JPH0722700B2 - Adsorption separation method of yttrium - Google Patents
Adsorption separation method of yttriumInfo
- Publication number
- JPH0722700B2 JPH0722700B2 JP63112139A JP11213988A JPH0722700B2 JP H0722700 B2 JPH0722700 B2 JP H0722700B2 JP 63112139 A JP63112139 A JP 63112139A JP 11213988 A JP11213988 A JP 11213988A JP H0722700 B2 JPH0722700 B2 JP H0722700B2
- Authority
- JP
- Japan
- Prior art keywords
- yttrium
- seawater
- uranium
- amidoxime
- acid
- 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 - Lifetime
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、イットリウムの吸着分離法に関するものであ
り、詳しくは、海水中のイットリウムをアミドキシム型
吸着材で吸着させたのち、特定濃度の酸と接触させてイ
ットリウムを濃縮分離する方法に関するものである。TECHNICAL FIELD The present invention relates to a method for adsorptive separation of yttrium, and more specifically, after adsorbing yttrium in seawater with an amidoxime type adsorbent, an acid having a specific concentration is used. The present invention relates to a method for concentrating and separating yttrium by contacting with.
＜従来の技術＞ 最近、超電導材料の研究が盛んに行われており、常温で
超電導を示すものが見いだされる可能性も高くなってい
る。<Prior Art> Recently, research on superconducting materials has been actively conducted, and there is a high possibility that a substance exhibiting superconductivity at room temperature will be found.
高温超電導材料の一つは銅、バリウム、及びイットリウ
ムの焼結体であり、製造法や超電導現象の解明について
盛んに研究されている。One of the high-temperature superconducting materials is a sintered body of copper, barium, and yttrium, which has been actively researched for its manufacturing method and elucidation of superconducting phenomenon.
現在、イットリウムは比較的安価に手に入れる事ができ
るが、わが国には産出されず、全量を海外からの輸入に
依存している。更に、資源が偏在しているため、イット
リウム等のレアメタルは備蓄対象元素になっている。Currently, yttrium can be obtained relatively cheaply, but it is not produced in Japan, and it depends entirely on imports from abroad. Furthermore, because the resources are unevenly distributed, rare metals such as yttrium are a target element for stockpiling.
このため新たなる資源の確保が必要であり、地表の７割
を占める海洋から有用資源を採取する技術を確立するこ
とが強く望まれている。Therefore, it is necessary to secure new resources, and it is strongly desired to establish a technology to extract useful resources from the ocean, which occupies 70% of the surface.
海水中のイットリウム濃度は海水中のウラン濃度の1/10
の0.3ppb以下であり、これまでに海水からイットリウム
を吸着したと言う報告は見当たらない。また、イットリ
ウムを吸着する吸着材の報告例も少ない。Yttrium concentration in seawater is 1/10 of uranium concentration in seawater
It is less than 0.3 ppb, and there is no report that yttrium has been adsorbed from seawater. There are also few reports of adsorbents that adsorb yttrium.
＜発明が解決しようとする課題＞ 本発明は、イットリウム用高性能吸着剤の開発及び希薄
溶液からイットリウムの吸着・分離技術を確立すること
を目的としたものである。更に、本発明のもう一つの課
題は海水ウラン採取工程において副産物としてのレアメ
タルの分離技術を確立することである。<Problems to be Solved by the Invention> The present invention aims to develop a high-performance adsorbent for yttrium and establish a technique for adsorbing / separating yttrium from a dilute solution. Another object of the present invention is to establish a technique for separating rare metals as by-products in the seawater uranium collecting process.
＜課題を解決するための手段＞ 本発明者等は、アミドキシム型キレート吸着剤を用いる
ウラン採取システムの研究において、ウラン以外の有用
元素の吸・脱着挙動を調べた結果、イットリウム等の有
用レアメタルがアミドキシム型吸着剤に吸着しているこ
とを見い出した。そしてまた、アミドキシム型吸着剤に
吸着したイットリウムの脱着分離について検討した結
果、希薄な酸溶液で溶離することによってウランと分別
脱着できることを見い出した。即ち、0.1〜１規定の酸
で処理するとウランが溶離する前にイットリウムが溶離
してくることを見い出した。<Means for Solving the Problems> As a result of investigating adsorption / desorption behavior of useful elements other than uranium in the study of a uranium extraction system using an amidoxime type chelate adsorbent, the present inventors have found that useful rare metals such as yttrium It was found that they were adsorbed on the amidoxime type adsorbent. As a result of investigating the desorption / separation of yttrium adsorbed on an amidoxime type adsorbent, it was found that it can be fractionally desorbed from uranium by eluting with a dilute acid solution. That is, it was found that yttrium was eluted before uranium was eluted when treated with 0.1 to 1 normal acid.
本発明は、上記知見を基に完成されたものであり、その
要旨は、アミドキシム型吸着材を海水と接触させてイッ
トリウムを該型吸着材に吸着させた後、0.1〜１規定の
酸と接触させてイットリウムを溶離させることを特徴と
するイットリウムの吸着分離法に存する。The present invention has been completed based on the above findings, and its gist is to bring an amidoxime type adsorbent into contact with seawater to adsorb yttrium on the type adsorbent and then to contact with an acid of 0.1 to 1N. The present invention resides in an adsorption and separation method for yttrium, which is characterized in that yttrium is eluted by the reaction.
