIG. 13 - BF 4 occurring when measured by the measurement system 1 did. The flow rate of the test solution was 5 mL / min.
まず、ＢＦ４ −標準溶液（１０ｐｐｍ）を被検溶液として３回連続で計測を実施した。結果を図１に示す。この場合には、１回目〜３回目の計測値に誤差は生じなかった。 First, BF 4 - was carried out measuring standard solution (10 ppm) three consecutive times as the test solution. The results are shown in FIG. In this case, no error occurred in the first to third measurement values.
次に、石炭火力発電所から排出された脱硫排水（脱硫排水Ａと呼ぶ）を被検溶液として３回連続で計測を実施した。結果を図２に示す。この場合には、計測回数の増加に伴って計測値に正誤差が生じ、正誤差は計測回数が増加する程大きくなった。 Next, the desulfurization waste water (referred to as desulfurization waste water A) discharged from the coal-fired power plant was measured three times continuously as a test solution. The results are shown in FIG. In this case, a positive error occurs in the measurement value as the number of measurements increases, and the positive error increases as the number of measurements increases.
次に、脱硫排水ＡにＢＦ４ −を５ｍｇ／Ｌ標準添加したものを被検溶液として３回連続で計測を実施した。結果を図３に示す。この場合にも、計測回数の増加に伴って計測値に正誤差が生じ、正誤差は計測回数が増加する程大きくなった。しかも、ＢＦ４ −を５ｍｇ／Ｌ標準添加していない場合（図２）と比較して、正誤差が拡大する傾向が見られた。 Next, measurement was carried out three times in succession using a desulfurization waste water A to which BF 4 − was added at a standard concentration of 5 mg / L as a test solution. The results are shown in FIG. Also in this case, a positive error occurs in the measurement value as the number of measurements increases, and the positive error increases as the number of measurements increases. In addition, the positive error tended to increase compared to the case where BF 4 − was not added at a standard of 5 mg / L (FIG. 2).
次に、ＢＦ４ −標準溶液（１０ｐｐｍ）を被検溶液として４回連続で計測を実施した。結果を図４に示す。この場合には、計測回数の増加に伴って計測値の正誤差が減少し、設定濃度（１０ｐｐｍ）に収束する傾向が見られた。 Next, BF 4 - was carried out measuring standard solution (10 ppm) in four consecutive as the test solution. The results are shown in FIG. In this case, as the number of measurements increased, the positive error of the measured value decreased and a tendency to converge to the set concentration (10 ppm) was observed.
以上の結果から、以下の知見が得られた。
・プロセス排水を被検溶液とすると２回目以降の計測値に正誤差が発生
・プロセス排水のＢＦ４ −濃度が高い程、正誤差が拡大
・正誤差が発生する状況でＢＦ４ −標準溶液をフローセル内に流通させると正誤差減少
From the above results, the following knowledge was obtained.
· The process wastewater positive error generated process waste water on the measurement values of second and subsequent When the test solution BF 4 - higher the concentration, in a situation where the positive error is larger, positive errors occur BF 4 - standard solutions Reduced positive error when distributed in flow cell
（３）正誤差の要因となるパラメータの推定
図１３に示すＢＦ４ −計測システム１によって計測した際に、ＢＦ４ −の計測値に正誤差を生じさせる要因となるパラメータについて検討した。
When measured by the measurement system 1, BF 4 - - (3 ) BF 4 shown in estimating Figure 13 causes a positive error parameters were considered in the measurement values for parameters becomes a factor causing a positive error.
まず、ＢＦ４ −標準溶液（１０ｐｐｍ）を被検溶液として、流速を振って（５ｍＬ／ｍｉｎ、７．５ｍＬ／ｍｉｎ、１０ｍＬ／ｍｉｎ）計測を実施した。結果を図５に示す。ＢＦ４ −の計測値は、流速にかかわらず、一定値（１０ｐｐｍ）を示した。 First, BF 4 - Standard solution (10 ppm) as the test solution was performed by shaking the flow rate (5mL / min, 7.5mL / min , 10mL / min) measurements. The results are shown in FIG. The measured value of BF 4 − showed a constant value (10 ppm) regardless of the flow rate.
上記（２）で使用した脱硫排水Ａとは異なるユニットから採取した脱硫排水Ｂを被検溶液として上記と同様の実験を実施した。結果を図６に示す。ＢＦ４ −の計測値は、時間の経過と共に上昇し、その傾きは流速に依存していた。 An experiment similar to the above was carried out using desulfurization wastewater B collected from a unit different from the desulfurization wastewater A used in (2) above as a test solution. The results are shown in FIG. The measured value of BF 4 − increased with time, and the slope thereof depended on the flow velocity.
