JP5852478B2 - Rare earth recovery method from rare earth containing scrap - Google Patents
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Description
本発明は、鉄を含む希土類含有スクラップからの希土類元素の回収方法に関する。 The present invention relates to a method for recovering rare earth elements from rare earth-containing scrap containing iron.
近年、永久磁石は飛躍的な進歩に端を発して様々な分野へ応用され、その性能の向上と新しい機器の開発が日々刻々となされている。特に、省エネや環境対策の観点から、ＩＴ、自動車、家電、ＦＡ分野などへの普及が急激に伸びている。
永久磁石の用途として、パソコンでは、ハードディスクドライブ用ボイスコイルモーターやＤＶＤ／ＣＤの光ピックアップ用部品、携帯電話では、マイクロスピーカーやバイブレーションモーター、家電や産業機器関連では、サーボモーターやリニアモーターなどの各種モーターがある。また、ＨＥＶなどのハイブリッド電気自動車には、１台当たり１００個以上の永久磁石が使用されている。
In recent years, permanent magnets have been applied to various fields as a result of dramatic progress, and improvements in their performance and development of new devices have been made every day. In particular, from the viewpoints of energy saving and environmental measures, the spread to IT, automobiles, home appliances, FA fields, etc. is growing rapidly.
Permanent magnet applications include voice coil motors for hard disk drives and optical pickup components for DVD / CD for personal computers, microspeakers and vibration motors for mobile phones, and servo motors and linear motors for home appliances and industrial equipment. There is a motor. Moreover, 100 or more permanent magnets are used for each hybrid electric vehicle such as HEV.
永久磁石として、アルニコ（Ａｌｎｉｃｏ）磁石、フェライト（Ｆｅｅｒｒｉｔｅ）磁石、サマコバ（ＳｍＣｏ）磁石、ネオジム（ＮｄＦｅＢ）磁石などが知られている。近年は、特にネオジム磁石の研究開発が活発であり、高性能化に向けて様々な取り組みが行われている。
ネオジム磁石は、通常、強磁性のＮｄ２Ｆｅ１４Ｂ金属間化合物（主相）、非磁性のＢリッチ相、非磁性のＮｄリッチ相、さらに不純物としての酸化物などから構成されている。さらに、これに種々の元素を添加するなどして、磁気特性を改善させる取り組みが行われている。
As a permanent magnet, an Alnico magnet, a ferrite magnet, a Samaco magnet, a neodymium (NdFeB) magnet, and the like are known. In recent years, research and development of neodymium magnets has been particularly active, and various efforts have been made toward higher performance.
A neodymium magnet is usually composed of a ferromagnetic Nd 2 Fe 14 B intermetallic compound (main phase), a nonmagnetic B-rich phase, a nonmagnetic Nd-rich phase, and an oxide as an impurity. Furthermore, efforts are being made to improve magnetic properties by adding various elements to this.
ネオジム磁石はその性能の高さから、その需要は今後も大幅に増大すると予想される。しかし、ネオジム磁石に含まれるＮｄやＤｙ等の希土類金属は資源供給上の問題があり、希土類金属の需要が大きくなれば、それらの金属の価格が急騰することが予想される。そのため、このような希土類磁石からの希土類金属の回収方法・分離方法に関する技術開発が活発に行われている。
例えば、特許文献１には、希土類元素−鉄含有合金を加熱して空気酸化した後、強酸を用いた酸浸出法により、希土類元素塩を生成して濾液中に溶解し、これを濾別して分離して、希土類元素を回収することが記載されている。
Neodymium magnets are expected to increase in demand in the future due to their high performance. However, rare earth metals such as Nd and Dy contained in neodymium magnets have a problem in resource supply, and if the demand for rare earth metals increases, the price of those metals is expected to rise rapidly. For this reason, technological development relating to a method for recovering and separating rare earth metals from such rare earth magnets has been actively conducted.
For example, in Patent Document 1, a rare earth element-iron-containing alloy is heated and oxidized in air, and then a rare earth element salt is generated and dissolved in a filtrate by an acid leaching method using a strong acid, and this is separated by filtration. Thus, it is described that rare earth elements are recovered.
