JPH0144644B2 - - Google Patents
Info
- Publication number
- JPH0144644B2 JPH0144644B2 JP12584480A JP12584480A JPH0144644B2 JP H0144644 B2 JPH0144644 B2 JP H0144644B2 JP 12584480 A JP12584480 A JP 12584480A JP 12584480 A JP12584480 A JP 12584480A JP H0144644 B2 JPH0144644 B2 JP H0144644B2
- Authority
- JP
- Japan
- Prior art keywords
- hafnium
- zirconium
- exchange resin
- solution
- basic anion
- 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.)
- Expired
Links
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 28
- 229910052726 zirconium Inorganic materials 0.000 claims description 28
- 229910052735 hafnium Inorganic materials 0.000 claims description 27
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 20
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 239000003957 anion exchange resin Substances 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 239000003729 cation exchange resin Substances 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- OBQPKGCVMCIETH-UHFFFAOYSA-N 1-chloro-1-(1-chloroethoxy)ethane Chemical compound CC(Cl)OC(C)Cl OBQPKGCVMCIETH-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 sulfuric acid Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】
本発明はジルコニウムとハフニウムとの相互分
離法に関するものである。詳しくは本発明はジル
コニウムとハフニウムとを、２種類のイオン交換
樹脂を用いて効率よく分離する方法に関するもの
である。
近年、原子力産業をはじめ種々の産業分野にお
いて、高純度のジルコニウムおよびハフニウムに
対する要求が増している。しかしジルコニウムと
ハフニウムとは、いずれも周期律表第−ａ族に
属する元素で、その化学的性質が極めて類似して
いるため、その相互分離が困難であることは周知
の通りである。
本発明によれば、ジルコニウムとハフニウムと
を含む溶液を弱塩基性陰イオン交換樹脂または強
酸性陽イオン交換樹脂と接触させてジルコニウム
またはハフニウムを選択的に吸着する工程と、こ
の工程の吸着残液または樹脂を酸水溶液で処理し
て得た溶離液を強酸性陽イオン交換樹脂または弱
塩基性陰イオン交換樹脂と接触させてハフニウム
またはジルコニウムを選択的に吸着する工程とを
組合せることにより、ジルコニウムとハフニウム
とを効率よく分離することができる。
本発明についてさらに詳細に説明すると、本発
明で処理の対象とするジルコニウムとハフニウム
とを含む溶液としては、硫酸、硝酸、塩酸等の鉱
酸々性水溶液が好ましい。特に好ましいのは硫
酸々性水溶液である。
弱塩基性陰イオン交換樹脂としては、通常、ス
チレンとジビニルベンゼンとの架橋共重合体をメ
チルクロロメチルエーテル等でハロメチル化した
のちジメチルアミンと反応させて得られる３級ア
ミノ基を交換基とする樹脂や、同じくハロメチル
化したのちポリアルキレンポリアミンと反応させ
て得られる１〜３級アミノ基を交換基とする樹脂
が用いられる。またビニルピリジンとジビニルベ
ンゼンとの架橋共重合体であるビニルピリジン樹
脂も用いられる。弱塩基性陰イオン交換樹脂はジ
ルコニウムとハフニウムとの共存する溶液からジ
ルコニウムを選択的に吸着する性質を有してい
る。また、弱塩基性陰イオン交換樹脂は、ジルコ
ニウムおよびハフニウム以外の金属、特に遷移金
属等の重金属が共存する溶液からでもジルコニウ
ムを選択的に吸着し、重金属は吸着しないので、
このような溶液の処理に特に好適である。
強酸性陽イオン交換樹脂としては、通常、スチ
レンとジビニルベンゼンとの架橋共重合体をスル
ホン化して得られるスルホン酸型の樹脂が用いら
れる。強酸性陽イオン交換樹脂はジルコニウムお
よびハフニウムを含む溶液から、ハフニウムを選
択的に吸着する性質を有している。本発明は、こ
のように選択吸着性が相反する２種類の樹脂を順
次用いて、ジルコニウムとハフニウムとの分離を
行なう方法である。本発明では処理対象とする溶
液を、先ず弱塩基性陰イオン交換樹脂または強酸
性陽イオン交換樹脂と接触させて、ジルコニウム
またはハフニウムを選択的に吸着させる。吸着方
法としては、溶液にイオン交換樹脂を投入して撹
拌する方法や、イオン交換樹脂の充填床に溶液を
流通させる方法など、通常のイオン交換樹脂を用
いる操作で常用されている任意の方法を用いるこ
とができる。この吸着処理によりジルコニウムま
たはハフニウムを選択的に吸着した後の溶液、ま
たは樹脂から硫酸等の鉱酸で吸着しているジルコ
ニウムおよびハフニウムを溶離させて得た溶液を
対象として、次いで強酸性陽イオン交換樹脂また
は弱塩基性陰イオン交換樹脂で処理して、ハフニ
ウムまたはジルコニウムを選択的に吸着させる。
例えば第１段の吸着処理に弱塩基性陰イオン交換
樹脂を用いた場合には、第１段で相対的にジルコ
ニウムの濃縮された溶離液とハフニウムの濃縮さ
れた吸着残液とが得られる。この溶離液を第２段
の吸着処理で強酸性陽イオン交換樹脂で処理する
と、吸着残液として更にジルコニウムの濃縮され
た溶液を得ることができる。また、第１段の吸着
残液を、所望により適宜濃縮して、強酸性陽イオ
ン交換樹脂で処理すると、第２段の溶離液として
相対的にさらにハフニウムの濃縮された溶液を得
ることができる。このように本発明によれば、２
種類のイオン交換樹脂を交互に使用して吸着処理
を行なうことにより、ジルコニウムとハフニウム
とを含む溶液からそれぞれを効率よく分離取得す
ることができる。
以下に実施例により本発明をさらに具体的に説
明するが、本発明はその要旨をこえない限り以下
の実施例に限定されるものではない。
実施例 １
0.0386モル／のジルコニウムと0.0374モル／
のハフニウムとを含む硫酸々性溶液（硫酸濃度
0.45モル／）250ml中に、硫酸負荷形の弱塩基
性陰イオン交換樹脂“ダイヤイオンWA30”（ダ
イヤイオンは三菱化成工業(株)の登録商標）10mlを
投入し、25℃で24時間振盪した。次いで過して
液中のジルコニウムおよびハフニウムを定量し
た。また、この液200ml中に水素形の強酸性陽
イオン交換樹脂“ダイヤイオンSK1B”３mlを投
入し、25℃で24時間振盪したのち、溶液中のジル
コニウムおよびハフニウムを定量した。結果を表
−１に示す。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for mutually separating zirconium and hafnium. Specifically, the present invention relates to a method for efficiently separating zirconium and hafnium using two types of ion exchange resins. In recent years, demand for high purity zirconium and hafnium has increased in various industrial fields including the nuclear industry. However, it is well known that zirconium and hafnium are both elements belonging to Group-a of the periodic table and have very similar chemical properties, so it is difficult to separate them from each other. According to the present invention, there is a step of selectively adsorbing zirconium or hafnium by contacting a solution containing zirconium and hafnium with a weakly basic anion exchange resin or a strongly acidic cation exchange resin, and an adsorption residual liquid of this step. Alternatively, by combining the process of selectively adsorbing hafnium or zirconium by contacting the eluent obtained by treating the resin with an acid aqueous solution with a strongly acidic cation exchange resin or a weakly basic anion exchange resin, zirconium and hafnium can be efficiently separated. To explain the present invention in more detail, the solution containing zirconium and hafnium to be treated in the present invention is preferably an acidic mineral aqueous solution such as sulfuric acid, nitric acid, or hydrochloric acid. Particularly preferred is an aqueous sulfuric acid solution. As a weakly basic anion exchange resin, the exchange group is usually a tertiary amino group obtained by halomethylating a crosslinked copolymer of styrene and divinylbenzene with methylchloromethyl ether, etc., and then reacting it with dimethylamine. Resins and resins having primary to tertiary amino groups as exchange groups obtained by halomethylating and reacting with polyalkylene polyamines are used. Vinylpyridine resin, which is a crosslinked copolymer of vinylpyridine and divinylbenzene, is also used. Weakly basic anion exchange resins have the property of selectively adsorbing zirconium from a solution in which zirconium and hafnium coexist. In addition, weakly basic anion exchange resins selectively adsorb zirconium even from solutions containing metals other than zirconium and hafnium, especially heavy metals such as transition metals, and do not adsorb heavy metals.
It is particularly suitable for processing such solutions. As the strongly acidic cation exchange resin, a sulfonic acid type resin obtained by sulfonating a crosslinked copolymer of styrene and divinylbenzene is usually used. Strongly acidic cation exchange resins have the property of selectively adsorbing hafnium from solutions containing zirconium and hafnium. The present invention is a method for separating zirconium and hafnium by sequentially using two types of resins having contradictory selective adsorption properties. In the present invention, a solution to be treated is first brought into contact with a weakly basic anion exchange resin or a strongly acidic cation exchange resin to selectively adsorb zirconium or hafnium. For the adsorption method, any method commonly used in operations using normal ion exchange resins can be used, such as adding an ion exchange resin to the solution and stirring it, or passing the solution through a packed bed of ion exchange resin. Can be used. The solution after selectively adsorbing zirconium or hafnium through this adsorption treatment, or the solution obtained by eluting adsorbed zirconium and hafnium from the resin with mineral acids such as sulfuric acid, is then subjected to strong acid cation exchange. Treatment with resin or weakly basic anion exchange resin to selectively adsorb hafnium or zirconium.
For example, when a weakly basic anion exchange resin is used in the first stage adsorption treatment, an eluate relatively enriched in zirconium and an adsorption residual solution relatively concentrated in hafnium are obtained in the first stage. When this eluate is treated with a strongly acidic cation exchange resin in the second adsorption treatment, a solution with further concentrated zirconium can be obtained as an adsorption residue. In addition, if the adsorption residual liquid from the first stage is appropriately concentrated as desired and treated with a strongly acidic cation exchange resin, a relatively further concentrated solution of hafnium can be obtained as the eluent for the second stage. . Thus, according to the present invention, 2
By performing adsorption treatment using different types of ion exchange resins, each of zirconium and hafnium can be efficiently separated and acquired from a solution containing them. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. Example 1 0.0386 mol/zirconium and 0.0374 mol/
sulfuric acid solution containing hafnium (sulfuric acid concentration
0.45 mol/), 10 ml of weakly basic anion exchange resin "Diaion WA30" (Diaion is a registered trademark of Mitsubishi Chemical Industries, Ltd.) loaded with sulfuric acid was added to 250 ml, and the mixture was shaken at 25°C for 24 hours. . Then, the zirconium and hafnium in the liquid was determined by filtration. Further, 3 ml of a hydrogen form strongly acidic cation exchange resin "Diaion SK1B" was added to 200 ml of this solution, and after shaking at 25°C for 24 hours, the amount of zirconium and hafnium in the solution was determined. The results are shown in Table-1. 【table】
Claims (1)
塩基性陰イオン交換樹脂または強酸性陽イオン交
換樹脂と接触させてジルコニウムまたはハフニウ
ムを選択的に吸着する工程と、この工程の吸着残
液または樹脂を酸水溶液で処理して得た溶離液を
強酸性陽イオン交換樹脂または弱塩基性陰イオン
交換樹脂と接触させてハフニウムまたはジルコニ
ウムを選択的に吸着する工程とを含むことを特徴
とするジルコニウムとハフニウムとの相互分離
法。1 A step in which a solution containing zirconium and hafnium is brought into contact with a weakly basic anion exchange resin or a strongly acidic cation exchange resin to selectively adsorb zirconium or hafnium, and the adsorption residual liquid or resin from this step is brought into contact with an acid aqueous solution. A process of selectively adsorbing hafnium or zirconium by contacting the eluate obtained by the treatment with a strongly acidic cation exchange resin or a weakly basic anion exchange resin. Mutual separation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12584480A JPS5751129A (en) | 1980-09-10 | 1980-09-10 | Mutual separation of zirconium and hafnium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12584480A JPS5751129A (en) | 1980-09-10 | 1980-09-10 | Mutual separation of zirconium and hafnium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5751129A JPS5751129A (en) | 1982-03-25 |
| JPH0144644B2 true JPH0144644B2 (en) | 1989-09-28 |
Family
ID=14920337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12584480A Granted JPS5751129A (en) | 1980-09-10 | 1980-09-10 | Mutual separation of zirconium and hafnium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5751129A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4994340B2 (en) * | 2008-09-26 | 2012-08-08 | 第一稀元素化学工業株式会社 | Method for separating zirconium and hafnium |
-
1980
- 1980-09-10 JP JP12584480A patent/JPS5751129A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5751129A (en) | 1982-03-25 |
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