JPH05111637A - Production of chelate resin adsorbent with polyamine compound fixed - Google Patents
Production of chelate resin adsorbent with polyamine compound fixedInfo
- Publication number
- JPH05111637A JPH05111637A JP27440991A JP27440991A JPH05111637A JP H05111637 A JPH05111637 A JP H05111637A JP 27440991 A JP27440991 A JP 27440991A JP 27440991 A JP27440991 A JP 27440991A JP H05111637 A JPH05111637 A JP H05111637A
- Authority
- JP
- Japan
- Prior art keywords
- adsorbent
- polymer
- polyamine compound
- chelate resin
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は精密電子工業、医療、製
薬、原子力発電などの各分野における用水や排水中に含
まれる金属イオンの除去に応用可能な新規吸着剤に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel adsorbent applicable to removal of metal ions contained in water or waste water in various fields such as precision electronics industry, medical care, pharmaceuticals, nuclear power generation and the like.
【０００２】[0002]
【従来の技術】従来の水処理技術においては、コバル
ト、ニッケル、水銀および銅などの有害重金属類を除去
するのに、ビーズ状のキレート樹脂が広く用いられてい
るが、低濃度の溶存金属イオンを効率的に吸着分離する
ことは困難であり、多量の樹脂を必要とする。また、形
状が約０.２〜０.８ｍｍ直径の真球であるため、充填塔
方式による使用形態に限られる。2. Description of the Related Art In conventional water treatment technology, bead-like chelating resins are widely used to remove harmful heavy metals such as cobalt, nickel, mercury and copper, but low concentration of dissolved metal ions Is difficult to adsorb and separate efficiently, and a large amount of resin is required. Further, since the shape is a true sphere having a diameter of about 0.2 to 0.8 mm, it is limited to the usage form by the packed column system.
【０００３】また、ビーズ状のキレート樹脂は通常のイ
オン交換樹脂と同様にジビニルベンゼンなどの架橋剤に
よって剛直な三次元構造を有しており、樹脂内部への金
属イオンおよび再生剤の拡散速度が十分ではない。さら
に、非再生で使用する場合にも、燃焼処分が困難なた
め、例えば、原子力発電所の放射性廃棄物である使用済
みイオン交換樹脂をいかに減容化するかが大問題となっ
ている。原子力発電所でなくとも、使用済みのキレート
樹脂の処理処分を誤ると。既に吸着済みの重金属イオン
（例えば、水銀やカドミウムなど）が他の場所へと拡散
し、深刻な二次汚染が発生する危険性がある。Further, the bead-like chelate resin has a rigid three-dimensional structure due to a cross-linking agent such as divinylbenzene similar to the ordinary ion exchange resin, and the diffusion rate of the metal ion and the regenerant inside the resin is high. Not enough. Furthermore, even when used in a non-recycled manner, it is difficult to dispose of it by combustion, so that how to reduce the volume of used ion-exchange resin, which is a radioactive waste of a nuclear power plant, has become a big problem. Even if it is not a nuclear power plant, it is wrong to dispose of used chelate resin. There is a risk that already adsorbed heavy metal ions (such as mercury and cadmium) will diffuse to other places, causing serious secondary pollution.
【０００４】[0004]
【発明が解決しようとする課題】本発明は水処理技術に
おいて、微量に溶存するコバルト、ニッケル、水銀、銅
などの重金属イオンを選択的に吸脱着し、容易に処分可
能な吸着剤を提供することにある。DISCLOSURE OF THE INVENTION The present invention provides an adsorbent for water treatment technology, which selectively adsorbs and desorbs a small amount of heavy metal ions such as cobalt, nickel, mercury, and copper, which are dissolved, and which can be easily disposed. Especially.
【０００５】[0005]
【課題を解決するための手段】本発明者等は前記目的を
達成する手段を鋭意研究した結果以下の手段によって達
成できることを見いだした。Means for Solving the Problems The inventors of the present invention have made extensive studies as to the means for achieving the above object, and have found that the following means can be achieved.
