JP6694346B2 - Iodic acid and / or antimony adsorbent - Google Patents
Iodic acid and / or antimony adsorbent Download PDFInfo
- Publication number
- JP6694346B2 JP6694346B2 JP2016144884A JP2016144884A JP6694346B2 JP 6694346 B2 JP6694346 B2 JP 6694346B2 JP 2016144884 A JP2016144884 A JP 2016144884A JP 2016144884 A JP2016144884 A JP 2016144884A JP 6694346 B2 JP6694346 B2 JP 6694346B2
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- JP
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- Prior art keywords
- antimony
- iodic acid
- adsorbent
- organic polymer
- oxide
- 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.)
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Images
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、液体中のヨウ素酸及び／又はアンチモンを吸着する吸着材及び吸着処理装置に関する。より詳しくは、本発明は、無機イオン吸着体と有機高分子樹脂を含有する多孔性粒状成形体の形態にあるヨウ素酸及び／又はアンチモン吸着材であって、無機イオン吸着体と外表面開口率がそれぞれ特定範囲内にあるもの、該吸着剤の製造方法、該吸着材を用いたヨウ素酸及び／又はアンチモン吸着処理装置、及び該吸着材の分散体に関する。 The present invention relates to an adsorbent that adsorbs iodic acid and / or antimony in a liquid and an adsorption treatment device. More specifically, the present invention relates to an iodic acid and / or antimony adsorbent in the form of a porous granular molding containing an inorganic ion adsorbent and an organic polymer resin, wherein the inorganic ion adsorbent and the outer surface opening ratio are Within a specific range, a method for producing the adsorbent, an iodic acid and / or antimony adsorption treatment apparatus using the adsorbent, and a dispersion of the adsorbent.
原子力設備において、原子炉格納容器や圧力容器から排出される廃水には、放射性ヨウ素酸や放射性アンチモンなどの放射性物質が含有されている。そのため、これらの廃水をそのまま原子力設備外に排出することはできず、廃水中の放射性物質を規制値以下に下げる必要がある。特に、福島原発においては事故の影響で多量の放射性物質を含む廃水が排出され続けている。放射性物質は、それぞれの放射性元素に適した吸着材をタンクに充填して廃水を通液することで吸着除去している。 In nuclear facilities, wastewater discharged from a reactor containment vessel and a pressure vessel contains radioactive substances such as radioactive iodic acid and radioactive antimony. Therefore, these wastewaters cannot be discharged as they are out of the nuclear facility, and it is necessary to reduce the radioactive substances in the wastewater to below the regulation value. In particular, at the Fukushima nuclear power plant, wastewater containing a large amount of radioactive substances continues to be discharged due to the impact of the accident. Radioactive substances are adsorbed and removed by filling the tank with an adsorbent suitable for each radioactive element and passing the wastewater.
以下の特許文献１には、ゼオライト、アルミナ、シリカ、チタニアなどの無機酸化物を担体として、Ｐｄをイオン交換法、浸漬法等で含有させたヨウ素酸捕捉材を水槽内に充填配置してヨウ素酸イオンを含む廃水からヨウ素酸を除去する方法が開示されている。
しかしながら、特許文献１に開示されるヨウ素酸捕捉材では、イオン吸着体の担持量が少ないため、吸着処理に供する際に、吸着処理液量が少ない段階からヨウ素酸が吸着されずに吸着処理液中に漏れ出す現象、いわゆる破過現象が認められる。また、担体として無機酸化物を使用するため細孔径が小さく、ヨウ素酸が捕捉材の内部にまで到達しにくい。高い通液速度での吸着処理に供した場合、すなわち、液体とヨウ素酸捕捉材との接触時間が短い吸着処理に供した場合には、ヨウ素酸捕捉材の表面近傍しか吸着処理に寄与しないため、吸着処理液量が少ない段階から破過現象が認められるため、ヨウ素酸捕捉材の交換頻度が高くなることで廃棄物となる捕捉材の量が多くなるという問題がある。
In
However, in the iodic acid-capturing material disclosed in
また、以下の特許文献２には、無機イオン吸着体を含有する、水酸基を有する有機高分子樹脂（ポリエーテルスルホン樹脂及び／又はポリスルホン樹脂）の多孔性成形体が開示されている。
しかしながら、特許文献２に開示されている多孔性成形体は、無機イオン吸着体と有機高分子樹脂の親和性が高いため、無機イオン吸着体が強く担持されており、繰り返し使用しても破砕することが少ない利点がある。また、無機イオン吸着体の担持量をさらに増やそうと仕込みの無機イオン吸着体量を増やすと、多孔性成形体から無機イオン吸着体が脱離する、いわゆる粉落ちが起こるという問題がある。
Further,
However, since the porous molded article disclosed in
上記従来技術の問題に鑑み、本発明が解決しようとする課題は、ヨウ素酸及び／又はアンチモンを含有する液体から、高速で通液しても長期間破過することなくヨウ素酸及び／又はアンチモンを吸着除去でき、かつ無機イオン吸着体の脱離が起こらない吸着材を提供することである。 In view of the above-mentioned problems of the prior art, the problem to be solved by the present invention is to solve the problem that the liquid containing iodic acid and / or antimony is iodic acid and / or antimony without breakthrough for a long time even when it is passed at a high speed. It is an object of the present invention to provide an adsorbent capable of adsorbing and removing hydrogen and not desorbing an inorganic ion adsorbent.
本発明者らは、上記課題を解決すべく鋭意検討し実験を重ねた結果、無機イオン吸着体と有機高分子樹脂を含有する多孔性粒状成形体の形態にあるヨウ素酸及び／又はアンチモン吸着材であって、無機イオン吸着体と外表面開口率がそれぞれ特定範囲内にあるものによって、上記課題を解決できることを見出し、本発明を完成するに至ったものである。 As a result of intensive studies and experiments to solve the above problems, the present inventors have found that iodic acid and / or antimony adsorbent in the form of a porous granular molding containing an inorganic ion adsorbent and an organic polymer resin. However, the inventors have found that the above-mentioned problems can be solved by the inorganic ion adsorbent and the outer surface aperture ratio being within specific ranges, respectively, and have completed the present invention.
すなわち、本発明は、以下のとおりのものである。
［１］無機イオン吸着体と有機高分子樹脂を含有する多孔性粒状成形体の形態にあるヨウ素酸及び／又はアンチモン吸着材であって、該多孔性粒状成形体の該無機イオン吸着体の担持量は、０．６〜１．２ｇ／ｍＬであり、かつ、該多孔性粒状成形体の３０ｎｍ以上の孔の外表面開口率は、３％以上１７％未満である、前記ヨウ素酸及び／又はアンチモン吸着材。
［２］前記無機イオン吸着体が、下記式（Ｉ）：
ＭＮｘＯｎ・ｍＨ２Ｏ ・・・（Ｉ）
｛式中、ｘは０〜３の数であり、ｎは１〜４の数であり、ｍは０〜６の数であり、Ｍ及びＮは、互いに独立して、Ｔｉ、Ｚｒ、Ｓｎ、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ａｌ、Ｓｉ、Ｃｒ、Ｃｏ、Ｇａ、Ｆｅ、Ｍｎ、Ｎｉ、Ｖ、Ｇｅ、Ｎｂ及びＴａからなる群から選ばれる金属元素である。｝で表される少なくとも一種の金属酸化物である、前記［１］に記載のヨウ素酸及び／又はアンチモン吸着材。
［３］前記金属酸化物が、下記（ａ）〜（ｃ）：
（ａ）水和酸化チタン、水和酸化ジルコニウム、水和酸化スズ、水和酸化セリウム、水和酸化ランタン及び水和酸化イットリウム、
（ｂ）チタン、ジルコニウム、スズ、セリウム、ランタン及びイットリウムからなる群から選ばれる少なくとも一種の金属元素と、アルミニウム、珪素及び鉄からなる群から選ばれる少なくとも一種の金属元素との複合金属酸化物、
（ｃ）活性アルミナ、
のいずれかの群から選ばれる少なくとも一種である、前記［２］に記載のヨウ素酸及び／又はアンチモン吸着材。
［４］前記多孔性粒状成形体は、平均粒径が１００〜２５００μｍの球状粒子である、前記［１］〜［３］のいずれかに記載のヨウ素酸及び／又はアンチモン吸着材。
［５］前記有機高分子樹脂が、エチレンビニルアルコール共重合体（ＥＶＯＨ）、ポリアクリロニトリル（ＰＡＮ）、ポリスルホン（ＰＳ）、ポリエーテルスルホン（ＰＥＳ）及びポリフッ化ビニリデン（ＰＶＤＦ）からなる群から選ばれる少なくとも一種である、前記［１］〜［４］のいずれかに記載のヨウ素酸及び／又はアンチモン吸着材。
［６］以下の工程：
（１）有機高分子樹脂の良溶媒と無機イオン吸着体を粉砕・混合してスラリーを得る工程、
（２）工程（１）で得られたスラリーに有機高分子樹脂を溶解して混合スラリーを得る工程、
（３）工程（２）で得られた混合スラリーを成形する工程、
（４）工程（３）で得られた成形品が接触する空間部の温度と湿度を制御して、該成形品の凝固を促進させる工程、
（５）工程（４）で得られた凝固が促進された成形品を、前記有機高分子樹脂の貧溶媒と良溶媒の混合液中10℃〜60℃の温度で凝固させる工程、
を含む、前記［１］〜［５］のいずれかに記載のヨウ素酸及び／又はアンチモン吸着材の製造方法。
［７］処理水導入口と導出口を有するカラムに前記［１］〜［５］のいずれかに記載のヨウ素酸及び／又はアンチモン吸着材が充填されたカラムと、該導出口より得られた処理水中のヨウ素酸及び／又はアンチモンを検出する検出器とを具備する、ヨウ素酸及び／又はアンチモン吸着処理装置。
［８］前記［１］〜［５］のいずれかに記載のヨウ素酸及び／又はアンチモン吸着材が水に分散している、ヨウ素酸及び／又はアンチモン吸着材の分散体。
That is, the present invention is as follows.
[1] An iodic acid and / or antimony adsorbent in the form of a porous granular shaped body containing an inorganic ion adsorbent and an organic polymer resin, wherein the inorganic ion adsorbent is supported on the porous granular shaped body. The amount of the iodic acid and / or the amount is 0.6 to 1.2 g / mL, and the outer surface open area ratio of the pores of 30 nm or more of the porous granular molded body is 3% or more and less than 17%. Antimony adsorbent.
[2] The inorganic ion adsorbent has the following formula (I):
MN x O n · mH 2 O (I)
{In the formula, x is a number of 0 to 3, n is a number of 1 to 4, m is a number of 0 to 6, M and N independently of each other are Ti, Zr, Sn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, Cr, Co, Ga, Fe, Mn, Ni, V, It is a metal element selected from the group consisting of Ge, Nb and Ta. } The iodic acid and / or antimony adsorbent according to the above [1], which is at least one metal oxide represented by the following formula.
