JP3653332B2 - Phosphorus removing material and phosphorus removing method using the same - Google Patents
Phosphorus removing material and phosphorus removing method using the same Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、河川、湖沼、海、生活排水、工業排水などに含まれる富栄養化の原因のひとつであるリン成分を除去するためのリン除去材に関し、とくに金属イオンを生成することにより、リン成分を不溶性のリン−金属化合物として析出させて除去するリン除去材に関する。
【０００２】
【従来の技術】
従来、鉄板をリン成分を含む被処理水に浸漬することにより、鉄板表面の電気化学的鉄腐食作用で鉄イオンを溶出させて、リン成分、とくにリン酸イオンを鉄イオンとの反応によって不溶性リン酸鉄塩として析出させ、これを被処理水から取り除くことによってリンを除去する方法が知られている。しかし、この方法では鉄イオンの溶出量が少なく、また溶出速度も遅いため、リン濃度の高い水域や、リン濃度が変動する水域では十分にリンが除去できなかった。
【０００３】
また、浸漬した鉄板を荷電して鉄イオンの溶出量を増加させる方法も提案されているが、この方法では通電が必要となるため、ランニングコストが高く、運転管理も面倒であった。
【０００４】
このため、本発明者らは、銅線で接続した鉄板と銅板を被処理水に浸漬し、電池反応を利用して、鉄板からの鉄イオンの溶出速度を増加させることを試みた。この方法では、鉄板のみを浸漬した場合と比べれば溶出速度は上がったが、まだ十分とは言えなかった。また、鉄板や銅板を交互に配置し、かつ銅線で結線しなければならないため、装置が大掛かりになる上に、配置に手間がかかるという問題もあった。
【０００５】
【発明が解決しようとする課題】
本発明は上記のような従来技術の欠点を解消するべくなされたものであり、金属イオンの溶出速度を高めることができ、コンパクトで、取扱いの容易なリン除去材を提供すること、及びそのリン除去材を用いてリンを簡便に効率よく除去する方法を提供することを課題とする。
【０００６】
【課題を解決するための手段】
上記の課題は、繊維径が１〜１０００μｍの鉄繊維である第１の金属繊維と、第１の金属繊維よりも電気化学的に貴であり且つステンレス繊維である第２の金属繊維とを接触した状態で含む繊維集合体からなることを特徴とするリン除去材によって達成される。
【０００７】
また、本発明は、繊維径が１〜１０００μｍである第１の金属繊維と、第１の金属繊維よりも電気化学的に貴であり且つ合金である第２の金属繊維とを接触した状態で含む繊維集合体からなり、繊維が３次元的に分布してなるリン除去材を、リン成分を含む水に入れ、さらに、リン成分を含む水に電解質を添加して、第１の金属繊維から金属イオンを溶出させることにより、不溶性のリン−金属化合物を形成させてリン成分を含む水からリンを除去することを特徴とするリン除去方法に関する。
【０００８】
【発明の実施の形態】
本発明のリン除去材は、第１の金属繊維と、第１の金属繊維よりも電気化学的に貴な第２の金属繊維とを接触した状態で含むので、リン成分を含む水に入れると、局部電池反応のような電気化学的反応により大きな表面積を持つ第１の金属繊維から金属イオンが溶出するため、金属イオンの溶出速度を大きくすることができる。溶出した金属イオンは被処理水中に含まれるリン酸イオンなどのリン成分と反応することにより、不溶性のリン酸金属塩などのリン−金属化合物を形成して析出するため、溶出速度が増すことによってリンの除去能力が向上する。また、本発明のリン除去材は金属繊維を用いるものであるため、コンパクトに形成でき、取扱い性が容易である。
【０００９】
本発明に用いる第１の金属繊維と第２の金属繊維には、電気化学的に見て相対的に差のある金属からなる繊維が用いられ、第２の金属繊維が第１の金属繊維よりも電気化学的に貴である金属からなる繊維が使用される。例えば、第１の金属繊維としては、鉄繊維、アルミニウム繊維、亜鉛繊維、マグネシウム繊維などが使用でき、第２の金属繊維としては、これらより電気化学的に貴である、ステンレス繊維などが使用できる。なお、各金属繊維を構成する金属は単体であってもよいし、合金であってもよい。但し本発明では、第２の金属繊維が合金である必要がある。また、各第１及び第２の金属繊維は各々１種類の金属繊維を用いてもよいし、２種類以上の金属繊維を用いてもよい。
