JPH04284853A - Ion exchange filtering method and apparatus therefor - Google Patents
Ion exchange filtering method and apparatus thereforInfo
- Publication number
- JPH04284853A JPH04284853A JP3047971A JP4797191A JPH04284853A JP H04284853 A JPH04284853 A JP H04284853A JP 3047971 A JP3047971 A JP 3047971A JP 4797191 A JP4797191 A JP 4797191A JP H04284853 A JPH04284853 A JP H04284853A
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- group
- anion
- organic polymer
- polymer
- 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.)
- Pending
Links
- 238000001914 filtration Methods 0.000 title claims abstract description 30
- 238000005342 ion exchange Methods 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 23
- 229920000620 organic polymer Polymers 0.000 claims abstract description 42
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract description 25
- 238000005349 anion exchange Methods 0.000 claims abstract description 24
- 238000005341 cation exchange Methods 0.000 claims abstract description 24
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims 2
- 239000004745 nonwoven fabric Substances 0.000 abstract description 14
- 239000010419 fine particle Substances 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 8
- -1 polypropylene Polymers 0.000 abstract description 6
- 239000012498 ultrapure water Substances 0.000 abstract description 5
- 239000004743 Polypropylene Substances 0.000 abstract description 4
- 150000001768 cations Chemical group 0.000 abstract description 4
- 229920001155 polypropylene Polymers 0.000 abstract description 4
- 229910021642 ultra pure water Inorganic materials 0.000 abstract description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract description 3
- 125000001174 sulfone group Chemical group 0.000 abstract description 3
- 150000001450 anions Chemical group 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 238000012423 maintenance Methods 0.000 abstract description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 abstract description 2
- 125000001302 tertiary amino group Chemical group 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000000178 monomer Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004750 melt-blown nonwoven Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- XESUCHPMWXMNRV-UHFFFAOYSA-M sodium;2-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=C XESUCHPMWXMNRV-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は液体の処理に関するもの
であり、特に純水の製造方法およびその装置に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the treatment of liquids, and more particularly to a method and apparatus for producing pure water.
【０００２】0002
【従来の技術】原子力発電プラント、半導体製造業およ
び医薬品製造業等においては、極めて純度の高い水が要
求される。例えば、半導体製造業においては工業用水等
を凝集沈殿、砂濾過を経てイオン交換処理し、この一次
純水を貯槽に蓄え、これを使用末端においてさらにイオ
ン交換、滅菌、多孔膜や逆浸透膜等による二次処理を行
い、半導体の洗浄に使用している。半導体の集積度が大
きくなるにつれて半導体の洗浄用の水には更に純度の高
い超純水が要求される。しかしながら、純度の高い水を
安定に且つ大量に供給するためには、その製造プロセス
が極めて複雑となり、それにしたがってメンテナンスも
頻繁に行う必要がある。したがって、かかる製造プロセ
スを簡素化することが急務となっている。BACKGROUND OF THE INVENTION Water of extremely high purity is required in nuclear power plants, semiconductor manufacturing, pharmaceutical manufacturing, and the like. For example, in the semiconductor manufacturing industry, industrial water, etc. is subjected to ion exchange treatment through coagulation sedimentation and sand filtration, and this primary pure water is stored in a storage tank. It undergoes secondary treatment and is used for cleaning semiconductors. As the degree of integration of semiconductors increases, ultrapure water with even higher purity is required as water for cleaning semiconductors. However, in order to stably supply high-purity water in large quantities, the manufacturing process becomes extremely complicated, and accordingly, maintenance must be performed frequently. Therefore, there is an urgent need to simplify such manufacturing processes.
【０００３】一方、原子力発電プラントにおいては、プ
ラントの健全性の向上、放射線被爆の低減、放射性廃棄
物の低減等の問題を解決することが不可欠である。かか
る問題を解決すべく、イオン交換を主とした復水や炉水
処理設備の改善、新技術の導入が常に検討されている。On the other hand, in nuclear power plants, it is essential to solve problems such as improving the health of the plant, reducing radiation exposure, and reducing radioactive waste. In order to solve these problems, improvements to condensate and reactor water treatment equipment, mainly ion exchange, and the introduction of new technologies are constantly being considered.
【０００４】0004
【発明が解決しようとする課題】上記問題に鑑み、本発
明の目的は、イオンおよび微粒子を同時に除去でき且つ
操作および維持管理が容易で再生も可能なイオン交換濾
過方法およびその装置を提供することにある。SUMMARY OF THE INVENTION In view of the above-mentioned problems, an object of the present invention is to provide an ion exchange filtration method and a device thereof that can simultaneously remove ions and fine particles, are easy to operate and maintain, and can be regenerated. It is in.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決すべく、
本発明のイオン交換濾過方法においては、カチオン交換
基を有するシート状有機高分子とアニオン交換基を有す
るシート状有機高分子とを交互に配列させることを特徴
とする。[Means for solving the problem] In order to solve the above problem,
The ion exchange filtration method of the present invention is characterized in that sheet-like organic polymers having cation exchange groups and sheet-like organic polymers having anion exchange groups are arranged alternately.
【０００６】本発明の方法において使用されるシート状
有機高分子は、繊維の集合体である織布若しくは不織布
または多孔性の膜であることが好ましい。後述するよう
に本発明においては電離性放射線によるグラフト重合を
利用してカチオンおよびアニオン交換基をシート状有機
高分子に導入するが、該シート状有機高分子が上記の形
態であることが本発明の効果を最も期待できるものであ
り、かつ種々の形態に加工することが容易だからである
。[0006] The sheet-like organic polymer used in the method of the present invention is preferably a woven fabric or nonwoven fabric that is an aggregate of fibers, or a porous membrane. As described later, in the present invention, cation and anion exchange groups are introduced into a sheet-like organic polymer using graft polymerization using ionizing radiation. This is because the effect can be expected the most and it is easy to process into various shapes.
【０００７】織布または不織布は通常の方法により製造
される。使用される繊維は、ステープルファイバーでも
よく、または連続フィラメントでもよい。織布の場合は
、織物および編物の双方の形態で用いることができる。
不織布の場合は、ステープルファイバーまたは連続フィ
ラメントが固定化されたウエブであってもよい。固定化
にはウエブをニードリングにより機械的に固定化する方
法、バインダーを用いて化学的に接着する方法、繊維を
熱融着させる方法等がある。これらの方法により製造さ
れる不織布は、例えばフエルト、カード不織布、スパン
ボンド不織布、メルトブロー不織布がある。[0007] Woven or nonwoven fabrics are manufactured by conventional methods. The fibers used may be staple fibers or continuous filaments. In the case of woven fabric, it can be used in both woven and knitted forms. In the case of a non-woven fabric, it may be a web to which staple fibers or continuous filaments are fixed. Fixation methods include a method of mechanically fixing the web by needling, a method of chemically bonding using a binder, and a method of heat-sealing the fibers. Nonwoven fabrics produced by these methods include, for example, felt, carded nonwoven fabric, spunbond nonwoven fabric, and meltblown nonwoven fabric.
【０００８】多孔性の膜には、フィルムを延伸して細孔
を設けた延伸加工膜や無機物をブレンドした膜原料から
膜を成型した後に該無機物を除去して細孔を設けた膜等
がある。前者の膜の細孔は直交型であるためプレッシャ
ードロップが小さいという特徴を有する。また、後者の
膜の細孔は三次元型であるため、濾過行路が長いという
特徴を有する。本発明においては目的、用途に応じてい
ずれの膜も使用することができる。Porous membranes include stretched membranes in which pores are formed by stretching a film, and membranes in which pores are formed by forming a membrane from membrane raw materials blended with inorganic substances and then removing the inorganic substances. be. Since the pores of the former membrane are orthogonal, it is characterized by a small pressure drop. Moreover, since the pores of the latter membrane are three-dimensional, it has a characteristic that the filtration path is long. In the present invention, any membrane can be used depending on the purpose and application.
