JPH04317738A - Production of fluoride ion adsorbing material - Google Patents
Production of fluoride ion adsorbing materialInfo
- Publication number
- JPH04317738A JPH04317738A JP3083735A JP8373591A JPH04317738A JP H04317738 A JPH04317738 A JP H04317738A JP 3083735 A JP3083735 A JP 3083735A JP 8373591 A JP8373591 A JP 8373591A JP H04317738 A JPH04317738 A JP H04317738A
- Authority
- JP
- Japan
- Prior art keywords
- fluoride ion
- zirconium
- cerium
- polystyrene particles
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000000463 material Substances 0.000 title abstract 3
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000004793 Polystyrene Substances 0.000 claims abstract description 21
- 229920002223 polystyrene Polymers 0.000 claims abstract description 21
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000003463 adsorbent Substances 0.000 claims description 18
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- -1 fluoride ions Chemical class 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 102100037487 Histone H1.0 Human genes 0.000 description 1
- 101001026554 Homo sapiens Histone H1.0 Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、フッ化物イオン吸着材
の製造法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fluoride ion adsorbent.
【０００２】0002
【従来の技術】フッ化物イオン吸着材としては、フッ化
物イオンがアルミニウム、鉄、ジルコニウム、希土類金
属等の金属と強い親和性有することを利用した、これら
金属とキレート樹脂の結合体が知られているが（特開昭
５１−１１５０５８号公報、特開昭５７−１０７２８７
号公報）、この結合体は、フッ化物イオン吸着後の樹脂
の再生処理の際に、フッ化物イオンとともに金属イオン
も脱離するため、これらのイオンの脱離後改めて金属イ
オンを結合させる処理を施すという煩雑な再生操作を必
要とする上に、コスト高となるのを免れなかった。この
ような不利は、キレート樹脂の配位子部分と金属イオン
とで形成される錯体の安定度が十分でないことから、樹
脂を再生する際に該金属イオンも樹脂から脱離するため
に生じるものと考えられる。[Prior Art] As a fluoride ion adsorbent, a combination of metals such as aluminum, iron, zirconium, rare earth metals, and chelate resins is known, which takes advantage of the strong affinity of fluoride ions with metals such as aluminum, iron, zirconium, and rare earth metals. Iruga (Japanese Unexamined Patent Application Publication No. 115058/1983, No. 107287/1983)
In this bond, metal ions are also desorbed along with fluoride ions during resin regeneration treatment after adsorption of fluoride ions, so after these ions have been desorbed, a treatment to bind metal ions is required. Not only does this require a complicated regeneration operation, but it also inevitably leads to high costs. This disadvantage arises because the complex formed between the ligand moiety of the chelate resin and the metal ion is not sufficiently stable, and the metal ion is also released from the resin when the resin is regenerated. it is conceivable that.
【０００３】一方、セリウムやジルコニウム等の金属の
含水酸化物がフッ化物イオンを選択的に吸着することや
、これらの含水酸化物が酸やアルカリや有機溶媒に難溶
である上に、酸化還元を受けにくいなど極めて安定な特
性を有することから、フッ化物イオン吸着材として有望
であることも報告されている（日本化学会誌、（１９８
７）、第８０７ページ）。On the other hand, hydrated oxides of metals such as cerium and zirconium selectively adsorb fluoride ions, and these hydrated oxides are sparingly soluble in acids, alkalis, and organic solvents, and are oxidation-reduction resistant. It has also been reported that it is promising as a fluoride ion adsorbent because it has extremely stable characteristics such as being resistant to fluoride ions (Journal of the Chemical Society of Japan, (1988)).
7), page 807).
【０００４】しかしながら、これらの含水酸化物は微粉
体であるため、吸着、溶離、再生の操作を行う上で取扱
いにくいという問題があった。また、セリウムやジルコ
ニウム等の金属の含水酸化物を多孔性担体上に析出させ
た樹脂が、フッ化物イオンの吸着材として有望であるこ
とも報告されている（特開平２−２１１２４４号公報）
。しかし、この多孔性担体は、高価になる。However, since these hydrous oxides are in the form of fine powder, there is a problem in that they are difficult to handle during adsorption, elution, and regeneration operations. It has also been reported that a resin in which hydrous oxides of metals such as cerium and zirconium are deposited on a porous carrier is promising as an adsorbent for fluoride ions (Japanese Unexamined Patent Publication No. 2-211244).
