JP3887484B2 - Filter device and liquid cleaning method using the filter device - Google Patents

Description

【００１４】
［式中、Ｇは糖アルコール残基または多価アルコール残基、
Ｒは水素原子、（低級）アルキル基または−Ｇ（Ｇは上記と同じ意味を表わし、上記Ｇと同一もしくは異なる基であってもよい）を表わす］
その中でも特に好ましいのは、前記式［Ｉ］中のＧが、Ｄ−グルカミンからアミノ基を除いた残基またはジヒドロキシプロピル基であり、Ｒが水素または低級アルキル基である。
【００１５】
これら類金属元素やその化合物とのキレート形成性能（以下、類金属キレート形能と言うことがある）を与えるために繊維分子中に導入される好ましい基は、繊維分子中の反応性官能基（ヒドロキシル基、アミノ基、イミノ基、アルデヒド基、カルボキシル基、チオール基など）等に直接結合していてもよく、あるいは架橋結合によって間接的に結合していても構わない。またベースとなる繊維としては、天然繊維、再生繊維、合成繊維のいずれも使用可能であるが、上記の様なキレート形成能を有する基を効率よく導入するうえで特に好ましいのは天然繊維もしくは再生繊維である。
【００１６】
なお、上記類金属キレート形成性繊維の製法は特に制限されないが、好ましいのは、繊維分子中の反応性官能基に、下記一般式［II］で示されるアミン化合物を直接反応させ、
【００１７】
【化３】

【００１８】
［式中、Ｇ，Ｒは前記と同じ意味］
あるいは、繊維分子中の反応性官能基に、分子中にエポキシ基、反応性二重結合、ハロゲン基、アルデヒド基、カルボキシル基、イソシアネート基などから選ばれる２個以上の基を有する化合物を反応させた後、前記式［２］で示されるアミン化合物を反応させるところに特徴を有している。ここで用いられるアミン化合物としては、類金属キレート形成能、繊維分子との反応性、コスト等を総合的に考えて最も実用的なのはＤ−グルカミンやＮ−メチル−Ｄ−グルカミンあるいはジヒドロキシプロピルアミンである。
【００１９】
【発明の実施の形態】
本発明に係るフィルター装置の構成素材となる類金属キレート形成性繊維は、
上記の様に、繊維の分子中にアミノ基と、ヒドロキシル基、好ましくは２個以上のヒドロキシル基を持った基、更に好ましくは、２個以上のヒドロキシル基が隣接する炭素原子に結合している基とを導入することによって、類金属キレート形成能を与えたところに特徴を有しており、例えば、Ｎ−メチル−Ｄ−グルカミン残基の導入された繊維による類金属キレート捕捉反応を、硼素を例にとって示すと下記式[III] に示す通りである。
【００２０】
【化４】

【００２１】
即ちこのキレート形成性繊維は、繊維分子中にアミノ基と２個以上のヒドロキシル基とを持った基、とりわけ隣接する炭素に結合した少なくとも２個のヒドロキシル基とを持った基が導入されており、硼素などの類金属元素に対して優れたキレート形成能を示し、それにより、類金属を効果的に捕捉することが可能となる。
【００２２】
類金属キレート形成能が付与されるベース繊維の種類は特に制限されず、例えば綿、麻などを始めとする種々の植物繊維；絹、羊毛などを始めとする種々の動物性繊維；ビスコースレーヨンなどを始めとする種々の再生繊維；ポリアミド、アクリル、ポリエステルなどを始めとする様々の合成繊維を使用することができ、これらの繊維は必要に応じて各種の変性を加えたものであっても構わない。
【００２３】
これらベース繊維の中でも特に好ましいのは、繊維分子中にヒドロキシル基やアミノ基等の反応性官能基を有する植物性繊維や動物性繊維、再生繊維であり、これらの繊維であれば、該繊維分子中の反応性官能基を利用して前述の様な類金属キレート形成能を持った基を容易に導入することができるので好ましい。もっとも、原料繊維自体が反応性官能基を有していない場合であっても、これを酸化など任意の手段で変性して反応性官能基を導入し、この官能基を利用して前述の様な基を導入することも可能である。
【００２４】
上記ベース繊維の形状にも格別の制限はなく、長繊維のモノフィラメント、マルチフィラメント、短繊維の紡績糸あるいはこれらを織物状もしくは編物状に製織もしくは製編した布帛や紐、更には不織布や紙であってもよい。また、２種以上の繊維を複合もしくは混紡した繊維や織・編物を使用することもできる。
【００２５】
上記ベース繊維に導入される基としては、前記式[III] からも明らかである様に、類金属とのキレートを形成することの必要上、アミノ基と、２個以上のヒドロキシル基、とりわけ隣接する炭素に結合した２個以上のヒドロキシル基を有することが必要となる。
【００２６】
この様な要件を満たす好ましい基は、前記式［Ｉ］として示した通りであり、該式［Ｉ］中、Ｇは糖アルコール残基または多価アルコール残基を示し、Ｒは水素原子、（低級）アルキル基または−Ｇ（Ｇは上記と同じ意味を表わし、前記−Ｇと同一もしくは異なるものであってもよい）を表わし、Ｒの中でも実用性の高いのは水素または（低級）アルキル基である。上記において（低級）アルキル基としてはＣ₁〜Ｃ₆のアルキル基が挙げられるが、中でも特に好ましいのはメチル基またはエチル基である。
【００２７】
上記一般式［Ｉ］で示される基の中でも特に好ましいのは、Ｇが糖アルコール残基または多価アルコール残基、Ｒが水素原子または（低級）アルキル基である基であり、具体例としては、Ｄ−グルカミン、Ｄ−ガラクタミン、Ｄ−マンノサミン、Ｄ−アラビチルアミン、Ｎ−メチル−Ｄ−グルカミン、Ｎ−エチル−Ｄ−グルカミン、Ｎ−メチル−Ｄ−ガラクタミン、Ｎ−エチル−Ｄ−ガラクタミン、Ｎ−メチル−Ｄ−マンノサミン、Ｎ−エチル−Ｄ−アラビチルアミンなどからアミノ基を除いた糖アルコール残基、あるいはジヒドロキシアルキル基が例示されるが、繊維分子への導入の容易性や原料の入手容易性等を考慮して最も好ましいのは、Ｄ−グルカミンやＮ−メチル−Ｄ−グルカミンのアミノ基を除いた残基あるいはジヒドロキシプロピル基である。
【００２８】
これら類金属キレート形成能を与えるため繊維分子中に導入される基は、繊維分子中の反応性官能基（例えば、ヒドロキシル基、アミノ基、イミノ基、カルボキシル基、アルデヒド基、チオール基など）等に直接結合していてもよく、あるいは架橋結合を介して間接的に結合していても構わないが、繊維分子への導入の容易性を考えると、後述する様な架橋結合を介して間接的に導入したものが、実用性の高いものとして推奨される。
【００２９】
また上記類金属キレート形成性繊維を製造する方法は特に制限されず、繊維分子が元々有している前述の様な反応性官能基もしくは変性によって導入した反応性官能基に、たとえば前記一般式［II］で示されるアミン化合物を直接反応させ、あるいは、該反応性官能基に、分子中にエポキシ基、反応性二重結合、ハロゲン基、アルデヒド基、カルボキシル基、イソシアネート基の如き官能基を２個以上有する化合物を反応させた後、前記式［II］で示されるアミン化合物を反応させる方法が採用される。
【００３０】
即ち、繊維分子が水酸基やカルボキシル基等を有している場合は、これらの基に前記一般式［II］で示されるアミン化合物を直接反応させ、これを繊維分子にペンダント状に導入することができ、この場合の代表的な反応を例示すると下記の通りである。
【００３１】
【化５】

【００３２】
また繊維分子中の反応性官能基とアミン化合物との反応性が乏しい場合は、繊維に先ず架橋剤を反応させることによって、前記アミン化合物との反応性の高い官能基をペンダント状に導入し、次いでこの官能基に前記アミン化合物を反応させることによって、類金属キレート形成能を有する基をペンダント状に導入することができる。特に後者の方法を採用すれば、繊維に対する架橋剤やアミン化合物の使用量を調整することによって、使用目的に応じた類金属捕捉能（即ち、類金属キレート形成能を有する基の導入量）を任意に制御することができるので好ましい。
【００３３】
ここで用いられる好ましい架橋剤としては、エポキシ基、反応性二重結合、ハロゲン基、アルデヒド基、カルボキシル基、イソシアネート基などを２個以上、好ましくは２個有する化合物が挙げられ、好ましい架橋剤の具体例としては、グリシジルメタクリレート、グリシジルアクリレート、アリルグリシジルエーテル、グリシジルソルベート、エピクロルヒドリン、エピブロモヒドリン、エチレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、マレイン酸、こはく酸、アジピン酸、グリオキザール、グリオキシル酸、トリレンジイソシアネート、ヘキサメチレンジイソシアネートなどが例示され、中でも特に好ましいのはグリシジルメタクリレート、エピクロルヒドリン、エチレングリコールジグリシジルエーテル等である。
【００３４】
上記の様な架橋剤を用いてアミン化合物を導入する際の具体的な反応を例示すると、次の通りである。
【００３５】
【化６】

【００３６】
これらの架橋剤を用いて類金属キレート形成能を有する基を繊維に導入する際の反応は特に制限されないが、好ましい方法を挙げると、ベース繊維と前記架橋剤を水あるいはＮ，Ｎ’−ジメチルホルムアミドやジメチルスルホキシド等の極性溶媒中で、必要により反応触媒、乳化剤等を併用して、６０〜１００℃程度で３０分〜数十時間程度反応させる方法であり、この反応により、架橋剤が繊維分子中の反応性官能基（例えば、ヒドロキシル基やアミノ基など）と反応して繊維と結合し、前記式［II］で示した様なアミン化合物と容易に反応する官能基を繊維分子中に導入することができる。次いで、該官能基を導入した繊維と前記アミン化合物を、水やＮ，Ｎ’−ジメチルホルムアミド、ジメチルスルホキシド等の極性溶媒中で、必要により反応触媒を用いて６０〜１００℃で３０分〜数十時間程度反応させると、上記アミン化合物のアミノ基が架橋剤の反応性官能基（例えばエポキシ基やハロゲン基など）と反応し、前記式［Ｉ］で示される類金属キレート形成能を有する基が繊維分子中にペンダント状に導入される。
【００３７】
この反応は、上記の様に通常は逐次的に行なわれるが、反応系によっては架橋剤とアミン化合物を同時に共存させ、繊維に対して同時並行的に反応させることも可能である。この反応に使用するベース繊維としては、長繊維のモノフィラメント、マルチフィラメント、短繊維の紡績糸あるいはこれらを織物状もしくは編物状に製織もしくは製編した布帛、更には不織布や紙等を任意に選択して使用することができ、また、２種以上の繊維を複合もしくは混紡した繊維や織・編物を使用し得ることは、先に説明した通りである。
【００３８】
ベース繊維に対する前記類金属キレート形成能を有する基の導入量は、ベース繊維分子中の反応性官能基の量を考慮し、その導入反応に用いるアミン化合物の量、あるいは架橋剤とアミン化合物の量や反応条件などによって任意に調整できるが、繊維に十分な類金属捕捉能を与えるには、下記式によって計算される置換率が１０重量％程度以上、より好ましくは２０重量％程度以上となる様に調整することが望ましい。
置換率（重量％）＝［（置換基導入後の繊維重量−置換基導入前の繊維重量）／置換基導入前の繊維重量］×１００
（ただし置換基とは、前記式［１］で示される基を表わす）
【００３９】
類金属捕捉能を高めるうえでは、上記置換率は高い程好ましく、従って置換率の上限は特に規定されないが、置換率が高くなり過ぎると置換基導入繊維の結晶性が高くなって繊維が脆弱になる傾向があるので、類金属捕捉材としての実用性や経済性などを総合的に考慮すると、置換率は１３０重量％程度以下、より好ましくは８０重量％程度以下に抑えることが望ましい。ただし、繊維分子中の官能基やアミン化合物、架橋剤の種類、あるいは用途等によっては、１５０〜２００重量％といった高レベルの置換率とすることにより、類金属捕捉能を高めることも可能である。
【００４０】
上記の様にして得られる類金属キレート形成性繊維は、用いるベース繊維の性状に応じてモノフィラメント状、マルチフィラメント状、紡績糸状、不織布状、繊維織・編物状、紐状、更には紙など任意の性状のものとして得ることができるが、いずれにしても細径の繊維の分子表面に導入された前述の類金属キレート形成性を有する基の実質的に全てが、類金属捕捉性能を有効に発揮するので、従来の粒状形態のものに比べて格段に優れた類金属捕捉能を発揮する。
【００４１】
この様に本発明で使用するキレート形成性繊維は、類金属イオンに対して優れたキレート捕捉能を有しているので、このキレート繊維をフィルター素材の一部もしくは全部として用いて必要に応じた繊維間隙間のフィルター装置を作製し、これに液体を通すと、該液体に含まれる類金属イオンがキレート捕捉されて除去されると共に、固体状態で混入している不溶性夾雑物も同時に除去され、被処理液体を一回の処理で高度に清浄化することが可能となる。
【００４２】
この場合、本発明で使用する類金属キレート形成性繊維は通常のフィルター素材に比べて高価であるので、好ましくは被処理液体中の不溶性夾雑物の大部分を適当な手段で予め除去しておき、その後で類金属キレート形成性繊維層を通すことによって、残りの不溶性夾雑物と類金属イオンを同時に除去することが望ましい。
【００４３】
尚フィルター装置の構成自体は格別特殊なものではなく、その用途に応じて前記キレート形成性繊維を一部もしくは全構成素材として使用し、任意の繊維間隙間を有する織・編物もしくは不織布からなる単層もしくは複層構造のマット状に成形して適当な支持体に組み付けた構造、あるいは通液性支持筒の外周側にキレート形成繊維からなる紐状物を綾巻状に複数層巻回した構造、または同繊維からなる織・編物もしくは不織布シートをプリーツ状に折り曲げて支持部材に装着した構造、同繊維を用いて作製した織・編物や不織布を袋状に成形したバグフィルタータイプなど、公知の全てのフィルター装置と同様に成形できる。
【００４４】
このとき、使用するキレート形成性繊維の太さや織・編密度、積層数や積層密度などを調整し、また紐状のキレート形成性繊維を複数層に巻回してフィルター装置とする場合は、巻回の密度や層厚、巻回張力などを調整することによって、繊維間隙間を任意に調整できるので、被処理液体中に混入している不溶性夾雑物の粒径に応じて該繊維間隙間を調整すれば、必要に応じた清浄化性能のフィルター装置を得ることができる。
【００４５】
なお本発明のフィルター装置は、フィルター素材の全てを前記キレート形成性繊維で構成し、フィルター層全体に類金属イオンと不溶性夾雑物に対する除去性能を与えることができるが、本発明のキレート形成性繊維は通常のフィルター素材に比べて高価であるので、被処理液体中に含まれる類金属イオンと不溶性夾雑物の含有比率に応じて、キレート形成性繊維と通常の濾過用フィルター素材を適当な比率で組み合わせ（混紡、混織・混編、積層など）、比較的低コストで高い清浄化効果が得られる様にすることも可能である。
【００４６】
また該フィルター装置の作製に当たっては、前述した様な方法によって作製した類金属キレート形成性繊維よりなる不織布、織・編物、紐などをフィルター装置内に組み込むことも勿論可能であるが、類金属キレート形成性化合物との反応性官能基を有する基を有し（あるいは導入された）繊維をフィルター素材とするフィルター装置に、類金属キレート形成性化合物含有液を循環させ、該フィルター素材に類金属キレート形成性官能基を事後的に導入することによって、キレート捕捉能を与えることも可能である。従って、例えばセルロース等をフィルター構成素材とする通常のフィルター装置を使用し、これに類金属キレート形成性官能基を導入することによって、類金属イオン除去性能を兼ね備えた本発明のフィルター装置とすることもできる。
【００４７】
本発明は以上の様に構成されており、フィルター素材としてキレート形成性繊維を使用することにより、次の様な利点を享受できる。
【００４８】