【０００９】シート状有機高分子自体は、微粒子のみを
除去する性能を有する。そして後述のグラフト重合を利
用してシート状有機高分子にカチオンおよびアニオン交
換基を導入することによって、イオンおよび微粒子を同
時に除去できる高機能性濾過膜となすことができる。電
離性放射線によるグラフト重合においては、グラフト基
材の形状によらずグラフト重合することができる。した
がって、繊維状若しくは膜状またはそれらの加工品等の
複雑な形状をした基材であってもグラフト重合すること
は可能である。[0009] The sheet-like organic polymer itself has the ability to remove only fine particles. By introducing cation and anion exchange groups into a sheet-like organic polymer using graft polymerization, which will be described later, a highly functional filtration membrane capable of simultaneously removing ions and fine particles can be obtained. In graft polymerization using ionizing radiation, graft polymerization can be carried out regardless of the shape of the graft base material. Therefore, it is possible to graft-polymerize even base materials having complex shapes such as fibers, membranes, or processed products thereof.
【００１０】本発明の方法に使用される有機高分子の材
質としては、成型加工が容易な熱可塑性樹脂が適してい
る。そのような樹脂は例えば、ポリエチレンおよびポリ
プロピレンに代表されるポリオレフィン類、ポリ四フッ
化エチレン（ＰＴＦＥ）およびポリ塩化ビニルに代表さ
れるハロゲン化ポリオレフィン類ならびにエチレン−四
フッ化エチレン共重合体およびエチレン−ビニルアルコ
ール共重合体（ＥＶＡ）に代表されるオレフィン−ハロ
ゲン化オレフィン共重合体である。As the organic polymer material used in the method of the present invention, a thermoplastic resin that can be easily molded is suitable. Examples of such resins include polyolefins such as polyethylene and polypropylene, halogenated polyolefins such as polytetrafluoroethylene (PTFE) and polyvinyl chloride, and ethylene-tetrafluoroethylene copolymers and ethylene-tetrafluoroethylene copolymers. It is an olefin-halogenated olefin copolymer typified by vinyl alcohol copolymer (EVA).
【００１１】本発明の方法に使用されるカチオン交換基
を有するシート状有機高分子の形状とアニオン交換基を
有するシート状有機高分子の形状とは同一でもよく又は
異なっていてもよい。同様に両者の材質は同一でもよく
又は異なっていてもよい。The shape of the sheet-like organic polymer having a cation-exchange group and the shape of the sheet-like organic polymer having an anion-exchange group used in the method of the present invention may be the same or different. Similarly, both materials may be the same or different.
【００１２】本発明においては、グラフト重合を利用し
てシート状有機高分子にイオン交換基を導入する。グラ
フト重合によるイオン交換体は従来のイオン交換樹脂と
は異なり架橋構造を有さない。したがって、本発明のイ
オン交換濾過膜は燃焼しやすく、廃棄処分が非常に容易
である。In the present invention, ion exchange groups are introduced into a sheet-like organic polymer using graft polymerization. Ion exchangers produced by graft polymerization do not have a crosslinked structure, unlike conventional ion exchange resins. Therefore, the ion exchange filtration membrane of the present invention is easily combustible and very easy to dispose of.
【００１３】イオン交換基は、イオン交換基を有する重
合性モノマーまたはイオン交換基に変換可能な基を有す
る重合性モノマーをグラフト重合させてシート状有機高
分子に導入することができる。そのような重合性モノマ
ーは、例えばアクリル酸またはメタクリル酸のようなカ
ルボン酸およびそのエステル類、メタクリル酸グリシジ
ル、ビニルベンゼンスルホン酸ソーダ、ビニルピリジン
、スチレン並びにクロロメチルスチレンである。以上の
重合性モノマーより得られるイオン交換基は、カチオン
交換基として代表的なものは、カルボキシル基、スルホ
ン基およびリン酸基等であり、アニオン交換基として代
表的なものは、四級アンモニウム基、二、三級アミノ基
およびピリジニウム基等である。グラフト重合に用いら
れる電離性放射線は、α線、β線、γ線、電子線および
紫外線等があり、限定されるものではない。本発明のグ
ラフト重合においてはγ線および電子線が特に適してい
る。The ion exchange group can be introduced into the sheet-like organic polymer by graft polymerizing a polymerizable monomer having an ion exchange group or a group convertible to an ion exchange group. Such polymerizable monomers are, for example, carboxylic acids such as acrylic acid or methacrylic acid and their esters, glycidyl methacrylate, sodium vinylbenzenesulfonate, vinylpyridine, styrene and chloromethylstyrene. The ion exchange groups obtained from the above polymerizable monomers include carboxyl groups, sulfone groups, phosphoric acid groups, etc. as cation exchange groups, and quaternary ammonium groups as typical anion exchange groups. , secondary and tertiary amino groups, and pyridinium groups. Ionizing radiation used in graft polymerization includes α rays, β rays, γ rays, electron beams, ultraviolet rays, and the like, but is not limited to these. Gamma rays and electron beams are particularly suitable for the graft polymerization of the present invention.
【００１４】シート状有機高分子に電離性放射線を照射
してグラフト重合させる方法としては、シート状有機高
分子と重合性モノマーの共存下に電離性放射線を照射す
る同時照射法と、予めシート状有機高分子に電離性放射
線を照射した後、重合性モノマーと接触させる前照射法
がある。前照射法は重合性モノマーの単独重合物の生成
が少ないため有利な方法である。[0014] Methods for graft polymerization by irradiating sheet-like organic polymers with ionizing radiation include a simultaneous irradiation method in which ionizing radiation is irradiated in the coexistence of sheet-like organic polymers and polymerizable monomers; There is a pre-irradiation method in which an organic polymer is irradiated with ionizing radiation and then brought into contact with a polymerizable monomer. The pre-irradiation method is an advantageous method because it produces less homopolymers of polymerizable monomers.
【００１５】グラフト重合によってシート状有機高分子
に導入されるイオン交換基の量は、カチオン交換基およ
びアニオン交換基ともに３．０ｍｅｑ／ｇを上限とする
ことが好ましい。[0015] The upper limit of the amount of ion exchange groups introduced into the sheet-like organic polymer by graft polymerization is preferably 3.0 meq/g for both cation exchange groups and anion exchange groups.
【００１６】シート状有機高分子と重合性モノマーを接
触させてグラフト重合する方法には、重合性モノマーが
液体である場合と気体である場合の二種類の方法がある
。前者は液相グラフト重合と呼ばれ、後者は気相グラフ
ト重合と呼ばれる。本発明においてはいずれの方法によ
りグラフト重合してもよい。There are two methods for graft polymerization by bringing a sheet-like organic polymer into contact with a polymerizable monomer: one in which the polymerizable monomer is in the form of a liquid, and the other in which the polymerizable monomer is in the form of a gas. The former is called liquid phase graft polymerization, and the latter is called gas phase graft polymerization. In the present invention, graft polymerization may be carried out by any method.
【００１７】気相グラフト重合は、重合後のシート状有
機高分子の強度が液相グラフト重合に比して優れている
。この理由は、液相グラフト重合では基材を膨潤させて
反応が進むため基材の中心付近まで均一にグラフト重合
が起こり基材本来の性質が失われるのに対して、気相グ
ラフト重合では重合が基材表面において起こりやすいた
め基材の芯部分は基材本来の強度が維持されるためであ
る。また気相グラフト重合ではイオン交換基がシート状
有機高分子の表面に集中したグラフト重合物が得られる
ため、原水をイオン交換する際のイオン交換速度が大と
なり極めて有利である。さらに、シート状有機高分子表
面のイオン交換基の密度が大きくなるとシート状有機高
分子の表面電荷も大きくなるため、原水中に存在するコ
ロイド物質等の微粒子に対する除去性能の向上も期待で
きる。そしてさらに、シート状有機高分子の形状が複雑
であってもグラフト重合することができ、また重合のコ
ストも小さい。以上の理由により本発明においては、液
相グラフト重合よりも気相グラフト重合の方が好ましい
ものである。Gas phase graft polymerization is superior to liquid phase graft polymerization in the strength of the sheet-like organic polymer after polymerization. The reason for this is that in liquid phase graft polymerization, the reaction progresses by swelling the base material, resulting in uniform graft polymerization near the center of the base material, resulting in loss of the original properties of the base material, whereas in gas phase graft polymerization, polymerization This is because the core portion of the base material maintains its original strength because this is likely to occur on the surface of the base material. In addition, in gas phase graft polymerization, a graft polymer in which ion exchange groups are concentrated on the surface of a sheet-like organic polymer is obtained, so that the ion exchange rate when ion-exchanging raw water becomes high, which is extremely advantageous. Furthermore, as the density of ion-exchange groups on the surface of the sheet-like organic polymer increases, the surface charge of the sheet-like organic polymer also increases, so it can be expected to improve the removal performance for fine particles such as colloidal substances present in raw water. Furthermore, even if the sheet-like organic polymer has a complicated shape, it can be graft-polymerized, and the cost of polymerization is low. For the above reasons, in the present invention, gas phase graft polymerization is more preferable than liquid phase graft polymerization.
【００１８】本発明の方法においては、原水はカチオン
交換濾過膜とアニオン交換濾過膜とを交互に通過する。
通過するイオン交換膜の数が多いほど純水の純度は向上
する。また、細孔の径によって捕捉される微粒子は異な
る。したがって、原水の種類や要求水質等に応じて、イ
オン交換膜の枚数、細孔径および厚さを変えることがで
きる。In the method of the present invention, raw water is passed alternately through a cation exchange filtration membrane and an anion exchange filtration membrane. The greater the number of ion exchange membranes that the water passes through, the higher the purity of the water. Furthermore, the types of fine particles that are captured differ depending on the diameter of the pores. Therefore, the number, pore diameter, and thickness of the ion exchange membranes can be changed depending on the type of raw water, the required water quality, etc.
【００１９】[0019]
【実施例】図１は本発明のイオン交換濾過膜を使用した
イオン交換濾過装置である。カチオン交換基およびアニ
オン交換基がそれぞれ導入された不織布を複数枚交互に
積層した。積層された該不織布を濾過器ハウジングに充
填した。濾過器ハウジングの底部には多孔性の支持床が
設けられており、該不織布を該支持床上に設置した。EXAMPLE FIG. 1 shows an ion exchange filtration device using the ion exchange filtration membrane of the present invention. A plurality of nonwoven fabrics into which cation exchange groups and anion exchange groups were introduced were alternately laminated. The laminated nonwoven fabric was filled into a filter housing. A porous support bed was provided at the bottom of the filter housing, and the nonwoven fabric was placed on the support bed.
【００２０】カチオン交換濾過膜は、ポリプロピレン製
不織布にスチレンをグラフト重合させた後、クロルスル
ホン酸でスルホン化したものである。電離性放射線は、
γ線を線量率１０ｋＧｙ／ｈｒで２０時間照射した。ス
ルホン基は、イオン交換容量２．８ｍｅｑ／ｇ導入され
た。アニオン交換濾過膜はポリプロピレン製不織布にク
ロロメチルスチレンをグラフト重合させた後、トリメチ
ルアミンで四級アンモニウム化しものである。電離性放
射線は、γ線を線量率１０ｋＧｙ／ｈｒで２０時間照射
した。アンモニウム基は、イオン交換容量２．３ｍｅｑ
／ｇ導入された。The cation exchange filtration membrane is made by graft polymerizing styrene onto a polypropylene nonwoven fabric and then sulfonating it with chlorosulfonic acid. Ionizing radiation is
γ-rays were irradiated for 20 hours at a dose rate of 10 kGy/hr. The sulfone group was introduced with an ion exchange capacity of 2.8 meq/g. The anion exchange filtration membrane is made by graft-polymerizing chloromethylstyrene onto a polypropylene nonwoven fabric and then converting it into quaternary ammonium with trimethylamine. The ionizing radiation was irradiated with gamma rays at a dose rate of 10 kGy/hr for 20 hours. Ammonium group has an ion exchange capacity of 2.3 meq
/g was introduced.
【００２１】原水はハウジング上部より通水させた。原
水中のイオンおよび微粒子は、カチオン交換濾過膜およ
びアニオン交換濾過膜に交互に接触することによって吸
着、捕捉された。処理水はハウジング下部の処理水出口
より得られた。[0021] Raw water was passed through the upper part of the housing. Ions and fine particles in the raw water were adsorbed and captured by alternately contacting the cation exchange filtration membrane and the anion exchange filtration membrane. The treated water was obtained from the treated water outlet at the bottom of the housing.
【００２２】図２は、カチオン交換濾過膜およびアニオ
ン交換濾過膜をそれぞれ一枚ずつ重ねてロール状に巻い
たものをイオン交換層としたものである。該ロールと直
交するように原水を通水して、カチオン交換濾過膜およ
びアニオン交換濾過膜の双方を切断することなくイオン
交換をすることができた。また通水抵抗が小さいため大
量の原水を高い濾過速度で処理することができた。原水
はカチオン交換基およびアニオン交換基にそれぞれ何度
も接触することにより、電気導電率０．１３μＳ／ｃｍ
の純水に精製された。これは混床式イオン交換装置と同
程度の電気導電率である。また微粒子は精密濾過と同等
か又はそれ以上除去された。原水の処理後はロールを巻
き戻して、カチオンとアニオンとを容易に且つ完全に分
離することができた。この再生操作によって、次回の処
理時に高純度の処理水質が保証された。FIG. 2 shows an ion exchange layer made by stacking one cation exchange filtration membrane and one anion exchange filtration membrane and winding them into a roll. By passing raw water perpendicularly to the roll, ion exchange could be performed without cutting both the cation exchange filtration membrane and the anion exchange filtration membrane. In addition, because the water flow resistance is low, a large amount of raw water can be processed at a high filtration rate. The raw water has an electrical conductivity of 0.13 μS/cm by contacting the cation exchange group and the anion exchange group many times.
purified to pure water. This is an electrical conductivity comparable to that of a mixed bed ion exchange device. In addition, fine particles were removed as much or better than microfiltration. After the raw water was treated, the roll was rewound and the cations and anions could be easily and completely separated. This regeneration operation ensured high purity treated water quality during the next treatment.
【００２３】[0023]
【発明の効果】本発明により、イオンおよび微粒子を同
時に除去することができ、再生が可能な濾過器が提供さ
れる。特に電子工業用、原子力発電用等の超純水を必要
不可欠とする分野において、超純水製造装置の小型化、
製造工程の簡略化、省エネルギー化が期待できる。Effects of the Invention According to the present invention, a filter capable of simultaneously removing ions and fine particles and capable of being regenerated is provided. In particular, in fields where ultrapure water is essential, such as electronic industry and nuclear power generation, miniaturization of ultrapure water production equipment,
It is expected to simplify the manufacturing process and save energy.
【図１】イオン交換濾過膜が積層されたイオン交換濾過
器を示す図である。FIG. 1 is a diagram showing an ion exchange filter in which ion exchange filtration membranes are stacked.
