JP2010264360A - Deionization module and electric deionized-water producing apparatus - Google Patents

Deionization module and electric deionized-water producing apparatus Download PDF

Info

Publication number
JP2010264360A
JP2010264360A JP2009116426A JP2009116426A JP2010264360A JP 2010264360 A JP2010264360 A JP 2010264360A JP 2009116426 A JP2009116426 A JP 2009116426A JP 2009116426 A JP2009116426 A JP 2009116426A JP 2010264360 A JP2010264360 A JP 2010264360A
Authority
JP
Japan
Prior art keywords
monolith
water
skeleton
exchanger
organic porous
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
Application number
JP2009116426A
Other languages
Japanese (ja)
Other versions
JP5383310B2 (en
Inventor
Hiroshi Inoue
洋 井上
Koji Yamanaka
弘次 山中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Organo Corp
Original Assignee
Organo Corp
Japan Organo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Organo Corp, Japan Organo Co Ltd filed Critical Organo Corp
Priority to JP2009116426A priority Critical patent/JP5383310B2/en
Priority to PCT/JP2010/053653 priority patent/WO2010104007A1/en
Priority to TW99106881A priority patent/TW201038490A/en
Publication of JP2010264360A publication Critical patent/JP2010264360A/en
Application granted granted Critical
Publication of JP5383310B2 publication Critical patent/JP5383310B2/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Water Treatment By Electricity Or Magnetism (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electric deionized-water producing apparatus which is high in the strength of an ion-exchanger, can reduce a pressure loss upon water passage and can improve the quality of treated water. <P>SOLUTION: The deionization module used for the electric deionized-water producing apparatus is fabricated by packing each of composite structural bodies which is composed of an organic porous body comprising a continuous skeleton phase and a continuous void phase, and a number of particulate bodies having a diameter of 4 to 40 &mu;m fixed to the surface of skeleton of the organic porous body or a number of protrusion bodies having a size of 4 to 40 &mu;m formed on the surface of skeleton of the organic porous body, that is, each of monolithic organic porous ion exchangers each having an average diameter of pores in the moisture wet state of 10 to 150 &mu;m, a total pore volume of 0.5 to 5 ml/g and an ion exchange capacity per volume in the moisture wet state of 0.2 mg-equivalent/ml or more into each of internal spaces formed by a cation exchange membrane sealed on one side of a frame body and an anion exchange membrane sealed on the other side the frame body. The electric deionized-water producing apparatus provided with the deionization module is also disclosed. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

本発明は、脱イオン水を用いる半導体製造工業、製薬工業、食品工業、発電所、研究所等の各種の工業あるいは糖液、ジュース、ワイン等の製造等で利用される電気式脱イオン液製造装置に好適に使用される脱イオンモジュール及び脱イオンモジュールを備える電気式脱イオン水製造装置に関するものである。   The present invention relates to the manufacture of electrical deionized liquid used in various industries such as semiconductor manufacturing industry, pharmaceutical industry, food industry, power plant, laboratory, etc. using deionized water, or the production of sugar liquid, juice, wine, etc. The present invention relates to a deionization module suitably used in the apparatus and an electric deionized water production apparatus including the deionization module.

従来から実用化されている電気式脱イオン水製造装置は、基本的にはカチオン交換膜とアニオン交換膜で形成される隙間に、イオン交換体としてアニオン交換樹脂とカチオン交換樹脂の混合イオン交換樹脂を充填して脱塩室とし、当該イオン交換樹脂に被処理水を通過させるとともに、前記両イオン交換膜を介して被処理水の流れに対して直角方向に直流電流を作用させて、両イオン交換膜の外側に流れている濃縮水中に被処理水中のイオンを電気的に排除しながら脱イオン水を製造するものである。このような操作によって被処理水中の不純物イオンは電気的に除去されるので、充填したイオン交換樹脂を薬液による再生を全く行うことなく脱イオン水を連続的に得ることができる。   An electric deionized water production apparatus that has been put into practical use is basically a mixed ion exchange resin of an anion exchange resin and a cation exchange resin as an ion exchanger in a gap formed by a cation exchange membrane and an anion exchange membrane. The desalting chamber is filled with water to pass the water to be treated through the ion exchange resin, and a direct current is applied to the water to be treated through the both ion exchange membranes in a direction perpendicular to both the ions. Deionized water is produced while electrically removing ions in the water to be treated in the concentrated water flowing outside the exchange membrane. Since impurity ions in the water to be treated are electrically removed by such an operation, deionized water can be continuously obtained without regenerating the filled ion exchange resin with a chemical solution at all.

電気式脱イオン水製造装置においては薬液による再生は不要であるため、その運転コストは消費電力量によって決定される。交流を直流に変換する際の整流ロスを除けば、電気式脱イオン水製造装置における消費電力は、両電極間の直流電流×電圧で表される。ここで、直流電流は、被処理水が含有するイオンの量、イオンの種類及び要求される処理水質によって決定される。すなわち、電気式脱イオン水製造装置においては、脱塩室でイオン交換樹脂に捕捉されたイオンを電気的泳動によって連続的に濃縮水側に排出する必要があり、イオンを泳動せしめるに必要な一定以上の電流は、電気式脱イオン水製造装置がその性能を正常に発揮するために必須のものである。よって、通常の場合、電気式脱イオン水製造装置においては、その運転条件において必要な最低電流値を上回る一定の電流値を保持する定電流運転が行われている。これに対して電圧は、前記両電極間の電気抵抗によって決定され、電気式脱イオン水製造装置に用いられるイオン交換膜やイオン交換樹脂の性能に大きく依存する。すなわち、該電気抵抗は、両電極間に配設された電極室、濃縮室及び脱塩室による電気抵抗の総和であり、電極間距離および運転温度を一定とすれば、電極水及び濃縮水に含有されるイオンの濃度と種類、イオン交換膜、イオン交換樹脂の種類とそのイオン交換基の対イオンの種類、更にイオン交換樹脂の充填方法（単床あるいは混床）、更にこれら全ての電気抵抗構成要素の界面における接点抵抗が影響を与えるものである。前記電気抵抗構成要素の内、電極水および濃縮水に含有されるイオンの濃度と種類は、被処理水の水質及び要求される処理水水質によって決定されるが、その他の要素は電気式脱イオン水製造装置に用いられるイオン交換体の性能とその使用方法に依存する。   In the electric deionized water production apparatus, regeneration with a chemical solution is unnecessary, and the operation cost is determined by the amount of power consumption. Except for the rectification loss when converting alternating current to direct current, the power consumption in the electrical deionized water production apparatus is expressed as direct current x voltage between both electrodes. Here, the direct current is determined by the amount of ions contained in the water to be treated, the kind of ions, and the required quality of the treated water. That is, in the electric deionized water production apparatus, it is necessary to continuously discharge ions captured by the ion exchange resin in the desalting chamber to the concentrated water side by electrophoretic migration, which is necessary for the migration of ions. The above current is indispensable for the electric deionized water production apparatus to exhibit its performance normally. Therefore, in a normal case, in the electric deionized water production apparatus, a constant current operation is performed in which a constant current value exceeding the minimum current value required under the operation conditions is maintained. On the other hand, the voltage is determined by the electric resistance between the two electrodes, and greatly depends on the performance of the ion exchange membrane or ion exchange resin used in the electric deionized water production apparatus. That is, the electric resistance is the sum of the electric resistance by the electrode chamber, the concentrating chamber, and the desalting chamber disposed between both electrodes. If the interelectrode distance and the operating temperature are constant, Concentration and type of ions contained, type of ion exchange membrane, type of ion exchange resin and type of counter ion of the ion exchange group, furthermore, ion exchange resin filling method (single bed or mixed bed), and all these electric resistances The contact resistance at the interface of the component influences. Among the electrical resistance components, the concentration and type of ions contained in the electrode water and the concentrated water are determined by the quality of the treated water and the required quality of the treated water, but the other elements are electric deionization. It depends on the performance of the ion exchanger used in the water production apparatus and its method of use.

しかしながら、従来の電気式脱イオン水製造装置においては、脱塩モジュールに充填されるイオン交換樹脂は、従前より普及していた汎用品がそのまま流用されており、電気式脱イオン水製造装置の運転コストを低減させるべく、前記電気抵抗値の極小化に配慮されたものとはなっていない。すなわち、従来の電気式脱イオン水製造装置では、イオン交換樹脂として、一般に、スチレンとジビニルベンゼン（ＤＶＢ）の共重合体に、陽イオン交換基としてはスルホン酸基（Ｒ-ＳＯ３ − Ｈ＋ ）を、陰イオン交換基としては第４級アンモニウム塩基（Ｒ-Ｎ＋ Ｒ１Ｒ２Ｒ３）を導入して得られた直径０．２〜０．５ｍｍ程度の球状のものが充填されている。この場合、イオン交換樹脂粒子内における電流伝達、すなわち、電子及びイオンの伝達は、高分子ゲル内に均一且つ密に存在するイオン交換基を介して低抵抗で行われるのに対し、イオン交換樹脂粒子界面においては、イオン及び電子の移動に際し、イオンの場合には該イオンの水中の泳動距離が、また、電子の場合には水分子間の水素結合を介した電子伝達経路が長く、かつ球状のため粒子同士の接触面積が小さいのでイオンの流れが該接点部に集中し、電流伝達の阻害要因、すなわち、電気抵抗の原因となり、イオン交換樹脂由来の電気抵抗の主要因となっている。 However, in the conventional electric deionized water production apparatus, as the ion exchange resin filled in the demineralization module, general-purpose products that have been widely used are used as they are, and the operation of the electric deionized water production apparatus is not performed. In order to reduce the cost, the electric resistance value is not considered to be minimized. That is, in the conventional electrodeionization water producing apparatus, as an ion-exchange resin, generally, a copolymer of styrene and divinylbenzene (DVB), as the cation exchange group a sulfonic acid group (R-SO 3 - H + ), and as the anion-exchange group is filled with those of the quaternary ammonium base (R-N + R 1 R 2 R 3) spherical diameter of about 0.2~0.5mm obtained by introducing the Yes. In this case, the current transfer in the ion exchange resin particles, that is, the transfer of electrons and ions, is performed with low resistance via the ion exchange groups present uniformly and densely in the polymer gel, whereas the ion exchange resin At the particle interface, when ions and electrons move, in the case of ions, the migration distance of the ions in water is long, and in the case of electrons, the electron transfer path via hydrogen bonds between water molecules is long and spherical. For this reason, since the contact area between the particles is small, the flow of ions concentrates on the contact portion, which is an obstacle to current transmission, that is, electric resistance, and is a main factor of electric resistance derived from the ion exchange resin.

また、従来の電気式脱イオン水製造装置は、汎用のイオン交換樹脂を脱イオンモジュールに充填するため、製作に相当の時間と労力を必要とする。特に、脱塩室を形成する脱イオンモジュールの組立は、サンドイッチ状の端を接着剤を用いて複数枚積層接着しつつ、湿潤したイオン交換樹脂を均一に充填しなければならず、製作には相当の熟練を要し自動化しにくい。また、接着剤を使用しない場合でも湿潤したイオン交換樹脂の取扱いは難しい。   Further, since the conventional electric deionized water production apparatus fills the deionization module with a general-purpose ion exchange resin, it requires considerable time and labor for production. In particular, the assembly of the deionization module that forms the desalination chamber must be uniformly filled with a wet ion exchange resin while laminating and bonding a plurality of sandwich-like edges using an adhesive. Requires considerable skill and is difficult to automate. Even when no adhesive is used, it is difficult to handle a wet ion exchange resin.

これらを解決するものとして、例えば、特開２００２−３０６９７６号公報には、互いにつながっているマクロポアとマクロポアの壁内に平均径が１〜１０００μｍのメソポアを有する連続気泡構造を有し、全細孔容積が１〜５０ｍｌ／ｇであり、イオン交換基が均一に分布され、イオン交換容量が０．５ｍｇ当量／ｇ乾燥多孔質体以上である多孔質イオン交換体を、枠体の一方の側に封着されたカチオン交換膜と他方の側に封着されたアニオン交換膜で形成される内部空間に充填してなるものであって、電気式脱イオン水製造装置に使用される脱イオンモジュールが開示されている。この脱イオンモジュールを使用した電気式脱イオン水製造装置は、脱塩効率が高いため、運転時の電圧を低下させて、消費電力の低減が可能な省電力型とすることができる。   As a solution to these problems, for example, Japanese Patent Application Laid-Open No. 2002-306976 has an open cell structure having macropores connected to each other and mesopores having an average diameter of 1 to 1000 μm in the walls of the macropores. A porous ion exchanger having a volume of 1 to 50 ml / g, an ion exchange group uniformly distributed, and an ion exchange capacity of 0.5 mg equivalent / g or more of a dry porous body is placed on one side of the frame. A deionization module used in an electric deionized water production apparatus is formed by filling an internal space formed by a sealed cation exchange membrane and an anion exchange membrane sealed on the other side. It is disclosed. Since the electric deionized water production apparatus using this deionization module has high demineralization efficiency, it can be a power-saving type capable of reducing power consumption by reducing the voltage during operation.

特開２００２−３０６９７６号公報（特許請求の範囲）JP 2002-306976 A (Claims) 特開２００９−６２５１２号公報JP 2009-62512 A 特開２００９−６７９８２号公報JP 2009-67982 A

しかしながら、特開２００２−３０６９７６号公報に記載の有機多孔質イオン交換体は、モノリスの共通の開口（メソポア）が１〜１，０００μｍと記載されているものの、全細孔容積５ｍｌ／ｇ以下の細孔容積の小さなモノリスについては、油中水滴型エマルジョン中の水滴の量を少なくする必要があるため共通の開口は小さくなり、実質的に開口の平均径２０μｍ以上のものは製造できない。このため、通水時の圧力損失が大きいという問題があった。また、体積当たりのイオン交換容量が小さく、処理水の水質が十分ではなく、かつ消費電力が少ないという問題があった。また、このような連続気泡構造（連続マクロポア）のモノリスに代わる新たな構造のモノリスの登場も望まれていた。   However, the organic porous ion exchanger described in JP-A No. 2002-306976 has a common monolithic opening (mesopore) of 1 to 1,000 μm, but has a total pore volume of 5 ml / g or less. For monoliths with a small pore volume, the amount of water droplets in the water-in-oil emulsion needs to be reduced, so the common opening becomes small, and those having an average diameter of 20 μm or more cannot be manufactured. For this reason, there existed a problem that the pressure loss at the time of water flow was large. Moreover, there existed a problem that the ion exchange capacity per volume was small, the quality of the treated water was not sufficient, and power consumption was low. In addition, the appearance of a monolith with a new structure to replace such a monolith with an open-cell structure (continuous macropore) has been desired.

従って、本発明の目的は、組み立てが容易で、簡易な構造の脱イオンモジュールを提供するものである。また、本発明の他の目的は、イオン交換体の強度が高く、通水時の圧力損失を低下させることができると共に、処理水の水質を向上させる電気式脱イオン水製造装置を提供することにある。   Accordingly, an object of the present invention is to provide a deionization module that is easy to assemble and has a simple structure. Another object of the present invention is to provide an electric deionized water production apparatus that has high ion exchanger strength, can reduce pressure loss during water flow, and improves the quality of treated water. It is in.

かかる実情において、本発明者らは、鋭意検討を行った結果、特開２００２−３０６９７６号公報記載の方法で得られた比較的大きな細孔容積を有するモノリス状有機多孔質体（中間体）の存在下に、特定の条件下、ビニルモノマーと架橋剤を有機溶媒中で静置重合すれば、有機多孔質体を構成する骨格表面上に直径２〜２０μｍの多数の粒子体が固着する又は突起体が形成された複合構造を有するモノリスが得られること、この複合モノリスにイオン交換基を導入した複合モノリスイオン交換体は、電気式脱イオン水製造装置のイオン交換体として用いれば、強度が高く、通水時の圧力損失を低下させることができると共に、処理水水質を向上させ、消費電力が少ないことなどを見出し、本発明を完成するに至った。   Under such circumstances, the present inventors have conducted intensive studies, and as a result, obtained a monolithic organic porous body (intermediate) having a relatively large pore volume obtained by the method described in JP-A-2002-306976. In the presence, if a vinyl monomer and a cross-linking agent are allowed to stand in an organic solvent under specific conditions, a large number of particles having a diameter of 2 to 20 μm are fixed on the surface of the skeleton constituting the organic porous material or protrusions A monolith having a composite structure in which a body is formed is obtained, and a composite monolith ion exchanger in which an ion exchange group is introduced into this composite monolith has high strength when used as an ion exchanger in an electric deionized water production apparatus. The inventors have found that the pressure loss during water flow can be reduced, the quality of treated water is improved, and the power consumption is low, and the present invention has been completed.

すなわち、本発明は、枠体の一方の側に封着されたカチオン交換膜と他方の側に封着されたアニオン交換膜で形成される内部空間にイオン交換体を充填してなる、電気式脱イオン水製造装置に使用される脱イオンモジュールであって、該イオン交換体が、連続骨格相と連続空孔相からなる有機多孔質体と、該有機多孔質体の骨格表面に固着する直径４〜４０μｍの多数の粒子体又は該有機多孔質体の骨格表面上に形成される大きさが４〜４０μｍの多数の突起体との複合構造体であって、水湿潤状態で孔の平均直径１０〜１５０μｍ、全細孔容積０．５〜５ｍｌ／ｇであり、水湿潤状態での体積当りのイオン交換容量０．２ｍｇ当量/ｍｌ以上であるモノリス状有機多孔質イオン交換体であることを特徴とする脱イオンモジュールを提供するものである。   That is, the present invention is an electric type in which an internal space formed by a cation exchange membrane sealed on one side of a frame and an anion exchange membrane sealed on the other side is filled with an ion exchanger. A deionization module used in a deionized water production apparatus, wherein the ion exchanger has an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a diameter fixed to the skeleton surface of the organic porous body It is a composite structure with a large number of particles having a size of 4 to 40 μm or a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the organic porous material, and the average diameter of the pores in a wet state It is a monolithic organic porous ion exchanger having a total pore volume of 10 to 150 μm, a total pore volume of 0.5 to 5 ml / g, and an ion exchange capacity of 0.2 mg equivalent / ml or more per volume in a water-wet state. Providing a feature deionization module It is.

また、本発明は、枠体の一方の側に封着されたカチオン交換膜と、該カチオン交換膜と他方の側に封着されたアニオン交換膜の間に配置された中間イオン交換膜で形成される第１内部空間に第１イオン交換体を充填し、該中間イオン交換膜と他方の側に封着されたアニオン交換膜で形成される第２内部空間に第２イオン交換体を充填してなる、電気式脱イオン水製造装置に使用される脱イオンモジュールであって、該第１イオン交換体及び該第２イオン交換体のいずれか一方又は両方が、連続骨格相と連続空孔相からなる有機多孔質体と、該有機多孔質体の骨格表面に固着する直径４〜４０μｍの多数の粒子体又は該有機多孔質体の骨格表面上に形成される大きさが４〜４０μｍの多数の突起体との複合構造体であって、水湿潤状態で孔の平均直径１０〜１５０μｍ、全細孔容積０．５〜５ｍｌ／ｇであり、水湿潤状態での体積当りのイオン交換容量０．２ｍｇ当量/ｍｌ以上であるモノリス状有機多孔質イオン交換体であることを特徴とする脱イオンモジュールを提供するものである。   Further, the present invention is formed by a cation exchange membrane sealed on one side of a frame and an intermediate ion exchange membrane disposed between the cation exchange membrane and an anion exchange membrane sealed on the other side. The first internal space is filled with the first ion exchanger, and the second internal space formed by the intermediate ion exchange membrane and the anion exchange membrane sealed on the other side is filled with the second ion exchanger. A deionization module used in an electrical deionized water production apparatus, wherein one or both of the first ion exchanger and the second ion exchanger are a continuous skeleton phase and a continuous pore phase. And a large number of particles having a diameter of 4 to 40 μm fixed to the skeleton surface of the organic porous body or a large number of 4 to 40 μm formed on the skeleton surface of the organic porous body. A composite structure with protrusions of It is a monolithic organic porous ion exchanger having a diameter of 10 to 150 μm, a total pore volume of 0.5 to 5 ml / g, and an ion exchange capacity of 0.2 mg equivalent / ml or more per volume in a water-wet state. The deionization module characterized by the above is provided.

また、本発明は、前記脱イオンモジュールを備える電気式脱イオン水製造装置を提供するものである。   The present invention also provides an electric deionized water production apparatus including the deionization module.

複合モノリスイオン交換体は、従来の連続気泡構造のモノリスや共連続構造のモノリスとは全く異なる新規な構造である。この脱イオンモジュールによれば、イオン交換膜間の空間に充填される多孔質イオン交換体は、例えば、平板状や円筒状に成形でき、且つ切断が容易なポリマー材を使用できるため、組み立てが容易で、簡易な構造とすることができる。また、本発明の電気式脱イオン水製造装置は、イオン交換体の強度が高く、通水時の圧力損失を低下させることができると共に、処理水水質を向上させることができる。   The composite monolith ion exchanger has a novel structure that is completely different from a conventional monolith having an open cell structure or a monolith having a bicontinuous structure. According to this deionization module, the porous ion exchanger filled in the space between the ion exchange membranes can be formed into, for example, a flat plate shape or a cylindrical shape, and a polymer material that can be easily cut can be used. An easy and simple structure can be obtained. Moreover, the electric deionized water production apparatus of the present invention has high ion exchanger strength, can reduce pressure loss during water flow, and can improve the quality of treated water.

参考例１で得られたモノリスの倍率１００のＳＥＭ画像である。4 is a SEM image of a monolith obtained in Reference Example 1 at a magnification of 100. FIG. 参考例１で得られたモノリスの倍率３００のＳＥＭ画像である。3 is a SEM image of a monolith obtained in Reference Example 1 at a magnification of 300. 参考例１で得られたモノリスの倍率３０００のＳＥＭ画像である。3 is an SEM image of the monolith obtained in Reference Example 1 at a magnification of 3000. 参考例１で得られたモノリスカチオン交換体の表面における硫黄原子の分布状態を示したＥＰＭＡ画像である。2 is an EPMA image showing the distribution state of sulfur atoms on the surface of the monolith cation exchanger obtained in Reference Example 1. FIG. 参考例１で得られたモノリスカチオン交換体の断面（厚み）方向における硫黄原子の分布状態を示したＥＰＭＡ画像である。2 is an EPMA image showing a distribution state of sulfur atoms in the cross-section (thickness) direction of the monolith cation exchanger obtained in Reference Example 1. FIG. 参考例２で得られたモノリスの倍率１００のＳＥＭ画像である。10 is a SEM image of a monolith obtained in Reference Example 2 at a magnification of 100. 参考例２で得られたモノリスの倍率６００のＳＥＭ画像である。6 is an SEM image of a monolith obtained in Reference Example 2 at a magnification of 600. 参考例２で得られたモノリスの倍率３０００のＳＥＭ画像である。4 is an SEM image of the monolith obtained in Reference Example 2 at a magnification of 3000. 参考例３で得られたモノリスの倍率６００のＳＥＭ画像である。10 is an SEM image of a monolith obtained in Reference Example 3 at a magnification of 600. 参考例３で得られたモノリスの倍率３０００のＳＥＭ画像である。10 is an SEM image of the monolith obtained in Reference Example 3 at a magnification of 3000. 参考例４で得られたモノリスの倍率３０００のＳＥＭ画像である。10 is a SEM image of the monolith obtained in Reference Example 4 at a magnification of 3000. 参考例５で得られたモノリスの倍率１００のＳＥＭ画像である。10 is an SEM image of a monolith obtained in Reference Example 5 at a magnification of 100. 参考例５で得られたモノリスの倍率３０００のＳＥＭ画像である。10 is a SEM image of the monolith obtained in Reference Example 5 at a magnification of 3000. 参考例６で得られたモノリスの倍率１００のＳＥＭ画像である。10 is a SEM image of a monolith obtained in Reference Example 6 at a magnification of 100. 参考例６で得られたモノリスの倍率６００のＳＥＭ画像である。10 is an SEM image of a monolith obtained in Reference Example 6 at a magnification of 600. 参考例６で得られたモノリスの倍率３０００のＳＥＭ画像である。10 is an SEM image of the monolith obtained in Reference Example 6 at a magnification of 3000. 本発明の脱イオンモジュールを説明する模式図である。It is a schematic diagram explaining the deionization module of this invention. 本発明の他の脱イオンモジュールを説明する模式図である。It is a schematic diagram explaining the other deionization module of this invention. 本発明の電気式脱イオン水製造装置を説明する模式図である。It is a schematic diagram explaining the electric deionized water manufacturing apparatus of this invention. 本発明の他の電気式脱イオン水製造装置を説明する模式図である。It is a schematic diagram explaining the other electric deionized water manufacturing apparatus of this invention. 本発明の他の電気式脱イオン水製造装置を説明する模式図である。It is a schematic diagram explaining the other electric deionized water manufacturing apparatus of this invention. 本発明の他の電気式脱イオン水製造装置を説明する模式図である。It is a schematic diagram explaining the other electric deionized water manufacturing apparatus of this invention. 突起体の模式的な断面図である。It is typical sectional drawing of a protrusion.

本発明の実施の形態における脱イオンモジュールにおいて、枠体の内部空間、及び中間膜を有する枠体の２つの内部空間の少なくとも一方に充填されるのは、複合構造のモノリス状多孔質イオン交換体である。本明細書中、「モノリス状有機多孔質体」を単に「複合モノリス」と、「モノリス状有機多孔質イオン交換体」を単に「複合モノリスイオン交換体」と、「モノリス状の有機多孔質中間体」を単に「モノリス中間体」とも言う。   In the deionization module according to the embodiment of the present invention, at least one of the internal space of the frame body and the two internal spaces of the frame body having the intermediate film is filled with a monolithic porous ion exchanger having a composite structure. It is. In this specification, “monolithic organic porous body” is simply “composite monolith”, “monolithic organic porous ion exchanger” is simply “composite monolithic ion exchanger”, and “monolithic organic porous intermediate”. "Body" is also simply called "monolith intermediate".

＜複合モノリスイオン交換体の説明＞
複合モノリスイオン交換体は、複合モノリスにイオン交換基を導入することで得られるものであり、連続骨格相と連続空孔相からなる有機多孔質体と、該有機多孔質体の骨格表面に固着する直径４〜４０μｍの多数の粒子体との複合構造体であるか、又は連続骨格相と連続空孔相からなる有機多孔質体と、該有機多孔質体の骨格表面上に形成される大きさが４〜４０μｍの多数の突起体との複合構造体であって、水湿潤状態で孔の平均直径１０〜１５０μｍ、全細孔容積０．５〜５ｍｌ／ｇであり、水湿潤状態での体積当りのイオン交換容量０．２ｍｇ当量/ｍｌ以上であり、イオン交換基が該複合構造体中に均一に分布している。なお、本明細書中、「粒子体」及び「突起体」を併せて「粒子体等」と言うことがある。 <Description of composite monolith ion exchanger>
A composite monolith ion exchanger is obtained by introducing an ion exchange group into a composite monolith, and is fixed to an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and to the skeleton surface of the organic porous body. An organic porous body consisting of a continuous skeleton phase and a continuous pore phase, and a size formed on the skeleton surface of the organic porous body. A composite structure with a large number of protrusions having a thickness of 4 to 40 μm, and having an average pore diameter of 10 to 150 μm and a total pore volume of 0.5 to 5 ml / g in a water wet state, The ion exchange capacity per volume is 0.2 mg equivalent / ml or more, and the ion exchange groups are uniformly distributed in the composite structure. In the present specification, “particle bodies” and “projections” may be collectively referred to as “particle bodies”.

有機多孔質体の連続骨格相と連続空孔相（乾燥体）は、ＳＥＭ画像により観察することができる。有機多孔質体の基本構造としては、連続マクロポア構造及び共連続構造が挙げられる。有機多孔質体の骨格相は、柱状の連続体、凹状の壁面の連続体あるいはこれらの複合体として表れるもので、粒子状や突起状とは明らかに相違する形状のものである。   The continuous skeleton phase and the continuous pore phase (dried body) of the organic porous body can be observed by an SEM image. Examples of the basic structure of the organic porous material include a continuous macropore structure and a co-continuous structure. The skeletal phase of the organic porous material appears as a columnar continuum, a concave wall continuum, or a composite thereof, and has a shape that is clearly different from a particle shape or a protrusion shape.

有機多孔質体の好ましい構造としては、気泡状のマクロポア同士が重なり合い、この重なる部分が水湿潤状態で平均直径３０〜１５０μｍの開口となる連続マクロポア構造体（以下、「第１の有機多孔質イオン交換体」とも言う。）及び水湿潤状態で平均の太さが１〜６０μｍの三次元的に連続した骨格と、その骨格間に平均直径が水湿潤状態で１０〜１００μｍの三次元的に連続した空孔とからなる共連続構造体（以下、「第２の有機多孔質イオン交換体」とも言う。）が挙げられる。   As a preferable structure of the organic porous body, a continuous macropore structure (hereinafter referred to as “first organic porous ion”) in which bubble-shaped macropores overlap each other, and the overlapping portion becomes an opening having an average diameter of 30 to 150 μm in a wet state. And a three-dimensional continuous skeleton having an average thickness of 1 to 60 μm in a water-wet state, and three-dimensional continuous having an average diameter of 10 to 100 μm in a water-wet state between the skeletons. A co-continuous structure (hereinafter, also referred to as “second organic porous ion exchanger”).

第１の有機多孔質イオン交換体の場合、有機多孔質体は、気泡状のマクロポア同士が重なり合い、この重なる部分が水湿潤状態で平均直径３０〜１５０μｍの開口（メソポア）となる連続マクロポア構造体である。複合モノリスイオン交換体の開口の平均直径は、モノリスにイオン交換基を導入する際、複合モノリス全体が膨潤するため、乾燥状態の複合モノリスの開口の平均直径よりも大となる。開口の平均直径が３０μｍ未満であると、通水時の圧力損失が大きくなってしまうため好ましくなく、開口の平均直径が大き過ぎると、流体とモノリスイオン交換体との接触が不十分となり、その結果、イオン交換特性が低下してしまうため好ましくない。   In the case of the first organic porous ion exchanger, the organic porous body is a continuous macropore structure in which bubble-shaped macropores are overlapped with each other, and the overlapping portions form openings (mesopores) having an average diameter of 30 to 150 μm in a wet state. It is. The average diameter of the opening of the composite monolith ion exchanger is larger than the average diameter of the opening of the composite monolith in a dry state because the entire composite monolith swells when an ion exchange group is introduced into the monolith. If the average diameter of the openings is less than 30 μm, the pressure loss at the time of water flow is increased, which is not preferable. If the average diameter of the openings is too large, contact between the fluid and the monolith ion exchanger becomes insufficient. As a result, the ion exchange characteristics deteriorate, which is not preferable.

なお、本発明では、乾燥状態のモノリス中間体の開口の平均直径、乾燥状態の複合モノリスの空孔又は開口の平均直径及び乾燥状態の複合モノリスイオン交換体の空孔又は開口の平均直径は、水銀圧入法により測定される値である。また、本発明では、水湿潤状態の複合モノリスイオン交換体の空孔又は開口の平均直径は、乾燥状態の複合モノリスイオン交換体の空孔又は開口の平均直径に、膨潤率を乗じて算出される値である。具体的には、水湿潤状態の複合モノリスイオン交換体の直径がｘ１（ｍｍ）であり、その水湿潤状態の複合モノリスイオン交換体を乾燥させ、得られる乾燥状態の複合モノリスイオン交換体の直径がｙ１（ｍｍ）であり、この乾燥状態の複合モノリスイオン交換体を水銀圧入法により測定したときの空孔又は開口の平均直径がｚ１（μｍ）であったとすると、水湿潤状態の複合モノリスイオン交換体の空孔又は開口の平均直径（μｍ）は、次式「水湿潤状態の複合モノリスイオン交換体の空孔又は開口の平均直径（μｍ）＝ｚ１×（ｘ１／ｙ１）」で算出される。また、イオン交換基導入前の乾燥状態の複合モノリスの空孔又は開口の平均直径、及びその乾燥状態の複合モノリスにイオン交換基導入したときの乾燥状態の複合モノリスに対する水湿潤状態の複合モノリスイオン交換体の膨潤率がわかる場合は、乾燥状態の複合モノリスの空孔又は開口の平均直径に、膨潤率を乗じて、複合モノリスイオン交換体の空孔の水湿潤状態の平均直径を算出することもできる。   In the present invention, the average diameter of the openings of the dry monolith intermediate, the average diameter of the pores or openings of the dry composite monolith, and the average diameter of the holes or openings of the dry composite monolith ion exchanger are: It is a value measured by the mercury intrusion method. In the present invention, the average diameter of the pores or openings of the composite monolith ion exchanger in the wet state is calculated by multiplying the average diameter of the pores or openings of the composite monolith ion exchanger in the dry state by the swelling rate. Value. Specifically, the diameter of the composite monolith ion exchanger in the water wet state is x1 (mm), the diameter of the composite monolith ion exchanger in the dry state obtained by drying the composite monolith ion exchanger in the water wet state. And y1 (mm), and the average diameter of the pores or openings when the dry monolithic ion exchanger is measured by mercury porosimetry is z1 (μm) The average diameter (μm) of the holes or openings of the exchanger is calculated by the following formula “average diameter of holes or openings (μm) = z1 × (x1 / y1) of the composite monolith ion exchanger in a water-wet state”. The Also, the average diameter of the pores or openings of the dry composite monolith before introduction of the ion exchange group, and the water-wetting composite monolith ion relative to the dry composite monolith when the ion exchange group is introduced into the dry composite monolith When the swelling ratio of the exchanger is known, the average diameter of the pores or openings of the composite monolith in the dry state is multiplied by the swelling ratio to calculate the average diameter of the pores of the composite monolith ion exchanger in the water wet state. You can also.

第２の有機多孔質体イオン交換体の場合、有機多孔質体は、水湿潤状態で平均直径が１〜６０μｍの三次元的に連続した骨格と、その骨格間に平均直径が水湿潤状態で１０〜１００μｍの三次元的に連続した空孔を有する共連続構造である。三次元的に連続した空孔の直径が１０μｍ未満であると、流体透過時の圧力損失が大きくなってしまうため好ましくなく、１００μｍを超えると、脱塩特性の均一性が失われるため好ましくない。   In the case of the second organic porous body ion exchanger, the organic porous body has a three-dimensionally continuous skeleton having an average diameter of 1 to 60 μm in a water-wet state, and an average diameter between the skeletons in a water-wet state. It is a co-continuous structure having three-dimensionally continuous pores of 10 to 100 μm. If the diameter of the three-dimensionally continuous pores is less than 10 μm, the pressure loss at the time of fluid permeation increases, which is not preferable, and if it exceeds 100 μm, the uniformity of the desalting characteristics is lost.

上記共連続構造の空孔の水湿潤状態での平均直径は、公知の水銀圧入法で測定した乾燥状態の複合モノリスイオン交換体の空孔の平均直径に、膨潤率を乗じて算出される値である。具体的には、水湿潤状態の複合モノリスイオン交換体の直径がｘ２（ｍｍ）であり、その水湿潤状態の複合モノリスイオン交換体を乾燥させ、得られる乾燥状態の複合モノリスイオン交換体の直径がｙ２（ｍｍ）であり、この乾燥状態の複合モノリスイオン交換体を水銀圧入法により測定したときの空孔の平均直径がｚ２（μｍ）であったとすると、複合モノリスイオン交換体の空孔の水湿潤状態での平均直径（μｍ）は、次式「複合モノリスイオン交換体の空孔の水湿潤状態の平均直径（μｍ）＝ｚ２×（ｘ２／ｙ２）」で算出される。また、イオン交換基導入前の乾燥状態の複合モノリスの空孔の平均直径、及びその乾燥状態の複合モノリスにイオン交換基導入したときの乾燥状態の複合モノリスに対する水湿潤状態の複合モノリスイオン交換体の膨潤率がわかる場合は、乾燥状態の複合モノリスの空孔の平均直径に、膨潤率を乗じて、複合モノリスイオン交換体の空孔の水湿潤状態の平均直径を算出することもできる。また、上記共連続構造体の骨格の水湿潤状態での平均太さは、乾燥状態の複合モノリスイオン交換体のＳＥＭ観察を少なくとも３回行い、得られた画像中の骨格の太さを測定し、その平均値に、膨潤率を乗じて算出される値である。具体的には、水湿潤状態の複合モノリスイオン交換体の直径がｘ３（ｍｍ）であり、その水湿潤状態の複合モノリスイオン交換体を乾燥させ、得られる乾燥状態の複合モノリスイオン交換体の直径がｙ３（ｍｍ）であり、この乾燥状態の複合モノリスイオン交換体のＳＥＭ観察を少なくとも３回行い、得られた画像中の骨格の太さを測定し、その平均値がｚ３（μｍ）であったとすると、複合モノリスイオン交換体の連続構造体の骨格の水湿潤状態での平均太さ（μｍ）は、次式「複合モノリスイオン交換体の連続構造体の骨格の水湿潤状態の平均太さ（μｍ）＝ｚ３×（ｘ３／ｙ３）」で算出される。また、イオン交換基導入前の乾燥状態の複合モノリスの骨格の平均太さ、及びその乾燥状態の複合モノリスにイオン交換基導入したときの乾燥状態の複合モノリスに対する水湿潤状態の複合モノリスイオン交換体の膨潤率がわかる場合は、乾燥状態の複合モノリスの骨格の平均太さに、膨潤率を乗じて、複合モノリスイオン交換体の骨格の水湿潤状態の平均太さを算出することもできる。なお、共連続構造を形成する骨格は棒状であり円形断面形状であるが、楕円断面形状等異径断面のものが含まれていてもよい。この場合の太さは短径と長径の平均である。   The average diameter of the co-continuous structure pores in the water-wet state is a value calculated by multiplying the average diameter of the pores of the composite monolith ion exchanger in the dry state measured by a known mercury intrusion method and the swelling ratio. It is. Specifically, the diameter of the composite monolith ion exchanger in the water wet state is x2 (mm), the diameter of the composite monolith ion exchanger in the dry state obtained by drying the composite monolith ion exchanger in the water wet state. Is y2 (mm), and the average diameter of the pores when the dried monolithic ion exchanger is measured by mercury porosimetry is z2 (μm), the pores of the composite monolith ion exchanger The average diameter (μm) in the water-wet state is calculated by the following formula: “Average diameter (μm) of the pores of the composite monolith ion exchanger in the water-wet state = z2 × (x2 / y2)”. In addition, the average diameter of the pores of the dry composite monolith before introduction of the ion exchange group, and the water-wet composite monolith ion exchanger with respect to the dry composite monolith when the ion exchange group is introduced into the dry composite monolith Can be calculated by multiplying the average diameter of the pores of the composite monolith in the dry state by the swelling ratio to calculate the average diameter of the pores of the composite monolith ion exchanger in the water-wet state. The average thickness of the skeleton of the co-continuous structure in the wet state is determined by performing SEM observation of the composite monolith ion exchanger in the dry state at least three times and measuring the thickness of the skeleton in the obtained image. The average value is calculated by multiplying the swelling ratio. Specifically, the diameter of the composite monolith ion exchanger in the water wet state is x3 (mm), the diameter of the composite monolith ion exchanger in the dry state obtained by drying the composite monolith ion exchanger in the water wet state. Y3 (mm), SEM observation of this dried composite monolith ion exchanger was performed at least three times, the thickness of the skeleton in the obtained image was measured, and the average value was z3 (μm). The average thickness (μm) of the skeleton of the continuous structure of the composite monolith ion exchanger in the water-wet state is expressed by the following formula: “average thickness of the skeleton of the continuous structure of the composite monolith ion exchanger in the water-wet state” (Μm) = z3 × (x3 / y3) ”. Further, the average thickness of the skeleton of the composite monolith in the dry state before the introduction of the ion exchange group, and the water-wet composite monolith ion exchanger with respect to the dry composite monolith when the ion exchange group is introduced into the dry composite monolith Can be calculated by multiplying the average thickness of the skeleton of the composite monolith in the dry state by the swell ratio to the water-wet state of the skeleton of the composite monolith ion exchanger. The skeleton forming the co-continuous structure is rod-shaped and has a circular cross-sectional shape, but may have a cross-section with different diameters such as an elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.

また、三次元的に連続した骨格の平均直径が１μｍ未満であると、体積当りのイオン交換容量が低下してしまうため好ましくなく、６０μｍを超えると、脱塩特性の均一性が失われるため好ましくない。   Further, if the average diameter of the three-dimensionally continuous skeleton is less than 1 μm, it is not preferable because the ion exchange capacity per volume decreases, and if it exceeds 60 μm, the uniformity of the desalting characteristics is lost. Absent.

複合モノリスイオン交換体の水湿潤状態での孔の平均直径の好ましい値は１０〜１２０μｍである。複合モノリスイオン交換体を構成する有機多孔質体が第１の有機多孔質体の場合、複合モノリスイオン交換体の孔径の好ましい値は３０〜１２０μｍ、複合モノリスイオン交換体を構成する有機多孔質体が第２の有機多孔質体の場合、複合モノリスイオン交換体の孔径の好ましい値は１０〜９０μｍである。   A preferable value of the average diameter of the pores of the composite monolith ion exchanger in a wet state with water is 10 to 120 μm. When the organic porous body constituting the composite monolith ion exchanger is the first organic porous body, the preferred pore diameter of the composite monolith ion exchanger is 30 to 120 μm, and the organic porous body constituting the composite monolith ion exchanger In the case of the second organic porous body, a preferable value of the pore diameter of the composite monolith ion exchanger is 10 to 90 μm.

本発明に係る複合モノリスイオン交換体において、水湿潤状態での粒子体の直径及び突起体の大きさは、４〜４０μｍ、好ましくは４〜３０μｍ、特に好ましくは４〜２０μｍである。なお、本発明において、粒子体及び突起体は、共に骨格表面に突起状に観察されるものであり、粒状に観察されるものを粒子体と称し、粒状とは言えない突起状のものを突起体と称する。図２３に、突起体の模式的な断面図を示す。図２３中の（Ａ）〜（Ｅ）に示すように、骨格表面６１から突き出している突起状のものが突起体６２であり、突起体６２には、（Ａ）に示す突起体６２ａのように粒状に近い形状のもの、（Ｂ）に示す突起体６２ｂのように半球状のもの、（Ｃ）に示す突起体６２ｃのように骨格表面の盛り上がりのようなもの等が挙げられる。また、他には、突起体６１には、（Ｄ）に示す突起体６２ｄのように、骨格表面６１の平面方向よりも、骨格表面６１に対して垂直方向の方が長い形状のものや、（Ｅ）に示す突起体６２ｅのように、複数の方向に突起した形状のものもある。また、突起体の大きさは、ＳＥＭ観察したときのＳＥＭ画像で判断され、個々の突起体のＳＥＭ画像での幅が最も大きくなる部分の長さを指す。   In the composite monolith ion exchanger according to the present invention, the diameter of the particles and the size of the protrusions in a wet state are 4 to 40 μm, preferably 4 to 30 μm, and particularly preferably 4 to 20 μm. In the present invention, both the particles and the protrusions are observed as protrusions on the surface of the skeleton, and the particles observed are referred to as particles, and the protrusions that are not granular are protrusions. Called the body. FIG. 23 shows a schematic cross-sectional view of the protrusion. As shown to (A)-(E) in FIG. 23, the protrusion-shaped thing protruded from the skeleton surface 61 is the protrusion 62, and the protrusion 62 is like the protrusion 62a shown to (A). The shape close to a granular shape, a hemispherical shape like a projection 62b shown in (B), and a swell of the skeleton surface like a projection 62c shown in (C). In addition, the protrusion 61 has a shape that is longer in the direction perpendicular to the skeleton surface 61 than in the plane direction of the skeleton surface 61, like the protrusion 62d shown in FIG. There is a thing of the shape which protruded in the several direction like the protrusion 62e shown to (E). Further, the size of the protrusions is determined by the SEM image when observed by SEM, and indicates the length of the portion where the width of each protrusion is the largest in the SEM image.

本発明に係る複合モノリスイオン交換体において、全粒子体等中、水湿潤状態で４〜４０μｍの粒子体等が占める割合は７０％以上、好ましくは８０％以上である。なお、全粒子体等中の水湿潤状態で４〜４０μｍの粒子体等が占める割合は、全粒子体等の個数に占める水湿潤状態で４〜４０μｍの粒子体等の個数割合を指す。また、骨格相の表面は全粒子体等により４０％以上、好ましくは５０％以上被覆されている。なお、粒子体等による骨格層の表面の被覆割合は、ＳＥＭにより表面観察にしたときのＳＥＭ画像上の面積割合、つまり、表面を平面視したときの面積割合を指す。壁面や骨格を被覆している粒子の大きさが上記範囲を逸脱すると、流体と複合モノリスイオン交換体の骨格表面及び骨格内部との接触効率を改善する効果が小さくなってしまうため好ましくない。なお、全粒子体等とは、水湿潤状態で４〜４０μｍの粒子体等以外の大きさの範囲の粒子体及び突起体も全て含めた、骨格層の表面に形成されている全ての粒子体及び突起体を指す。   In the composite monolith ion exchanger according to the present invention, the proportion of 4 to 40 μm particles in a wet state in water is 70% or more, preferably 80% or more. In addition, the ratio which 4-40 micrometers particle bodies etc. occupy in the water wet state in all the particle bodies etc. points out the number ratio of 4-40 micrometers particle bodies etc. in the water wet state which occupy the number of all particle bodies. Further, the surface of the skeletal phase is covered by 40% or more, preferably 50% or more by the whole particles. The coverage ratio of the surface of the skeleton layer with particles or the like refers to the area ratio on the SEM image when the surface is observed by SEM, that is, the area ratio when the surface is viewed in plan. If the size of the particle covering the wall surface or the skeleton deviates from the above range, the effect of improving the contact efficiency between the fluid and the skeleton surface of the composite monolith ion exchanger and the inside of the skeleton is not preferable. In addition, all the particulate bodies etc. are all the particulate bodies formed on the surface of the skeleton layer including all the particulate bodies and protrusions in the size range other than the 4-40 μm particulate bodies in the wet state. And a protrusion.

上記複合モノリスイオン交換体の骨格表面に付着した粒子体等の水湿潤状態での直径又は大きさは、乾燥状態の複合モノリスイオン交換体のＳＥＭ画像の観察により得られる粒子体等の直径又は大きさに、乾燥状態から湿潤状態となった際の膨潤率を乗じて算出した値、又はイオン交換基導入前の乾燥状態の複合モノリスのＳＥＭ画像の観察により得られる粒子体等の直径又は大きさに、イオン交換基導入前後の膨潤率を乗じて算出した値である。具体的には、水湿潤状態の複合モノリスイオン交換体の直径がｘ４（ｍｍ）であり、その水湿潤状態の複合モノリスイオン交換体を乾燥させ、得られる乾燥状態の複合モノリスイオン交換体の直径がｙ４（ｍｍ）であり、この乾燥状態の複合モノリスイオン交換体をＳＥＭ観察したときのＳＥＭ画像中の粒子体等の直径又は大きさがｚ４（μｍ）であったとすると、水湿潤状態の複合モノリスイオン交換体の粒子体等の直径又は大きさ（μｍ）は、次式「水湿潤状態の複合モノリスイオン交換体の粒子体等の直径又は大きさ（μｍ）＝ｚ４×（ｘ４／ｙ４）」で算出される。そして、乾燥状態の複合モノリスイオン交換体のＳＥＭ画像中に観察される全ての粒子体等の直径又は大きさを測定して、その値を基に、１視野のＳＥＭ画像中の全粒子体等の水湿潤状態での直径又は大きさを算出する。この乾燥状態の複合モノリスイオン交換体のＳＥＭ観察を少なくとも３回行い、全視野において、ＳＥＭ画像中の全粒子体等の水湿潤状態での直径又は大きさを算出して、直径又は大きさが４〜４０μｍにある粒子体等が観察されるか否かを確認し、全視野において確認された場合、複合モノリスイオン交換体の骨格表面上に、直径又は大きさが水湿潤状態で４〜４０μｍにある粒子体が形成されていると判断する。また、上記に従って１視野毎にＳＥＭ画像中の全粒子体等の水湿潤状態での直径又は大きさを算出し、各視野毎に、全粒子体等に占める水湿潤状態で４〜４０μｍの粒子体等の割合を求め、全視野において、全粒子体等中の水湿潤状態で４〜４０μｍの粒子体等が占める割合が７０％以上であった場合には、複合モノリスイオン交換体の骨格表面に形成されている全粒子体等中、水湿潤状態で４〜４０μｍの粒子体等が占める割合は７０％以上であると判断する。また、上記に従って１視野毎にＳＥＭ画像中の全粒子体等による骨格層の表面の被覆割合を求め、全視野において、全粒子体等による骨格層の表面の被覆割合が４０％以上であった場合には、複合モノリスイオン交換体の骨格層の表面が全粒子体等により被覆されている割合が４０％以上であると判断する。また、イオン交換基導入前の乾燥状態の複合モノリスの粒子体等の直径又は大きさと、その乾燥状態のモノリスにイオン交換基導入したときの乾燥状態の複合モノリスに対する水湿潤状態の複合モノリスイオン交換体の膨潤率とがわかる場合は、乾燥状態の複合モノリスの粒子体等の直径又は大きさに、膨潤率を乗じて、水湿潤状態の複合モノリスイオン交換体の粒子体等の直径又は大きさを算出して、上記と同様にして、水湿潤状態の複合モノリスイオン交換体の粒子体等の直径又は大きさ、全粒子体等中、水湿潤状態で４〜４０μｍの粒子体等が占める割合、粒子体等による骨格層の表面の被覆割合を求めることもできる。   The diameter or size of the particles attached to the surface of the skeleton of the composite monolith ion exchanger in the water-wet state is the diameter or size of the particles obtained by observing the SEM image of the composite monolith ion exchanger in the dry state. Further, the value calculated by multiplying the swelling rate when the dry state is changed to the wet state, or the diameter or size of the particulates obtained by observing the SEM image of the composite monolith in the dry state before introducing the ion exchange group And a value calculated by multiplying the swelling ratio before and after introduction of the ion exchange group. Specifically, the diameter of the composite monolith ion exchanger in the water wet state is x4 (mm), the diameter of the composite monolith ion exchanger in the dry state obtained by drying the composite monolith ion exchanger in the water wet state. Is y4 (mm), and the diameter or size of the particles in the SEM image of the dried composite monolith ion exchanger observed by SEM is z4 (μm). The diameter or size (μm) of the particles of the monolith ion exchanger is expressed by the following formula: “diameter or size (μm) of the particles of the composite monolith ion exchanger in a water-wet state” = z4 × (x4 / y4) Is calculated. Then, the diameter or size of all particles observed in the SEM image of the composite monolith ion exchanger in the dry state is measured, and based on the value, all particles in one field of view SEM image, etc. The diameter or size of the water in a wet state is calculated. The SEM observation of the dried composite monolith ion exchanger is performed at least three times, and the diameter or size of the whole particle in the SEM image in the water-wet state is calculated in all fields of view. It is confirmed whether or not a particle body or the like at 4 to 40 μm is observed, and when it is confirmed in the entire visual field, the diameter or size is 4 to 40 μm in a wet state on the skeleton surface of the composite monolith ion exchanger. It is determined that the particle body at is formed. Further, according to the above, the diameter or size in the water wet state of all particles in the SEM image is calculated for each visual field, and the particle size of 4 to 40 μm in the water wet state occupying in the whole particles for each visual field. When the proportion of the particles, etc. is 40% or more in the wet state in all the particles in the entire visual field, the skeleton surface of the composite monolith ion exchanger is obtained. It is determined that the proportion of 4 to 40 μm particles in the wet state is 70% or more in all particles formed in the above. Further, according to the above, the coverage ratio of the surface of the skeletal layer with all particles in the SEM image was determined for each field of view, and the coverage ratio of the surface of the skeleton layer with all particles in all fields was 40% or more. In this case, it is determined that the ratio of the surface of the skeleton layer of the composite monolith ion exchanger covered with all the particulates is 40% or more. In addition, the diameter or size of the particles of the composite monolith in the dry state before the introduction of the ion exchange group and the composite monolith ion exchange in the wet state with respect to the dry composite monolith when the ion exchange group is introduced into the monolith in the dry state If the swelling rate of the body is known, the diameter or size of the particles of the composite monolith in the dry state is multiplied by the swelling rate to obtain the diameter or size of the particles of the composite monolith ion exchanger in the water wet state. In the same manner as described above, the diameter or size of the particles of the composite monolith ion exchanger in the water wet state, the ratio of the particles of 4 to 40 μm in the water wet state, etc. in the total particles, etc. In addition, the coverage ratio of the surface of the skeleton layer with particle bodies or the like can be obtained.

粒子体等による骨格相表面の被覆率が４０％未満であると、流体と複合モノリスイオン交換体の骨格内部及び骨格表面との接触効率を改善する効果が小さくなり、脱塩挙動の均一性が損なわれてしまうため好ましくない。上記粒子体等による被覆率の測定方法としては、モノリス（乾燥体）のＳＥＭ画像による画像解析方法が挙げられる。   If the coverage of the skeletal phase surface with particles and the like is less than 40%, the effect of improving the contact efficiency between the fluid and the inside of the skeleton of the composite monolith ion exchanger and the skeleton surface is reduced, and the desalting behavior is uniform. Since it will be damaged, it is not preferable. Examples of the method for measuring the coverage with the particulates include an image analysis method using a monolith (dry body) SEM image.

また、複合モノリスイオン交換体の全細孔容積は、複合モノリスの全細孔容積と同様である。すなわち、複合モノリスにイオン交換基を導入することで膨潤し開口径が大きくなっても、骨格相が太るため全細孔容積はほとんど変化しない。全細孔容積が０．５ｍｌ／ｇ未満であると、流体透過時の圧力損失が大きくなってしまうため好ましくなく、更に、単位断面積当りの透過流体量が小さくなり、処理能力が低下してしまうため好ましくない。一方、全細孔容積が５ｍｌ／ｇを超えると、体積当りのイオン交換容量が低下してしまうため好ましくない。なお、複合モノリス（モノリス中間体、複合モノリス、複合モノリスイオン交換体）の全細孔容積は、乾燥状態でも、水湿潤状態でも、同じである。   The total pore volume of the composite monolith ion exchanger is the same as the total pore volume of the composite monolith. That is, even when the ion exchange group is introduced into the composite monolith to swell and increase the opening diameter, the total pore volume hardly changes because the skeletal phase is thick. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of fluid permeation increases, which is not preferable. Further, the amount of permeated fluid per unit cross-sectional area decreases, and the processing capacity decreases. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the ion exchange capacity per volume decreases, which is not preferable. Note that the total pore volume of the composite monolith (monolith intermediate, composite monolith, composite monolith ion exchanger) is the same both in the dry state and in the water wet state.

なお、複合モノリスイオン交換体に水を透過させた際の圧力損失は、複合モノリスに水を透過させた際の圧力損失と同様である。   Note that the pressure loss when water is permeated through the composite monolith ion exchanger is the same as the pressure loss when water is permeated through the composite monolith.

本発明の複合モノリスイオン交換体は、水湿潤状態での体積当りのイオン交換容量が０．２ｍｇ当量/ｍｌ以上、好ましくは０．３〜１．８ｍｇ当量／ｍｌのイオン交換容量を有する。体積当りのイオン交換容量が０．２ｍｇ当量／ｍｌ未満であると、脱塩効率が低下してしまうため好ましくない。なお、本発明の複合モノリスイオン交換体の乾燥状態における重量当りのイオン交換容量は特に限定されないが、イオン交換基が複合モノリスの骨格表面及び骨格内部にまで均一に導入しているため、３〜５ｍｇ当量/ｇである。なお、イオン交換基が骨格の表面のみに導入された有機多孔質体のイオン交換容量は、有機多孔質体やイオン交換基の種類により一概には決定できないものの、せいぜい５００μｇ当量/ｇである。   The composite monolith ion exchanger of the present invention has an ion exchange capacity per volume in a water-wet state of 0.2 mg equivalent / ml or more, preferably 0.3 to 1.8 mg equivalent / ml. If the ion exchange capacity per volume is less than 0.2 mg equivalent / ml, the desalting efficiency is lowered, which is not preferable. In addition, the ion exchange capacity per weight in the dry state of the composite monolith ion exchanger of the present invention is not particularly limited, but since the ion exchange groups are uniformly introduced to the skeleton surface and the skeleton inside the composite monolith, 5 mg equivalent / g. The ion exchange capacity of the organic porous material in which the ion exchange group is introduced only on the surface of the skeleton cannot be determined depending on the kind of the organic porous material or the ion exchange group, but is 500 μg equivalent / g at most.

本発明の複合モノリスに導入するイオン交換基としては、スルホン酸基、カルボン酸基、イミノ二酢酸基、リン酸基、リン酸エステル基等のカチオン交換基；四級アンモニウム基、三級アミノ基、二級アミノ基、一級アミノ基、ポリエチレンイミン基、第三スルホニウム基、ホスホニウム基等のアニオン交換基が挙げられる。イオン交換基がカチオン交換体であれば、半導体デバイスに特に悪影響を及ぼす金属類を効果的に除去することができる。   Examples of the ion exchange group to be introduced into the composite monolith of the present invention include cation exchange groups such as a sulfonic acid group, a carboxylic acid group, an iminodiacetic acid group, a phosphoric acid group, and a phosphoric acid ester group; a quaternary ammonium group and a tertiary amino group. And anion exchange groups such as secondary amino group, primary amino group, polyethyleneimine group, tertiary sulfonium group, and phosphonium group. If the ion exchange group is a cation exchanger, it is possible to effectively remove metals that adversely affect the semiconductor device.

本発明の複合モノリスイオン交換体において、導入されたイオン交換基は、複合モノリスの骨格の表面のみならず、骨格相内部にまで均一に分布している。ここで言う「イオン交換基が均一に分布している」とは、イオン交換基の分布が少なくともμｍオーダーで骨格相の表面および骨格相の内部に均一に分布していることを指す。イオン交換基の分布状況は、ＥＰＭＡ等を用いることで、比較的簡単に確認することができる。また、イオン交換基が、複合モノリスの表面のみならず、骨格相の内部にまで均一に分布していると、表面と内部の物理的性質及び化学的性質を均一にできるため、膨潤及び収縮に対する耐久性が向上する。   In the composite monolith ion exchanger of the present invention, the introduced ion exchange groups are uniformly distributed not only on the surface of the skeleton of the composite monolith but also inside the skeleton phase. Here, “the ion exchange groups are uniformly distributed” means that the distribution of the ion exchange groups is uniformly distributed at least on the order of μm on the surface of the skeleton phase and inside the skeleton phase. The distribution of ion exchange groups can be confirmed relatively easily by using EPMA or the like. In addition, when the ion exchange groups are uniformly distributed not only on the surface of the composite monolith but also inside the skeleton phase, the physical and chemical properties of the surface and the interior can be made uniform, so that the swelling and shrinkage can be prevented. Durability is improved.

本発明の複合モノリスイオン交換体は、その厚みが１ｍｍ以上であり、膜状の多孔質体とは区別される。厚みが１ｍｍ未満であると、多孔質体一枚当りのイオン交換容量が極端に低下してしまうため好ましくない。該複合モノリスイオン交換体の厚みは、好適には３ｍｍ〜１０００ｍｍである。また、本発明の複合モノリスイオン交換体は、骨格の基本構造が連続空孔構造であるため、機械的強度が高い。   The composite monolith ion exchanger of the present invention has a thickness of 1 mm or more, and is distinguished from a membrane-like porous body. When the thickness is less than 1 mm, the ion exchange capacity per porous body is extremely reduced, which is not preferable. The thickness of the composite monolith ion exchanger is preferably 3 mm to 1000 mm. In addition, the composite monolith ion exchanger of the present invention has high mechanical strength because the basic structure of the skeleton is a continuous pore structure.

本発明の複合モノリスイオン交換体は、イオン交換基を含まない油溶性モノマー、一分子中に少なくとも２個以上のビニル基を有する第１架橋剤、界面活性剤及び水の混合物を撹拌することにより油中水滴型エマルジョンを調製し、次いで油中水滴型エマルジョンを重合させて全細孔容積が５〜３０ｍｌ/ｇの連続マクロポア構造のモノリス状の有機多孔質中間体を得るＩ工程、ビニルモノマー、一分子中に少なくとも２個以上のビニル基を有する第２架橋剤、ビニルモノマーや第２架橋剤は溶解するがビニルモノマーが重合して生成するポリマーは溶解しない有機溶媒及び重合開始剤からなる混合物を調製するＩＩ工程、ＩＩ工程で得られた混合物を静置下、且つ該Ｉ工程で得られたモノリス状の有機多孔質中間体の存在下で重合を行うＩＩＩ工程、ＩＩＩ工程で得られたモノリス状有機多孔質体にイオン交換基を導入するＩＶ工程、を行い、モノリス状有機多孔質体を製造する際に、下記（１）〜（５）：
（１）ＩＩＩ工程における重合温度が、重合開始剤の１０時間半減温度より、少なくとも５℃低い温度である；
（２）ＩＩ工程で用いる第２架橋剤のモル％が、Ｉ工程で用いる第１架橋剤のモル％の２倍以上である；
（３）ＩＩ工程で用いるビニルモノマーが、Ｉ工程で用いた油溶性モノマーとは異なる構造のビニルモノマーである；
（４）ＩＩ工程で用いる有機溶媒が、分子量２００以上のポリエーテルである；
（５）ＩＩ工程で用いるビニルモノマーの濃度が、ＩＩ工程の混合物中、３０重量％以下である；の条件のうち、少なくとも一つを満たす条件下でＩＩ工程又はＩＩＩ工程を行うことにより得られる。 The composite monolith ion exchanger of the present invention is obtained by stirring a mixture of an oil-soluble monomer containing no ion exchange group, a first crosslinking agent having at least two or more vinyl groups in one molecule, a surfactant and water. Preparing a water-in-oil emulsion and then polymerizing the water-in-oil emulsion to obtain a monolithic organic porous intermediate having a continuous macropore structure with a total pore volume of 5 to 30 ml / g, vinyl monomer, A mixture comprising a second crosslinking agent having at least two vinyl groups in one molecule, an organic solvent that dissolves the vinyl monomer or the second crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, and a polymerization initiator. Step II for preparing the compound II. The mixture obtained in Step II is allowed to stand, and polymerization is performed in the presence of the monolithic organic porous intermediate obtained in Step I II When the monolithic organic porous material is produced by performing the IV step of introducing an ion exchange group into the monolithic organic porous material obtained in the steps I and III, the following (1) to (5):
(1) The polymerization temperature in step III is at least 5 ° C. lower than the 10-hour half-life temperature of the polymerization initiator;
(2) The mol% of the second cross-linking agent used in step II is at least twice the mol% of the first cross-linking agent used in step I;
(3) The vinyl monomer used in Step II is a vinyl monomer having a structure different from that of the oil-soluble monomer used in Step I;
(4) The organic solvent used in step II is a polyether having a molecular weight of 200 or more;
(5) The concentration of the vinyl monomer used in Step II is 30% by weight or less in the mixture of Step II; obtained by performing Step II or Step III under conditions that satisfy at least one of the conditions .

（モノリス中間体の製造方法）
本発明のモノリスの製造方法において、Ｉ工程は、イオン交換基を含まない油溶性モノマー、一分子中に少なくとも２個以上のビニル基を有する第１架橋剤、界面活性剤及び水の混合物を撹拌することにより油中水滴型エマルジョンを調製し、次いで油中水滴型エマルジョンを重合させて全細孔容積が５〜３０ｍｌ/ｇの連続マクロポア構造のモノリス中間体を得る工程である。このモノリス中間体を得るＩ工程は、特開２００２−３０６９７６号公報記載の方法に準拠して行なえばよい。 (Method for producing monolith intermediate)
In the method for producing a monolith according to the present invention, in the step I, an oil-soluble monomer not containing an ion exchange group, a first crosslinking agent having at least two or more vinyl groups in one molecule, a mixture of a surfactant and water are stirred. In this step, a water-in-oil emulsion is prepared, and then the water-in-oil emulsion is polymerized to obtain a monolith intermediate having a continuous macropore structure having a total pore volume of 5 to 30 ml / g. The step I for obtaining the monolith intermediate may be performed according to the method described in JP-A-2002-306976.

イオン交換基を含まない油溶性モノマーとしては、例えば、カルボン酸基、スルホン酸基、四級アンモニウム基等のイオン交換基を含まず、水に対する溶解性が低く、親油性のモノマーが挙げられる。これらモノマーの好適なものとしては、スチレン、α−メチルスチレン、ビニルトルエン、ビニルベンジルクロライド、ジビニルベンゼン、エチレン、プロピレン、イソブテン、ブタジエン、エチレングリコールジメタクリレート等が挙げられる。これらモノマーは、１種単独又は２種以上を組み合わせて使用することができる。   Examples of the oil-soluble monomer that does not contain an ion exchange group include an oleophilic monomer that does not contain an ion exchange group such as a carboxylic acid group, a sulfonic acid group, and a quaternary ammonium group, has low solubility in water. Preferable examples of these monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene, ethylene, propylene, isobutene, butadiene, ethylene glycol dimethacrylate, and the like. These monomers can be used alone or in combination of two or more.

一分子中に少なくとも２個以上のビニル基を有する第１架橋剤としては、ジビニルベンゼン、ジビニルナフタレン、ジビニルビフェニル、エチレングリコールジメタクリレート等が挙げられる。これら架橋剤は、１種単独又は２種以上を組み合わせて使用することができる。好ましい第１架橋剤は、機械的強度の高さから、ジビニルベンゼン、ジビニルナフタレン、ジビニルビフェニル等の芳香族ポリビニル化合物である。第１架橋剤の使用量は、ビニルモノマーと第１架橋剤の合計量に対して０．３〜１０モル％、特に０．３〜５モル％、更に０．３〜３モル％であることが好ましい。第１架橋剤の使用量が０．３モル％未満であると、モノリスの機械的強度が不足するため好ましくない。一方、１０モル％を越えると、モノリスの脆化が進行して柔軟性が失われる、イオン交換基の導入量が減少してしまうといった問題点が生じるため好ましくない。   Examples of the first crosslinking agent having at least two or more vinyl groups in one molecule include divinylbenzene, divinylnaphthalene, divinylbiphenyl, and ethylene glycol dimethacrylate. These crosslinking agents can be used singly or in combination of two or more. A preferred first cross-linking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl because of its high mechanical strength. The amount of the first crosslinking agent used is 0.3 to 10 mol%, particularly 0.3 to 5 mol%, and more preferably 0.3 to 3 mol%, based on the total amount of the vinyl monomer and the first crosslinking agent. Is preferred. If the amount of the first crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, if it exceeds 10 mol%, the monolith becomes more brittle and the flexibility is lost, and the amount of ion exchange groups introduced decreases, which is not preferable.

界面活性剤は、イオン交換基を含まない油溶性モノマーと水とを混合した際に、油中水滴型（Ｗ／Ｏ）エマルジョンを形成できるものであれば特に制限はなく、ソルビタンモノオレエート、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタントリオレエート、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンソルビタンモノオレエート等の非イオン界面活性剤；オレイン酸カリウム、ドデシルベンゼンスルホン酸ナトリウム、スルホコハク酸ジオクチルナトリウム等の陰イオン界面活性剤；ジステアリルジメチルアンモニウムクロライド等の陽イオン界面活性剤；ラウリルジメチルベタイン等の両性界面活性剤を用いることができる。これら界面活性剤は１種単独又は２種類以上を組み合わせて使用することができる。なお、油中水滴型エマルジョンとは、油相が連続相となり、その中に水滴が分散しているエマルジョンを言う。上記界面活性剤の添加量としては、油溶性モノマーの種類および目的とするエマルジョン粒子（マクロポア）の大きさによって大幅に変動するため一概には言えないが、油溶性モノマーと界面活性剤の合計量に対して約２〜７０％の範囲で選択することができる。   The surfactant is not particularly limited as long as it can form a water-in-oil (W / O) emulsion when an oil-soluble monomer containing no ion exchange group and water are mixed, and sorbitan monooleate, Nonionic surfactants such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether, polyoxyethylene sorbitan monooleate; potassium oleate Anionic surfactants such as sodium dodecylbenzenesulfonate and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyldimethylammonium chloride; amphoteric surfactants such as lauryldimethylbetaine can be used . These surfactants can be used alone or in combination of two or more. The water-in-oil emulsion refers to an emulsion in which an oil phase is a continuous phase and water droplets are dispersed therein. The amount of the surfactant added may vary depending on the type of oil-soluble monomer and the size of the target emulsion particles (macropores), but it cannot be generally stated, but the total amount of oil-soluble monomer and surfactant Can be selected within a range of about 2 to 70%.

また、Ｉ工程では、油中水滴型エマルジョン形成の際、必要に応じて重合開始剤を使用してもよい。重合開始剤は、熱及び光照射によりラジカルを発生する化合物が好適に用いられる。重合開始剤は水溶性であっても油溶性であってもよく、例えば、２，２’-アゾビス（イソブチロニトリル）、２，２’-アゾビス（２，４-ジメチルバレロニトリル）、２，２’-アゾビス（２−メチルブチロニトリル）、２，２’-アゾビス（４-メトキシ-２，４-ジメチルバレロニトリル）、２，２’-アゾビスイソ酪酸ジメチル、４，４’-アゾビス（４-シアノ吉草酸）、１，１’-アゾビス（シクロヘキサン-1-カルボニトリル）、過酸化ベンゾイル、過酸化ラウロイル、過硫酸カリウム、過硫酸アンモニウム、過酸化水素−塩化第一鉄、過硫酸ナトリウム−酸性亜硫酸ナトリウム等が挙げられる。   In Step I, a polymerization initiator may be used as necessary when forming a water-in-oil emulsion. As the polymerization initiator, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator may be water-soluble or oil-soluble. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2 , 2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis ( 4-Cyanovaleric acid), 1,1'-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate- Examples include acidic sodium sulfite.

イオン交換基を含まない油溶性モノマー、第１架橋剤、界面活性剤、水及び重合開始剤とを混合し、油中水滴型エマルジョンを形成させる際の混合方法としては、特に制限はなく、各成分を一括して一度に混合する方法、油溶性モノマー、第１架橋剤、界面活性剤及び油溶性重合開始剤である油溶性成分と、水や水溶性重合開始剤である水溶性成分とを別々に均一溶解させた後、それぞれの成分を混合する方法などが使用できる。エマルジョンを形成させるための混合装置についても特に制限はなく、通常のミキサーやホモジナイザー、高圧ホモジナイザー等を用いることができ、目的のエマルジョン粒径を得るのに適切な装置を選択すればよい。また、混合条件についても特に制限はなく、目的のエマルジョン粒径を得ることができる攪拌回転数や攪拌時間を、任意に設定することができる。   There is no particular limitation on the mixing method when mixing the oil-soluble monomer containing no ion exchange group, the first cross-linking agent, the surfactant, water and the polymerization initiator to form a water-in-oil emulsion, A method of mixing components all at once, an oil-soluble monomer, a first crosslinking agent, a surfactant, an oil-soluble component that is an oil-soluble polymerization initiator, and a water-soluble component that is water or a water-soluble polymerization initiator For example, a method in which each component is mixed after being uniformly dissolved separately can be used. There is no particular limitation on the mixing apparatus for forming the emulsion, and a normal mixer, homogenizer, high-pressure homogenizer, or the like can be used, and an appropriate apparatus may be selected to obtain the desired emulsion particle size. Moreover, there is no restriction | limiting in particular about mixing conditions, The stirring rotation speed and stirring time which can obtain the target emulsion particle size can be set arbitrarily.