[3] The metal oxide has the following (a) to (c):
(A) hydrated titanium oxide, hydrated zirconium oxide, hydrated tin oxide, hydrated cerium oxide, hydrated lanthanum oxide and hydrated yttrium oxide,
(B) a composite metal oxide of at least one metal element selected from the group consisting of titanium, zirconium, tin, cerium, lanthanum and yttrium and at least one metal element selected from the group consisting of aluminum, silicon and iron,
(C) activated alumina,
The iodic acid and / or antimony adsorbent according to the above [2], which is at least one selected from the group of:
[4] The iodic acid and / or antimony adsorbent according to any of [1] to [3], wherein the porous granular molded body is spherical particles having an average particle size of 100 to 2500 μm.
[5] The organic polymer resin is selected from the group consisting of ethylene vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), polysulfone (PS), polyether sulfone (PES) and polyvinylidene fluoride (PVDF). The iodic acid and / or antimony adsorbent according to any one of the above [1] to [4], which is at least one kind.
[6] The following steps:
(1) A step of pulverizing and mixing a good solvent of an organic polymer resin and an inorganic ion adsorbent to obtain a slurry,
(2) Step (1) obtaining a slurry in an organic polymer trees mixed slurry to dissolve the fat obtained in,
(3) a step of shaping the mixed slurry obtained in the step (2),
(4) A step of controlling the temperature and humidity of a space portion in contact with the molded article obtained in the step (3) to accelerate the solidification of the molded article,
(5) A step of coagulating the molded article having accelerated coagulation obtained in the step (4) at a temperature of 10 ° C to 60 ° C in a mixed solution of the poor solvent and the good solvent of the organic polymer resin,
The method for producing an iodic acid and / or antimony adsorbent according to any one of [1] to [5] above, comprising:
[7] A column having treated water inlets and outlets filled with the iodic acid and / or antimony adsorbent according to any one of the above [1] to [5], and a column obtained from the outlets. An iodic acid and / or antimony adsorption treatment apparatus comprising a detector for detecting iodic acid and / or antimony in treated water.
[8] A dispersion of iodic acid and / or antimony adsorbent, wherein the iodic acid and / or antimony adsorbent according to any one of [1] to [5] is dispersed in water.
本発明に係るヨウ素酸及び／又はアンチモン吸着材は、無機イオン吸着体の担持量が０．６〜１．２ｇ／ｍＬと高く、かつ、３０ｎｍ以上の孔の外表面開口率が３％以上１７％未満であるため、ヨウ素酸及び／又はアンチモンを含有する液体を高速で通液しても長期間破過することなくヨウ素酸及び／又はアンチモンを吸着除去でき、かつ無機イオン吸着体の脱離が起こらない吸着材を提供することができる。 The iodic acid and / or antimony adsorbent according to the present invention has a high supported amount of the inorganic ion adsorbent of 0.6 to 1.2 g / mL , and the outer surface open area ratio of the pores of 30 nm or more is 3% or more. Since it is less than 17%, even if a liquid containing iodic acid and / or antimony is passed at a high speed, iodic acid and / or antimony can be adsorbed and removed without breakthrough for a long period of time, and the inorganic ion adsorbent can be removed. It is possible to provide an adsorbent that does not separate.
以下、本発明を実施するための形態（以下、「本実施形態」という。）について以下詳細に説明する。尚、本発明は本実施形態に限定されるものでなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, modes for carrying out the present invention (hereinafter, referred to as “this embodiment”) will be described in detail below. It should be noted that the present invention is not limited to this embodiment, and various modifications can be carried out within the scope of the gist thereof.
（ヨウ素酸及び／又はアンチモン吸着材）
本実施形態のヨウ素酸及び／又はアンチモン吸着材は、無機イオン吸着体と有機高分子樹脂を含有する多孔性粒状成形体の形態にあるヨウ素酸及び／又はアンチモン吸着材であって、該多孔性粒状成形体の該無機イオン吸着体の担持量は、０．６〜１．２ｇ／ｍＬであり、かつ、該多孔性粒状成形体の３０ｎｍ以上の孔の外表面開口率は、３％以上１７％未満である、前記ヨウ素酸及び／又はアンチモン吸着材である。多孔性粒状成形体は、連通孔を有し多孔質な構造を有する。
(Iodine acid and / or antimony adsorbent)
The iodic acid and / or antimony adsorbent of the present embodiment is an iodic acid and / or antimony adsorbent in the form of a porous granular molded body containing an inorganic ion adsorbent and an organic polymer resin, The amount of the inorganic ion adsorbent supported on the granular molded body is 0.6 to 1.2 g / mL , and the outer surface open area ratio of the pores of 30 nm or more of the porous granular molded body is 3% or more. The iodic acid and / or antimony adsorbent is less than 17%. The porous granular molding has a porous structure having communicating holes.
本実施形態における多孔性粒状成形体の無機イオン吸着体の担持量は、０．６〜１．２ｇ／ｍＬであり、好ましくは０．７〜１．１ｇ／ｍＬである。 The amount of the inorganic ion adsorbent supported on the porous granular molded body in the present embodiment is 0.6 to 1.2 g / mL, and preferably 0.7 to 1.1 g / mL.
多孔性粒状成形体の３０ｎｍ以上の孔の外表面開口率は、３％以上１７％未満であり、好ましくは４％以上１５％未満であり、さらに好ましくは５％以上１３％未満であり、よりさらに好ましくは７〜８％である。
本実施形態において、外表面開口率とは、走査型電子顕微鏡で多孔性成形体の外表面を観察した視野の面積中に占める３０ｎｍ以上の孔の開口面積の和の割合を意味する。
３０ｎｍ以上の孔からなる外表面開口率が３％以上であれば、ヨウ素酸やアンチモン等の吸着対象物質が吸着材内部にまで浸透しやすく、吸着材を効率よく使用することができる。他方、３０ｎｍ以上の孔からなる外表面開口率が１７％未満であれば、無機イオン吸着体の担持量が０．６〜１．２ｇ／ｍＬと非常に大きい場合でも、多孔性粒状成形体からの無機イオン吸着体の脱離を防ぐことができる。
本実施形態においては、１００，０００倍で多孔性粒状成形体の外表面を観察して外表面開口率を実測する。具体的には、実施例に記載の方法により、外表面開口率を測定することができる。
The outer surface open area ratio of 30 nm or more pores of the porous granular molded body is 3% or more and less than 17%, preferably 4% or more and less than 15%, more preferably 5% or more and less than 13%, and More preferably, it is 7 to 8%.
In the present embodiment, the outer surface opening ratio means the ratio of the sum of the opening areas of pores of 30 nm or more in the area of the visual field when the outer surface of the porous molded body is observed with a scanning electron microscope.
When the outer surface open area ratio of pores of 30 nm or more is 3% or more, a substance to be adsorbed such as iodic acid or antimony easily penetrates into the adsorbent, and the adsorbent can be used efficiently. On the other hand, if the outer surface open area ratio of pores of 30 nm or more is less than 17%, even if the amount of the inorganic ion adsorbent supported is very large at 0.6 to 1.2 g / mL, it will be It is possible to prevent desorption of the inorganic ion adsorbent.
In this embodiment, the outer surface aperture ratio is measured by observing the outer surface of the porous granular molded body at 100,000 times. Specifically, the outer surface aperture ratio can be measured by the method described in the examples.
本実施形態における多孔性粒状成形体は、実質的に球状であり、その平均粒径は、好ましくは１００〜２５００μｍ、より好ましくは１５０〜２０００μｍ、さらに好ましくは２００〜１５００μｍである。
本実施形態の多孔性粒状成形体は、実質的に球状粒子であることが好ましく、球状粒子は、真球状のみならず、楕円球状であってもよい。
平均粒径が１００μｍ以上であれば、多孔性粒状成形体をカラムやタンク等へ充填した際に圧カ損失が小さいため高速通水処理に適している。他方、平均粒径が２５００μｍ以下であれば、多孔性粒状成形体をカラムやタンクに充填したときの表面積を大きくすることができ、高速で通液処理してもイオンを確実に吸着することができる。
本実施形態において、平均粒径は、多孔性粒状成形体を球状とみなして、レーザー光による回折の散乱光強度の角度分布から求めた球相当径のメディアン径を意味する。
The porous granular molded body in the present embodiment has a substantially spherical shape, and the average particle size thereof is preferably 100 to 2500 μm, more preferably 150 to 2000 μm, and further preferably 200 to 1500 μm.
The porous granular molded article of the present embodiment is preferably substantially spherical particles, and the spherical particles may be not only spherical but elliptic spherical.
When the average particle diameter is 100 μm or more, the loss of pressure force when the porous granular molded body is packed in a column, a tank or the like is small, which is suitable for high-speed water flow treatment. On the other hand, if the average particle diameter is 2500 μm or less, the surface area of the porous granular molded body when packed in a column or a tank can be increased, and ions can be reliably adsorbed even when the liquid is passed through at high speed. it can.
In the present embodiment, the average particle diameter means a median diameter of a sphere-equivalent diameter obtained from the angular distribution of scattered light intensity of diffraction by laser light, regarding the porous granular molded body as a spherical shape.
本実施形態の多孔性粒状成形体のかさ比重の測定方法は、以下のとおりである。
多孔性成形体が、球状、円柱状、中空円柱状等であり、その形状が短いものは、湿潤状態の多孔性粒状成形体を、メスシリンダー等を用いて、１ｍＬを１ｃｍ３としてみかけの体積を測定する。その後、室温で真空乾燥して重量を求め、重量／体積として、かさ比重を算出する。
多孔性粒状成形体が、糸状、中空糸状、シート状等であり、その形状が長いものは、湿潤時の断面積と長さを測定して、両者の積から体積を算出する。その後、室温で真空乾燥して重量を求め、重量／体積として、かさ比重を算出する。
本実施形態の多孔性成形体のかさ比重は、０．８２ｇ／ｃｍ３以上、好ましくは０．９５ｇ／ｃｍ３以上であり、上限は、好ましくは１．３５ｇ／ｃｍ３以下である。かさ比重が０．８２ｇ／ｃｍ３以上になるほど破過通液倍率が高くなる傾向にあり、他方、１．３５ｇ／ｃｍ３以下であれば粉落ちが少なくなる傾向がある。
The method for measuring the bulk specific gravity of the porous granular molded body of this embodiment is as follows.
The porous molded body has a spherical shape, a cylindrical shape, a hollow cylindrical shape, or the like, and if the shape is short, a porous granular molded body in a wet state is used to measure an apparent volume of 1 mL as 1 cm 3 using a graduated cylinder or the like. To measure. Then, it is vacuum dried at room temperature to obtain the weight, and the bulk specific gravity is calculated as the weight / volume.
If the porous granular molded body is in the form of a thread, a hollow fiber, a sheet, or the like and has a long shape, the cross-sectional area and length when wet are measured, and the volume is calculated from the product of the two. Then, it is vacuum dried at room temperature to obtain the weight, and the bulk specific gravity is calculated as the weight / volume.