▲１▼従来の粒状キレート樹脂には、キレート捕捉に機能する部位として外周面と細孔部があるが、細孔部は拡散が遅くて実質的に全官能基がキレート捕捉に寄与し得ないので、キレート樹脂全体としては有効活用率が極めて低く、且つ捕捉し得る元素の絶対量も不十分とならざるを得ず、また不溶性夾雑物に対する除去性能は殆んど期待できないが、本発明のフィルターでは、繊維表面に導入されたキレート形成性官能基の全てが類金属成分のキレート捕捉に有効に活用されると共に有効比表面積も大きいので、少量の使用で極めて高いキレート捕捉能が得られると共に、繊維間隙間を調整することによって、被処理液体中の不溶性夾雑物を同時に除去することができ、一回の処理で高い清浄化効果が得られる。
【００４９】
▲２▼キレート形成性官能基がフィルター素材を構成する繊維表面に露出しているので、吸着速度が高い。
【００５０】
▲３▼粒状キレート樹脂は一般に乾燥すると脆弱になって微粉化し、実用できなくなるが、本発明で使用するキレート繊維は、繊維素材にキレート形成性官能基を導入したものであるから、乾燥しても脆化することがなく、再生による繰り返し使用も容易である。
【００５１】
▲４▼粒状キレート樹脂では、充填容器の形状によって使用形態が制限されるが、本発明はキレート形成性繊維をフィルター素材とするものであるから、不織布状や織編物状、紐状などとすることにより、使用目的に応じた任意の形状のフィルターに成形できる。
【００５２】
▲５▼粒状キレート樹脂では、粒径によって空隙率が自動的に決まってくるが、キレート繊維であれば、形態を変えることによって充填密度や繊維間空隙を任意に変更できるので、被処理液体中に含まれる不溶性夾雑物の粒径に応じた高い清浄化効果を確保できる。
【００５３】
▲６▼本発明のフィルターを使用すれば、キレート形成性繊維で類金属成分と不溶性夾雑物を捕捉した後、例えば塩酸や硫酸等の強酸水溶液で処理することにより、キレートを形成して捕捉された類金属元素のみを簡単に離脱させることができ、それにより再生液から類金属成分を有価成分として回収することも可能となる。
【００５４】
尚、本発明で使用する前記のキレート形成性繊維は、上記の様に繊維状とすることによってもたらされる利点に加えて、他の金属イオン、例えばＭｇ，Ｃａ，Ｚｎ，Ｎａ，Ｋ等の金属、あるいはその他の陰イオン、たとえばフッ素、塩素、沃素等のハロゲンイオン等が共存する場合でも類金属成分と選択的にキレートを形成するという特性を有しており、類金属の選択的捕捉材としても極めて有効に活用することができる。従って、様々の製造工程において、Ｍｇ，Ｃａ，Ｎａ，Ｋなどが含まれる工程液から有害な類金属だけを除去し、あるいは、例えば飲料水や食品加工用水中に含まれることのあるＭｇ，Ｃａ，Ｎａ，Ｋ等を残して有害な類金属のみを除去することも可能である。
【００５５】
かくして本発明のフィルター装置であれば、構成素材として使用するキレート形成性繊維独自の類金属キレート形成能によって類金属を効率よく除去できると共に、不溶性夾雑物を同時に除去することができ、例えば次に示す様な被処理液体の清浄化に有効に活用できる。
【００５６】
ａ．飲料水や食品加工用水の浄化（特に類金属を含む有害イオン性物質と不溶性夾雑物の同時除去）。
ｂ．ポリエステル製造時に未反応物として留去されるエチレングリコール中に重合触媒として混入してくるゲルマニウムの除去。
【００５７】
ｃ．食用油脂などに含まれることのあるひ素と共に不溶性夾雑物の除去。
ｄ．エンジンオイルやモータオイル等の廃油中に防錆成分として含まれることのある硼素の除去（廃油処理）。
【００５８】
ｅ．超純水製造時における硼素や珪素と共に不溶性夾雑物の除去。
ｆ．石炭を燃料とする火力発電設備から排出される排水中に混入してくるセレン等と共に不溶性夾雑物の除去清浄化。
【００５９】
ｇ．原子力発電設備や天然ガス利用設備から排出される排水中に混入してくる硼素と共に不溶性夾雑物の除去清浄化。
ｈ．石炭塵灰洗浄排水から硼素と共に不溶性介在物の除去清浄化。
【００６０】
【実施例】
次に本発明の実施例を示すが、本発明はもとより下記実施例によって制限を受けるものではなく、前後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に含まれる。
【００６１】
実施例
綿製の紡績糸をステンレス製のコア材に綾巻き状に巻回した市販のカートリッジフィルター（アドバンテック東洋社製、商品名「ＴＣＷ−１−ＣＳＳ」：公称孔径１μｍ）を、ポリプロピレン製ハウジング（アドバンテック東洋社製、商品名「１ＰＰ−１−ＦＳ−０００」）に装着し、これに、グリシジルメタクリレート５３．６ｇ、非イオン界面活性剤（第一工業製薬社製、商品名「ノイゲンＥＡ１２６」）２．７ｇ、非イオン界面活性剤（日本油脂社製、商品名「ノニオンＯＴ−２２１」）２．７ｇ、３１％Ｈ₂ Ｏ₂ 水５．８ｇ、０．５％二酸化チオ尿素水溶液４７１．２ｇを、蒸留水７０００ｍｌに溶解した溶液を、循環ポンプを用いて１５リットル／分の流速で６０℃×１時間循環させ、綿紡績糸分子中にグリシジルメタクリレートをグラフトさせ、次いで反応液を排出した後、蒸留水３０００ｍｌを循環させて洗浄した。
【００６２】
次に、蒸留水３０００ｍｌにＮ−メチル−Ｄ−グルカミン１５００ｇを溶解させた溶液を、グリシジルメタクリレートをグラフトさせた前記フィルターに８０℃で２時間循環させ、フィルターを構成する綿紡績糸に類金属キレート形成性官能基を導入し、その後蒸留水を用いて洗浄液が中性になるまで循環・廃液を繰り返して類金属キレート形成性フィルターを得た。
【００６３】
この類金属キレート形成性フィルターを、前記ポリプロピレン製ハウジングに装着し、硼酸を蒸留水に溶解して硼素濃度を１０ｐｐｍに調整した溶液１０リットルに、不溶性夾雑物として平均粒径１０μｍの二酸化珪素微粉末２．０１ｇを分散させた試験液を１５リットル／分の流速で２５℃で３０分間循環させた。
【００６４】
その後、試験液の硼素濃度を定量したところ、１ｐｐｍ以下に低減していることが確認された。また該試験液１リットルを孔径０．１μｍのメンブランフィルターに通し残存する二酸化珪素量を測定することによってその除去率を求めたところ、９６％であることが確認された。
【００６５】
実施例２
上記実施例１と同様にして得た類金属キレート形成性フィルターを、前記ポリプロピレン製ハウジングに装着し、酸化ゲルマニウムをアルカリ溶解させた後中性にしてゲルマニウム濃度を１０ｐｐｍに調整した溶液１０リットルに、不溶性夾雑物として平均粒径１０μｍの二酸化珪素微粉末１．９８ｇを分散させた試験液を、１５リットル／分の流速で２５℃で３０分間循環させた。
【００６６】
その後、試験液のゲルマニウム濃度を定量したところ、１ｐｐｍ以下に低減していることが確認された。また該試験液１リットルを孔径０．１μｍのメンブランフィルターに通し残存する二酸化珪素量を測定することによってその除去率を求めたところ、９７％であることが確認された。
【００６７】
実施例３
上記実施例１と同様にして得た類金属キレート形成性フィルターを、前記ポリプロピレン製ハウジングに装着し、三酸化ひ素をアルカリ溶解させてひ素濃度を１０ｐｐｍに調整溶液５リットルに、不溶性夾雑物として平均粒径１０μｍの二酸化珪素微粉末１．０４ｇを分散させた試験液を、１５リットル／分の流速で２５℃で３０分間循環させた。
【００６８】
その後、試験液のひ素濃度を定量したところ、１ｐｐｍ以下に低減していることが確認された。また該試験液１リットルを孔径０．１μｍのメンブランフィルターに通し残存する二酸化珪素量を測定することによってその除去率を求めたところ、９７％であることが確認された。
【００６９】
実施例４
上記実施例１において、綿製の紡績糸をステンレス製のコア材に綾巻き状に巻回したカートリッジフィルターに代えて、セルロース繊維ろ紙をプリーツ状に成型したカートリッジフィルター（アドバンテック東洋社製、商品名「ＴＣ−１」：公称孔径１μｍ）を使用した以外は実施例１と同様にして類金属キレート形成性フィルターを得た。
【００７０】