【０００６】基材がオレフィンまたはハロゲン化ポリオ
レフィンの重合体または共重合体からなる高分子成型品
に電離性放射線を作用させ、エポキシ基を含有する重合
性単量体をグラフト重合した後、そのグラフト重合体の
側鎖にポリアミン化合物を固定化することにより、水溶
液中の微量の重金属成分を効率よく分離、除去すること
が可能であり、化学的、物理的に安定な吸着剤が得られ
ることを見いだした。Ionizing radiation is applied to a polymer molded product whose base material is a polymer or copolymer of an olefin or a halogenated polyolefin to graft-polymerize a polymerizable monomer containing an epoxy group, and then the grafting is carried out. By immobilizing a polyamine compound on the side chain of a polymer, it is possible to efficiently separate and remove a trace amount of heavy metal components in an aqueous solution, and to obtain a chemically and physically stable adsorbent. I found it.
【０００７】以下、本発明においてグラフト重合させる
基材は、ポリエチレン、ポリプロピレン、ポリスルホ
ン、ポリテトラフルオロエチレン、またはエチレン、プ
ロピレン、ブテン、ヘキセン、テトラフルオロエチレ
ン、クロロトリフルオロエチレンの単独または共重合体
から選択される。ただし、使用済みの樹脂を燃焼させる
ことを考慮すると、ハロゲンや硫黄を含有しないものの
方が好ましい。The base material to be graft-polymerized in the present invention is a homopolymer or a copolymer of polyethylene, polypropylene, polysulfone, polytetrafluoroethylene, ethylene, propylene, butene, hexene, tetrafluoroethylene or chlorotrifluoroethylene. To be selected. However, in consideration of burning the used resin, a resin containing no halogen or sulfur is preferable.
【０００８】基材として用いられる高分子成型体の形状
は、繊維やその集合体である織布や不織布、粒子、粉
末、シートあるいはそれらの加工品など各種の形状から
選択することができる。特に、本発明の方法は、形状に
限定されることがなく、ポリアミン化合物を固定化でき
ることが特徴である。The shape of the polymer molded body used as the base material can be selected from various shapes such as fibers and aggregates thereof such as woven and non-woven fabrics, particles, powders, sheets and processed products thereof. In particular, the method of the present invention is not limited to the shape and is characterized in that the polyamine compound can be immobilized.
【０００９】基材にグラフト重合される重合性単量体
は、グリシジルメタクリレート、グリシジルアクリレー
ト、グリシジルメタイタコナート、エチルグリシジルメ
タイタコナート、エチルグリシジルマレアート、グリシ
ジルビニルスルホナートなどが用いられ、エポキシ基を
含有すれば特に限定されるものではないが、グリシジル
メタクリレートおよびグリシジルアクリレートなどが適
している。As the polymerizable monomer graft-polymerized on the substrate, glycidyl methacrylate, glycidyl acrylate, glycidyl metaitaconate, ethyl glycidyl metaitaconate, ethyl glycidyl maleate, glycidyl vinyl sulfonate, etc. are used, and an epoxy group is used. It is not particularly limited as long as it contains, but glycidyl methacrylate and glycidyl acrylate are suitable.
【００１０】本発明のグラフト重合に際して用いる電離
性放射線は、α線、β線、γ線、加速電子線、Ｘ線、紫
外線などであるが、実用的には加速電子線またはγ線が
好ましい。The ionizing radiation used in the graft polymerization of the present invention is α-ray, β-ray, γ-ray, accelerated electron beam, X-ray, ultraviolet ray and the like, but accelerated electron beam or γ-ray is preferable for practical use.
【００１１】本発明にしたがって、基材と重合性単量体
をグラフト重合させる方法としては、基材と重合性単量
体とを共存下放射線を照射する同時照射法と、基材のみ
に予め放射線を照射した後、重合性単量体と基材とを接
触させる前照射法のいずれでも可能であるが、前照射法
がグラフト重合以外の副反応を生成しにくい特徴を有す
る。According to the present invention, as a method for graft-polymerizing the substrate and the polymerizable monomer, a simultaneous irradiation method in which the substrate and the polymerizable monomer are coexistent and radiation is applied, and only the substrate is previously prepared. Although any of the pre-irradiation methods in which the polymerizable monomer and the substrate are brought into contact with each other after irradiation with radiation is possible, the pre-irradiation method is characterized in that side reactions other than graft polymerization are unlikely to occur.
【００１２】グラフト重合の際に、基材と単量体とを接
触させる方法は液状の単量体あるいは単量体溶液と直接
接触させる液相重合法と、重合性単量体の蒸気あるいは
気化状態で接触させる気相グラフト重合法とがあるが、
いずれの方法も目的にあった選択が可能である。In the graft polymerization, the method of contacting the substrate with the monomer is a liquid phase polymerization method of directly contacting with a liquid monomer or a monomer solution, and vaporization or vaporization of the polymerizable monomer. There is a gas phase graft polymerization method of contacting in a state,
Either method can be selected according to the purpose.
【００１３】ポリアミン化合物として、エチレンジアミ
ン、ヘキサメチレンジアミン、ジエチレントリアミン、
トリエチレントリアミン、テトラエチレンペンタミン、
フェニレンジアミン、ペンタメチレンヘキサミン、ヘキ
サメチレンヘプタミン、ヒドラジン、フェニルヒドラジ
ン、ポリエチレンイミンなどが用いられる。As the polyamine compound, ethylenediamine, hexamethylenediamine, diethylenetriamine,
Triethylenetriamine, tetraethylenepentamine,
Phenylenediamine, pentamethylenehexamine, hexamethyleneheptamine, hydrazine, phenylhydrazine, polyethyleneimine and the like are used.
【００１４】[0014]
【実施例】以下、実施例により、本発明の構成および効
果を具体的に述べるが、いずれも本発明を限定するもの
ではない。EXAMPLES The constitution and effects of the present invention will be specifically described below with reference to examples, but they do not limit the present invention.
【００１５】（実施例１）ポリエチレン製極細繊維に電
子線加速器（加速電圧２ＭｅＶ、電子線電流１ｍＡ）を
用いて、窒素雰囲気下で２００ＫＧｙを照射した後、減
圧下でグリシジルメタクリレートの蒸気と４０℃で６時
間接触させ、気相グラフト重合反応を行った。このとき
の重量増加率は１３０％であった。エチレンジアミンの
液中にグラフト樹脂を浸して、６０℃で３時間反応させ
た。その結果、エチレンジアミンが反応生成物１ｇあた
り２．９ｍｍｏｌのキレート樹脂を得た。この樹脂を１
０ｍｍφのガラスカラムに１ｇを充填し、Ｃｏ濃度が１
ｐｐｍ ａｓＣｏの塩化コバルト水溶液をＳＶ１０の速
度で通液した。カラムの流出液を５０ｍｌずつ分画した
結果、５０分画においても流出液中のコバルト濃度は５
ｐｐｂ以下であった。エチレンジアミンを固定化したキ
レート樹脂がコバルトイオンに対して明らかに優れた結
果を得た。Example 1 Polyethylene ultrafine fibers were irradiated with 200 KGy in a nitrogen atmosphere using an electron beam accelerator (accelerating voltage: 2 MeV, electron beam current: 1 mA), and then vaporized with glycidyl methacrylate and 40 ° C. under reduced pressure. And the gas phase graft polymerization reaction was carried out. The weight increase rate at this time was 130%. The graft resin was immersed in a solution of ethylenediamine and reacted at 60 ° C. for 3 hours. As a result, ethylenediamine obtained a chelate resin of 2.9 mmol per 1 g of the reaction product. This resin is 1
1 g was packed in a 0 mmφ glass column and Co concentration was 1
An aqueous cobalt chloride solution containing ppm asCo was passed at a speed of SV10. As a result of fractionating 50 ml of the column effluent, the cobalt concentration in the effluent was 5 even in 50 fractions.
It was ppb or less. The chelating resin having ethylenediamine immobilized thereon was clearly superior to cobalt ion.
