JP3582874B2 - Metal scavenger - Google Patents

Description

【００１１】
【化５】

【００１２】
【化６】

【００１３】
本発明の金属捕集剤は、１級アミノ基や２級アミノ基を２個以上有するポリアミノ化合物の窒素原子に結合した活性水素原子と置換した置換基として、上記化４で示される（ａ）群の官能基、化５で示される（ｂ）群の官能基の２種の官能基と、上記化６で示される（ｃ）群の官能基、（ｄ）群の官能基の少なくとも１種とを導入することにより得られる。上記ポリアミノ化合物としては、ポリアミン類や、これらポリアミン類とエピハロヒドリンとが重縮合した重縮合ポリアミン、ポリアミン類と下記化７で示される化合物との共重合体、或いは下記化８や化９で示される単位を１分子中に２以上含有する化合物等が挙げられるが、１分子中に１級アミノ基や２級アミノ基を２個以上有する化合物であればこれらに限定されることなく使用可能である。
【００１５】
【化７】

【００１６】
【化８】

【００１７】
【化９】

【００１８】
上記ポリアミン類としては、例えばエチレンジアミン、プロピレンジアミン、ブチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、ジプロピレンジアミン、ジブチレントリアミン、トリエチレンテトラミン、トリプロピレンテトラミン、トリブチレンテトラミン、テトラエチレンペンタミン、テトラプロピレンペンタミン、テトラブチレンペンタミン、ペンタエチレンヘキサミン、イミノビスプロピルアミン、モノメチルアミノプロピルアミン、メチルイミノビスプロピルアミン等の脂肪族ポリアミン；フェニレンジアミン、ｏ−，ｍ−，ｐ−キシリレンジアミン、３，５−ジアミノクロロベンゼン等の芳香族ポリアミン；１，３−ビス（アミノメチル）シクロヘキサン等のシクロアルカン系ポリアミン；１−アミノエチルピペラジン、ピペラジン等のピペラジン類；ポリエチレンイミン、ポリプロピレンイミン、ポリ−３−メチルプロピルイミン、ポリ−２−エチルプロピルイミン等の環状イミンの重合体；ポリビニルアミン、ポリアリルアミン等の不飽和アミンの重合体；ビニルアミン、アリルアミン等の不飽和アミンと、アクリルアミド、ジメチルアクリルアミド、スチレン、アクリル酸メチル、メタクリル酸メチル、アクリル酸、メタクリル酸、スチレンスルホン酸、イタコン酸、マレイン酸等及びその塩類等の、共重合可能な不飽和結合を有する他のモノマーとの共重合体が挙げられる。環状イミンの重合体、不飽和アミンの重合体及びその共重合体の場合、平均分子量３００〜２００万のものが好ましく、１０００〜５０万のものがより好ましい。
【００１９】
重縮合ポリアミンとしては、上記ポリアミン類と、エピクロルヒドリン、エピブロモヒドリン、エピヨードヒドリン、ブロモメチルオキシラン、クロロメチルオキシラン、ヨードメチルオキシラン等のエピハロヒドリンとの重縮合体が挙げられる。但し重縮合ポリアミンは、１分子中に１級アミノ基、２級アミノ基が２個以上残存していることが必要である。
【００２０】
上記化７で示される化合物としては、エポキシ化合物、環状スルフィド化合物、環状エーテル類、環状ホルマール類、Ｎ−置換アルキレンイミン類等の如き、酸素、硫黄、窒素を含有する環状化合物の単独重合体又は共重合体と、エピハロヒドリン、ホルムアルデヒドとを反応させて得られ、一端にエポキシ基又はアルデヒド基を有する化合物であるか、両末端にエポキシ基及び／又はアルデヒド基を有する化合物である。この化合物は平均分子量が５０万程度以下、特に５００〜２０万のものが好ましい。尚、前記化７で示す一般式中における添字“ｍ”は、化７の化合物の分子量が上記の範囲となる正の整数である。
【００２１】
上記化７で示される化合物を構成するエポキシ化合物は、下記化１０で示される化合物であり、例えばエチレンオキシド、プロピレンオキシド、１，２−エポキシアルカン等が例示される。
【００２２】
【化１０】

【００２３】
また上記化７で示される化合物を構成する環状フルフィド化合物としては、上記エポキシ化合物のエポキシ基の酸素と硫黄が置換した構造の下記化１１で示される化合物が挙げられ、例えばエチレンスルフィド、プロピレンスルフィド等が例示され、環状エーテル類としてはオキセタン、モノ又はビスアルキル（アルキル基の炭素数１〜５）オキセタン、モノ又はビスクロロメチルオキセタン、テトラヒドロフラン、モノ又はビスアルキル（アルキル基の炭素数１〜５）テトラヒドロフラン等が挙げられる。
【００２４】
【化１１】

【００２５】
更に上記化７の化合物を構成する環状ホルマール類としては、下記化１２で示される１，３−ジオキソフラン等の化合物やトリオキサン等が挙げられ、Ｎ−置換アルキレンイミン類としては、下記化１３で示される化合物が挙げられる。
【００２６】
【化１２】