【００１０】
第１の金属繊維と第２の金属繊維の組合わせは、電気化学的に見て相対的に差があればとくに限定されないが、できるだけこの差の大きいものを選択することが望ましい。電気化学的な差は、例えば金属繊維を構成する金属の飽和甘こう電極基準電位などから推定できる。ただし、金属の種類や使用状態によっては、酸化被膜を生じることなどにより安定な状態になってイオンの溶出が減るため、必ずしもこの電位差が大きい組合わせがリン除去に優れているとは限らない。例えば、第１の金属繊維では、鉄繊維よりもアルミニウム繊維の方が飽和甘こう電極基準電位が低く、第２の金属繊維に同じものを用いれば、アルミニウム繊維との組合わせの方がイオンの溶出速度が大きいはずであるが、実際には鉄繊維の方がイオンの溶出速度が大きくなる。
【００１１】
第１の金属繊維としては、他の電気化学的に卑な金属繊維と比べて酸化被膜を形成しにくく、イオンの溶出速度が大きく、汎用されていて入手しやすいことから、鉄繊維、とくにスチールウールを用いることがとくに望ましい。また、第１の金属繊維に鉄繊維を用いる場合、第２の金属繊維としてはステンレス繊維と組合わせると鉄イオンの溶出速度が大きくなり、リン除去能力が向上する。
【００１２】
また、第１の金属繊維は、繊維径が細いほど装置をコンパクトにできると共に金属イオンの溶出速度が大きくなる傾向があるが、あまり繊維径が細くなりすぎると使用寿命が短くなると共に保形性が低下するため、その繊維径は１〜１０００μｍ、より好ましくは１０〜５００μｍであるのがよい。
【００１３】
本発明のリン除去材は第１の金属繊維と第２の金属繊維を含む繊維集合体からなる。繊維集合体としては、フェルト、不織布などの繊維質シートや、水の出入りが可能な容器中に繊維を詰めたものや、集積した繊維を水透過性の材料で覆ったものなどが使用できる。この内、フェルト、不織布や、水の出入りが可能な容器中に繊維を詰めたものや、集積した繊維を水透過性の材料で覆ったものなどは、繊維が３次元的に分布した構造となり、被処理水との接触面積が増えるので好ましい。とくに、フェルトや不織布は、２次加工により、通水抵抗が小さく、表面積の大きな立体形状に成形できるのでよい。このような立体形状としては、ダンボール形状、ハニカム形状、プリーツ形状、菊花状断面を有する棒形状などがある。なお、菊花状断面を有する棒形状は、複数枚の不織布を積層したものに、線状の結合部を形成することより得られ、結合部から放射状に不織布片が伸びる菊花状断面を持つ。
【００１４】
不織布からなるリン除去材を作製する場合、各金属繊維の結合は、通常の不織布を製造する場合と同様に、機械的絡合、接着剤による結合、接着繊維による結合などにより行うことができるが、とくにニードルパンチなどによる機械的絡合により結合することが望ましい。機械的絡合によれば、繊維が絡合することにより第１の金属繊維と第２の金属繊維の接触点を増やすことができるため、局部電池反応による第１の金属繊維からの金属イオンの溶出を安定に行わせることができると共に、金属繊維と水との接触を妨げたり、水に溶出したりするおそれのある接着剤などを用いずに強度のある不織布が得られるため、安全で、取扱い性の良いリン除去材を提供できる。
【００１５】
本発明のリン除去材は、上記の繊維集合体において、第１の金属繊維と第２の金属繊維とが混合された構造となっているか、または第１の金属繊維層と第２の金属繊維層とが積層された構造となっていることが望ましい。
【００１６】
第１の金属繊維と第２の金属繊維が混合された構造となっている場合には、第１の金属繊維と第２の金属繊維は繊維集合体のどの部位においても接触しており、２種の金属繊維の間で電気化学的反応が生じて、第１の金属繊維から金属イオンが溶出する。このため、厚みを厚くしても十分なリン除去能力を発揮する。ただし、このように作用させるためには、第２の金属繊維が繊維集合体全体に一様に分布していることが望ましく、第２の金属繊維が比較的多く必要となる。
【００１７】
