JP3924617B2 - Highly sensitive measurement method for weakly basic ions by ion exclusion separation-conductivity enhancement system - Google Patents
Highly sensitive measurement method for weakly basic ions by ion exclusion separation-conductivity enhancement system Download PDFInfo
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- JP3924617B2 JP3924617B2 JP2003320284A JP2003320284A JP3924617B2 JP 3924617 B2 JP3924617 B2 JP 3924617B2 JP 2003320284 A JP2003320284 A JP 2003320284A JP 2003320284 A JP2003320284 A JP 2003320284A JP 3924617 B2 JP3924617 B2 JP 3924617B2
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- 150000002500 ions Chemical class 0.000 title claims description 64
- 230000007717 exclusion Effects 0.000 title claims description 26
- 238000000691 measurement method Methods 0.000 title description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 78
- -1 ammonium ions Chemical class 0.000 claims description 71
- 238000000926 separation method Methods 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000003957 anion exchange resin Substances 0.000 claims description 50
- 238000001514 detection method Methods 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 37
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 30
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 28
- 239000003729 cation exchange resin Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 230000002378 acidificating effect Effects 0.000 claims description 27
- 150000001768 cations Chemical class 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 23
- 238000005259 measurement Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000003480 eluent Substances 0.000 claims description 17
- 230000007613 environmental effect Effects 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 15
- 238000004086 separation measurement method Methods 0.000 claims description 15
- 150000004679 hydroxides Chemical class 0.000 claims description 11
- 230000035945 sensitivity Effects 0.000 claims description 11
- 150000001450 anions Chemical class 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 235000013305 food Nutrition 0.000 claims description 6
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002537 cosmetic Substances 0.000 claims description 5
- 239000012493 hydrazine sulfate Substances 0.000 claims description 5
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims description 5
- 238000012544 monitoring process Methods 0.000 claims description 5
- 230000008685 targeting Effects 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 150000003973 alkyl amines Chemical class 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 238000001032 ion-exclusion chromatography Methods 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 2
- 241000251468 Actinopterygii Species 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- DVHXJLRODLTJOD-UHFFFAOYSA-N aminoazanium;bromide Chemical compound Br.NN DVHXJLRODLTJOD-UHFFFAOYSA-N 0.000 claims description 2
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 claims description 2
- RAESLDWEUUSRLO-UHFFFAOYSA-O aminoazanium;nitrate Chemical compound [NH3+]N.[O-][N+]([O-])=O RAESLDWEUUSRLO-UHFFFAOYSA-O 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229940107816 ammonium iodide Drugs 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- XLVPCRSPMUNYAD-UHFFFAOYSA-N hydrazine;hydroiodide Chemical compound I.NN XLVPCRSPMUNYAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 235000013372 meat Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000013535 sea water Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 description 19
- 238000011088 calibration curve Methods 0.000 description 15
- 239000002585 base Substances 0.000 description 11
- 239000007785 strong electrolyte Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 238000004737 colorimetric analysis Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000002169 ethanolamines Chemical class 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000011896 sensitive detection Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PMUNIMVZCACZBB-UHFFFAOYSA-N 2-hydroxyethylazanium;chloride Chemical class Cl.NCCO PMUNIMVZCACZBB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Description
本発明は、溶離液として水を用い、弱塩基性陰イオン交換樹脂カラムのイオン排除作用により、共存する強塩基性陽イオン（ナトリウムやカリウムイオン）から弱塩基性成分（アンモニウム及びヒドラジンイオン等）を選択的に分離した後、イオン交換反応を利用することにより、その導電率増大効果によりｐｐｂオーダー以下の検出限界及び広範囲な検量線の直線性を示す計測方法を実現する弱塩基性イオンの分離計測方法に関するものである。
本発明は、例えば、ヒドラジンを分析対象試料とし、第１導電率増大カラムを硫酸イオン型強塩基性陰イオン交換樹脂とした場合、水酸化物イオン型弱塩基性陰イオン交換樹脂分離カラムにより、ヒドラジンイオンを水酸化ヒドラジンとしてイオン排除効果により分離後、それを第１導電率増大カラムである硫酸イオン型強塩基性陰イオン交換樹脂カラムにより硫酸ヒドラジンに変換し、次に第２導電率増大カラムである水素イオン型強酸性陽イオン交換樹脂カラムによって、高い極限イオン当量導電率を有する硫酸に変換し、検出するものである。
本発明は、従来の方法と比べ、弱塩基性イオンが約２〜４０倍の導電率検出器応答の増大と、約０．００１〜１００ｐｐｍの注入試料濃度における広範囲な検量線の直線性を示すものであり、更に、分離から検出までのプロセスが水のみで達成できることから、２次汚染を生じない無（低）公害かつ簡便な計測方法を提供するものでもある。
In the present invention, water is used as an eluent, and weak basic anions (sodium and potassium ions) to weak basic components (ammonium and hydrazine ions, etc.) due to ion exclusion of weak basic anion exchange resin columns. Separation of weakly basic ions by using ion exchange reaction after selective separation to realize a measurement method that shows the detection limit below ppb order and the linearity of a wide range of calibration curve due to its conductivity increase effect It relates to the measurement method.
In the present invention, for example, when hydrazine is an analysis target sample and the first conductivity increasing column is a sulfate ion type strongly basic anion exchange resin, a hydroxide ion type weak base anion exchange resin separation column is used. After separation of hydrazine ions as hydrazine hydroxide due to the ion exclusion effect, the hydrazine ions are converted to hydrazine sulfate by a sulfate ion type strongly basic anion exchange resin column which is a first conductivity increasing column, and then a second conductivity increasing column. The hydrogen ion type strongly acidic cation exchange resin column is converted into sulfuric acid having a high ultimate ion equivalent conductivity and detected.
The present invention shows a conductivity detector response increase of about 2-40 times for weakly basic ions and a broad calibration curve linearity at an injected sample concentration of about 0.001-100 ppm compared to conventional methods. Furthermore, since the process from separation to detection can be achieved only with water, it provides a non- (low) pollution and simple measurement method that does not cause secondary contamination.
ＪＩＳやＩＳＯなどの公定法によるアンモニウムイオンの計測は、主に比色法（非特許文献１）やイオン電極法などによって行われている。比色法の場合、反応試薬は有害なフェノール類を使用するのに加え、測定操作が煩雑で共存物の影響を受けやすい。また、イオン電極法では、強アルカリ条件（ｐＨ１２以上）においてアンモニウム透過性膜を用いているため、膜への透過率の変化などによる再現性に問題がある（非特許文献２）。従って、これらの方法は、無公害かつ高精度なアンモニウムイオンの計測には不向きである。
また、ヒドラジンは、ＮＨ2 ・ＮＨ2 の化学式で示される無機化合物であり、ボイラー給水の溶存酸素除去剤として用いられ、特に火力発電に使われるボイラー水は高度な水質管理が要求されている（非特許文献３）。近年では、産業・農業排水に含まれるヒドラジンの人体への悪影響が懸念されており、各分野でのヒドラジン計測の開発が要求されている（非特許文献４）。ヒドラジンの定量は、比色法（非特許文献５）、分光光度法（非特許文献６）、あるいは電位差滴定法（非特許文献７）等で行なわれている。いずれの方法も、選択的なヒドラジンの高感度計測を可能にするものの、それらの反応試薬が有害化学物質である場合が多く、測定廃液による２次汚染の危険性が伴う。
The measurement of ammonium ions by an official method such as JIS or ISO is mainly performed by a colorimetric method (Non-patent Document 1) or an ion electrode method. In the case of the colorimetric method, in addition to using harmful phenols, the reaction reagent is complicated and easily affected by coexisting substances. Further, in the ion electrode method, an ammonium permeable membrane is used under strong alkaline conditions (pH 12 or higher), and thus there is a problem in reproducibility due to a change in transmittance to the membrane (Non-patent Document 2). Therefore, these methods are unsuitable for pollution-free and highly accurate measurement of ammonium ions.
Hydrazine is an inorganic compound represented by the chemical formula NH 2 · NH 2 , and is used as a dissolved oxygen remover for boiler feed water. In particular, boiler water used for thermal power generation requires advanced water quality management ( Non-patent document 3). In recent years, there are concerns about the adverse effects of hydrazine contained in industrial and agricultural wastewater on the human body, and development of hydrazine measurement in each field is required (Non-Patent Document 4). Hydrazine is quantified by a colorimetric method (Non-patent document 5), a spectrophotometric method (Non-patent document 6), a potentiometric titration method (Non-patent document 7), or the like. Any of these methods enables selective high-sensitivity measurement of hydrazine, but these reaction reagents are often harmful chemical substances, and there is a risk of secondary contamination by measurement waste liquid.
以上を含め、いずれの化学物質を対象とした環境計測においても可能な限り無（低）公害な分析法の開発が重要であると考えられる。
特に、アンモニウムやエタノールアミン類などの弱塩基性成分の計測は、塩基性陰イオン交換樹脂を充填した分離カラムを用い、溶離液を水としたイオン排除作用に基づいたイオン排除型クロマトグラフィーを駆使して行われており、いくつかの報告例もある（非特許文献８−１０、１２）、この計測法の利点は、高濃度の強塩基性成分から選択的に分離し、更に、再現性の高い定量結果が得られ、溶離液が水であるため、計測後の廃液による２次汚染が最小限に抑制できることである。
その際の試料の検出は、電気伝導度検出器やＵＶ吸光検出を用いていることが多いが、いずれの弱塩基成分も検出感度が低く、検出限界が約０．１〜１０ｐｐｍと種々な実際試料に適用する上では高く、イオン排除型クロマトグラフィーでの重要な問題点であった。
Including the above, it is thought that it is important to develop as little (low) pollution-free analytical methods as possible in environmental measurement for any chemical substance.
In particular, weak basic components such as ammonium and ethanolamines are measured using a separation column packed with basic anion exchange resin and ion exclusion chromatography based on ion exclusion using water as the eluent. There are also some reports (Non-Patent Documents 8-10, 12). The advantage of this measurement method is that it is selectively separated from high-concentration strongly basic components, and further, reproducibility. Since the eluent is water, secondary contamination by waste liquid after measurement can be suppressed to a minimum.
In this case, the sample is often detected using an electrical conductivity detector or UV absorption detection. However, any weak base component has a low detection sensitivity and a detection limit of about 0.1 to 10 ppm. It was high in application to samples, and was an important problem in ion exclusion chromatography.
以前、田中らは、水酸化物イオン型強塩基性陰イオン交換樹脂を分離カラムとして用い、第１導電率増大カラムを塩化物イオン型強塩基性陰イオン交換樹脂、第２導電率増大カラムを水素イオン型強酸性陽イオン交換樹脂として、生物学的硝化―脱窒素処理工程水中のアンモニウムイオンを最終的に塩酸に変換した高感度検出を行っている（非特許文献２）。
しかし、水酸化物イオン型強塩基性陰イオン交換樹脂によってアンモニウムイオンとヒドラジンの分離を行った場合、図１で示すように、イオン排除効果が弱く分離が達成されないことがわかり、共存物の妨害を避けることができない。また、この手法での検出限界が約５００ｐｐｂであり、ボイラー水中の数十〜数百ｐｐｂオーダーのヒドラジンを精度よく検出することは困難である。
Previously, Tanaka et al. Used a hydroxide ion type strongly basic anion exchange resin as a separation column, a first conductivity increasing column as a chloride ion type strongly basic anion exchange resin, and a second conductivity increasing column. As a hydrogen ion type strongly acidic cation exchange resin, highly sensitive detection is performed by finally converting ammonium ions into water in biological nitrification-denitrogenation process water (Non-patent Document 2).
However, when ammonium ions and hydrazine are separated using a hydroxide ion type strongly basic anion exchange resin, as shown in FIG. 1, it can be seen that the ion exclusion effect is weak and the separation cannot be achieved. Cannot be avoided. Moreover, the detection limit by this method is about 500 ppb, and it is difficult to accurately detect hydrazine in the order of several tens to several hundreds ppb in boiler water.
また、分離カラムによるアンモニウムイオンのイオン排除分離の後に、陽イオン交換膜（サプレッサー）を接続することによって、イオン交換を利用しつつ最終的に塩酸に変換することによる導電率検出器応答の増大が試みられている（非特許文献１１）。
しかし、この手法は、検出器応答の増加に用いられる陽イオン交換膜の効果が、製品毎によって異なった結果を示す点が問題とされている。更に、導電率検出器によって得られる検量線の非直線性を示すことが一つの問題となっている（非特許文献１３、１４）。
In addition, by connecting a cation exchange membrane (suppressor) after ion exclusion separation of ammonium ions by a separation column, the conductivity detector response can be increased by finally converting to hydrochloric acid using ion exchange. Attempts have been made (Non-Patent Document 11).
However, this method is problematic in that the effect of the cation exchange membrane used to increase the detector response shows different results depending on the product. Furthermore, one problem is the non-linearity of the calibration curve obtained by the conductivity detector (Non-Patent Documents 13 and 14).
本発明は、はじめに分離カラムの選択により、環境水中に高濃度に共存する強塩基性イオンから、イオン排除作用による選択的・高分解能な弱塩基性イオンの分離を達成し、分離カラムの後に接続される導電率検出器応答増大カラムにより、各々分離された試料の高感度化を図る方法を提供することを目的とするものである。 The present invention first achieves separation of weakly basic ions selectively and with high resolution by ion exclusion from strong basic ions coexisting at high concentration in environmental water by selecting a separation column, and is connected after the separation column. It is an object of the present invention to provide a method for increasing the sensitivity of each separated sample by using a conductivity detector response increasing column.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）試料中のアンモニウム、ヒドラジン、アルカノールアミン及びアルキルアミンの弱塩基性イオンを対象とし、これらを選択的にかつ導電率検出応答を増大させて高感度に同時計測する導電率検出イオン排除型クロマトグラフィーであって、分離カラムとして水酸化物型の弱塩基性陰イオン交換樹脂カラム並びに溶離液として水を用い、弱塩基性イオンを水酸化物型としてイオン排除作用により他の共存陽イオンから分離した後、これらを強酸陰イオン型強塩基性陰イオン交換樹脂を充填した第１導電率検出増大カラム及び水素イオン型強酸性陽イオン交換樹脂を充填した第２導電率検出増大カラムにより強酸に変換して導電率を検出することを特徴とする弱塩基性イオンの分離計測方法。
（２）環境水試料中のアンモニウムイオン及びヒドラジンイオンを対象とし、弱塩基牲イオンを水酸化物としてイオン排除作用により共存陽イオンから分離した後、塩化物イオン型強塩基性陰イオン交換樹脂を充填した第１導電率検出増大カラムにより塩化アンモニウム及び塩化ヒドラジンに変換し、水素イオン型強酸性陽イオン交換樹脂を充填した第２導電率検出増大カラムにより共に塩酸に変換して導電率を検出する、前記（１）に記載の分離計測方法。
（３）環境水試料中のアンモニウムイオン及びヒドラジンイオンを対象とし、弱塩基性イオンを水酸化物としてイオン排除作用により共存陽イオンから分離した後、硝酸イオン型強塩基性陰イオン交換樹脂を充填した第１導電率検出増大カラムにより硝酸アンモニウム及び硝酸ヒドラジンに変換し、水素イオン型強酸性陽イオン交換樹脂を充填した第２導電率検出増大カラムにより共に硝酸に変換して導電率を検出する、前記（１）に記載の分離計測方法。
（４）環境水試料中のアンモニウムイオン及びヒドラジンイオンを対象とし、弱塩基牲イオンを水酸化物としてイオン排除作用により共存陽イオンから分離した後、臭化物イオン型強塩基性陰イオン交換樹脂を充填した第１導電率検出増大カラムにより臭化アンモニウム及び臭化ヒドラジンに変換し、水素イオン型強酸性陽イオン交換樹脂を充填した第２導電率検出増大カラムにより臭化水素に変換して導電率を検出する、前記（１）に記載の分離計測方法。
（５）環境水試料中のアンモニウムイオン及びヒドラジンイオンを対象とし、弱塩基牲イオンを水酸化物としてイオン排除作用により共存陽イオンから分離した後、ヨウ化物イオン型強塩基性陰イオン交換樹脂を充填した第１導電率検出増大カラムによりヨウ化アンモニウム及びヨウ化ヒドラジンに変換し、水素イオン型強酸性陽イオン交換樹脂を充填した第２導電率検出増大カラムによりヨウ化水素に変換して導電率を検出する、前記（１）に記載の分離計測方法。
（６）ボイラー水中のヒドラジンイオンを対象とし、ヒドラジンイオンを水酸化ヒドラジンとしてイオン排除作用により他の共存陽イオンから選択的に分離した後、これを硫酸イオン型強塩基性陰イオン交換樹脂を充填した第１導電率増大カラムにより硫酸ヒドラジンに変換し、水素イオン型強酸性陽イオン交換樹脂を充填した第２導電率検出増大カラムにより硫酸に変換して導電率を検出する、前記（１）に記載の分離計測方法。
（７）雨水・河川水及び海水中のアンモニウムイオンを対象とし、アンモニウムイオンを水酸化アンモニウムとしてイオン排除作用により他の共存陽イオンから選択的に分離した後、これを硫酸イオン型強塩基性陰イオン交換樹脂を充填した第１導電率増大カラムにより硫酸アンモニウムに変換し、水素イオン型強酸性陽イオン交換樹脂を充填した第２導電率検出増大カラムにより硫酸に変換して導電率を検出する、前記（１）に記載の分離計測方法。
（８）肉及び魚を含めた生鮮食品の腐食状態をモニターするためのアンモニウムイオン及びモノ−、ジ−、トリメチルアミンを対象とし、これらを水酸化物としてイオン排除作用により他の共存陽イオンから選択的に分離した後、これらを硫酸イオン型強塩基性陰イオン交換樹脂を充填した第１導電率増大カラムと水素イオン型強酸性陽イオン交換樹脂を充填した第２導電率検出増大カラムにより硫酸に変換して導電率を検出する、前記（１）に記載の分離計測方法。
（９）食品、化粧品又は薬品中のモノ−、ジ−、トリエタノールアミンを対象とし、これらを水酸化物としてイオン排除作用により他の共存陽イオンから選択的に分離した後、これらを硫酸イオン型強塩基性陰イオン交換樹脂を充填した第１導電率増大カラムと水素イオン型強酸性陽イオン交換樹脂を充填した第２導電率検出増大カラムにより硫酸に変換して導電率を検出する、請求項１に記載の分離計測方法。
The present invention for solving the above-described problems comprises the following technical means.
(1) Ammonium in the sample, and hydrazine, directed to weakly basic ion alkanolamines and alkylamine emissions, they selectively and conductivity detection ion exclusion for simultaneous measurement with high sensitivity by increasing the conductivity detector response met chromatography using water as the weakly basic anion exchange resin column and eluent of hydroxide type, a weakly basic ion from other coexisting cations by ion exclusion act as a hydroxide type as a separation column After separation, these are converted into strong acids by the first conductivity detection increasing column packed with a strong acid anion type strongly basic anion exchange resin and the second conductivity detection increasing column packed with a hydrogen ion type strongly acidic cation exchange resin. A method for separating and measuring weakly basic ions, comprising converting and detecting conductivity.
(2) Targeting ammonium ions and hydrazine ions in environmental water samples, using weakly basic ions as hydroxides and separating them from the coexisting cations by ion exclusion, then using a chloride ion type strongly basic anion exchange resin Converted to ammonium chloride and hydrazine chloride by packed first conductivity detection increasing column, and converted to hydrochloric acid by second conductivity detection increasing column packed with hydrogen ion type strongly acidic cation exchange resin to detect conductivity The separation measurement method according to (1).
(3) directed to ammonium ions and hydrazine ions environmental water samples, after separation from the coexisting cations by ion exclusion effect a weakly basic ion as a hydroxide, filling the nitrate ion type strongly basic anion exchange resin Converted to ammonium nitrate and hydrazine nitrate by the first conductivity detection increasing column, and converted to nitric acid by the second conductivity detection increasing column filled with a hydrogen ion type strongly acidic cation exchange resin to detect conductivity. The separation measurement method according to (1).
(4) Targeting ammonium ions and hydrazine ions in environmental water samples, using weakly basic ions as hydroxides, separating them from coexisting cations by ion exclusion, and then filling with bromide ion type strongly basic anion exchange resin The first conductivity detection increasing column converts to ammonium bromide and hydrazine bromide, and the second conductivity detection increasing column packed with hydrogen ion type strongly acidic cation exchange resin converts to hydrogen bromide. The separation measurement method according to (1), wherein detection is performed.
(5) Ammonium ions and hydrazine ions in environmental water samples are targeted, and weakly basic ions as hydroxides are separated from coexisting cations by ion exclusion, and then an iodide ion type strongly basic anion exchange resin is used. Conversion to ammonium iodide and hydrazine iodide by the first conductivity detection increasing column packed, and conversion to hydrogen iodide by the second conductivity detection increasing column packed with the hydrogen ion type strongly acidic cation exchange resin The separation measurement method according to (1), wherein:
(6) For hydrazine ions in boiler water, hydrazine ions are selectively separated from other coexisting cations by ionic exclusion as hydrazine hydroxide, and then filled with sulfate ion type strongly basic anion exchange resin The first conductivity increasing column converts to hydrazine sulfate, and the second conductivity detection increasing column packed with hydrogen ion type strongly acidic cation exchange resin converts to sulfuric acid to detect conductivity. The separation measurement method described.
(7) Ammonium ions in rainwater, river water, and seawater are targeted, and ammonium ions are converted to ammonium hydroxide and selectively separated from other coexisting cations by ion-exclusion. The first conductivity increasing column packed with ion exchange resin is converted to ammonium sulfate, and the second conductivity detection increasing column packed with hydrogen ion type strongly acidic cation exchange resin is converted to sulfuric acid to detect conductivity. The separation measurement method according to (1).
(8) Ammonium ions and mono-, di-, and trimethylamine for monitoring the corrosive state of fresh foods including meat and fish are selected as hydroxides and selected from other coexisting cations by ion exclusion. After separation, the first conductivity increasing column packed with sulfate ion type strongly basic anion exchange resin and the second conductivity detection increasing column packed with hydrogen ion type strongly acidic cation exchange resin were converted into sulfuric acid. The separation measurement method according to (1), wherein the conductivity is detected by conversion.
(9) Mono-, di-, and triethanolamine in foods , cosmetics, and medicines are targeted, and these are selectively separated from other coexisting cations by ion-exclusion action as hydroxides, and then these are sulfate ions Conversion to sulfuric acid by a first conductivity increasing column packed with a strongly basic anion exchange resin and a second conductivity detecting increasing column packed with a hydrogen ion strongly acidic cation exchange resin to detect conductivity Item 2. The separation measurement method according to Item 1.
次に、本発明について更に詳細に説明する。
本発明は、溶離液として水を用い、分離カラムとして水酸化物イオン型弱塩基性陰イオン交換樹脂を用い、弱塩基性イオンを選択的に分離した後、その分析試料を強酸イオン型強塩基性陰イオン交換樹脂を充填した第１導電率増大カラムと、水素イオン型の強酸性陽イオン交換樹脂を充填した第２導電率増大カラムを用いることにより、高い極限モル伝導率を有する強酸に変換させ、導電率検出器応答に対する高感度化を達成することを特徴とするものである。
Next, the present invention will be described in more detail.
In the present invention, water is used as an eluent, a hydroxide ion type weakly basic anion exchange resin is used as a separation column, and after weakly basic ions are selectively separated, an analysis sample thereof is a strong acid ion type strong base. Conversion to strong acid with high ultimate molar conductivity by using a first conductivity increasing column packed with a cationic anion exchange resin and a second conductivity increasing column packed with a hydrogen ion type strongly acidic cation exchange resin And achieving high sensitivity to the conductivity detector response.
本発明では、はじめに弱塩基性イオンのイオン排除分離の改善を行なうため、溶離液の種類やｐＨによってイオン排除効果の大きさを容易に制御しうる弱塩基性陰イオン交換樹脂分離カラムを適用している。
これは、水酸化物イオン型弱塩基陰イオン交換樹脂カラムにより、弱塩基性イオン試料を水酸化物に変換し、イオン排除効果を向上させる能力が、水酸化物イオン型強塩基性陰イオン交換樹脂カラムよりも優れているからである。
次に分離後の弱塩基性イオンの導電率検出器における感度増大の課題を解決するため、できる限り大きい極限モル伝導率を有する陰イオンを強塩基性陰イオン交換樹脂に吸着させ、充填したカラムを第１導電率増大カラムとし、分離カラムの直後に接続する。
In the present invention, in order to improve ion exclusion separation of weakly basic ions, a weakly basic anion exchange resin separation column that can easily control the magnitude of ion exclusion effect depending on the type and pH of the eluent is applied. ing.
This is a hydroxide ion type weak base anion exchange resin column, which has the ability to convert weak basic ion samples into hydroxides and improve the ion exclusion effect. This is because it is superior to the resin column.
Next, in order to solve the problem of increased sensitivity in the conductivity detector of weakly basic ions after separation, a column in which anions having the highest possible molar conductivity are adsorbed onto a strongly basic anion exchange resin and packed Is the first conductivity increasing column and is connected immediately after the separation column.
第１導電率増大カラムの効果は、水酸化物イオン型弱塩基性陰イオン交換樹脂カラムにより水酸化物型として分離された弱電解質成分である弱塩基性陰イオンを、イオン交換作用により、強電解質成分に変換することである。これは、弱電解質の導電率に対する低い検出器応答を、強電解質に変換することによって、その課題を克服するものである。
例えば、アンモニウムイオンを分析対象試料とした場合、分離カラムによって水酸化物アンモニウム（弱電解質）に変換され分離した後、第１導電率増大カラム（硫酸イオン型強塩基性陰イオン交換樹脂カラム）によって強電解質の硫酸アンモニウムに変換される。結果として、強電解質である硫酸アンモニウムは、良好な導電率検出器応答の増幅が得られる。
更に、導電率検出器応答の増大を実施するために、第１導電率増大カラムの直後に第２導電率増大カラム（水素イオン型強酸性陽イオン交換樹脂カラム）を接続する。この効果は、第１導電率増大カラムによって強電解質（例えば、硫酸アンモニウム）に変換された弱塩基試料の検出感度を上げるために、第２導電率増大カラムにより最大の陽イオンの極限モル伝導率を有する水素イオンに交換することにより、際立った検出器応答の強電解質（例えば、硫酸）に変換することができる。
The effect of the first conductivity increasing column is that the weak basic anion, which is a weak electrolyte component separated as a hydroxide type by the hydroxide ion type weak base anion exchange resin column, is strongly converted by the ion exchange action. It is to convert to an electrolyte component. This overcomes that challenge by converting the low detector response to the weak electrolyte conductivity into a strong electrolyte.
For example, when ammonium ion is used as a sample to be analyzed, it is converted into ammonium hydroxide (weak electrolyte) by a separation column and separated, and then the first conductivity increasing column (sulfuric acid ion type strongly basic anion exchange resin column) is used. Converted to strong electrolyte ammonium sulfate. As a result, ammonium sulfate, which is a strong electrolyte, provides a good conductivity detector response amplification.
Further, in order to increase the conductivity detector response, a second conductivity increasing column (hydrogen ion type strongly acidic cation exchange resin column) is connected immediately after the first conductivity increasing column. This effect is achieved by increasing the maximum cation molar conductivity of the second cation increased column to increase the detection sensitivity of weak base samples converted to strong electrolytes (eg, ammonium sulfate) by the first conductivity increasing column. By replacing it with hydrogen ions, it can be converted to a strong electrolyte (eg, sulfuric acid) with outstanding detector response.
このように、上述した効果は、アンモニウムイオンを含め、酸解離定数（ｐＫｂ）が３よりも大きい弱塩基性イオンであれば、他の共存陽イオン成分から分離され、更に従来法（非特許文献８−１０、１２）よりも、最低でも約２〜３倍以上の検出器応答の増大が可能となるものである。特に、ヒドラジン（ｐＫｂ＝５．７７）やトリエタノールアミン（ｐＫｂ＝６．２４）のような酸解離係数が大きい弱塩基性イオンは、他の弱塩基性イオンよりもきわめて高い値を示す。
このとき、第１導電率増大カラムである強塩基性陰イオン交換樹脂上に吸着させる陰イオンは、硫酸イオン、塩化物イオン、硝酸イオン、ヨウ化物イオン、臭化物イオンといった極限モル伝導率の高い強酸性陰イオンが好ましい。これは、分析対象試料である弱塩基性イオンを速やかに強電解質にし、最終的に強酸に変換させるために重要である。
As described above, the effects described above can be separated from other coexisting cation components as long as the acid dissociation constant (pKb) is larger than 3 including ammonium ions, and the conventional method (non-patent document). It is possible to increase the detector response at least about 2-3 times or more than 8-10, 12). In particular, weakly basic ions having a large acid dissociation coefficient, such as hydrazine (pKb = 5.77) and triethanolamine (pKb = 6.24), have extremely higher values than other weakly basic ions.
At this time, the anions adsorbed on the strongly basic anion exchange resin, which is the first conductivity increasing column, are strong acids having a high ultimate molar conductivity such as sulfate ions, chloride ions, nitrate ions, iodide ions and bromide ions. Sexual anions are preferred. This is important in order to quickly convert a weak basic ion, which is a sample to be analyzed, into a strong electrolyte and finally convert it into a strong acid.