【００２７】
【化１３】

【００２８】
上記化８で示される単位を１分子中に２以上有する化合物は、以下の方法で製造することができる。まず第１の方法は、ポリアクリロニトリル又はポリアクリルアミドを還元する方法である。ポリアクリロニトリルは、水素添加触媒の存在下で水素を添加する方法により還元することができ、具体的にはポリアクリロニトリルをＤＭＦ、ＤＭＳＯ等の溶媒に溶解し、ラネーニッケルを触媒として用い、高圧下（３．５ｋｇ／ｃｍ^２ 程度）で水素を添加する方法が挙げられる。
【００２９】
ポリアクリロニトリルの還元には、ポリアクリルアミドをＴＨＦ、ＤＭＦ、ＤＭＳＯ等の溶媒に溶解し、水素化アルミニウムリチウムやナトリウムメチラート等の金属アルコラートを用いて還元する方法を採用することができる。
【００３０】
第２の製造方法は、アリルアミンを重合する方法である。アリルアミンを重合する方法としては、例えばアリルアミンを塩酸塩等にした後、レドックス系開始剤、またはラジカル重合開始剤等を用いて重合する。この際、アリルアミンを単独で重合しても、ジメチルアクリルアミド、スチレン、メタクリル酸メチル、アクリル酸メチル、アクリル酸、メタクリル酸、スチレンスルホン酸等及びその塩類等の如き、アリルアミンと共重合可能な不飽和結合を有する他のモノマーと共重合しても良い。共重合する場合、アリルアミン成分が５モル％以上、特に１５モル％以上含まれるようにすることが好ましい。
【００３１】
上記化９で示される単位を１分子中に２以上含有する化合物は、ポリアクリルアミドやアクリルアミドと、メタクリルアミド、アクリル酸の低級アルキルエステル、アクリル酸、メタクリル酸等のα、β−不飽和化合物との共重合体を、ホフマン転位させる方法や、Ｎ−ビニルフタルイミド、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミドを重合させた後、加水分解する等の方法で得ることができる。
【００３２】
更に上記ポリアミノ化合物は、ヒドロキシアルキル基、アシル基、アルキル基等をＮ−置換基として有するものでも良いが、１分子中に２個以上の置換基を導入し得るように、Ｎ−置換基を導入した後において、１分子中に１級アミノ基、２級アミノ基が２個以上残存している必要がある。Ｎ−ヒドロキシアルキル置換基は、上記ポリアミン類とエポキシアルカンとを反応させることにより導入することができ、Ｎ−アシル置換基は、上記ポリアミン類と脂肪酸類を反応させることにより導入され、またＮ−アルキル置換基は上記ポリアミン類とハロゲン化アルキルを作用させることにより導入される。Ｎ−ヒドロキシアルキル置換基は、アルキル基の炭素数が２〜２８であることが好ましく、Ｎ−アシル置換基は炭素数２〜２４であることが好ましい。またＮ−アルキル置換基は炭素数２〜１８であることが好ましい。
【００３３】
本発明金属捕集剤において、ジチオ酸基、アルキレンカルボン酸基、アルキレンリン酸基の塩である、ジチオ酸塩基、アルキレンカルボン酸塩基、アルキレンリン酸塩基としては、これらの基のアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩が挙げられる。
【００３４】
本発明の金属捕集剤において、（ａ）群の官能基は、例えば上記ポリアミノ化合物を、水、アルコール等の溶媒に溶解させ、これに二硫化炭素を添加して反応させる等の方法により導入することができる（ジチオ酸基が導入される。）。また上記反応終了後、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物や、水酸化カルシウム、水酸化マグネシウム等のアルカリ土類金属水酸化物、或いはアンモニア等のアルカリで処理するか、ポリアミノ化合物と二硫化炭素との反応をこれらのアルカリの存在下で行うことにより、官能基をジチオ酸塩基とすることができる。ジチオ酸基とジチオ酸塩基は、金属捕集剤１分子中に、どちらか一方のみが存在しても両方が存在しても良い。
【００３５】
また本発明の金属捕集剤における、（ｂ）群の官能基であるアルキレンカルボン酸基は、モノハロゲンカルボン酸やそのエステル、又はビニル基を有するカルボン酸塩やエステル、或いはアクリロニトリル、メタクリルニトリル等を、上記ポリアミノ化合物に付加することにより導入され、またこの付加物をケン化することによりアルキレンカルボン酸基をアルキレンカルボン酸塩基とすることができる。アルキレンカルボン酸基、アルキレンカルボン酸塩基におけるアルキレン基としては、炭素数１〜３のものが好ましい。
【００３６】
更に本発明の金属捕集剤における（ｃ）群の官能基である、アルキレンリン酸基はポリアミノ化合物に、酸性下においてアルデヒド類と亜リン酸類とを反応させる方法で導入することができ、またそれをアルカリ性化合物等で処理することによりアルキレンリン酸基をアルキレンリン酸塩基とすることができる。アルキレンリン酸基、アルキレンリン酸塩基のアルキレン基は、炭素数が１〜２のものが好ましい。
【００３７】
（ｄ）群の官能基は、オキシム基又はアミドキシム基であり、オキシム基はポリアミノ化合物にカルボン酸エステル類を反応させた後、ヒドロキシルアミンを反応することにより導入され、アミドキシム基はポリアミノ化合物にシアノ化合物を反応させた後、ヒドロキシルアミンを反応させることにより導入される。オキシム基におけるアルキル基は炭素数１〜３が好ましい。
【００３８】
本発明の金属捕集剤は、上記（ａ）群の官能基と、（ｂ）群の官能基とともに、（ｃ）群の官能基又は（ｄ）群の官能基のいずれか一方を有していれば良いが、（ｃ）群の官能基、（ｄ）群の官能基の両方を有しているものであっても良い。また（ｃ）群の官能基の２種以上や、（ｄ）群の官能基の２種以上を有していても良い。本発明の金属捕集剤において、元のポリアミノ化合物の窒素原子に結合した活性水素原子に対する、上記置換基合計の置換率は２０〜１００％である。また全置換基中、（ａ）群の置換基と、（ｂ）群の置換基の合計した割合は、２０〜９０％である。金属捕集剤中に導入されている置換基の、元のポリアミノ化合物の活性水素に対する置換率や、（ａ）群の置換基と（ｂ）群の置換基の全置換基中の割合が上記の範囲にあることにより、水銀等の“ハード”な金属と、亜鉛等の“ソフト”な金属の両方に対し優れた捕集能を発現するとともに、廃水処理時に、金属捕集剤が廃水中の金属を捕集して生成したフロックからの金属の溶出が少なく、安定して廃水中の金属処理が行えるとともに、カルシウムイオンを多量に含む廃水についても、廃水中の金属に対して優れた捕集能力を発現し、捕集した金属の再溶出の少ない安定なフロックを生成する。
【００３９】
本発明の金属捕集剤は単独又は２種以上混合して用いることができ、金属イオンを含む廃水等の処理、ガス化した金属を含む廃ガス（ゴミ焼却場の排煙等）の処理、金属を含有する飛灰（ＥＰ灰、サイクロン灰、バグフィルター灰等）、鉱滓、汚泥、土壌等の固体物質中の金属の固定化処理等に利用することができる。また本発明の金属捕集剤による、廃水、廃ガス、固体廃棄物の処理に際し、トリメルカプトトリアジン又はその塩類、一硫化ナトリウム、硫化水素ナトリウム、二硫化ナトリウム、三硫化ナトリウム、四硫化ナトリウム、五硫化ナトリウム等のポリ硫化ナトリウム等と併用することができ、これらを併用すると金属捕集効率が高められる。中でも硫化水素ナトリウム、ポリ硫化ナトリウムとの併用が好ましい。
【００４０】
廃水等の処理法としては、例えば本発明の金属捕集剤水溶液を廃水等に添加し、廃水等に含まれる金属イオンと本発明の金属捕集剤とが反応して生成したフロックを分離除去した後、廃水を放流する等の方法が、排煙等の処理には、本発明の金属捕集剤水溶液を排煙等に噴霧し、排煙等の中に含まれるガス化した金属イオンを捕集剤によって捕集して排煙等の中から分離除去した後、排煙を放出する等の方法が挙げられる。また固体廃棄物の処理法としては、固体廃棄物に本発明の金属捕集剤を添加して金属捕集剤と固体廃棄物中の金属とを反応させて金属が固体廃棄物中から溶出しないように固定化した後、固体廃棄物をコンクリート等で固めて地中や海中に投棄する等の方法が挙げられる。
【００４１】
【実施例】
以下、実施例を挙げて本発明を更に詳細に説明する。尚、以下の実施例、比較例において使用した金属捕集剤は以下の通りである。
【００４２】
▲１▼金属捕集剤ａ（本発明金属捕集剤）
テトラエチレンペンタミンの窒素原子に結合した水素原子と置換して導入された置換基として、ジチオ酸アンモニウム基と、メチレンカルボン酸アンモニウム基と、メチレンリン酸アンモニウム基とを、４：３：６の比率で含有する化合物（ポリアミノ化合物中の窒素原子に結合した置換可能な水素原子に対する置換基の置換率８５％）
【００４３】
▲２▼金属捕集剤ｂ（本発明金属捕集剤）
ビニルアミン６５モル％とメタクリル酸ナトリウム３５モル％とからなる共重合体（ＭＷ＝３９００００）の窒素原子に結合した水素原子と置換して導入された置換基として、ジチオ酸カリウム塩基と、プロピレンカルボン酸カリウム塩基と、オキシム基とを、３：３：２の比率で含有する化合物（ポリアミノ化合物中の窒素原子に結合した置換可能な水素原子に対する置換基の置換率８２％）
【００４４】
▲３▼金属捕集剤ｃ（本発明金属捕集剤）
アリルアミン２０モル％とジメチルアクリルアミド８０モル％とからなる共重合体（ＭＷ＝１１００００）の窒素原子に結合した水素原子と置換して導入された置換基として、ジチオ酸ナトリウム塩基と、メチレンカルボン酸ナトリウム塩基と、アミドキシム基とを、７：１：２の比率で含有する化合物（ポリアミノ化合物中の窒素原子に結合した置換可能な水素原子に対する置換基の置換率１００％）
【００４５】
▲４▼金属捕集剤ｄ（本発明金属捕集剤）
ポリプロピレンイミン４０モル％とポリエチレンオキシドにエピクロルヒドリンを付加したジエポキシドとからなる共重合体（ＭＷ＝４３００）の窒素原子に結合した水素原子と置換して導入された置換基として、ジチオ酸ナトリウム塩基と、エチレンカルボン酸ナトリウム塩基と、メチレンリン酸ナトリウム塩基及びオキシム基を、それぞれ４：６：２：１の比率で含有する化合物（ポリアミノ化合物中の窒素原子に結合した置換可能な水素原子に対する置換基の置換率６５％）
【００４６】
▲５▼金属捕集剤ｅ（本発明金属捕集剤）
ポリエチレンイミン（ＭＷ＝１４０００）の窒素原子に結合した水素原子と置換して導入された置換基として、ジチオ酸ナトリウム塩基と、メチレンカルボン酸ナトリウム塩基と、メチレンリン酸ナトリウム塩基及びアミドキシム基を、それぞれ２：３：２：１の比率で含有する化合物（ポリアミノ化合物中の窒素原子に結合した置換可能な水素原子に対する置換基の置換率４４％）
【００４７】
▲６▼金属捕集剤ｆ（本発明の金属捕集剤）
キシリレンジアミンとエピクロルヒドリン重縮合物（ＭＷ＝２３００）の窒素原子と置換して導入された置換基として、ジチオ酸カリウム塩基と、エチレンカルボン酸カリウム塩基と、オキシム基及びアミドキシム基を、それぞれ２：１：８：３の比率で含有する化合物（ポリアミノ化合物中の窒素原子に結合した置換可能な水素原子に対する置換基の置換率７０％）
【００４８】
▲７▼金属捕集剤ｇ（従来の金属捕集剤）
キシリレンジアミン−エピクロルヒドリン重縮合体（ＭＷ＝１６００）の窒素原子に結合した水素原子と置換して導入された置換基として、ジチオ酸基を有する化合物（ポリアミノ化合物中の窒素原子に結合した置換可能な水素原子に対する置換基の置換率６０％）
【００４９】
実施例１〜６、比較例１
水銀４．４ｍｇ／リットル、鉛２．１ｍｇ／リットル、亜鉛４．２ｍｇ／リットル、カドミウム９．４ｍｇ／リットル、ニッケル１．４ｍｇ／リットルを含有する廃水を、水酸化カルシウム及び表１に示す金属捕集剤を用いて処理した。水酸化カルシウムは廃水１リットル当たり１００ｍｇ添加し、金属捕集剤は廃水１リットル当たり５０ｍｇを添加し、１０分間攪拌した後、静置して生成したフロックが沈降するまでの時間を測定した。また沈殿したフロックを分離除去してフロックの生成量を測定するとともに、フロック除去後の廃水中に残存する金属濃度を原子吸光分析法により測定した。これらの結果を表１に示す。
【００５０】
【表１】