【００１６】（実施例２）粉末ポリエチレンを基材にし
て、実施例１と同様な方法でグリシジルメタクリレート
をグラフトした結果、グラフト率１００％のグラフト樹
脂粉末を得た。ヘキサメチレンジアミンの液中にグラフ
ト樹脂を浸して、６０℃で３時間反応させた。その結
果、ヘキサメチレンジアミンが反応生成物１ｇ当たり
２．３５ｍｍｏｌのキレート樹脂を得た。コバルト濃度
が１ｐｐｍ ａｓＣｏに調整した塩化コバルト水溶液５
００ｍｌを５００ｍｌビーカにいれ、さらにキレート樹
脂０．１ｇを加えて、１０時間撹拌した。この液をＮ
ｏ．５Ａ瀘紙にて瀘過し、瀘液のコバルト濃度を測定し
た結果７ｐｐｂであり、ヘキサメチレンジアミンを固定
化したキレート樹脂がコバルトイオンに対し明らかに優
れた結果を得た。(Example 2) Grafting resin powder having a graft ratio of 100% was obtained as a result of grafting glycidyl methacrylate in the same manner as in Example 1, using powdered polyethylene as a base material. The graft resin was immersed in a solution of hexamethylenediamine and reacted at 60 ° C. for 3 hours. As a result, a hexamethylenediamine obtained a chelate resin of 2.35 mmol per 1 g of the reaction product. Cobalt chloride aqueous solution 5 with cobalt concentration adjusted to 1 ppm asCo
00 ml was put into a 500 ml beaker, 0.1 g of chelate resin was further added, and the mixture was stirred for 10 hours. This liquid is N
o. It was 7 ppb as a result of measuring the cobalt concentration of the filtrate by filtering with a 5A filter paper, and the chelating resin having hexamethylenediamine immobilized thereon was clearly superior to the cobalt ion.
【００１７】（実施例３）ポリプロピレン製ろ布を基材
として実施例１と同様な方法でグラフト重合反応および
エチレンジアミンの固定化を行った結果、グラフト率１
１０％、エチレンジアミンの固定化量が反応生成物１ｇ
あたり２．４ｍｍｏｌのキレート樹脂を得た。これを直
径３０ｍｍの円形に打ち抜き、１０枚重ねて内径３０ｍ
ｍのガラスカラムに充填した。このカラムにニッケル濃
度が１ｐｐｍ ａｓＮｉの塩化コバルト水溶液をＳＶ１
０で通液したところ、充填体積の１００倍量を通液した
時点でカラム出口のニッケル濃度が１８ｐｐｂであり、
未だブレークの徴候は認められなかった。ろ布状のキレ
ート樹脂においてもニッケルイオンに対し優れた吸着性
能を得た。(Example 3) A graft polymerization reaction and immobilization of ethylenediamine were carried out in the same manner as in Example 1 using a polypropylene filter cloth as a base material, resulting in a graft ratio of 1
10%, immobilized amount of ethylenediamine is 1 g of reaction product
Thus, 2.4 mmol of chelating resin was obtained. This is punched out into a circle with a diameter of 30 mm, 10 pieces are stacked and the inner diameter is 30 m.
m glass column. An aqueous cobalt chloride solution having a nickel concentration of 1 ppm asNi was applied to this column by SV1.
When the solution was passed at 0, the nickel concentration at the column outlet was 18 ppb at the time when 100 times the packed volume was passed.
No signs of a break were observed yet. Excellent adsorption performance for nickel ions was obtained even with the filter cloth chelate resin.
【００１８】[0018]
【発明の効果】本発明により、水溶液中の重金属イオン
に対して高い吸着性能を示すキレート樹脂吸着剤を提供
することが可能となった。原子力発電、精密電子工業な
どにおける用水や排水中からの重金属イオンを効率良く
除去でき、取り扱いや処分も容易なため、環境保護など
産業界への社会的な要請が大きい昨今、極めて有用な材
料である。Industrial Applicability According to the present invention, it has become possible to provide a chelate resin adsorbent having a high adsorption performance for heavy metal ions in an aqueous solution. Since heavy metal ions from water and wastewater in nuclear power generation, precision electronics industry, etc. can be efficiently removed and they are easy to handle and dispose of, they are extremely useful materials nowadays due to the great social demands of the industrial world such as environmental protection. is there.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 丸山 真策 東京都大田区羽田旭町11番１号 株式会社 荏原製作所内 (72)発明者 関口 英明 東京都大田区羽田旭町11番１号 株式会社 荏原製作所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinsaku Maruyama 11-1 Haneda Asahi-cho, Ota-ku, Tokyo Inside the EBARA CORPORATION (72) Inventor Hideaki Sekiguchi 11-11 Haneda-Asahi-cho, Ota-ku, Tokyo Stocks Inside the EBARA CORPORATION
Claims (4)
体の側鎖にポリアミン化合物を固定化することを特徴と
する吸着剤の製造方法1. A method for producing an adsorbent, which comprises fixing a polyamine compound to a side chain of a graft polymer using a polymer molding as a substrate.