得られた類金属キレート形成性フィルター素材を、前記と同じポリプロピレン製ハウジングに装着し、硼酸を蒸留水に溶解して硼素濃度を１０ｐｐｍに調整した溶液１０リットルに、不溶性夾雑物として平均粒径１０μｍの二酸化珪素微粉末１．８９ｇを分散させた試験液を１５リットル／分の流速で２５℃で３０分間循環させた。
【００７１】
その後、試験液の硼素濃度を定量したところ、１ｐｐｍ以下に低減していることが確認された。また該試験液１リットルを孔径０．１μｍのメンブランフィルターに通し残存する二酸化珪素量を測定することによってその除去率を求めたところ、９７％であることが確認された。
【００７２】
実施例５
上記実施例１と同様にして得た類金属キレート形成性フィルターを、ステンレス製ハウジング（アドバンテック東洋社製、商品名「１ＴＳ」）に装着し、これに、硼素濃度３５ｐｐｍのエンジンオイル２リットルに、不溶性夾雑物として平均粒径１０μｍの二酸化珪素微粉末０．４６ｇを分散させた試験液を、１リットル／分の流速で２５℃で３０分間循環させた。
【００７３】
その後、試験液の硼素濃度を定量したところ、１ｐｐｍ以下に低減していることが確認された。また該試験液１リットルをミネラルスピレットで希釈した後、孔径０．１μｍのメンブランフィルターに通し残存する二酸化珪素量を測定することによってその除去率を求めたところ、９５％であることが確認された。
【００７４】
【発明の効果】
本発明は以上の様に構成されており、フィルター素材として類金属成分に対して高い捕捉能を有し且つ不溶夾雑物除去性能を兼ね備えた類金属キレート捕捉性繊維を使用することによって、被処理液体中の類金属成分と不溶性夾雑物を同時に除去することができ、それらの清浄化を極めて効率よく行なうことができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel filter device capable of efficiently removing and cleaning particularly similar metal ions and insoluble impurities in an untreated liquid, and a liquid cleaning method using the filter device. This filter device efficiently removes similar metals (boron, germanium, arsenic, antimony, selenium, tellurium, etc.) contained in aqueous liquids and oily liquids, and insoluble impurities contained in these liquids to be treated. Since it can be removed at the same time, for example, purification of drinking water, water for food processing, etc. (especially simultaneous removal of harmful ionic substances including inferior metals and insoluble impurities), ethylene glycol distilled off as unreacted substances during polyester production Remove and purify insoluble impurities together with germanium mixed in as a polymerization catalyst, arsenic that may be contained in edible oils and fats, etc. It can be effectively used at the time.
[0002]
[Prior art]
Boron and boron compounds, one of the group metal elements, are widely distributed in nature and are essential elements for the human body, but on the other hand, it has been confirmed that adverse effects will be caused if the intake is excessive. . In addition, there are reports of cases that appear to be human pollution due to boron components contained in rivers and groundwater, and there is concern about adverse effects on water reuse. In the reuse, it is necessary to remove insoluble contaminants in addition to removing boron components and the like, but no apparatus capable of performing these two simultaneously has been proposed.
[0003]
In addition to boron, for example, arsenic and arsenic compounds are harmful to the human body, and it is necessary to remove insoluble inclusions together with the compounds from drinking water and the like that are likely to be mixed. I can't do that either.
[0004]
The present invention efficiently removes these metallic elements and their compounds from a liquid to be treated such as water or edible oil, and simultaneously efficiently removes and purifies insoluble impurities contained in the liquid to be treated. The present invention also provides a technique capable of cleaning a liquid to be treated such as water and oil using the filter apparatus.
[0005]
As a method for removing a similar metal such as boron in water, a method using a basic ion exchange resin is conceivable. However, according to the present inventors, the basic ion exchange resin for a similar metal such as boron is considered. The selective adsorptivity is extremely low, and when other anions coexist in the treatment system, the trapping performance of the metal-like component is extremely lowered.