以上の結果から、ＢＦ４ −の計測値の正誤差の要因となるパラメータは、液体膜型ＢＦ４ −電極６の電極感応膜を通過する排水量、即ち被検溶液中の計測妨害成分の濃度ではなく、電極感応膜を通過した計測妨害成分の絶対量であることが明らかとなった。 These results, BF 4 - Parameters causes positive errors in measured values of the liquid film type BF 4 - amount of waste water that passes through the electrode sensitive membrane electrode 6, that is, the concentration of the measuring disturbance component of the test solution It became clear that it was the absolute quantity of the measurement interference component which passed the electrode sensitive film | membrane.
尚、本実施例において使用した脱硫排水Ａと脱硫排水Ｂの性状を以下に示す。 In addition, the property of the desulfurization waste_water | drain A and the desulfurization waste_water | drain B used in the present Example is shown below.
（４）正誤差の解消に関する検討Ａ
ＢＦ４ −の計測値の正誤差の解消に関する検討として、プロセス排水の希釈について検討した。
(4) Examination of elimination of positive error A
As a study on eliminating the positive error of the measured value of BF 4 − , dilution of process wastewater was examined.
まず、本実施例において構築した計測システム１の定量性について検討した結果、０．１ｍｇ／ＬオーダーのＢＦ４ −の定量が可能であることが確認できた。そこで、脱硫排水（Ａ、Ｂ）について、希釈の有無による計測値の変化を検討した。結果を表２と表３に示す。尚、表３に示されているＢＦ４ −の濃度は、希釈分を考慮して換算したＢＦ４ −の濃度である。 First, as a result of examining the quantitativeness of the measurement system 1 constructed in this example, it was confirmed that BF 4 − on the order of 0.1 mg / L could be quantified. Therefore, for desulfurized effluents (A, B), changes in measured values depending on the presence or absence of dilution were examined. The results are shown in Tables 2 and 3. The concentration of BF 4 − shown in Table 3 is the concentration of BF 4 − converted in consideration of dilution.
尚、表２及び表３において、「脱硫排水Ａ＋５ｐｐｍ ＢＦ４」とは、脱硫排水ＡにＢＦ４ −を５ｍｇ／Ｌ標準添加したことを意味している。また、「脱硫排水Ｂ＋５ｐｐｍ ＢＦ４」とは、脱硫排水ＢにＢＦ４ −を５ｍｇ／Ｌ標準添加したことを意味している。 In Tables 2 and 3, “desulfurization effluent A + 5 ppm BF4” means that BF 4 − is added to desulfurization effluent A at a standard rate of 5 mg / L. Further, “desulfurization wastewater B + 5 ppm BF4” means that BF 4 − is added to the desulfurization wastewater B at a standard rate of 5 mg / L.
また、この実験では、被検溶液の流速を５ｍＬ／ｍｉｎとした。さらに、計測終了後はフローセル３内に純水を流通（５ｍＬ／ｍｉｎ、７分、以下、この処理を純水洗浄と呼ぶこともある）させ、次の計測を実行した。 In this experiment, the flow rate of the test solution was 5 mL / min. Further, after the measurement was completed, pure water was circulated in the flow cell 3 (5 mL / min, 7 minutes, hereinafter, this process may be referred to as pure water cleaning), and the next measurement was performed.
表２及び表３に示される結果から、純水による１０倍希釈を行うことで、標準添加したＢＦ４ −の濃度が計測値としてより正確に反映されることが明らかとなった。 From the results shown in Tables 2 and 3, it was revealed that the concentration of BF 4 − added as a standard was more accurately reflected as a measurement value by performing 10-fold dilution with pure water.