Ｉ工程で得られるモノリス中間体は、連続マクロポア構造を有する。これを重合系に共存させると、そのモノリス中間体の構造を鋳型として連続マクロポア構造の骨格相の表面に粒子体等が形成したり、共連続構造の骨格相の表面に粒子体等が形成したりする。また、モノリス中間体は、架橋構造を有する有機ポリマー材料である。該ポリマー材料の架橋密度は特に限定されないが、ポリマー材料を構成する全構成単位に対して、０．３〜１０モル％、好ましくは０．３〜５モル％の架橋構造単位を含んでいることが好ましい。架橋構造単位が０．３モル％未満であると、機械的強度が不足するため好ましくない。一方、１０モル％を越えると、多孔質体の脆化が進行し、柔軟性が失われるため好ましくない。   The monolith intermediate obtained in Step I has a continuous macropore structure. When this coexists in the polymerization system, particles or the like are formed on the surface of the skeleton phase of the continuous macropore structure using the structure of the monolith intermediate as a template, or particles or the like are formed on the surface of the skeleton phase of the co-continuous structure. Or The monolith intermediate is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 10 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all the structural units constituting the polymer material. Is preferred. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 10 mol%, the porous body becomes brittle and the flexibility is lost, which is not preferable.

モノリス中間体の全細孔容積は、５〜３０ｍｌ／ｇ、好適には６〜２８ｍｌ／ｇである。全細孔容積が小さ過ぎると、ビニルモノマーを重合させた後で得られるモノリスの全細孔容積が小さくなりすぎ、流体透過時の圧力損失が大きくなるため好ましくない。一方、全細孔容積が大き過ぎると、ビニルモノマーを重合させた後で得られるモノリスの構造が不均一になりやすく、場合によっては構造崩壊を引き起こすため好ましくない。モノリス中間体の全細孔容積を上記数値範囲とするには、モノマーと水の比（重量）を、概ね１：５〜１：３５とすればよい。   The total pore volume of the monolith intermediate is 5-30 ml / g, preferably 6-28 ml / g. If the total pore volume is too small, the total pore volume of the monolith obtained after polymerizing the vinyl monomer becomes too small, and the pressure loss during fluid permeation increases, which is not preferable. On the other hand, if the total pore volume is too large, the structure of the monolith obtained after polymerizing the vinyl monomer tends to be non-uniform, and in some cases, the structure collapses, which is not preferable. In order to set the total pore volume of the monolith intermediate in the above numerical range, the ratio (weight) of the monomer to water may be set to approximately 1: 5 to 1:35.

このモノマーと水との比を、概ね１：５〜１：２０とすれば、モノリス中間体の全細孔容積が５〜１６ｍｌ/ｇの連続マクロポア構造のものが得られ、ＩＩＩ工程を経て得られる複合モノリスの有機多孔質体が第１の有機多孔質体のものが得られる。また、該配合比率を、概ね１：２０〜１：３５とすれば、モノリス中間体の全細孔容積が１６ｍｌ/ｇを超え、３０ｍｌ/ｇ以下の連続マクロポア構造のものが得られ、ＩＩＩ工程を経て得られる複合モノリスの有機多孔質体が第２の有機多孔質体のものが得られる。   When the ratio of this monomer to water is approximately 1: 5 to 1:20, a monolith intermediate having a total pore volume of 5 to 16 ml / g and a continuous macropore structure can be obtained and obtained through Step III. The obtained composite monolithic organic porous body is the first organic porous body. Further, if the blending ratio is approximately 1:20 to 1:35, a monolith intermediate having a total pore volume of more than 16 ml / g and a continuous macropore structure of 30 ml / g or less can be obtained. The organic porous body of the composite monolith obtained through the above is obtained as the second organic porous body.

また、モノリス中間体は、マクロポアとマクロポアの重なり部分である開口（メソポア）の平均直径が乾燥状態で２０〜１００μｍである。開口の平均直径が２０μｍ未満であると、ビニルモノマーを重合させた後で得られるモノリスの開口径が小さくなり、通水過時の圧力損失が大きくなってしまうため好ましくない。一方、１００μｍを超えると、ビニルモノマーを重合させた後で得られるモノリスの開口径が大きくなりすぎ、被処理水とモノリスイオン交換体との接触が不十分となり、その結果、イオン成分の除去効率が低下してしまうため好ましくない。モノリス中間体は、マクロポアの大きさや開口の径が揃った均一構造のものが好適であるが、これに限定されず、均一構造中、均一なマクロポアの大きさよりも大きな不均一なマクロポアが点在するものであってもよい。   Moreover, the average diameter of the opening (mesopore) which is an overlap part of a macropore and a macropore is 20-100 micrometers in a dry state in a monolith intermediate. When the average diameter of the openings is less than 20 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss at the time of passing water becomes large, which is not preferable. On the other hand, if it exceeds 100 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, and the contact between the water to be treated and the monolith ion exchanger becomes insufficient. As a result, the removal efficiency of ion components Is unfavorable because it decreases. Monolith intermediates preferably have a uniform structure with uniform macropore size and aperture diameter, but are not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do.

（複合モノリスの製造方法）
ＩＩ工程は、ビニルモノマー、一分子中に少なくとも２個以上のビニル基を有する第２架橋剤、ビニルモノマーや第２架橋剤は溶解するがビニルモノマーが重合して生成するポリマーは溶解しない有機溶媒及び重合開始剤からなる混合物を調製する工程である。なお、Ｉ工程とＩＩ工程の順序はなく、Ｉ工程後にＩＩ工程を行ってもよく、ＩＩ工程後にＩ工程を行ってもよい。 (Production method of composite monolith)
Step II is an organic solvent in which a vinyl monomer, a second cross-linking agent having at least two vinyl groups in one molecule, a vinyl monomer or a second cross-linking agent dissolves, but a polymer formed by polymerization of the vinyl monomer does not dissolve. And a step of preparing a mixture comprising a polymerization initiator. In addition, there is no order of I process and II process, II process may be performed after I process, and I process may be performed after II process.

ＩＩ工程で用いられるビニルモノマーとしては、分子中に重合可能なビニル基を含有し、有機溶媒に対する溶解性が高い親油性のビニルモノマーであれば、特に制限はない。これらビニルモノマーの具体例としては、スチレン、α-メチルスチレン、ビニルトルエン、ビニルベンジルクロライド、ビニルビフェニル、ビニルナフタレン等の芳香族ビニルモノマー；エチレン、プロピレン、１-ブテン、イソブテン等のα-オレフィン；ブタジエン、イソプレン、クロロプレン等のジエン系モノマー；塩化ビニル、臭化ビニル、塩化ビニリデン、テトラフルオロエチレン等のハロゲン化オレフィン；アクリロニトリル、メタクリロニトリル等のニトリル系モノマー；酢酸ビニル、プロピオン酸ビニル等のビニルエステル；アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２-エチルヘキシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸２−エチルヘキシル、メタクリル酸シクロヘキシル、メタクリル酸ベンジル、メタクリル酸グリシジル等の（メタ）アクリル系モノマーが挙げられる。これらモノマーは、１種単独又は２種以上を組み合わせて使用することができる。本発明で好適に用いられるビニルモノマーは、スチレン、ビニルベンジルクロライド等の芳香族ビニルモノマーである。   The vinyl monomer used in step II is not particularly limited as long as it is a lipophilic vinyl monomer that contains a polymerizable vinyl group in the molecule and has high solubility in an organic solvent. Specific examples of these vinyl monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl and vinyl naphthalene; α-olefins such as ethylene, propylene, 1-butene and isobutene; Diene monomers such as butadiene, isoprene and chloroprene; halogenated olefins such as vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl such as vinyl acetate and vinyl propionate Esters: methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-methacrylic acid 2- Hexyl, cyclohexyl methacrylate, benzyl methacrylate, and (meth) acrylic monomer of glycidyl methacrylate. These monomers can be used alone or in combination of two or more. The vinyl monomer suitably used in the present invention is an aromatic vinyl monomer such as styrene or vinyl benzyl chloride.

これらビニルモノマーの添加量は、重合時に共存させるモノリス中間体に対して、重量で３〜４０倍、好ましくは４〜３０倍である。ビニルモノマー添加量が多孔質体に対して３倍未満であると、生成したモノリスの骨格に粒子体を形成できず、イオン交換基導入後の体積当りのイオン交換容量が小さくなってしまうため好ましくない。一方、ビニルモノマー添加量が４０倍を超えると、開口径が小さくなり、流体透過時の圧力損失が大きくなってしまうため好ましくない。   The added amount of these vinyl monomers is 3 to 40 times, preferably 4 to 30 times, by weight with respect to the monolith intermediate coexisting during polymerization. If the amount of vinyl monomer added is less than 3 times that of the porous body, it is preferable because the particles cannot be formed in the skeleton of the produced monolith, and the ion exchange capacity per volume after introduction of the ion exchange groups is reduced. Absent. On the other hand, if the amount of vinyl monomer added exceeds 40 times, the opening diameter becomes small and the pressure loss during fluid permeation increases, which is not preferable.

ＩＩ工程で用いられる第２架橋剤は、分子中に少なくとも２個の重合可能なビニル基を含有し、有機溶媒への溶解性が高いものが好適に用いられる。第２架橋剤の具体例としては、ジビニルベンゼン、ジビニルナフタレン、ジビニルビフェニル、エチレングリコールジメタクリレート、トリメチロールプロパントリアクリレート、ブタンジオールジアクリレート等が挙げられる。これら第２架橋剤は、１種単独又は２種以上を組み合わせて使用することができる。好ましい第２架橋剤は、機械的強度の高さと加水分解に対する安定性から、ジビニルベンゼン、ジビニルナフタレン、ジビニルビフェニル等の芳香族ポリビニル化合物である。第２架橋剤の使用量は、ビニルモノマーと第２架橋剤の合計量に対して０．３〜２０モル％、特に０．３〜１０モル％であることが好ましい。架橋剤使用量が０．３モル％未満であると、モノリスの機械的強度が不足するため好ましくない。一方、２０モル％を越えると、モノリスの脆化が進行して柔軟性が失われる、イオン交換基の導入量が減少してしまうといった問題点が生じるため好ましくない。   As the second crosslinking agent used in Step II, one having at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the second crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These 2nd crosslinking agents can be used individually by 1 type or in combination of 2 or more types. A preferred second crosslinking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl because of its high mechanical strength and stability to hydrolysis. The amount of the second crosslinking agent used is preferably 0.3 to 20 mol%, particularly 0.3 to 10 mol%, based on the total amount of the vinyl monomer and the second crosslinking agent. When the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, if it exceeds 20 mol%, the monolith becomes more brittle and the flexibility is lost, and the amount of ion exchange groups introduced decreases, which is not preferable.

ＩＩ工程で用いられる有機溶媒は、ビニルモノマーや第２架橋剤は溶解するがビニルモノマーが重合して生成するポリマーは溶解しない有機溶媒、言い換えると、ビニルモノマーが重合して生成するポリマーに対する貧溶媒である。該有機溶媒は、ビニルモノマーの種類によって大きく異なるため一般的な具体例を列挙することは困難であるが、例えば、ビニルモノマーがスチレンの場合、有機溶媒としては、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、オクタノール、2-エチルヘキサノール、デカノール、ドデカノール、プロピレングリコール、テトラメチレングリコール等のアルコール類；ジエチルエーテル、ブチルセロソルブ、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等の鎖状（ポリ）エーテル類；ヘキサン、ヘプタン、オクタン、イソオクタン、デカン、ドデカン等の鎖状飽和炭化水素類；酢酸エチル、酢酸イソプロピル、酢酸セロソルブ、プロピオン酸エチル等のエステル類が挙げられる。また、ジオキサンやＴＨＦ、トルエンのようにポリスチレンの良溶媒であっても、上記貧溶媒と共に用いられ、その使用量が少ない場合には、有機溶媒として使用することができる。これら有機溶媒の使用量は、上記ビニルモノマーの濃度が５〜８０重量％となるように用いることが好ましい。有機溶媒使用量が上記範囲から逸脱してビニルモノマー濃度が５重量％未満となると、重合速度が低下してしまうため好ましくない。一方、ビニルモノマー濃度が８０重量％を超えると、重合が暴走する恐れがあるため好ましくない。   The organic solvent used in step II is an organic solvent that dissolves the vinyl monomer and the second cross-linking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, in other words, a poor solvent for the polymer formed by polymerization of the vinyl monomer. It is. Since the organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general specific examples. For example, when the vinyl monomer is styrene, the organic solvent includes methanol, ethanol, propanol, butanol, Alcohols such as hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, propylene glycol, tetramethylene glycol; chain (poly) ethers such as diethyl ether, butyl cellosolve, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, dodecane, etc .; Ethyl acetate, isopropyl acetate, cellosolve acetate, ethyl propionate, etc. Ethers, and the like. Moreover, even if it is a good solvent of polystyrene like a dioxane, THF, and toluene, when it is used with the said poor solvent and the usage-amount is small, it can be used as an organic solvent. These organic solvents are preferably used so that the concentration of the vinyl monomer is 5 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the vinyl monomer concentration is less than 5% by weight, the polymerization rate is lowered, which is not preferable. On the other hand, if the vinyl monomer concentration exceeds 80% by weight, the polymerization may run away, which is not preferable.

重合開始剤としては、熱及び光照射によりラジカルを発生する化合物が好適に用いられる。重合開始剤は油溶性であるほうが好ましい。本発明で用いられる重合開始剤の具体例としては、２，２’-アゾビス（イソブチロニトリル）、２，２’-アゾビス（２，４-ジメチルバレロニトリル）、２，２’-アゾビス（２−メチルブチロニトリル）、２，２’-アゾビス（４-メトキシ-２，４-ジメチルバレロニトリル）、２，２’-アゾビスイソ酪酸ジメチル、４，４’-アゾビス（４-シアノ吉草酸）、１，１’-アゾビス（シクロヘキサン-1-カルボニトリル）、過酸化ベンゾイル、過酸化ラウロイル、テトラメチルチウラムジスルフィド等が挙げられる。重合開始剤の使用量は、モノマーの種類や重合温度等によって大きく変動するが、ビニルモノマーと第２架橋剤の合計量に対して、約０．０１〜５％の範囲で使用することができる。   As the polymerization initiator, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator is preferably oil-soluble. Specific examples of the polymerization initiator used in the present invention include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis ( 2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid) 1,1′-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, tetramethylthiuram disulfide and the like. The amount of polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but can be used in a range of about 0.01 to 5% with respect to the total amount of vinyl monomer and second crosslinking agent. .

ＩＩＩ工程は、ＩＩ工程で得られた混合物を静置下、且つ該Ｉ工程で得られたモノリス中間体の存在下、重合を行い、複合モノリスを得る工程である。ＩＩＩ工程で用いるモノリス中間体は、本発明の斬新な構造を有するモノリスを創出する上で、極めて重要な役割を担っている。特表平７−５０１１４０号等に開示されているように、モノリス中間体不存在下でビニルモノマーと第２架橋剤を特定の有機溶媒中で静置重合させると、粒子凝集型のモノリス状有機多孔質体が得られる。それに対して、本発明のように上記重合系に連続マクロポア構造のモノリス中間体を存在させると、重合後のモノリスの構造は劇的に変化し、粒子凝集構造は消失し、上述の特定の骨格構造を有するモノリスが得られる。   In step III, the mixture obtained in step II is allowed to stand, and in the presence of the monolith intermediate obtained in step I, polymerization is performed to obtain a composite monolith. The monolith intermediate used in the step III plays a very important role in creating the monolith having the novel structure of the present invention. As disclosed in JP-A-7-501140 and the like, when a vinyl monomer and a second cross-linking agent are allowed to stand in a specific organic solvent in the absence of a monolith intermediate, a particle aggregation type monolithic organic material is obtained. A porous body is obtained. On the other hand, when a monolith intermediate having a continuous macropore structure is present in the polymerization system as in the present invention, the structure of the monolith after polymerization changes dramatically, the particle aggregation structure disappears, and the specific skeleton described above is lost. A monolith having a structure is obtained.

反応容器の内容積は、モノリス中間体を反応容器中に存在させる大きさのものであれば特に制限されず、反応容器内にモノリス中間体を載置した際、平面視でモノリスの周りに隙間ができるもの、反応容器内にモノリス中間体が隙間無く入るもののいずれであってもよい。このうち、重合後のモノリスが容器内壁から押圧を受けることなく、反応容器内に隙間無く入るものが、モノリスに歪が生じることもなく、反応原料などの無駄がなく効率的である。なお、反応容器の内容積が大きく、重合後のモノリスの周りに隙間が存在する場合であっても、ビニルモノマーや架橋剤は、モノリス中間体に吸着、分配されるため、反応容器内の隙間部分に粒子凝集構造物が生成することはない。   The internal volume of the reaction vessel is not particularly limited as long as it is large enough to allow the monolith intermediate to exist in the reaction vessel. When the monolith intermediate is placed in the reaction vessel, there is a gap around the monolith in plan view. Or a monolith intermediate in the reaction vessel with no gap. Of these, the monolith after polymerization does not receive any pressure from the inner wall of the vessel and enters the reaction vessel without any gap, so that the monolith is not distorted and the reaction raw materials are not wasted and efficient. Even when the internal volume of the reaction vessel is large and there are gaps around the monolith after polymerization, the vinyl monomer and the crosslinking agent are adsorbed and distributed on the monolith intermediate, so the gaps in the reaction vessel A particle aggregate structure is not generated in the portion.

ＩＩＩ工程において、反応容器中、モノリス中間体は混合物（溶液）で含浸された状態に置かれる。ＩＩ工程で得られた混合物とモノリス中間体の配合比は、前述の如く、モノリス中間体に対して、ビニルモノマーの添加量が重量で３〜４０倍、好ましくは４〜３０倍となるように配合するのが好適である。これにより、適度な開口径を有しつつ、特定の骨格を有するモノリスを得ることができる。反応容器中、混合物中のビニルモノマーと架橋剤は、静置されたモノリス中間体の骨格に吸着、分配しされ、モノリス中間体の骨格内で重合が進行する。   In step III, the monolith intermediate is placed in a reaction vessel impregnated with the mixture (solution). As described above, the blending ratio of the mixture obtained in Step II and the monolith intermediate is 3 to 40 times by weight, preferably 4 to 30 times by weight, relative to the monolith intermediate. It is suitable to mix. Thereby, it is possible to obtain a monolith having a specific skeleton while having an appropriate opening diameter. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate that has been allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate.

重合条件は、モノマーの種類、開始剤の種類により様々な条件が選択できる。例えば、開始剤として２，２’-アゾビス（イソブチロニトリル）、２，２’-アゾビス（２，４-ジメチルバレロニトリル）、過酸化ベンゾイル、過酸化ラウロイル等を用いたときには、不活性雰囲気下の密封容器内において、２０〜１００℃で１〜４８時間加熱重合させればよい。加熱重合により、モノリス中間体の骨格に吸着、分配したビニルモノマーと架橋剤が該骨格内で重合し、該特定の骨格構造を形成させる。重合終了後、内容物を取り出し、未反応ビニルモノマーと有機溶媒の除去を目的に、アセトン等の溶剤で抽出して特定骨格構造のモノリスを得る。   Various polymerization conditions can be selected depending on the type of monomer and the type of initiator. For example, when 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, or the like is used as an initiator, an inert atmosphere What is necessary is just to heat-polymerize at 20-100 degreeC for 1 to 48 hours in the lower sealed container. By heat polymerization, the vinyl monomer adsorbed and distributed on the skeleton of the monolith intermediate and the crosslinking agent are polymerized in the skeleton to form the specific skeleton structure. After completion of the polymerization, the content is taken out and extracted with a solvent such as acetone for the purpose of removing unreacted vinyl monomer and organic solvent to obtain a monolith having a specific skeleton structure.

上述の複合モノリスを製造する際に、下記（１）〜（５）の条件のうち、少なくとも一つを満たす条件下でＩＩ工程又はＩＩＩ工程行うと、本発明の特徴的な構造である、骨格表面に粒子体等が形成された複合モノリスを製造することができる。   When the above-mentioned composite monolith is produced, the skeleton, which is the characteristic structure of the present invention, is obtained by performing the II step or the III step under the conditions satisfying at least one of the following conditions (1) to (5). A composite monolith having particles or the like formed on the surface can be produced.

（１）ＩＩＩ工程における重合温度が、重合開始剤の１０時間半減温度より、少なくとも５℃低い温度である。
（２）ＩＩ工程で用いる第２架橋剤のモル％が、Ｉ工程で用いる第１架橋剤のモル％の２倍以上である。
（３）ＩＩ工程で用いるビニルモノマーが、Ｉ工程で用いた油溶性モノマーとは異なる構造のビニルモノマーである。
（４）ＩＩ工程で用いる有機溶媒が、分子量２００以上のポリエーテルである。
（５）ＩＩ工程で用いるビニルモノマーの濃度が、ＩＩ工程の混合物中、３０重量％以下である。 (1) The polymerization temperature in step III is a temperature that is at least 5 ° C. lower than the 10-hour half-life temperature of the polymerization initiator.
(2) The mol% of the second cross-linking agent used in step II is at least twice the mol% of the first cross-linking agent used in step I.
(3) The vinyl monomer used in step II is a vinyl monomer having a structure different from that of the oil-soluble monomer used in step I.
(4) The organic solvent used in step II is a polyether having a molecular weight of 200 or more.
(5) The concentration of the vinyl monomer used in Step II is 30% by weight or less in the mixture of Step II.

（上記（１）の説明）
１０時間半減温度は重合開始剤の特性値であり、使用する重合開始剤が決まれば１０時間半減温度を知ることができる。また、所望の１０時間半減温度があれば、それに該当する重合開始剤を選択することができる。ＩＩＩ工程において、重合温度を低下させることで、重合速度が低下し、骨格相の表面に粒子体等を形成させることができる。その理由は、モノリス中間体の骨格相の内部でのモノマー濃度低下が緩やかとなり、液相部からモノリス中間体へのモノマー分配速度が低下するため、余剰のモノマーがモノリス中間体の骨格層の表面近傍で濃縮され、その場で重合したためと考えられる。 (Description of (1) above)
The 10-hour half temperature is a characteristic value of the polymerization initiator, and if the polymerization initiator to be used is determined, the 10-hour half temperature can be known. Moreover, if there exists desired 10-hour half temperature, the polymerization initiator applicable to it can be selected. In step III, the polymerization rate is lowered by lowering the polymerization temperature, and particles and the like can be formed on the surface of the skeleton phase. The reason for this is that the monomer concentration drop inside the skeleton phase of the monolith intermediate becomes gradual, and the monomer distribution rate from the liquid phase part to the monolith intermediate decreases, so the surplus monomer is on the surface of the skeleton layer of the monolith intermediate. It is thought that it was concentrated in the vicinity and polymerized in situ.

重合温度の好ましいものは、用いる重合開始剤の１０時間半減温度より少なくとも１０℃低い温度である。重合温度の下限値は特に限定されないが、温度が低下するほど重合速度が低下し、重合時間が実用上許容できないほど長くなってしまうため、重合温度を１０時間半減温度に対して５〜２０℃低い範囲に設定することが好ましい。   The preferred polymerization temperature is a temperature that is at least 10 ° C. lower than the 10-hour half-life temperature of the polymerization initiator used. Although the lower limit of the polymerization temperature is not particularly limited, the polymerization rate decreases as the temperature decreases, and the polymerization time becomes unacceptably long. Therefore, the polymerization temperature is 5 to 20 ° C. with respect to the 10-hour half temperature. It is preferable to set to a low range.