特許文献２には、希土類元素・鉄系磁石材料を鉱酸溶液中に溶解し、次いで、フッ酸イオン含有溶液を添加して希土類フッ化物を沈殿生成し、沈殿物を分離して、希土類元素を回収することが記載されている。
また、特許文献３には、希土類−遷移金属合金スクラップを、鉱酸アンモニウム塩水溶液に浸漬し、これに酸素を含む気体を流通させて、スクラップを酸化させて酸化物及び水酸化物の粉末を含む沈殿物を得て、これを鉱酸アンモニウム塩水溶液から分離して、この分離した沈殿物から希土類元素を回収する方法が記載されている。
また、特許文献４には、溶融塩電解浴に希土類酸化物スクラップを投入し、電解浴中にこのスクラップを希土類酸化物と磁石合金部に溶融分離させ、電解浴に溶解した希土類酸化物を電解により希土類金属に還元し、磁石合金部を希土類金属と合金化させ、希土類金属−遷移金属−ボロン合金として再生することが記載されている。
In Patent Document 2, a rare earth element / iron-based magnet material is dissolved in a mineral acid solution, then a hydrofluoric acid ion-containing solution is added to precipitate a rare earth fluoride, the precipitate is separated, and the rare earth element is separated. Is described.
Patent Document 3 discloses that a rare earth-transition metal alloy scrap is immersed in an aqueous mineral acid ammonium salt solution, a gas containing oxygen is circulated therein, and the scrap is oxidized to produce oxide and hydroxide powders. A method is described in which a precipitate is obtained, which is separated from an aqueous mineral acid ammonium salt solution, and the rare earth element is recovered from the separated precipitate.
In Patent Document 4, rare earth oxide scrap is put into a molten salt electrolytic bath, and the scrap is melted and separated into a rare earth oxide and a magnet alloy portion in the electrolytic bath, and the rare earth oxide dissolved in the electrolytic bath is electrolyzed. It is described that it is reduced to a rare earth metal, and the magnet alloy part is alloyed with a rare earth metal to be regenerated as a rare earth metal-transition metal-boron alloy.
従来、鉄を含有する希土類磁石スクラップから希土類元素が回収する場合、塩酸、硝酸、硫酸などの酸を用いて、希土類を浸出させることが行われている。しかし、このような酸浸出によると、鉄が溶出しやすく、希土類の浸出率を上げると、浸出液中の鉄濃度が上昇して脱鉄がうまく行われないといった問題がある。また、沈降性及び濾過性の悪い水酸化鉄ができやすいといった問題がある。さらに、希土類磁石スクラップの全てを溶解するためには、多量の塩酸などを使用する必要あるという問題がある。 Conventionally, when a rare earth element is recovered from a rare earth magnet scrap containing iron, the rare earth is leached using an acid such as hydrochloric acid, nitric acid or sulfuric acid. However, according to such acid leaching, iron is likely to be eluted, and if the leaching rate of the rare earth is increased, there is a problem that the iron concentration in the leaching solution increases and deironing is not performed well. Further, there is a problem that iron hydroxide having poor sedimentation and filterability is easily formed. Furthermore, there is a problem that it is necessary to use a large amount of hydrochloric acid in order to dissolve all of the rare earth magnet scrap.
上記の課題を解決するために、本発明者らは鋭意研究を行った結果、希土類磁石スクラップの酸化粉を電解液に混合し、これを電解することにより、希土類元素を極めて簡便かつ効率良く回収することができることを見出した。 In order to solve the above-mentioned problems, the present inventors have conducted intensive research, and as a result, rare earth element scraps are extremely easily and efficiently recovered by mixing rare earth magnet scrap oxide powder into an electrolyte and electrolyzing it. Found that you can.
