JP2005349241A - Material that removes cations in water at high speed and high efficiency, and secondary treatment of wastewater using this material - Google Patents
Material that removes cations in water at high speed and high efficiency, and secondary treatment of wastewater using this material Download PDFInfo
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Abstract
【課題】 本発明は、金属除去材料単位容積当たりに処理水を高速で通水でき、高効率で金属を除去し、溶出物が少なく、繰り返し使用可能な繊維物質から構成される金属除去材料を提供することを課題とする。
【解決手段】 金属陽イオンに対してイオン交換能又はキレート交換能を有する機能性官能基を、グラフト重合法により、繊維径２デニールのポリエチレン系短繊維からなる繊維材料に導入して形成したことを特徴とする金属除去材料、及びそれを含むフィルター製品。イオン交換能を有する機能性官能基は、スルホン酸基、カルボン酸基、又はそれらの組み合わせであり、キレート形成能を有する機能性官能基は、イミノジ酢酸基、エチレンジアミン三酢酸基、イミノジエタノール基、又はそれらの組み合わせである。
【選択図】 図１
PROBLEM TO BE SOLVED: To provide a metal removing material composed of a fiber substance that can pass treated water at a high speed per unit volume of a metal removing material, removes metal with high efficiency, has few eluates, and can be used repeatedly. The issue is to provide.
SOLUTION: A functional functional group having ion exchange ability or chelate exchange ability with respect to a metal cation is introduced into a fiber material made of polyethylene short fibers having a fiber diameter of 2 denier by graft polymerization. Metal removal material characterized by, and filter products including the same. The functional functional group having ion exchange ability is a sulfonic acid group, a carboxylic acid group, or a combination thereof, and the functional functional group having chelating ability is iminodiacetic acid group, ethylenediaminetriacetic acid group, iminodiethanol group, Or a combination thereof.
[Selection] Figure 1
Description
本発明は、水中に存在する微量の陽イオンを高速かつ高効率で除去する材料に関するものであり、より詳しくは、ポリエチレン系高分子材料を用いた陽イオン除去材料、並びにこの材料を用いて工場廃水や水道水中の非常に低濃度の陽イオンを吸着する方法に関するものである。 The present invention relates to a material that removes a small amount of cations present in water with high speed and high efficiency. More specifically, the present invention relates to a cation removing material using a polyethylene-based polymer material, and a factory using this material. The present invention relates to a method for adsorbing a very low concentration of cations in waste water or tap water.
水中から金属を除去する材料は、イオン交換樹脂、平膜、中空糸膜、不織布、繊維と多種多様であるが、このうち、イオン交換樹脂は拡散により処理水を通水するために処理水の流速を上げることができない。また、平膜、中空糸膜は、開孔率が小さいために単位容積当たりの処理量を大きくすることが不可能であった。繊維については、充填する際に開孔率を一定に保つことが難しいために処理水の通水量をコントロールすることができず、空間速度（ＳＶ）も８００ｈ-1が上限であった（非特許文献１参照）。 There are a wide variety of materials for removing metals from water, such as ion exchange resins, flat membranes, hollow fiber membranes, non-woven fabrics, and fibers. Of these, ion exchange resins pass treated water through diffusion to pass treated water. The flow rate cannot be increased. Further, since the flat membrane and the hollow fiber membrane have a small hole area ratio, it is impossible to increase the processing amount per unit volume. For the fiber, it is difficult to keep the open area ratio constant when filling, so the flow rate of treated water cannot be controlled, and the upper limit of the space velocity (SV) is 800 h −1 (non-patent) Reference 1).
不織布は、開孔率が大きいため単位容積当たりの処理量を大きくすることは可能であったが、材料となる繊維がポリエチレン／ポリプロピレンや高密度ポリエチレン／低密度ポリエチレン等のコンジュゲート繊維であり、異種繊維間にモノマーが残留するという問題が存在していた。更に、金属の吸着と溶離を繰り返すことにより異繊維間に剥離が起こるため、耐久性のある材料ではなく、水処理に適する材料ではなかった。また、高密度ポリエチレン１００％の短繊維については、繊維径が６デニールと太いために比表面積が小さいので、処理水との接触効率が低くなり、水溶液中に微量に存在する陽イオンを効率良く吸着することはできなかった。 The non-woven fabric was able to increase the processing amount per unit volume because of its high porosity, but the material fiber is a conjugate fiber such as polyethylene / polypropylene or high-density polyethylene / low-density polyethylene, There has been a problem that monomers remain between different kinds of fibers. Furthermore, peeling between different fibers occurs due to repeated adsorption and elution of metal, so that it is not a durable material and is not a material suitable for water treatment. In addition, the short fiber of 100% high-density polyethylene has a small specific surface area because the fiber diameter is as thick as 6 denier, so the contact efficiency with the treated water is low, and the cation present in a trace amount in the aqueous solution is efficiently removed. Adsorption was not possible.