【００５１】
実施例７〜１２、比較例２
上記実施例１〜６、比較例１で用いたと同様の廃水に、水酸化カルシウムを併用して添加することなく、表２に示す金属捕集剤のみを、廃水１リットル当たりに対し、７５ｍｇ添加し、１０分間攪拌した後、静置して生成したフロックが沈殿するまでの時間を測定した。また沈殿したフロックを分離除去してフロックの生成量を測定するとともに、フロック除去後の廃水中に残存する金属濃度を原子吸光分析法により測定した。これらの結果を表２に示す。
【００５２】
【表２】

【００５３】
実施例１３〜１８、比較例３
銅５８４００ｍｇ／ｋｇ、鉛２５５ｍｇ／ｋｇ、亜鉛１３５０ｍｇ／ｋｇ、カドミウム５８４０ｍｇ／ｋｇ、ニッケル３４５０ｍｇ／ｋｇ、鉄１３２０ｍｇ／ｋｇ、クロム９８３ｍｇ／ｋｇを含有する鉱滓を、表３に示す金属捕集剤を用いて処理した。処理法としては鉱滓１００ｇ当たりに対し、金属捕集剤の水溶液を固型分の添加量が０．９ｇとなるように鉱滓表面に噴霧して混練した後、１００分間放置した。処理後の鉱滓５０ｇを、ｐＨ＝７に調整した純水５００ミリリットル中で、常温で６０分間振とうし、水中に溶出した金属濃度を原子吸光分析法によって測定した。また金属捕集剤による処理を施していない未処理鉱滓についても上記と同様の溶出試験を行った（参考例１）。結果を表３に示す。
【００５４】
【表３】

【００５５】
実施例１９〜２４、比較例４
水銀９３４ｍｇ／ｋｇ、鉛３５６０ｍｇ／ｋｇ、銅２５４０ｍｇ／ｋｇ、カドミウム１３９ｍｇ／ｋｇを含む、ゴミ焼却場から得た飛灰（ＥＰ灰）５０ｇ当たりに対し、表４に示す金属捕集剤の水溶液を固型分の添加量が０．５ｇとなるように添加し、２０分間混練した。次いでこの処理済の飛灰５０ｇを、ｐＨ＝５に調整した純水５００ミリリットル中で、常温で１００分間振とうし、水中に溶出した金属濃度を原子吸光分析法によって測定した。また金属捕集剤による処理を施していない未処理飛灰について同様の溶出試験を行った（参考例２）。結果を表４に示す。
【００５６】
【表４】

【００５７】
実施例２５〜３０、比較例５
鉛４３２０ｍｇ／ｋｇ、水銀１３９ｍｇ／ｋｇ、クロム１８５０ｍｇ／ｋｇ、鉄３５６ｍｇ／ｋｇ、カドミウム５３２ｍｇ／ｋｇを含有する汚泥（含水率８２％）７０ｇの表面に、表５に示す金属捕集剤水溶液を固型分の添加量が０．１ｇとなるように吹き付けた後混練し、８０分間放置した。放置後の汚泥５０ｇを、ｐＨ＝６に調整した純水５００ミリリットル中で、常温で１００分間振とうし、水中に溶出した金属濃度を原子吸光分析法によって測定した。また金属捕集剤による処理を施していない未処理汚泥についても同様の溶出試験を行った（参考例３）。結果を表５に示す。
【００５８】
【表５】

【００５９】
実施例３１〜３６、比較例６
水銀２５０ｍｇ／Ｎｍ^３ 、カドミウム１２ｍｇ／Ｎｍ^３ 、ダスト１５ｍｇ／Ｎｍ^３ を含む排煙に、表６に示す金属捕集剤の水溶液を、３ｍｇ／時間（固型分として）の割合で煙路中に噴霧し、バッグフィルターにて捕集した。金属捕集剤水溶液を噴霧処理後の排煙中に残留する水銀、カドミウムを吸収液に吸収させた後、各金属濃度を原子吸光分析法により測定した。結果を表６に示す。
【００６０】
【表６】