また、３回連続計測結果（計測終了後に純水洗浄を行い次の計測を実行）を図７〜図１０に示す。図７が被検溶液を脱硫排水Ａ（希釈無し）とした結果を示す図であり、図８が被検溶液を脱硫排水Ａ＋５ｐｐｍ ＢＦ４（希釈無し）とした結果を示す図であり、図９が被検溶液を脱硫排水Ａ（１０倍希釈）とした結果を示す図であり、図１０が被検溶液を脱硫排水Ａ＋５ｐｐｍ ＢＦ４（希釈無し）とした結果を示す図である。 In addition, FIG. 7 to FIG. 10 show the results of three consecutive measurements (cleaning with pure water after the measurement is completed and executing the next measurement). FIG. 7 is a diagram showing the results when the test solution was desulfurized effluent A (no dilution), FIG. 8 is a diagram showing the results when the test solution was desulfurized effluent A + 5 ppm BF4 (no dilution), and FIG. It is a figure which shows the result which made the test solution the desulfurization waste water A (10 times dilution), and FIG. 10 is a figure which shows the result which made the test solution the desulfurization waste water A + 5 ppm BF4 (no dilution).
図７〜図１０に示されるいずれの結果においても、計測回数の増加と共にＢＦ４ −の計測値に正誤差が生じ、しかも計測回数の増加に伴って正誤差が大きくなる傾向が見られた。また、ＢＦ４ −を標準添加した被検溶液を計測した場合の方が、ＢＦ４ −の計測値の正誤差が拡大する傾向が見られた。 In any of the results shown in FIGS. 7 to 10, a positive error occurred in the measured value of BF 4 − with the increase in the number of measurements, and the positive error tended to increase with the increase in the number of measurements. Further, when the test solution to which BF 4 − was standardly added was measured, the positive error of the measured value of BF 4 − tended to increase.
以上の結果から、被検溶液の希釈によって、計測妨害成分の影響を低減して、ＢＦ４ −の計測値をより正確なものとできる効果が奏されることを確認できた。しかしながら、被検溶液の希釈によって、２回目以降のＢＦ４ −の計測値に正誤差が生じることを解消することはできなかった。 From the above results, it was confirmed that the effect of reducing the influence of the measurement interfering component and making the measured value of BF 4 − more accurate by dilution of the test solution was confirmed. However, it has not been possible to eliminate the occurrence of a positive error in the second and subsequent measurement values of BF 4 − due to dilution of the test solution.
（５）正誤差の解消に関する検討Ｂ
上記（２）において、プロセス排水を被検溶液として計測に供した後に、ＢＦ４ −標準溶液をフローセル３内に流通させると、ＢＦ４ −の計測値の正誤差が減少して設定値に収束する傾向が見られた。そこで、計測終了後にＢＦ４ −標準溶液（１００ｐｐｍ）を流速５ｍＬ／ｍｉｎで７分以上フローセル３内に流通させ（以下、この処理をＢＦ４ −洗浄と呼ぶこともある）、１０倍希釈した脱硫排水Ａを被検溶液として３回連続計測した際のＢＦ４ −の計測値の正誤差の発生状況を検討した。また、比較試験として、ＢＦ４ −洗浄に替えて純水洗浄を行った場合についても検討した。結果を図１１に示す。尚、図１１において、右側が計測終了毎にＢＦ４ −洗浄を行った結果を示す図であり、左側が計測終了毎に純水洗浄を行った結果を示す図である。
(5) Study B on eliminating positive errors B
In the above (2), the process wastewater after being subjected to the measurement as a sample solution, BF 4 - convergence of the set value a positive error is reduced measured values - standard solutions when circulating in the flow cell 3, BF 4 The tendency to do was seen. Therefore, BF 4 after the end of the measurement - standard solution (100 ppm) was passed through the flow rate 5 mL / min at 7 minutes or more flow cell 3 (hereinafter, this process BF 4 - sometimes referred to as washing), desulfurized diluted 10-fold The occurrence of a positive error in the measured value of BF 4 − when the wastewater A was continuously measured three times as a test solution was examined. As a comparative test, BF 4 - was also examined when performing cleaning with pure water in place of washing. The results are shown in FIG. In FIG. 11, right BF 4 for each measurement end - a graph showing the results of wash is a diagram showing a result of the left side makes a pure water washing every measurement end.
図１１に示される結果から、ＢＦ４ −洗浄を行うことで、ＢＦ４ −の計測値の正誤差の発生をほぼ完全に抑えられることが明らかとなった。したがって、計測終了後のＢＦ４ −洗浄は、次回の計測において、ＢＦ４ −の計測値の正誤差の発生を解消する有効な手法であることが確かめられた。 From the results shown in FIG. 11, it has been clarified that the occurrence of a positive error in the measured value of BF 4 − can be almost completely suppressed by performing the BF 4 − cleaning. Therefore, after completion of measurement BF 4 - cleaning, in the next measurement, BF 4 - it was confirmed that an effective technique for the eliminating the occurrence of positive errors in measured values.