一方、第１の金属繊維層と第２の金属繊維層とが積層された構造となっている場合には、主として各層の界面付近で、２種の金属繊維の間で電気化学的反応が生じて、第１の金属繊維から金属イオンが溶出する。このため、溶出しない第２の金属繊維層は薄い層でも十分に機能を発揮するので、第２の金属繊維の量を少なくできる。ただし、第１の金属繊維層の厚みがあまり厚いと、電気化学的反応による第１の金属繊維からの金属イオンの溶出は期待できなくなる。
【００１８】
リン除去材に含まれる第１の金属繊維と第２の金属繊維の重量割合は、繊維集合体の種類や、繊維径、繊維の配置によっても異なるが、大体、１：１〜１：０．２の範囲にあることが望ましく、これより第１の金属繊維の割合が少ないと溶出する金属イオンの量が不足すると共に、短期間で第１の金属繊維が消費されてしまって使用寿命が短くなり、これより第２の金属繊維の割合が少なくなると、第２の金属繊維と接触できない第１の金属繊維の割合が増え、電気化学的反応による金属イオンの溶出が減り、リン除去材からの金属イオンの溶出速度が低下する。とくに、好ましい第１の金属繊維と第２の金属繊維との重量割合は１：１〜１：０．５である。
【００１９】
本発明においては、上記本発明のリン除去材をリン成分を含む水に入れて、第１の金属繊維から金属イオンを溶出させることにより、不溶性のリン−金属化合物を形成させてリン成分を含む水からリンを除去する。例えば、第１の金属繊維として鉄繊維を、第２の金属繊維としてステンレス繊維を用いたリン除去材の場合には、鉄繊維とステンレス繊維が接触していれば、局部電池反応による電気化学的反応によって鉄繊維から鉄イオンが溶出し、この鉄イオンがリン酸イオンなどのリン成分と反応して水不溶性のリン酸鉄塩となって析出する。この析出したリン酸鉄塩を捕集して水中から取り出せば、水からリン成分を除去することができる。
【００２０】
なお、本発明のリン除去材はリン成分を含む河川、湖沼、海、排水路などに直接設置してリンの除去を行ってもよいが、これらから水を取り出した処理用の水路や処理水槽などに設置してリンを除去してもよい。
【００２１】
また、リン除去を促進するために、リン除去材を配置する場所またはその近傍で曝気を行ってもよい。曝気を行って溶存酸素量を調節することによって第１の金属繊維からの金属イオンの溶出速度を大きくすることができる。
【００２２】
また、被処理水中に塩化ナトリウム、塩化アンモニウムなどの電解質を添加して電気伝導度を高めることによって、第１の金属繊維の金属イオンの溶出速度を高めることができる。
【００２３】
【実施例】
実施例１
繊維径１０μｍのスチールウールと、繊維径１０μｍのステンレスウールとを重量比１：１の割合で混合した繊維ウェブをニードルパンチ機により絡合して、面密度１ｋｇ／ｍ2 、厚さ２０ｍｍのニードルパンチ不織布からなるリン除去材を作製した。塩化ナトリウム０．８ｇ／ｌを含む水道水からなる試験水２ｌ中にリン除去材４０ｇを入れ、曝気により溶存酸素濃度を８ｍｇ／ｌに調整しながら２時間攪拌した後、リン除去材を試験水中から取り出して、試験水中の鉄イオン濃度を測定し、鉄１ｇ当たりの鉄イオンの溶出速度を求めて表１に示した。また、塩化ナトリウム０．８ｇ／ｌとリン酸二水素カリウム４．４ｍｇ／ｌを含む水道水からなるリン濃度（ＰＯ4 -3 −Ｐ）１ｍｇ／ｌに調整した試験水３ｌ中にリン除去材４０ｇを入れ、曝気により溶存酸素濃度を８ｍｇ／ｌに調整しながら５０分間攪拌した後、リン除去材を試験水中から取り出して、試験水中のリン（ＰＯ4 -3 −Ｐ）濃度を測定し、表１に示した。
【００２４】
実施例２
繊維径１００μｍのスチールウールと、繊維径１００μｍのステンレスウールとを重量比１：１の割合で混合した繊維ウェブをニードルパンチ機により絡合して、面密度１ｋｇ／ｍ2 、厚さ２０ｍｍのニードルパンチ不織布からなるリン除去材を作製した。このリン除去材の鉄イオンの溶出速度とリン除去材で処理した後の試験水のリン（ＰＯ4 -3 −Ｐ）濃度を、実施例１と同様にして求め、結果を表１に示した。
【００２５】
実施例３
繊維径５００μｍのスチールウールと、繊維径５００μｍのステンレスウールとを重量比１：１の割合で混合した繊維ウェブをニードルパンチ機により絡合して、面密度１ｋｇ／ｍ2 、厚さ２０ｍｍのニードルパンチ不織布からなるリン除去材を作製した。このリン除去材の鉄イオンの溶出速度とリン除去材で処理した後の試験水のリン（ＰＯ4 -3 −Ｐ）濃度を、実施例１と同様にして求め、結果を表１に示した。