一方、金属を除去するためのフィルター製品については、従来、イミノジ酢酸基に工業排水に含まれるコバルト、ニッケル、水銀、銅などの金属の陽イオンを吸着する作用があることが知られており、当該吸着基を基材に重合させた材料が開発されている（例えば、特許文献１参照）。浄水器用途についても既知であり（例えば、特許文献２参照）、また、エアーフィルター、純水製造用イオン交換フィルター等に用いる素材である、放射線グラフト重合を用いて機能性官能基を導入されたポリエチレン材料も開示されている（例えば、特許文献３参照）。
したがって、本発明は、従来技術の問題点を解消する金属除去材料を提供することを課題とする。すなわち、本発明は、金属除去材料単位容積当たりに処理水を高速で通水でき、高効率で金属を除去し、溶出物が少なく、繰り返し使用可能な繊維物質から構成される金属除去材料を提供することを課題とする。 Therefore, an object of the present invention is to provide a metal removal material that solves the problems of the prior art. That is, the present invention provides a metal removal material composed of a fibrous material that can be used at high speed to remove treated metal per unit volume of the metal removal material, removes metal with high efficiency, and has few eluates and can be used repeatedly. The task is to do.
本発明においては、繊維径が２デニールのポリエチレン系短繊維からなる繊維材料の繊維表面に、陽イオン交換能又はキレート形成能を有する機能性官能基をグラフト重合法により導入した金属除去材料であって、開孔率、比表面積が大きく、ポリエチレン繊維の柔軟性を保持した材料を構成することを課題解決手段とする。 In the present invention, it is a metal removing material in which a functional functional group having a cation exchange ability or a chelate forming ability is introduced onto a fiber surface of a fiber material composed of polyethylene short fibers having a fiber diameter of 2 denier by a graft polymerization method. Thus, an object of the present invention is to constitute a material having a high porosity and a specific surface area and maintaining the flexibility of polyethylene fibers.
上記の構成を採用する本発明の金属除去材料は、不織布の開孔率に依存して処理量が大きく、繊維が単一成分からなることから異種繊維由来の問題がなく、繊維径が細く比表面積が大きいことから、処理水との接触効率が高いという利点を有しており、この材料を用いることにより、高速かつ高効率で金属の陽イオンを除去することが可能となる。 The metal removing material of the present invention adopting the above configuration has a large processing amount depending on the open area ratio of the nonwoven fabric, and since the fiber is composed of a single component, there is no problem derived from different fibers, and the fiber diameter is small. Since it has a large surface area, it has an advantage of high contact efficiency with treated water. By using this material, it becomes possible to remove metal cations at high speed and high efficiency.
すなわち、本発明の金属除去材料は、金属陽イオンに対してイオン交換能又はキレート交換能を有する機能性官能基を、グラフト重合法により、繊維径２デニールのポリエチレン系短繊維からなる繊維材料に導入して形成したことを特徴とするものである。 That is, the metal removing material of the present invention is a fiber material composed of polyethylene-based short fibers having a fiber diameter of 2 denier by graft polymerization with functional functional groups having ion exchange ability or chelate exchange ability for metal cations. It is characterized by being introduced and formed.
また、本発明の金属除去材料は、上記の金属除去材料において、金属陽イオンに対してイオン交換能を有する機能性官能基が、スルホン酸基、カルボン酸基、又はそれらの組み合わせであることを特徴とするものである。 Further, in the metal removing material of the present invention, in the above metal removing material, the functional functional group having ion exchange ability with respect to the metal cation is a sulfonic acid group, a carboxylic acid group, or a combination thereof. It is a feature.
また、本発明の金属除去材料は、上記いずれかの金属除去材料において、金属陽イオンに対してキレート形成能を有する機能性官能基が、イミノジ酢酸基、エチレンジアミン三酢酸基、イミノジエタノール基、又はそれらの組み合わせであることを特徴とするものである。 In the metal removing material of the present invention, in any one of the above metal removing materials, the functional functional group having the ability to form a chelate with respect to a metal cation is an iminodiacetic acid group, an ethylenediaminetriacetic acid group, an iminodiethanol group, or It is a combination thereof.
また、本発明の金属除去材料は、上記いずれかの金属除去材料において、ポリエチレン系短繊維からなる繊維材料が、織布若しくは不織布、又はそれらの成型加工品であることを特徴とするものである。 The metal removing material of the present invention is characterized in that, in any one of the above metal removing materials, the fiber material made of polyethylene short fibers is a woven fabric or a nonwoven fabric, or a molded product thereof. .
また、本発明の金属除去材料は、上記いずれかの金属除去材料において、繊維材料が、化学組成が高密度ポリエチレン１００％である短繊維を１０〜１００重量％含むことを特徴とするものである。 The metal removing material of the present invention is characterized in that, in any one of the above metal removing materials, the fiber material contains 10 to 100% by weight of short fibers whose chemical composition is 100% high-density polyethylene. .
更に、本発明は、上記いずれかの金属除去材料を含むフィルター製品を課題解決手段とするものである。 Furthermore, this invention makes the filter product containing one of the said metal removal materials make a subject solution means.
本発明においては、通水量を大きくすることが可能な不織布に金属除去のための官能基を導入することにより、単位時間当たりの処理水を増大させることが可能となる。
金属除去材料に吸着された金属陽イオンは酸により溶離することができ、材料はその素材が単一成分の繊維より構成されるため、溶離のあとも繰り返しの使用による耐性を有している。
In the present invention, it is possible to increase treated water per unit time by introducing a functional group for removing metal into a nonwoven fabric capable of increasing the amount of water flow.
The metal cation adsorbed on the metal removal material can be eluted by an acid, and the material is resistant to repeated use after elution since the material is composed of single component fibers.
本発明の金属除去材料は、ポリエチレン系繊維の柔軟性を保持したまま官能基が導入されたものであるため、カット性がよく、プリーツ加工、ロール加工など、現状の織布又は不織布が成型加工される様々な用途に適用可能な材料として利用することができる。 Since the metal removal material of the present invention has a functional group introduced while maintaining the flexibility of the polyethylene fiber, it has good cutting properties, and the current woven or non-woven fabric such as pleating and roll processing is molded. It can be used as a material applicable to various uses.
本発明の金属除去材料は、金属陽イオンに対してイオン交換能又はキレート交換能を有する機能性官能基を、グラフト重合法により、繊維径２デニールのポリエチレン系短繊維からなる繊維材料に導入して形成したことを特徴とするものである。 In the metal removing material of the present invention, a functional functional group having an ion exchange ability or a chelate exchange ability with respect to a metal cation is introduced into a fiber material composed of polyethylene short fibers having a fiber diameter of 2 denier by graft polymerization. It is characterized by being formed.
本発明において、金属陽イオンに対してイオン交換能を有する機能性官能基としては、スルホン酸基又はカルボン酸基を使用することができるが、それら両方を組み合わせて使用してもよい。金属陽イオンに対してキレート形成能を有する機能性官能基としては、イミノジ酢酸基、エチレンジアミン三酢酸基、又はイミノジエタノール基を使用することができるが、それらを組み合わせて使用してもよい。更に、本発明の別の態様においては、イオン交換能を有する官能基とキレート形成能を有する官能基とを組み合わせて使用してもよい。 In the present invention, a sulfonic acid group or a carboxylic acid group can be used as the functional functional group having ion exchange ability with respect to the metal cation, but both of them may be used in combination. As the functional functional group capable of forming a chelate with respect to a metal cation, an iminodiacetic acid group, an ethylenediaminetriacetic acid group, or an iminodiethanol group can be used, but they may be used in combination. Furthermore, in another aspect of the present invention, a functional group having ion exchange ability and a functional group having chelate forming ability may be used in combination.