（（２）の説明）
ＩＩ工程で用いる第２架橋剤のモル％を、Ｉ工程で用いる第１架橋剤のモル％の２倍以上に設定して重合すると、本発明の複合モノリスが得られる。その理由は、モノリス中間体と含浸重合によって生成したポリマーとの相溶性が低下し相分離が進行するため、含浸重合によって生成したポリマーはモノリス中間体の骨格相の表面近傍に排除され、骨格相表面に粒子体等の凹凸を形成したものと考えられる。なお、架橋剤のモル％は、架橋密度モル％であって、ビニルモノマーと架橋剤の合計量に対する架橋剤量（モル％）を言う。 (Description of (2))
When the mol% of the second cross-linking agent used in Step II is set to be twice or more of the mol% of the first cross-linking agent used in Step I, the composite monolith of the present invention is obtained. The reason for this is that the compatibility between the monolith intermediate and the polymer produced by impregnation polymerization is reduced and phase separation proceeds, so the polymer produced by impregnation polymerization is excluded in the vicinity of the surface of the skeleton phase of the monolith intermediate, It is considered that irregularities such as particles are formed on the surface. In addition, mol% of a crosslinking agent is a crosslinking density mol%, Comprising: The amount of crosslinking agents (mol%) with respect to the total amount of a vinyl monomer and a crosslinking agent is said.

ＩＩ工程で用いる第２架橋剤モル％の上限は特に制限されないが、第２架橋剤モル％が著しく大きくなると、重合後のモノリスにクラックが発生する、モノリスの脆化が進行して柔軟性が失われる、イオン交換基の導入量が減少してしまうといった問題点が生じるため好ましくない。好ましい第２架橋剤モル％の倍数は２倍〜１０倍である。一方、Ｉ工程で用いる第１架橋剤モル％をＩＩ工程で用いられる第２架橋剤モル％に対して２倍以上に設定しても、骨格相表面への粒子体等の形成は起こらず、本発明の複合モノリスは得られない。   The upper limit of the second crosslinker mol% used in step II is not particularly limited, but if the second crosslinker mol% is extremely large, cracks occur in the monolith after polymerization, and the brittleness of the monolith proceeds and flexibility is increased. This is not preferable because it causes a problem that the amount of ion exchange groups to be lost is reduced. A preferred multiple of the second crosslinking agent mol% is 2 to 10 times. On the other hand, even when the mol% of the first cross-linking agent used in step I is set to be twice or more the mol% of the second cross-linking agent used in step II, the formation of particles on the surface of the skeleton phase does not occur. The composite monolith of the present invention cannot be obtained.

（（３）の説明）
ＩＩ工程で用いるビニルモノマーが、Ｉ工程で用いた油溶性モノマーとは異なる構造のビニルモノマーであると、本発明の複合モノリスが得られる。例えば、スチレンとビニルベンジルクロライドのように、ビニルモノマーの構造が僅かでも異なると、骨格相表面に粒子体等が形成された複合モノリスが生成する。一般に、僅かでも構造が異なる二種類のモノマーから得られる二種類のホモポリマーは互いに相溶しない。したがって、Ｉ工程で用いたモノリス中間体形成に用いたモノマーとは異なる構造のモノマー、すなわち、Ｉ工程で用いたモノリス中間体形成に用いたモノマー以外のモノマーをＩＩ工程で用いてＩＩＩ工程で重合を行うと、ＩＩ工程で用いたモノマーはモノリス中間体に均一に分配や含浸がされるものの、重合が進行してポリマーが生成すると、生成したポリマーはモノリス中間体とは相溶しないため、相分離が進行し、生成したポリマーはモノリス中間体の骨格相の表面近傍に排除され、骨格相の表面に粒子体等の凹凸を形成したものと考えられる。 (Explanation of (3))
When the vinyl monomer used in Step II is a vinyl monomer having a structure different from that of the oil-soluble monomer used in Step I, the composite monolith of the present invention is obtained. For example, if the structures of vinyl monomers are slightly different, such as styrene and vinyl benzyl chloride, a composite monolith having particles or the like formed on the surface of the skeleton phase is generated. In general, two types of homopolymers obtained from two types of monomers that are slightly different in structure are not compatible with each other. Therefore, a monomer having a structure different from that of the monomer used for forming the monolith intermediate used in Step I, that is, a monomer other than the monomer used for forming the monolith intermediate used in Step I is used in Step II to polymerize in Step III. The monomer used in Step II is uniformly distributed and impregnated into the monolith intermediate, but when the polymerization proceeds and the polymer is produced, the produced polymer is not compatible with the monolith intermediate. Separation proceeds, and the produced polymer is considered to be excluded in the vicinity of the surface of the skeleton phase of the monolith intermediate, and irregularities such as particles are formed on the surface of the skeleton phase.

（（４）の説明）
ＩＩ工程で用いる有機溶媒が、分子量２００以上のポリエーテルであると、本発明の複合モノリスが得られる。ポリエーテルはモノリス中間体との親和性が比較的高く、特に低分子量の環状ポリエーテルはポリスチレンの良溶媒、低分子量の鎖状ポリエーテルは良溶媒ではないがかなりの親和性を有している。しかし、ポリエーテルの分子量が大きくなると、モノリス中間体との親和性は劇的に低下し、モノリス中間体とほとんど親和性を示さなくなる。このような親和性に乏しい溶媒を有機溶媒に用いると、モノマーのモノリス中間体の骨格内部への拡散が阻害され、その結果、モノマーはモノリス中間体の骨格の表面近傍のみで重合するため、骨格相表面に粒子体等が形成され骨格表面に凹凸を形成したものと考えられる。 (Explanation of (4))
When the organic solvent used in step II is a polyether having a molecular weight of 200 or more, the composite monolith of the present invention is obtained. Polyethers have a relatively high affinity with monolith intermediates, especially low molecular weight cyclic polyethers are good solvents for polystyrene, and low molecular weight chain polyethers are not good solvents but have considerable affinity. . However, as the molecular weight of the polyether increases, the affinity with the monolith intermediate dramatically decreases and shows little affinity with the monolith intermediate. When such a solvent having poor affinity is used as the organic solvent, diffusion of the monomer into the skeleton of the monolith intermediate is inhibited, and as a result, the monomer is polymerized only near the surface of the skeleton of the monolith intermediate. It is considered that particles and the like are formed on the phase surface and irregularities are formed on the skeleton surface.

ポリエーテルの分子量は、２００以上であれば上限に特に制約はないが、あまりに高分子量であると、ＩＩ工程で調製される混合物の粘度が高くなり、モノリス中間体内部への含浸が困難になるため好ましくない。好ましいポリエーテルの分子量は２００〜１０００００、特に好ましくは２００〜１００００である。また、ポリエーテルの末端構造は、未修飾の水酸基であっても、メチル基やエチル基等のアルキル基でエーテル化されていてもよいし、酢酸、オレイン酸、ラウリン酸、ステアリン酸等でエステル化されていてもよい。   The upper limit of the molecular weight of the polyether is not particularly limited as long as it is 200 or more. However, when the molecular weight is too high, the viscosity of the mixture prepared in the step II becomes high, and it is difficult to impregnate the monolith intermediate. Therefore, it is not preferable. The molecular weight of the preferred polyether is 200 to 100,000, particularly preferably 200 to 10,000. The terminal structure of the polyether may be an unmodified hydroxyl group, etherified with an alkyl group such as a methyl group or an ethyl group, or esterified with acetic acid, oleic acid, lauric acid, stearic acid, or the like. It may be made.

（（５）の説明）
ＩＩ工程で用いるビニルモノマーの濃度が、ＩＩ工程中の混合物中、３０重量％以下であると、本発明の複合モノリスが得られる。ＩＩ工程でモノマー濃度を低下させることで、重合速度が低下し、前記（１）と同様の理由で、骨格相表面に粒子体等が形成でき、骨格相表面に凹凸を形成されることができる。モノマー濃度の下限値は特に限定されないが、モノマー濃度が低下するほど重合速度が低下し、重合時間が実用上許容できないほど長くなってしまうため、モノマー濃度は１０〜３０重量％に設定することが好ましい。 (Explanation of (5))
When the concentration of the vinyl monomer used in Step II is 30% by weight or less in the mixture in Step II, the composite monolith of the present invention is obtained. By reducing the monomer concentration in the step II, the polymerization rate is reduced, and for the same reason as the above (1), particles and the like can be formed on the surface of the skeleton phase, and irregularities can be formed on the surface of the skeleton phase. . Although the lower limit of the monomer concentration is not particularly limited, the polymerization rate decreases as the monomer concentration decreases and the polymerization time becomes unacceptably long, so the monomer concentration may be set to 10 to 30% by weight. preferable.

ＩＩＩ工程で得られた複合モノリスは、連続骨格相と連続空孔相からなる有機多孔質体と、該有機多孔質体の骨格表面に固着する多数の粒子体又は該有機多孔質体の骨格表面上に形成される多数の突起体との複合構造体である。有機多孔質体の連続骨格相と連続空孔相は、ＳＥＭ画像により観察することができる。有機多孔質体の基本構造は、連続マクロポア構造か、共連続構造である。   The composite monolith obtained in the step III includes an organic porous body composed of a continuous skeleton phase and a continuous pore phase, a large number of particles fixed to the skeleton surface of the organic porous body, or a skeleton surface of the organic porous body. It is a composite structure with a number of protrusions formed on it. The continuous skeleton phase and the continuous pore phase of the organic porous body can be observed by SEM images. The basic structure of the organic porous body is a continuous macropore structure or a co-continuous structure.

複合モノリスにおける連続マクロポア構造は、気泡状のマクロポア同士が重なり合い、この重なる部分が乾燥状態での平均直径２０〜１００μｍの開口となるものであり、複合モノリスにおける共連続構造体は、平均の太さが乾燥状態で０．８〜４０μｍの三次元的に連続した骨格と、その骨格間に乾燥で平均直径が８〜８０μｍの三次元的に連続した空孔とからなるものである。   The continuous macropore structure in the composite monolith is such that bubble-shaped macropores overlap each other, and the overlapping portion becomes an opening having an average diameter of 20 to 100 μm in a dry state. The bicontinuous structure in the composite monolith has an average thickness. Is composed of a three-dimensionally continuous skeleton of 0.8 to 40 μm in a dry state and three-dimensionally continuous pores having an average diameter of 8 to 80 μm by drying between the skeletons.

ＩＶ工程は、ＩＩＩ工程で得られた複合モノリスにイオン交換基を導入する工程である。この導入方法によれば、得られる複合モノリスイオン交換体の多孔構造を厳密にコントロールできる。   Step IV is a step of introducing an ion exchange group into the composite monolith obtained in step III. According to this introduction method, the porous structure of the obtained composite monolith ion exchanger can be strictly controlled.

上記複合モノリスにイオン交換基を導入する方法としては、特に制限はなく、高分子反応やグラフト重合等の公知の方法を用いることができる。例えば、スルホン酸基を導入する方法としては、複合モノリスがスチレン-ジビニルベンゼン共重合体等であればクロロ硫酸や濃硫酸、発煙硫酸を用いてスルホン化する方法；複合モノリスに均一にラジカル開始基や連鎖移動基を骨格表面及び骨格内部に導入し、スチレンスルホン酸ナトリウムやアクリルアミド−２−メチルプロパンスルホン酸をグラフト重合する方法；同様にグリシジルメタクリレートをグラフト重合した後、官能基変換によりスルホン酸基を導入する方法等が挙げられる。また、四級アンモニウム基を導入する方法としては、複合モノリスがスチレン-ジビニルベンゼン共重合体等であればクロロメチルメチルエーテル等によりクロロメチル基を導入した後、三級アミンと反応させる方法；複合モノリスをクロロメチルスチレンとジビニルベンゼンの共重合により製造し、三級アミンと反応させる方法；モノリスに、均一にラジカル開始基や連鎖移動基を骨格表面及び骨格内部導入し、Ｎ，Ｎ，Ｎ−トリメチルアンモニウムエチルアクリレートやＮ，Ｎ，Ｎ−トリメチルアンモニウムプロピルアクリルアミドをグラフト重合する方法；同様にグリシジルメタクリレートをグラフト重合した後、官能基変換により四級アンモニウム基を導入する方法等が挙げられる。これらの方法のうち、スルホン酸基を導入する方法については、クロロ硫酸を用いてスチレン-ジビニルベンゼン共重合体にスルホン酸基を導入する方法が、四級アンモニウム基を導入する方法としては、スチレン-ジビニルベンゼン共重合体にクロロメチルメチルエーテル等によりクロロメチル基を導入した後、三級アミンと反応させる方法やクロロメチルスチレンとジビニルベンゼンの共重合によりモノリスを製造し、三級アミンと反応させる方法が、イオン交換基を均一かつ定量的に導入できる点で好ましい。なお、導入するイオン交換基としては、カルボン酸基、イミノ二酢酸基、スルホン酸基、リン酸基、リン酸エステル基等のカチオン交換基；四級アンモニウム基、三級アミノ基、二級アミノ基、一級アミノ基、ポリエチレンイミン基、第三スルホニウム基、ホスホニウム基等のアニオン交換基が挙げられる。   The method for introducing an ion exchange group into the composite monolith is not particularly limited, and a known method such as polymer reaction or graft polymerization can be used. For example, as a method of introducing a sulfonic acid group, if the composite monolith is a styrene-divinylbenzene copolymer, etc., a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid, or fuming sulfuric acid; radical initiating groups uniformly on the composite monolith And a method of grafting sodium styrene sulfonate or acrylamido-2-methylpropane sulfonic acid by introducing a chain transfer group into the skeleton surface or inside the skeleton; Similarly, after graft polymerization of glycidyl methacrylate, the sulfonic acid group is converted by functional group conversion. The method etc. which introduce | transduce are mentioned. In addition, as a method of introducing a quaternary ammonium group, if the composite monolith is a styrene-divinylbenzene copolymer or the like, a method of introducing a chloromethyl group with chloromethyl methyl ether or the like and then reacting with a tertiary amine; Monolith is produced by copolymerization of chloromethylstyrene and divinylbenzene and reacted with a tertiary amine; radical initiation groups and chain transfer groups are uniformly introduced into the monolith, and the N, N, N- Examples include a method of graft polymerization of trimethylammonium ethyl acrylate or N, N, N-trimethylammonium propylacrylamide; a method of grafting glycidyl methacrylate in the same manner and then introducing a quaternary ammonium group by functional group conversion. Among these methods, the method of introducing a sulfonic acid group includes a method of introducing a sulfonic acid group into a styrene-divinylbenzene copolymer using chlorosulfuric acid, and a method of introducing a quaternary ammonium group includes styrene. -Introducing a chloromethyl group into the divinylbenzene copolymer with chloromethyl methyl ether, etc., then reacting with a tertiary amine, or producing a monolith by copolymerization of chloromethylstyrene and divinylbenzene and reacting with a tertiary amine The method is preferable in that the ion exchange group can be introduced uniformly and quantitatively. The ion exchange groups to be introduced include cation exchange groups such as carboxylic acid groups, iminodiacetic acid groups, sulfonic acid groups, phosphoric acid groups, and phosphoric ester groups; quaternary ammonium groups, tertiary amino groups, and secondary amino groups. Groups, primary amino groups, polyethyleneimine groups, tertiary sulfonium groups, phosphonium groups and the like.

本発明の電気式脱イオン水製造装置に使用される脱イオンモジュールとしては、例えば、図１７に示すように、板状に成形した多孔質イオン交換体１００を、枠体１０３の一方の側に封着されたカチオン交換膜１０１と、他方の側に封着されたアニオン交換膜１０２で形成される内部空間１０４に充填してなる脱イオンモジュール１０Ａ、あるいは、図１８に示すように、板状に成形した多孔質イオン交換体１００ａを枠体１０３ａの一方の側に封着されたカチオン交換膜１０１と、枠体１０３ａと枠体１０３ｂの間に封着された中間イオン交換膜１０５とで形成される第１内部空間１０４ａに充填し、更に、板状に成形した多孔質イオン交換体１００ｂを中間イオン交換膜１０５と枠体１０３ｂの他方の側に封着されたアニオン交換膜１０２とで形成される第２内部空間１０４ｂに充填してなる脱イオンモジュール１０Ｂが挙げられる。なお、脱イオンモジュール１０Ｂにおいて、板状に成形した多孔質イオン交換体は、第１内部空間１０４ａ又は第２内部空間１０４ｂのいずれか一方に充填し、他方の内部空間には粒状のイオン交換樹脂を充填するものであってもよい。すなわち、本発明の多孔質イオン交換体の脱イオンモジュールへの充填の態様は、脱イオン水製造の目的を達成するものであれば特に制限されるものではないが、従来の脱イオンモジュールにおけるイオン交換体を本発明の多孔質イオン交換体で置き換えた充填態様を採ることができる。また、本発明の脱イオンモジュールは、枠体を使用することなく、イオン交換膜と多孔質イオン交換体を予め、接着剤などを用いて張り合わせて作製することができ、電気式脱イオン水製造装置の組み立て作業を簡便化することができる。   As a deionization module used in the electric deionized water production apparatus of the present invention, for example, as shown in FIG. 17, a porous ion exchanger 100 formed into a plate shape is placed on one side of a frame 103. A deionization module 10A formed by filling the internal space 104 formed by the sealed cation exchange membrane 101 and the anion exchange membrane 102 sealed on the other side, or as shown in FIG. A porous ion exchanger 100a formed into a cation exchange membrane 101 sealed on one side of a frame 103a and an intermediate ion exchange membrane 105 sealed between the frame 103a and the frame 103b. The porous ion exchanger 100b, which is filled in the first internal space 104a and formed into a plate shape, is sealed on the other side of the intermediate ion exchange membrane 105 and the frame body 103b. Deionized module 10B and the like formed by filling the second internal space 104b formed between. In the deionization module 10B, the plate-shaped porous ion exchanger is filled in either the first internal space 104a or the second internal space 104b, and the other internal space has a granular ion exchange resin. May be filled. That is, the aspect of filling the deionization module of the porous ion exchanger of the present invention is not particularly limited as long as the purpose of producing deionized water is achieved, but the ion in the conventional deionization module is not limited. A packing mode in which the exchanger is replaced with the porous ion exchanger of the present invention can be employed. In addition, the deionization module of the present invention can be prepared by pasting together an ion exchange membrane and a porous ion exchanger using an adhesive or the like without using a frame. Assembling work of the apparatus can be simplified.

本発明の電気式脱イオン水製造装置としては、上記脱イオンモジュールを備えるものであり、多孔質イオン交換体に捕捉せしめた不純物イオンを電気的に排除して、脱イオン水を製造する装置であれば、特に制限されず、平板型、円筒型及びスパイラル型の電気式脱イオン水製造装置が挙げられる。平板型電気式脱イオン水製造装置は、例えば、カチオン交換膜とアニオン交換膜との間に多孔質イオン交換体を充填してなる脱塩室と、上記カチオン交換膜、アニオン交換膜を介して脱塩室の両側に設けられた濃縮室と、これらの両側に配置された陽極と、陰極とを備えてなる装置、カチオン交換膜と、カチオン交換膜とアニオン交換膜の間に配置される中間イオン交換膜とで形成される第１小脱塩室、及び該中間イオン交換膜とアニオン交換膜とで形成される第２小脱塩室に、それぞれ多孔質イオン交換体を充填してなる脱塩室と、上記カチオン交換膜、アニオン交換膜を介して脱塩室の両側に設けられた濃縮室と、これらの両側に配置された陽極と、陰極とを備えてなる装置、が使用できる。   The electric deionized water production apparatus of the present invention includes the deionization module described above, and is an apparatus for producing deionized water by electrically removing impurity ions trapped by the porous ion exchanger. If there are, it will not restrict | limit in particular, The electric deionized water manufacturing apparatus of a flat plate type, a cylindrical type, and a spiral type is mentioned. The flat plate type electric deionized water production apparatus includes, for example, a desalination chamber in which a porous ion exchanger is filled between a cation exchange membrane and an anion exchange membrane, and the cation exchange membrane and the anion exchange membrane. A device comprising a concentrating chamber provided on both sides of a desalting chamber, an anode and a cathode disposed on both sides thereof, a cation exchange membrane, and an intermediate disposed between the cation exchange membrane and the anion exchange membrane The first small desalting chamber formed by the ion exchange membrane and the second small desalting chamber formed by the intermediate ion exchange membrane and the anion exchange membrane are each filled with a porous ion exchanger. An apparatus comprising a salt chamber, a concentration chamber provided on both sides of the desalting chamber via the cation exchange membrane and the anion exchange membrane, an anode and a cathode arranged on both sides thereof can be used.

以下、本発明の実施の形態における電気式脱イオン水製造装置を図１９を参照して説明する。図１９において、１は脱塩室、２は濃縮室で、これらの脱塩室１を構成するには前述の様なモジュール品として作製される。脱イオンモジュールの数は処理能力などの使用条件によって適宜に決定されるもので、図１９では、図面の簡素化を目的に脱イオンモジュールは２個で表示する。図１９の装置で使用される脱イオンモジュール１０Ａは、カチオン交換基を導入した多孔質カチオン交換体１００ｄ、アニオン交換基を導入した多孔質アニオン交換体１００ｅ、をそれぞれ小ブロック状に製作し、被処理水の流入側より多孔質カチオン交換体１００ｄ、多孔質アニオン交換体１００ｅ、多孔質カチオン交換体１００ｄ、多孔質アニオン交換体１００ｅとなるように積層し、これをアニオン交換膜１０２とカチオン交換膜１０１で挟むように構成した態様である。脱イオンモジュール１０Ａは離間して複数並設される。各脱イオンモジュール１０Ａ、１０Ａ間には枠状に形成されたゴムパッキン等の水密部材からなるスペーサー（不図示）が介在され、このようにして形成される空間部を濃縮室２として構成する。脱塩室１と濃縮室２との交互配列体の両側部に陽極１１０と陰極１０９を配置し、陽極１１０、陰極１０９の近傍にそれぞれ仕切り膜１１３、１１４を設け、該仕切り膜１１３と陽極１１０との間の空間部を陽極室１１１とし、該仕切り膜１１４と陰極１０９との間の空間部を陰極室１１２として構成する。図１９では図示の関係で多孔質イオン交換体とその両側に位置するアニオン交換膜１０２、カチオン交換膜１０１とは離間しているようになっているが、実際は多孔質イオン交換体とアニオン交換膜１０２、カチオン交換膜１０１とは密着している。なお、後述する図２０〜図２２においても脱塩室を形成するモノリス状の多孔質イオン交換体とイオン交換膜は密着している。   Hereinafter, an electrical deionized water production apparatus according to an embodiment of the present invention will be described with reference to FIG. In FIG. 19, reference numeral 1 denotes a desalting chamber, and 2 denotes a concentrating chamber, and these desalting chambers 1 are manufactured as module products as described above. The number of deionization modules is appropriately determined according to usage conditions such as processing capability. In FIG. 19, two deionization modules are displayed for the purpose of simplifying the drawing. The deionization module 10A used in the apparatus of FIG. 19 is manufactured by making a porous cation exchanger 100d introduced with a cation exchange group and a porous anion exchanger 100e introduced with an anion exchange group into small blocks. The porous cation exchanger 100d, the porous anion exchanger 100e, the porous cation exchanger 100d, and the porous anion exchanger 100e are stacked from the inflow side of the treated water, and the anion exchange membrane 102 and the cation exchange membrane are laminated. 101 is configured to be sandwiched between 101. A plurality of deionization modules 10A are arranged side by side. Between each of the deionization modules 10A and 10A, a spacer (not shown) made of a watertight member such as a rubber packing formed in a frame shape is interposed, and the space formed in this way is configured as the concentration chamber 2. The anode 110 and the cathode 109 are arranged on both sides of the alternate arrangement of the desalting chamber 1 and the concentration chamber 2, and partition films 113 and 114 are provided in the vicinity of the anode 110 and the cathode 109, respectively. A space between the partition film 114 and the cathode 109 is defined as a cathode chamber 112. In FIG. 19, the porous ion exchanger and the anion exchange membrane 102 and the cation exchange membrane 101 located on both sides of the porous ion exchanger are separated from each other. However, in actuality, the porous ion exchanger and the anion exchange membrane are actually separated. 102 and the cation exchange membrane 101 are in close contact with each other. 20 to 22 described later, the monolithic porous ion exchanger forming the desalting chamber and the ion exchange membrane are in close contact with each other.