このような知見に基づき、本発明は、
１）鉄を含有する希土類含有スクラップの酸化粉を電解法により、希土類元素を溶出することを特徴とするスクラップからの希土類元素の回収方法、
２）電解液に電導塩を含有させることを特徴とする上記１記載のスクラップからの希土類元素の回収方法、
３）電解液のｐＨを２〜８、電解液の液温を１０〜９０℃とすることを特徴とする上記１又は２のいずれか一に記載のスクラップからの希土類元素の回収方法、
４）攪拌しながら電解を行うことを特徴とする上記１〜３のいずれか一に記載のスクラップからの希土類元素の回収方法、
５）電解によって酸化鉄がＦｅ３Ｏ４（黒色）からＦｅ２Ｏ３（褐色）に変化すことを特徴とする上記１〜４に記載のスクラップからの希土類元素の回収方法、
６）希土類元素が溶出した溶液から、希土類元素を回収することを特徴とする上記１〜５のいずれか一に記載のスクラップからの希土類元素の回収方法、
７）希土類元素が溶出した溶液から、溶媒抽出あるいは結晶化法により、希土類元素を回収することを特徴とする上記１〜６のいずれか一に記載のスクラップからの希土類元素の回収方法、を提供する。
Based on such knowledge, the present invention
1) A method for recovering rare earth elements from scrap, characterized by eluting rare earth elements by electrolysis of rare earth-containing scrap oxide containing iron,
2) A method for recovering rare earth elements from scrap as described in 1 above, wherein the electrolytic solution contains a conductive salt;
3) The method for recovering rare earth elements from scrap according to any one of the above 1 or 2, wherein the pH of the electrolyte is 2 to 8, and the temperature of the electrolyte is 10 to 90 ° C.
4) The method for recovering rare earth elements from scrap according to any one of 1 to 3 above, wherein electrolysis is performed with stirring,
5) a method for recovering rare earth elements from scrap according to the 1 to 4, wherein the to change the Fe 2 O 3 iron oxide is Fe 3 O 4 (black) (brown) by electrolysis,
6) The method for recovering a rare earth element from scrap according to any one of 1 to 5 above, wherein the rare earth element is recovered from a solution from which the rare earth element is eluted,
7) A method for recovering a rare earth element from scrap as described in any one of 1 to 6 above, wherein the rare earth element is recovered from a solution from which the rare earth element is eluted by solvent extraction or crystallization. To do.
本発明は、使用済みの永久磁石又は製造時に発生する端材等のスクラップから得られた酸化粉を使用し、これを電解するだけなので、希土類元素を極めて簡便かつ効率良く回収することができるという優れた方法である。 The present invention uses oxidized powder obtained from scraps such as used permanent magnets or scraps generated during production, and only electrolyzes them, so that rare earth elements can be recovered very simply and efficiently. It is an excellent method.
本発明は、鉄（鉄金属、鉄合金、鉄酸化物、鉄化合物など）を含む希土類含有スクラップの酸化粉を電解液中に混合し、これを電解により、希土類元素を溶出することを特徴とする、スクラップからの希土類元素の回収方法、を提供する。
本発明の回収方法は、鉄を主成分とする希土類永久磁石であれば、公知の希土類磁石に適用することができ、その成分組成に特に制限はない。公知の希土類磁石としては、例えば、Ｎｄ−Ｆｅ−Ｂ系希土類永久磁石などがあり、これはＮｄ、Ｆｅ、Ｂを典型的な成分とし、必要に応じて、Ｄｙ、Ｐｒ、Ｔｂ、Ｈｏ、Ｓｍなどの希土類元素や、Ｃｏ、Ｃｕ、Ｃｒ、Ｎｉ、Ａｌなどの遷移金属元素を含むものである。
The present invention is characterized by mixing rare earth-containing scrap oxide powder containing iron (iron metal, iron alloy, iron oxide, iron compound, etc.) in an electrolytic solution, and eluting the rare earth element by electrolysis. And a method for recovering rare earth elements from scrap.
The recovery method of the present invention can be applied to a known rare earth magnet as long as it is a rare earth permanent magnet mainly composed of iron, and the component composition is not particularly limited. Known rare earth magnets include, for example, Nd—Fe—B rare earth permanent magnets, which have Nd, Fe, and B as typical components, and if necessary, Dy, Pr, Tb, Ho, Sm. And rare earth elements such as Co, Cu, Cr, Ni and Al.