以下、本発明を更に詳細に説明する。Hereinafter, the present invention will be described in more detail.
本発明で使用されるアミドキシム型樹脂は、アミドキシ
ム基を官能基として有するキレート樹脂で、公知の種々
の方法で製造される。すなわち、ニトリル基を有する重
合体をヒドロキシルアミンと反応させることにより製造
される。例えば、海水からウランを採取する方法に関す
る特開昭61−219718号、同61−219719号等の記載に従っ
て製造することができる。The amidoxime type resin used in the present invention is a chelate resin having an amidoxime group as a functional group and can be produced by various known methods. That is, it is produced by reacting a polymer having a nitrile group with hydroxylamine. For example, it can be produced according to the description of JP-A-61-219718, JP-A-61-219719 and the like regarding a method for collecting uranium from seawater.
アミドキシム型樹脂は粒状、球状等、カラム充填に都合
のよい形状が好ましい。粒径は100μｍないしは1mm程度
が好ましい。The amidoxime type resin preferably has a shape convenient for column packing, such as a granular shape or a spherical shape. The particle size is preferably about 100 μm or 1 mm.
アミドキシム型樹脂を海水と接触させてイットリウムを
吸着させる方法は特に限定されない。海流や波力等の自
然エネルギーを利用して海水と接触させる方法、ポンプ
を使用して海水と接触させる方法等、各種の方法が利用
できる。The method of bringing the amidoxime type resin into contact with seawater to adsorb yttrium is not particularly limited. Various methods such as a method of contacting with seawater by utilizing natural energy such as ocean current or wave force, a method of contacting with seawater by using a pump, etc. can be used.
第１表は、アミドキシム樹脂に吸着した海水中の諸元素
の分析結果を示すものである。すなわち、後記実施例に
おける海水接触処理を行ったアミドキシム樹脂に吸着し
ている元素を無機質量分析計を用いて定量した結果であ
る。Table 1 shows the analysis results of various elements in seawater adsorbed on the amidoxime resin. That is, it is the result of quantifying the elements adsorbed on the amidoxime resin subjected to the seawater contact treatment in the Examples described later using an inorganic mass spectrometer.
上記第１表によれば、ウラン吸着量は約1mg/g程度であ
り、この他、鉄、バナジウム、マグネシウム、カルシウ
ム等をそれぞれ7mg/g、8mg/g、20mg/g、10mg/g吸着して
いた。バナジウム吸着量が非常に高いこと、また、イッ
トリウムが50μg/gも吸着していること、及びランタ
ン、ネオジウム等のレアメタルがわずかながら吸着して
いることは注目すべきことである。 According to Table 1 above, the amount of uranium adsorbed is about 1 mg / g, and in addition to this, iron, vanadium, magnesium, calcium, etc. are adsorbed at 7 mg / g, 8 mg / g, 20 mg / g, and 10 mg / g, respectively. Was there. It is noteworthy that the vanadium adsorption amount is very high, that yttrium adsorbs as much as 50 μg / g, and that rare metals such as lanthanum and neodymium are slightly adsorbed.
本発明方法においては、イットリウムを吸着したアミド
キシム樹脂に0.1〜１規定の酸を接触させることが重要
であり、かかる溶離操作によってイットリウムをウラン
と分離して回収分離することができる。この場合、酸濃
度が１規定より高いとウランとの分離が良好とならず、
逆に、0.1規定より小さいと溶出速度が小さくなり過ぎ
る。In the method of the present invention, it is important to contact the amidoxime resin having adsorbed yttrium with 0.1 to 1 normal acid, and yttrium can be separated and recovered from uranium by such an elution operation. In this case, if the acid concentration is higher than 1N, the separation from uranium will not be good,
On the other hand, if it is less than 0.1 normal, the dissolution rate will be too low.
使用する酸は、特に限定されるものではなく、塩酸、硫
酸、硝酸、リン酸等が好適に使用される。溶離操作は撹
拌槽内で吸着剤スラリーに酸を添加する方法や、吸着剤
をカラムに充填し酸水溶液を下向流又は上向流で通液す
る方法等で適宜おこなわれる。The acid used is not particularly limited, and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc. are preferably used. The elution operation is appropriately performed by a method of adding an acid to the adsorbent slurry in a stirring tank, a method of filling the adsorbent in a column and passing an aqueous acid solution in a downward flow or an upward flow, and the like.
好ましい溶離操作は、カラム使用する連続法であり、こ
の場合、カラムの層高は通常2m以上、好ましくは3m以
上、流速は空塔線速度で通常9m/hr以下、好ましくは3m/
hr以下である。温度は特に限定されず、常温近くでよ
い。A preferred elution operation is a continuous method using a column, in which case the bed height of the column is usually 2 m or more, preferably 3 m or more, and the flow velocity is 9 m / hr or less, preferably 3 m / hr in superficial linear velocity.