. However, this porous carrier is expensive.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、このような
従来のフッ化物イオン吸着材の持つ欠点を克服し、水溶
液中などのフッ化物イオンを効率的に、しかも繰返し再
現性良く吸着除去しうる安価なフッ化物イオン吸着材の
製造法を提供することを目的とする。[Problems to be Solved by the Invention] The present invention overcomes the drawbacks of conventional fluoride ion adsorbents and adsorbs and removes fluoride ions from aqueous solutions efficiently and with good repeatability. The purpose of the present invention is to provide a method for manufacturing a fluoride ion adsorbent that is highly efficient and inexpensive.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、ジルコニ
ウムやセリウムのアルコキシドの溶液をポリスチレン系
粒子に接触させ、ついで該金属アルコキシドを加水分解
することにより、含水酸化物をポリスチレン系担体の表
面に均一に析出させることができ、前記目的を達成しう
ることを見出し、この知見に基づいて本発明を完成する
に至った。[Means for Solving the Problems] The present inventors brought a solution of zirconium or cerium alkoxide into contact with polystyrene particles, and then hydrolyzed the metal alkoxide to bring the hydrous oxide onto the surface of a polystyrene support. The inventors have discovered that the above object can be achieved by uniformly depositing the particles, and based on this finding, the present invention has been completed.
【０００７】すなわち、本発明は、ジルコニウムまたは
セリウムの含水酸化物を担体に担持させたフッ化物イオ
ン吸着材を製造するに当り、担体にポリスチレン系粒子
を用い、一般式（Ｉ）
Ｍ（ＯＲ）４ （Ｉ）
（式中のＭはジルコニウムまたはセリウムを示し、Ｒは
炭素原子数５以下のアルキル基を示す）で示される金属
アルコキシドの溶液を、ポリスチレン系粒子に接触させ
たのち、これを加水分解処理することを特徴とするフッ
化物イオン吸着材の製造法に関する。That is, in producing a fluoride ion adsorbent in which a hydrous oxide of zirconium or cerium is supported on a carrier, the present invention uses polystyrene-based particles as the carrier, and the general formula (I) M(OR) 4 (I) (In the formula, M represents zirconium or cerium, and R represents an alkyl group having 5 or less carbon atoms) is brought into contact with polystyrene particles, and then hydrated. The present invention relates to a method for producing a fluoride ion adsorbent, which is characterized by decomposition treatment.
【０００８】以下、本発明を詳細に説明する。本発明に
用いられるポリスチレン系粒子としては、例えば、ポリ
スチレン、スチレンと他のビニル系単量体との共重合体
、スチレンとジビニルベンゼンとの共重合体ゲルなどが
あげられるが、工業的入手しやすさを考慮すると、発泡
ポリスチレンの用途に使用される発泡剤含浸前のポリス
チレン粒子が好ましい。粒子径は、２０〜２００メッシ
ュのものが好ましい。The present invention will be explained in detail below. Examples of the polystyrene particles used in the present invention include polystyrene, copolymers of styrene and other vinyl monomers, copolymer gels of styrene and divinylbenzene, etc., but none of them are industrially available. Considering ease of use, polystyrene particles used in expanded polystyrene applications before being impregnated with a blowing agent are preferred. The particle size is preferably 20 to 200 mesh.
【０００９】本発明において、前記一般式（Ｉ）で表わ
される金属アルコキシドの溶液をポリスチレン系粒子に
接触させることが必要である。すなわち、一般式（Ｉ）
Ｍ（ＯＲ）４ （Ｉ）
（式中のＭはジルコニウムまたはセリウムを示し、Ｒは
炭素原子数５以下のアルキル基を示す）で示される金属
アルコキシドを、適当な有機溶媒に溶解し、この溶液を
ポリスチレン系粒子と接触させたのち、前記有機溶媒を
留去等により除去すればよい。In the present invention, it is necessary to bring the solution of the metal alkoxide represented by the general formula (I) into contact with the polystyrene particles. That is, general formula (I)
A metal alkoxide represented by M(OR)4 (I) (in the formula, M represents zirconium or cerium, and R represents an alkyl group having 5 or less carbon atoms) is dissolved in a suitable organic solvent, and this solution is dissolved. After contacting the polystyrene particles, the organic solvent may be removed by distillation or the like.