The bulk specific gravity of the porous molded article of the present embodiment is 0.82 g / cm 3 or more, preferably 0.95 g / cm 3 or more, and the upper limit is preferably 1.35 g / cm 3 or less. If the bulk specific gravity is 0.82 g / cm 3 or more, the breakthrough liquid ratio tends to be high, while if it is 1.35 g / cm 3 or less, powder drop tends to be small.
（有機高分子樹脂）
本実施形態における多孔性粒状成形体を構成する有機高分子樹脂は、特に限定されないが、湿式相分離による多孔化手法が可能な樹脂であることが好ましい。
有機高分子樹脂としては、例えば、ポリスルホン系ポリマー、ポリフッ化ビニリデン系ポリマー、ポリ塩化ビニリデン系ポリマー、アクリロニトリル系ポリマー、ポリメタクリル酸メチル系ポリマー、ポリアミド系ポリマー、ポリイミド系ポリマー、セルロース系ポリマー、エチレンビニルアルコール共重合体系ポリマー、多糖類等が挙げられる。
中でも、水中での非膨潤性と耐生分解性、さらに製造の容易さから、エチレンビニルアルコール共重合体（ＥＶＯＨ）、ポリアクリロニトリル（ＰＡＮ）、ポリスルホン（ＰＳ）、ポリエーテルスルホン（ＰＥＳ）及びポリフッ化ビニリデン（ＰＶＤＦ）が好ましい。
ポリエーテルスルホンは、末端に水酸基を有しているものが好ましい。末端基として水酸基を有していることによって、本実施形態の多孔性粒状成形体において、優れた無機イオン吸着体の担持性能が発揮できる。加えて、疎水性が高い有機高分子樹脂が、末端に水酸基を有しているため親水性が向上し、多孔性成形体にファウリングが発生しにくい。
(Organic polymer resin)
The organic polymer resin that constitutes the porous granular molded body in the present embodiment is not particularly limited, but is preferably a resin that allows a porosification method by wet phase separation.
Examples of the organic polymer resin include polysulfone-based polymers, polyvinylidene fluoride-based polymers, polyvinylidene chloride-based polymers, acrylonitrile-based polymers, polymethyl methacrylate-based polymers, polyamide-based polymers, polyimide-based polymers, cellulose-based polymers, ethylene vinyl. Examples thereof include alcohol copolymer polymers and polysaccharides.
Among them, ethylene vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), polysulfone (PS), polyether sulfone (PES) and polyfluoride are preferred because of their non-swelling property in water, biodegradation resistance, and ease of production. Vinylidene chloride (PVDF) is preferred.
The polyether sulfone preferably has a hydroxyl group at the terminal. By having a hydroxyl group as a terminal group, the porous granular molded article of the present embodiment can exhibit excellent performance of supporting an inorganic ion adsorbent. In addition, since the organic polymer resin having high hydrophobicity has a hydroxyl group at the terminal, hydrophilicity is improved, and fouling hardly occurs in the porous molded body.
（無機イオン吸着体）
本実施形態における多孔性粒状成形体を構成する無機イオン吸着体とは、イオン吸着現象又はイオン交換現象を示す無機物質を意味する。
天然物系の無機イオン吸着体としては、例えば、ゼオライト、モンモリロナイト等の各種の鉱物性物質等が挙げられる。
各種の鉱物性物質の具体例としては、アルミノケイ酸塩で単一層格子をもつカオリン鉱物、２層格子構造の白雲母、海緑石、鹿沼土、パイロフィライト、タルク、３次元骨組み構造の長石、ゼオライト、モンモリロナイト等が挙げられる。
合成物系の無機イオン吸着体としては、例えば、金属酸化物、多価金属の塩及び不溶性の含水酸化物等が挙げられる。金属酸化物としては、複合金属酸化物、複合金属水酸化物及び金属の含水酸化物等を含む。
(Inorganic ion adsorbent)
The inorganic ion adsorbent constituting the porous granular molded body in the present embodiment means an inorganic substance exhibiting an ion adsorption phenomenon or an ion exchange phenomenon.
Examples of natural inorganic ion adsorbents include various mineral substances such as zeolite and montmorillonite.
Specific examples of various mineral substances include kaolin minerals having a single layer lattice of aluminosilicate, muscovite with two-layer lattice structure, glauconite, Kanuma soil, pyrophyllite, talc, and feldspar with three-dimensional framework structure. , Zeolite, montmorillonite and the like.
Examples of the synthetic inorganic ion adsorbents include metal oxides, polyvalent metal salts, insoluble hydrous oxides, and the like. The metal oxide includes a composite metal oxide, a composite metal hydroxide, a metal hydrous oxide and the like.
無機イオン吸着体は、吸着対象物、中でも、ヨウ素酸及び／又はアンチモンの吸着性能の観点で、下記式（Ｉ）：
ＭＮｘＯｎ・ｍＨ２Ｏ ・・・（Ｉ）
で表される金属酸化物を含有することが好ましい。
上記式（Ｉ）中、ｘは０〜３の数であり、ｎは１〜４の数であり、ｍは０〜６であり、Ｍ及びＮは、互いに独立して、Ｔｉ、Ｚｒ、Ｓｎ、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ａｌ、Ｓｉ、Ｃｒ、Ｃｏ、Ｇａ、Ｆｅ、Ｍｎ、Ｎｉ、Ｖ、Ｇｅ、Ｎｂ及びＴａからなる群から選ばれる金属元素である。
金属酸化物は、上記式（Ｉ）中のｍが０である未含水（未水和）の金属酸化物であってもよいし、ｍが０以外の数値である金属の含水酸化物（水和金属酸化物）であってもよい。
上記式（Ｉ）中のｘが０以外の数値である場合の金属酸化物は、含有される各金属元素が規則性を持って酸化物全体に均一に分布し、金属酸化物に含有される各金属元素の組成比が一定に定まった化学式で表される複合金属酸化物である。
具体的には、ペロブスカイト構造、スピネル構造等を形成するもの、ニッケルフェライト（ＮｉＦｅ２Ｏ４）、ジルコニウムの含水亜鉄酸塩（Ｚｒ・Ｆｅ２Ｏ４・ｍＨ２Ｏ、ここで、ｍは０．５〜６である。）等が挙げられる。
無機イオン吸着体は、上記式（Ｉ）で表される金属酸化物を複数種含有していてもよい。
The inorganic ion adsorbent is represented by the following formula (I) from the viewpoint of adsorption performance of an adsorption target, especially iodic acid and / or antimony:
MN x O n · mH 2 O (I)
It is preferable to contain a metal oxide represented by
In the above formula (I), x is a number of 0 to 3, n is a number of 1 to 4, m is 0 to 6, M and N are independently of each other Ti, Zr, Sn. , Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, Cr, Co, Ga, Fe, Mn, Ni, V , Ge, Nb, and Ta are metal elements selected from the group.
The metal oxide may be a non-hydrated (unhydrated) metal oxide in which m in the formula (I) is 0, or a hydrous oxide of a metal (water A metal oxide).
In the metal oxide in the case where x in the above formula (I) is a value other than 0, each metal element contained is uniformly distributed throughout the oxide with regularity and is contained in the metal oxide. It is a composite metal oxide represented by a chemical formula in which the composition ratio of each metal element is fixed.
Specifically, those forming a perovskite structure, a spinel structure, etc., nickel ferrite (NiFe 2 O 4 ), zirconium hydrous ferrite (Zr.Fe 2 O 4 .mH 2 O, where m is 0). .5 to 6) and the like.
The inorganic ion adsorbent may contain a plurality of types of metal oxides represented by the above formula (I).
無機イオン吸着体としては、ヨウ素酸、アンチモン、リン、ホウ素、フッ素及び／又はヒ素の吸着性能に優れているという観点から、下記（ａ）〜（ｃ）：
（ａ）水和酸化チタン、水和酸化ジルコニウム、水和酸化スズ、水和酸化セリウム、水和酸化ランタン及び水和酸化イットリウム、
（ｂ）チタン、ジルコニウム、スズ、セリウム、ランタン及びイットリウムからなる群から選ばれる少なくとも一種の金属元素と、アルミニウム、珪素及び鉄からなる群から選ばれる少なくとも一種の金属元素との複合金属酸化物、
（ｃ）活性アルミナ、
のいずれかの群から選ばれる少なくとも一種であることが好ましい。
（ａ）〜（ｃ）群のいずれかの群から選択される材料であってもよく、（ａ）〜（ｃ）群のいずれかの群から選択される材料を組み合わせて用いてもよく、（ａ）〜（ｃ）群のそれぞれにおける材料を組み合わせて用いてもよい。組み合わせて用いる場合には、（ａ）〜（ｃ）群のいずれかの群から選ばれる２種以上の材料の混合物であってもよく、（ａ）〜（ｃ）群の２つ以上の群から選ばれる２種以上の材料の混合物であってもよい。
無機イオン吸着体は、安価で吸着性が高いという観点から、硫酸アルミニウム添着活性アルミナを含有してもよい。
The inorganic ion adsorbent has the following (a) to (c) from the viewpoint of excellent adsorption performance for iodic acid, antimony, phosphorus, boron, fluorine and / or arsenic:
(A) hydrated titanium oxide, hydrated zirconium oxide, hydrated tin oxide, hydrated cerium oxide, hydrated lanthanum oxide and hydrated yttrium oxide,
(B) a composite metal oxide of at least one metal element selected from the group consisting of titanium, zirconium, tin, cerium, lanthanum and yttrium and at least one metal element selected from the group consisting of aluminum, silicon and iron,
(C) activated alumina,
It is preferable that at least one selected from the group
A material selected from any of the groups (a) to (c) may be used, or a material selected from any of the groups (a) to (c) may be used in combination, The materials in each of the groups (a) to (c) may be used in combination. When used in combination, it may be a mixture of two or more kinds of materials selected from any of the groups (a) to (c), and two or more groups of the groups (a) to (c). It may be a mixture of two or more materials selected from.
The inorganic ion adsorbent may contain aluminum sulfate-impregnated activated alumina from the viewpoint of being inexpensive and having high adsorbability.
無機イオン吸着体としては、上記式（Ｉ）で表される金属酸化物に加え、上記Ｍ及びＮ以外の金属元素がさらに固溶したものは、無機イオンの吸着性や製造コストの観点から、より好ましい。
例えば、ＺｒＯ２・ｍＨ２Ｏ（ｍが０以外の数値である。）で表される水和酸化ジルコニウムに、鉄が固溶したものが挙げられる。
As the inorganic ion adsorbent, in addition to the metal oxide represented by the above formula (I), those in which a metal element other than M and N is further solid-solubilized are, from the viewpoint of adsorbability of inorganic ions and production cost, More preferable.
For example, hydrated zirconium oxide represented by ZrO 2 · mH 2 O (m is a value other than 0) in which iron is solid-dissolved can be mentioned.
多価金属の塩としては、例えば、下記式（ＩＩ）：
Ｍ２＋ （１−ｐ）Ｍ３＋ ｐ（ＯＨ−）（２＋ｐ−ｑ）（Ａｎ−）ｑ／ｒ ・・・（ＩＩ）
で表されるハイドロタルサイト系化合物が挙げられる。
上記式（ＩＩ）中、Ｍ２＋は、Ｍｇ２＋、Ｎｉ２＋、Ｚｎ２＋、Ｆｅ２＋、Ｃａ２＋及びＣｕ２＋からなる群から選ばれる少なくとも一種の二価の金属イオンである。
Ｍ３＋は、Ａｌ３＋及びＦｅ３＋からなる群から選ばれる少なくとも一種の三価の金属イオンである。
Ａｎ−は、ｎ価のアニオンである。
０．１≦ｐ≦０．５であり、０．１≦ｑ≦０．５であり、ｒは１又は２である。
上記式（ＩＩ）で表されるハイドロタルサイト系化合物は、無機イオン吸着体として原料が安価であり、吸着性が高いことから好ましい。
不溶性の含水酸化物としては、例えば、不溶性のヘテロポリ酸塩及び不溶性ヘキサシアノ鉄酸塩等が挙げられる。
Examples of the salt of polyvalent metal include the following formula (II):
M 2+ (1-p) M 3+ p (OH − ) (2 + p−q) (A n− ) q / r ... (II)
The hydrotalcite-based compound represented by
In the above formula (II), M 2+ is at least one divalent metal ion selected from the group consisting of Mg 2+ , Ni 2+ , Zn 2+ , Fe 2+ , Ca 2+ and Cu 2+ .
M 3+ is at least one trivalent metal ion selected from the group consisting of Al 3+ and Fe 3+ .
A n- is an n-valent anion.
0.1 ≦ p ≦ 0.5, 0.1 ≦ q ≦ 0.5, and r is 1 or 2.
The hydrotalcite-based compound represented by the above formula (II) is preferable because it is inexpensive as a raw material for the inorganic ion adsorbent and has high adsorbability.
Examples of the insoluble hydrous oxide include insoluble heteropolyacid salt and insoluble hexacyanoferrate.
本実施形態の多孔性粒状成形体を構成する無機イオン吸着体は、その製造方法等に起因して混入する不純物元素を、本実施形態の多孔性粒状成形体の機能を阻害しない範囲で含有していてもよい。混入する可能性がある不純物元素としては、例えば、窒素（硝酸態、亜硝酸態、アンモニウム態）、ナトリウム、マグネシウム、イオウ、塩素、カリウム、カルシウム、銅、亜鉛、臭素、バリウム、ハフニウム等が挙げられる。 The inorganic ion adsorbent constituting the porous granular molded body of the present embodiment contains an impurity element mixed due to the manufacturing method thereof, etc. within a range not impairing the function of the porous granular molded body of the present embodiment. May be. Examples of impurity elements that may be mixed include nitrogen (nitrate, nitrite, ammonium), sodium, magnesium, sulfur, chlorine, potassium, calcium, copper, zinc, bromine, barium, hafnium, and the like. Be done.
〔多孔性粒状成形体の製造方法〕
本実施形態の多孔性粒状成形体の製造方法は、（１）有機高分子樹脂の良溶媒と無機イオン吸着体を粉砕・混合してスラリーを得る工程、（２）工程（１）で得られたスラリーに有機高分子樹脂及び場合により任意成分として水溶性高分子を溶解して混合スラリーを得る工程、（３）工程（２）で得られた混合スラリーを成形する工程、（４）工程（３）で得られた成形品が接触する空間部の温度と湿度を制御して該成形品の凝固を促進させる工程、及び（５）工程（４）で得られた凝固が促進された成形品を貧溶媒中で凝固させる工程を含む。
[Method for producing porous granular molded body]
The method for producing a porous granular molded article of the present embodiment is obtained in (1) a step of pulverizing and mixing a good solvent of an organic polymer resin and an inorganic ion adsorbent to obtain a slurry, and (2) step (1). A step of dissolving the organic polymer resin and optionally a water-soluble polymer as an optional component in the slurry to obtain a mixed slurry, a step of molding the mixed slurry obtained in (3) step (2), and a step (4) ( 3) a step of controlling the temperature and humidity of the space where the molded article comes into contact to promote the solidification of the molded article, and (5) the molded article obtained in the step (4) with accelerated solidification Is coagulated in a poor solvent.
（工程（１）：粉砕・混合工程）
工程（１）において、有機高分子樹脂の良溶媒と無機イオン吸着体を、粉砕・混合してスラリーを得る。
無機イオン吸着体を有機高分子樹脂の良溶媒中で湿式粉砕することにより、無機イオン吸着体を微粒子化できる。その結果、成形後の多孔性粒状成形体に担持された無機イオン吸着体は、二次凝集物が少ないものとなる。
(Process (1): crushing / mixing process)
In step (1), a good solvent for the organic polymer resin and the inorganic ion adsorbent are crushed and mixed to obtain a slurry.
The inorganic ion adsorbent can be made into fine particles by wet pulverizing the inorganic ion adsorbent in a good solvent for the organic polymer resin. As a result, the inorganic ion adsorbent supported on the molded porous granular material has a small amount of secondary aggregates.
＜有機高分子樹脂の良溶媒＞
工程（１）における有機高分子樹脂の良溶媒としては、多孔性粒状成形体の製造条件において有機高分子樹脂を安定に１質量％を超えて溶解するものであれば、特に限定されるものではなく、従来公知のものを使用できる。
良溶媒としては、例えば、Ｎ−メチル−２ピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）等が挙げられる。
良溶媒は１種のみを用いてもよく、２種以上を混合して用いてもよい。
<Good solvent for organic polymer resin>
The good solvent for the organic polymer resin in the step (1) is not particularly limited as long as it can stably dissolve the organic polymer resin in an amount of more than 1% by mass under the manufacturing conditions of the porous granular molded body. Instead, a conventionally known one can be used.
Examples of the good solvent include N-methyl-2pyrrolidone (NMP), N, N-dimethylacetamide (DMAC), N, N-dimethylformamide (DMF) and the like.
As the good solvent, only one kind may be used, or two or more kinds may be mixed and used.
＜粉砕+混合手段＞
工程（１）において、スラリーを得るために用いられる粉砕+混合手段は、無機イオン吸着体及び有機高分子樹脂の良溶媒を合わせて粉砕・混合できるものであれば、特に限定されるものではない。
粉砕混合手段として、例えば、加圧型破壊、機械的磨砕、超音波処理等の物理的破砕方法に用いられる手段を用いることができる。
粉砕混合手段の具体例としては、ジェネレーターシャフト型ホモジナイザー、ワーリングブレンダー等のブレンダー、サンドミル、ボールミル、アトライタ、ビーズミル等の媒体撹拌型ミル、ジェットミル、乳鉢と乳棒、らいかい器、超音波処理器等が挙げられる。
中でも、粉砕効率が高く、粘度の高いものまで粉砕できることから、媒体撹拌型ミルが好ましい。
媒体撹拌型ミルに使用するボール径は、特に限定されるものではないが、０．１〜１０ｍｍであることが好ましい。ボール径が０．１ｍｍ以上であれば、ボール質量が充分あるので粉砕力があり粉砕効率が高く、ボール径が１０ｍｍ以下であれば、微粉砕する能力に優れる。
媒体攪拌型ミルに使用するボールの材質は、特に限定されるものではないが、鉄やステンレス等の金属、アルミナやジルコニア等の酸化物類、窒化ケイ素や炭化ケイ素等の非酸化物類の各種セラミック等が挙げられる。中でも、耐摩耗性に優れ、製品へのコンタミネーション（摩耗物の混入）が少ない点で、ジルコニアが優れている。
<Crushing + mixing means>
In the step (1), the pulverization + mixing means used for obtaining the slurry is not particularly limited as long as it can pulverize and mix the inorganic ion adsorbent and the good solvent of the organic polymer resin together. ..
As the pulverizing and mixing means, for example, means used in a physical crushing method such as pressure crushing, mechanical grinding, and ultrasonic treatment can be used.
Specific examples of the pulverizing and mixing means include a generator shaft type homogenizer, a blender such as a Waring blender, a media agitating mill such as a sand mill, a ball mill, an attritor, and a bead mill, a jet mill, a mortar and pestle, a raker, an ultrasonic treatment device, etc. Is mentioned.
Among them, the medium agitation type mill is preferable because it has high pulverization efficiency and can pulverize to a high viscosity.
The diameter of the balls used in the medium stirring mill is not particularly limited, but is preferably 0.1 to 10 mm. If the ball diameter is 0.1 mm or more, the mass of the ball is sufficient, so that there is a crushing force and the crushing efficiency is high.
The material of the balls used in the medium agitation mill is not particularly limited, but various metals such as metals such as iron and stainless steel, oxides such as alumina and zirconia, and non-oxides such as silicon nitride and silicon carbide. Examples include ceramics. Among them, zirconia is excellent in that it has excellent wear resistance and little contamination (contamination of wear products) with the product.
＜分散剤＞
工程（１）においては、多孔性粒状成形体の構造に影響しない範囲で、粉砕・混合する際、無機イオン吸着体を混合した有機高分子樹脂の良溶媒中に界面活性剤等の公知の分散剤を添加してもよい。
<Dispersant>
In the step (1), a known dispersion of a surfactant or the like in a good solvent of the organic polymer resin mixed with the inorganic ion adsorbent when pulverizing and mixing is performed within a range that does not affect the structure of the porous granular molded body. Agents may be added.
（工程（２）：溶解工程）
工程（２）においては、工程（１）により得られたスラリーに、有機高分子樹脂及び場合により任意成分として水溶性高分子を溶解させて、成形用（混合）スラリーを得る。
有機高分子樹脂の添加量は、有機高分子樹脂／（有機高分子樹脂＋水溶性高分子＋有機高分子樹脂の良溶媒）の割合が、３〜４０質量％となるようにすることが好ましく、４〜３０質量％であることがより好ましい。有機高分子樹脂の含有率が３質量％以上であれば、強度の高い多孔性成形体が得られ、４０質量％以下であれば、空孔率の高い多孔性粒状成形体が得られる。
(Process (2): Dissolution process)
In step (2), an organic polymer resin and optionally a water-soluble polymer as an optional component are dissolved in the slurry obtained in step (1) to obtain a molding (mixing) slurry.
The addition amount of the organic polymer resin is preferably such that the ratio of organic polymer resin / (organic polymer resin + water-soluble polymer + good solvent of organic polymer resin) is 3 to 40% by mass. It is more preferably 4 to 30% by mass. When the content of the organic polymer resin is 3% by mass or more, a porous molded product having high strength is obtained, and when the content is 40% by mass or less, a porous granular molded product having high porosity is obtained.
＜水溶性高分子＞
工程（２）における水溶性高分子は、有機高分子樹脂の良溶媒と有機高分子樹脂とに対して相溶性のあるものであれば、特に限定されるものではない。
水溶性高分子としては、天然高分子、半合成高分子、合成高分子のいずれも使用できる。
天然高分子としては、例えば、グアーガム、ローカストビーンガム、カラーギナン、アラビアゴム、トラガント、ペクチン、デンプン、デキストリン、ゼラチン、カゼイン、コラーゲン等が挙げられる。
半合成高分子としては、例えば、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、エチルヒドロキシエチルセルロース、カルボキシメチルデンプン、メチルデンプン等が挙げられる。
合成高分子としては、例えば、ポリビニルアルコール、ポリビニルピロリドン、ポリビニルメチルエーテル、カルボキシビニルポリマー、ポリアクリル酸ナトリウム、テトラエチレングリコール、トリエチレングリコール等のポリエチレングリコール類等が挙げられる。
中でも、無機イオン吸着体の担持性を高める点から、合成高分子が好ましく、多孔性が向上する点から、ポリビニルピロリドン、ポリエチレングリコール類がより好ましい。
ポリビニルピロリドンとポリエチレングリコール類の質量平均分子量は、４００〜３５，０００，０００であることが好ましく、１，０００〜１，０００，０００であることがより好ましく、２，０００〜１００，０００であることがさらに好ましい。
質量平均分子量が２，０００以上であれば、表面開口性の高い多孔性粒状成形体が得られ、１，０００，０００以下であれば、成形する時のスラリーの粘度が低いので成形が容易になる傾向がある。
水溶性高分子の質量平均分子量は、水溶性高分子を所定の溶媒に溶解し、ゲル浸透クロマトグラフィー（ＧＰＣ）分析により測定できる。
<Water-soluble polymer>
The water-soluble polymer in step (2) is not particularly limited as long as it is compatible with the good solvent of the organic polymer resin and the organic polymer resin.
As the water-soluble polymer, any of natural polymer, semi-synthetic polymer and synthetic polymer can be used.
Examples of the natural polymer include guar gum, locust bean gum, color ginnan, gum arabic, tragacanth, pectin, starch, dextrin, gelatin, casein, collagen and the like.
Examples of the semi-synthetic polymer include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl starch, methyl starch and the like.
Examples of the synthetic polymer include polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, sodium polyacrylate, polyethylene glycols such as tetraethylene glycol and triethylene glycol.
Among them, synthetic polymers are preferable from the viewpoint of enhancing the supportability of the inorganic ion adsorbent, and polyvinylpyrrolidone and polyethylene glycols are more preferable from the viewpoint of improving porosity.
The mass average molecular weight of polyvinylpyrrolidone and polyethylene glycol is preferably 400 to 35,000,000, more preferably 1,000 to 1,000,000, and more preferably 2,000 to 100,000. Is more preferable.
When the mass average molecular weight is 2,000 or more, a porous granular molded product having a high surface openability can be obtained, and when the mass average molecular weight is 1,000,000 or less, the viscosity of the slurry at the time of molding is low, which facilitates the molding. Tend to be.
The mass average molecular weight of the water-soluble polymer can be measured by dissolving the water-soluble polymer in a predetermined solvent and then performing gel permeation chromatography (GPC) analysis.
水溶性高分子の添加量は、水溶性高分子／（水溶性高分子＋有機高分子樹脂＋有機高分子樹脂の良溶媒）の割合が、０．１〜４０質量％となるようにすることが好ましく、０．５〜３０質量％であることがより好ましく、１〜１０質量％であることがさらに好ましい。
水溶性高分子の添加量が０．１質量％以上であれば、多孔性粒状成形体の外表面及び内部に三次元的に連続した網目構造を形成する繊維状の構造体を含む多孔性粒状成形体が均一に得られる。他方、水溶性高分子の添加量が４０質量％以下であれば、外表面開口率が適当であり、多孔性粒状成形体の外表面の無機イオン吸着体の存在量が多いため、高速で通液処理してもイオンを確実に吸着できる吸着材が得られる。
The amount of water-soluble polymer added should be such that the ratio of water-soluble polymer / (water-soluble polymer + organic polymer resin + good solvent for organic polymer resin) is 0.1-40% by mass. Is preferable, 0.5 to 30 mass% is more preferable, and 1 to 10 mass% is further preferable.
If the addition amount of the water-soluble polymer is 0.1% by mass or more, the porous granular material includes a fibrous structure that forms a three-dimensionally continuous network structure on the outer surface and inside of the porous granular material. A molded body can be obtained uniformly. On the other hand, when the addition amount of the water-soluble polymer is 40% by mass or less, the outer surface opening ratio is appropriate and the amount of the inorganic ion adsorbent on the outer surface of the porous granular molded body is large, so that the high speed passage is achieved. It is possible to obtain an adsorbent that can surely adsorb ions even after liquid treatment.
（工程（３）：成形工程）
工程（３）においては、工程（２）により得られた混合スラリー（成形用スラリー）を成形する。成形用スラリーは、有機高分子樹脂と、有機高分子樹脂の良溶媒と、無機イオン吸着体と、水溶性高分子の混合スラリーである。
本実施形態の多孔性成形体の形態は、成形用スラリーを成形する方法によって、粒子状、糸状、シート状、中空糸状、円柱状、中空円柱状等の任意の形態を採ることができる。
(Process (3): molding process)
In step (3), the mixed slurry (forming slurry) obtained in step (2) is formed. The molding slurry is a mixed slurry of an organic polymer resin, a good solvent for the organic polymer resin, an inorganic ion adsorbent, and a water-soluble polymer.
The form of the porous formed article of the present embodiment can take any form such as a particle form, a yarn form, a sheet form, a hollow fiber form, a cylindrical form, a hollow cylindrical form, etc., depending on the method of forming the forming slurry.
粒子状の形態に成形する方法としては、特に限定されないが、例えば、図１に示すように、回転する容器の側面に設けたノズルから、容器中に収納されている成形用スラリーを飛散させて、液滴を形成させる回転ノズル法等が挙げられる。回転ノズル法により、粒度分布が揃った粒子状の形態に成形することができる。
具体的には、１流体ノズルや２流体ノズルから、成形用スラリーを噴霧して凝固浴中で凝固する方法が挙げられる。
ノズルの径は、０．１〜１０ｍｍであることが好ましく、０．１〜５ｍｍであることがより好ましい。ノズルの径が０．１ｍｍ以上であれば、液滴が飛散しやすく、１０ｍｍ以下であれば、粒度分布を均一にすることができる。
遠心力は、遠心加速度で表され、５〜１５００Ｇであることが好ましく、１０〜１０００Ｇであることがより好ましく、１０〜８００Ｇであることがさらに好ましい。
遠心加速度が５Ｇ以上であれば、液滴の形成と飛散が容易であり、１５００Ｇ以下であえば、成形用スラリーが糸状にならずに吐出し、粒度分布が広くなるのを抑えることができる。粒度分布が狭いことにより、カラムに多孔性粒状成形体を充填した時に水の流路が均一になるため、超高速通水処理に用いても通水初期からイオン（吸着対象物）が漏れ出す（破過する）ことが無いという利点を有している。
The method of molding into a particulate form is not particularly limited, but for example, as shown in FIG. 1, a molding slurry contained in the container is scattered from a nozzle provided on the side surface of a rotating container. A rotating nozzle method for forming droplets can be used. By the rotating nozzle method, it is possible to mold into a particulate form having a uniform particle size distribution.
Specifically, a method of spraying a molding slurry from a one-fluid nozzle or a two-fluid nozzle to coagulate in a coagulating bath can be mentioned.
The diameter of the nozzle is preferably 0.1 to 10 mm, more preferably 0.1 to 5 mm. When the diameter of the nozzle is 0.1 mm or more, droplets are easily scattered, and when it is 10 mm or less, the particle size distribution can be made uniform.
The centrifugal force is represented by centrifugal acceleration, and is preferably 5 to 1500 G, more preferably 10 to 1000 G, and further preferably 10 to 800 G.
If the centrifugal acceleration is 5 G or more, droplets can be easily formed and scattered. If the centrifugal acceleration is 1500 G or less, it is possible to prevent the molding slurry from being discharged in the form of threads and prevent the particle size distribution from being widened. The narrow particle size distribution makes the flow path of water uniform when the column is filled with porous granular moldings, so even when used for ultra-high-speed water treatment, ions (adsorption target) leak out from the beginning of water passage. It has the advantage of not (breakthrough).
糸状又はシート状の形態に成形する方法としては、該当する形状の紡口、ダイスから成形用スラリーを押し出し、貧溶媒中で凝固させる方法が挙げられる。
中空糸状の多孔性粒状成形体を成形する方法としては、環状オリフィスからなる紡口を用いることで、糸状やシート状の多孔性粒状成形体を成形する方法と同様にして成形できる。
円柱状又は中空円柱状の多孔性粒状成形体を成形する方法としては、紡口から成形用スラリーを押し出す際、切断しながら貧溶媒中で凝固させてもよいし、糸状に凝固させてから後に切断しても構わない。
Examples of the method for forming into a thread-like or sheet-like form include a method in which a forming slurry is extruded from a spinneret or a die having a corresponding shape and coagulated in a poor solvent.
As a method for molding the hollow fiber-shaped porous granular molding, a spinner having an annular orifice is used, and the hollow fiber-shaped porous granular molding can be molded in the same manner as the thread-shaped or sheet-shaped porous granular molding.
As a method for molding a cylindrical or hollow cylindrical porous granular molded body, when the molding slurry is extruded from the spinneret, it may be solidified in a poor solvent while cutting, or after it is solidified into a thread-like shape. You can cut it.
（工程（４）：凝固促進工程）
工程（４）においては、工程（３）により得られた成形品を貧溶媒中で凝固させるまでの間、成形品が接触する空間部の温度と湿度を制御して凝固を促進させる。
工程（４）により、外表面開口率を調整することができ、無機イオン吸着体の存在量が高い成形体が得られるため、被処理水中のイオン、中でも、ヨウ素酸及び又はアンチモンを高速除去でき、かつ吸着容量が大きい多孔性粒状成形体を提供することができる。
空間部の温度と湿度は、貧溶媒が貯留される凝固槽と回転容器との空間をカバーで覆い、貧溶媒の温度を調整して制御する。
空間部の温度は１０〜９０℃であることが好ましく、１０〜８５℃であることがより好ましく、１０〜８０℃であることがさらに好ましい。
空間部の温度が１０℃以上であれば、多孔性粒状成形体の外表面に緻密層が形成されずに開口するため、被処理水中のイオン、中でも、ヨウ素酸及び又はアンチモンを高速除去できる。９０℃以下であれば、多孔性粒状成形体の構造が良好で、担持した無機イオン吸着体の脱離を防ぐ効果が得られる。
空間部の湿度は、温度に対する相対湿度で２０〜９０％であることが好ましく、３０〜８５％であることがより好ましく、４０〜８０％であることがさらに好ましい。
相対湿度が２０％以上であれば、多孔性成形体の外表面に緻密層が形成されずに開口するため、被処理水中のイオン、中でも、ヨウ素酸及び又はアンチモンを高速除去できる。９０％以下であれば、多孔性粒状成形体の構造が良好で、担持した無機イオン吸着体の脱離を防ぐ効果が得られる。
(Process (4): solidification promoting process)
In the step (4), the solidification is promoted by controlling the temperature and humidity of the space portion in contact with the molded product until the molded product obtained in the step (3) is solidified in the poor solvent.