これらの官能基を導入するための基材として、本発明では、ポリエチレン系短繊維からなる繊維材料を使用する。ここで、「ポリエチレン系短繊維からなる繊維材料」とは、ポリエチレンを主構成要素とする短繊維からつくった織布若しくは不織布、又はそれらの成型加工品を意味するものとする。繊維材料は、従来技術における異種繊維由来の問題を解消するため実質的に単一成分の短繊維で構成されることを要するが、上述の問題を生じない程度に異なる組成の繊維を含んでいてもよい。本発明の好ましい態様においては、繊維材料は、化学組成が高密度ポリエチレン１００％である短繊維を１０〜１００重量％含む。ポリエチレン系短繊維の繊維径は、処理水との接触効率が高くするため、比表面積が大きい、すなわち繊維径が細いことが望ましい。したがって、好ましい基材は、繊維径２デニールの高密度ポリエチレン短繊維１００％からつくった、目付け６０〜７０ｇ／ｍ2、厚さ０．３０〜０．４０ｍｍの不織布である。 In the present invention, a fiber material made of polyethylene short fibers is used as a base material for introducing these functional groups. Here, the “fiber material composed of polyethylene short fibers” means a woven or non-woven fabric made of short fibers mainly composed of polyethylene, or a molded product thereof. The fiber material needs to be composed of substantially single-component short fibers in order to eliminate the problems derived from different kinds of fibers in the prior art, but contains fibers having different compositions to such an extent that the above-mentioned problems do not occur. Also good. In a preferred embodiment of the present invention, the fiber material contains 10 to 100% by weight of short fibers having a chemical composition of 100% high-density polyethylene. The fiber diameter of the polyethylene-based short fibers is preferably large in specific surface area, that is, the fiber diameter is thin, in order to increase the contact efficiency with treated water. Therefore, a preferable base material is a nonwoven fabric made from 100% high-density polyethylene short fibers having a fiber diameter of 2 denier and having a basis weight of 60 to 70 g / m 2 and a thickness of 0.30 to 0.40 mm.
機能性官能基を繊維材料に導入する方法としては、レドックス重合触媒等の触媒を使用する方法、放射線照射を行なう方法などがあるが、機能性官能基導入後の触媒による汚染を生じさせないという観点等から、放射線グラフト重合法が好ましい。 As a method for introducing a functional functional group into a fiber material, there are a method using a catalyst such as a redox polymerization catalyst, a method of performing radiation irradiation, etc., but a viewpoint that does not cause contamination by the catalyst after the introduction of the functional functional group Therefore, the radiation graft polymerization method is preferable.
かかる方法としては、予め基材に放射線を照射してラジカルを形成した後、重合性単量体（モノマー）を接触させる前照射グラフト重合法と、基材にモノマーの存在下で放射線を照射する同時照射グラフト重合法とがあるが、副生成物である単独重合物の生成量が少ないことから、前照射グラフト重合法が好ましい。 Such methods include pre-irradiation graft polymerization in which a substrate is irradiated with radiation in advance to form radicals and then contacted with a polymerizable monomer (monomer), and the substrate is irradiated with radiation in the presence of the monomer. There is a simultaneous irradiation graft polymerization method, but the pre-irradiation graft polymerization method is preferred because the amount of by-product homopolymer produced is small.
本発明の別の態様においては、照射済みの基材をモノマー液に浸漬したままグラフト重合する、液相グラフト重合法を採用することができる。この場合には、反応温度２０〜８０℃、反応時間２〜１０時間が好適である。 In another embodiment of the present invention, a liquid phase graft polymerization method in which an irradiated base material is graft polymerized while being immersed in a monomer liquid can be employed. In this case, a reaction temperature of 20 to 80 ° C. and a reaction time of 2 to 10 hours are preferable.
また、本発明の更に別の態様においては、照射済み基材に所定量のモノマーを付与して、真空中又は不活性ガス中で反応させることによりグラフト重合する、含浸グラフト重合法を採用することができる。この場合には反応温度２０〜８０℃、反応温度０．２〜８時間が好適である。なお、この方法では、グラフト重合後の基材が乾燥状態で得られることから、基材の取り扱いが簡単で廃液の発生量が少ない等の利点がある。 In yet another aspect of the present invention, an impregnation graft polymerization method is employed in which a predetermined amount of monomer is imparted to the irradiated base material and the graft polymerization is performed by reacting in a vacuum or an inert gas. Can do. In this case, a reaction temperature of 20 to 80 ° C. and a reaction temperature of 0.2 to 8 hours are preferable. In this method, since the base material after graft polymerization is obtained in a dry state, there are advantages such as easy handling of the base material and a small amount of waste liquid generated.