【００２６】
実施例４
繊維径１０μｍのスチールウールと、繊維径１０μｍのステンレスウールとを重量比２：１の割合で混合した繊維ウェブをニードルパンチ機により絡合して、面密度１ｋｇ／ｍ2 、厚さ２０ｍｍのニードルパンチ不織布からなるリン除去材を作製した。このリン除去材の鉄イオンの溶出速度とリン除去材で処理した後の試験水のリン（ＰＯ4 -3 −Ｐ）濃度を、実施例１と同様にして求め、結果を表１に示した。
【００２７】
実施例５
繊維径１０μｍのスチールウールからなる繊維ウェブと、繊維径１０μｍのステンレスウールからなる繊維ウェブとを重量比が１：１となるように積層し、面密度１ｋｇ／ｍ2 、厚さ２０ｍｍの積層不織布からなるリン除去材を作製した。このリン除去材の鉄イオンの溶出速度とリン除去材で処理した後の試験水のリン（ＰＯ4 -3 −Ｐ）濃度を、実施例１と同様にして求め、結果を表１に示した。
【００２８】
比較例１
縦５ｃｍ×横５ｃｍ×厚さ０．２ｃｍの鉄板（重さ４０ｇ）３枚を、実施例１のリン除去材の代りに用いたこと以外は、実施例１と同様にして鉄イオンの溶出速度と鉄板で処理した後の試験水のリン（ＰＯ4 -3 −Ｐ）濃度を、結果を表１に示した。
【００２９】
比較例２
縦５ｃｍ×横５ｃｍ×厚さ０．２ｃｍの鉄板（重さ４０ｇ）と縦５ｃｍ×横５ｃｍ×厚さ０．２ｃｍのステンレス板（重さ４０ｇ）各３枚を交互に４ｃｍ間隔で並べ、各板を銅線で連結したものを、実施例１のリン除去材の代りに用いたこと以外は、実施例１と同様にして鉄イオンの溶出速度と鉄板とステンレス板で処理した後の試験水のリン（ＰＯ4 -3 −Ｐ）濃度を求め、結果を表１に示した。
【００３０】
比較例３
繊維径５００μｍのスチールウールからなる繊維ウェブをニードルパンチ機により絡合して、面密度１ｋｇ／ｍ2 、厚さ２０ｍｍのニードルパンチ不織布からなるリン除去材を得た。このリン除去材の鉄イオンの溶出速度とリン除去材で処理した後の試験水のリン（ＰＯ4 -3 −Ｐ）濃度を、実施例１と同様にして求め、結果を表１に示した。
【００３１】
【表１】
実施例６
初期リン濃度（ＰＯ4 -3 −Ｐ）１．５ｍｇ／ｌの生活排水が流れる排水路に、実施例１のリン除去材４８０ｇ（９．６ｌ）を充填したプラスチック容器を、排水路の上流側の生活排水がプラスチック容器の流入口から流入し、排水路の下流側へプラスチック容器の流出口から流出するように設置した。プラスチック容器内の生活排水を曝気により溶存酸素濃度を８ｍｇ／ｌに調整しながら、排水を２分間リン除去材と接触するように流量４．８ｌ／分で流した。リン除去材を通過した生活排水を取り出して、リン（ＰＯ4 -3 −Ｐ）濃度を測定したところ０．１ｍｇ／ｌに低下していた。また、リン除去材を通過した生活排水の鉄のイオン濃度を測定して鉄の溶出速度を求めたところ１２ｍｇ／ｇ・ｈｒであった。
【００３３】
【発明の効果】
本発明のリン除去材は、金属イオンの溶出速度が大きいためリンの除去能力が高く、しかもコンパクトに形成でき、取扱い性が容易である。このため、リン成分を含む河川、湖沼、海、排水路などの水に作業性よく設置することができると共に、効率よくリン成分を除去できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a phosphorus removal material for removing a phosphorus component that is one of the causes of eutrophication contained in rivers, lakes, seas, domestic wastewater, industrial wastewater, etc., and in particular, by generating metal ions, The present invention relates to a phosphorus removing material that deposits and removes components as insoluble phosphorus-metal compounds.