[0006]
On the other hand, there is a chelate resin having the capability of capturing boron components, and a method for removing boron components contained in irrigation water using the chelate resin is also known, but these are chelate captures of ionized boron components. There is no way to actively remove insoluble contaminants at the same time. This chelate resin is a bead-like or granular resin in which an aminopolyol group is introduced into a rigid three-dimensional cross-linked polymer such as styrene-divinylbenzene type or phenolaldehyde type. It is pointed out that the regeneration rate is very slow when regenerating a chelate resin that is small and captures the boron component.
[0007]
Therefore, in order to increase the trapping speed and regeneration speed of the metal ions by increasing the diffusion penetration rate of the above metal ions and regenerant, the particle size of the chelate resin is reduced to increase the surface area, and contact with the liquid to be treated. A method of increasing the effective area is also conceivable. However, for that purpose, the particle size of the chelate resin must be reduced, so that the chelate resin is easily scattered and not only is troublesome to handle, but also the flow resistance of the chelate resin packed layer when performing water treatment or the like. Increases, and the problem of deteriorating the processing efficiency arises.
[0008]
In addition, when a chelate resin that has lost its regenerative ability is discarded, it is pointed out that in the case of a bead-like or granular chelate resin, the incineration process is difficult or the volume reduction process is complicated.
[0009]
Furthermore, although the conventional chelate resin exhibits a certain level of metal ion scavenging ability although it is low efficiency as described above, the effect of removing insoluble suspended impurities mixed in the liquid to be treated is not limited. Almost no. Therefore, in order to remove these floating contaminants and sufficiently clean the liquid to be treated, the floating impurities in the liquid to be treated must be removed before or after removal of metal ions by the chelate resin, To obtain a reliable cleaning effect, at least two processes are required.
[0010]
[Problems to be solved by the invention]
The present invention has been made by paying attention to the above-mentioned circumstances, and its first object is to have an excellent trapping performance for similar metal elements such as boron and germanium and compounds thereof. In addition, the present invention provides a chelate-forming fiber that is easy to incinerate and can be manufactured at a low cost by a simple and safe method, and makes the best use of the special properties of the chelate fiber to The object is to develop a filter device capable of efficiently removing metal ions and insoluble impurities simultaneously, and to establish a method capable of efficiently cleaning a liquid using the filter device.
[0011]
[Means for Solving the Problems]
The filter device according to the present invention that has solved the above-mentioned problems includes a group having an amino group and at least two hydroxyl groups, particularly at least two hydroxyl groups bonded to adjacent carbons, in a fiber molecule. It has a gist where the chelate-forming fiber having an excellent chelate-forming ability with respect to a similar metal element or a compound thereof is arranged as at least a part of the filter material. By adjusting the interfiber gaps of the chelate-forming fibers according to the size of the insoluble contaminants mixed in the liquid to be treated, the insoluble contaminants can be removed together with the metal ions, and the treated liquid can be removed. Liquid can be cleaned efficiently with simple processing.
[0012]
A preferred group to be introduced into the fiber molecule in order to give the chelate-forming fiber, which is the main constituent material of the filter, to form a chelate with a similar metal element or a compound thereof, is represented by the following general formula [I]. Can be represented by
[0013]
[Chemical 2]

[0014]
[Wherein G is a sugar alcohol residue or a polyhydric alcohol residue,
R represents a hydrogen atom, a (lower) alkyl group, or -G (G represents the same meaning as described above, and may be the same or different group as G)]
Among these, G in the formula [I] is particularly preferably a residue obtained by removing an amino group from D-glucamine or a dihydroxypropyl group, and R is hydrogen or a lower alkyl group.
[0015]
A preferred group introduced into the fiber molecule in order to give chelate-forming performance (hereinafter sometimes referred to as metal-like chelate formability) with these metal group elements and compounds thereof is a reactive functional group ( A hydroxyl group, an amino group, an imino group, an aldehyde group, a carboxyl group, a thiol group, and the like), or may be indirectly bonded by a cross-linking bond. As the base fiber, any of natural fiber, regenerated fiber, and synthetic fiber can be used, but natural fiber or regenerated fiber is particularly preferable for efficiently introducing the group having the chelate forming ability as described above. Fiber.
[0016]
The method for producing the metal chelate-forming fiber is not particularly limited. Preferably, the reactive functional group in the fiber molecule is directly reacted with an amine compound represented by the following general formula [II],
[0017]
[Chemical 3]

[0018]
[Wherein G and R have the same meaning as described above]
Alternatively, the reactive functional group in the fiber molecule is reacted with a compound having two or more groups selected from epoxy group, reactive double bond, halogen group, aldehyde group, carboxyl group, isocyanate group, etc. in the molecule. Thereafter, the amine compound represented by the formula [2] is reacted. As the amine compound used here, D-glucamine, N-methyl-D-glucamine or dihydroxypropylamine is most practical in consideration of the metal chelate forming ability, reactivity with fiber molecules, cost, etc. is there.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
The metal-like chelate-forming fiber that is the constituent material of the filter device according to the present invention,
As described above, an amino group and a hydroxyl group, preferably a group having two or more hydroxyl groups, more preferably two or more hydroxyl groups are bonded to adjacent carbon atoms in the fiber molecule. And a group having a metal group chelate-forming ability. For example, a metal group chelate scavenging reaction by a fiber into which an N-methyl-D-glucamine residue has been introduced can be obtained. Is shown by the following formula [III].
[0020]
[Formula 4]

[0021]
That is, in this chelate-forming fiber, a group having an amino group and two or more hydroxyl groups, particularly a group having at least two hydroxyl groups bonded to adjacent carbons is introduced into the fiber molecule. It exhibits an excellent chelate-forming ability with respect to a group metal element such as boron, and thereby it is possible to effectively capture the group metal.
[0022]
The type of base fiber to which the metal chelate-forming ability is imparted is not particularly limited, for example, various plant fibers such as cotton and hemp; various animal fibers such as silk and wool; viscose rayon Various synthetic fibers such as polyamide, acrylic, polyester and the like can be used, and these fibers may be variously modified as required. I do not care.
[0023]
Among these base fibers, particularly preferred are plant fibers, animal fibers, and regenerated fibers having a reactive functional group such as hydroxyl group or amino group in the fiber molecule. The group having the ability to form a metal chelate as described above can be easily introduced using the reactive functional group therein, which is preferable. However, even if the raw fiber itself does not have a reactive functional group, it is modified by any means such as oxidation to introduce a reactive functional group, and this functional group is used as described above. It is also possible to introduce various groups.
[0024]
There is no particular limitation on the shape of the base fiber, and it is possible to use long-fiber monofilaments, multifilaments, spun yarns of short fibers, or fabrics or strings woven or knitted in a woven or knitted shape, and also non-woven fabric or paper There may be. Further, a fiber or a woven / knitted fabric obtained by combining or blending two or more kinds of fibers can also be used.
[0025]
As is apparent from the above formula [III], the group to be introduced into the base fiber is required to form a chelate with a similar metal, so that an amino group and two or more hydroxyl groups, particularly adjacent groups are used. It is necessary to have two or more hydroxyl groups bonded to the carbon to be used.
[0026]
A preferred group satisfying such requirements is as shown in the formula [I], wherein G represents a sugar alcohol residue or a polyhydric alcohol residue, R represents a hydrogen atom, ( Lower) alkyl group or -G (G represents the same meaning as described above, and may be the same as or different from -G). Among R, hydrogen or (lower) alkyl group is highly practical. It is. In the above, the (lower) alkyl group is C ₁ ~ C ₆ Among them, a methyl group or an ethyl group is particularly preferable.