更に、本発明の別の態様においては、照射済み基材とモノマー蒸気とを接触させる、気相グラフト重合法を採用することができる。この方法は、比較的蒸気圧の高いモノマーにしか適応できず、グラフトむらが発生しやすいが、廃液発生量が少なく、グラフト重合後の基材が乾燥状態で得られるという利点がある。この場合には、反応温度として２０〜８０℃、反応時間２〜１０時間が好適である。 Furthermore, in another aspect of the present invention, a gas phase graft polymerization method in which the irradiated substrate and the monomer vapor are brought into contact can be employed. This method can be applied only to monomers having a relatively high vapor pressure, and graft unevenness is likely to occur. However, there is an advantage that the amount of waste liquid generated is small and the base material after graft polymerization can be obtained in a dry state. In this case, the reaction temperature is preferably 20 to 80 ° C. and the reaction time is 2 to 10 hours.
本発明においては、上記のいずれの放射線グラフト重合法も用いることができる。放射線グラフト重合によってポリエチレン基材に導入する重合性単量体としては、それ自体が機能性官能基を有する重合性単量体や、或いはそれをグラフトした後に更に２次反応を行なうことによって機能性官能基を導入することのできる重合性単量体を用いることができる。重合性単量体は、特に限定はないが、グリシジルメタクリレート、アクリル酸、メタクリル酸、アクリルアミドが挙げられる。 In the present invention, any of the radiation graft polymerization methods described above can be used. As the polymerizable monomer introduced into the polyethylene substrate by radiation graft polymerization, the polymerizable monomer itself has a functional functional group, or the functionality is obtained by further performing a secondary reaction after grafting it. A polymerizable monomer capable of introducing a functional group can be used. The polymerizable monomer is not particularly limited, and examples thereof include glycidyl methacrylate, acrylic acid, methacrylic acid, and acrylamide.
本発明の金属除去材料は、これに限定されるものではないが、例えば、適するサイズのカラムに積層することにより、フィルター製品として使用することができる。また、ポリエチレン系繊維の柔軟性を保持しているため、カット性がよく、プリーツ加工、ロール加工など、現状の織布又は不織布が成型加工される様々な用途に適用可能な材料として利用することができる。本発明の金属除去材料を含むフィルター製品は、無機系凝集剤や高分子系凝集剤により処理された工場廃水の２次処理に適用して、廃水中に含まれる銅、鉛、水銀、ニッケル、カドミウムなどの重金属イオンを除去することができる。また、本発明の別の態様においては、金属除去材料を含むフィルター製品を水道水の処理に適用して、鉛イオンを除去することができる。金属除去材料に吸着された金属陽イオンは酸により溶離することができ、材料はその素材が単一成分の繊維より構成されるため、溶離のあとも繰り返しの使用による耐性を有している。 Although the metal removal material of this invention is not limited to this, For example, it can use as a filter product by laminating | stacking on the column of a suitable size. In addition, because it retains the flexibility of polyethylene fibers, it has good cutting properties and should be used as a material that can be used in various applications where woven or non-woven fabrics are molded, such as pleating and roll processing. Can do. The filter product containing the metal removing material of the present invention is applied to the secondary treatment of factory wastewater treated with an inorganic flocculant or a polymer flocculant, and contains copper, lead, mercury, nickel, Heavy metal ions such as cadmium can be removed. Moreover, in another aspect of the present invention, a lead product can be removed by applying a filter product containing a metal removing material to the treatment of tap water. The metal cation adsorbed on the metal removal material can be eluted by an acid, and the material is resistant to repeated use after elution since the material is composed of single component fibers.
以下、本発明を実施例により説明するが、これらの実施例は本発明を例示するものであり、何ら限定するものではない。
実施例
実施例１
高密度ポリエチレン１００％よりなる繊維径２デニールの短繊維をカーディングし、クロスレイヤーにて積層し均一なウェブ（クロスウェブ）を得た。これを熱ゾーン（熱フラットロール対）に搬送して、ポリエチレンの融点である１３５℃で繊維同士を融着し、目付け６５ｇ／ｍ2のシート状物とした。
Hereinafter, the present invention will be described by way of examples. However, these examples illustrate the present invention and are not intended to limit the present invention.
Example Example 1
Short fibers having a fiber diameter of 2 denier made of 100% high-density polyethylene were carded and laminated with a cross layer to obtain a uniform web (cross web). This was conveyed to a heat zone (a pair of heat flat rolls), and the fibers were fused at 135 ° C., which is the melting point of polyethylene, to obtain a sheet-like material having a basis weight of 65 g / m 2 .