[0002]
[Prior art]
Conventionally, by immersing an iron plate in water to be treated containing a phosphorus component, iron ions are eluted by electrochemical iron corrosion on the surface of the iron plate, and phosphorus components, particularly phosphate ions, react with the iron ions to dissolve insoluble phosphorus. There is known a method of removing phosphorus by precipitating as an acid iron salt and removing it from the water to be treated. However, in this method, the amount of iron ions eluted is small and the elution rate is slow, so that phosphorus could not be removed sufficiently in water areas with high phosphorus concentrations or water areas with varying phosphorus concentrations.
[0003]
In addition, a method has been proposed in which the immersed iron plate is charged to increase the elution amount of iron ions. However, since this method requires energization, the running cost is high and the operation management is troublesome.
[0004]
For this reason, the present inventors tried to increase the elution rate of iron ions from the iron plate by immersing the iron plate and the copper plate connected by the copper wire in the water to be treated and utilizing the battery reaction. In this method, the elution rate was increased as compared with the case where only the iron plate was immersed, but it was still not sufficient. In addition, since iron plates and copper plates must be alternately arranged and connected with copper wires, there is a problem that the apparatus becomes large and the arrangement is troublesome.
[0005]
[Problems to be solved by the invention]
The present invention has been made to eliminate the above-described drawbacks of the prior art, and can provide a phosphorus removal material that can increase the elution rate of metal ions, is compact, and can be easily handled. It is an object of the present invention to provide a method for easily and efficiently removing phosphorus using a removing material.
[0006]
[Means for Solving the Problems]
The above-described problem is that a first metal fiber that is an iron fiber having a fiber diameter of 1 to 1000 μm is brought into contact with a second metal fiber that is electrochemically more noble than the first metal fiber and is a stainless fiber. It is accomplished by removal of phosphorus material characterized by comprising a fiber aggregate containing at state.
[0007]
In the present invention, the first metal fiber having a fiber diameter of 1 to 1000 μm and the second metal fiber that is electrochemically noble and alloyed with the first metal fiber are in contact with each other. A phosphorus removal material comprising a fiber assembly including three-dimensionally distributed fibers is placed in water containing a phosphorus component, and an electrolyte is further added to the water containing the phosphorus component. The present invention relates to a phosphorus removal method characterized in that metal ions are eluted to form an insoluble phosphorus-metal compound to remove phosphorus from water containing a phosphorus component.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Since the phosphorus removing material of the present invention includes the first metal fiber and the second metal fiber that is electrochemically more noble than the first metal fiber in contact with the first metal fiber, Since metal ions are eluted from the first metal fiber having a large surface area by an electrochemical reaction such as a local battery reaction, the elution rate of the metal ions can be increased. The eluted metal ions react with phosphorus components such as phosphate ions contained in the water to be treated to form and deposit phosphorus-metal compounds such as insoluble metal phosphates, increasing the dissolution rate. Improves phosphorus removal ability. Moreover, since the phosphorus removal material of this invention uses a metal fiber, it can form compactly and it is easy to handle.
[0009]
For the first metal fiber and the second metal fiber used in the present invention, fibers made of metals that are relatively different from each other in electrochemical terms are used, and the second metal fiber is more than the first metal fiber. Also, fibers made of metals that are electrochemically noble are used. For example, iron fibers, aluminum fibers, zinc fibers, magnesium fibers and the like can be used as the first metal fibers, and stainless fibers and the like that are electrochemically more noble than these can be used as the second metal fibers. . The metal constituting each metal fiber may be a single element or an alloy. However, in the present invention, the second metal fiber needs to be an alloy. In addition, each of the first and second metal fibers may use one type of metal fiber or two or more types of metal fibers.
[0010]
The combination of the first metal fiber and the second metal fiber is not particularly limited as long as there is a relative difference in electrochemical terms, but it is desirable to select a combination having as large a difference as possible. The electrochemical difference can be estimated from, for example, the saturated sweet ginger electrode reference potential of the metal constituting the metal fiber. However, depending on the type of metal and the state of use, it becomes stable due to the formation of an oxide film and the elution of ions is reduced. Therefore, a combination with a large potential difference is not always excellent in phosphorus removal. For example, in the first metal fiber, the aluminum fiber has a lower saturated ginger electrode reference potential than the iron fiber, and if the same metal fiber is used for the second metal fiber, the combination with the aluminum fiber is more ionic. Although the elution rate should be higher, in reality, the elution rate of ions is higher with iron fibers.
[0011]
As the first metal fiber, it is difficult to form an oxide film compared to other electrochemically base metal fibers, the elution rate of ions is large, and it is widely used and easily available. It is particularly desirable to use wool. Moreover, when using an iron fiber for a 1st metal fiber, when it combines with a stainless steel fiber as a 2nd metal fiber, the elution rate of an iron ion will become large and a phosphorus removal capability will improve.