図１９の電気式脱イオン水製造装置は、次のように操作される。先ず、被処理水を脱塩室１内に流入し、濃縮水を濃縮室２内に流入し、且つ陽極室１１１、陰極室１１２にそれぞれ電極水を流入する。濃縮水としては、通常、脱塩室１に供給する被処理水と同じものが使用される。一方、陽極１１０、陰極１０９間に電圧を印加し、被処理水、濃縮水の流れ方向に対して直角方向に直流電流を通じる。脱塩室１内に流入された被処理水は、多孔質イオン交換体のマクロポア及びメソポア（開口）からなる連続気泡構造内あるいは共連続構造内を流通する際、該連続気泡構造内に導入されたイオン交換基にイオンが捕捉され、該イオンはイオン交換膜１０１、１０２を通って濃縮室２内に排除される。   The electric deionized water production apparatus of FIG. 19 is operated as follows. First, water to be treated flows into the desalting chamber 1, concentrated water flows into the concentration chamber 2, and electrode water flows into the anode chamber 111 and the cathode chamber 112, respectively. As the concentrated water, the same water as the treated water supplied to the desalting chamber 1 is usually used. On the other hand, a voltage is applied between the anode 110 and the cathode 109 to pass a direct current in a direction perpendicular to the flow direction of the water to be treated and the concentrated water. The treated water that has flowed into the desalting chamber 1 is introduced into the open cell structure when it flows through the open cell structure or the co-continuous structure composed of macropores and mesopores (openings) of the porous ion exchanger. Ions are trapped by the ion exchange groups, and the ions pass through the ion exchange membranes 101 and 102 and are excluded into the concentration chamber 2.

他の実施の形態の電気式脱イオン水製造装置を図２０〜図２２に示す。図２０〜図２２において、同一構成要素には同一符号を付して、その説明を省略し、異なる点について主に説明する。図２０において、図１９と異なる点は、脱イオンモジュールの積層形態を変えた点にあり、図２０の装置で使用される脱イオンモジュール１０Ａは、多孔質カチオン交換体１００ｄと多孔質アニオン交換体１００ｅを、互いに多孔質イオン交換体の側面を当接させ、該当接面とは反対側の両側をアニオン交換膜１０２とカチオン交換膜１０１で挟むように構成した態様である。   An electric deionized water production apparatus according to another embodiment is shown in FIGS. 20 to 22, the same components are denoted by the same reference numerals, description thereof is omitted, and different points are mainly described. 20 is different from FIG. 19 in that the deionization module stacking form is changed. The deionization module 10A used in the apparatus of FIG. 20 includes a porous cation exchanger 100d and a porous anion exchanger. 100e is a configuration in which the side surfaces of the porous ion exchanger are brought into contact with each other, and both sides opposite to the corresponding contact surface are sandwiched between the anion exchange membrane 102 and the cation exchange membrane 101.

図２１において、図１９と異なる点は、２個の脱イオンモジュールを直列に接続し、一方の脱イオンモジュールの流出水を他方の脱イオンモジュールの被処理水とした点にある。すなわち、図２１の装置で使用される脱イオンモジュール１０Ａは、カチオン交換基を導入した多孔質カチオン交換体１００ｄとアニオン交換基を導入した多孔質アニオン交換体１００ｅをそれぞれアニオン交換膜１０２とカチオン交換膜１０１で挟むように充填して、それぞれを脱カチオンモジュール１０Ａ１と脱アニオンモジュール１０Ａ２とし、脱アニオンモジュール１０Ａ２の流出水を脱カチオンモジュール１０Ａ１の被処理水としたものである。 21 is different from FIG. 19 in that two deionization modules are connected in series, and the outflow water of one deionization module is treated water of the other deionization module. That is, the deionization module 10A used in the apparatus shown in FIG. 21 includes a cation exchange group introduced into the porous cation exchanger 100d and an anion exchange group introduced into the porous anion exchanger 100e. filled so as to sandwich the membrane 101, in which the respectively decationized module 10A 1 and the de-anion module 10A 2, the effluent leaving the anion module 10A 2 water to be treated of decationized module 10A 1.

図１９〜図２１の装置で使用される脱イオンモジュールはいずれも、図１７に示す脱イオンモジュール１０Ａが使用できる。   The deionization module 10A shown in FIG. 17 can be used for any of the deionization modules used in the apparatus shown in FIGS.

一方、図２２の装置で使用される脱イオンモジュールは、図１８に示す脱イオンモジュール１０Ｂが使用できる。すなわち、図２２の装置は、一側のカチオン交換膜１０１、他側のアニオン交換膜１０２及びカチオン交換膜１０１とアニオン交換膜１０２の間に位置する中間イオン交換膜１０５で区画される２つの小脱塩室１ａ、１ｂのカチオン交換膜１０１側の小脱塩室１ｂに多孔質アニオン交換体と多孔質カチオン交換体の積層体１００ｆを充填し、アニオン交換膜１０２側の小脱塩室１ａに多孔質アニオン交換体１００ｅを充填して脱塩室１を構成し、カチオン交換膜１０１、アニオン交換膜１０２を介して脱塩室の両側に濃縮室２を設け、これらの脱塩室１及び濃縮室２を陽極１１０と陰極１０９の間に配置して構成される。本例では、中間イオン交換膜１０５はアニオン交換膜を使用している。   On the other hand, the deionization module 10B shown in FIG. 18 can be used as the deionization module used in the apparatus of FIG. That is, the apparatus of FIG. 22 is divided into two small cation exchange membranes 101, an anion exchange membrane 102 on the other side, and two intermediate ion exchange membranes 105 positioned between the cation exchange membrane 101 and the anion exchange membrane 102. A small desalting chamber 1b on the cation exchange membrane 101 side of the desalting chambers 1a and 1b is filled with a laminate 100f of a porous anion exchanger and a porous cation exchanger, and the small desalting chamber 1a on the anion exchange membrane 102 side is filled. The desalination chamber 1 is configured by filling the porous anion exchanger 100e, and the concentration chambers 2 are provided on both sides of the desalination chamber via the cation exchange membrane 101 and the anion exchange membrane 102. The chamber 2 is arranged between the anode 110 and the cathode 109. In this example, the intermediate ion exchange membrane 105 uses an anion exchange membrane.

図２２の電気式脱イオン水製造装置は、次のように操作される。先ず、被処理水を小脱塩室１ａ内に流入し、次いで、小脱塩室１ａの流出水を隣接する他の小脱塩室１ｂに流入し、濃縮水を濃縮室２内に流入し、且つ陽極室１１１、陰極室１１２にそれぞれ電極水を流入する。濃縮水としては、通常、小脱塩室１ａに供給する被処理水と同じものが使用される。一方、陽極１１０、陰極１０９間に電圧を印加し、被処理水、濃縮水の流れ方向に対して直角方向に直流電流を通じる。小脱塩室１ａ内に流入された被処理水は、多孔質アニオン交換体１００ｅのマクロポア及びメソポアからなる連続気泡構造内あるいは共連続構造内を流通する際、該連続気泡構造内に導入されたイオン交換基にイオンが捕捉され、除去される。更に、小脱塩室１ａの流出水は多孔質アニオン交換体と多孔質カチオン交換体の積層体１００ｆのマクロポア及びメソポアからなる連続気泡構造内あるいは共連続構造内を流通する際、該連続気泡構造内に導入されたイオン交換基にイオンが捕捉され、除去される。濃縮水は各濃縮室を上昇し、カチオン交換膜１０１及びアニオン交換膜１０２を介して移動してくる不純物イオンを受取り、不純物イオンを濃縮した濃縮水として系外へ排出される。   The electric deionized water production apparatus of FIG. 22 is operated as follows. First, the water to be treated flows into the small desalination chamber 1a, then the effluent from the small desalination chamber 1a flows into another adjacent small desalination chamber 1b, and the concentrated water flows into the concentration chamber 2. In addition, electrode water flows into the anode chamber 111 and the cathode chamber 112, respectively. As the concentrated water, the same water as the treated water supplied to the small desalting chamber 1a is usually used. On the other hand, a voltage is applied between the anode 110 and the cathode 109 to pass a direct current in a direction perpendicular to the flow direction of the water to be treated and the concentrated water. The water to be treated that flowed into the small desalting chamber 1a was introduced into the open cell structure when it circulated in the open cell structure or the co-continuous structure composed of macropores and mesopores of the porous anion exchanger 100e. Ions are trapped and removed from the ion exchange groups. Furthermore, when the effluent of the small desalting chamber 1a flows through the open cell structure or the co-continuous structure composed of macropores and mesopores of the laminate 100f of the porous anion exchanger and porous cation exchanger, the open cell structure Ions are trapped and removed by the ion exchange groups introduced into the inside. The concentrated water ascends in each concentration chamber, receives impurity ions moving through the cation exchange membrane 101 and the anion exchange membrane 102, and is discharged out of the system as concentrated water in which the impurity ions are concentrated.

（実施例）
次に、実施例を挙げて、本発明を更に具体的に説明するが、これは単に例示であって、本発明を制限するものではない。 (Example)
EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.

参考例１
（Ｉ工程；モノリス中間体の製造）
スチレン９．２８ｇ、ジビニルベンゼン０．１９ｇ、ソルビタンモノオレエート（以下ＳＭＯと略す）０．５０ｇおよび２,２’-アゾビス（イソブチロニトリル）０．２６ｇを混合し、均一に溶解させた。次に，当該スチレン/ジビニルベンゼン/ＳＭＯ/２,２’-アゾビス（イソブチロニトリル）混合物を１８０ｇの純水に添加し、遊星式撹拌装置である真空撹拌脱泡ミキサー（イーエムイー社製）を用いて５〜２０℃の温度範囲において減圧下撹拌して、油中水滴型エマルションを得た。このエマルションを反応容器に速やかに移し、密封後静置下で６０℃、２４時間重合させた。重合終了後、内容物を取り出し、イソプロパノールで抽出した後、減圧乾燥して、連続マクロポア構造を有するモノリス中間体を製造した。水銀圧入法により測定した該モノリス中間体のマクロポアとマクロポアが重なる部分の開口（メソポア）の平均直径は４０μｍ、全細孔容積は１５．８ｍｌ／ｇであった。 Reference example 1
(Step I; production of monolith intermediate)
9.28 g of styrene, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Corp.) which is a planetary stirring device. Was used under reduced pressure in a temperature range of 5 to 20 ° C. to obtain a water-in-oil emulsion. The emulsion was immediately transferred to a reaction vessel, and after sealing, it was allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with isopropanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. The average diameter of the openings (mesopores) where the macropores and macropores of the monolith intermediate were measured by mercury porosimetry was 40 μm, and the total pore volume was 15.8 ml / g.

（複合モノリスの製造）
次いで、スチレン３６．０ｇ、ジビニルベンゼン４．０ｇ、１-デカノール６０ｇ、２,２’-アゾビス（２,４-ジメチルバレロニトリル）０．４ｇを混合し、均一に溶解させた（ＩＩ工程）。重合開始剤として用いた２,２’-アゾビス（２,４-ジメチルバレロニトリル）の１０時間半減温度は、５１℃であった。モノリス中間体の架橋密度１．３モル％に対して、ＩＩ工程で用いたスチレンとジビニルベンゼンの合計量に対するジビニルベンゼンの使用量は６．６モル％であり、架橋密度比は５．１倍であった。次に上記モノリス中間体を外径７０ｍｍ、厚さ約２０ｍｍの円盤状に切断して、３．２ｇ分取した。分取したモノリス中間体を内径７３ｍｍの反応容器に入れ、当該スチレン/ジビニルベンゼン/１-デカノール/２,２’-アゾビス（２,４-ジメチルバレロニトリル）混合物に浸漬させ、減圧チャンバー中で脱泡した後、反応容器を密封し、静置下６０℃で２４時間重合させた。重合終了後、厚さ約３０ｍｍのモノリス状の内容物を取り出し、アセトンでソックスレー抽出した後、８５℃で一夜減圧乾燥した（ＩＩＩ工程）。 (Manufacture of composite monolith)
Next, 36.0 g of styrene, 4.0 g of divinylbenzene, 60 g of 1-decanol, and 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). The 10-hour half-life temperature of 2,2′-azobis (2,4-dimethylvaleronitrile) used as the polymerization initiator was 51 ° C. The amount of divinylbenzene used is 6.6 mol% with respect to the total amount of styrene and divinylbenzene used in Step II, while the crosslink density of the monolith intermediate is 1.3 mol%, and the crosslink density ratio is 5.1 times. Met. Next, the monolith intermediate was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 20 mm, and 3.2 g was collected. The separated monolith intermediate is placed in a reaction vessel having an inner diameter of 73 mm, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and removed in a vacuum chamber. After bubbling, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the monolith-like contents having a thickness of about 30 mm were taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C. overnight (step III).

このようにして得られたスチレン/ジビニルベンゼン共重合体よりなる複合モノリス（乾燥体）の内部構造を、ＳＥＭにより観察した結果を図１〜図３に示す。図１〜図３のＳＥＭ画像は、倍率が異なるものであり、モノリスを任意の位置で切断して得た切断面の任意の位置における画像である。図１〜図３から明らかなように、当該複合モノリスは連続マクロポア構造を有しており、連続マクロポア構造体を構成する骨格相の表面は、平均粒子径４μｍの粒子体で被覆され、全粒子体等による骨格表面の粒子被覆率は８０％であった。また、粒径３〜５μｍの粒子体が全体の粒子体に占める割合は９０％であった。   The results of observing the internal structure of the composite monolith (dried body) composed of the styrene / divinylbenzene copolymer thus obtained by SEM are shown in FIGS. The SEM images in FIGS. 1 to 3 are different in magnification, and are images at arbitrary positions on a cut surface obtained by cutting a monolith at an arbitrary position. As apparent from FIGS. 1 to 3, the composite monolith has a continuous macropore structure, and the surface of the skeletal phase constituting the continuous macropore structure is coated with particles having an average particle diameter of 4 μm. The particle coverage of the skeleton surface by the body and the like was 80%. Moreover, the ratio for which the particle body with a particle size of 3-5 micrometers occupied to the whole particle body was 90%.

また、水銀圧入法により測定した当該複合モノリスの開口の平均直径は１６μｍ、全細孔容積は２．３ｍｌ/ｇであった。その結果を表１及び表２にまとめて示す。表１中、仕込み欄は左から順に、ＩＩ工程で用いたビニルモノマー、架橋剤、有機溶媒、Ｉ工程で得られたモノリス中間体を示す。また、粒子体等は粒子で示した。   Moreover, the average diameter of the opening of the composite monolith measured by mercury porosimetry was 16 μm, and the total pore volume was 2.3 ml / g. The results are summarized in Tables 1 and 2. In Table 1, the preparation column shows the vinyl monomer, the crosslinking agent, the organic solvent used in Step II, and the monolith intermediate obtained in Step I in order from the left. Further, the particle bodies and the like are shown as particles.

（複合モノリスカチオン交換体の製造）
上記の方法で製造した複合モノリスを、外径７０ｍｍ、厚み約１５ｍｍの円盤状に切断した。モノリスの重量は１９．６ｇであった。これにジクロロメタン１５００ｍｌを加え、３５℃で１時間加熱した後、１０℃以下まで冷却し、クロロ硫酸９８．９ｇを徐々に加え、昇温して３５℃で２４時間反応させた。その後、メタノールを加え、残存するクロロ硫酸をクエンチした後、メタノールで洗浄してジクロロメタンを除き、更に純水で洗浄して複合モノリスカチオン交換体を得た。 (Production of complex monolith cation exchanger)
The composite monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The weight of the monolith was 19.6 g. To this, 1500 ml of dichloromethane was added and heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or less, 98.9 g of chlorosulfuric acid was gradually added, and the temperature was raised and reacted at 35 ° C. for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was then washed with methanol to remove dichloromethane and further washed with pure water to obtain a composite monolith cation exchanger.

得られたカチオン交換体の反応前後の膨潤率は１．３倍であり、体積当りのイオン交換容量は、水湿潤状態で１．１１ｍｇ当量/ｍｌであった。水湿潤状態での有機多孔質イオン交換体の開口の平均直径を、有機多孔質体の値と水湿潤状態のカチオン交換体の膨潤率から見積もったところ２１μｍであり、同様の方法で求めた被覆粒子の平均粒径は５μｍであった。なお、全粒子体等による骨格表面の粒子被覆率は８０％、全細孔容積は２．３ｍｌ/ｇであった。また、粒径４〜７μｍの粒子体が全体の粒子体に占める割合は９０％であった。また、水を透過させた際の圧力損失の指標である差圧係数は、０．０５７ＭＰａ/ｍ・ＬＶであり、実用上要求される圧力損失と比較して、それを下回る低い圧力損失であった。更に、イオン交換帯長さは９ｍｍであり、著しく短い値を示した。結果を表２にまとめて示す。   The swelling rate before and after the reaction of the obtained cation exchanger was 1.3 times, and the ion exchange capacity per volume was 1.11 mg equivalent / ml in a water wet state. The average diameter of the openings of the organic porous ion exchanger in the water wet state was 21 μm as estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water wet state. The average particle size of the particles was 5 μm. The particle coverage of the skeletal surface with all particles was 80%, and the total pore volume was 2.3 ml / g. Moreover, the ratio for which the particle body of 4-7 micrometers of particle | grains accounts to the whole particle body was 90%. The differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.057 MPa / m · LV, which is a lower pressure loss than that required for practical use. It was. Further, the length of the ion exchange zone was 9 mm, showing a remarkably short value. The results are summarized in Table 2.

次に、複合モノリスカチオン交換体中のスルホン酸基の分布状態を確認するため、ＥＰＭＡにより硫黄原子の分布状態を観察した。その結果を図４及び図５に示す。図４及び図５共に、左右の写真はそれぞれ対応している。図４は硫黄原子のカチオン交換体の表面における分布状態を示したものであり、図５は硫黄原子のカチオン交換体の断面（厚み）方向における分布状態を示したものである。図４及び図５より、スルホン酸基はカチオン交換体の骨格表面及び骨格内部（断面方向）にそれぞれ均一に導入されていることがわかる。   Next, in order to confirm the distribution state of the sulfonic acid group in the composite monolith cation exchanger, the distribution state of sulfur atoms was observed by EPMA. The results are shown in FIGS. 4 and 5, the left and right photographs correspond to each other. FIG. 4 shows the distribution of sulfur atoms on the surface of the cation exchanger, and FIG. 5 shows the distribution of sulfur atoms in the cross-section (thickness) direction of the cation exchanger. 4 and 5, it can be seen that the sulfonic acid groups are uniformly introduced on the skeleton surface of the cation exchanger and inside the skeleton (cross-sectional direction).

参考例２〜５
（複合モノリスの製造）
ビニルモノマーの使用量、架橋剤の使用量、有機溶媒の種類と使用量、ＩＩＩ工程で重合時に共存させるモノリス中間体の多孔構造、架橋密度と使用量及び重合温度を表１に示す配合量に変更した以外は、参考例１と同様の方法でモノリスを製造した。その結果を表１及び表２に示す。また、複合モノリス（乾燥体）の内部構造を、ＳＥＭにより観察した結果を図６〜図１３に示す。図６〜図８は参考例２、図９及び図１０は参考例３、図１１は参考例４、図１２及び図１３は参考例５のものである。なお、参考例２については架橋密度比（２．５倍）、参考例３については有機溶媒の種類（ＰＥＧ；分子量４００）、参考例４についてはビニルモノマー濃度（２８．０％）、参考例５については重合温度（４０℃；重合開始剤の１０時間半減温度より１１℃低い）について、本発明の製造条件を満たす条件で製造した。図６〜図１３から参考例３〜５の複合モノリスの骨格表面に付着しているものは粒子体というよりは突起体であった。突起体の「粒子平均径」は突起体の大きさ（最大径）の平均径である。図６〜図１３及び表２から、参考例２〜６のモノリス骨格表面に付着している粒子の平均径は３〜８μｍ、全粒子体等による骨格表面の粒子被覆率は５０〜９５％であった。また、参考例２が粒径３〜６μｍの粒子体が全体の粒子体に占める割合は８０％、参考例３が粒径３〜１０μｍの突起体が全体の粒子体に占める割合は８０％、参考例４が粒径３〜５μｍの粒子体が全体の粒子体に占める割合は９０％、参考例５が粒径３〜７μｍの粒子体が全体の粒子体に占める割合は９０％であった。 Reference Examples 2-5
(Manufacture of composite monolith)
The amount of vinyl monomer used, the amount of crosslinking agent used, the type and amount of organic solvent used, the porous structure of the monolith intermediate that coexists during polymerization in step III, the crosslinking density and the amount used, and the polymerization temperature are shown in Table 1. A monolith was produced in the same manner as in Reference Example 1 except for the change. The results are shown in Tables 1 and 2. Moreover, the result of having observed the internal structure of composite monolith (dry body) by SEM is shown in FIGS. 6 to 8 are of Reference Example 2, FIGS. 9 and 10 are of Reference Example 3, FIG. 11 is of Reference Example 4, and FIGS. 12 and 13 are of Reference Example 5. For Reference Example 2, the crosslinking density ratio (2.5 times), for Reference Example 3, the type of organic solvent (PEG; molecular weight 400), for Reference Example 4, the vinyl monomer concentration (28.0%), Reference Example For No. 5, the polymerization temperature (40 ° C .; 11 ° C. lower than the 10-hour half-life temperature of the polymerization initiator) was produced under conditions satisfying the production conditions of the present invention. From FIG. 6 to FIG. 13, what adhered to the skeleton surface of the composite monoliths of Reference Examples 3 to 5 were protrusions rather than particles. The “particle average diameter” of the protrusion is the average diameter of the protrusions (maximum diameter). From FIG. 6 to FIG. 13 and Table 2, the average diameter of the particles adhering to the surface of the monolith skeleton of Reference Examples 2 to 6 is 3 to 8 μm, and the particle coverage of the skeleton surface by all particles is 50 to 95%. there were. In addition, the proportion of Reference Example 2 in which particles having a particle diameter of 3 to 6 μm occupy the entire particle body is 80%, and the ratio of Reference Example 3 in which protrusions having a particle diameter of 3 to 10 μm occupy the entire particle is 80%. In Reference Example 4, the proportion of particles having a particle diameter of 3 to 5 μm in the total particle body was 90%, and in Reference Example 5, the proportion of particles having a particle diameter of 3 to 7 μm in the entire particle body was 90%. .

（複合モノリスカチオン交換体の製造）
上記の方法で製造した複合モノリスを、それぞれ参考例１と同様の方法でクロロ硫酸と反応させ、複合モノリスカチオン交換体を製造した。その結果を表２に示す。参考例２〜５における複合モノリスカチオン交換体の連続細孔の平均直径は２１〜５２μｍであり、骨格表面に付着している粒子体等の平均径は５〜１３μｍ、全粒子体等による骨格表面の粒子被覆率も５０〜９５％と高く、差圧係数も０．０１０〜０．０５７ＭＰａ/ｍ・ＬＶと小さい上に、イオン交換帯長さも８〜１２ｍｍと著しく小さな値であった。また、粒径５〜１０μｍの粒子体が全体の粒子体に占める割合は９０％であった。 (Production of complex monolith cation exchanger)
The composite monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 1 to produce a composite monolith cation exchanger. The results are shown in Table 2. The average diameter of the continuous pores of the composite monolith cation exchanger in Reference Examples 2 to 5 is 21 to 52 μm, the average diameter of the particles attached to the skeleton surface is 5 to 13 μm, the skeleton surface due to all the particles, etc. The particle coverage was as high as 50 to 95%, the differential pressure coefficient was as small as 0.010 to 0.057 MPa / m · LV, and the ion exchange zone length was as extremely small as 8 to 12 mm. Moreover, the ratio for which the particle body with a particle size of 5-10 micrometers occupied to the whole particle body was 90%.

参考例６
（複合モノリスの製造）
ビニルモノマーの種類とその使用量、架橋剤の使用量、有機溶媒の種類と使用量、ＩＩＩ工程で重合時に共存させるモノリス中間体の多孔構造、架橋密度および使用量を表１に示す配合量に変更した以外は、参考例１と同様の方法でモノリスを製造した。その結果を表１及び表２に示す。また、複合モノリス（乾燥体）の内部構造を、ＳＥＭにより観察した結果を図１４〜図１６に示す。参考例６の複合モノリスの骨格表面に付着しているものは突起体であった。参考例６のモノリスは、表面に形成された突起体の最大径の平均径が１０μｍであり、全粒子体等による骨格表面の粒子被覆率は１００％であった。また、粒径６〜１２μｍの粒子体が全体の粒子体に占める割合は８０％であった。 Reference Example 6
(Manufacture of composite monolith)
Table 1 shows the type and amount of vinyl monomer used, amount of crosslinking agent used, type and amount of organic solvent, monolith intermediate porous structure coexisting during polymerization in step III, crosslinking density and amount used. A monolith was produced in the same manner as in Reference Example 1 except for the change. The results are shown in Tables 1 and 2. Moreover, the result of having observed the internal structure of composite monolith (dry body) by SEM is shown in FIGS. What adhered to the skeleton surface of the composite monolith of Reference Example 6 was a protrusion. In the monolith of Reference Example 6, the average diameter of the maximum diameter of the protrusions formed on the surface was 10 μm, and the particle coverage of the skeletal surface with all the particulates was 100%. Moreover, the ratio for which the particle body with a particle size of 6-12 micrometers occupied to the whole particle body was 80%.

（複合モノリスアニオン交換体の製造）
上記の方法で製造した複合モノリスを、外径７０ｍｍ、厚み約１５ｍｍの円盤状に切断した。複合モノリスの重量は１７．９ｇであった。これにテトラヒドロフラン１５００ｍｌを加え、４０℃で１時間加熱した後、１０℃以下まで冷却し、トリメチルアミン３０％水溶液１１４．５ｇを徐々に加え、昇温して４０℃で２４時間反応させた。反応終了後、メタノールで洗浄してテトラヒドロフランを除き、更に純水で洗浄してモノリスアニオン交換体を得た。 (Production of complex monolith anion exchanger)
The composite monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The weight of the composite monolith was 17.9 g. To this was added 1500 ml of tetrahydrofuran, heated at 40 ° C. for 1 hour, cooled to 10 ° C. or lower, gradually added 114.5 g of a 30% trimethylamine aqueous solution, heated to react at 40 ° C. for 24 hours. After completion of the reaction, the resultant was washed with methanol to remove tetrahydrofuran, and further washed with pure water to obtain a monolith anion exchanger.

得られた複合アニオン交換体の反応前後の膨潤率は２．０倍であり、体積当りのイオン交換容量は、水湿潤状態で０．３２ｍｇ当量/ｍｌであった。水湿潤状態での有機多孔質イオン交換体の連続細孔の平均直径を、モノリスの値と水湿潤状態のモノリスアニオン交換体の膨潤率から見積もったところ５８μｍであり、同様の方法で求めた突起体の平均径は２０μｍ、全粒子体等による骨格表面の粒子被覆率は１００％、全細孔容積は２．１ｍｌ/ｇであった。また、イオン交換帯長さは１６ｍｍと非常に短い値を示した。なお、水を透過させた際の圧力損失の指標である差圧係数は、０．０４１ＭＰａ/ｍ・ＬＶであり、実用上要求される圧力損失と比較して、それを下回る低い圧力損失であった。また、粒径１２〜２４μｍの粒子体が全体の粒子体に占める割合は８０％であった。その結果を表２にまとめて示す。   The obtained composite anion exchanger had a swelling ratio of 2.0 times before and after the reaction, and the ion exchange capacity per volume was 0.32 mg equivalent / ml in a water-wet state. The average diameter of the continuous pores of the organic porous ion exchanger in the water wet state was 58 μm as estimated from the value of the monolith and the swelling ratio of the monolith anion exchanger in the water wet state. The average diameter of the body was 20 μm, the particle coverage of the skeletal surface with all particles was 100%, and the total pore volume was 2.1 ml / g. Moreover, the ion exchange zone length was as short as 16 mm. The differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.041 MPa / m · LV, which is a lower pressure loss than that required for practical use. It was. Moreover, the ratio for which the particle body with a particle size of 12-24 micrometers occupied to the whole particle body was 80%. The results are summarized in Table 2.

次に、多孔質アニオン交換体中の四級アンモニウム基の分布状態を確認するため、アニオン交換体を塩酸水溶液で処理して塩化物型とした後、ＥＰＭＡにより塩素原子の分布状態を観察した。その結果、塩素原子はアニオン交換体の骨格表面のみならず、骨格内部にも均一に分布しており、四級アンモニウム基がアニオン交換体中に均一に導入されていることが確認できた。   Next, in order to confirm the distribution state of the quaternary ammonium groups in the porous anion exchanger, the anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride form, and then the distribution state of chlorine atoms was observed by EPMA. As a result, it was confirmed that the chlorine atoms were uniformly distributed not only on the skeleton surface of the anion exchanger but also inside the skeleton, and the quaternary ammonium groups were uniformly introduced into the anion exchanger.

参考例７
（モノリス中間体の製造）
参考例１と同様の方法で行いモノリス中間体を得た。 Reference Example 7
(Manufacture of monolith intermediates)
A monolith intermediate was obtained in the same manner as in Reference Example 1.

（複合モノリスの製造）
スチレン３８．０ｇ、ジビニルベンゼン２．０ｇ、１-デカノール６０ｇ、２,２’-アゾビス（２,４-ジメチルバレロニトリル）０．４ｇを混合し、均一に溶解させた（ＩＩ工程）。重合開始剤として用いた２,２’-アゾビス（２,４-ジメチルバレロニトリル）の１０時間半減温度は、５１℃であった。モノリス中間体の架橋密度１．３モル％に対して、ＩＩ工程で用いたスチレンとジビニルベンゼンの合計量に対するジビニルベンゼンの使用量は３．３モル％であり、架橋密度比は２．５倍であった。次に上記モノリス中間体を直径７０ｍｍ、厚さ約３０ｍｍの円盤状に切断して３．３ｇを分取した。分取したモノリス中間体を内径７３ｍｍの反応容器に入れ、当該スチレン/ジビニルベンゼン/1-デカノール/２,２’-アゾビス（２,４-ジメチルバレロニトリル）混合物に浸漬させ、減圧チャンバー中で脱泡した後、反応容器を密封し、静置下６０℃で２４時間重合させた。重合終了後、厚さ約３０ｍｍのモノリス状の内容物を取り出し、アセトンでソックスレー抽出した後、８５℃で一夜減圧乾燥した（ＩＩＩ工程）。 (Manufacture of composite monolith)
38.0 g of styrene, 2.0 g of divinylbenzene, 60 g of 1-decanol, and 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). The 10-hour half-life temperature of 2,2′-azobis (2,4-dimethylvaleronitrile) used as the polymerization initiator was 51 ° C. The amount of divinylbenzene used is 3.3 mol% with respect to the total amount of styrene and divinylbenzene used in Step II, with a crosslink density ratio of 2.5 times the crosslink density of the monolith intermediate of 1.3 mol%. Met. Next, the monolith intermediate was cut into a disk shape having a diameter of 70 mm and a thickness of about 30 mm to obtain 3.3 g. The separated monolith intermediate is put in a reaction vessel having an inner diameter of 73 mm, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and removed in a vacuum chamber. After bubbling, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the monolith-like contents having a thickness of about 30 mm were taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C. overnight (step III).

このようにして得られたスチレン/ジビニルベンゼン共重合体よりなる架橋成分を３．３モル％含有したモノリス（乾燥体）の内部構造を、ＳＥＭにより観察した。当該モノリスは連続マクロポア構造を有しており、連続マクロポア構造体を構成する骨格相の表面は、平均粒子径５μｍの粒子体で被覆され、全粒子体等による骨格表面の粒子被覆率は５０％であった。また、粒径３〜７μｍの粒子体が全体の粒子体に占める割合は９０％であった。また、水銀圧入法により測定した当該モノリスの開口の平均直径は３５μｍ、全細孔容積は３．８ｍｌ/ｇであった。   The internal structure of the monolith (dry body) containing 3.3 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained was observed by SEM. The monolith has a continuous macropore structure, and the surface of the skeleton phase constituting the continuous macropore structure is coated with particles having an average particle diameter of 5 μm, and the particle coverage of the skeleton surface by all particles is 50%. Met. Moreover, the ratio for which the particle body with a particle size of 3-7 micrometers occupied to the whole particle body was 90%. Moreover, the average diameter of the opening of the monolith measured by mercury porosimetry was 35 μm, and the total pore volume was 3.8 ml / g.

（複合モノリスアニオン交換体の製造）
上記の方法で製造したモノリスを、直径７０ｍｍ、厚み約１５ｍｍの円盤状に切断した。これにジメトキシメタン１４００ｍｌ、四塩化スズ２０ｍｌを加え、氷冷下クロロ硫酸５６０ｍｌを滴下した。滴下終了後、昇温して３５℃で５時間反応させ、クロロメチル基を導入した。反応終了後、母液をサイフォンで抜き出し、ＴＨＦ/水＝２/１の混合溶媒で洗浄した後、更にＴＨＦで洗浄した。このクロロメチル化モノリスにＴＨＦ１０００ｍｌとトリメチルアミン３０％水溶液６００ｍｌを加え、６０℃、６時間反応させた。反応終了後、生成物をメタノール/水混合溶媒で洗浄し、次いで純水で洗浄して単離した。 (Production of complex monolith anion exchanger)
The monolith produced by the above method was cut into a disk shape having a diameter of 70 mm and a thickness of about 15 mm. To this, 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling. After completion of the dropping, the temperature was raised and the reaction was carried out at 35 ° C. for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was extracted with a siphon, washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolith, 1000 ml of THF and 600 ml of a 30% trimethylamine aqueous solution were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with a methanol / water mixed solvent, then washed with pure water and isolated.

得られたモノリスアニオン交換体の反応前後の膨潤率は１．５倍であり、体積当りのアニオン交換容量は水湿潤状態で０．７２ｍｇ当量/ｍｌであった。水湿潤状態でのモノリスアニオン交換体の開口の平均直径を、モノリスの値と水湿潤状態のモノリスアニオン交換体の膨潤率から見積もったところ５３μｍであり、同様の方法で求めた被覆粒子の平均粒径は８μｍであった。なお、骨格表面の全粒子体等による骨格表面の粒子被覆率は５０％、全細孔容積は３．８ｍｌ/ｇであった。また、粒径４〜８μｍの粒子体が全体の粒子体に占める割合は９０％であった。   The swelling ratio of the obtained monolith anion exchanger before and after the reaction was 1.5 times, and the anion exchange capacity per volume was 0.72 mg equivalent / ml in a water wet state. The average diameter of the openings of the monolith anion exchanger in the water wet state was estimated from the value of the monolith and the swelling ratio of the monolith anion exchanger in the water wet state to be 53 μm. The diameter was 8 μm. The particle coverage of the skeleton surface by all particles on the skeleton surface was 50%, and the total pore volume was 3.8 ml / g. Moreover, the ratio for which the particle diameter of 4-8 micrometers was occupied to the whole particle body was 90%.

また、水を透過させた際の圧力損失の指標である差圧係数は、０．０１７ＭＰａ/ｍ・ＬＶであり、実用上支障のない低い圧力損失であった。更に、該モノリスアニオン交換体のフッ化物イオンに関するイオン交換帯長さを測定したところ、ＬＶ=２０ｍ/ｈにおけるイオン交換帯長さは１４ｍｍであり、市販の強塩基性アニオン交換樹脂であるアンバーライトＩＲＡ４０２ＢＬ（ロームアンドハース社製）の値（１６５ｍｍ）に比べて圧倒的に短かった。   The differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.017 MPa / m · LV, which is a low pressure loss that does not cause any practical problems. Furthermore, when the ion exchange zone length regarding the fluoride ion of the monolith anion exchanger was measured, the ion exchange zone length at LV = 20 m / h was 14 mm, and amberlite which is a commercially available strong basic anion exchange resin. It was overwhelmingly shorter than the value (165 mm) of IRA402BL (made by Rohm and Haas).

次に、モノリスアニオン交換体中の四級アンモニウム基の分布状態を確認するため、モノリスアニオン交換体を塩酸水溶液で処理して塩化物型とした後、ＥＰＭＡにより塩化物イオンの分布状態を観察した。その結果、塩化物イオンはモノリスアニオン交換体の骨格表面のみならず、骨格内部にも均一に分布しており、四級アンモニウム基がモノリスアニオン交換体中に均一に導入されていることが確認できた。   Next, in order to confirm the distribution state of the quaternary ammonium group in the monolith anion exchanger, the monolith anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride form, and then the distribution state of chloride ions was observed by EPMA. . As a result, it was confirmed that the chloride ions were uniformly distributed not only on the skeleton surface of the monolith anion exchanger but also inside the skeleton, and the quaternary ammonium groups were uniformly introduced into the monolith anion exchanger. It was.

参考例８
（モノリスの製造）
ビニルモノマーの使用量、架橋剤の使用量、有機溶媒の種類と使用量、ＩＩＩ工程で重合時に共存させるモノリス中間体の使用量を表１に示す配合量に変更した以外は、実施例１と同様の方法でモノリスを製造した。その結果を表１及び表２に示す。なお、不図示のＳＥＭ写真から骨格表面には粒子体や突起体の形成は全く認められなかった。表１及び表２から、本発明の特定の製造条件と逸脱する条件、すなわち、上記（１）〜（５）の要件から逸脱した条件下でモノリスを製造すると、モノリス骨格表面での粒子生成が認められないことがわかる。 Reference Example 8
(Manufacture of monoliths)
Except for changing the usage amount of the vinyl monomer, the usage amount of the crosslinking agent, the type and usage amount of the organic solvent, and the usage amount of the monolith intermediate coexisting during the polymerization in Step III to the blending amounts shown in Table 1, Example 1 and A monolith was produced in a similar manner. The results are shown in Tables 1 and 2. From the SEM photograph (not shown), the formation of particles and protrusions was not observed at all on the skeleton surface. From Table 1 and Table 2, when a monolith is produced under conditions deviating from the specific production conditions of the present invention, that is, conditions deviating from the requirements (1) to (5) above, particle formation on the surface of the monolith skeleton is caused. It turns out that it is not recognized.

（モノリスカチオン交換体の製造）
上記の方法で製造したモノリスを、参考例１と同様の方法でクロロ硫酸と反応させ、モノリスカチオン交換体を製造した。結果を表２に示す。得られたモノリスカチオン交換体のイオン交換帯長さは２６ｍｍであり、参考例１〜７と比較して大きな値であった。 (Production of monolith cation exchanger)
The monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 1 to produce a monolith cation exchanger. The results are shown in Table 2. The obtained monolith cation exchanger had an ion exchange zone length of 26 mm, which was a large value as compared with Reference Examples 1-7.

参考例９〜１１
（モノリスの製造）
ビニルモノマーの使用量、架橋剤の使用量、有機溶媒の種類と使用量、ＩＩＩ工程で重合時に共存させるモノリス中間体の多孔構造、架橋密度および使用量を表１に示す配合量に変更した以外は、参考例１と同様の方法でモノリスを製造した。その結果を表１及び表２に示す。なお、参考例９については架橋密度比（０．２倍）、参考例１０については有機溶媒の種類（２-（２-メトキシエトキシ）エタノール；分子量１２０）、参考例１１については重合温度（５０℃；重合開始剤の１０時間半減温度より１℃低い）について、本発明の製造条件を満たさない条件で製造した。結果を表２に示す。参考例９、１１のモノリスについては骨格表面での粒子生成はなかった。また、参考例１０では単離した生成物は透明であり、多孔構造が崩壊、消失していた。 Reference Examples 9-11
(Manufacture of monoliths)
The amount of vinyl monomer used, the amount of crosslinking agent used, the type and amount of organic solvent used, the porous structure of the monolith intermediate that coexists during polymerization in step III, the crosslinking density, and the amount used were changed to the amounts shown in Table 1. Produced a monolith in the same manner as in Reference Example 1. The results are shown in Tables 1 and 2. For Reference Example 9, the crosslinking density ratio (0.2 times), for Reference Example 10, the type of organic solvent (2- (2-methoxyethoxy) ethanol; molecular weight 120), and for Reference Example 11, the polymerization temperature (50 C .: 1 ° C. lower than the 10-hour half-life temperature of the polymerization initiator) was produced under conditions that did not satisfy the production conditions of the present invention. The results are shown in Table 2. For the monoliths of Reference Examples 9 and 11, there was no particle formation on the skeleton surface. In Reference Example 10, the isolated product was transparent, and the porous structure was collapsed and disappeared.

（モノリスカチオン交換体の製造）
参考例１０を除き、上記の方法で製造した有機多孔質体を、参考例８と同様の方法でクロロ硫酸と反応させ、モノリスカチオン交換体を製造した。その結果を表２に示す。得られたモノリスカチオン交換体のイオン交換帯長さは２３〜２６ｍｍであり、参考例１〜７と比較して大きな値であった。 (Production of monolith cation exchanger)
Except for Reference Example 10, the organic porous material produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 8 to produce a monolith cation exchanger. The results are shown in Table 2. The obtained monolith cation exchanger had an ion exchange zone length of 23 to 26 mm, which was a large value as compared with Reference Examples 1 to 7.

参考例１２
（モノリスの製造）
ビニルモノマーの使用量、架橋剤の使用量、有機溶媒の使用量、ＩＩＩ工程で重合時に共存させるモノリス中間体の多孔構造および使用量を表１に示す配合量に変更した以外は、参考例８と同様の方法でモノリスを製造した。その結果を表１及び表２に示すが、本発明の特定の製造条件を逸脱してモノリスを製造すると、モノリス骨格表面での粒子生成が認められないことがわかる。 Reference Example 12
(Manufacture of monoliths)
Reference Example 8 except that the use amount of the vinyl monomer, the use amount of the crosslinking agent, the use amount of the organic solvent, the porous structure and the use amount of the monolith intermediate coexisting during the polymerization in Step III were changed to the blending amounts shown in Table 1. A monolith was produced in the same manner as described above. The results are shown in Tables 1 and 2, and it can be seen that when a monolith is produced outside the specific production conditions of the present invention, no particle formation is observed on the surface of the monolith skeleton.

（モノリスアニオン交換体の製造）
上記の方法で製造したモノリスを、直径７０ｍｍ、厚み約１５ｍｍの円盤状に切断した。これにジメトキシメタン１４００ｍｌ、四塩化スズ２０ｍｌを加え、氷冷下クロロ硫酸５６０ｍｌを滴下した。滴下終了後、昇温して３５℃で５時間反応させ、クロロメチル基を導入した。反応終了後、母液をサイフォンで抜き出し、ＴＨＦ/水＝２/１の混合溶媒で洗浄した後、更にＴＨＦで洗浄した。このクロロメチル化モノリスにＴＨＦ１０００ｍｌとトリメチルアミン３０％水溶液６００ｍｌを加え、６０℃、６時間反応させた。反応終了後、生成物をメタノール/水混合溶媒で洗浄し、次いで純水で洗浄して単離した。結果を表２に示が、得られたモノリスアニオン交換体のイオン交換帯長さは４７ｍｍであり、参考例１〜７と比較して大きな値であった。表１及び２中、メソポア直径及び細孔の値はそれぞれ平均値を示す。 (Production of monolith anion exchanger)
The monolith produced by the above method was cut into a disk shape having a diameter of 70 mm and a thickness of about 15 mm. To this, 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling. After completion of the dropping, the temperature was raised and the reaction was carried out at 35 ° C. for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was extracted with a siphon, washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolith, 1000 ml of THF and 600 ml of a 30% trimethylamine aqueous solution were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with a methanol / water mixed solvent, then washed with pure water and isolated. The results are shown in Table 2. The obtained monolith anion exchanger had an ion exchange zone length of 47 mm, which was a large value compared to Reference Examples 1-7. In Tables 1 and 2, the mesopore diameter and pore value are average values.

参考例１３
（モノリスカチオン交換体（公知）の製造）
スチレン２７．７ｇ、ジビニルベンゼン６．９ｇ、アゾビスイソブチロニトリル（ＡＢＩＢＮ）０．１４ｇ及びソルビタンモノオレエート３．８ｇを混合し、均一に溶解させた。次に、当該スチレン/ジビニルベンゼン/アゾビスイソブチロニトリル/ソルビタンモノオレエート混合物を４５０ｍｌの純水に添加し、ホモジナイザーを用いて２万回転/分で２分間攪拌し、油中水滴型エマルジョンを得た。乳化終了後、油中水滴型エマルジョンをステンレス製のオートクレーブに移し、窒素で十分置換した後密封し、静置下６０℃で２４時間重合させた。重合終了後、内容物を取り出し、イソプロパノールで１８時間ソックスレー抽出し、未反応モノマーとソルビタンモノオレエートを除去した後、４０℃で一昼夜減圧乾燥した。このようにして得られたスチレン/ジビニルベンゼン共重合体よりなる架橋成分を１４モル％含有した有機多孔質体１１．５ｇを分取し、ジクロロエタン８００ｍｌを加え、６０℃で３０分加熱した後、室温まで冷却し、クロロ硫酸５９．１ｇを徐々に加え、室温で２４時間反応させた。その後、酢酸を加え、多量の水中に反応物を投入し、水洗、乾燥して多孔質カチオン交換体を得た。この多孔質体のイオン交換容量は、乾燥多孔質体換算で４．４ｍｇ当量/ｇ、湿潤体積換算で、０．３２ｍｇ当量／ｍｌであり、ＥＰＭＡを用いた硫黄原子のマッピングにより、スルホン酸基が多孔質体に均一に導入されていることを確認した。また、ＳＥＭ観察の結果、この有機多孔質体の内部構造は本発明のような粒子体等の形成がない連続気泡構造を有しており、平均径３０μｍのマクロポアの大部分が重なり合い、マクロポアとマクロポアの重なりで形成されるメソポアの孔径は５μｍであり、全細孔容積は、１０．１ｍｌ/ｇ、ＢＥＴ比表面積は１０ｍ２/ｇであった。 Reference Example 13
(Production of monolith cation exchanger (known))
27.7 g of styrene, 6.9 g of divinylbenzene, 0.14 g of azobisisobutyronitrile (ABIBN) and 3.8 g of sorbitan monooleate were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / azobisisobutyronitrile / sorbitan monooleate mixture is added to 450 ml of pure water and stirred for 2 minutes at 20,000 rpm with a homogenizer, and a water-in-oil emulsion. Got. After emulsification, the water-in-oil emulsion was transferred to a stainless steel autoclave, sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with Soxhlet for 18 hours with isopropanol, unreacted monomer and sorbitan monooleate were removed, and dried under reduced pressure at 40 ° C. overnight. After separating 11.5 g of an organic porous material containing 14 mol% of a crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained, 800 ml of dichloroethane was added, and the mixture was heated at 60 ° C. for 30 minutes. After cooling to room temperature, 59.1 g of chlorosulfuric acid was gradually added and reacted at room temperature for 24 hours. Thereafter, acetic acid was added, the reaction product was poured into a large amount of water, washed with water and dried to obtain a porous cation exchanger. The ion exchange capacity of this porous body is 4.4 mg equivalent / g in terms of dry porous body and 0.32 mg equivalent / ml in terms of wet volume. By mapping sulfur atoms using EPMA, sulfonic acid groups It was confirmed that was uniformly introduced into the porous body. Further, as a result of SEM observation, the internal structure of this organic porous body has an open-cell structure without the formation of particles or the like as in the present invention, and most of the macropores having an average diameter of 30 μm overlap with each other. The pore diameter of the mesopore formed by the macropore overlap was 5 μm, the total pore volume was 10.1 ml / g, and the BET specific surface area was 10 m 2 / g.

参考例１４
（多孔質アニオン交換体（公知）の製造）
スチレン２７．７ｇに代えて、ｐ- クロロメチルスチレン１８．０ｇを用い、ジビニルベンゼン６．９ｇに代えて、ジビニルベンゼン１７．３ｇを用い、アゾビスイソブチロニトリル０．１４ｇに代えて、アゾビスイソブチロニトリル０．２６ｇを用いた以外は、参考例１３と同様の油中水滴型エマルジョンの重合を行い、ｐ−クロロメチルスチレン／ジビニルベンゼン共重合体よりなる架橋成分を５０モル％含有した多孔質体を製造した。この多孔質体５ｇを分取し、ジオキサン５００ｇを加え８０℃で３０分加熱した後、室温まで冷却し、トリメチルアミン（３０％）水溶液６５ｇを徐々に加え、５０℃で３時間反応させた後、室温で一昼夜放置した。反応終了後、多孔質体を取り出し、アセトンで洗浄後水洗し、乾燥して多孔質アニオン交換体を得た。この多孔質体のイオン交換容量は、乾燥多孔質体換算で２．５ｍｇ当量／ｇであり、ＳＩＭＳにより、トリメチルアンモニウム基が多孔質体に均一に導入されていることを確認した。また、ＳＥＭ観察の結果、この多孔質体の内部構造は、連続気泡構造を有しており、平均径３０μｍのマクロポアの大部分が重なり合い、マクロポアとマクロポアの重なりで形成されるメソポアの直径の平均値は４μｍ、全細孔容積は９．９ｍｌ/ｇであった。また、上記多孔質体を１０ｍｍの厚みに切り出し、水透過速度を測定したところ、１２，０００ｌ/分・ｍ２・ＭＰａであった。 Reference Example 14
(Production of porous anion exchanger (known))
Instead of 27.7 g of styrene, 18.0 g of p-chloromethylstyrene is used, 17.3 g of divinylbenzene is used instead of 6.9 g of divinylbenzene, and azobisisobutyronitrile is used instead of 0.14 g. A water-in-oil emulsion was polymerized in the same manner as in Reference Example 13 except that 0.26 g of bisisobutyronitrile was used, and contained 50 mol% of a cross-linking component composed of a p-chloromethylstyrene / divinylbenzene copolymer. A porous body was produced. After separating 5 g of this porous material, adding 500 g of dioxane and heating at 80 ° C. for 30 minutes, the mixture was cooled to room temperature, 65 g of a trimethylamine (30%) aqueous solution was gradually added, and reacted at 50 ° C. for 3 hours. It was left overnight at room temperature. After completion of the reaction, the porous body was taken out, washed with acetone, washed with water, and dried to obtain a porous anion exchanger. The ion exchange capacity of this porous material was 2.5 mg equivalent / g in terms of dry porous material, and it was confirmed by SIMS that trimethylammonium groups were uniformly introduced into the porous material. Moreover, as a result of SEM observation, the internal structure of this porous body has an open cell structure, most of the macropores having an average diameter of 30 μm overlap, and the average diameter of the mesopores formed by the overlap of the macropores and the macropores. The value was 4 μm and the total pore volume was 9.9 ml / g. The porous body was cut out to a thickness of 10 mm, and the water permeation rate was measured. As a result, it was 12,000 l / min · m 2 · MPa.

（脱イオンモジュールＡの作製）
参考例２及び参考例７で得られた多孔質カチオン交換体及び多孔質アニオン交換体を縦１２５ｍｍ、横１００ｍｍ、幅８ｍｍの大きさに切断して、それぞれ４個の小ブロックとした。すなわち、多孔質カチオン交換体１００ｄ及び多孔質アニオン交換体１００ｅ、をそれぞれ小ブロック状に製作し、被処理水の流入側より多孔質カチオン交換体１００ｄ、多孔質アニオン交換体１００ｅ、多孔質カチオン交換体１００ｄ、多孔質アニオン交換体１００ｅとなるように積層し、これをアニオン交換膜１０２とカチオン交換膜１０１で挟むように充填して、図１９の装置で使用されるような脱イオンモジュールＡを得た。 (Production of deionization module A)
The porous cation exchanger and the porous anion exchanger obtained in Reference Example 2 and Reference Example 7 were cut into a size of 125 mm in length, 100 mm in width, and 8 mm in width to form four small blocks. That is, the porous cation exchanger 100d and the porous anion exchanger 100e are manufactured in small blocks, respectively, and the porous cation exchanger 100d, the porous anion exchanger 100e, and the porous cation exchange are formed from the inflow side of the water to be treated. Body 100d and porous anion exchanger 100e are stacked so as to be sandwiched between anion exchange membrane 102 and cation exchange membrane 101, and deionization module A as used in the apparatus of FIG. Obtained.

（電気式脱イオン水製造装置Ａの製造及び運転）
得られた脱イオンモジュールＡを脱塩室として電気式脱イオン水製造装置Ａを製造した。電気式脱イオン水製造装置は、脱塩室１室、陽極室１室、陰極室１室よりなる装置とした。脱塩室と陽極室との間、脱塩室と陰極室との間にはそれぞれスペーサを挿入して濃縮室を形成した。この電気式脱イオン水製造装置に、市水を逆浸透膜で処理した導電率が３．６μＳ／ｃｍの水を被処理水として１６Ｌ/ｈで供給し、運転した。電気式脱イオン水製造装置の操作電流０．１６Ａで、比抵抗１３．０ＭΩｃｍの処理水を得た。このときの、操作電圧は１２Ｖであった。また、このときの脱塩室への通水差圧は６４ｋＰａであった。 (Production and operation of electric deionized water production apparatus A)
An electric deionized water production apparatus A was produced using the obtained deionization module A as a demineralization chamber. The electric deionized water production apparatus was an apparatus composed of one desalting chamber, one anode chamber, and one cathode chamber. A concentrating chamber was formed by inserting spacers between the desalting chamber and the anode chamber and between the desalting chamber and the cathode chamber, respectively. The electric deionized water production apparatus was operated by supplying water having a conductivity of 3.6 μS / cm obtained by treating city water with a reverse osmosis membrane as treated water at 16 L / h. Treated water having a specific resistance of 13.0 MΩcm was obtained at an operating current of 0.16 A of the electrical deionized water production apparatus. The operating voltage at this time was 12V. Moreover, the water flow differential pressure to the desalting chamber at this time was 64 kPa.

比較例１
（脱イオンモジュールＢの作製）
参考例２の多孔質カチオン交換体に代えて、参考例１３の多孔質カチオン交換体を使用したこと、参考例７の多孔質アニオン交換体に代えて、参考例１４の多孔質アニオン交換体を使用したこと以外は、実施例１と同様の方法により、脱イオンモジュールＢを作製した。
比較例２ Comparative Example 1
(Preparation of deionization module B)
The porous cation exchanger of Reference Example 13 was used instead of the porous cation exchanger of Reference Example 2, and the porous anion exchanger of Reference Example 14 was replaced with the porous anion exchanger of Reference Example 7. A deionization module B was produced in the same manner as in Example 1 except that it was used.
Comparative Example 2

（電気式脱イオン水製造装置Ｂの製造及び運転）
脱イオンモジュールＡに代えて、脱イオンモジュールＢを使用した以外は、実施例２と同様の方法で電気式脱イオン水製造装置Ｂを製造し、運転した。その結果、電気式脱イオン水製造装置の操作電流０．１６Ａで、比抵抗５．０ＭΩｃｍの処理水を得た。このときの、操作電圧は２０Ｖであった。また、このときの脱塩室への通水差圧は５１０ｋＰａであった。 (Production and operation of electric deionized water production apparatus B)
An electric deionized water production apparatus B was produced and operated in the same manner as in Example 2 except that the deionization module B was used instead of the deionization module A. As a result, treated water having a specific resistance of 5.0 MΩcm was obtained at an operating current of 0.16 A of the electrical deionized water production apparatus. The operating voltage at this time was 20V. Moreover, the water flow differential pressure to the desalting chamber at this time was 510 kPa.

実施例２で使用した複合モノリスイオン交換体は、比較例２で使用したモノリスイオン交換体と対比して、通水差圧が小さく、また電気式脱イオン水製造装置の操作電圧を低減し消費電力を節約でき、良好な処理水を得られることが確認できた。   Compared with the monolith ion exchanger used in Comparative Example 2, the composite monolith ion exchanger used in Example 2 has a low water flow differential pressure and reduces the operating voltage of the electric deionized water production apparatus. It was confirmed that power can be saved and good treated water can be obtained.

１ 脱塩室
２ 濃縮室
１０Ａ、１０Ａ１ 、１０Ａ２ 、１０Ｂ 脱イオンモジュール
１００、１００ａ、１００ｂ 多孔質イオン交換体
１００ｄ 多孔質カチオン交換体
１００ｅ 多孔質アニオン交換体
１００ｆ 多孔質カチオン交換体と多孔質アニオン交換体の積層体
１０１ カチオン交換膜
１０２ アニオン交換膜
１０３、１０３ａ、１０３ｂ 枠体
１０４、１０４ａ、１０４ｂ 空間部
１０５ 中間イオン交換膜
１０９ 陰極
１１０ 陽極 1 desalting chamber 2 concentration compartments 10A, 10A 1, 10A 2, 10B deionized module 100, 100a, 100b porous ion exchanger 100d porous cation exchanger 100e porous anion exchanger 100f porous cation exchanger and porous Laminated body of anion exchanger 101 Cation exchange membrane 102 Anion exchange membrane 103, 103a, 103b Frame 104, 104a, 104b Space 105 Intermediate ion exchange membrane 109 Cathode 110 Anode

Claims (6)

枠体の一方の側に封着されたカチオン交換膜と他方の側に封着されたアニオン交換膜で形成される内部空間にイオン交換体を充填してなる、電気式脱イオン水製造装置に使用される脱イオンモジュールであって、該イオン交換体が、連続骨格相と連続空孔相からなる有機多孔質体と、該有機多孔質体の骨格表面に固着する直径４〜４０μｍの多数の粒子体又は該有機多孔質体の骨格表面上に形成される大きさが４〜４０μｍの多数の突起体との複合構造体であって、水湿潤状態で孔の平均直径１０〜１５０μｍ、全細孔容積０．５〜５ｍｌ／ｇであり、水湿潤状態での体積当りのイオン交換容量０．２ｍｇ当量/ｍｌ以上であるモノリス状有機多孔質イオン交換体であることを特徴とする脱イオンモジュール。   An electrical deionized water production apparatus comprising an ion exchanger filled in an internal space formed by a cation exchange membrane sealed on one side of a frame and an anion exchange membrane sealed on the other side. A deionization module to be used, in which the ion exchanger includes an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a large number of 4 to 40 μm in diameter fixed to the skeleton surface of the organic porous body. A composite structure with a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the particle body or the organic porous body, and having an average pore diameter of 10 to 150 μm in the water wet state, A deionization module characterized by being a monolithic organic porous ion exchanger having a pore volume of 0.5 to 5 ml / g and an ion exchange capacity per volume of 0.2 mg equivalent / ml or more in a wet state of water . 枠体の一方の側に封着されたカチオン交換膜と、該カチオン交換膜と他方の側に封着されたアニオン交換膜の間に配置された中間イオン交換膜で形成される第１内部空間に第１イオン交換体を充填し、該中間イオン交換膜と他方の側に封着されたアニオン交換膜で形成される第２内部空間に第２イオン交換体を充填してなる、電気式脱イオン水製造装置に使用される脱イオンモジュールであって、該第１イオン交換体及び該第２イオン交換体のいずれか一方又は両方が、連続骨格相と連続空孔相からなる有機多孔質体と、該有機多孔質体の骨格表面に固着する直径４〜４０μｍの多数の粒子体又は該有機多孔質体の骨格表面上に形成される大きさが４〜４０μｍの多数の突起体との複合構造体であって、水湿潤状態で孔の平均直径１０〜１５０μｍ、全細孔容積０．５〜５ｍｌ／ｇであり、水湿潤状態での体積当りのイオン交換容量０．２ｍｇ当量/ｍｌ以上であるモノリス状有機多孔質イオン交換体であることを特徴とする脱イオンモジュール。   A first internal space formed by a cation exchange membrane sealed on one side of the frame, and an intermediate ion exchange membrane disposed between the cation exchange membrane and the anion exchange membrane sealed on the other side The first ion exchanger is filled, and the second ion exchanger is filled in the second internal space formed by the intermediate ion exchange membrane and the anion exchange membrane sealed on the other side. A deionization module used in an ionized water production apparatus, wherein one or both of the first ion exchanger and the second ion exchanger are composed of a continuous skeleton phase and a continuous pore phase. And a large number of particles having a diameter of 4 to 40 μm fixed to the skeleton surface of the organic porous body or a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the organic porous body A structure having an average pore diameter of 10 to 150 in a wet state; It is a monolithic organic porous ion exchanger having a pore size of μm and a total pore volume of 0.5 to 5 ml / g, and an ion exchange capacity of 0.2 mg equivalent / ml or more per volume in a wet state of water. Deionizing module. 前記有機多孔質体が、気泡状のマクロポア同士が重なり合い、この重なる部分が水湿潤状態で平均直径３０〜１５０μｍの開口となる連続マクロポア構造体であることを特徴とする請求項１又は２記載の脱イオンモジュール。   The organic porous body is a continuous macropore structure in which bubble-shaped macropores overlap each other, and the overlapping portion forms an opening having an average diameter of 30 to 150 µm in a wet state. Deionization module. 前記有機多孔質体が、水湿潤状態で平均の太さが１〜６０μｍの三次元的に連続した骨格と、その骨格間に平均直径が水湿潤状態で１０〜１００μｍの三次元的に連続した空孔とからなる共連続構造体であることを特徴とする請求項１又は２記載の脱イオンモジュール。   The organic porous body is a three-dimensionally continuous skeleton having an average thickness of 1 to 60 μm in a water-wet state, and a three-dimensionally continuous skeleton having an average diameter of 10 to 100 μm in a water-wet state between the skeletons. The deionization module according to claim 1 or 2, wherein the deionization module is a co-continuous structure including pores. 前記中間イオン交換膜がアニオン交換膜であり、前記第１イオン交換体がモノリス状有機多孔質アニオン交換体とモノリス状有機多孔質カチオン交換体の積層体であり、前記第２イオン交換体がモノリス状有機多孔質アニオン交換体であることを特徴とする請求項２記載の脱イオンモジュール。   The intermediate ion exchange membrane is an anion exchange membrane, the first ion exchanger is a laminate of a monolithic organic porous anion exchanger and a monolithic organic porous cation exchanger, and the second ion exchanger is a monolith. The deionization module according to claim 2, wherein the deionization module is an organic porous anion exchanger. 前記請求項１〜５のいずれか１項に記載の脱イオンモジュールを備える電気式脱イオン水製造装置。   An electric deionized water production apparatus comprising the deionization module according to any one of claims 1 to 5.
JP2009116426A 2009-03-10 2009-05-13 Deionization module and electric deionized water production apparatus Expired - Fee Related JP5383310B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2009116426A JP5383310B2 (en) 2009-05-13 2009-05-13 Deionization module and electric deionized water production apparatus
PCT/JP2010/053653 WO2010104007A1 (en) 2009-03-10 2010-03-05 Deionization module and electric device for producing deionized water
TW99106881A TW201038490A (en) 2009-03-10 2010-03-10 Deionizing module and electric deionized water production apparatus

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2009116426A JP5383310B2 (en) 2009-05-13 2009-05-13 Deionization module and electric deionized water production apparatus

Publications (2)

Publication Number Publication Date
JP2010264360A true JP2010264360A (en) 2010-11-25
JP5383310B2 JP5383310B2 (en) 2014-01-08

Family

ID=43361840

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2009116426A Expired - Fee Related JP5383310B2 (en) 2009-03-10 2009-05-13 Deionization module and electric deionized water production apparatus

Country Status (1)

Country Link
JP (1) JP5383310B2 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010264362A (en) * 2009-05-13 2010-11-25 Japan Organo Co Ltd Electric deionized-water producing apparatus
JP2010264361A (en) * 2009-05-13 2010-11-25 Japan Organo Co Ltd Electric deionized-water producing apparatus
JP2010264375A (en) * 2009-05-14 2010-11-25 Japan Organo Co Ltd Electric deionized-water producing apparatus
JP2010284639A (en) * 2009-05-14 2010-12-24 Japan Organo Co Ltd Electric apparatus for producing deionized water and method for operating the apparatus
WO2011152226A1 (en) * 2010-06-03 2011-12-08 オルガノ株式会社 Electric device for production of deionized water
WO2011152227A1 (en) * 2010-06-03 2011-12-08 オルガノ株式会社 Electric device for producing deionized water
WO2012108310A1 (en) * 2011-02-08 2012-08-16 オルガノ株式会社 Electric device for producing deionized water
JP2013000720A (en) * 2011-06-21 2013-01-07 Japan Organo Co Ltd Electric device for producing deionized water
JP2013000721A (en) * 2011-06-21 2013-01-07 Japan Organo Co Ltd Electric deionized water production apparatus
JP2013000723A (en) * 2011-06-21 2013-01-07 Japan Organo Co Ltd Electric deionized water production apparatus
JP5661930B2 (en) * 2011-08-04 2015-01-28 オルガノ株式会社 Electric deionized water production equipment
CN111615497A (en) * 2018-01-19 2020-09-01 奥加诺株式会社 Electric deionizing device for producing deionized water

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002083770A1 (en) * 2001-04-13 2002-10-24 Organo Corporation Composite porous ion-exchanger, method of manufacturing the ion-exchanger, deionization module using the ion- exchanger, and electric deionized water manufacturing device
JP2003230886A (en) * 2002-02-08 2003-08-19 Japan Organo Co Ltd Electric deionized water making apparatus
JP2003334560A (en) * 2002-05-15 2003-11-25 Japan Organo Co Ltd Electric deionized water producing apparatus
JP2006159064A (en) * 2004-12-06 2006-06-22 Japan Organo Co Ltd Electric deionized liquid production apparatus and method for producing deionized liquid
WO2008016055A1 (en) * 2006-08-02 2008-02-07 Kurita Water Industries Ltd. Electrodeionizer
JP2008055388A (en) * 2006-09-04 2008-03-13 Japan Organo Co Ltd Electric deionized water making apparatus and its operation method
JP2009019187A (en) * 2007-06-12 2009-01-29 Japan Organo Co Ltd Monolith-shaped organic porous body, its manufacturing method, monolith-shaped organic porous ion exchanger and chemical filter
JP2009035668A (en) * 2007-08-03 2009-02-19 Japan Organo Co Ltd Monolithic organic porous ion exchanger, method of use thereof, production method of the same, and casting mold used in production of the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002083770A1 (en) * 2001-04-13 2002-10-24 Organo Corporation Composite porous ion-exchanger, method of manufacturing the ion-exchanger, deionization module using the ion- exchanger, and electric deionized water manufacturing device
JP2003230886A (en) * 2002-02-08 2003-08-19 Japan Organo Co Ltd Electric deionized water making apparatus
JP2003334560A (en) * 2002-05-15 2003-11-25 Japan Organo Co Ltd Electric deionized water producing apparatus
JP2006159064A (en) * 2004-12-06 2006-06-22 Japan Organo Co Ltd Electric deionized liquid production apparatus and method for producing deionized liquid
WO2008016055A1 (en) * 2006-08-02 2008-02-07 Kurita Water Industries Ltd. Electrodeionizer
JP2008055388A (en) * 2006-09-04 2008-03-13 Japan Organo Co Ltd Electric deionized water making apparatus and its operation method
JP2009019187A (en) * 2007-06-12 2009-01-29 Japan Organo Co Ltd Monolith-shaped organic porous body, its manufacturing method, monolith-shaped organic porous ion exchanger and chemical filter
JP2009035668A (en) * 2007-08-03 2009-02-19 Japan Organo Co Ltd Monolithic organic porous ion exchanger, method of use thereof, production method of the same, and casting mold used in production of the same

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010264362A (en) * 2009-05-13 2010-11-25 Japan Organo Co Ltd Electric deionized-water producing apparatus
JP2010264361A (en) * 2009-05-13 2010-11-25 Japan Organo Co Ltd Electric deionized-water producing apparatus
JP2010264375A (en) * 2009-05-14 2010-11-25 Japan Organo Co Ltd Electric deionized-water producing apparatus
JP2010284639A (en) * 2009-05-14 2010-12-24 Japan Organo Co Ltd Electric apparatus for producing deionized water and method for operating the apparatus
JP5385457B2 (en) * 2010-06-03 2014-01-08 オルガノ株式会社 Electric deionized water production equipment
WO2011152226A1 (en) * 2010-06-03 2011-12-08 オルガノ株式会社 Electric device for production of deionized water
WO2011152227A1 (en) * 2010-06-03 2011-12-08 オルガノ株式会社 Electric device for producing deionized water
US8871073B2 (en) 2010-06-03 2014-10-28 Organo Corporation Electrodeionization apparatus for producing deionized water
WO2012108310A1 (en) * 2011-02-08 2012-08-16 オルガノ株式会社 Electric device for producing deionized water
JP2012161758A (en) * 2011-02-08 2012-08-30 Japan Organo Co Ltd Electric device for producing deionized water
KR101526093B1 (en) * 2011-02-08 2015-06-04 오르가노 가부시키가이샤 Electric device for producing deionized water
CN103370281A (en) * 2011-02-08 2013-10-23 奥加诺株式会社 Electric deionization device for producing deionized water
JP2013000720A (en) * 2011-06-21 2013-01-07 Japan Organo Co Ltd Electric device for producing deionized water
JP2013000723A (en) * 2011-06-21 2013-01-07 Japan Organo Co Ltd Electric deionized water production apparatus
JP2013000721A (en) * 2011-06-21 2013-01-07 Japan Organo Co Ltd Electric deionized water production apparatus
JP5661930B2 (en) * 2011-08-04 2015-01-28 オルガノ株式会社 Electric deionized water production equipment
US9896357B2 (en) 2011-08-04 2018-02-20 Organo Corporation Electrodeionization apparatus for producing deionized water
CN111615497A (en) * 2018-01-19 2020-09-01 奥加诺株式会社 Electric deionizing device for producing deionized water
CN111615497B (en) * 2018-01-19 2022-05-31 奥加诺株式会社 Electric deionizing device for producing deionized water

Also Published As

Publication number Publication date
JP5383310B2 (en) 2014-01-08

Similar Documents

Publication Publication Date Title
JP5383310B2 (en) Deionization module and electric deionized water production apparatus
JP4633955B2 (en) Porous ion exchanger, deionization module and electric deionized water production apparatus using the same
JP3773190B2 (en) Electric deionized water production equipment
JP4453982B2 (en) Method for producing composite porous ion exchanger
TW200303782A (en) Electrodeionization water producing apparatus and method of producing deionized water using same
JP5864648B2 (en) Deionization module and electric deionized water production apparatus
JP5864649B2 (en) Electric deionized water production equipment
JP5137896B2 (en) Electric deionized water production apparatus and deionized water production method
JP5030181B2 (en) Electric deionized water production equipment
JP5431196B2 (en) Electric deionized water production apparatus and operation method thereof
JP5048712B2 (en) Electric deionized water production equipment
JP5431194B2 (en) Electric deionized water production equipment
JP5431195B2 (en) Electric deionized water production equipment
WO2010104007A1 (en) Deionization module and electric device for producing deionized water
JP5431197B2 (en) Electric deionized liquid production equipment
JP2010264345A (en) Ion adsorption module and water treatment method
JP5718435B2 (en) Ion chromatography device column, suppressor and ion chromatography device
JP5586979B2 (en) Electric deionized water production apparatus and operation method thereof
JP5497468B2 (en) Electric deionized water production equipment
KR20200116516A (en) Ultrapure water production method, ultrapure water production system and ion exchanger charging module
JP5030182B2 (en) Electric deionized liquid production equipment

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20120417

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20130904

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20131001

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

LAPS Cancellation because of no payment of annual fees