【００６１】
【発明の効果】
以上説明したように本発明の金属捕集剤は、ジチオ酸基及び／又はジチオ酸塩基と、アルキレンカルボン酸基及び／又はアルキレンカルボン酸塩基とを有し、かつアルキレンリン酸基及び／又はアルキレンリン酸塩基、オキシム基及び／又はアミドキシム基のうちの少なくとも１種とを有し、且つ置換基が特定の置換率で導入されているとともに、ジチオ酸基及び／又はジチオ酸塩基と、アルキレンカルボン酸基及び／又はアルキレンカルボン酸塩基が全置換基中の特定の割合を占めることにより、水酸化カルシウムをアルカリとして使用した中和凝集沈殿法と併用した場合でも、廃水中からカルシウムイオンを、他の金属イオンとともに効果的に捕集除去でき、しかもフロックの沈降性に優れる効果がある。また本発明の金属捕集剤は従来の金属捕集剤が比較的苦手としていた、所謂“ソフト”な金属イオンに対する捕集能にも優れ、廃水、廃ガス中の金属（金属イオン）を確実に捕集除去できるとともに、固体廃棄物中から金属が溶出しないように、固体廃棄物中の金属を確実に固定化できる等の効果を有する。[0001]
[Industrial applications]
The present invention relates to a metal collecting agent.
[0002]
[Prior art]
Strict regulations are set for metals contained in wastewater, especially metals such as mercury, cadmium, zinc, lead, copper, and chromium, which are harmful to the human body. Methods have been considered.
[0003]
As a method for removing metal ions contained in wastewater and the like, an ion flotation method, an ion exchange method, an electrolytic flotation method, an electrodialysis method, an adsorption method, a reverse osmosis method, and the like are conventionally known. However, in the case of the ion flotation method, the ion exchange method, the electrolytic flotation method, the electrodialysis method, the adsorption method, and the reverse osmosis method, there are problems in a metal ion removal rate, operability, running cost, and the like, and some of them have problems. It is used only for special wastewater treatment. On the other hand, a neutralization coagulation sedimentation method is also used in which an alkali such as sodium hydroxide or calcium hydroxide is added to the wastewater, and metal ions in the wastewater are converted into hydroxides, which are then coagulated and precipitated by a polymer coagulant to remove them. However, the neutralization coagulation sedimentation method must treat a large amount of the generated metal hydroxide sludge, which causes problems in work efficiency and recycles metal ions from waste sludge into rivers and seawater. There are problems such as dissolving to cause secondary pollution and making it difficult to reduce the concentration of metal ions in wastewater to a standard value or less regulated by the government.
[0004]
Therefore, instead of these methods, a method of collecting and removing metal ions in wastewater using a metal collecting agent has been widely used. As the metal collecting agent, a compound having a dithioacid group or a dithioacid group as a functional group, which exhibits excellent adsorption power to mercury and lead, is widely used. For example, as proposed by the present applicant, dithioic acid groups and dithioic acid bases are bonded to nitrogen atoms of polyalkylene polyamines such as ethylenediamine and triethylenetetramine and polyamines such as polyethyleneimine. A method using a metal collecting agent having the above structure (Japanese Patent Publication No. 5-7079, Japanese Patent Publication No. 5-7080, etc.) and the like are known.
[0005]
[Problems to be solved by the invention]
By the way, as described in the above-mentioned Japanese Patent Publication Nos. 5-7079 and 5-7080, metal collectors having a dithioacid group or a dithioacid group as a functional group include mercury, lead, gold, silver, and the like. It is said to have excellent trapping ability for metals such as zinc, cadmium, copper and chromium. However, metal scavengers that have dithioate groups or dithioate groups as functional groups generally have very good trapping capabilities for "hard" metals such as mercury, lead, gold, silver, etc. On the other hand, the ability to capture "soft" metals such as zinc, cadmium, nickel and the like was not always sufficient.
[0006]
In addition, the method of treating wastewater only with a metal collecting agent has a problem that the cost is relatively high. For this reason, conventionally, the neutralization coagulation sedimentation method and the collection with a metal collecting agent have been used in combination. In this method, the amount of the metal collecting agent used can be reduced as compared with the case where the treatment is performed only with the metal collecting agent, so that the processing cost can be reduced. It does not generate a large amount of metal hydroxide sludge as in the case of treatment, and due to the combined action of the neutralization coagulation sedimentation method and the metal collecting agent, more than when these methods are performed alone. There is an advantage that metal ions can be effectively removed.
[0007]
One of the purposes of using the above-mentioned treatment with the metal collecting agent and the neutralization coagulation sedimentation method together is to reduce the amount of the metal collecting agent used and to reduce the processing cost. As the alkali used in the precipitation method, calcium hydroxide, which is cheaper than sodium hydroxide, is mainly used. However, when calcium hydroxide is used, the concentration of calcium ions in the wastewater increases, and the calcium ions are not collected by the conventional metal collecting agent, so that the wastewater is released with the calcium ions remaining. The sediment caused by the calcium ions accumulates in the wastewater pipes and narrows the flow path to prevent the discharge of wastewater, and requires complicated operations for removing the sediment. Problem had arisen.
[0008]
The present inventors have conducted intensive studies to solve the above problems, and as a result, having a dithioacid group and / or a dithioacid group, an alkylenecarboxylic acid group and / or an alkylenecarboxylic acid group, and an alkylenephosphate group, Calcium ions remaining in wastewater even when a metal scavenger having at least one of an alkylene phosphate group, an oxime group and an amide oxime group is used in combination with a neutralization coagulation precipitation method using calcium hydroxide. Can effectively solve the above-mentioned conventional problems by collecting and removing metal ions, and also has a very high sedimentation rate of flocs generated by the metal-collecting agent capturing metal ions, and also has a "soft" reactivity to metals. Was found to be superior to conventional metal collectors, and completed the present invention.
[0009]
[Means for Solving the Problems]
That is, the metal scavenger of the present invention comprises, as a substituent bonded to a nitrogen atom of the polyamino compound, at least one functional group selected from the group (a) among the functional groups of the following groups (a) to (c): It has a group, and at least one functional group selected from the group (b), and (c) groups, have at least one functional group of at least one group of group (d), the original With respect to the active hydrogen bonded to the nitrogen atom of the polyamino compound, the total substitution ratio of the above-mentioned substituents is 20 to 100%, and among all the substituents, the substituent of the group (a) and the substituent of the group (b) Occupies 20 to 90% .
(A) a group represented by the following formula 1 (b) a group represented by the following formula 2 (c) a group represented by the following formula 3 (d) an oxime group or an amidoxime group
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[0011]
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[0012]
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[0013]
The metal scavenger of the present invention is represented by the above formula (a) as a substituent substituted by an active hydrogen atom bonded to a nitrogen atom of a polyamino compound having two or more primary amino groups or secondary amino groups. Group (b), at least one of the functional groups of (c) and (d), represented by Chemical Formula 6; And is obtained by introducing Examples of the polyamino compound include polyamines, polycondensed polyamines obtained by polycondensation of these polyamines and epihalohydrin, copolymers of polyamines and compounds represented by the following formula 7, or represented by the following formulas 8 and 9 Examples include compounds containing two or more units in one molecule, but any compound having two or more primary amino groups or secondary amino groups in one molecule can be used without limitation. .
[0015]
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[0016]
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[0017]
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[0018]