[0012]
In addition, the first metal fiber has a tendency that the smaller the fiber diameter, the more compact the device and the greater the elution rate of metal ions. However, if the fiber diameter becomes too small, the service life is shortened and the shape retention is reduced. Therefore, the fiber diameter should be 1-1000 μm, more preferably 10-500 μm.
[0013]
The phosphorus removal material of this invention consists of a fiber assembly containing a 1st metal fiber and a 2nd metal fiber. As the fiber assembly, there can be used a fibrous sheet such as felt or non-woven fabric, a product in which fibers are packed in a container capable of entering and exiting water, and a product in which accumulated fibers are covered with a water-permeable material. Of these, felt, non-woven fabrics, or a container filled with fibers in a container capable of entering and exiting water, and those in which accumulated fibers are covered with a water-permeable material have a structure in which the fibers are distributed three-dimensionally. It is preferable because the contact area with the water to be treated increases. In particular, felt and non-woven fabric may be formed into a three-dimensional shape having a low surface resistance and a large surface area by secondary processing. Examples of such a three-dimensional shape include a cardboard shape, a honeycomb shape, a pleat shape, and a rod shape having a chrysanthemum cross section. The rod shape having a chrysanthemum cross section is obtained by forming a linear coupling portion on a laminate of a plurality of non-woven fabrics, and has a chrysanthemum cross section in which the nonwoven fabric pieces extend radially from the coupling portion.
[0014]
When producing a phosphorus removing material made of a nonwoven fabric, each metal fiber can be bonded by mechanical entanglement, bonding by an adhesive, bonding by an adhesive fiber, etc., as in the case of manufacturing a normal nonwoven fabric. In particular, it is desirable to couple by mechanical entanglement with a needle punch or the like. According to the mechanical entanglement, since the contact point between the first metal fiber and the second metal fiber can be increased by the entanglement of the fiber, the metal ions from the first metal fiber due to the local battery reaction can be increased. Elution can be performed stably, and since a strong nonwoven fabric can be obtained without using an adhesive that may interfere with the contact between metal fibers and water, or may be eluted in water, it is safe. It is possible to provide a phosphorus removal material with good handleability.
[0015]
The phosphorus removing material of the present invention has a structure in which the first metal fiber and the second metal fiber are mixed in the above fiber assembly, or the first metal fiber layer and the second metal fiber. It is desirable to have a structure in which layers are laminated.
[0016]
When the first metal fiber and the second metal fiber have a mixed structure, the first metal fiber and the second metal fiber are in contact at any part of the fiber assembly, and 2 An electrochemical reaction occurs between the seed metal fibers, and metal ions are eluted from the first metal fibers. For this reason, even if the thickness is increased, sufficient phosphorus removal ability is exhibited. However, in order to make it act in this way, it is desirable that the second metal fibers are uniformly distributed throughout the fiber assembly, and a relatively large number of second metal fibers are required.
[0017]
On the other hand, when the first metal fiber layer and the second metal fiber layer are laminated, an electrochemical reaction occurs between the two types of metal fibers mainly near the interface between the layers. Thus, metal ions are eluted from the first metal fiber. For this reason, since the second metal fiber layer that does not elute sufficiently functions even in a thin layer, the amount of the second metal fiber can be reduced. However, if the thickness of the first metal fiber layer is too thick, elution of metal ions from the first metal fiber due to electrochemical reaction cannot be expected.
[0018]
The weight ratio of the first metal fiber and the second metal fiber contained in the phosphorus removal material varies depending on the type of fiber assembly, fiber diameter, and fiber arrangement, but is generally 1: 1 to 1: 0. If the ratio of the first metal fiber is less than this, the amount of metal ions to be eluted is insufficient, and the first metal fiber is consumed in a short period of time, resulting in a short service life. When the ratio of the second metal fiber is smaller than this, the ratio of the first metal fiber that cannot contact with the second metal fiber increases, the elution of metal ions due to the electrochemical reaction decreases, and the phosphorus removal material The elution rate of metal ions decreases. In particular, the weight ratio between the first metal fiber and the second metal fiber is preferably 1: 1 to 1: 0.5.