[0027]
Among the groups represented by the above general formula [I], particularly preferred is a group in which G is a sugar alcohol residue or a polyhydric alcohol residue, R is a hydrogen atom or a (lower) alkyl group, , D-glucamine, D-galactamine, D-mannosamine, D-arabitylamine, N-methyl-D-glucamine, N-ethyl-D-glucamine, N-methyl-D-galactamine, N-ethyl-D -Examples include galactamine, N-methyl-D-mannosamine, N-ethyl-D-arabitylamine, sugar alcohol residues obtained by removing amino groups, or dihydroxyalkyl groups, but easy introduction into fiber molecules In view of the properties and the availability of raw materials, the most preferred is a residue or dihydroxy group excluding the amino group of D-glucamine or N-methyl-D-glucamine. It is a pill group.
[0028]
The group introduced into the fiber molecule to give these metal chelate forming ability is a reactive functional group in the fiber molecule (for example, hydroxyl group, amino group, imino group, carboxyl group, aldehyde group, thiol group, etc.), etc. It may be directly bonded to each other, or may be indirectly bonded via a cross-linked bond. However, in view of ease of introduction into the fiber molecule, it is indirectly bonded via a cross-linked bond as described later. The one introduced in is recommended as a highly practical one.
[0029]
The method for producing the metal chelate-forming fiber is not particularly limited. For example, the general functional formula [ II] or directly reacting the reactive functional group with 2 functional groups such as an epoxy group, a reactive double bond, a halogen group, an aldehyde group, a carboxyl group, and an isocyanate group in the molecule. A method of reacting an amine compound represented by the above formula [II] after reacting at least one compound is employed.
[0030]
That is, when the fiber molecule has a hydroxyl group, a carboxyl group or the like, the amine compound represented by the general formula [II] can be directly reacted with these groups and introduced into the fiber molecule in a pendant form. The typical reaction in this case is exemplified as follows.
[0031]
[Chemical formula 5]

[0032]
In addition, when the reactivity between the reactive functional group in the fiber molecule and the amine compound is poor, a functional group having high reactivity with the amine compound is introduced in a pendant form by first reacting the fiber with a crosslinking agent, Next, by reacting the functional group with the amine compound, a group having a metal-like chelate-forming ability can be introduced in a pendant form. In particular, if the latter method is adopted, by adjusting the amount of the crosslinking agent or amine compound used for the fiber, the metal group scavenging ability (that is, the introduction amount of a group having a metal group chelate forming ability) according to the purpose of use can be obtained. It is preferable because it can be arbitrarily controlled.
[0033]
Preferred cross-linking agents used here include compounds having two or more, preferably two epoxy groups, reactive double bonds, halogen groups, aldehyde groups, carboxyl groups, isocyanate groups, etc. Specific examples include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, glycidyl sorbate, epichlorohydrin, epibromohydrin, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin diglycidyl ether, polypropylene glycol diglycidyl ether, Examples include maleic acid, succinic acid, adipic acid, glyoxal, glyoxylic acid, tolylene diisocyanate, and hexamethylene diisocyanate. It is given to glycidyl methacrylate, epichlorohydrin, ethylene glycol diglycidyl ether.
[0034]
An example of a specific reaction when the amine compound is introduced using the crosslinking agent as described above is as follows.
[0035]
[Chemical 6]

[0036]
The reaction for introducing a group having a metal-chelate-forming ability into these fibers using these cross-linking agents is not particularly limited. To give a preferred method, the base fiber and the cross-linking agent are either water or N, N′-dimethyl. In a polar solvent such as formamide or dimethyl sulfoxide, a reaction catalyst, an emulsifier, etc. are used together as necessary, and the reaction is carried out at about 60 to 100 ° C. for about 30 minutes to several tens of hours. A functional group that reacts with a reactive functional group in the molecule (for example, a hydroxyl group or an amino group) and binds to a fiber, and easily reacts with an amine compound as shown in the formula [II] in the fiber molecule. Can be introduced. Next, the fiber into which the functional group has been introduced and the amine compound are mixed in a polar solvent such as water, N, N′-dimethylformamide, or dimethyl sulfoxide, if necessary, using a reaction catalyst at 60 to 100 ° C. for 30 minutes to several times. When the reaction is carried out for about 10 hours, the amino group of the amine compound reacts with a reactive functional group (for example, an epoxy group or a halogen group) of the crosslinking agent, and a group having the ability to form a metal chelate represented by the formula [I] Is introduced into the fiber molecule in a pendant form.
[0037]
This reaction is usually carried out sequentially as described above. However, depending on the reaction system, it is possible to cause the crosslinking agent and the amine compound to coexist at the same time and react with the fibers simultaneously. As the base fibers used in this reaction, long-fiber monofilaments, multifilaments, spun yarns of short fibers, fabrics woven or knitted from these fabrics or knitted fabrics, and further nonwoven fabrics and papers are arbitrarily selected. As described above, it is also possible to use a fiber or a woven / knitted fabric obtained by combining or blending two or more kinds of fibers.
[0038]
The amount of the group having the ability to form a metal chelate to the base fiber is determined in consideration of the amount of the reactive functional group in the base fiber molecule, and the amount of the amine compound used for the introduction reaction or the amount of the crosslinking agent and the amine compound. However, in order to give the fibers sufficient metal-capturing ability, the substitution rate calculated by the following formula is about 10% by weight or more, more preferably about 20% by weight or more. It is desirable to adjust to.
Substitution rate (% by weight) = [(fiber weight after introduction of substituent−fiber weight before introduction of substituent) / fiber weight before introduction of substituent] × 100
(However, the substituent represents a group represented by the formula [1])
[0039]
In order to enhance the ability to capture a metal, the higher the substitution rate, the better. Therefore, the upper limit of the substitution rate is not particularly specified, but if the substitution rate is too high, the crystallinity of the substituent-introduced fiber becomes high and the fiber becomes brittle. Therefore, when comprehensively considering the practicality and economical efficiency as a similar metal-trapping material, the substitution rate is desirably about 130% by weight or less, more preferably about 80% by weight or less. However, depending on the functional group in the fiber molecule, the amine compound, the kind of the crosslinking agent, or the use, it is possible to enhance the metal-like capturing ability by setting the substitution rate at a high level of 150 to 200% by weight. .
[0040]
The metal chelate-forming fibers obtained as described above can be arbitrarily selected from monofilament, multifilament, spun yarn, nonwoven fabric, fiber woven / knitted fabric, string, and paper depending on the properties of the base fiber used. In any case, substantially all of the aforementioned group having a metal chelate-forming property introduced on the molecular surface of a fine fiber effectively improves the metal group scavenging performance. Since it exhibits, it exhibits a metal-trapping ability that is far superior to that of conventional granular forms.
[0041]
As described above, the chelate-forming fiber used in the present invention has an excellent chelate-capturing ability for metal ions, so that this chelate fiber is used as a part or all of the filter material as needed. When a filter device between the fiber gaps is made and a liquid is passed through, the metal-like ions contained in the liquid are removed by chelate trapping, and insoluble contaminants mixed in the solid state are simultaneously removed, The liquid to be treated can be highly purified by a single treatment.
