JP2006326465A - Chelating resin - Google Patents
Chelating resin Download PDFInfo
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- JP2006326465A JP2006326465A JP2005152535A JP2005152535A JP2006326465A JP 2006326465 A JP2006326465 A JP 2006326465A JP 2005152535 A JP2005152535 A JP 2005152535A JP 2005152535 A JP2005152535 A JP 2005152535A JP 2006326465 A JP2006326465 A JP 2006326465A
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- amine
- containing polymer
- acetic acid
- chelate resin
- halogenated acetic
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Abstract
Description
本発明は有害金属、重金属イオンを効率良く捕捉できるキレート樹脂に関する。該キレート樹脂は、金属イオンの吸着量が多く、かつ、脱着速度が速いので、廃液処理用の他分析用前処理剤にも用いることが出来る。 The present invention relates to a chelate resin capable of efficiently capturing harmful metal and heavy metal ions. Since the chelate resin has a large amount of adsorption of metal ions and has a high desorption rate, it can be used as a pretreatment agent for analysis other than waste liquid treatment.
キレート樹脂とは、２つ以上の官能基を有し，キレート結合により特定のイオンを選択的吸着する。キレート結合にあずかる官能基の組み合わせが（Ｎ，Ｏ）の場合を例にとると、一般的には、クロロメチル化したスチレンとジビニルベンゼンとの共重合体を処理してイミノジ酢酸型，イミノジプロピオン酸型が作製される。ナトリウムイオン，カルシウムイオン，マグネシウムイオン等が多量に存在し、普通のイオン交換だと実用上使用できない廃水中の重金属の選択除去に用いられる（化学大辞典） （１２９６の化学商品）。担体に導入する イミノジ酢酸（ＩＤＡ），イミノプロピオン酸等のイミノジカルボン酸は、金属の選択性も小さく、吸着量が十分でない等の課題がある。従って，従来のイミノジ酢酸（ＩＤＡ）型は、マトリックスの多い試料中の金属を濃縮する目的としては必ずしもベストではない。
また、銅等とキレ−ト化率の高いアミノトリ酢酸（ＮＴＡ），エチレンジアミンテトラ酢酸等は、試薬が高価で実用化できないという問題もあった。
The chelate resin has two or more functional groups and selectively adsorbs specific ions by chelate bonds. For example, in the case where the combination of functional groups involved in the chelate bond is (N, O), generally, a copolymer of chloromethylated styrene and divinylbenzene is treated to give an iminodiacetic acid type, iminodiamine. A propionic acid form is created. A large amount of sodium ions, calcium ions, magnesium ions, etc. are used to selectively remove heavy metals in wastewater that cannot be used practically by ordinary ion exchange (Daily Chemical Dictionary) (1296 chemical products). Iminodicarboxylic acids such as iminodiacetic acid (IDA) and iminopropionic acid to be introduced into the carrier have problems such as low metal selectivity and insufficient adsorption. Therefore, the conventional iminodiacetic acid (IDA) type is not always the best for the purpose of concentrating metals in a sample having a large matrix.
Further, aminotriacetic acid (NTA), ethylenediaminetetraacetic acid and the like, which have a high chelating rate with copper or the like, have a problem that the reagents are expensive and cannot be put into practical use.
本発明は，アミノトリ酢酸（ＮＴＡ），エチレンジアミンテトラ酢酸等の高価なイミノジカルボン酸等の試薬を用いず、有害金属、重金属イオン等の金属の吸着性が高いキレート樹脂を提供することを目的とした。 An object of the present invention is to provide a chelate resin having high adsorptivity for metals such as harmful metals and heavy metal ions without using expensive reagents such as aminotriacetic acid (NTA) and ethylenediaminetetraacetic acid. .
本発明者らは、アミノトリ酢酸（ＮＴＡ）、エチレンジアミンテトラ酢酸等の高価なイミノジカルボン酸等の試薬を用いず、アミン含有ポリマに安価なハロゲン化酢酸を反応させることにより、金属の吸着性が高いキレート樹脂ができることを見出し、本発明に達した。
本発明は次の発明に関する。
＜１＞ アミン含有ポリマにハロゲン化酢酸を反応させて製造されるキレート樹脂。
＜２＞ アミン含有ポリマが、ポリアルキルアミンまたはポリアリルアミンである＜１＞記載のキレート樹脂。
＜３＞ ハロゲン化酢酸をアミン含有ポリマのアミン量に対し、１０〜９０％導入したことを特徴とする＜１＞記載のキレート樹脂。
The present inventors have a high metal adsorptivity by reacting an amine-containing polymer with an inexpensive halogenated acetic acid without using an expensive reagent such as aminotriacetic acid (NTA) or ethylenediaminetetraacetic acid. The present inventors have found that a chelate resin can be formed and have reached the present invention.
