JPS6325603B2 - - Google Patents
Info
- Publication number
- JPS6325603B2 JPS6325603B2 JP10119184A JP10119184A JPS6325603B2 JP S6325603 B2 JPS6325603 B2 JP S6325603B2 JP 10119184 A JP10119184 A JP 10119184A JP 10119184 A JP10119184 A JP 10119184A JP S6325603 B2 JPS6325603 B2 JP S6325603B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- chelate
- reaction
- ethylamino
- chelate resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920005989 resin Polymers 0.000 claims description 45
- 239000011347 resin Substances 0.000 claims description 45
- 239000013522 chelant Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 5
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 claims description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 125000005843 halogen group Chemical group 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 2-[2-(2-pyridyl)-ethylamino]-ethylamino group Chemical group 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- IPWSANYYLVGECF-UHFFFAOYSA-N n'-(2-pyridin-2-ylethyl)ethane-1,2-diamine Chemical compound NCCNCCC1=CC=CC=N1 IPWSANYYLVGECF-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- SESSOVUNEZQNBV-UHFFFAOYSA-M sodium;2-bromoacetate Chemical compound [Na+].[O-]C(=O)CBr SESSOVUNEZQNBV-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDPAWGWELVVRCH-UHFFFAOYSA-N bromoacetic acid Chemical compound OC(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007265 chloromethylation reaction Methods 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
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、重金属イオンに対して優れた吸着能
を示す新規なキレート樹脂の製造方法、さらに詳
しくいえばキレート形成基としてＮ，N′−ビス
（カルボキシメチル）置換２−〔２−（２−ピリジ
ル）−エチルアミノ〕−エチルアミノ基をもつキレ
ート樹脂の製造方法に関するものである。
従来、産業廃水、鉱山廃水などの廃水からの有
害金属の除去、あるいはこれらの廃水や海水から
未利用資源としての重金属の回収が図られ、その
１つの方法としてキレート樹脂を用いる方法が提
案されている〔例えば「ケミカル・インダストリ
ー（Chem.Ind.）」、1975年、第634頁、及び同誌
1977年、第706頁参照〕。
そして、現在実用に供されているキレート樹脂
としては、アルキルポリアミン型、イミノ二酢酸
型などが知られているが、これらは多くの金属イ
オンに対し、優れた吸着能を有する反面、各金属
に対する吸着容量、選択性の点で必ずしも十分で
ないため、さらに改良が望まれている。
本発明者らは、このような実情に鑑み、従来の
キレート樹脂よりも、さらに優れた吸着容量と選
択性を備えたキレート樹脂を開発すべく鋭意研究
を重ねた結果、キレート形成基として、Ｎ，
N′−ビス（カルボキシメチル）置換２−〔２−
（２−ピリジル）−エチルアミノ〕−エチルアミノ
基を有するキレート樹脂とすることにより、その
目的を達成することを見出し、この知見に基づい
て本発明をなすに至つた。
すなわち、本発明は、式
で示される２−〔２−（２−ピリジル）−エチルア
ミノ〕−エチルアミノ基をもつ樹脂に、上記置換
基中のアミノ窒素原子１ｇ原子当り２ｇ分子以上
のモノハロゲノ酢酸塩を反応させることを特徴と
する、式
で示されるＮ，N′−ビス（カルボキシメチル）
置換２−〔２−（２−ピリジル）−エチルアミノ〕−
エチルアミノ基をもつキレート樹脂の製造方法を
提供するものである。
本発明方法の原料として用いられる、前記式
（）の置換基をもつ樹脂は、文献未載の物質で
あつて、例えばハロゲン原子をもつ樹脂に、式
で示される化合物を反応させることによつて製造
することができる。
この際用いられるハロゲン原子をもつ樹脂は、
基本分子鎖に直接ハロゲン原子が結合しているも
のであつてもよいし、またペンダント基中にハロ
ゲン原子をもつものであつてもよい。このような
ハロゲン原子をもつ樹脂としては、例えばポリ塩
化ビニル、ポリ塩化ビニリデンのようなハロゲン
化オレフインの重合体、ポリエチレン、ポリプロ
ピレン、ポリスチレンのような重合体のハロゲン
化物などを挙げることができる。また、これらの
重合体を形成する単量体と他のエチレン系不飽和
単量体との共重合体であつてもよい。特に好まし
いのは、ゲル型又は巨大網目状ポリスチレン−ジ
ビニルベンゼン共重合体クロルメチル化した樹脂
である。
また、このハロゲン原子をもつ樹脂と反応させ
るＮ−〔２−（２−ピリジル）−エチル〕−エチレン