[0042]
In this case, the metal-chelate-forming fibers used in the present invention are more expensive than ordinary filter materials, so that most of the insoluble contaminants in the liquid to be treated are preferably removed in advance by appropriate means. Thereafter, it is desirable to remove the remaining insoluble impurities and the metal ions at the same time by passing the metal metal chelate-forming fiber layer.
[0043]
Note that the configuration of the filter device itself is not particularly special. Depending on the application, the chelate-forming fiber is used as a part or all of the constituent material, and a single woven / knitted or non-woven fabric having an arbitrary inter-fiber gap is used. A structure in which a layer or multi-layer structure is formed and assembled to a suitable support, or a structure in which a string of chelate-forming fibers is wound around a liquid-permeable support cylinder in a traverse shape. Or a woven / knitted or non-woven sheet made of the same fiber folded into a pleated shape and attached to a support member, or a bag filter type in which a woven / knitted or non-woven fabric produced using the same fiber is formed into a bag shape, etc. Can be molded in the same way as all filter devices.
[0044]
At this time, when adjusting the thickness, weaving / knitting density, the number of layers, the lamination density, etc. of the chelate-forming fibers to be used and winding the string-like chelate-forming fibers in a plurality of layers to form a filter device, By adjusting the density, layer thickness, winding tension, etc., the inter-fiber gap can be adjusted arbitrarily, so that the inter-fiber gap is set according to the particle size of the insoluble contaminants mixed in the liquid to be treated. If it adjusts, the filter apparatus of the cleaning performance as needed can be obtained.
[0045]
In the filter device of the present invention, all of the filter material is composed of the chelate-forming fiber, and the entire filter layer can be provided with the ability to remove similar metal ions and insoluble impurities, but the chelate-forming fiber of the present invention. Is expensive compared to normal filter materials, so chelate-forming fibers and normal filter materials are used at an appropriate ratio according to the content ratio of metal ions and insoluble impurities contained in the liquid to be treated. It is also possible to obtain a high cleaning effect at a relatively low cost by combining (mixed spinning, mixed weaving / knitting, lamination, etc.).
[0046]
In producing the filter device, it is of course possible to incorporate a non-woven fabric, woven / knitted fabric, string, etc. made of a metal-like chelate-forming fiber produced by the method as described above into the filter device. A metal-containing chelate-forming compound-containing liquid is circulated through a filter device using a fiber having a functional group reactive with a forming compound (or introduced) as a filter material, and the filter material contains a metal-like chelate. It is also possible to provide chelating scavenging ability by introducing a forming functional group afterwards. Therefore, for example, by using a normal filter device using, for example, cellulose or the like as a filter constituent material and introducing a metal-like chelate-forming functional group into this, the filter device of the present invention having metal-like ion removal performance is obtained. You can also.
[0047]
This invention is comprised as mentioned above and can enjoy the following advantages by using chelate-forming fiber as a filter material.
[0048]
(1) The conventional granular chelate resin has an outer peripheral surface and pores as sites that function for chelate capture, but the pores are slow to diffuse and virtually all functional groups cannot contribute to chelate capture. Therefore, the effective utilization rate of the chelate resin as a whole is extremely low, the absolute amount of elements that can be captured must be insufficient, and the removal performance for insoluble contaminants can hardly be expected. In the filter, all the chelate-forming functional groups introduced on the fiber surface are effectively used for chelate capture of metal-like components and the effective specific surface area is large, so that a very high chelate capture ability can be obtained with a small amount of use. By adjusting the inter-fiber gap, insoluble impurities in the liquid to be treated can be removed at the same time, and a high cleaning effect can be obtained by a single treatment.
[0049]
(2) Since the chelate-forming functional group is exposed on the surface of the fibers constituting the filter material, the adsorption rate is high.
[0050]
(3) The granular chelate resin generally becomes brittle and finely pulverized when dried, making it impractical. However, the chelate fiber used in the present invention has a chelate-forming functional group introduced into the fiber material. Are not brittle and can be used repeatedly by regeneration.
[0051]
(4) The usage of the granular chelate resin is limited depending on the shape of the filled container, but since the present invention uses chelate-forming fibers as a filter material, it is made into a nonwoven fabric, woven or knitted fabric, string, etc. Therefore, it can be formed into a filter having an arbitrary shape according to the purpose of use.
[0052]
(5) In granular chelate resins, the porosity is automatically determined by the particle size, but in the case of chelate fibers, the packing density and inter-fiber voids can be changed arbitrarily by changing the form, so A high cleaning effect according to the particle size of the insoluble contaminants contained in can be ensured.
[0053]
(6) If the filter of the present invention is used, a metal compound component and insoluble impurities are captured with a chelate-forming fiber, and then treated with a strong acid aqueous solution such as hydrochloric acid or sulfuric acid to form a chelate and be captured. Only the similar metal element can be easily removed, and it is possible to recover the similar metal component as a valuable component from the regenerated liquid.
[0054]
The chelate-forming fiber used in the present invention has other metal ions such as Mg, Ca, Zn, Na, and K in addition to the advantages brought about by making the fiber as described above. In addition, even when other anions such as halogen ions such as fluorine, chlorine, iodine, etc. coexist, it has the property of selectively forming a chelate with a similar metal component, and as a selective trapping material for similar metals Can be used very effectively. Therefore, in various manufacturing processes, only harmful similar metals are removed from process liquids containing Mg, Ca, Na, K, or the like, or Mg, Ca that may be contained in drinking water or food processing water, for example. , Na, K, etc. can be removed to remove only harmful metal species.
[0055]
Thus, with the filter device of the present invention, it is possible to efficiently remove similar metals by the unique chelate-forming ability of the chelate-forming fiber used as the constituent material, and simultaneously remove insoluble impurities. It can be effectively used to clean the liquid to be treated as shown.
[0056]
a. Purification of drinking water and food processing water (especially simultaneous removal of harmful ionic substances including insoluble metals and insoluble impurities).
b. Removal of germanium mixed as a polymerization catalyst in ethylene glycol distilled off as an unreacted product during polyester production.
[0057]
c. Removal of insoluble impurities along with arsenic that may be contained in edible oils and fats.
d. Removal of boron that may be contained as a rust preventive component in waste oil such as engine oil and motor oil (waste oil treatment).
[0058]
e. Removal of insoluble impurities along with boron and silicon during ultrapure water production.
f. Removal and purification of insoluble impurities together with selenium mixed in waste water discharged from thermal power generation facilities using coal as fuel.
[0059]
g. Removal and purification of insoluble impurities together with boron mixed in wastewater discharged from nuclear power generation facilities and natural gas utilization facilities.
h. Removal of insoluble inclusions along with boron from coal dust ash washing effluent.
[0060]
【Example】
Next, examples of the present invention will be shown. However, the present invention is not limited by the following examples as a matter of course, and it is needless to say that the present invention can be implemented with appropriate modifications within a range that can meet the gist of the preceding and following descriptions. These are all included in the technical scope of the present invention.