本発明の鉄を含有する希土類含有スクラップの酸化粉は、例えば、大気中で希土類磁石スクラップを焙焼することにより得ることができる。スクラップが粉砕粉や研磨粉等の細かいものであれば、直接焙焼してもよいが、使用済みの永久磁石などの形状のある大きなものは細かく粉砕してから、焙焼するのが好ましい。また、本発明の酸化粉は、全量において酸化物となっていなくともよく、部分的に酸化物となっていれば、本発明の回収方法を適用することができる。 The rare earth-containing scrap oxide powder containing iron of the present invention can be obtained, for example, by roasting rare earth magnet scrap in the atmosphere. If the scrap is fine, such as pulverized powder or abrasive powder, it may be directly baked. However, it is preferable to pulverize a large one having a shape such as a used permanent magnet before it is baked. Further, the oxide powder of the present invention does not have to be an oxide in the whole amount, and the recovery method of the present invention can be applied if it is partially an oxide.
この酸化粉を電導塩と純水で調合した電解液に混合して電気分解する。電導塩として、例えば、硫酸アンモニウム、硝酸アンモニウム、塩化アンモニウム、塩化ナトリウム、硫酸ナトリウムなどを用いることができる。このとき、電解液のｐＨは２〜８に調整することが好ましい。ｐＨが低い（酸性）と、Ｆｅが多く溶け出し残渣のろ過性が悪くなり、ｐＨが高い（アルカリ性）と希土類金属の溶出率が低下するからである。
また、電解条件は材料の種類、性質、量などによって異なるため、適宜選択して実施することができる。コストなどを考慮すると、好適な条件として、電解液の液温を１０〜９０℃とすることができる。電解温度が１０℃未満では希土類金属の溶出率が低下し、９０℃超では電解液の蒸発等で電解が困難となるからである。
This oxidized powder is mixed with an electrolytic solution prepared with a conductive salt and pure water and electrolyzed. As the conductive salt, for example, ammonium sulfate, ammonium nitrate, ammonium chloride, sodium chloride, sodium sulfate and the like can be used. At this time, it is preferable to adjust pH of electrolyte solution to 2-8. This is because if the pH is low (acidic), a large amount of Fe dissolves and the filterability of the residue deteriorates, and if the pH is high (alkaline), the elution rate of rare earth metals decreases.
In addition, since the electrolysis conditions vary depending on the type, nature, amount, etc. of the material, it can be selected as appropriate. Considering the cost and the like, as a suitable condition, the liquid temperature of the electrolytic solution can be set to 10 to 90 ° C. This is because when the electrolysis temperature is less than 10 ° C., the elution rate of the rare earth metal decreases, and when it exceeds 90 ° C., electrolysis becomes difficult due to evaporation of the electrolytic solution.
本発明において、特に重要な点は、酸化粉を含む電解液を電解して、希土類元素をイオンとして溶出させることである。これは、次の電気的化学的な反応によって生じると考えられる。酸化粉は、その大部分がＦｅ３Ｏ４から構成されており(希土類は主として、ＲｅＦｅＯ３：Ｒｅは希土類、から構成されている)、これがアノードで電子を受け取りＦｅ２Ｏ３に変化する。その際に、酸化粉に含まれている希土類元素が酸化粉から分離して、希土類イオンとして電解液中に溶出するのである。これに関しては、酸化鉄を含む電解液の色が黒色（Ｆｅ３Ｏ４由来）から赤褐色（Ｆｅ２Ｏ３由来）へと変化していることからも、このような現象が起こっていると考えられる。 In the present invention, a particularly important point is to electrolyze an electrolytic solution containing oxide powder and to elute rare earth elements as ions. This is considered to be caused by the following electrochemical reaction. Most of the oxide powder is composed of Fe 3 O 4 (rare earth is mainly composed of ReFeO 3 : Re is a rare earth), which receives electrons at the anode and changes to Fe 2 O 3 . At that time, the rare earth element contained in the oxide powder is separated from the oxide powder and eluted into the electrolyte as rare earth ions. In this regard, it is considered that such a phenomenon occurs because the color of the electrolyte containing iron oxide has changed from black (from Fe 3 O 4 ) to reddish brown (from Fe 2 O 3 ). It is done.
また、このような電気的化学的な反応を効率的に進めるために、酸化粉がアノードとできるだけ接触するようにすることが大切である。したがって、例えば、電解液を攪拌することで接触回数を増やしたり、アノードの面積を大きくして接触面積を広げたり、することが有効である。 Further, in order to advance such an electrochemical reaction efficiently, it is important to make the oxide powder contact the anode as much as possible. Therefore, for example, it is effective to increase the number of contacts by stirring the electrolytic solution or to increase the contact area by increasing the area of the anode.