ジアミンは既知の化合物であり、例えば「インオ
ーガニツク・ケミストリー（Inorg.Chem.）」、第
３巻、第881頁（1964年）に記載されている方法
によつて製造することができる。
このアミンはキレート形成に有効な多座配位子
であり、また末端に芳香族性を持つピリジン環を
有していることにより、ハロゲン含有樹脂と反応
する際に高分子鎖間あるいは高分子鎖内の架橋反
応が著しく抑制されるという利点をもつている。
ハロゲン原子をもつ樹脂と上記のアミンとの反
応は、溶媒中で該樹脂のハロゲン１ｇ原子に対し
て１ｇ分子以上のアミンを用いて行われるが、反
応で生成される塩酸を除去するために、２〜５ｇ
分子のピリジルアルキルアミンを用いるので有利
である。この際の溶媒としては、水、メチルアル
コール、エチルアルコール、プロピルアルコー
ル、テトラヒドロフラン、ジオキサン、ベンゼ
ン、トルエン、Ｎ，Ｎ−ジメチルホルムアミド、
Ｎ，Ｎ−ジメチルスルホキシドなどが用いられ
る。特に反応温度との関係でジオキサンが好まし
い。反応の温度としては90〜110℃の範囲が用い
られる。上記温度以上では、原料アミンの熱分解
反応あるいはハロゲン含有樹脂の脱ハロゲン反応
が起るし、また上記温度以下では反応率が低下
し、いずれの場合も得られた反応生成物の金属イ
オン吸着能が低下するので好ましくない。反応の
時間は通常１時間以上であるが、反応時間が短い
と、反応率が低下するので12〜48時間が適当であ
る。
本発明方法においては、このようにして得た樹
脂に、モノハロゲノ酢酸塩例えばモノクロル酢酸
ナトリウム又はモノブロモ酢酸ナトリウムを反応
させてアミノポリカルボン酸型キレート樹脂を製
造する。この反応は、樹脂中に含まれるアミノ窒
素原子１ｇ原子に対して１ｇ分子以上好ましくは
２〜４ｇ分子のモノハロゲノ酢酸塩を水溶液の形
で加えることによつて行われる。このモノハロゲ
ノ酢酸塩としては反応温度を低くする関係上、反
応性の高いモノブロモ酢酸ナトリウムが好まし
い。反応温度としては、10〜60℃の範囲内で選ば
れ、反応時間は通常24〜48時間の範囲で十分であ
る。
このようにして得られた生成物は、洗浄、乾燥
したのち、そのままキレート樹脂として使用する
ことができる。
本発明により得られるキレート樹脂は、モリブ
デン（）、バナジウム（）、コバルト（）、
ニツケル（）、銅（）などと安定な錯体を形
成するので、これらの金属の分離、回収用として
好適である。
本発明により得られるキレート樹脂は、従来の
ものに比して極めて優れた金属イオン吸着能と、
選択性を有しており、各種廃水、鉱内水、海水等
から金属イオンを吸着採取するのに有効であり、
再生繰り返し使用においてもほとんど樹脂吸着能
に低下が見られないという利点を有する。
次に実施例により、さらに詳細に説明する。
参考例
スチレンと２重量％のジビニルベンゼンとから
成るゲル型共重合体（200〜400メツシユ）を、公
知の方法〔ジヤーナル・オブ・ケミカル・ソサエ
テイ（J.Chem.Soc.）」、1953年、第4097頁〕に従
つてクロルメチル化して、塩素含有率20.82％
（5.8ｍmole／ｇ−乾燥樹脂）のクロルメチルポ
リスチレン樹脂を製造した。
次に、ジオキサン250ml中に前記のクロルメチ
ルポリスチレン17.3ｇとＮ−〔２−（２−ピリジ
ル）−エチル〕−エチレンジアミン66ｇを加え、
100℃で48時間かきまぜた。この反応生成物をろ
過し、水、ジオキサンで十分に洗浄し、乾燥する
ことにより、次の分析値を示す淡黄色樹脂22ｇを
得た。以下この樹脂をキレート樹脂Ａという。
元素分析値 Cl：2.29％、Ｎ：10.68％
配位子含有率 2.54ｍmole／ｇ−乾燥樹脂
実施例
モノブロモ酢酸54ｇを含む水溶液150mlに、氷
冷下、水酸化ナトリウム31ｇを含む水溶液150ml
を滴下した。滴下終了後、参考例で得た、キレー
ト樹脂A17ｇを加え室温で120時間かきまぜた。
次いで樹脂を取し、2M塩酸で洗浄した後、
液が中性になるまで十分に水洗し、乾燥し、次の
分析値を示す淡黄色樹脂20.7ｇを得た。（本樹脂
をキレート樹脂Ｂという）。
元素分析値 Cl：0.44％、Ｎ：8.46％
配位子含有率 2.01ｍmole／ｇ−乾燥樹脂
応用例 １
実施例で得たキレート樹脂Ｂ及び市販のイミノ
ジ酢酸型キレート樹脂C500mgを10ｍＭのモリブ
デン（）を含む1000ml水溶液に加え、所定のPH
に調整した。室温で３時間かきまぜた後、溶液を
分離し、樹脂に吸着されたモリブデン（）を
2M水酸化ナトリウムにより溶離した。この溶離
液を定量し、吸着量を求めた。第１表に樹脂１ｇ
当りの最大吸着量とその時のPHを示す。
The present invention relates to a method for producing a novel chelate resin that exhibits excellent adsorption ability for heavy metal ions, and more specifically, to a method for producing a novel chelate resin that exhibits excellent adsorption ability for heavy metal ions. The present invention relates to a method for producing a chelate resin having a pyridyl)-ethylamino]-ethylamino group. Conventionally, efforts have been made to remove harmful metals from wastewater such as industrial wastewater and mine wastewater, or to recover heavy metals as unused resources from these wastewaters and seawater, and a method using chelate resin has been proposed as one method. [For example, "Chem.Ind.", 1975, p. 634, and the same magazine]
1977, p. 706]. As chelate resins currently in practical use, alkyl polyamine type and iminodiacetic acid type are known, but while these have excellent adsorption ability for many metal ions, Since the adsorption capacity and selectivity are not necessarily sufficient, further improvements are desired. In view of these circumstances, the present inventors have conducted extensive research to develop a chelate resin with even better adsorption capacity and selectivity than conventional chelate resins. ，
N′-bis(carboxymethyl) substituted 2-[2-
It was discovered that the object could be achieved by using a chelate resin having a (2-pyridyl)-ethylamino]-ethylamino group, and based on this knowledge, the present invention was accomplished. That is, the present invention provides the formula A resin having a 2-[2-(2-pyridyl)-ethylamino]-ethylamino group represented by is reacted with 2 g or more molecules of monohalogenoacetate per 1 g of amino nitrogen atom in the above substituent. , the expression N,N'-bis(carboxymethyl) represented by
Substituted 2-[2-(2-pyridyl)-ethylamino]-
The present invention provides a method for producing a chelate resin having an ethylamino group. The resin having a substituent of the formula () used as a raw material in the method of the present invention is a substance not yet described in the literature, and for example, a resin having a halogen atom has the formula It can be produced by reacting the compounds shown in The resin with halogen atoms used at this time is
It may be one in which a halogen atom is directly bonded to the basic molecular chain, or it may be one having a halogen atom in a pendant group. Examples of such resins having halogen atoms include polymers of halogenated olefins such as polyvinyl chloride and polyvinylidene chloride, and halogenated polymers such as polyethylene, polypropylene, and polystyrene. It may also be a copolymer of the monomers forming these polymers and other ethylenically unsaturated monomers. Particularly preferred is a chloromethylated resin of gel type or macromesh polystyrene-divinylbenzene copolymer. In addition, N-[2-(2-pyridyl)-ethyl]-ethylenediamine, which is reacted with this resin having a halogen atom, is a known compound, for example, "Inorganic Chem." Vol., p. 881 (1964). This amine is a polydentate ligand that is effective for chelate formation, and because it has an aromatic pyridine ring at the end, it can be used between polymer chains or between polymer chains when reacting with a halogen-containing resin. This has the advantage that the cross-linking reaction within is significantly suppressed. The reaction between the resin having a halogen atom and the above-mentioned amine is carried out in a solvent using 1 g or more of amine molecules per 1 g of halogen atom of the resin, but in order to remove the hydrochloric acid produced in the reaction, 2-5g
It is advantageous to use molecular pyridylalkylamines. Solvents used in this case include water, methyl alcohol, ethyl alcohol, propyl alcohol, tetrahydrofuran, dioxane, benzene, toluene, N,N-dimethylformamide,
N,N-dimethyl sulfoxide and the like are used. Dioxane is particularly preferred in relation to the reaction temperature. The reaction temperature used is a range of 90 to 110°C. Above the above temperature, a thermal decomposition reaction of the raw material amine or a dehalogenation reaction of the halogen-containing resin occurs, and below the above temperature, the reaction rate decreases, and in either case, the metal ion adsorption capacity of the reaction product obtained This is not preferable because it reduces the The reaction time is usually 1 hour or more, but if the reaction time is short, the reaction rate will decrease, so 12 to 48 hours is appropriate. In the method of the present invention, the resin thus obtained is reacted with a monohalogenoacetate such as sodium monochloroacetate or sodium monobromoacetate to produce an aminopolycarboxylic acid type chelate resin. This reaction is carried out by adding 1 g or more preferably 2 to 4 g of monohalogenoacetate in the form of an aqueous solution per 1 g of amino nitrogen atoms contained in the resin. As the monohalogenoacetate, sodium monobromoacetate, which has high reactivity, is preferred in order to lower the reaction temperature. The reaction temperature is selected within the range of 10 to 60°C, and the reaction time is usually sufficient within the range of 24 to 48 hours. The product thus obtained can be used as it is as a chelate resin after being washed and dried. The chelate resin obtained by the present invention includes molybdenum (), vanadium (), cobalt (),
Since it forms stable complexes with nickel (), copper (), etc., it is suitable for separating and recovering these metals. The chelate resin obtained by the present invention has extremely superior metal ion adsorption ability compared to conventional ones,
It has selectivity and is effective in adsorbing and collecting metal ions from various wastewaters, mine water, seawater, etc.
It has the advantage that there is almost no decrease in resin adsorption capacity even after repeated reuse. Next, a more detailed explanation will be given with reference to Examples. Reference Example A gel-type copolymer (200 to 400 mesh) consisting of styrene and 2% by weight of divinylbenzene was prepared by a known method [Journal of Chemical Society (J.Chem.Soc.), 1953, Chloromethylation according to page 4097], chlorine content 20.82%
(5.8 mmole/g-dry resin) of chloromethyl polystyrene resin was produced. Next, 17.3 g of the above chloromethyl polystyrene and 66 g of N-[2-(2-pyridyl)-ethyl]-ethylenediamine were added to 250 ml of dioxane.
Stir at 100℃ for 48 hours. This reaction product was filtered, thoroughly washed with water and dioxane, and dried to obtain 22 g of a pale yellow resin having the following analytical values. This resin will be referred to as chelate resin A hereinafter. Elemental analysis values Cl: 2.29%, N: 10.68% Ligand content 2.54 mmole/g - Dry resin example 150 ml of an aqueous solution containing 54 g of monobromoacetic acid and 150 ml of an aqueous solution containing 31 g of sodium hydroxide under ice cooling
was dripped. After the addition was completed, 17 g of chelate resin A obtained in Reference Example was added and stirred at room temperature for 120 hours.
Next, the resin was removed and washed with 2M hydrochloric acid, and then
The solution was thoroughly washed with water until it became neutral and dried to obtain 20.7 g of a pale yellow resin having the following analytical values. (This resin is referred to as chelate resin B). Elemental analysis values Cl: 0.44%, N: 8.46% Ligand content 2.01 mmole/g - Dry resin application example 1 500 mg of chelate resin B obtained in Example and commercially available iminodiacetic acid type chelate resin C were mixed with 10 mM molybdenum () Add to 1000ml aqueous solution containing
Adjusted to. After stirring for 3 hours at room temperature, the solution was separated and the molybdenum () adsorbed on the resin was removed.
Eluted with 2M sodium hydroxide. This eluent was quantified to determine the amount of adsorption. Table 1 shows 1g of resin.
The maximum adsorption amount per unit and the pH at that time are shown.
【表】
応用例 ２
実施例で得たキレート樹脂Ｂ及び市販のイミノ
ジ酢酸型キレート樹脂Ｃのそれぞれ500mgを20ｍ
Ｍのバナジウム（）の水溶液100mlに加え、応
用例１と同様の方法でPHを変化させ樹脂への吸着
量を求めた。最大吸着量とその時のPHを第２表に
示す。[Table] Application example 2 500 mg each of chelate resin B obtained in Example and commercially available iminodiacetic acid type chelate resin C was added to 20 m
In addition to 100 ml of an aqueous solution of vanadium (M), the pH was changed in the same manner as in Application Example 1 to determine the amount of adsorption onto the resin. Table 2 shows the maximum adsorption amount and the pH at that time.
Claims (1)
エチルアミノ基をもつ樹脂に、該置換基中のアミ
ノ窒素原子１ｇ原子当り１ｇ分子以上のモノハロ
ゲノ酢酸塩を反応させることを特徴とするＮ，
N′−ビス（カルボキシメチル）置換２−〔２−
（２−ピリジル）−エチルアミノ〕−エチルアミノ
基をもつキレート樹脂の製造方法。[Claims] 1 2-[2-(2-pyridyl)-ethylamino]-
N, characterized in that a resin having an ethylamino group is reacted with 1 g or more of monohalogenoacetate per 1 g of amino nitrogen atoms in the substituent,
N′-bis(carboxymethyl) substituted 2-[2-
A method for producing a chelate resin having a (2-pyridyl)-ethylamino]-ethylamino group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10119184A JPS60123508A (en) | 1984-05-19 | 1984-05-19 | Production of pyridylalkylaminopolycarboxylic acid type chelate resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10119184A JPS60123508A (en) | 1984-05-19 | 1984-05-19 | Production of pyridylalkylaminopolycarboxylic acid type chelate resin |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14009082A Division JPS5939442B2 (en) | 1982-08-11 | 1982-08-11 | Manufacturing method of new chelate resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60123508A JPS60123508A (en) | 1985-07-02 |
| JPS6325603B2 true JPS6325603B2 (en) | 1988-05-26 |
Family
ID=14294061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10119184A Granted JPS60123508A (en) | 1984-05-19 | 1984-05-19 | Production of pyridylalkylaminopolycarboxylic acid type chelate resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60123508A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5017801B2 (en) * | 2005-05-25 | 2012-09-05 | 日立化成工業株式会社 | Chelating resin |
-
1984
- 1984-05-19 JP JP10119184A patent/JPS60123508A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60123508A (en) | 1985-07-02 |
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