Examples of the polyamines include ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, dipropylenediamine, dibutylenetriamine, triethylenetetramine, tripropylenetetramine, trifluorobutyltetramine, tetraethylenepentamine, and tetrapropylenepentamine. Aliphatic polyamines such as tetrabutylenepentamine, pentaethylenehexamine, iminobispropylamine, monomethylaminopropylamine and methyliminobispropylamine; phenylenediamine, o-, m-, p-xylylenediamine, 3,5- Aromatic polyamines such as diaminochlorobenzene; cycloalkane polyamines such as 1,3-bis (aminomethyl) cyclohexane; 1-aminoethyl Piperazines such as perazine and piperazine; polymers of cyclic imines such as polyethyleneimine, polypropyleneimine, poly-3-methylpropylimine and poly-2-ethylpropylimine; polymers of unsaturated amines such as polyvinylamine and polyallylamine Copolymerization of unsaturated amines such as vinylamine and allylamine with acrylamide, dimethylacrylamide, styrene, methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, styrene sulfonic acid, itaconic acid, maleic acid, etc. and salts thereof. Copolymers with other monomers having possible unsaturated bonds are mentioned. In the case of a polymer of cyclic imine, a polymer of unsaturated amine and a copolymer thereof, those having an average molecular weight of 300 to 2,000,000 are preferable, and those having an average molecular weight of 1,000 to 500,000 are more preferable.
[0019]
Examples of polycondensation polyamines include polycondensates of the above polyamines and epihalohydrins such as epichlorohydrin, epibromohydrin, epiiodohydrin, bromomethyloxirane, chloromethyloxirane, and iodomethyloxirane. However polycondensation polyamine, primary amino groups in one molecule, it is necessary to secondary amino groups are still present 2 or more.
[0020]
Examples of the compound represented by the above formula 7 include a homopolymer of a cyclic compound containing oxygen, sulfur, and nitrogen, such as an epoxy compound, a cyclic sulfide compound, a cyclic ether, a cyclic formal, and an N-substituted alkyleneimine. It is a compound obtained by reacting a copolymer with epihalohydrin or formaldehyde and having an epoxy group or an aldehyde group at one end, or a compound having an epoxy group and / or an aldehyde group at both ends. This compound is an average molecular weight of about 500,000 or less, especially those of 500 to 200,000 preferred. The subscript “m” in the general formula shown in Chemical Formula 7 is a positive integer in which the molecular weight of the compound of Chemical Formula 7 falls within the above range.
[0021]
The epoxy compound constituting the compound represented by the above formula 7 is a compound represented by the following formula 10, and examples thereof include ethylene oxide, propylene oxide, and 1,2-epoxyalkane.
[0022]
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[0023]
Examples of the cyclic sulfide compound constituting the compound represented by the above formula 7 include a compound represented by the following formula 11 having a structure in which the oxygen and the sulfur of the epoxy group of the above epoxy compound are substituted, and examples thereof include ethylene sulfide and propylene sulfide. Examples of the cyclic ethers include oxetane, mono- or bis-alkyl (alkyl group having 1 to 5 carbon atoms) oxetane, mono- or bis-chloromethyloxetane, tetrahydrofuran, mono- or bis-alkyl (alkyl group having 1 to 5 carbon atoms) Tetrahydrofuran and the like.
[0024]
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[0025]
Further, examples of the cyclic formal constituting the compound of the above formula 7 include compounds such as 1,3-dioxofuran and trioxane shown in the following formula 12, and examples of the N-substituted alkyleneimines are shown in the following formula 13. Compounds.
[0026]
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[0027]
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[0028]
The compound having two or more units represented by the above formula in one molecule can be produced by the following method. First first method is a method of reducing the polyacrylonitrile or polyacrylamide. Polyacrylonitrile can be reduced by a method in which hydrogen is added in the presence of a hydrogenation catalyst. Specifically, polyacrylonitrile is dissolved in a solvent such as DMF or DMSO, and Raney nickel is used as a catalyst under high pressure (3 (About 0.5 kg / cm ² ).
[0029]
For the reduction of polyacrylonitrile, a method of dissolving polyacrylamide in a solvent such as THF, DMF, DMSO or the like and reducing it using a metal alcoholate such as lithium aluminum hydride or sodium methylate can be adopted.
[0030]
The second production method is a method of polymerizing allylamine. As a method for polymerizing allylamine, for example, after converting allylamine into a hydrochloride or the like, polymerization is performed using a redox initiator, a radical polymerization initiator, or the like. In this case, even when allylamine is polymerized alone, unsaturated copolymerizable with allylamine, such as dimethylacrylamide, styrene, methyl methacrylate, methyl acrylate, acrylic acid, methacrylic acid, styrene sulfonic acid, and salts thereof. bond may be copolymerized with other monomers having. When copolymerizing allylamine component 5 mol% or more, it is preferable to be included in particular 15 mol% or more.
[0031]
Compounds containing two or more units represented by the above formula in one molecule include polyacrylamide and acrylamide, methacrylamide, lower alkyl esters of acrylic acid, acrylic acid and α, β-unsaturated compounds such as methacrylic acid. Can be obtained by a method such as Hofmann rearrangement, a method of polymerizing N-vinylphthalimide, N-vinylformamide, or N-vinylacetamide, followed by hydrolysis.
[0032]
Further, the polyamino compound may have a hydroxyalkyl group, an acyl group, an alkyl group or the like as an N-substituent, but may have an N-substituent such that two or more substituents can be introduced in one molecule. After the introduction, two or more primary amino groups and secondary amino groups must remain in one molecule. N-hydroxyalkyl substituents can be introduced by reacting the polyamines with epoxyalkanes, N-acyl substituents are introduced by reacting the polyamines with fatty acids, Alkyl substituents are introduced by the action of the above polyamines and alkyl halides. The N-hydroxyalkyl substituent preferably has 2 to 28 carbon atoms in the alkyl group, and the N-acyl substituent preferably has 2 to 24 carbon atoms. The N-alkyl substituent preferably has 2 to 18 carbon atoms.
[0033]
In the metal-collecting agent of the present invention, dithioacid groups, alkylenecarboxylic acid groups, salts of alkylenephosphate groups, dithioacid groups, alkylenecarboxylate groups, and alkylenephosphate groups include alkali metal salts of these groups, Alkaline earth metal salts and ammonium salts.
[0034]
In the metal collecting agent of the present invention, the functional group of the group (a) is introduced by, for example, dissolving the above polyamino compound in a solvent such as water or alcohol, and adding carbon disulfide thereto to react. (A dithioic acid group is introduced). After completion of the above reaction, treatment with an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide, or an alkali such as ammonia, or polyamino acid By performing the reaction between the compound and carbon disulfide in the presence of these alkalis, the functional group can be a dithioacid group. Either one or both of the dithioacid group and the dithioacid group may be present in one molecule of the metal collecting agent.
[0035]
In the metal-collecting agent of the present invention, the alkylenecarboxylic acid group which is a functional group of the group (b) is a monohalogencarboxylic acid or an ester thereof, a carboxylate or an ester having a vinyl group, acrylonitrile, methacrylonitrile, or the like. Is added to the above polyamino compound, and the alkylenecarboxylic acid group can be converted to an alkylenecarboxylic acid salt group by saponifying the adduct. The alkylene carboxylic acid group and the alkylene group in the alkylene carboxylate group preferably have 1 to 3 carbon atoms.
[0036]
Further, the alkylene phosphate group, which is a functional group of the group (c) in the metal scavenger of the present invention, can be introduced into the polyamino compound by reacting aldehydes and phosphorous acid under acidic conditions. By treating it with an alkaline compound or the like, the alkylene phosphate group can be converted to an alkylene phosphate group. The alkylene phosphate group and the alkylene group of the alkylene phosphate group preferably have 1 to 2 carbon atoms.