By the step (4), the outer surface aperture ratio can be adjusted, and a molded product having a high abundance of the inorganic ion adsorbent can be obtained, so that ions in the water to be treated, especially iodic acid and / or antimony can be removed at high speed. It is also possible to provide a porous granular molded body having a large adsorption capacity.
The temperature and humidity of the space are controlled by covering the space between the coagulation tank in which the poor solvent is stored and the rotary container with a cover and adjusting the temperature of the poor solvent.
The temperature of the space is preferably 10 to 90 ° C, more preferably 10 to 85 ° C, and further preferably 10 to 80 ° C.
When the temperature of the space is 10 ° C. or higher, a dense layer is not formed on the outer surface of the porous granular molded body and the porous surface is opened, so that ions in the water to be treated, in particular, iodic acid and / or antimony can be removed at high speed. When the temperature is 90 ° C. or lower, the structure of the porous granular molded body is good, and the effect of preventing desorption of the supported inorganic ion adsorbent can be obtained.
The humidity of the space is preferably 20 to 90% relative to the temperature, more preferably 30 to 85%, and further preferably 40 to 80%.
When the relative humidity is 20% or more, the dense layer is not formed on the outer surface of the porous molded article and the pores are opened, so that ions in the water to be treated, especially iodic acid and / or antimony can be removed at high speed. When it is 90% or less, the structure of the porous granular molded article is good, and the effect of preventing desorption of the carried inorganic ion adsorbent can be obtained.
（工程（５）：凝固工程）
工程（５）においては、工程（４）で得られた凝固が促進された成形品を貧溶媒中で凝固させて、多孔性成形体を得る。
(Process (5): solidification process)
In step (5), the molded article obtained in step (4) with accelerated coagulation is coagulated in a poor solvent to obtain a porous molded body.
＜貧溶媒＞
工程（５）における貧溶媒としては、工程（５）の条件において有機高分子樹脂の溶解度が１質量％以下の溶媒を使用することができ、例えば、水、メタノール、エタノール等のアルコール類、エーテル類、ｎ−ヘキサン、ｎ−ヘプタン等の脂肪族炭化水素類等が挙げられる。中でも、貧溶媒としては、水が好ましい。
<Poor solvent>
As the poor solvent in the step (5), a solvent having a solubility of the organic polymer resin of 1% by mass or less under the condition of the step (5) can be used, and examples thereof include water, alcohols such as methanol and ethanol, and ether. And aliphatic hydrocarbons such as n-hexane and n-heptane. Of these, water is preferable as the poor solvent.
工程（５）では、先行する工程から良溶媒が持ち込まれ、良溶媒の濃度が、凝固工程開始時と終点で、変化してしまう。そのため、予め良溶媒を加えた貧溶媒としてもよく、初期の濃度を維持するように水等を別途加えながら濃度を管理して凝固工程を行うことが好ましい。
良溶媒の濃度を調整することで、多孔性粒状成形体の構造（外表面開口率及び粒子形状）を制御できる。
貧溶媒が水又は有機高分子樹脂の良溶媒と水の混合物の場合、凝固工程において、有機高分子樹脂の良溶媒の含有率は、０〜８０質量％であることが好ましく、０〜６０質量％であることがより好ましい。
有機高分子樹脂の良溶媒の含有量が８０質量％以下であれば、多孔性粒状成形体の形状が良好になる効果が得られる。
凝固液の温度は、多孔性粒状成形体の構造（外表面開口率及び粒子形状）を制御する観点から、１０〜６０℃であることが好ましく、１０〜５０℃であることがより好ましく、１０〜４０℃であることがさらに好ましい。貧溶媒の温度が１０℃以上であれば、多孔性成形体の外表面に緻密層が形成されずに開口するため、被処理水中のイオン、中でも、ヨウ素酸及び又はアンチモンを高速除去できる。他方、６０℃以下であれば、多孔性粒状成形体の構造が良好で、担持した無機イオン吸着体の脱離を防ぐ効果が得られる。
In the step (5), the good solvent is brought in from the preceding step, and the concentration of the good solvent changes at the start and the end of the coagulation step. Therefore, a poor solvent obtained by adding a good solvent in advance may be used, and it is preferable to perform the coagulation step by controlling the concentration while separately adding water or the like so as to maintain the initial concentration.
By adjusting the concentration of the good solvent, the structure (outer surface aperture ratio and particle shape) of the porous granular molded body can be controlled.
When the poor solvent is water or a mixture of water with a good solvent for the organic polymer resin, the content of the good solvent for the organic polymer resin in the coagulation step is preferably 0 to 80% by mass, and 0 to 60% by mass. % Is more preferable.
When the content of the good solvent of the organic polymer resin is 80% by mass or less, the effect of improving the shape of the porous granular molded body can be obtained.
The temperature of the coagulating liquid is preferably 10 to 60 ° C., more preferably 10 to 50 ° C., from the viewpoint of controlling the structure (outer surface aperture ratio and particle shape) of the porous granular molded body. It is more preferably -40 ° C. If the temperature of the poor solvent is 10 ° C. or higher, a dense layer is not formed on the outer surface of the porous molded article and is opened, so that ions in the water to be treated, in particular, iodic acid and / or antimony can be removed at high speed. On the other hand, when the temperature is 60 ° C. or lower, the structure of the porous granular molded body is good, and the effect of preventing desorption of the supported inorganic ion adsorbent can be obtained.
（多孔性粒状成形体の製造装置）
図１に例示するように、本実施形態における多孔性粒状成形体の製造装置は、液滴を遠心力で飛散させる回転容器（５）と、凝固液を貯留する凝固槽（４）とを備え、回転容器と凝固槽の間の空間部分を覆う空間部カバー（３）を具備し、空間部の温度と湿度を制御する制御手段を備える。
(Production device for porous granular molding)
As illustrated in FIG. 1, the porous granular molded body manufacturing apparatus according to the present embodiment includes a rotary container (5) that scatters droplets by centrifugal force, and a coagulation tank (4) that stores a coagulating liquid. A space cover (3) covering the space between the rotary container and the coagulation tank is provided, and a control means for controlling the temperature and humidity of the space is provided.
液滴を遠心力で飛散させる回転容器は、成形用スラリーを球状の液滴にして遠心力で飛散する機能があれば、特定の構造からなるものに限定されず、例えば、周知の回転ディスク、回転ノズル等が挙げられる。
回転ディスクは、成形用スラリーが回転するディスクの中心に供給され、回転するディスクの表面に沿って成形用スラリーが均一な厚みでフィルム状に展開し、ディスクの周縁から遠心力で滴状に分裂して微小液滴を飛散させるものである。
回転ノズルは、中空円盤型の回転容器の周壁に多数の貫通孔を形成するか、又は周壁に貫通させてノズルを取付け、回転容器内に成形用スラリーを供給すると共に回転容器を回転させ、その際に貫通孔又はノズルから遠心力により成形用スラリーを吐出させて液滴を形成するものである。
The rotating container that scatters the droplets by centrifugal force is not limited to one having a specific structure as long as it has a function of making the molding slurry into spherical droplets and scattering by the centrifugal force, for example, a well-known rotating disc, A rotating nozzle or the like can be used.
In the rotating disk, the molding slurry is supplied to the center of the rotating disk, and the molding slurry spreads in a film shape with a uniform thickness along the surface of the rotating disk, and is divided into drops by centrifugal force from the peripheral edge of the disk. Then, fine droplets are scattered.
The rotating nozzle forms a large number of through holes in the peripheral wall of the hollow disk type rotating container, or a nozzle is attached by penetrating the peripheral wall to supply the molding slurry into the rotating container and rotate the rotating container. At this time, the forming slurry is discharged from the through hole or the nozzle by centrifugal force to form droplets.
凝固液を貯留する凝固槽は、凝固液を貯留できる機能があれば、特定の構造からなるものに限定されず、例えば、周知の上面開口の凝固槽や、回転容器を囲むように配置した筒体の内面に沿って凝固液を重力により自然流下させる構造の凝固槽等が挙げられる。
上面開口の凝固槽は、回転容器から水平方向に飛散した液滴を自然落下させ、上面が開口した凝固槽に貯留した凝固液の水面で液滴を捕捉する装置である。
回転容器を囲むように配置した筒体の内面に沿って凝固液を重力により自然流下させる構造の凝固槽は、凝固液を筒体の内面に沿わせて周方向にほぼ均等な流量で流出させ、内面に沿って自然流下する凝固液流中に液滴を捕捉して凝固させる装置である。
The coagulation tank that stores the coagulation liquid is not limited to one having a specific structure as long as it has a function of storing the coagulation liquid. For example, a coagulation tank having a well-known upper surface opening or a cylinder arranged so as to surround a rotating container. A coagulation tank having a structure in which the coagulation liquid naturally flows down along the inner surface of the body by gravity is used.
The coagulation tank with the upper surface opening is a device that naturally drops the liquid droplets scattered horizontally from the rotary container and captures the liquid droplets with the water surface of the coagulation liquid stored in the coagulation tank with the upper surface opened.
The coagulation tank, which has a structure in which the coagulation liquid naturally flows down by gravity along the inner surface of the cylindrical body that surrounds the rotating container, allows the coagulation liquid to flow along the inner surface of the cylindrical body at a substantially uniform flow rate in the circumferential direction. , A device that traps and solidifies droplets in a coagulating liquid flow that naturally flows along the inner surface.
空間部の温度と湿度の制御手段は、回転容器と凝固槽の間の空間部を覆うカバーを具備し、空間部の温度と湿度を制御する手段である。
空間部を覆うカバーは、空間部を外部の環境から隔離して、空間部の温度及び湿度を現実的に制御し易くする機能があれば、特定の構造からなるものに限定されず、例えば、箱状、筒状、傘状の形状とすることができる。
カバーの材質は、例えば、金属のステンレス鋼やプラスチック等が挙げられる。外部環境と隔離する点で、公知の断熱材で覆うこともできる。カバーには、一部開口部を設けて、温度及び湿度を調整してもよい。
The temperature and humidity control means for the space is a means for controlling the temperature and humidity of the space, including a cover that covers the space between the rotary container and the coagulation tank.
The cover that covers the space is not limited to one having a specific structure as long as it has a function of isolating the space from the external environment and making it easy to control the temperature and humidity of the space practically. It can be box-shaped, tubular, or umbrella-shaped.
Examples of the material of the cover include metallic stainless steel and plastic. It may be covered with a known heat insulating material so as to be isolated from the external environment. The cover may be provided with an opening to adjust the temperature and humidity.
空間部の温度及び湿度の制御手段は、空間部の温度と湿度を制御する機能があればよく、特定の手段に限定されず、例えば、電気ヒーター、スチームヒーター等の加熱器、超音波式加湿器、加熱式加湿器等の加湿器が挙げられる。 The means for controlling the temperature and humidity of the space portion need only have a function of controlling the temperature and humidity of the space portion, and is not limited to a specific means, and examples thereof include a heater such as an electric heater and a steam heater, ultrasonic humidification. Examples of the humidifier include a heater and a heating humidifier.