ここで得られた不織布に、窒素雰囲気下で２００ｋＧｙの電子線を照射した。次いで、この不織布に１００％のメタクリル酸グリシジルを含浸させ、５０℃で２時間反応させて、メタクリル酸グリシジルのグラフト率１６５％のグラフト物を得た。 The nonwoven fabric obtained here was irradiated with a 200 kGy electron beam in a nitrogen atmosphere. The nonwoven fabric was then impregnated with 100% glycidyl methacrylate and allowed to react at 50 ° C. for 2 hours to obtain a graft product of 165% glycidyl methacrylate.
ここで、グラフト率は以下の式にしたがって算出した。
グラフト率（％）＝１００×（グラフト重合物の重量（ｇ））／（基材不織布の重量（ｇ））
このグラフト物を、０．４２ｍｏｌのイミノジ酢酸水溶液に浸漬し、８０℃で２０時間処理をして、グリシジル基にイミノジ酢酸基を開環反応させてアミノ化し、キレート型不織布を得た。
Here, the graft ratio was calculated according to the following formula.
Graft ratio (%) = 100 × (weight of graft polymer (g)) / (weight of base nonwoven fabric (g))
This graft product was immersed in 0.42 mol of iminodiacetic acid aqueous solution, treated at 80 ° C. for 20 hours, and aminated by allowing the glycidyl group to undergo ring-opening reaction of iminodiacetic acid group to obtain a chelate-type nonwoven fabric.
この金属除去材料について、鉛イオンを除去対象として性能評価を行った。内径７ｍｍのカラムに、イミノジ酢酸基が導入された不織布を、厚みが６ｍｍとなるように積層した（不織布の容積は０．２３１ｍｌ）。硝酸鉛８ｍｇを量りとり、精製水に溶解して５０リットル（鉛イオン濃度１００ｐｐｂ）とした試料溶液を、ポンプを用いて一定の流速でカラムに通水した。カラム通水後の処理液をフラクションコレクターにより分画し、ICP質量分析装置により鉛イオン濃度を測定した。 About this metal removal material, performance evaluation was performed for lead ion as an object of removal. A non-woven fabric introduced with iminodiacetic acid groups was laminated on a column having an inner diameter of 7 mm so as to have a thickness of 6 mm (the non-woven fabric has a volume of 0.231 ml). 8 mg of lead nitrate was weighed and dissolved in purified water to make 50 liters (lead ion concentration 100 ppb), and the sample solution was passed through the column at a constant flow rate using a pump. The treatment liquid after passing through the column was fractionated with a fraction collector, and the lead ion concentration was measured with an ICP mass spectrometer.
流速１１５５ｍｌ／時間（空間速度５０００ｈ-1）、及び流速２７７２ｍｌ／時間（空間速度１２０００ｈ-1）で得られた破過曲線をそれぞれ図１及び図２に示す。陽イオン交換容量は、基材の乾燥重量基準で２．１ｍｍｏｌ／ｇであった。 Flow rate 1155Ml / time (space velocity 5000h -1), and a flow rate of 2772ml / time shows a breakthrough curve obtained in (space velocity 12000h -1) in FIGS. 1 and 2, respectively. The cation exchange capacity was 2.1 mmol / g based on the dry weight of the substrate.
実施例２
高密度ポリエチレン１００％よりなる繊維径２デニールの短繊維をカーディングし、得られたパラレルウェブをコンデンスロールにより圧縮し、繊維をランダムに配向させ、セミランダムウェブを形成した。これをエンボスロールにて熱圧着し、目付け５０ｇ／ｍ2のシート状物を得た。
Example 2
Short fibers having a fiber diameter of 2 denier made of 100% high-density polyethylene were carded, and the obtained parallel web was compressed by a condensation roll, and the fibers were randomly oriented to form a semi-random web. This was thermocompression-bonded with an embossing roll to obtain a sheet-like material having a basis weight of 50 g / m 2 .
これに窒素雰囲気下で、２００ｋＧｙの電子線を照射したあと、１０％のメタクリル酸グリシジル溶液（溶媒：ジメチルスルホキシド）に浸漬し、４０℃で５時間反応させて、メタクリル酸グリシジルのグラフト率２００％のグラフト物を得た。 This was irradiated with an electron beam of 200 kGy in a nitrogen atmosphere, then immersed in a 10% glycidyl methacrylate solution (solvent: dimethyl sulfoxide), reacted at 40 ° C. for 5 hours, and a glycidyl methacrylate graft ratio of 200%. The graft product was obtained.