It is less than or equal to hr. The temperature is not particularly limited and may be near room temperature.
次に本発明を実施例及び比較例によって具体的に説明す
るが、本発明はその要旨を超えない限り、以下の実施例
に限定されるものではない。Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.
実施例１ 混合溶媒中でテトラエチレングリコールジメタクリレー
ト（TEGDM）とジビニルベンゼン（DVB）を22:18の割合
で混合し、アクリロニトリルを重合して得られたメソポ
アを有する多孔質の基体を用いて調整したCuに対して2.
4meq/g−樹脂の飽和吸着量をもつアミドキシム樹脂10L
を断面積0.1m2、高さ1.2mの流動床カラムに充填し、SV:
100h-1天然海水を750日間上向流で通水した。Example 1 Preparation using a porous substrate having mesopores obtained by mixing tetraethylene glycol dimethacrylate (TEGDM) and divinylbenzene (DVB) in a mixed solvent at a ratio of 22:18 and polymerizing acrylonitrile. For Cu which was 2.
Amidoxime resin 10L with a saturated adsorption capacity of 4 meq / g-resin
Was packed in a fluidized bed column with a cross-sectional area of 0.1 m 2 and a height of 1.2 m, and SV:
100 h -1 natural seawater was passed as an upward flow for 750 days.
次いで、上記樹脂20mlを精秤し、200mlの三角フラスコ
に入れ、0.1N塩酸水溶液50mlを添加し、室温で30分間振
とうした後、ロート上で吸引ろ過し、樹脂とろ液を分離
し、ろ液中のウランとイットリウムの濃度を無機質量分
析計を用いて分析した。Next, 20 ml of the above resin was precisely weighed, put in a 200 ml Erlenmeyer flask, 50 ml of 0.1N hydrochloric acid aqueous solution was added, and after shaking at room temperature for 30 minutes, suction filtration was performed on the funnel to separate the resin and the filtrate, The concentrations of uranium and yttrium in the liquid were analyzed using an inorganic mass spectrometer.
さらに、樹脂を200mlの三角フラスコに入れ、同様な操
作を３回繰り返して行なった。Further, the resin was placed in a 200 ml Erlenmeyer flask and the same operation was repeated 3 times.
次いで、0.1N塩酸水溶液の代りに1N、次ぎに6N HCl水溶
液を使用してそれぞれ１回づつ上記と同様な操作を繰り
返した。各処理工程時のろ液中のウランとイットリウム
の濃度を第２表に示した。Then, the same operation as described above was repeated once using 1N instead of 0.1N hydrochloric acid aqueous solution and then using 6N HCl aqueous solution. Table 2 shows the concentrations of uranium and yttrium in the filtrate at each treatment step.
イットリウムは0.1N塩酸水溶液で溶離され、ウランと分
別回収することができた。 Yttrium was eluted with 0.1N hydrochloric acid aqueous solution and could be recovered separately from uranium.
＜発明の効果＞ 本発明によれば、ウラン採取用に使用可能なアミドキシ
ム型樹脂を吸着剤に用いて海水からイットリウムをウラ
ンと分離して回収することができるので、ウラン採取技
術の実用化への前進に寄与するとともに、レアメタル資
源のないわが国に対する貢献が大である。<Effects of the Invention> According to the present invention, yttrium can be separated from uranium from seawater and recovered by using an amidoxime type resin that can be used for uranium extraction as an adsorbent. In addition to contributing to Japan's progress, it also makes a major contribution to Japan, which has no rare metal resources.
Claims (1)
海水中のイットリウムを該吸着材に吸着させた後、0.1
〜１規定の酸と接触させて吸着されたイットリウムを溶
離させることを特徴とするイットリウムの吸着分離法。1. An amidoxime-type adsorbent is brought into contact with seawater to adsorb yttrium in seawater onto the adsorbent, and then 0.1
A method for adsorptive separation of yttrium, which comprises contacting with 1N acid to elute the adsorbed yttrium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63112139A JPH0722700B2 (en) | 1988-05-09 | 1988-05-09 | Adsorption separation method of yttrium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63112139A JPH0722700B2 (en) | 1988-05-09 | 1988-05-09 | Adsorption separation method of yttrium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01284336A JPH01284336A (en) | 1989-11-15 |
| JPH0722700B2 true JPH0722700B2 (en) | 1995-03-15 |
Family
ID=14579188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63112139A Expired - Lifetime JPH0722700B2 (en) | 1988-05-09 | 1988-05-09 | Adsorption separation method of yttrium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0722700B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012132076A (en) * | 2010-12-22 | 2012-07-12 | Ihi Corp | System and method for collecting metal |
| CN111867989B (en) * | 2018-01-12 | 2023-09-26 | 南佛罗里达大学 | Functionalized porous organic polymers as uranium nanotraps for efficient uranium extraction |
| WO2019140338A1 (en) | 2018-01-12 | 2019-07-18 | University Of South Florida | Multifunctional porous materials for water purification and remediation |
-
1988
- 1988-05-09 JP JP63112139A patent/JPH0722700B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01284336A (en) | 1989-11-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |