JP2007161967A - Scavenging/detecting agent for high-valence metal ion - Google Patents
Scavenging/detecting agent for high-valence metal ion Download PDFInfo
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- JP2007161967A JP2007161967A JP2005363924A JP2005363924A JP2007161967A JP 2007161967 A JP2007161967 A JP 2007161967A JP 2005363924 A JP2005363924 A JP 2005363924A JP 2005363924 A JP2005363924 A JP 2005363924A JP 2007161967 A JP2007161967 A JP 2007161967A
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- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 32
- 230000002000 scavenging effect Effects 0.000 title abstract 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 15
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229920002678 cellulose Polymers 0.000 claims description 24
- 239000001913 cellulose Substances 0.000 claims description 24
- UBQYURCVBFRUQT-UHFFFAOYSA-N N-benzoyl-Ferrioxamine B Chemical compound CC(=O)N(O)CCCCCNC(=O)CCC(=O)N(O)CCCCCNC(=O)CCC(=O)N(O)CCCCCN UBQYURCVBFRUQT-UHFFFAOYSA-N 0.000 claims description 22
- 238000001514 detection method Methods 0.000 claims description 19
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 abstract description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 239000013522 chelant Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 235000009518 sodium iodide Nutrition 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000000589 Siderophore Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 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 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- RRUDCFGSUDOHDG-UHFFFAOYSA-N acetohydroxamic acid Chemical compound CC(O)=NO RRUDCFGSUDOHDG-UHFFFAOYSA-N 0.000 description 1
- 229960001171 acetohydroxamic acid Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VDEUYMSGMPQMIK-UHFFFAOYSA-N benzhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1 VDEUYMSGMPQMIK-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- -1 dissolved this Chemical compound 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 1
- OUDSFQBUEBFSPS-UHFFFAOYSA-N ethylenediaminetriacetic acid Chemical compound OC(=O)CNCCN(CC(O)=O)CC(O)=O OUDSFQBUEBFSPS-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- HBROZNQEVUILML-UHFFFAOYSA-N salicylhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1O HBROZNQEVUILML-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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- 230000000007 visual effect Effects 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本発明は、高原子価金属イオンを捕集・検出する捕集、検出剤に関するものである。さらに詳しくは、ヒドロキサム酸基を担体に導入し、例えば、バナジウム、鉄、チタン等の高原子価金属イオンを高価な分析機器を使用することなく、容易に捕集・検出できる捕集・検出剤に関するものである。 The present invention relates to a collection and detection agent for collecting and detecting high-valent metal ions. More specifically, a collecting / detecting agent that introduces a hydroxamic acid group into a carrier and can easily collect / detect high-valent metal ions such as vanadium, iron, and titanium without using an expensive analytical instrument. It is about.
河川や廃水等に含まれるカルシウム、マグネシウム、マンガン、鉄、銅、亜鉛等の金属イオンの除去あるいは有益金属イオンの捕捉にはイオン交換樹脂が広く利用されているが、低濃度の金属イオンを選択的に吸着する効果は必ずしも満足し得るものとは言えない。 Ion exchange resins are widely used to remove metal ions such as calcium, magnesium, manganese, iron, copper, and zinc contained in rivers and wastewater, or to capture beneficial metal ions. Select low-concentration metal ions. The effect of adsorption is not necessarily satisfactory.
一方、重金属イオンとの間で、キレートを形成してこれらを選択的に捕捉する性質を持ったキレート樹脂は、水処理分野での銅、亜鉛、ニッケル、コバルト、バナジウム等重金属イオンの除去や捕捉などに利用されている。その構造は、ジビニルベンゼン等の架橋剤によって形成された剛直な三次元構造の担体に、イミノジ酢酸、エチレンジアミン二酢酸、エチレンジアミン三酢酸、チオグリコール酸、チオリンゴ酸、リン酸等が導入されたものが一般的である。また、キレート樹脂に吸着された金属イオンの検出、濃度測定は、吸着金属を強酸、キレート剤、有機溶媒等で溶出し、その後、吸光光度計、蛍光分光器、原子吸光光度計などの高価な分析機器により行われることが多い。 On the other hand, chelate resins that have the property of selectively capturing these by forming chelates with heavy metal ions remove and capture heavy metal ions such as copper, zinc, nickel, cobalt, and vanadium in the water treatment field. It is used for such as. The structure is such that iminodiacetic acid, ethylenediaminediacetic acid, ethylenediaminetriacetic acid, thioglycolic acid, thiomalic acid, phosphoric acid, etc. are introduced into a rigid three-dimensional carrier formed by a crosslinking agent such as divinylbenzene. It is common. In addition, the detection and concentration measurement of metal ions adsorbed on the chelate resin are performed by eluting the adsorbed metal with a strong acid, a chelating agent, an organic solvent, etc. Often done with analytical instruments.
しかし、上記のイオン交換樹脂やキレート樹脂は、吸着対象となる金属イオンを含む試料溶液が弱酸性〜中性である場合において効率的に対象金属イオンを吸着するものであり、ｐＨ２以上の強酸下において、特に原子価が３以上の高原子価金属イオンを効率良く選択的に吸着することは困難であった。 However, the above ion exchange resin or chelate resin is one that efficiently adsorbs target metal ions when the sample solution containing the metal ions to be adsorbed is weakly acidic to neutral, and has a pH of 2 or higher. In particular, it is difficult to efficiently and selectively adsorb high-valent metal ions having a valence of 3 or more.
また、従来のキレート樹脂の大半は、上記したようにジビニルベンゼン等の架橋剤によって形成された剛直な三次元構造の担体を有するビーズ状の樹脂であるため、疎水性が高く、樹脂内部への金属イオンや再生剤の拡散速度が遅く、処理効率に問題がある。 In addition, most of the conventional chelate resins are bead-like resins having a rigid three-dimensional structure formed by a cross-linking agent such as divinylbenzene as described above. The diffusion rate of metal ions and regenerants is slow and there is a problem in processing efficiency.
更に、キレート樹脂に吸着された金属イオンの検出、濃度測定は、上記の通りであるため、コストや分析時間がかかる等の問題があった。
本発明は、媒体中に含まれる原子価が３以上の高原子価金属イオンを効率良く選択的に捕集し、かつ容易にその検出、濃度測定を行うことができる捕集・検出剤を提供することを目的とするものである。 The present invention provides a collection / detection agent capable of efficiently and selectively collecting high-valence metal ions having a valence of 3 or more contained in a medium, and easily detecting and measuring the concentration thereof. It is intended to do.
本発明者らは、ヒドロキサム酸基を有する化合物を導入した担体を捕集・検出剤として用いることで、媒体中に含まれる高原子価金属イオンを容易に捕集・検出できることを見出し、本発明を為すに至った。 The present inventors have found that a high-valent metal ion contained in a medium can be easily collected and detected by using a carrier into which a compound having a hydroxamic acid group is introduced as a collecting and detecting agent. I came to do it.
すなわち、本発明は、下記（１）〜（５）に記載の事項をその特徴とするものである。 That is, the present invention is characterized by the following items (1) to (5).
（１）ヒドロキサム酸基を有する化合物を担体に導入してなる原子価３以上の金属イオンの捕集・検出剤。 (1) An agent for collecting and detecting metal ions having a valence of 3 or more, wherein a compound having a hydroxamic acid group is introduced into a carrier.
（２）前記担体がセルロースである上記（１）記載の捕集・検出剤。 (2) The collection / detection agent according to (1), wherein the carrier is cellulose.
（３）捕集・検出対象の金属イオンを含む溶液のｐＨが２以下である上記（１）または（２）記載の捕集・検出剤。 (3) The collection / detection agent according to (1) or (2) above, wherein the pH of the solution containing the metal ions to be collected / detected is 2 or less.
（４）捕集・検出対象の金属イオンがバナジウムイオンである上記（１）〜（３）いずれかに記載の捕集・検出剤。 (4) The collection / detection agent according to any one of (1) to (3), wherein the metal ion to be collected / detected is vanadium ion.
（５）前記ヒドロキサム酸基を有する化合物がデスフェリオキサミンＢ（ＤＦＢ）である上記（１）〜（４）いずれかに記載の捕集・検出剤。 (5) The collection / detection agent according to any one of (1) to (4), wherein the compound having a hydroxamic acid group is desferrioxamine B (DFB).
本発明によれば、媒体中に含まれる原子価が３以上の高原子価金属イオンを効率良く選択的に捕集し、かつ容易にその検出、濃度測定を行うことができる捕集・検出剤を提供することが可能となる。 According to the present invention, a collection / detection agent capable of efficiently and selectively collecting a high-valence metal ion having a valence of 3 or more contained in a medium and easily detecting and measuring the concentration thereof. Can be provided.
以下、本発明の実施形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明の捕集・検出剤は、担体にヒドロキサム酸基を有する化合物を導入してなるものであることをその特徴とし、特に、チタン（ＩＶ）、バナジウム（Ｖ）、鉄（ＩＩＩ）、モリブデン（ＶＩ）、ニオブ（Ｖ）、タンタル（Ｖ）、ジルコニウム（ＩＶ）等の原子価３以上の高原子価金属イオンを効率良く選択的に捕集し、かつ容易にその検出、濃度測定を行うことができるものである。 The collection / detection agent of the present invention is characterized in that a compound having a hydroxamic acid group is introduced into a carrier, and in particular, titanium (IV), vanadium (V), iron (III), molybdenum. Efficiently and selectively collects high-valence metal ions having a valence of 3 or more such as (VI), niobium (V), tantalum (V), zirconium (IV), etc., and easily detects and measures the concentration. It is something that can be done.
ヒドロキサム酸基は、高原子価金属イオンをシデロホア構造でとらえるため、ｐＨ２以下の強酸性下でも安定な巻きつき型の錯体を形成し、高原子価金属イオンを捕集できる。また、ヒドロキサム酸基は、高原子価金属イオンを捕集すると発色する特性を持っているので発色の強度により濃度が分かるという特長がある。ヒドロキサム酸基を有する化合物としては、アセトヒドロキサム酸、サリチルヒドロキサム酸、ベンゾヒドロキサム酸、アミノベンゾジヒドロキサム酸、デスフェリオキサミンＢ（ＤＦＢ）等が挙げられる。シデロホア構造を取りやすくするために、１分子中に３個以上のヒドロキサム酸基を有するＤＦＢが好ましく、担体への導入を容易にするために、末端にＨ３Ｎ＋を持つＤＦＢがさらに好ましい。 Since the hydroxamic acid group captures a high-valent metal ion with a siderophore structure, it can form a stable wound-type complex even under strong acidity of pH 2 or lower, and can collect the high-valent metal ion. In addition, hydroxamic acid groups have the property of developing color when high-valent metal ions are collected, and thus have a feature that the concentration can be determined by the intensity of color development. Examples of the compound having a hydroxamic acid group include acetohydroxamic acid, salicylhydroxamic acid, benzohydroxamic acid, aminobenzodihydroxamic acid, desferrioxamine B (DFB), and the like. In order to facilitate the formation of a siderophore structure, a DFB having three or more hydroxamic acid groups in one molecule is preferable, and in order to facilitate introduction into a carrier, a DFB having a terminal H 3 N + is more preferable.
下記に好ましいＤＦＢの構造を示す。
担体としては、例えば、スチレン−ジビニルベンゼン、アクリレート、メタクリレート、ポリビニルアルコール、セルロース等、試料溶媒に溶解しないものならいずれでもよく、またこれに限定するものではない。しかし、金属イオンは水溶液試料に溶解していることが多いので、好ましくは親水性のアクリレート、メタクリレート、ポリビニルアルコール、セルロース等が好ましい。綿状や粉末状の分離剤、ろ紙、メンブラン化、試験紙などの形状に加工しやすい点からセルロースが特に好ましい。 As the carrier, for example, styrene-divinylbenzene, acrylate, methacrylate, polyvinyl alcohol, cellulose and the like which are not soluble in the sample solvent may be used, and the carrier is not limited thereto. However, since metal ions are often dissolved in an aqueous solution sample, hydrophilic acrylate, methacrylate, polyvinyl alcohol, cellulose and the like are preferable. Cellulose is particularly preferred because it can be easily processed into a cotton-like or powder-like separating agent, filter paper, membrane, test paper and the like.
次に、本発明の捕集・検出剤の作製方法を示す。ここでは、担体としてセルロースのろ紙を用い、ヒドロキサム酸基を有する化合物として上記ＤＦＢを用いた場合を示すが、本発明はこれに限定されるものではない。また、セルロースに対する一般的な化学修飾は、反応性の容易さから、酢酸セルロースやニトロセルロースなどの反応性の高いセルロース誘導体が利用されるが、これらのセルロース誘導体は、純粋なセルロースと化学的・物理的な物性が全く異なるため、紙、試験紙、インディケーター紙としての役割を果たさない。そこで、ここでは特にセルロースの特性を保持したまま、上記ＤＦＢを結合させる合成法を示す。すなわち、セルロースの水酸基の一部をクロライド化し、そのハロゲン化された部分にのみにＤＦＢを導入する方法である。 Next, a method for producing the collection / detection agent of the present invention will be described. Here, a case where cellulose filter paper is used as a carrier and the above DFB is used as a compound having a hydroxamic acid group is shown, but the present invention is not limited thereto. In addition, for general chemical modification to cellulose, highly reactive cellulose derivatives such as cellulose acetate and nitrocellulose are used because of their easy reactivity. These cellulose derivatives are chemically and purely cellulose. Since physical properties are completely different, it does not serve as paper, test paper, or indicator paper. Therefore, here, a synthesis method in which the DFB is bonded while maintaining the characteristics of cellulose in particular will be shown. That is, this is a method in which a part of the hydroxyl group of cellulose is chlorinated and DFB is introduced only into the halogenated part.
まず、セルロースの水酸基の一部をクロライド化するために、ろ紙（セルロース）をバイアルに入れ、溶媒を加えて十分に浸した後、塩化チオニルを加えて反応させる。ろ紙（セルロース）と塩化チオニル量比は、セルロース１ｇに対し、塩化チオニル６．１７×１０−４ｍｏｌ（セルロース中のグルコースユニット量）であることが望ましく、それより多い場合も、少ない場合も高原子価金属イオンの捕集量、特にバナジウムの捕集量が減少する傾向にある。ろ紙を浸す溶媒は、特に限定しないが、セルロースになじんで、塩化チオニルをよく溶解することからジメチルホルムアミド（ＤＭＦ）が望ましく、溶媒量は、２０〜２００ｍｌの範囲であることが望ましい。また、クロライド化の反応条件は、８０〜１００℃で、１〜３時間反応させることが望ましい。反応温度が８０℃未満であると、クロライド化が不十分となる恐れがあり、１００℃を超えると副反応が起き易くなる。また、反応時間が１時間未満の場合は、クロライド化が不十分となる恐れがあり、一方、３時間を超えてもクロライドの導入量はあまり変化しない。 First, in order to chlorinate a part of the hydroxyl groups of cellulose, filter paper (cellulose) is put in a vial, and after adding a solvent and sufficiently immersed, thionyl chloride is added and reacted. The ratio of the amount of filter paper (cellulose) and thionyl chloride is desirably 6.17 × 10 −4 mol of thionyl chloride (the amount of glucose units in cellulose) with respect to 1 g of cellulose. There is a tendency for the amount of valence metal ions collected, particularly the amount of vanadium collected, to decrease. The solvent in which the filter paper is soaked is not particularly limited, but dimethylformamide (DMF) is desirable because it is familiar with cellulose and dissolves thionyl chloride well, and the amount of solvent is desirably in the range of 20 to 200 ml. The reaction conditions for the chlorination are desirably 80 to 100 ° C. and the reaction is preferably performed for 1 to 3 hours. If the reaction temperature is less than 80 ° C., there is a risk that the chlorination will be insufficient, and if it exceeds 100 ° C., side reactions tend to occur. On the other hand, if the reaction time is less than 1 hour, the formation of chloride may be insufficient. On the other hand, even if the reaction time exceeds 3 hours, the amount of chloride introduced does not change much.
上記のようにしてろ紙をクロライド化した後に、すぐＤＦＢを反応させても良いが、その導入率を高くするには、予めヨウ化ナトリウムでクロルを置換しておくことが望ましい。この場合、上記で得たろ紙を取り出し、アセトンで十分に洗浄した後、これを、ヨウ化ナトリウム３．０×１０−５〜３．０×１０−３ｍｏｌ（／セルロース１ｇ）がアセトンに溶解した溶液中に３時間以上浸し、置換反応を行う。アセトンの量は１０〜１００ｍｌであることが望ましい。また、反応温度は、室温付近が良く、より高温条件ではアセトンが揮発してしまう恐れがある。 Although the DFB may be reacted immediately after the filter paper is chlorinated as described above, in order to increase the introduction rate, it is desirable to substitute chloro with sodium iodide in advance. In this case, extraction of filter paper obtained above, was thoroughly washed with acetone, dissolved this, sodium iodide 3.0 × 10 -5 ~3.0 × 10 -3 mol (/ cellulose 1g) is acetone Immerse it in the solution for 3 hours or more to perform the substitution reaction. The amount of acetone is desirably 10 to 100 ml. The reaction temperature is preferably near room temperature, and acetone may volatilize under higher temperature conditions.