The present invention relates to the following inventions.
<1> A chelate resin produced by reacting an amine-containing polymer with a halogenated acetic acid.
<2> The chelate resin according to <1>, wherein the amine-containing polymer is polyalkylamine or polyallylamine.
<3> The chelate resin according to <1>, wherein 10 to 90% of the halogenated acetic acid is introduced with respect to the amine amount of the amine-containing polymer.
本発明のキレート樹脂を用いれば、有害金属、重金属イオン等の金属を効率良く捕捉することが容易となる。 When the chelate resin of the present invention is used, it becomes easy to efficiently capture metals such as harmful metals and heavy metal ions.
本発明は、アミン含有ポリマ（例えば、式（２）、（３））にハロゲン化酢酸を反応させてできるキレート樹脂に関するものであり、詳しくは、ポリアリルアミン、ポリアルキルアミン等の担体のポリアミン鎖をハロゲン化酢酸等でカルボキシメチル化し、ポリアミン−ポリカルボン酸型キレート樹脂を製造して得られる。 The present invention relates to a chelate resin formed by reacting an amine-containing polymer (for example, formulas (2) and (3)) with a halogenated acetic acid, and more specifically, a polyamine chain of a carrier such as polyallylamine or polyalkylamine. Is obtained by producing a polyamine-polycarboxylic acid type chelate resin by carboxymethylation with halogenated acetic acid or the like.
以下、本発明の実施形態を詳細に説明する。
アミン含有ポリマは，ハロゲン化酢酸が反応できるものであれば特に限定しないが、ポリアリルアミン、ポリアルキルアミン、ポリアクリルアミンが望ましい。
上記アミン含有ポリマに、ハロゲン化酢酸でカルボキシメチル化することにより、キレート樹脂が作製できる。ハロゲン化酢酸としては、クロロ酢酸，ブロモ酢酸等が挙げられる。
ハロゲン化酢酸は、すべてのアミンに導入する必要はない。導入するハロゲン化酢酸の量は１０〜９０％、好ましくは３０〜７０％がよい。ハロゲン化酢酸の導入量が多いと、酸性下におけるアミンへのプロトネ−ションによる排除効果が起きにくくなり、アルカリ土類金属などを捕捉するようになり、ハロゲン化酢酸の導入量が少ないと、イオン排除効果は高くなるが、キレート効果は低くなる。
Hereinafter, embodiments of the present invention will be described in detail.
The amine-containing polymer is not particularly limited as long as it can react with halogenated acetic acid, but polyallylamine, polyalkylamine, and polyacrylamine are preferable.
A chelate resin can be prepared by carboxymethylating the amine-containing polymer with a halogenated acetic acid. Examples of the halogenated acetic acid include chloroacetic acid and bromoacetic acid.
Halogenated acetic acid need not be introduced into every amine. The amount of halogenated acetic acid to be introduced is 10 to 90%, preferably 30 to 70%. If the amount of halogenated acetic acid introduced is large, the elimination effect due to the amine amine under acidic conditions becomes difficult to occur, and alkaline earth metals are captured. If the amount of halogenated acetic acid introduced is small, The exclusion effect is high, but the chelation effect is low.
以下実施例により本発明を説明する。 The following examples illustrate the invention.
実施例１
（ａ）担体の製造
１Ｍ ＮａＯＨ水溶液１００ｍｌにクロロ酢酸ナトリウム５．８ｇを溶解し、ポリアリルアミン（ＰＡＡ−０１：日東紡株式会社製）１１３ｇを入れ、４０℃で５時間反応させ、キレート樹脂を得た。
（ｂ）評価
重金属イオン（Ｃｕ、Ｆｅ）で汚染されたヘキサン１００ｇに本発明の実施例１で得たキレート樹脂を２ｇ分散させ、攪拌羽根を用いて５００ｒｐｍで３０分間攪拌した。その後、分液ロートに超純水５００ｍＬをともに入れてよく振り混ぜ、ヘキサン層に含まれるＣｕ，Ｆｅを原子吸光フレーム法にて測定した。
Example 1
(A) Production of carrier In 100 ml of 1M NaOH aqueous solution, 5.8 g of sodium chloroacetate was dissolved, 113 g of polyallylamine (PAA-01: manufactured by Nittobo Co., Ltd.) was added, and reacted at 40 ° C. for 5 hours to obtain a chelate resin. It was.