[0019]
In the present invention, the phosphorus removing material of the present invention is placed in water containing a phosphorus component, and metal ions are eluted from the first metal fiber to form an insoluble phosphorus-metal compound, thereby including the phosphorus component. Remove phosphorus from water. For example, in the case of a phosphorus removal material using iron fiber as the first metal fiber and stainless fiber as the second metal fiber, if the iron fiber and the stainless fiber are in contact with each other, the electrochemical by local cell reaction Iron ions are eluted from the iron fiber by the reaction, and the iron ions react with phosphorus components such as phosphate ions to precipitate as water-insoluble iron phosphate salts. If the precipitated iron phosphate salt is collected and taken out from the water, the phosphorus component can be removed from the water.
[0020]
The phosphorus removing material of the present invention may be installed directly in rivers, lakes, seas, drainage channels, etc. containing phosphorus components to remove phosphorus, but a treatment channel or treated water tank from which water is taken out For example, phosphorus may be removed.
[0021]
In order to promote phosphorus removal, aeration may be performed at or near the place where the phosphorus removing material is disposed. The elution rate of metal ions from the first metal fiber can be increased by performing aeration and adjusting the amount of dissolved oxygen.
[0022]
Moreover, the elution rate of the metal ion of a 1st metal fiber can be raised by adding electrolytes, such as sodium chloride and ammonium chloride, to a to-be-processed water, and raising an electrical conductivity.
[0023]
【Example】
Example 1
A fiber web prepared by mixing steel wool having a fiber diameter of 10 μm and stainless wool having a fiber diameter of 10 μm at a weight ratio of 1: 1 is entangled by a needle punch machine, and a needle having a surface density of 1 kg / m 2 and a thickness of 20 mm. The phosphorus removal material which consists of punch nonwoven fabrics was produced. 40 g of a phosphorus removing material is put in 2 l of test water made of tap water containing 0.8 g / l of sodium chloride, stirred for 2 hours while adjusting the dissolved oxygen concentration to 8 mg / l by aeration, and then the phosphorus removing material is added to the test water. The iron ion concentration in the test water was measured and the elution rate of iron ions per gram of iron was determined and shown in Table 1. Further, a phosphorus removal material in 3 l of test water adjusted to a phosphorus concentration (PO 4 -3 -P) of 1 mg / l composed of tap water containing 0.8 g / l of sodium chloride and 4.4 mg / l of potassium dihydrogen phosphate. After adding 40 g and stirring for 50 minutes while adjusting the dissolved oxygen concentration to 8 mg / l by aeration, the phosphorus removal material was taken out from the test water and the phosphorus (PO 4 -3- P) concentration in the test water was measured. It is shown in Table 1.
[0024]
Example 2
A fiber web obtained by mixing steel wool having a fiber diameter of 100 μm and stainless wool having a fiber diameter of 100 μm at a weight ratio of 1: 1 is entangled by a needle punch machine, and a needle having an areal density of 1 kg / m 2 and a thickness of 20 mm. The phosphorus removal material which consists of punch nonwoven fabrics was produced. The elution rate of iron ions of this phosphorus removal material and the phosphorus (PO 4 -3- P) concentration of test water after treatment with the phosphorus removal material were determined in the same manner as in Example 1, and the results are shown in Table 1. .
[0025]
Example 3
A fiber web obtained by mixing steel wool having a fiber diameter of 500 μm and stainless wool having a fiber diameter of 500 μm at a weight ratio of 1: 1 is entangled by a needle punch machine, and a needle having an areal density of 1 kg / m 2 and a thickness of 20 mm. The phosphorus removal material which consists of punch nonwoven fabrics was produced. The elution rate of iron ions of this phosphorus removal material and the phosphorus (PO 4 -3- P) concentration of test water after treatment with the phosphorus removal material were determined in the same manner as in Example 1, and the results are shown in Table 1. .
[0026]
Example 4
A fiber web in which steel wool having a fiber diameter of 10 μm and stainless wool having a fiber diameter of 10 μm is mixed at a ratio of 2: 1 by weight is entangled by a needle punch machine, and a needle having a surface density of 1 kg / m 2 and a thickness of 20 mm. The phosphorus removal material which consists of punch nonwoven fabrics was produced. The elution rate of iron ions of this phosphorus removal material and the phosphorus (PO 4 -3- P) concentration of test water after treatment with the phosphorus removal material were determined in the same manner as in Example 1, and the results are shown in Table 1. .
[0027]
Example 5
A laminated web made of steel wool having a fiber diameter of 10 μm and a fiber web made of stainless wool having a fiber diameter of 10 μm are laminated so that the weight ratio is 1: 1, and a laminated nonwoven fabric having a surface density of 1 kg / m 2 and a thickness of 20 mm. The phosphorus removal material which consists of was produced. The elution rate of iron ions of this phosphorus removal material and the phosphorus (PO 4 -3- P) concentration of test water after treatment with the phosphorus removal material were determined in the same manner as in Example 1, and the results are shown in Table 1. .