一方、別バイアルに、ＤＦＢを溶媒に加えて加熱し、完全にＤＦＢを溶解させる。ここで用いる溶媒はピリジン等の塩基性溶媒であることが望ましく、ＤＭＦ、ジメチルスルホキシド（ＤＭＳＯ）では反応が進行しない。ＤＦＢ濃度は６．１７×１０−４ｍｏｌ（／セルロース１ｇ）以上必要で、６．１７×１０−４ｍｏｌ（／セルロース１ｇ）に満たない場合は高原子価金属イオンの捕集量、特にバナジウムの捕集量が減少する傾向にある。 Meanwhile, in a separate vial, DFB is added to the solvent and heated to completely dissolve the DFB. The solvent used here is preferably a basic solvent such as pyridine, and the reaction does not proceed with DMF or dimethyl sulfoxide (DMSO). DFB concentration required 6.17 × 10 -4 mol (/ cellulose 1g) above, 6.17 × 10 -4 mol (/ cellulose 1g) collection amount of high-valence metal ions if less than, in particular vanadium There is a tendency for the amount of collected to decrease.
ついで、上記ＤＦＢ・ピリジン溶液に、ヨウ化ナトリウムで処理したろ紙を添加し、８０〜１００℃で、２．５〜１２時間攪拌する。その後、ＤＦＢが導入されたセルロースろ紙をメタノールで十分に洗浄し、乾燥する。乾燥は、２０〜４０℃で８〜２４時間行うことが望ましい。 Next, filter paper treated with sodium iodide is added to the DFB / pyridine solution, and the mixture is stirred at 80 to 100 ° C. for 2.5 to 12 hours. Thereafter, the cellulose filter paper into which DFB is introduced is thoroughly washed with methanol and dried. The drying is desirably performed at 20 to 40 ° C. for 8 to 24 hours.
上記した方法に従えば、原子価が３以上の高原子価金属イオンを効率良く選択的に捕集し、容易に検出できる捕集・検出剤を作製することができ、特に、バナジウムをｐＨ２以下の強酸性下においても捕集・検出できる捕集・検出剤を作製することができる。 According to the above method, a high-valence metal ion having a valence of 3 or more can be efficiently and selectively collected, and a collection / detection agent that can be easily detected can be produced. It is possible to produce a collection / detection agent that can be collected / detected even under strong acidity.
以下、実施例により本発明の捕集・検出剤とその使用方法について具体的に説明するが、当該実施例によって本発明が制限されるものではない。 EXAMPLES Hereinafter, although the collection / detection agent of the present invention and the method of using the same will be described in detail with reference to examples, the present invention is not limited to the examples.
（実施例１）
＜捕集・検出剤の作製＞
ろ紙（セルロース）１ｇをバイアルに入れ、ＤＭＦ５０ｍｌを加えて十分に浸し、塩化チオニル６．１７×１０−４ｍｏｌを加えて９０℃で２時間反応させた。次に、クロライド化したろ紙を取り出し、アセトンで十分に洗浄した後、これを再びバイアルに入れて、ヨウ化ナトリウム１×１０−４ｍｏｌが溶解したアセトン５０ｍｌに３０℃で４時間浸した。一方、別バイアルにおいて、ＤＦＢ６．１７×１０−４ｍｏｌをピリジン５０ｍｌに加えて完全にＤＦＢを溶解させた。ついで、ＤＦＢ・ピリジン溶液に、ヨウ化ナトリウムで処理したろ紙を添加し、９０℃で３時間反応させた後、ろ紙を取り出し、メタノールで十分に洗浄し風乾することで、ＤＦＢが導入されたセルロースろ紙（捕集・検出剤）を作製した。
Example 1
<Production of collection / detection agent>
Put filter paper (cellulose) 1 g in a vial, fully immersed added 50 ml of DMF, was added thionyl chloride 6.17 × 10 -4 mol to 2 hours at 90 ° C.. Next, the chlorinated filter paper was taken out and thoroughly washed with acetone, and then again put in a vial and immersed in 50 ml of acetone in which 1 × 10 −4 mol of sodium iodide was dissolved at 30 ° C. for 4 hours. On the other hand, in another vial, 6.17 × 10 −4 mol of DFB was added to 50 ml of pyridine to completely dissolve DFB. Next, filter paper treated with sodium iodide is added to the DFB / pyridine solution, and after reacting at 90 ° C. for 3 hours, the filter paper is taken out, thoroughly washed with methanol, and air-dried, so that DFB is introduced into the cellulose. A filter paper (collecting / detecting agent) was prepared.