このグラフト物を、１０％亜硫酸ナトリウム水溶液に浸漬し、８０℃で３時間反応させてスルホン化を行い、イオン交換不織布を得た。
この金属除去材料について、カリウムイオンを除去対象として性能評価を行った。内径７ｍｍのカラムに、スルホン酸基が導入された不織布を、厚みが６ｍｍとなるように積層した。塩化カリウム１．９１ｍｇを量りとり、精製水に溶解して１００リットル（カリウムイオン濃度１０ｐｐｂ）とした試料溶液を、ポンプを用いて、１１５５ｍｌ／時間の流速（空間速度５０００ｈ-1）でカラムに通水した。カラム通水後の処理液をフラクションコレクターにより分画し、ICP質量分析装置によりカリウムイオン濃度を測定した。
This grafted product was immersed in a 10% aqueous sodium sulfite solution and reacted at 80 ° C. for 3 hours for sulfonation to obtain an ion exchange nonwoven fabric.
About this metal removal material, performance evaluation was performed for potassium ion as a removal target. A non-woven fabric into which a sulfonic acid group was introduced was laminated on a column having an inner diameter of 7 mm so as to have a thickness of 6 mm. 1.91 mg of potassium chloride was weighed and dissolved in purified water to a 100 liter (
得られた破過曲線を図３に示す。陽イオン交換容量は、基材の乾燥重量基準で２．５ｍｍｏｌ／ｇであった。 The obtained breakthrough curve is shown in FIG. The cation exchange capacity was 2.5 mmol / g based on the dry weight of the substrate.
Claims (6)
The filter product containing the metal removal material of any one of Claims 1-5.
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| JP2004169481A JP2005349241A (en) | 2004-06-08 | 2004-06-08 | Material that removes cations in water at high speed and high efficiency, and secondary treatment of wastewater using this material |
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| CN100432126C (en) * | 2006-11-09 | 2008-11-12 | 上海大学 | Method for preparing polyethylene ion chelating membrane by radiation graft method |
| WO2012147937A1 (en) * | 2011-04-27 | 2012-11-01 | 株式会社カネカ | Ion-exchange fibers and method for producing same, method for removing and adsorbing chemical substance in water, and device for removing and adsorbing chemical substance in water |
| JP2014188434A (en) * | 2013-03-27 | 2014-10-06 | Asahi Kasei Chemicals Corp | Metal collecting material |
| CN110177616A (en) * | 2017-03-30 | 2019-08-27 | 仓敷纤维加工株式会社 | Cartridges and Filters |
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2004
- 2004-06-08 JP JP2004169481A patent/JP2005349241A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100432126C (en) * | 2006-11-09 | 2008-11-12 | 上海大学 | Method for preparing polyethylene ion chelating membrane by radiation graft method |
| WO2012147937A1 (en) * | 2011-04-27 | 2012-11-01 | 株式会社カネカ | Ion-exchange fibers and method for producing same, method for removing and adsorbing chemical substance in water, and device for removing and adsorbing chemical substance in water |
| CN103502527A (en) * | 2011-04-27 | 2014-01-08 | 株式会社钟化 | Ion-exchange fiber and method for producing same, method for removing and adsorbing chemical substance in water, and device for removing and adsorbing chemical substance in water |
| JP5545412B2 (en) * | 2011-04-27 | 2014-07-09 | 株式会社カネカ | Ion exchange fiber and method for producing the same, removal / adsorption method for chemical substances in water, and removal / adsorption apparatus for chemical substances in water |
| CN103502527B (en) * | 2011-04-27 | 2015-11-25 | 株式会社钟化 | Ion exchange fiber and method for producing same, method for removing and adsorbing chemical substances in water, and device for removing and adsorbing chemical substances in water |
| US9205422B2 (en) | 2011-04-27 | 2015-12-08 | Kaneka Corporation | Ion-exchange fibers and method for producing and using same |
| JP2014188434A (en) * | 2013-03-27 | 2014-10-06 | Asahi Kasei Chemicals Corp | Metal collecting material |
| CN110177616A (en) * | 2017-03-30 | 2019-08-27 | 仓敷纤维加工株式会社 | Cartridges and Filters |
| CN110177616B (en) * | 2017-03-30 | 2022-10-04 | 仓敷纤维加工株式会社 | Filter cartridge and filter |
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