ン化オレフィンの重合体または共重合体よりなることを
特徴とする特許請求の範囲第１項記載の吸着剤の製造方
法2. The method for producing an adsorbent according to claim 1, wherein the polymer molding is made of a polymer or copolymer of olefin or halogenated olefin.
放射線を用いることを特徴とする特許請求の範囲第１項
または第２項記載の吸着剤の製造方法3. The method for producing an adsorbent according to claim 1 or 2, wherein the graft polymerization method uses ultraviolet rays and ionizing radiation.
ポキシ基を含有することを特徴とする特許請求の範囲第
１、第２または第３項記載の吸着剤の製造方法。4. The method for producing an adsorbent according to claim 1, 2, or 3, wherein the polymerizable monomer in the graft polymerization contains an epoxy group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27440991A JP3150173B2 (en) | 1991-10-23 | 1991-10-23 | Method for producing chelating resin adsorbent having immobilized polyamine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27440991A JP3150173B2 (en) | 1991-10-23 | 1991-10-23 | Method for producing chelating resin adsorbent having immobilized polyamine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05111637A true JPH05111637A (en) | 1993-05-07 |
| JP3150173B2 JP3150173B2 (en) | 2001-03-26 |
Family
ID=17541273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27440991A Expired - Fee Related JP3150173B2 (en) | 1991-10-23 | 1991-10-23 | Method for producing chelating resin adsorbent having immobilized polyamine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3150173B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001113272A (en) * | 1999-10-20 | 2001-04-24 | Agency Of Ind Science & Technol | Method for capturing selenium or arsenic in aqueous solution |
| JP2002253962A (en) * | 2001-02-28 | 2002-09-10 | Tosoh Corp | Adsorbent and production method therefor |
| JP2004337749A (en) * | 2003-05-16 | 2004-12-02 | Kankyo Joka Kenkyusho:Kk | Boron catching material and its production method |
| JP2016013500A (en) * | 2014-06-30 | 2016-01-28 | 住友金属鉱山株式会社 | Method of manufacturing resin for recovering platinum group element |
| EP2893975A4 (en) * | 2012-09-05 | 2016-05-25 | Nippon Filcon Kk | Fibrous metal adsorbent |
| CN109289807A (en) * | 2018-10-31 | 2019-02-01 | 扬州金珠树脂有限公司 | A kind of preparation method of mercury ion absorption resin |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10364397B2 (en) | 2017-04-18 | 2019-07-30 | King Fahd University Of Petroleum And Minerals | Mercury removal from liquid hydrocarbons by 1,4-benzenediamine alkyldiamine cross-linked polymers |
-
1991
- 1991-10-23 JP JP27440991A patent/JP3150173B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001113272A (en) * | 1999-10-20 | 2001-04-24 | Agency Of Ind Science & Technol | Method for capturing selenium or arsenic in aqueous solution |
| JP2002253962A (en) * | 2001-02-28 | 2002-09-10 | Tosoh Corp | Adsorbent and production method therefor |
| JP2004337749A (en) * | 2003-05-16 | 2004-12-02 | Kankyo Joka Kenkyusho:Kk | Boron catching material and its production method |
| EP2893975A4 (en) * | 2012-09-05 | 2016-05-25 | Nippon Filcon Kk | Fibrous metal adsorbent |
| JP2016013500A (en) * | 2014-06-30 | 2016-01-28 | 住友金属鉱山株式会社 | Method of manufacturing resin for recovering platinum group element |
| CN109289807A (en) * | 2018-10-31 | 2019-02-01 | 扬州金珠树脂有限公司 | A kind of preparation method of mercury ion absorption resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3150173B2 (en) | 2001-03-26 |
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