【００１０】接触させる方法としては、例えば、塗布、
浸漬、混合、含浸等があり、２以上の方法を組み合わせ
ることができる。この際に用いられる一般式（Ｉ）で示
される金属アルコキシドにおいて、炭素数が５以下のア
ルキル基としては、メチル、エチル、ｎ−プロピル、イ
ソプロピル、ｎ−ブチル、イソブチル、ｔｅｒｔ−ブチ
ル、ｎ−アミル、イソアミル等があげられる。また、こ
の際に用いられる有機溶媒としては、ポリスチレン系粒
子を溶解させずに、一般式の金属アルコキシドを溶解さ
せるものがよく炭素原子数が５以下のアルコールが好適
である。[0010] Examples of the contacting method include coating,
There are dipping, mixing, impregnation, etc., and two or more methods can be combined. In the metal alkoxide represented by the general formula (I) used in this case, examples of the alkyl group having 5 or less carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n- Examples include amyl and isoamyl. The organic solvent used in this case is preferably one that dissolves the metal alkoxide of the general formula without dissolving the polystyrene particles, and alcohols having 5 or less carbon atoms are preferred.
【００１１】つぎに、このようにしてポリスチレン系粒
子に担持された金属アルコキシドを水や水性媒体などで
処理することにより、ポリスチレン系粒子表面の金属ア
ルコキシドＭ（ＯＲ）４を加水分解する必要がある。加
水分解によって、含水金属酸化物（ＭＯ２・Ｈ２Ｏ）を
形成させ、含水金属酸化物をポリスチレン系粒子に担持
させることができる（ＭＯ２・Ｈ２Ｏからなる極めて薄
い膜がポリスチレン系粒子の表面に形成される）。なお
、加水分解は、次式のように起こる。
Ｍ（ＯＲ）４＋３Ｈ２Ｏ→ＭＯ２・Ｈ２Ｏ＋４ＲＯＨ（
式中のＭは一般式（Ｉ）と同じ意味である）Next, it is necessary to hydrolyze the metal alkoxide M(OR)4 on the surface of the polystyrene particles by treating the metal alkoxide supported on the polystyrene particles with water or an aqueous medium. . Through hydrolysis, a hydrated metal oxide (MO2/H2O) can be formed and the hydrated metal oxide can be supported on the polystyrene particles (an extremely thin film composed of MO2/H2O is formed on the surface of the polystyrene particles). ). Note that hydrolysis occurs as shown in the following equation. M(OR)4+3H2O→MO2・H2O+4ROH(
M in the formula has the same meaning as general formula (I))
【００１２
】この際のｐＨには特に制限はないが、ｐＨ１〜２の酸
性水溶液や、ｐＨ１１〜１４のアルカリ水溶液が好適に
用いられる。また、この際の水溶液の温度には特に制限
はないが、高温になるほど、加水分解は速やかで、えら
れた吸着材内での含水金属酸化物とポリスチレン系粒子
の密着性が良好になる。0012
] There is no particular restriction on the pH at this time, but an acidic aqueous solution with a pH of 1 to 2 or an alkaline aqueous solution with a pH of 11 to 14 are preferably used. Further, there is no particular restriction on the temperature of the aqueous solution at this time, but the higher the temperature, the faster the hydrolysis and the better the adhesion between the hydrous metal oxide and the polystyrene particles in the obtained adsorbent.
【００１３】[0013]
【実施例】つぎに実施例によって本発明をさらに詳細に
説明する。EXAMPLES Next, the present invention will be explained in more detail with reference to examples.