[0037]
The functional group of the group (d) is an oxime group or an amidoxime group. The oxime group is introduced by reacting a carboxylic acid ester with a polyamino compound and then reacting with a hydroxylamine. After reacting the compound, it is introduced by reacting with hydroxylamine. The alkyl group in the oxime group preferably has 1 to 3 carbon atoms.
[0038]
The metal collecting agent of the present invention has either the functional group of the group (c) or the functional group of the group (d) together with the functional group of the group (a) and the functional group of the group (b). However, it may have both the functional group of the group (c) and the functional group of the group (d). Further, it may have two or more kinds of the functional groups of the group (c) or two or more kinds of the functional groups of the group (d). In the metal scavenger of the present invention, for binding the active hydrogen atoms on the nitrogen atom of the original polyamino compound, substitution rate of the substituents sum is 2 0-100%. The total percentage of the total in the substituent, the substituent of the group (a), (b) a group of substituents, Ru 20% to 90% der. The substitution rate of the substituent introduced into the metal collecting agent with respect to the active hydrogen of the original polyamino compound and the ratio of the substituent of the group (a) to the substituent of the group (b) in the total substituent are as described above. In this range, excellent collection performance is exhibited for both "hard" metals such as mercury and "soft" metals such as zinc. Metals in the wastewater can be stably treated with little elution of metals from flocs generated by collecting metals in the wastewater, and also excellent wastewater containing a large amount of calcium ions can be trapped in the wastewater. A stable floc that develops the ability to collect and has little re-elution of the collected metal.
[0039]
The metal collecting agent of the present invention can be used alone or as a mixture of two or more kinds, and can be used for treatment of wastewater containing metal ions, treatment of waste gas containing gasified metal (such as exhaust gas from garbage incineration plants), It can be used for immobilizing metals in solid substances such as fly ash containing metals (EP ash, cyclone ash, bag filter ash, etc.), slag, sludge, soil and the like. In the treatment of waste water, waste gas and solid waste by the metal collector of the present invention, trimercaptotriazine or a salt thereof, sodium monosulfide, sodium hydrogen sulfide, sodium disulfide, sodium trisulfide, sodium tetrasulfide, sodium pentasulfide, It can be used in combination with sodium polysulfide such as sodium sulfide and the like, and when these are used in combination, metal collection efficiency can be increased. Among them, combination use with sodium hydrogen sulfide and sodium polysulfide is preferable.
[0040]
As a method for treating wastewater or the like, for example, an aqueous solution of the metal-collecting agent of the present invention is added to wastewater or the like, and the flocs generated by the reaction between the metal ions contained in the wastewater and the metal-collecting agent of the present invention are separated and removed. After that, the method of discharging the wastewater, etc., for the treatment of flue gas, etc., spray the aqueous solution of the metal-collecting agent of the present invention on the flue gas, etc., and remove the gasified metal ions contained in the flue gas, etc. After collecting with a collecting agent and separating and removing from smoke and the like, there is a method of discharging the smoke and the like. Further, as a method for treating solid waste, the metal collecting agent of the present invention is added to solid waste to react the metal in the solid waste with the metal collecting agent so that the metal is not eluted from the solid waste. After immobilization, solid waste is solidified with concrete or the like and dumped in the ground or in the sea.
[0041]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. The metal scavengers used in the following Examples and Comparative Examples are as follows.
[0042]
{Circle around (1)} Metal collecting agent a (metal collecting agent of the present invention)
As a substituent introduced by replacing a hydrogen atom bonded to a nitrogen atom of tetraethylenepentamine, an ammonium dithioate group, an ammonium methylene carboxylate group, and an ammonium methylene phosphate group in a ratio of 4: 3: 6 Compounds contained in a ratio (substitution ratio of substituents to replaceable hydrogen atoms bonded to nitrogen atoms in a polyamino compound is 85%)
[0043]
(2) Metal collecting agent b (metal collecting agent of the present invention)
As a substituent introduced by replacing a hydrogen atom bonded to a nitrogen atom of a copolymer (MW = 390000) of 65 mol% of vinylamine and 35 mol% of sodium methacrylate, potassium dithioate base and propylene carboxylic acid A compound containing a potassium base and an oxime group in a ratio of 3: 3: 2 (substitution ratio of a substituent to a replaceable hydrogen atom bonded to a nitrogen atom in a polyamino compound is 82%)
[0044]
(3) Metal collecting agent c (metal collecting agent of the present invention)
As a substituent introduced by replacing a hydrogen atom bonded to a nitrogen atom of a copolymer (MW = 1110,000) composed of 20 mol% of allylamine and 80 mol% of dimethylacrylamide, sodium dithioate base and sodium methylene carboxylate are introduced as substituents. A compound containing a base and an amidoxime group in a ratio of 7: 1: 2 (substitution ratio of a substituent to a replaceable hydrogen atom bonded to a nitrogen atom in a polyamino compound is 100%)
[0045]
{Circle around (4)} Metal collecting agent d (metal collecting agent of the present invention)
Sodium dithioate base as a substituent introduced by replacing a hydrogen atom bonded to a nitrogen atom of a copolymer (MW = 4300) of a copolymer (MW = 4300) of polypropyleneimine (40 mol%) and a diepoxide obtained by adding epichlorohydrin to polyethylene oxide; Compounds containing a sodium ethylene carboxylate base, a sodium methylene phosphate base and an oxime group in a ratio of 4: 6: 2: 1, respectively (the substitution of a substituent for a substitutable hydrogen atom bonded to a nitrogen atom in a polyamino compound) (Replacement rate 65%)
[0046]
(5) Metal collecting agent e (metal collecting agent of the present invention)
As a substituent introduced by replacing a hydrogen atom bonded to a nitrogen atom of polyethyleneimine (MW = 14000), sodium dithioate, sodium methylenecarboxylate, sodium methylenephosphate and amidoxime are respectively Compounds contained at a ratio of 2: 3: 2: 1 (substitution ratio of substituents to replaceable hydrogen atoms bonded to nitrogen atoms in a polyamino compound is 44%)
[0047]
{Circle around (6)} Metal collecting agent f (metal collecting agent of the present invention)
As a substituent introduced by substituting with a nitrogen atom of xylylenediamine and epichlorohydrin polycondensate (MW = 2300), potassium dithioate, potassium potassium ethylenecarboxylate, oxime group and amidoxime group are respectively 2: Compounds containing at a ratio of 1: 8: 3 (substitution ratio of substituents to replaceable hydrogen atoms bonded to nitrogen atoms in polyamino compound is 70%)
[0048]
(7) Metal collecting agent g (conventional metal collecting agent)
A compound having a dithioic acid group as a substituent introduced by replacing a hydrogen atom bonded to a nitrogen atom of a xylylenediamine-epichlorohydrin polycondensate (MW = 1600) (substitutable to a nitrogen atom in a polyamino compound; 60% of the substitution ratio of the substituent to a hydrogen atom)
[0049]
Examples 1 to 6, Comparative Example 1
Wastewater containing 4.4 mg / L of mercury, 2.1 mg / L of lead, 4.2 mg / L of zinc, 9.4 mg / L of cadmium, and 1.4 mg / L of nickel was treated with calcium hydroxide and the metal trap shown in Table 1. The treatment was carried out using a collector. 100 mg of calcium hydroxide was added per liter of wastewater, and 50 mg of metal collector was added per liter of wastewater, and the mixture was stirred for 10 minutes, and then allowed to stand. The precipitated floc was separated and removed to measure the amount of floc produced, and the concentration of the metal remaining in the wastewater after removing the floc was measured by atomic absorption spectrometry. Table 1 shows the results.
[0050]
[Table 1]