(B) Evaluation 2 g of the chelate resin obtained in Example 1 of the present invention was dispersed in 100 g of hexane contaminated with heavy metal ions (Cu, Fe), and stirred at 500 rpm for 30 minutes using a stirring blade. Thereafter, 500 mL of ultrapure water was placed in a separatory funnel and shaken well, and Cu and Fe contained in the hexane layer were measured by an atomic absorption flame method.
実施例２
（ａ）担体の製造
１Ｍ ＮａＯＨ水溶液１００ｍｌにクロロ酢酸ナトリウム５．８ｇを溶解し、ポリアリルアミン（ＰＡＡ−Ｄ−１１ＨＣｌ：日東紡株式会社製）８０ｇを入れ、４０℃で５時間反応させ、キレート樹脂を得た。
（ｂ）評価
重金属イオン（Ｃｕ、Ｆｅ）で汚染されたヘキサン１００ｇに本発明の実施例２で得たキレート樹脂を２ｇ分散させ、攪拌羽根を用いて５００ｒｐｍで３０分間攪拌した。その後、分液ロートに超純水５００ｍＬをともに入れてよく振り混ぜ、ヘキサン層に含まれるＣｕ，Ｆｅを原子吸光フレーム法にて測定した。
実施例１，２で測定したＣｕ、Ｆｅの濃度を表１に纏めて示した。汚染されたヘキサン中には、銅イオンが１００ｐｐｂ含まれていたが、本発明のキレート樹脂を用いることにより、検出装置の検出限界まで未検出（ＮＤ）であった。同様に、１６０ｐｐｂ含まれていた鉄イオンも、本発明のキレート樹脂を用いることにより未検出となった。
上記のように、本発明のキレート樹脂は、金属の吸着能に優れている。
Example 2
(A) Preparation of carrier 5.8 g of sodium chloroacetate was dissolved in 100 ml of 1M NaOH aqueous solution, and 80 g of polyallylamine (PAA-D-11HCl: manufactured by Nittobo Co., Ltd.) was added and reacted at 40 ° C. for 5 hours to give a chelate resin Got.
(B) Evaluation 2 g of the chelate resin obtained in Example 2 of the present invention was dispersed in 100 g of hexane contaminated with heavy metal ions (Cu, Fe), and stirred at 500 rpm for 30 minutes using a stirring blade. Thereafter, 500 mL of ultrapure water was placed in a separatory funnel and shaken well, and Cu and Fe contained in the hexane layer were measured by an atomic absorption flame method.
The concentrations of Cu and Fe measured in Examples 1 and 2 are summarized in Table 1. The contaminated hexane contained 100 ppb of copper ions, but by using the chelate resin of the present invention, it was not detected (ND) to the detection limit of the detection device. Similarly, the iron ion contained in 160 ppb was not detected by using the chelate resin of the present invention.
As described above, the chelate resin of the present invention is excellent in metal adsorption ability.
Claims (3)
The chelate resin according to claim 1, wherein 10 to 90% of halogenated acetic acid is introduced with respect to the amine amount of the amine-containing polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005152535A JP2006326465A (en) | 2005-05-25 | 2005-05-25 | Chelating resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005152535A JP2006326465A (en) | 2005-05-25 | 2005-05-25 | Chelating resin |
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| JP2006326465A true JP2006326465A (en) | 2006-12-07 |
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| JP2005152535A Pending JP2006326465A (en) | 2005-05-25 | 2005-05-25 | Chelating resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013121863A1 (en) * | 2012-02-14 | 2013-08-22 | 日本フイルコン株式会社 | Metal-adsorbing gel and adsorbent supporting metal-adsorbing gel |
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2005
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013121863A1 (en) * | 2012-02-14 | 2013-08-22 | 日本フイルコン株式会社 | Metal-adsorbing gel and adsorbent supporting metal-adsorbing gel |
| JP2013166090A (en) * | 2012-02-14 | 2013-08-29 | Nippon Filcon Co Ltd | Gel-like metal adsorbing material and gel-like metal adsorbing material supported adsorbent |
| US9592489B2 (en) | 2012-02-14 | 2017-03-14 | Nippon Filcon Co., Limited | Metal-adsorbing gel and adsorbent supporting metal-adsorbing gel |
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