本実施形態のヨウ素酸及び／又はアンチモン吸着処理装置は、本実施形態のヨウ素酸及び／又はアンチモン吸着材を含む。ヨウ素酸及び／又はアンチモン吸着処理装置としては、ヨウ素酸及び／又はアンチモン吸着材をタンクに充填して、ヨウ素酸及び／又はアンチモンを含有する被処理液を通液することが好ましい。 The iodic acid and / or antimony adsorption treatment apparatus of the present embodiment includes the iodic acid and / or antimony adsorption material of the present embodiment. As the iodic acid and / or antimony adsorption treatment apparatus, it is preferable to fill the tank with iodic acid and / or antimony adsorbent and pass the liquid to be treated containing iodic acid and / or antimony.
(吸着材を用いた装置)
上記の製造条件で得られたヨウ素酸及び／又はアンチモン吸着材は、処理水を導入する導入口と導出する導出口を有するカラムに充填した状態で使用することができる。
ここで、カラムの形状は、導入口及び導出口を有する限りにおいて特に制限はなく、円筒状、直方体状等、の形状を取ることが可能である。そして、カラムの材質については、用いる処理水に含まれる溶媒に対して耐久性があれば特に制限はなく、炭素鋼、ステンレス、チタン、ハステロイ、ジルコニウム、鋳鉄等の金属、金属をガラスライニングしたもの、金属を耐薬品性樹脂ライニングしたもの、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリエチレン、ポリプロピレン等の樹脂、不飽和ポリエステルやビニルエステル等の樹脂をガラス繊維等で強化した繊維強化プラスチック等を利用することができる。
そして、上記カラムと、上記カラムの導出口を経て得られた処理水中のヨウ素酸及び／又はアンチモンを検出する検出器とを組み合わせることで、ヨウ素酸及び／又はアンチモンの吸着処理装置を構成することができる。
(Device using adsorbent)
The iodic acid and / or antimony adsorbent obtained under the above production conditions can be used in a state of being packed in a column having an inlet for introducing treated water and an outlet for introducing treated water.
Here, the shape of the column is not particularly limited as long as it has an inlet and an outlet, and can take a cylindrical shape, a rectangular parallelepiped shape, or the like. And, the material of the column is not particularly limited as long as it is durable against the solvent contained in the treated water to be used, and a metal such as carbon steel, stainless steel, titanium, hastelloy, zirconium, cast iron, or a glass-lined metal , Use metal-resistant resin lining, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, etc., resin, unsaturated polyester, vinyl ester, etc. You can
And, by combining the column and a detector for detecting iodic acid and / or antimony in the treated water obtained through the outlet of the column, an adsorption treatment device for iodic acid and / or antimony is configured. You can
(ヨウ素酸及び／又はアンチモン吸着材の分散体)
前記ヨウ素酸及び／又はアンチモン吸着材は乾燥固体のままでカラムに充填して使用してもよいし、製造過程で乾燥固体とすることなく溶媒、例えば、水中に分散した分散体とした状態でカラムに充填することも可能である。
分散体である方が吸着材の擦れによる粉落ちを防ぎやすくなり、搬送も行いやすくなる。
(Dispersion of iodic acid and / or antimony adsorbent)
The iodic acid and / or antimony adsorbent may be used by being packed in a column as a dry solid, or may be used as a dispersion dispersed in a solvent, for example, water without being a dry solid in the production process. It is also possible to fill the column.
Dispersion makes it easier to prevent powder from falling off due to rubbing of the adsorbent, and facilitates transport.
以下、実施例及び比較例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。多孔性粒状成形体の物性は、以下の方法により測定した。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The physical properties of the porous granular molded product were measured by the following methods.
〔水和酸化セリウムの担持量測定〕
メスシリンダーで水中で測り取った吸着材３ｍＬを電気炉内８００℃で焼成した。焼成後の重量から酸化セリウムの担持量（ｇ／ｍＬ）を算出した。
[Measurement of amount of hydrated cerium oxide]
3 mL of the adsorbent measured in water with a measuring cylinder was fired at 800 ° C. in an electric furnace. The amount of cerium oxide supported (g / mL) was calculated from the weight after firing.
〔外表面開口率〕
多孔性粒状成形体を、圧力４Ｔｏｒｒ未満、トラップ冷却温度−８５℃の条件で凍結乾燥した後、走査型電子顕微鏡（ＳＥＭ）を用いて撮影した多孔性粒状成形体の外表面の画像を、画像解析ソフト（ＷｉｎＲＯＯＦ６．１．３（商品名））を用いて解析して求めた。ＳＥＭ画像の「ノイズ除去」を数値「２０」によって行い、「コントラスト」を数値「８０」とし、単一しきい値による二値化により、「しきい値：３０」で二値化した。得られた二値化画像のから各孔の円相当径を求め、３０ｎｍ以上の円相当径を持つ孔の占有面積を求めることにより、３０ｎｍ以上の孔からなる外表面開口率を求めた。
[Aperture ratio of outer surface]
An image of the outer surface of the porous granular molded article taken by using a scanning electron microscope (SEM) was obtained by freeze-drying the porous granular molded article under the conditions of a pressure of less than 4 Torr and a trap cooling temperature of -85 ° C. It was determined by analysis using analysis software (WinROOF6.1.3 (trade name)). "Noise removal" of the SEM image was performed by the numerical value "20", "Contrast" was set by the numerical value "80", and binarization was performed by the single threshold value, and "Threshold value: 30". The circle-equivalent diameter of each hole was obtained from the obtained binarized image, and the occupied area of the hole having a circle-equivalent diameter of 30 nm or more was obtained to obtain the outer surface aperture ratio of the holes of 30 nm or more.
〔多孔性粒状成形体の平均粒径及び水和酸化セリウムの平均粒径〕
多孔性粒状成形体の平均粒径及び水和酸化セリウムの平均粒径は、レーザー回折／散乱式粒度分布測定装置（ＨＯＲＩＢＡ社製のＬＡ-９５０（商品名））で測定した。分散媒体は水を用いた。
[Average Particle Diameter of Porous Granular Compact and Average Particle Diameter of Hydrated Cerium Oxide]
The average particle size of the porous granular molded product and the average particle size of hydrated cerium oxide were measured with a laser diffraction / scattering particle size distribution analyzer (LA-950 (trade name) manufactured by HORIBA). Water was used as the dispersion medium.
〔実施例１〕
Ｎ−メチル−２ピロリドン（ＮＭＰ、三菱化学（株））１４０ｇと、平均粒径３０μｍの水和酸化セリウム粉末（岩谷産業（株））３００ｇを、直径５ｍｍφのステンレス製ボール１．５ｋｇを充填した容積１Ｌのステンレス製ボールミルポットに投入し、７５ｒｐｍの回転数で１５０分間粉砕・混合処理を行い黄色のスラリーを得た。得られたスラリーに、ポリエーテルスルホン（住友化学（株）、スミカエクセル５００３ＰＳ（商品名）、ＯＨ末端グレード、末端水酸基組成９０（モル％））１１ｇを加えて、溶解槽中にて、６０℃に加温して撹拌羽根を用いて撹拌・溶解し、均一な成形用スラリー溶液を得た。
得られた成形用スラリー溶液を６０℃に加温し、側面に直径４ｍｍのノズルを開けた円筒状回転容器の内部に供給し、この容器を回転させ、遠心力（１５Ｇ）によりノズルから液滴を形成させた。続いて、回転容器と凝固槽の間の空間部をポリプロピレン製のカバーで覆って空間部の温度を２５℃、相対湿度を６３％に制御した空間部を飛行させ、水に対するＮＭＰの含有量が５０質量％の凝固液を２５℃にして貯留した、上面開口の凝固槽中に着水させ、成形用スラリーを凝固させた。この際の凝固浴の濁りの有無を以下の表１に示す。
さらに、洗浄、分級を行い、球状の多孔性粒状成形体を得た。
[Example 1]
140 g of N-methyl-2pyrrolidone (NMP, Mitsubishi Chemical Co., Ltd.), 300 g of hydrated cerium oxide powder (Iwatani Sangyo Co., Ltd.) having an average particle size of 30 μm, and 1.5 kg of stainless steel balls having a diameter of 5 mm were filled. The mixture was placed in a stainless steel ball mill pot having a volume of 1 L and pulverized and mixed for 150 minutes at a rotation speed of 75 rpm to obtain a yellow slurry. To the obtained slurry, 11 g of polyether sulfone (Sumitomo Chemical Co., Ltd., Sumika Excel 5003PS (trade name), OH terminal grade, terminal hydroxyl group composition 90 (mol%)) was added, and at 60 ° C. in a dissolution tank. The mixture was heated to and stirred and dissolved using a stirring blade to obtain a uniform molding slurry solution.
The obtained molding slurry solution was heated to 60 ° C., supplied to the inside of a cylindrical rotary container with a nozzle having a diameter of 4 mm opened on the side surface, the container was rotated, and droplets were generated from the nozzle by centrifugal force (15 G). Was formed. Next, the space between the rotating container and the coagulation tank was covered with a polypropylene cover, and the space was controlled to have a temperature of 25 ° C. and a relative humidity of 63%. 50% by mass of a coagulation liquid was stored at 25 ° C., and the water was made to enter a coagulation tank having an upper surface opening to coagulate the molding slurry. The presence or absence of turbidity in the coagulation bath at this time is shown in Table 1 below.
Further, washing and classification were performed to obtain a spherical porous granular molded body.
（ヨウ素酸通液吸着試験）
得られた粒状成形体２０ｍＬを内径１５ｍｍの円筒形のカラム内に充填した。人工海水（大阪薬研（株）、マリンアートＳＦ−１（商品名））を純水で３倍に希釈した３倍希釈人工海水にヨウ素酸ナトリウムを溶解して作製したヨウ素濃度１０ｍｇ／Ｌの原水を作製し、この原水をカラムに通液速度（ＳＶ Space Velocity）１０ｈ−１の下降流で通液した。そしてカラム下部から流出する吸着処理水中のヨウ素濃度をＩＣＰ発光分析法で測定した。処理水中に１ｍｇ／Ｌのヨウ素が検出された時点の吸着材量に対する通液倍率を、ヨウ素酸１０％破過通液倍率とし、以下の表１に示す。
(Iodine acid permeation adsorption test)
20 mL of the obtained granular molded body was packed in a cylindrical column having an inner diameter of 15 mm. Artificial seawater (Osaka Yakken Co., Ltd., Marine Art SF-1 (trade name)) is diluted 3 times with pure water. Raw water with an iodine concentration of 10 mg / L prepared by dissolving sodium iodate in 3-fold diluted artificial seawater. Was prepared, and this raw water was passed through the column at a descending flow rate of 10 h −1 (SV Space Velocity). Then, the concentration of iodine in the adsorption-treated water flowing out from the lower part of the column was measured by ICP emission spectrometry. The permeation ratio to the amount of the adsorbent at the time when 1 mg / L iodine was detected in the treated water was defined as the iodic acid 10% breakthrough permeation ratio and is shown in Table 1 below.
（アンチモン通液吸着試験）
得られた粒状成形体２０ｍＬを内径１５ｍｍの円筒形のカラム内に充填した。人工海水（大阪薬研（株）、マリンアートＳＦ−１（商品名））を純水で３倍に希釈した３倍希釈人工海水に塩化アンチモン（III）を溶解して作製したアンチモン濃度５ｍｇ／Ｌの原水を作製し、この原水をカラムに通液速度（ＳＶ Space Velocity）１０ｈ−１の下降流で通液した。そしてカラム下部から流出する吸着処理水中のアンチモン濃度をＩＣＰ発光分析法で測定した。処理水中に０．５ｍｇ／Ｌのアンチモンが検出された時点の吸着材量に対する通液倍率を、アンチモン１０％破過通液倍率とし、以下の表１に示す。
(Antimony permeation adsorption test)
20 mL of the obtained granular molded body was packed in a cylindrical column having an inner diameter of 15 mm. Artificial seawater (Osaka Yakken Co., Ltd., Marine Art SF-1 (trade name)) was diluted 3 times with pure water. Antimony (III) chloride was dissolved in 3-fold diluted artificial seawater to prepare an antimony concentration of 5 mg / L. Was prepared, and this raw water was passed through the column at a descending flow rate of 10 h −1 (SV Space Velocity). Then, the concentration of antimony in the adsorption-treated water flowing out from the lower part of the column was measured by ICP emission spectrometry. The liquid passage ratio with respect to the amount of the adsorbent at the time when 0.5 mg / L of antimony was detected in the treated water was taken as the antimony 10% breakthrough liquid passage ratio and is shown in Table 1 below.
〔実施例２〕
ポリエーテルスルホンの仕込み量を１０ｇとし、水和酸化セリウムの仕込み量を３５０ｇとしたこと以外は実施例１に記載の方法と同様にして、球状の多孔性成形体を得た。
[Example 2]
A spherical porous compact was obtained in the same manner as in Example 1 except that the amount of polyether sulfone charged was 10 g and the amount of hydrated cerium oxide was 350 g.
〔実施例３〕
有機高分子樹脂を、アクリロニトリル９１．５質量％、アクリル酸メチル８．０質量％、メタリルスルホン酸ソーダ０．５質量％からなる極限粘度［η］＝１．２の共重合体（有機高分子樹脂、ＰＡＮ）としたこと以外は実施例１に記載の方法と同様にして、球状の多孔性成形体を得た。
[Example 3]
A copolymer of organic polymer resin consisting of 91.5% by mass of acrylonitrile, 8.0% by mass of methyl acrylate and 0.5% by mass of sodium methallyl sulfonate and having an intrinsic viscosity [η] = 1.2 (organic polymer A spherical porous molded body was obtained in the same manner as in Example 1 except that the molecular resin and PAN) were used.
〔比較例１〕
ポリエーテルスルホンの仕込み量を１０ｇ、ＮＭＰの仕込み量を１１０ｇ、水和酸化セリウムの仕込み量を５０ｇとし、凝固液の温度を６０℃にしたこと以外は実施例１に記載の方法と同様にして、多孔性粒状成形体を得た。この時の空間部の温度は３７℃、相対湿度は８０％だった。
[Comparative Example 1]
The same procedure as in Example 1 was repeated except that the amount of polyether sulfone charged was 10 g, the amount of NMP charged was 110 g, the amount of hydrated cerium oxide was 50 g, and the temperature of the coagulating liquid was 60 ° C. A porous granular molded body was obtained. At this time, the temperature of the space was 37 ° C. and the relative humidity was 80%.
〔比較例２〕
有機高分子樹脂の良溶媒を、ジメチルスルホキシド（ＤＭＳＯ、関東化学（株））１４０ｇ、有機高分子樹脂をエチレンビニルアルコール共重合体（ＥＶＯＨ、日本合成化学工業（株）、ソアノールＥ３８０３（商品名））２０ｇ、水和酸化セリウム粉末２００ｇとし、さらに凝固液を水としたこと以外は実施例１に記載の方法と同様にして、多孔性粒状成形体を得た。この時の空間部の温度は２５℃、相対湿度は６３％だった。
[Comparative Example 2]
140 g of dimethyl sulfoxide (DMSO, Kanto Chemical Co., Inc.) as a good solvent for the organic polymer resin, ethylene vinyl alcohol copolymer (EVOH, Nippon Synthetic Chemical Industry Co., Ltd., Soarnol E3803 (trade name)) as the organic polymer resin ) 20 g, hydrated cerium oxide powder 200 g, and the coagulation liquid was water, and a porous granular molded body was obtained in the same manner as in Example 1. At this time, the temperature of the space was 25 ° C. and the relative humidity was 63%.
〔比較例３〕
ポリエーテルスルホンの仕込み量を１５ｇとし、凝固液を８０℃にした以外は実施例１に記載の方法と同様にして、多孔性粒状成形体を得た。この時の空間部の温度は５０℃、相対湿度は１００％だった。
[Comparative Example 3]
A porous granular molded body was obtained in the same manner as in Example 1 except that the charged amount of polyether sulfone was 15 g and the coagulating liquid was 80 ° C. At this time, the temperature of the space was 50 ° C. and the relative humidity was 100%.
実施例１〜３、比較例１〜３で得られた多孔性成形体の物性及び実施例１と同条件で実施したヨウ素酸通液吸着試験及びアンチモン通液吸着試験の１０％破過通液倍率と、凝固浴槽に濁りの有無とを以下の表１に示す。 Physical properties of the porous molded bodies obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and 10% breakthrough liquid flow of iodic acid permeation adsorption test and antimony permeation adsorption test conducted under the same conditions as in Example 1. The magnification and the presence or absence of turbidity in the coagulation bath are shown in Table 1 below.
本発明に係るヨウ素酸及び／又はアンチモン吸着材は、無機イオン吸着体の担持量が０．６〜１．２ｇ／ｍＬと高く、かつ、３０ｎｍ以上の孔の外表面開口率が３％以上１７％未満であるため、ヨウ素酸及び／又はアンチモンを含有する液体を高速で通液しても長期間破過することなくヨウ素酸及び／又はアンチモンを吸着除去でき、かつ、無機イオン吸着体の脱離が起こらない吸着材であるため、ヨウ素酸及び／又はアンチモン処理法等において好適に利用可能である。 The iodic acid and / or antimony adsorbent according to the present invention has a high supported amount of the inorganic ion adsorbent of 0.6 to 1.2 g / mL , and the outer surface open area ratio of the pores of 30 nm or more is 3% or more. Since it is less than 17%, even if a liquid containing iodic acid and / or antimony is passed at a high speed, iodic acid and / or antimony can be adsorbed and removed without breakthrough for a long period of time, and an inorganic ion adsorbent Since it is an adsorbent that does not cause desorption, it can be suitably used in the iodic acid and / or antimony treatment method and the like.
１ タンク
２ ポンプ
３ 空間部カバー
４ 凝固槽
５ 回転容器
６ 回転軸
７ ホース
８ ヒーター
ａ 成形用スラリー
ｂ 開口部
ｃ 空間部
ｄ 凝固液
1
Claims (8)
ＭＮｘＯｎ・ｍＨ２Ｏ ・・・（Ｉ）
｛式中、ｘは０〜３の数であり、ｎは１〜４の数であり、ｍは０〜６の数であり、Ｍ及びＮは、互いに独立して、Ｔｉ、Ｚｒ、Ｓｎ、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ａｌ、Ｓｉ、Ｃｒ、Ｃｏ、Ｇａ、Ｆｅ、Ｍｎ、Ｎｉ、Ｖ、Ｇｅ、Ｎｂ及びＴａからなる群から選ばれる金属元素である。｝で表される少なくとも一種の金属酸化物である、請求項１に記載のヨウ素酸及び／又はアンチモン吸着材。 The inorganic ion adsorbent has the following formula (I):
MN x O n · mH 2 O (I)
{In the formula, x is a number of 0 to 3, n is a number of 1 to 4, m is a number of 0 to 6, M and N independently of each other are Ti, Zr, Sn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, Cr, Co, Ga, Fe, Mn, Ni, V, It is a metal element selected from the group consisting of Ge, Nb and Ta. } The iodic acid and / or antimony adsorption material of Claim 1 which is at least 1 type of metal oxide represented by these.
（ａ）水和酸化チタン、水和酸化ジルコニウム、水和酸化スズ、水和酸化セリウム、水和酸化ランタン及び水和酸化イットリウム、
（ｂ）チタン、ジルコニウム、スズ、セリウム、ランタン及びイットリウムからなる群から選ばれる少なくとも一種の金属元素と、アルミニウム、珪素及び鉄からなる群から選ばれる少なくとも一種の金属元素との複合金属酸化物、
（ｃ）活性アルミナ、
のいずれかの群から選ばれる少なくとも一種である、請求項２に記載のヨウ素酸及び／又はアンチモン吸着材。 The metal oxide has the following (a) to (c):
(A) hydrated titanium oxide, hydrated zirconium oxide, hydrated tin oxide, hydrated cerium oxide, hydrated lanthanum oxide and hydrated yttrium oxide,
(B) a composite metal oxide of at least one metal element selected from the group consisting of titanium, zirconium, tin, cerium, lanthanum and yttrium and at least one metal element selected from the group consisting of aluminum, silicon and iron,
(C) activated alumina,
The iodic acid and / or antimony adsorbent according to claim 2, which is at least one selected from the group consisting of:
（１）有機高分子樹脂の良溶媒と無機イオン吸着体を粉砕・混合してスラリーを得る工程、
（２）工程（１）で得られたスラリーに有機高分子樹脂を溶解して混合スラリーを得る工程、
（３）工程（２）で得られた混合スラリーを成形する工程、
（４）工程（３）で得られた成形品が接触する空間部の温度と湿度を制御して、該成形品の凝固を促進させる工程、
（５）工程（４）で得られた凝固が促進された成形品を、前記有機高分子樹脂の貧溶媒と良溶媒の混合液中10℃〜60℃の温度で凝固させる工程、
を含む、請求項１〜５のいずれか一項に記載のヨウ素酸及び／又はアンチモン吸着材の製造方法。 The following steps:
(1) A step of pulverizing and mixing a good solvent of an organic polymer resin and an inorganic ion adsorbent to obtain a slurry,
(2) Step (1) obtaining a slurry in an organic polymer trees mixed slurry to dissolve the fat obtained in,
(3) a step of shaping the mixed slurry obtained in the step (2),
(4) A step of controlling the temperature and humidity of a space portion in contact with the molded article obtained in the step (3) to accelerate the solidification of the molded article,
(5) A step of coagulating the molded article having accelerated coagulation obtained in the step (4) at a temperature of 10 ° C to 60 ° C in a mixed solution of the poor solvent and the good solvent of the organic polymer resin,
The method for producing an iodic acid and / or antimony adsorbent according to any one of claims 1 to 5, comprising:
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