【００１４】実施例１
テトラ（ｎ−ブトキシ）ジルコニウム１２０ｇを３００
ｍｌの乾燥ｎ−ブタノールに溶解し、この溶液にあらか
じめ洗浄、乾燥したポリスチレン粒子（粒径１４〜２２
メッシュ、ＧＰＣによる数平均分子量１．０×１０４
重量平均分子量３．３×１０５）１００ｇを加え混合物
を約１時間減圧に置いた後、ｎ−ブタノールを減圧蒸留
によって除去し、乾燥状態の樹脂ビーズを得た。これを
ビーカに移し、ｐＨ２．０の水５００ｍｌを加え、２時
間静置したのち、上澄みを捨て、この中に、再びｐＨ２
．０の水５００ｍｌを加え、２４時間加熱還流した。つ
いで、粒子をろ過し、水、エタノールで順次洗浄し、目
的物のフッ化物イオン吸着材を得た。Example 1 120g of tetra(n-butoxy)zirconium was
ml of dry n-butanol, and pre-washed and dried polystyrene particles (particle size 14-22
Mesh, number average molecular weight by GPC 1.0 x 104
After adding 100 g of the mixture having a weight average molecular weight of 3.3×10 5 and leaving the mixture under reduced pressure for about 1 hour, n-butanol was removed by distillation under reduced pressure to obtain dry resin beads. Transfer this to a beaker, add 500 ml of pH 2.0 water, let it stand for 2 hours, discard the supernatant, and add it again to pH 2.0.
．． 0 ml of water was added thereto, and the mixture was heated under reflux for 24 hours. Next, the particles were filtered and washed with water and ethanol in order to obtain the target fluoride ion adsorbent.
【００１５】応用例１
実施例１で得た吸着材５ｇ（湿潤体積１０．２ｍｌ）を
、内径１．０ｃｍのカラムに充填し、ｐＨ３．０の水で
洗ったのち、フッ化物イオンを１００ｐｐｍ（ＮａＦと
して溶解）含有するｐＨ３．０の水溶液を２ｍｌ／ｍｉ
ｎで通液し、樹脂塔通過後のフッ化物イオン濃度を測定
した。その結果、樹脂体積の５０倍の通液点（カラムに
充填した吸着剤の体積をｘｍｌとすると、通液を開始し
てから５０ｘｍｌ溶出した点をいう）でのフッ化物イオ
ン濃度は１ｐｐｍ以下であり、７０倍の通液点までで１
０ｐｐｍ以下であった。Application Example 1 5 g (wet volume 10.2 ml) of the adsorbent obtained in Example 1 was packed into a column with an inner diameter of 1.0 cm, and after washing with water of pH 3.0, fluoride ions were added to 100 ppm ( 2 ml/mi of an aqueous solution containing pH 3.0 (dissolved as NaF)
After passing through the resin column, the fluoride ion concentration was measured. As a result, the fluoride ion concentration at the point where 50 times the resin volume was passed (when the volume of the adsorbent packed in the column is xml, 50xml was eluted from the start of passing) was found to be 1 ppm or less. Yes, up to 70 times the liquid flow point
It was 0 ppm or less.
【００１６】応用例２
応用例１でフッ化物イオンを吸着したカラムに、１Ｍ水
酸化ナトリウム水溶液２００ｍｌを２ｍｌ／ｍｉｎで通
液してフッ化物イオンの溶出をおこなった。カラム通液
後の水酸化ナトリウム水溶液中には、応用例１で吸着し
たフッ化物イオンの全量の９７ｗｔ％が含まれており、
またジルコニウムは、全く検出されなかった。次に、ｐ
Ｈ１．０の塩酸水溶液を、漏出液のｐＨが１．０になる
まで通液し、さらにカラムを水洗した後、応用例１と同
組成の被処理液を、応用例１と同様の方法で通液し、カ
ラム通過後のフッ化物イオン濃度を測定したところ、応
用例１と同様の結果を得た。Application Example 2 Fluoride ions were eluted by passing 200 ml of a 1M aqueous sodium hydroxide solution through the column that had adsorbed fluoride ions in Application Example 1 at a rate of 2 ml/min. The sodium hydroxide aqueous solution after passing through the column contained 97 wt% of the total amount of fluoride ions adsorbed in Application Example 1,
Also, no zirconium was detected. Then p
After passing an aqueous hydrochloric acid solution of H1.0 until the pH of the leaked liquid becomes 1.0 and washing the column with water, a solution to be treated having the same composition as in Application Example 1 was added in the same manner as in Application Example 1. When the solution was passed through the column and the fluoride ion concentration was measured after passing through the column, the same results as in Application Example 1 were obtained.