[0061]
Example
A commercially available cartridge filter (Advantech Toyo Co., Ltd., trade name “TCW-1-CSS”: nominal pore diameter 1 μm) wound with a cotton spun yarn around a stainless steel core material in a polypropylene housing (Advantech) It is attached to Toyo Co., Ltd., trade name “1PP-1-FS-000”), and glycidyl methacrylate 53.6 g, nonionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., trade name “Neugen EA126”) 2 0.7 g, nonionic surfactant (Nippon Yushi Co., Ltd., trade name “Nonion OT-221”) 2.7 g, 31% H ₂ O ₂ A solution obtained by dissolving 5.8 g of water and 471.2 g of a 0.5% aqueous thiourea dioxide solution in 7000 ml of distilled water was circulated at 60 ° C. for 1 hour at a flow rate of 15 liters / minute using a circulation pump, and cotton spun yarn After glycidyl methacrylate was grafted into the molecule and the reaction solution was discharged, 3000 ml of distilled water was circulated and washed.
[0062]
Next, a solution prepared by dissolving 1500 g of N-methyl-D-glucamine in 3000 ml of distilled water was circulated at 80 ° C. for 2 hours through the above-mentioned filter grafted with glycidyl methacrylate, and a metal chelate was added to the cotton spun yarn constituting the filter. A formable functional group was introduced, and then circulation / waste liquid was repeated using distilled water until the washing liquid became neutral to obtain a metal-chelate-forming filter.
[0063]
This metal chelate-forming filter is mounted on the polypropylene housing, 10 liters of a solution in which boric acid is dissolved in distilled water and the boron concentration is adjusted to 10 ppm, and silicon dioxide fine powder having an average particle size of 10 μm as an insoluble contaminant. The test liquid in which 2.01 g was dispersed was circulated at 25 ° C. for 30 minutes at a flow rate of 15 liters / minute.
[0064]
Thereafter, when the boron concentration of the test solution was quantified, it was confirmed that the concentration was reduced to 1 ppm or less. Further, when the removal rate was determined by passing 1 liter of the test solution through a membrane filter having a pore size of 0.1 μm and measuring the amount of silicon dioxide remaining, it was confirmed to be 96%.
[0065]
Example 2
A metal chelate-forming filter obtained in the same manner as in Example 1 above was attached to the polypropylene housing, and the germanium oxide was neutralized after the germanium oxide was dissolved in an alkali solution, and the germanium concentration was adjusted to 10 ppm. A test liquid in which 1.98 g of silicon dioxide fine powder having an average particle diameter of 10 μm was dispersed as an insoluble contaminant was circulated at 25 ° C. for 30 minutes at a flow rate of 15 liters / minute.
[0066]
Then, when the germanium concentration of the test solution was quantified, it was confirmed that the concentration was reduced to 1 ppm or less. Further, when the removal rate was determined by passing 1 liter of the test solution through a membrane filter having a pore diameter of 0.1 μm and measuring the amount of silicon dioxide remaining, it was confirmed to be 97%.
[0067]
Example 3
The metal chelate-forming filter obtained in the same manner as in Example 1 above was attached to the polypropylene housing, and arsenic trioxide was dissolved in an alkali to adjust the arsenic concentration to 10 ppm. A test solution in which 1.04 g of silicon dioxide fine powder having a particle size of 10 μm was dispersed was circulated at 25 ° C. for 30 minutes at a flow rate of 15 liters / minute.
[0068]
Thereafter, when the arsenic concentration of the test solution was quantified, it was confirmed that the concentration was reduced to 1 ppm or less. Further, when the removal rate was determined by passing 1 liter of the test solution through a membrane filter having a pore diameter of 0.1 μm and measuring the amount of silicon dioxide remaining, it was confirmed to be 97%.
[0069]
Example 4
In Example 1 above, instead of a cartridge filter in which a cotton spun yarn is wound around a stainless steel core material in a twill form, a cartridge filter formed by cellulose fiber filter paper in a pleated shape (manufactured by Advantech Toyo Co., Ltd., trade name) [TC-1]: A metal chelate-forming filter was obtained in the same manner as in Example 1 except that the nominal pore diameter was 1 μm.
[0070]
The obtained metal-like chelate-forming filter material is mounted on the same polypropylene housing as described above, dissolved in boric acid in distilled water and adjusted to a boron concentration of 10 ppm, 10 liters of an average particle size of 10 μm as an insoluble contaminant. A test solution in which 1.89 g of fine silicon dioxide powder was dispersed was circulated at 25 ° C. for 30 minutes at a flow rate of 15 liters / minute.
[0071]
Thereafter, when the boron concentration of the test solution was quantified, it was confirmed that the concentration was reduced to 1 ppm or less. Further, when the removal rate was determined by passing 1 liter of the test solution through a membrane filter having a pore diameter of 0.1 μm and measuring the amount of silicon dioxide remaining, it was confirmed to be 97%.
[0072]
Example 5
The metal chelate-forming filter obtained in the same manner as in Example 1 above was mounted on a stainless steel housing (trade name “1TS” manufactured by Advantech Toyo Co., Ltd.), and this was added to 2 liters of engine oil having a boron concentration of 35 ppm. A test solution in which 0.46 g of silicon dioxide fine powder having an average particle diameter of 10 μm was dispersed as an insoluble contaminant was circulated at 25 ° C. for 30 minutes at a flow rate of 1 liter / min.
[0073]
Thereafter, when the boron concentration of the test solution was quantified, it was confirmed that the concentration was reduced to 1 ppm or less. Further, after diluting 1 liter of the test solution with a mineral spinet, the removal rate was determined by measuring the amount of silicon dioxide remaining through a membrane filter having a pore size of 0.1 μm, and it was confirmed to be 95%. It was.
[0074]
【The invention's effect】
The present invention is configured as described above, and by using a metal-like chelate-capturing fiber having a high scavenging ability for a metal-like component as a filter material and also having insoluble contaminant removal performance, The metal-like component and the insoluble impurities in the liquid can be removed at the same time, and their cleaning can be performed very efficiently.

Claims (11)

As at least a part of the filter material, in the molecule of the natural fiber or regenerated fiber, it the amino group, at least two chelating fiber groups having a hydroxyl group is introduced bonded to carbon is located Filter device characterized by. An amino group, a group having at least two hydroxyl groups attached to the carbon, the filter device according to claim 1 is a group represented by the following formula [I].

[Wherein G is a sugar alcohol residue or a polyhydric alcohol residue, R is a hydrogen atom, a (lower) alkyl group or -G (G represents the same meaning as described above, Represents)]   The filter device according to claim 2, wherein G in the formula [I] is a residue obtained by removing an amino group from D-glucamine, and R is a hydrogen atom or a lower alkyl group. The filter device according to claim 2 , wherein G in the formula [I] is a dihydroxypropyl group, and R is hydrogen or a lower alkyl group. The group having an amino group and at least two hydroxyl groups bonded to carbon is directly bonded to a reactive functional group in a molecule of natural fiber or regenerated fiber. Filter device. A group having an amino group and at least two hydroxyl groups bonded to carbon is introduced via a crosslink to a reactive functional group in a natural fiber or regenerated fiber molecule. The filter apparatus in any one. The filter device according to any one of claims 1 to 6 , wherein the chelate-forming fiber has a capability of chelating and capturing a metal group element or a compound thereof. 8. The filter device according to claim 7 , wherein the metal group element or a compound thereof is boron or a boron compound. Cleaning method of the liquid, characterized in that through the liquid to the filter device to remove ionic substances and insoluble impurities in the liquid according to any of claims 1 to 8. The cleaning method according to claim 9 , wherein the liquid is an aqueous liquid. The cleaning method according to claim 9 , wherein the liquid is an oily liquid.