そして、計測終了後の２次汚染の発生を最小限に抑えることについても、計測過程において水のみで実施することから、０．１ｍＬの注入試料以外はほとんど無公害である。
これにより、弱塩基性イオンの分離改善のみならず、各々の試料の広範囲な検量線の直線性（約０．００１〜１００ｐｐｍ）と、検出限界の拡大（約０．１ｐｐｂ）が示され、雨水中のアンモニウムイオン、ボイラー中のアンモニウムイオンとヒドラジンイオンの同時計測及び化粧品中のトリエタノールアミンの定量など、幅広い実際試料への適用を可能にするものである。
Further, minimizing the occurrence of secondary contamination after completion of measurement is carried out only with water in the measurement process, and therefore, there is almost no pollution except for the 0.1 mL injection sample.
This not only improves the separation of weakly basic ions, but also shows the linearity (about 0.001 to 100 ppm) of a wide range of calibration curves for each sample and the expansion of the detection limit (about 0.1 ppb). It enables application to a wide range of actual samples such as simultaneous measurement of ammonium ions in boilers, ammonium ions and hydrazine ions in boilers, and determination of triethanolamine in cosmetics.
本発明は、分離カラムだけを用いる従来法よりも、更に広範囲な検量線の直線性と、検出感度の増大が可能になり、ボイラー中に含まれる微量のヒドラジンイオンを共存するアンモニウムイオンを避けながら計測できる利点がある。
溶離液として水を用い、水酸化物イオン型弱塩基性陰イオン交換樹脂を充填した分離カラムを用いることによって、共存する強塩基性イオンからアンモニウムイオン、ヒドラジン、トリエタノールアミン及び各種弱塩基性イオンの分離を選択的に達成することができる。
分離カラムと導電率検出器の間に、高い極限イオン当量伝導率を有する陰イオンを吸着させた強塩基性陰イオン交換樹脂を充填したカラムを第１導電率増大カラムとし、水素イオン型強酸性陽イオン交換樹脂を充填したカラムを第２導電率増大カラムとすることによって、全ての塩基類に対し約２〜４０倍の導電率検出応答の増大が見られる。
The present invention makes it possible to increase the linearity of a broader calibration curve and the detection sensitivity than the conventional method using only a separation column, while avoiding ammonium ions coexisting with a trace amount of hydrazine ions contained in the boiler. There is an advantage that can be measured.
By using a separation column filled with hydroxide ion type weakly basic anion exchange resin using water as an eluent, ammonium ions, hydrazine, triethanolamine and various weakly basic ions can be used. Can be selectively achieved.
A column filled with a strongly basic anion exchange resin adsorbing an anion having a high ultimate ion equivalent conductivity between the separation column and the conductivity detector is a first conductivity increasing column, and a hydrogen ion type strongly acidic By using the column filled with the cation exchange resin as the second conductivity increasing column, the conductivity detection response is increased by about 2 to 40 times with respect to all the bases.
本法で用いられたカラムは全て１ｍｅｑ／ｍｌ以上の高交換容量を有するものであり、これらのカラムの寿命はかなり長いものと考えられる。本発明では、検量線作成において、０．００１−１００ｐｐｍまでの標準試料、５種類の雨水そして１種類のボイラー試料を計１００回以上カラムに注入したが、分離カラム及び２本の導電率増大カラムはいずれも再生処理することなく連続使用が可能である。
再生処理について、分離カラムは、導電率増大カラムを接続する前に、０．１Ｍ水酸化ナトリウムを１０〜３０分通液することによって再生が可能である。また、２本の導電率増大カラムの再生は、例えば、第１導電率増大カラムが硫酸イオン型強塩基性陰イオン交換樹脂カラムであり、第２導電率増大カラムが水素イオン型強酸性陽イオン交換樹脂カラムである場合は、２本の導電率増大カラムを繋げたまま、０．１Ｍの希硫酸を約１０分間通液するのみで簡単に再生が可能である。
All the columns used in this method have a high exchange capacity of 1 meq / ml or more, and the lifetime of these columns is considered to be considerably long. In the present invention, in preparing a calibration curve, a standard sample of up to 0.001-100 ppm, 5 types of rainwater, and 1 type of boiler sample were injected into the column a total of 100 times or more. However, a separation column and two conductivity increasing columns were used. Both can be used continuously without reprocessing.
Regarding the regeneration treatment, the separation column can be regenerated by passing 0.1 M sodium hydroxide for 10 to 30 minutes before connecting the conductivity increasing column. In addition, the regeneration of the two conductivity increasing columns is performed by, for example, the first conductivity increasing column being a sulfate ion type strongly basic anion exchange resin column and the second conductivity increasing column being a hydrogen ion type strongly acidic cation. In the case of an exchange resin column, it can be easily regenerated by simply passing 0.1 M dilute sulfuric acid for about 10 minutes while connecting the two conductivity increasing columns.
本システムにおいて計測された試料の検出限界は、弱塩基性成分全てに対し、１０ｐｂｂ以下であるため、環境から生体関連まで幅広い分野での実際試料に適用することが可能である。
ナトリウム、カリウム、カルシウムあるいはマグネシウムイオンなどの強塩基性成分は、相互の分離は達成されないものの、本発明を適用することによって、約１．５倍から２倍の範囲での導電率検出器応答の増大が可能である。
本発明は、分離カラムによって分離された試料が、２本の導電率増大カラムを通過した後も、その分離状態を保つことができる。
使用されるカラムの全体の長さを短くする（例えば、２０ｃｍ以下にする）ことによって、ポータブル型のイオンクロマトグラフにも導入することができ、オンサイトでの環境モニタリングが可能である。
Since the detection limit of the sample measured in this system is 10 pbb or less for all weakly basic components, it can be applied to actual samples in a wide range of fields, from the environment to biological subjects.
Although strongly basic components such as sodium, potassium, calcium or magnesium ions cannot be separated from each other, by applying the present invention, the conductivity detector response in the range of about 1.5 to 2 times is obtained. An increase is possible.
The present invention can maintain the separated state after the sample separated by the separation column passes through the two conductivity increasing columns.
By shortening the total length of the column used (for example, 20 cm or less), it can be introduced into a portable ion chromatograph, and on-site environmental monitoring is possible.
本発明により、（１）分離カラムだけを用いる従来法（非特許文献２、７−１２）よりも、更に広範囲な検量線の直線性と、検出感度の増大が示されることから、雨水、上水道、ボイラー水などに微量に含まれるアンモニウムイオンやヒドラジンイオンの同時定量や、河川、下水道、工業排水など多量に含まれるアンモニウムイオンの定量が可能となる、（２）化粧品や薬品などのｐＨ緩衝剤として用いられるエタノールアミン類、とりわけトリエタノールアミンの品質管理のための計測に対し高い適用能力を示す、（３）本発明は、複雑な前処理を必要としない簡便・迅速・高選択的な高感度測定法であり、種々な環境水中のアンモニウムイオンやヒドラジンイオンの簡便、迅速で選択的な分離計測を可能にし、従来の公定法（インドフェノール法やネスラー法等）のように複雑な操作や有害な試薬を使用することのない、無（低）公害な計測法である、という効果が奏される。 According to the present invention, (1) the linearity of a broader calibration curve and the increase in detection sensitivity are shown compared to the conventional method using only a separation column (Non-patent Documents 2 and 7-12). It enables simultaneous determination of ammonium ions and hydrazine ions contained in trace amounts in boiler water, etc., and determination of ammonium ions contained in large quantities in rivers, sewers, industrial effluents, etc. (2) pH buffering agents for cosmetics and medicines Show high applicability for measurement for quality control of ethanolamines, especially triethanolamine used as a base, (3) The present invention is simple, quick and highly selective without requiring complicated pretreatment This is a sensitivity measurement method that enables simple, rapid and selective separation and measurement of ammonium ions and hydrazine ions in various environmental waters. Without the use of complex operations or harmful reagents as Lumpur method or Nessler method), a free (low) pollution measurement method, the effect is exhibited that.
次に、実施例に基づいて本発明を具体的に説明するが、本発明は、以下の実施例によって何ら限定されるものではない。 EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.
本実施例では、分離カラムとして水酸化物イオン型弱塩基性陰イオン交換樹脂を充填したものを用い、第１導電率増大カラムとして硫酸イオン型強塩基性陰イオン交換樹脂カラムを用い、第２導電率増大カラムとして水素イオン型強酸性陽イオン交換樹脂カラムを用いた。
以下に、実験条件について述べる。
用いたイオンクロマトグラフは、ＣＭ−８０２０型電気伝導率検出器、ＤＰ−８０２０型送液ポンプ、ＣＯ−８０２０型カラム恒温槽及びＳＤ−８０２２型オンラインデガッサーで構成され、全て東ソー製のものである。また、得られたデータの解析・管理は、専用のＬＣ−８０２０−Ｍｏｄｅｌ ＩＩデータプロセッサーを用いて行った。試料注入量は１００μＬとし、分離カラム温度及び溶離液流速は、本法での最適条件を検討する上で適宜変化させた。
In this example, a separation column filled with a hydroxide ion type weakly basic anion exchange resin is used, and a sulfate ion type strongly basic anion exchange resin column is used as the first conductivity increasing column. A hydrogen ion type strongly acidic cation exchange resin column was used as the conductivity increasing column.
The experimental conditions are described below.
The ion chromatograph used was composed of CM-8020 type conductivity detector, DP-8020 type liquid feed pump, CO-8020 type column thermostat and SD-8022 type online degasser, all made by Tosoh. is there. The obtained data was analyzed and managed using a dedicated LC-8020-Model II data processor. The sample injection amount was 100 μL, and the separation column temperature and the eluent flow rate were appropriately changed in examining the optimum conditions in this method.
分離カラムは、ポリメタクリレートをマトリックスとする弱塩基性陰イオン交換樹脂ＴＳＫｇｅｌ ＤＥＡＥ−５ＰＷ（長さ７．５ｃｍ、内径７．８ｍｍ）を水酸化物イオン型として用いた。第１導電率増大カラムは、ポリジビニルベンゼンをマトリックスとする強塩基性陰イオン交換樹脂ＴＳＫｇｅｌ ＳＡＸ（長さ４．５ｃｍ、内径４．８ｍｍ）を硫酸イオン型として用い、第２導電率増大カラムは、ポリジビニルベンゼンをマトリックスとする強酸性陽イオン交換樹脂ＴＳＫｇｅｌ ＳＣＸ（長さ４．５ｃｍ、内径４．８ｍ）を水素イオン型として用いた。このシステムのフローシートを図２に示す。 For the separation column, a weakly basic anion exchange resin TSKgel DEAE-5PW (length 7.5 cm, inner diameter 7.8 mm) using polymethacrylate as a matrix was used as a hydroxide ion type. The first conductivity increasing column uses a strongly basic anion exchange resin TSKgel SAX (length 4.5 cm, inner diameter 4.8 mm) having polydivinylbenzene as a matrix as a sulfate ion type, and the second conductivity increasing column is A strongly acidic cation exchange resin TSKgel SCX (length 4.5 cm, inner diameter 4.8 m) using polydivinylbenzene as a matrix was used as a hydrogen ion type. A flow sheet of this system is shown in FIG.
図２のフローシートは、１は水溶離液、２は送液ポンプ（１ｍｌ／ｍｉｎ）、３は試料導入部（１００μｌ）、４は分離カラム（水酸化物イオン型弱塩基性陰イオン交換樹脂）、５は第１導電率増大カラム（硫酸イオン型強塩基性陰イオン交換樹脂）、６は第２導電率増大カラム（水素イオン型強酸性陽イオン交換樹脂）、７は導電率検出器、そして、８は記録計を示している。 2 is a water eluent, 2 is a liquid feed pump (1 ml / min), 3 is a sample introduction part (100 μl), 4 is a separation column (hydroxide ion type weakly basic anion exchange resin) ) 5 is a first conductivity increasing column (sulfate ion type strongly basic anion exchange resin), 6 is a second conductivity increasing column (hydrogen ion type strongly acidic cation exchange resin), 7 is a conductivity detector, Reference numeral 8 denotes a recorder.
標準試料として用いた試薬（全て和光純薬製のもの）は、目的に応じて適宜希釈して調製した。標準試薬は、ナトリウム、アンモニウム、ヒドラジン、アルキルアミン、エチレンジアミン、エタノールアミン類の塩化物をそれぞれ０．１Ｍ水溶液に調製し、適宜希釈して使用した。なお、溶離液及び標準試料に用いた水は、いずれもイオン交換後の蒸留水である。
ボイラー水試料は、ボイラー給水（東ソー株式会社（山口県周南市）において用いられる）から採取し、直ちに孔径０．２μｍのメンブランフィルターによってろ過後、分離カラム内に注入した。
Reagents used as standard samples (all manufactured by Wako Pure Chemical Industries, Ltd.) were prepared by diluting appropriately according to the purpose. As the standard reagents, sodium, ammonium, hydrazine, alkylamine, ethylenediamine, and ethanolamine chlorides were prepared in 0.1 M aqueous solutions, respectively, and diluted appropriately. The water used for the eluent and the standard sample are both distilled water after ion exchange.
A boiler water sample was collected from boiler feed water (used in Tosoh Corporation (Shunan City, Yamaguchi Prefecture)), immediately filtered through a membrane filter having a pore size of 0.2 μm, and then injected into a separation column.
以下に、実施結果について述べる。
図３は、分離カラムの後に接続されている第１及び第２導電率増大カラムの効果を検討するために、試料として１ｐｐｍのナトリウム、アンモニウム、ヒドラジンイオン水溶液を分離カラムに注入し、各々のカラムの直後で導電率をモニターし、得られたクロマトグラムを比較したものである。
図３（Ａ）で示されるように、水溶離液と分離カラムでの分離は、強塩基性陽イオンであるナトリウムイオン、弱塩基性陽イオンのアンモニウム及びヒドラジンイオンがイオン排除作用によって良好な分離を示した。このような分離挙動は、水酸化物イオン型弱塩基性陰イオン交換樹脂カラムを分離カラムとしてのみ達成されるものである。
しかしながら、分離カラムから溶出した水酸化アンモニウム及び水酸化ヒドラジンは弱電解質であるため、強電解質である水酸化ナトリウムよりもかなり低い導電率検出器応答を示していた。
The implementation results are described below.
FIG. 3 shows an example in which 1 ppm of sodium, ammonium, and hydrazine ion aqueous solutions are injected into the separation columns as samples in order to examine the effects of the first and second conductivity increasing columns connected after the separation columns. Immediately after, the conductivity was monitored, and the obtained chromatograms were compared.
As shown in FIG. 3 (A), the separation between the water eluent and the separation column is a good separation of the strong basic cation sodium ion, the weak basic cation ammonium and the hydrazine ion by the ion exclusion action. showed that. Such separation behavior is achieved only by using a hydroxide ion type weakly basic anion exchange resin column as a separation column.
However, since ammonium hydroxide and hydrazine hydroxide eluted from the separation column are weak electrolytes, they showed a much lower conductivity detector response than sodium hydroxide, which is a strong electrolyte.
第１導電率カラムの直後でモニターされたクロマトグラムでは、図３（Ｂ）に示されるように、ナトリウムイオンは０．４倍、アンモニウムイオンは０．９倍、そして、ヒドラジンイオンは６．４倍の検出器の増大が認められる。これは、水酸化ヒドラジンが強電解質である硫酸ヒドラジンに変換されたために解離度が増大し、検出器応答が増大したものである。一方、水酸化アンモニウムから変換された硫酸アンモニウムも強電解質であるが、その変換が十分になされなかったために減少し、更に、水酸化ナトリウムから変換された硫酸ナトリウムは弱電解質であるため、極限イオン当量導電率が減少したものである。 In the chromatogram monitored immediately after the first conductivity column, sodium ion was 0.4 times, ammonium ion was 0.9 times, and hydrazine ion was 6.4, as shown in FIG. A double detector increase is observed. This is because the degree of dissociation is increased because the hydrazine hydroxide is converted to hydrazine sulfate, which is a strong electrolyte, and the detector response is increased. On the other hand, ammonium sulfate converted from ammonium hydroxide is also a strong electrolyte, but it is decreased because the conversion is not sufficiently performed. Furthermore, since sodium sulfate converted from sodium hydroxide is a weak electrolyte, the ultimate ion equivalent is reduced. The conductivity is reduced.
第２導電率カラムの直後でモニターし、得られたクロマトグラムは、図３（Ｃ）で示されるように、硫酸アンモニム及び硫酸ヒドラジンが完全解離し、かつその陽イオン（水素イオン）が際立って大きな極限イオン当量伝導率を持つ硫酸に変換されるために、試料の検出器応答が際立って増大する。即ち、ヒドラジンイオンは水酸化ヒドラジンから硫酸への変換により２６．８倍の導電率増大が、アンモニウムイオンは水酸化アンモニウムから硫酸への変換により６．１倍の増大が得られる（表１も参照）。 As shown in FIG. 3C, the chromatogram obtained by monitoring immediately after the second conductivity column shows that ammonium sulfate and hydrazine sulfate are completely dissociated, and their cations (hydrogen ions) stand out. Due to the conversion to sulfuric acid with a large limiting ionic equivalent conductivity, the detector response of the sample is significantly increased. That is, hydrazine ions have a 26.8-fold increase in conductivity due to conversion from hydrazine hydroxide to sulfuric acid, and ammonium ions have a 6.1-fold increase due to conversion from ammonium hydroxide to sulfuric acid (see also Table 1). ).
本発明は、３本の異なったカラムを直列に連結させ、水溶離液により強塩基性のアルカリ金属・アルカリ土類金属からアンモニウム及びヒドラジンイオンを水酸化物として選択的に分離し、更に、各成分をイオン交換反応に基づく導電率増大カラムによって高感度に計測できる方法であることを認めた。
分離カラムから溶出した水酸化アンモニウム及び水酸化ヒドラジンは、その弱電解質性のために解離度が濃度の増大に伴って低下するため、導電率検出器によって得られた検量線は非直線性を示すことが知られている（非特許文献２）。また、これと同様な現象は、炭酸や脂肪酸などの弱酸（非特許文献１３、１４）並びに、脂肪族アミン類などの弱塩基（非特許文献９）の場合でも同じような傾向が見られ、弱電解質の導電率検出器の適応における一つの問題となっている。
In the present invention, three different columns are connected in series, and ammonium and hydrazine ions are selectively separated from the strongly basic alkali metal / alkaline earth metal as hydroxides by a water eluent. It was found that this method can measure the components with high sensitivity by using a conductivity increasing column based on ion exchange reaction.
The calibration curve obtained by the conductivity detector shows non-linearity because ammonium hydroxide and hydrazine hydroxide eluted from the separation column decrease with increasing concentration due to their weak electrolyte properties. It is known (Non-Patent Document 2). In addition, the same phenomenon is observed in the case of weak acids such as carbonic acid and fatty acids (Non-Patent Documents 13 and 14) and weak bases such as aliphatic amines (Non-Patent Document 9). This is one problem in the application of weak electrolyte conductivity detectors.
そこで、水溶離と分離カラムのみ用いた場合と、更に、イオン交換型導電率増大カラムを組み合わせた場合でのアンモニウムイオンとヒドラジンイオンの検量線を比較した。
図４で示すように、水酸化物として検出されたアンモニウム及びヒドラジンの検量線は、非直線性を示したが、第２導電率増大カラムの直後でモニターされたアンモニウム及びヒドラジンの検量線は、０．００１ｐｐｍから１００ｐｐｍの濃度範囲において良好な直線性を示すことができる。
この検量線の直線性は、第２導電率増大カラムによって、水酸化アンモニウム及び水酸化ヒドラジンが広い濃度範囲において直線性を示す強電解質の硫酸に変換されたために達成されたものである。このように、イオン交換樹脂を用いて、弱電解質を強電解質に変換して導電率によって検出する方法は、検量線の直線性の点でも有効な手段である。
Therefore, the calibration curves of ammonium ion and hydrazine ion were compared between the case where only the water elution and separation column were used and the case where the ion exchange type conductivity increasing column was further combined.
As shown in FIG. 4, the calibration curve for ammonium and hydrazine detected as hydroxide showed non-linearity, but the calibration curve for ammonium and hydrazine monitored immediately after the second conductivity increasing column was Good linearity can be exhibited in the concentration range of 0.001 ppm to 100 ppm.
This linearity of the calibration curve was achieved because the second conductivity increasing column converted ammonium hydroxide and hydrazine hydroxide into strong electrolyte sulfuric acid showing linearity in a wide concentration range. As described above, the method of detecting by the conductivity by converting the weak electrolyte to the strong electrolyte using the ion exchange resin is also an effective means in terms of the linearity of the calibration curve.
本発明の実施例として、工場（東ソー株式会社）の火力発電として用いられているボイラー水中のヒドラジンの定量に用いられた。このとき、サンプリングは、異なった４箇所で行なわれた（表２を参照）。 As an example of the present invention, it was used for quantification of hydrazine in boiler water used as thermal power generation in a factory (Tosoh Corporation). At this time, sampling was performed at four different locations (see Table 2).
図５は、０．２μｍメンブランフィルターでろ過後の実際試料のクロマトグラムを示す。特に試料２は、ｐＨ調整剤として添加したアンモニウムのピークが大きく検出されているにもかかわらず、ヒドラジンの単離したピークが検出されていた。本法から得られた結果、試料１は５４．５ｐｐｂ、そして、試料２は２４．２ｐｐｂであることがわかった。この結果は、工場で実際に行なわれている比色法での測定結果（試料１＝５５ｐｐｂ、試料２＝２４ｐｐｂ）と一致していることを示した。更に、その他のボイラー試料に関するヒドラジンの定量結果は、上記の試料を含め表２にまとめた。 FIG. 5 shows a chromatogram of an actual sample after filtration through a 0.2 μm membrane filter. In particular, in Sample 2, an isolated peak of hydrazine was detected although a large peak of ammonium added as a pH adjuster was detected. As a result obtained from this method, it was found that Sample 1 was 54.5 ppb, and Sample 2 was 24.2 ppb. This result showed that it was in agreement with the measurement result (sample 1 = 55 ppb, sample 2 = 24 ppb) by the colorimetric method actually performed in the factory. Furthermore, the quantification results of hydrazine for other boiler samples are summarized in Table 2 including the above samples.
硫酸としてモニターされたアンモニウム及びヒドラジンの検出限界は、Ｓ／Ｎ＝３において、各々５．７ｐｐｂ及び２．９ｐｐｂであり、この手法が高感度な方法であることを認めた。
本法で用いられたカラムは全て１ｍｅｑ／ｍｌ以上の高交換容量を有するものであり、これらのカラムの寿命はかなり長いものと考えられる。今回の実験では、検量線作成において、０．００１−１００ｐｐｍまでの標準試料並びに３種類のボイラー試料を計６０回カラムに注入したが、２種の導電率増大カラムはいずれも再生処理することなく連続使用が可能であった。
なお、２本の導電率増大カラムは、０．１Ｍあるいは１Ｍの硫酸を１０分間流通することによって同時に再生することができる。
The detection limits for ammonium and hydrazine monitored as sulfuric acid were 5.7 ppb and 2.9 ppb, respectively, at S / N = 3, which confirmed that this technique is a sensitive method.
All the columns used in this method have a high exchange capacity of 1 meq / ml or more, and the lifetime of these columns is considered to be considerably long. In this experiment, in preparing a calibration curve, a standard sample of up to 0.001-100 ppm and three types of boiler samples were injected into the column 60 times in total, but neither of the two types of conductivity increasing columns was regenerated. Continuous use was possible.
The two conductivity increasing columns can be simultaneously regenerated by flowing 0.1 M or 1 M sulfuric acid for 10 minutes.
本法における有用性を示すために、他の弱塩基性化合物への導電率増大カラムの効果を検討した。数種のアミン類を検討した結果、表１で示すように、酸解離定数（ｐＫｂ１）が最も高いトリエタノールアミンが、第２導電率増大カラム通過した後、４０倍を超える検出器応答の増大があることがわかった。他のアミン類に関しても、全て２倍以上の検出器応答の増大が認められた。このように、本法は、他の弱塩基性アミンの導電率検出にも対応可能であることがわかった。 In order to show the usefulness in this method, the effect of the conductivity increasing column on other weakly basic compounds was examined. As a result of studying several amines, as shown in Table 1, triethanolamine having the highest acid dissociation constant (pKb1) passed through the second conductivity increasing column, and the detector response increased by more than 40 times. I found out that For all other amines, an increase in detector response of more than 2 times was observed. Thus, it was found that this method can also be used for detecting the conductivity of other weakly basic amines.
本発明は、環境水中のアンモニウムイオン及びヒドラジンイオンなどの弱塩基性成分の高分解能な分離と導電率検出器に対する高感度な応答を同時に可能とするものである。そのため、次のような特徴と展開が挙げられる。
このシステムの大きな特徴として、一つ目は、水酸化物イオンを吸着した弱塩基性陰イオン交換樹脂カラムと水溶離液の組合せによって、強塩基性陽イオン、アンモニウムイオン、エチレンジアミン、ヒドラジン、ジエタノールアミン、トリエタノールアミンの順で完全分離が達成されることである。仮に上述以外の弱塩基性イオンが共存している場合でも、実際試料においては、これら全てのイオンが共存することはないため、特別な薬品を用いることなく、希釈や固形物除去の前処理のみで、分離カラムに注入でき、分離が達成される。
The present invention enables high-resolution separation of weakly basic components such as ammonium ions and hydrazine ions in environmental water and a highly sensitive response to a conductivity detector at the same time. Therefore, the following features and developments can be mentioned.
As a major feature of this system, the first is a combination of a weakly basic anion exchange resin column that adsorbs hydroxide ions and a water eluent, and thus a strongly basic cation, ammonium ion, ethylenediamine, hydrazine, diethanolamine, Complete separation is achieved in the order of triethanolamine. Even if weak basic ions other than those mentioned above coexist, in the actual sample, all these ions do not coexist, so only pretreatment for dilution and solid removal without using special chemicals. Can then be injected into the separation column and separation is achieved.
二つ目は、導電率検出増大カラムの調整が、硫酸や塩酸など大きな極限モル伝導率を有する陰イオンを含む酸を用いることによって簡単に処理できるため、特別な反応薬品の調製、特別なコーティングなどのスキームを必要とせず、扱うイオンクロマト装置が上記と異なったとしても対応が可能である。
三つ目は、カラムの長さにあまり依存することなく、目的物質の分離及び高感度検出が可能であるため、更に、カラム内に充填されるゲルの表面積が大きくなれば、カラムの全長が数ｃｍの大変コンパクトな形態になるため、環境計測におけるオンサイト化のためのポータブル型弱塩基イオンモニターへの進展が十分に期待できる。
Second, the adjustment of the conductivity detection enhancement column can be easily handled by using an acid containing anions with a large limiting molar conductivity, such as sulfuric acid and hydrochloric acid. Therefore, even if the ion chromatograph apparatus to be handled is different from the above, it is possible to cope with it.
Third, because the target substance can be separated and sensitive detection is possible without much depending on the length of the column, if the surface area of the gel packed in the column is increased, the total length of the column is reduced. Since it becomes a very compact form of several centimeters, progress toward portable weak base ion monitor for on-site environmental measurement can be fully expected.
これにより、本発明は、生活排水、河川水、雨水などの環境水中やボイラー水中のアンモニウムイオン及びヒドラジンイオンの同時計測、生鮮食品の腐敗原因物質でアルキルアミン類のモニター、あるいは食品や化粧品などに添加されているエタノールアミン類の品質管理などを簡便かつ高精度に計測情報を処理することが可能となり、種々な実際試料に対応した新規なモニタリングシステムになりうる高いポテンシャルを有するものである。 また、本法によって、近年話題になっている光触媒材料による有害なアルキルアミン類からアンモニウムイオン、そしてアンモニウムイオンの酸化分解過程による濃度の減少を同時に観察することが可能である。
最後に、本システムにおいての溶離液が脱イオン化した蒸留水でのみであることから、２次汚染を極力低減させた計測法として大変有力である。また、本研究の特徴を生かし、環境計測システムの分野だけでなく、無（低）公害なものつくりを目指す新しい研究分野（グリーンケミストリー）における「２次汚染防止のための安全管理システム」へ展開することによって、一層の利用拡大が期待できるものと捉えている。
As a result, the present invention is applicable to simultaneous measurement of ammonium ion and hydrazine ion in environmental water such as domestic wastewater, river water, rainwater, and boiler water, monitor of alkylamines as a causative substance of fresh food, or food and cosmetics. Measurement information can be easily and accurately processed for quality control of added ethanolamines, and has a high potential to be a new monitoring system corresponding to various actual samples. In addition, by this method, it is possible to simultaneously observe a decrease in concentration of harmful ammonium ions from ammonium ions and oxidative decomposition of ammonium ions due to photocatalytic materials that have become a hot topic in recent years.
Finally, since the eluent in this system is only deionized distilled water, it is very effective as a measurement method that reduces secondary contamination as much as possible. Utilizing the characteristics of this research, it will be deployed not only in the field of environmental measurement systems, but also in a new research field (green chemistry) that aims to create non- (polluted) pollution. By doing so, we believe that further expansion of usage can be expected.
（図２の符号）
１ 水溶離液
２ ポンプ（１ｍｌ／ｍｉｎ）
３ 試料導入部（１００μｌ）
４ 分離カラム（水酸化物イオン型弱塩基性陰イオン交換樹脂）
５ 第１導電率増大カラム（硫酸イオン型強塩基性陰イオン交換樹脂）
６ 第２導電率増大カラム（水素イオン型強酸性陽イオン交換樹脂）
７ 導電率検出器
８ 記録計
(Reference in FIG. 2)
1 Water eluent 2 Pump (1 ml / min)
3 Sample introduction part (100 μl)
4 Separation column (hydroxide ion type weakly basic anion exchange resin)
5 First conductivity increasing column (sulfate ion type strongly basic anion exchange resin)
6 Second conductivity increasing column (hydrogen ion type strongly acidic cation exchange resin)
7 Conductivity detector 8 Recorder
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