【図２】イオン交換濾過膜がロール状に巻かれたイオン
交換濾過器を示す図である。FIG. 2 is a diagram showing an ion exchange filter in which an ion exchange filtration membrane is wound into a roll.
１ ハウジング ２ 原水入口 ３ 処理水出口 ４ カチオン交換不織布 ５ アニオン交換不織布 ６ 多孔板支持床 ７ 多孔管 1 Housing 2 Raw water entrance 3. Treated water outlet 4 Cation exchange nonwoven fabric 5 Anion exchange nonwoven fabric 6 Perforated plate support floor 7 Porous pipe
Claims (10)
高分子とアニオン交換基を有するシート状有機高分子と
が交互に配列された濾過層に液体を通過させることを特
徴とするイオン交換濾過方法。1. An ion exchange filtration method comprising passing a liquid through a filtration layer in which sheet organic polymers having cation exchange groups and sheet organic polymers having anion exchange groups are arranged alternately.
は電離性放射線のグラフト重合によってシート状有機高
分子に導入されたものである請求項１に記載の方法。2. The method according to claim 1, wherein the cation exchange group and the anion exchange group are introduced into the sheet-like organic polymer by graft polymerization with ionizing radiation.
よび／または多孔性膜である請求項１または２に記載の
方法。3. The method according to claim 1, wherein the sheet-like organic polymer is an aggregate of fibers and/or a porous membrane.
ン交換基を有するシート状有機高分子とアニオン交換基
を有するシート状有機高分子とを交互に積層させたもの
である請求項１〜３のいずれか一項に記載の方法。4. The filtration layer is formed by alternately laminating sheet-like organic polymers having cation-exchange groups and sheet-like organic polymers having anion-exchange groups on a perforated plate support bed. 3. The method according to any one of 3 to 3.
ート状有機高分子とアニオン交換基を有するシート状有
機高分子とを重ねて巻き込んだものである請求項１〜３
のいずれか一項に記載の方法。5. The filtration layer is formed by wrapping a sheet-like organic polymer having a cation exchange group and a sheet-like organic polymer having an anion-exchange group in a layered manner.
The method described in any one of the above.
高分子とアニオン交換基を有するシート状有機高分子と
が交互に配列された濾過層を有することを特徴とするイ
オン交換濾過装置。6. An ion exchange filtration device comprising a filtration layer in which sheet-like organic polymers having cation exchange groups and sheet-like organic polymers having anion exchange groups are arranged alternately.
は電離性放射線のグラフト重合によってシート状有機高
分子に導入されたものである請求項６に記載の装置。7. The device according to claim 6, wherein the cation exchange group and the anion exchange group are introduced into the sheet-like organic polymer by graft polymerization with ionizing radiation.
よび／または多孔性膜である請求項６または７に記載の
装置。8. The device according to claim 6, wherein the sheet-like organic polymer is an aggregate of fibers and/or a porous membrane.
ン交換基を有するシート状有機高分子とアニオン交換基
を有するシート状有機高分子とを交互に積層させたもの
である請求項６〜８のいずれか一項に記載の装置。9. The filtration layer is formed by alternately laminating sheet-like organic polymers having cation exchange groups and sheet-like organic polymers having anion-exchange groups on a porous plate support bed. 9. The device according to any one of 8 to 8.
シート状有機高分子とアニオン交換基を有するシート状
有機高分子とを重ねて巻き込んだものである請求項６〜
８のいずれか一項に記載の装置。10. The filtration layer is formed by stacking and wrapping a sheet-like organic polymer having a cation exchange group and a sheet-like organic polymer having an anion exchange group.