（６）計測妨害成分の特定
脱硫排水（Ａ、Ｂ）に含まれる計測妨害成分の特定を行った。
(6) Identification of measurement interference components Measurement interference components included in the desulfurization effluent (A, B) were identified.
以下の被検溶液について、計測終了毎にＢＦ４ −洗浄を行い３回連続で計測を実施した。
（ａ）脱硫排水Ａを１０倍希釈
（ｂ）脱硫排水Ａを陰イオン除去処理した後、１０倍希釈
（ｃ）脱硫排水Ａを有機物除去処理した後、１０倍希釈
The following test solutions, BF 4 for each end of the measurement - was carried out measuring washed 3 times successively carried out.
(A) Desulfurization effluent A is diluted 10 times (b) Desulfurization effluent A is anion-removed and then diluted 10 times (c) Desulfurization effluent A is subjected to organic matter removal and then diluted 10 times
また、以下の被検溶液について、計測終了毎にＢＦ４ −洗浄を行い３回連続で計測を実施した。但し、（ｅ）についてのみ、計測終了毎にＢＦ４ −洗浄した場合と純水洗浄した場合について検討を行った。
（ｄ）脱硫排水Ｂを１０倍希釈
（ｅ）脱硫排水Ｂを有機物除去処理した後、１０倍希釈
Moreover, the following test solutions, BF 4 for each end of the measurement - was carried out measuring washed 3 times successively carried out. However, BF 4 only for, for each measurement end (e) - was studied when washed with pure water when washing.
(D) 10-fold dilution of desulfurization wastewater B (e) 10-fold dilution after desulfurization drainage B is treated for organic matter removal
尚、陰イオン除去処理と有機物除去処理は、ジーエルサイエンス社製のイオンクロマトグラフィー向け前処理カートリッジＭｅｔａＳＥＰ（登録商標）ＩＣを用いて行った。陰イオン除去処理にはＭｅｔａＳＥＰ ＩＣ−ＭＡを用い、有機物除去処理にはＭｅｔａＳＥＰ ＩＣ−ＲＰを用いた。結果を表４に示す。 The anion removal treatment and the organic matter removal treatment were performed using a pretreatment cartridge MetaSEP (registered trademark) IC for ion chromatography manufactured by GL Sciences. MetaSEP IC-MA was used for the anion removal treatment, and MetaSEP IC-RP was used for the organic matter removal treatment. The results are shown in Table 4.
陰イオン除去処理を行った場合には、ＢＦ４ −濃度が著しく低くなった。このことから、陰イオン除去処理を行うと、ＢＦ４ −が除去されてしまうことが明らかとなった。 When performing an anion removing treatment, BF 4 - concentration significantly lower. From this, it has been clarified that BF 4 − is removed when the anion removal treatment is performed.
有機物除去処理を行った場合には、ＢＦ４ −洗浄を行った場合だけでなく、純水洗浄を行った場合にも、ＢＦ４ −計測値に正誤差が生じなかった。このことから、ＢＦ４ −計測値に正誤差を生じさせる要因が、被検溶液中の有機物であると考えられた。 When performing organics removal process, BF 4 - not only when performing the cleaning, even when subjected to pure water cleaning, BF 4 - positive error did not occur in the measurement value. Therefore, BF 4 - factors that cause positive errors in measured values were considered to be organic in a test solution.
そして、上記（５）において、計測終了毎にＢＦ４ −洗浄を行うことで、ＢＦ４ −の計測値の正誤差の発生を解消できることが示されたことから、ＢＦ４ −洗浄には、液体膜型ＢＦ４ −電極６の電極感応膜に付着（吸着）した有機物を除去する作用があり、この作用によって、計測妨害成分を排除して、ＢＦ４ −の計測値の正誤差の発生を解消できているものと考えられた。 Then, in the above (5), BF 4 for each measurement end - by performing washing, BF 4 - the generation of a positive error in the measurement value since it has been shown that can eliminate, BF 4 - to the washing liquid film type BF 4 - attached to the electrode sensitive membrane electrode 6 has the effect of removing (suction) organics, by the action, with the exclusion of measurement interfering components, BF 4 - eliminate the occurrence of the positive error of the measured value It was thought that it was made.
３（３ａ） 流通路（フローセル）
６ 液体膜型ＢＦ４ −電極
3 (3a) Flow path (flow cell)
6 Liquid membrane type BF 4 - electrode
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