[0028]
Comparative Example 1
Elution rate of iron ions in the same manner as in Example 1, except that 3 iron plates (40 g in weight) 5 cm long x 5 cm wide x 0.2 cm thick were used instead of the phosphorus removal material of Example 1. Table 1 shows the phosphorus (PO 4 -3- P) concentration of the test water after the treatment with the iron plate.
[0029]
Comparative Example 2
5 cm long x 5 cm wide x 0.2 cm thick steel plate (weight 40 g) and 5 cm long x 5 cm wide x 0.2 cm thick stainless steel plate (weight 40 g), arranged alternately at 4 cm intervals, Test water after treatment with iron ion elution rate and iron plate and stainless steel plate in the same manner as in Example 1, except that the plates connected by copper wire were used instead of the phosphorus removal material of Example 1. The phosphorus (PO 4 -3- P) concentration was determined and the results are shown in Table 1.
[0030]
Comparative Example 3
A fiber web made of steel wool having a fiber diameter of 500 μm was entangled with a needle punch machine to obtain a phosphorus removing material made of a needle punched nonwoven fabric having a surface density of 1 kg / m 2 and a thickness of 20 mm. The elution rate of iron ions of this phosphorus removal material and the phosphorus (PO 4 -3- P) concentration of test water after treatment with the phosphorus removal material were determined in the same manner as in Example 1, and the results are shown in Table 1. .
[0031]
[Table 1]
Example 6
A plastic container filled with 480 g (9.6 l) of the phosphorus removing material of Example 1 in a drainage channel through which domestic wastewater with an initial phosphorus concentration (PO 4 -3 -P) of 1.5 mg / l flows is placed upstream of the drainage channel. Was installed so that the domestic wastewater flowed in from the inlet of the plastic container and flowed out of the outlet of the plastic container to the downstream side of the drainage channel. While adjusting the dissolved oxygen concentration to 8 mg / l by aeration, domestic wastewater in the plastic container was flowed at a flow rate of 4.8 l / min so as to contact the phosphorus removal material for 2 minutes. The domestic wastewater that passed through the phosphorus removing material was taken out and the phosphorus (PO 4 -3- P) concentration was measured and found to be 0.1 mg / l. Moreover, when the ion concentration of the iron of the domestic wastewater which passed the phosphorus removal material was measured and the elution rate of iron was calculated | required, it was 12 mg / g * hr.
[0033]
【The invention's effect】
The phosphorus removal material of the present invention has a high phosphorus ion removal capability because of its high metal ion elution rate, can be formed compactly, and is easy to handle. For this reason, while being able to install with sufficient workability | operativity in water, such as a river, lake, marine, and a drainage channel containing a phosphorus component, a phosphorus component can be removed efficiently.
Claims (6)
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| JP09201596A JP3653332B2 (en) | 1996-03-21 | 1996-03-21 | Phosphorus removing material and phosphorus removing method using the same |
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| JP09201596A JP3653332B2 (en) | 1996-03-21 | 1996-03-21 | Phosphorus removing material and phosphorus removing method using the same |
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| JP4362644B2 (en) * | 2003-08-22 | 2009-11-11 | 城戸 敏弘 | Metal ion water making tool |
| JP4556038B2 (en) * | 2008-06-11 | 2010-10-06 | 石井商事株式会社 | Water purification material |
| JP4572302B2 (en) * | 2009-01-29 | 2010-11-04 | 独立行政法人国立高等専門学校機構 | Method and apparatus for removing phosphorus in human wastewater |
| JP4996656B2 (en) * | 2009-09-02 | 2012-08-08 | 石井商事株式会社 | Method for using blue-green suppressing material and blue-water suppressing device |
| JP2011050934A (en) * | 2009-09-04 | 2011-03-17 | Nihon Technical Development Center Co Ltd | Solid matter for water purification and marine resource growth |
| JP4917655B2 (en) * | 2010-03-30 | 2012-04-18 | 石井商事株式会社 | Water purification material |
| JP5612364B2 (en) * | 2010-06-04 | 2014-10-22 | 小島 昭 | Environmental water purification method |
| JP4882038B1 (en) * | 2010-08-05 | 2012-02-22 | 石井商事株式会社 | Decolorization and water purification methods |
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