8. The device according to any one of 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3047971A JPH04284853A (en) | 1991-03-13 | 1991-03-13 | Ion exchange filtering method and apparatus therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3047971A JPH04284853A (en) | 1991-03-13 | 1991-03-13 | Ion exchange filtering method and apparatus therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04284853A true JPH04284853A (en) | 1992-10-09 |
Family
ID=12790206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3047971A Pending JPH04284853A (en) | 1991-03-13 | 1991-03-13 | Ion exchange filtering method and apparatus therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04284853A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004050056A (en) * | 2002-07-19 | 2004-02-19 | Kurita Water Ind Ltd | Ion exchanger and ultrapure water manufacturing apparatus |
| EP1251144A4 (en) * | 1999-10-21 | 2004-03-31 | Ebara Corp | Organic polymeric material, process for producing the same, and heavy-metal ion remover comprising the same |
| EP1231231A4 (en) * | 1999-10-21 | 2004-03-31 | Ebara Corp | Material having separating function |
| JP2009050761A (en) * | 2007-08-23 | 2009-03-12 | Nomura Micro Sci Co Ltd | Module for removing metal |
| JP2010158606A (en) * | 2009-01-06 | 2010-07-22 | Kurita Water Ind Ltd | Filter, method of manufacturing the same, and method of treating fluid |
| JP2012040526A (en) * | 2010-08-20 | 2012-03-01 | Kurita Water Ind Ltd | Filter for liquid filtration, and liquid filtration method |
| WO2018180430A1 (en) * | 2017-03-30 | 2018-10-04 | 倉敷繊維加工株式会社 | Filter cartridge and filter |
| CN111467874A (en) * | 2019-01-24 | 2020-07-31 | 仓敷纤维加工株式会社 | Method for filtering medical liquid containing carboxylic acid derivative |
-
1991
- 1991-03-13 JP JP3047971A patent/JPH04284853A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1251144A4 (en) * | 1999-10-21 | 2004-03-31 | Ebara Corp | Organic polymeric material, process for producing the same, and heavy-metal ion remover comprising the same |
| EP1231231A4 (en) * | 1999-10-21 | 2004-03-31 | Ebara Corp | Material having separating function |
| US6844371B1 (en) | 1999-10-21 | 2005-01-18 | Ebara Corporation | Material having separating function |
| JP2004050056A (en) * | 2002-07-19 | 2004-02-19 | Kurita Water Ind Ltd | Ion exchanger and ultrapure water manufacturing apparatus |
| JP2009050761A (en) * | 2007-08-23 | 2009-03-12 | Nomura Micro Sci Co Ltd | Module for removing metal |
| JP2010158606A (en) * | 2009-01-06 | 2010-07-22 | Kurita Water Ind Ltd | Filter, method of manufacturing the same, and method of treating fluid |
| JP2012040526A (en) * | 2010-08-20 | 2012-03-01 | Kurita Water Ind Ltd | Filter for liquid filtration, and liquid filtration method |
| WO2018180430A1 (en) * | 2017-03-30 | 2018-10-04 | 倉敷繊維加工株式会社 | Filter cartridge and filter |
| JP2018167223A (en) * | 2017-03-30 | 2018-11-01 | 倉敷繊維加工株式会社 | Filter cartridge and filter |
| CN110177616A (en) * | 2017-03-30 | 2019-08-27 | 仓敷纤维加工株式会社 | Filter cylinder and filter |
| CN110177616B (en) * | 2017-03-30 | 2022-10-04 | 仓敷纤维加工株式会社 | Filter cartridge and filter |
| CN111467874A (en) * | 2019-01-24 | 2020-07-31 | 仓敷纤维加工株式会社 | Method for filtering medical liquid containing carboxylic acid derivative |
| JP2020116524A (en) * | 2019-01-24 | 2020-08-06 | 倉敷繊維加工株式会社 | Method for filtering liquid medicine containing carboxylic acid derivative |
| CN111467874B (en) * | 2019-01-24 | 2023-02-28 | 仓敷纤维加工株式会社 | Method for filtering medical liquid containing carboxylic acid derivative |
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