[0051]
Examples 7 to 12, Comparative Example 2
Without adding calcium hydroxide to wastewater similar to that used in Examples 1 to 6 and Comparative Example 1, 75 mg of only the metal collecting agent shown in Table 2 was added per liter of wastewater. After stirring for 10 minutes, the solution was allowed to stand, and the time required for floc generated to precipitate was measured. The precipitated floc was separated and removed to measure the amount of floc produced, and the concentration of the metal remaining in the wastewater after removing the floc was measured by atomic absorption spectrometry. Table 2 shows the results.
[0052]
[Table 2]

[0053]
Examples 13 to 18, Comparative Example 3
Slags containing 58400 mg / kg of copper, 255 mg / kg of lead, 1350 mg / kg of zinc, 5840 mg / kg of cadmium, 3450 mg / kg of nickel, 1320 mg / kg of iron, and 983 mg / kg of chromium were used using the metal collecting agents shown in Table 3. Processed. As a treatment method, an aqueous solution of a metal collecting agent was sprayed and kneaded on the surface of the slag such that the amount of the solid component added was 0.9 g per 100 g of the slag, and the mixture was allowed to stand for 100 minutes. 50 g of the slag after the treatment was shaken at room temperature for 60 minutes in 500 ml of pure water adjusted to pH = 7, and the metal concentration eluted in the water was measured by atomic absorption spectrometry. Further, an untreated slag not treated with the metal-collecting agent was subjected to the same dissolution test as described above (Reference Example 1). Table 3 shows the results.
[0054]
[Table 3]