＜評価＞
原子価が３以上の高原子価金属イオン（バナジウムイオン）を含むサンプル溶液として、市販されている飲料用ミネラルウォーターを使用した。
<Evaluation>
Commercially available mineral water for beverages was used as a sample solution containing a high-valence metal ion (vanadium ion) having a valence of 3 or more.
まず、前処理として、サンプル溶液５００ｍＬに塩酸を数滴加えた後、蒸発により１０ｍＬ以下まで濃縮し、さらにこの溶液に塩酸を加えて、塩酸濃度が０．１ｍｏｌＬ−１になるように調整し、全量を１０ｍＬとした（５０倍濃縮、ｐＨ２）。ついで、この濃縮溶液に上記で作製したＤＦＢ−ろ紙（捕集・検出剤）を室温（２５℃）で５分間浸した後、これを取り出し、ＤＦＢ−ろ紙に捕集されたバナジウムイオン濃度を反射分光計を用いて測定した（測定波長：４８０ｎｍ、測定径：３×３ｍｍ、使用機器：日立製作所製２００−２０型）。その結果、捕集されたバナジウムの濃度は２．５ｐｐｍであった。また、同時に目視による比色測定でその濃度を評価したところ、２．５ｐｐｍとなり、反射分光計の測定値と一致した。なお、反射分光計による濃度測定では、バナジウムイオンの濃度が０、０．５、１、２．５、５、１０ｐｐｍの溶液に浸漬して取り出した各ＤＦＢ−ろ紙の吸光度を予め測定し作成した検量線と試料ろ紙の吸光度とからその濃度を算出した。また、比色測定では、上記と同様にして得た各ＤＦＢ−ろ紙の色を基準とし、これと試料ろ紙の色を目視で比較し判定した。 First, as a pretreatment, several drops of hydrochloric acid were added to 500 mL of the sample solution, and then concentrated to 10 mL or less by evaporation. Further, hydrochloric acid was added to this solution to adjust the hydrochloric acid concentration to 0.1 mol L −1 , The total volume was 10 mL (50-fold concentration, pH 2). Next, the DFB-filter paper (collecting / detecting agent) prepared above was immersed in this concentrated solution for 5 minutes at room temperature (25 ° C.), then taken out, and the vanadium ion concentration collected on the DFB-filter paper was reflected. Measurement was performed using a spectrometer (measurement wavelength: 480 nm, measurement diameter: 3 × 3 mm, equipment used: Hitachi Model 200-20). As a result, the concentration of the collected vanadium was 2.5 ppm. Moreover, when the density | concentration was evaluated by the colorimetric measurement by visual observation simultaneously, it became 2.5 ppm and corresponded with the measured value of a reflection spectrometer. In addition, in the density | concentration measurement by a reflection spectrometer, the light absorbency of each DFB-filter paper taken out by immersing in the solution whose vanadium ion density | concentration is 0, 0.5, 1, 2.5, 5, 10ppm was created beforehand The concentration was calculated from the calibration curve and the absorbance of the sample filter paper. Further, in the colorimetric measurement, the color of each DFB-filter paper obtained in the same manner as above was used as a reference, and this was compared with the color of the sample filter paper for judgment.
（比較例１）
イミノジ酢酸をアクリル樹脂に固定したカートリッジ（Ｉｎｅｒｔｓｅｐ ＭＥ１；ジーエルサイエンス社製）に、実施例１で用いたものと同じ濃縮溶液をカートリッジに通液後、超純水２０ｍｌで洗浄し、１Ｎ硝酸１ｍｌ（ｐＨ１以下）で溶出した。ついで、原子吸光光度法により溶出液中のバナジウムイオンの濃度を測定したところ、検出されなかった。
(Comparative Example 1)
The same concentrated solution used in Example 1 was passed through a cartridge in which iminodiacetic acid was fixed to an acrylic resin (Inertsep ME1; manufactured by GL Sciences Inc.), then washed with 20 ml of ultrapure water, and 1 ml of 1N nitric acid ( elution at pH 1 or less). Subsequently, when the concentration of vanadium ion in the eluate was measured by atomic absorption spectrophotometry, it was not detected.
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| JP2008214551A (en) * | 2007-03-06 | 2008-09-18 | Hitachi Chem Co Ltd | Collecting agent for high valent metal ion |
| JP2013523975A (en) * | 2010-04-06 | 2013-06-17 | ナルコ カンパニー | Metal capture polymer |
| JPWO2014038191A1 (en) * | 2012-09-04 | 2016-08-08 | アトナープ株式会社 | System and method for detecting metals in solution |
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