【００１７】[0017]
【発明の効果】本発明によれば、安価なポリスチレン担
体表面に含水金属酸化物を均一に析出させることができ
る。さらに、この吸着材は、吸着されたフッ化物イオン
を０．１〜２Ｍ程度のアルカリ水溶液等で処理すること
により定量的に溶離させ、酸洗い、水洗後、再び繰返し
再現性良くしようとすることができるという利点がある
。According to the present invention, a hydrous metal oxide can be uniformly deposited on the surface of an inexpensive polystyrene carrier. Furthermore, this adsorbent can be quantitatively eluted by treating the adsorbed fluoride ions with an aqueous alkali solution of about 0.1 to 2M, and after pickling and water washing, it can be repeated again to improve reproducibility. It has the advantage of being able to
【００１８】また、この吸着材では、担持されたジルコ
ニウムやセリウムの含水酸化物が酸やアルカリへの溶解
度が極めて小さいため、フッ化物イオンの溶出と吸着材
の再生を行う際の金属の溶解は、無視しうる程小さく、
この点からも繰返し再現性良くもちいることが可能であ
る。In addition, in this adsorbent, the supported hydrous oxides of zirconium and cerium have extremely low solubility in acids and alkalis, so the dissolution of metals during elution of fluoride ions and regeneration of the adsorbent is difficult. , so small that it can be ignored,
From this point of view as well, it can be used repeatedly with good reproducibility.
Claims (1)
化物を担体に担持させたフッ化物イオン吸着材を製造す
るに当り、担体にポリスチレン系粒子を用い、一般式（
Ｉ） Ｍ（ＯＲ）４ （Ｉ） （式中のＭはジルコニウムまたはセリウムを示し、Ｒは
炭素原子数５以下のアルキル基を示す）で示される金属
アルコキシドの溶液を、ポリスチレン系粒子に接触させ
たのち、これを加水分解処理することを特徴とするフッ
化物イオン吸着材の製造法。Claim 1: In producing a fluoride ion adsorbent in which a hydrous oxide of zirconium or cerium is supported on a carrier, polystyrene-based particles are used as the carrier, and the general formula (
I) A solution of a metal alkoxide represented by M(OR)4 (I) (in the formula, M represents zirconium or cerium, and R represents an alkyl group having 5 or less carbon atoms) is brought into contact with polystyrene particles. A method for producing a fluoride ion adsorbent, which is characterized in that the fluoride ion adsorbent is then subjected to a hydrolysis treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3083735A JPH04317738A (en) | 1991-04-16 | 1991-04-16 | Production of fluoride ion adsorbing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3083735A JPH04317738A (en) | 1991-04-16 | 1991-04-16 | Production of fluoride ion adsorbing material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04317738A true JPH04317738A (en) | 1992-11-09 |
Family
ID=13810788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3083735A Pending JPH04317738A (en) | 1991-04-16 | 1991-04-16 | Production of fluoride ion adsorbing material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04317738A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009285541A (en) * | 2008-05-27 | 2009-12-10 | Mitsui Mining & Smelting Co Ltd | Titanium group element based fluorine adsorbing-desorbing agent for fluorine-containing process liquid treatment for wet zinc smelting, and method for removing fluorine |
| WO2011052008A1 (en) * | 2009-10-29 | 2011-05-05 | 株式会社Ｎｈｖコーポレーション | Adsorbent, method for producing same, and use of same |
| CN110382442A (en) * | 2017-01-31 | 2019-10-25 | 三井金属矿业株式会社 | Formed body |
-
1991
- 1991-04-16 JP JP3083735A patent/JPH04317738A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009285541A (en) * | 2008-05-27 | 2009-12-10 | Mitsui Mining & Smelting Co Ltd | Titanium group element based fluorine adsorbing-desorbing agent for fluorine-containing process liquid treatment for wet zinc smelting, and method for removing fluorine |
| WO2011052008A1 (en) * | 2009-10-29 | 2011-05-05 | 株式会社Ｎｈｖコーポレーション | Adsorbent, method for producing same, and use of same |
| JP5316645B2 (en) * | 2009-10-29 | 2013-10-16 | 株式会社Ｎｈｖコーポレーション | Adsorbent manufacturing method |
| CN110382442A (en) * | 2017-01-31 | 2019-10-25 | 三井金属矿业株式会社 | Formed body |
| US11123709B2 (en) | 2017-01-31 | 2021-09-21 | Mitsui Mining & Smelting Co., Ltd. | Molded article |
| CN110382442B (en) * | 2017-01-31 | 2022-04-01 | 三井金属矿业株式会社 | Shaped body |
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