[0055]
Examples 19 to 24, Comparative Example 4
For each 50 g of fly ash (EP ash) obtained from a garbage incineration plant containing 934 mg / kg of mercury, 3560 mg / kg of lead, 2540 mg / kg of copper, and 139 mg / kg of cadmium, an aqueous solution of the metal collector shown in Table 4 was used. It was added so that the amount of the solid component added became 0.5 g, and kneaded for 20 minutes. Then, 50 g of the treated fly ash was shaken at room temperature for 100 minutes in 500 ml of pure water adjusted to pH = 5, and the concentration of the metal eluted in the water was measured by atomic absorption spectrometry. A similar dissolution test was performed on untreated fly ash that had not been treated with a metal collecting agent (Reference Example 2). Table 4 shows the results.
[0056]
[Table 4]

[0057]
Examples 25 to 30, Comparative Example 5
An aqueous solution of the metal collector shown in Table 5 was solidified on the surface of 70 g of sludge (water content: 82%) containing 4320 mg / kg of lead, 139 mg / kg of mercury, 1850 mg / kg of chromium, 356 mg / kg of iron, and 532 mg / kg of cadmium. The mixture was sprayed so that the amount of the mold component added was 0.1 g, kneaded, and allowed to stand for 80 minutes. 50 g of the sludge after standing was shaken in 500 ml of pure water adjusted to pH = 6 at room temperature for 100 minutes, and the concentration of the metal eluted in the water was measured by atomic absorption spectrometry. The same dissolution test was also performed on untreated sludge that had not been treated with a metal collecting agent (Reference Example 3). Table 5 shows the results.
[0058]
[Table 5]

[0059]
Examples 31 to 36, Comparative Example 6
Mercury 250 mg / Nm ^3, cadmium 12 mg / Nm ^3, the flue gas containing dust 15 mg / Nm ^3, the aqueous solution of a metal scavenger as shown in Table 6, the smoke path at a rate of 3 mg / time (as solid content) And collected with a bag filter. After mercury and cadmium remaining in the smoke after the spray treatment of the aqueous solution of the metal-collecting agent were absorbed by the absorbing solution, the concentrations of the respective metals were measured by atomic absorption spectrometry. Table 6 shows the results.
[0060]
[Table 6]

[0061]
【The invention's effect】
As described above, the metal scavenger of the present invention has a dithioacid group and / or a dithioacid group, an alkylene carboxylate group and / or an alkylene carboxylate group, and has an alkylene phosphate group and / or an alkylene carboxylate group. phosphate groups, possess at least one of the oxime group and / or amidoxime groups, and with the substituent has been introduced at a specific substitution rate, the dithio group and / or dithio acid salt, an alkylene carboxylate When the acid group and / or alkylene carboxylate group occupies a specific ratio in all the substituents, calcium ions can be removed from the wastewater even when used in combination with the neutralization aggregation precipitation method using calcium hydroxide as an alkali. Can be effectively collected and removed together with the metal ions, and has the effect of excellent floc sedimentation. Further, the metal collecting agent of the present invention is excellent in the collecting ability for so-called "soft" metal ions, which is relatively weak to the conventional metal collecting agents, and ensures the metal (metal ions) in wastewater and waste gas. This has the effect that the metal in the solid waste can be securely fixed so that the metal is not eluted from the solid waste.

Claims (1)

As a substituent bonded to the nitrogen atom of the polyamino compound, at least one functional group selected from the group (a) and a functional group selected from the group (b) among the functional groups of the following groups (a) to (c): at least one monomer has a functional group, and the group (c), (d) group have at least one functional group of at least one group, bonded active hydrogen to the nitrogen atom of the original polyamino compound And the total substitution ratio of the above substituents is 20 to 100%, and the ratio of the total of the substituents of group (a) and the total of the substituents of group (b) is 20 to 90% in all the substituents. Metal collector characterized by occupying .
(A) a group represented by the following chemical formula 1 (b) a group represented by the following chemical formula 2 (c) a group represented by the following chemical formula 3 (d) an oxime group or an amidoxime group