以下、実施例および比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例によって何ら制限されるものではない。すなわち、本発明は特許請求の範囲によってのみ制限されるものであり、本発明に含まれる実施例以外の種々の変形を包含するものである。 Hereinafter, description will be made based on Examples and Comparative Examples. In addition, a present Example is an example to the last, and is not restrict | limited at all by this example. In other words, the present invention is limited only by the scope of the claims, and includes various modifications other than the examples included in the present invention.
（実施例１）
Ｆｅを含有する希土類含有スクラップ(希土類元素：Ｎｄ、Ｄｙ、Ｐｒ含有)を焙焼し、得られた酸化粉５０ｇを、塩化ナトリウムを含有する純水１Ｌでスラリー化し、電解を行った。このとき、電解条件は、ｐＨ：２〜３、電解温度：２０℃、電流：１０Ａ、電解時間２０時間とした。この結果、Ｎｄの溶出率は５０％、Ｄｙの溶出率は６０％、Ｐｒの溶出率は５０％であった。Ｆｅについては、微量溶出した程度であった。
次に、電解終了後、溶液中の残渣をろ過除去して、この濾液を抽出剤：２−エチルヘキシル−２−エチルヘキシル−ホスホン酸[2-ethylhexyl-2-ethylhexyl-phosphonic acid] （大八化学工業社製、商品名「ＰＣ８８Ａ」）を用いて、溶媒抽出法により、希土類元素分離して、Ｎｄ、Ｄｙ、Ｐｒの希土類金属を回収した。
以上より、希土類含有スクラップからＮｄ、Ｄｙ、Ｐｒの希土類金属を、効率的に回収することができ、また、良好なろ過性を得ることができた。そして、このＮｄ、Ｄｙ、Ｐｒは再生永久磁石の原料として使用可能であった。
なお、溶出率（％）とは、スクラップ中の金属含有重量：Ａ、電解後の残渣中の金属含有重量：Ｂとし、該金属が溶液中に溶け出した割合を示すものであり、溶出率（％）＝(Ａ−Ｂ)/ Ａ×１００で計算される（以下、実施例、比較例も同様とする）。
Example 1
A rare earth-containing scrap containing Fe (rare earth elements: containing Nd, Dy, Pr) was roasted, and 50 g of the obtained oxide powder was slurried with 1 L of pure water containing sodium chloride and electrolyzed. At this time, the electrolysis conditions were pH: 2 to 3, electrolysis temperature: 20 ° C., current: 10 A, and electrolysis time 20 hours. As a result, the elution rate of Nd was 50%, the elution rate of Dy was 60%, and the elution rate of Pr was 50%. As for Fe, only a small amount was eluted.
Next, after the electrolysis is completed, the residue in the solution is removed by filtration, and the filtrate is extracted with an extractant: 2-ethylhexyl-2-ethylhexyl-phosphonic acid (Daihachi Chemical Industry). Rare earth elements such as Nd, Dy, and Pr were recovered by solvent extraction using a product name “PC88A”) manufactured by the same company.
As described above, Nd, Dy and Pr rare earth metals can be efficiently recovered from the rare earth-containing scrap, and good filterability can be obtained. And this Nd, Dy, Pr could be used as a raw material of a reproduction | regeneration permanent magnet.
The dissolution rate (%) is the metal content weight in scrap: A, the metal content weight in residue after electrolysis: B, and indicates the ratio of the metal dissolved into the solution. (%) = (A−B) / A × 100 (hereinafter, the same applies to Examples and Comparative Examples).
（実施例２）
Ｆｅを含有する希土類含有スクラップ(希土類元素：Ｎｄ、Ｄｙ、Ｐｒ含有)を焙焼し、得られた酸化粉２００ｇを、硫酸ナトリウムを含有する純水１Ｌでスラリー化し、電解を行った。このとき、電解条件は、ｐＨ：４、電解温度：６０℃、電流：５Ａ、電解時間２０時間とした。この結果、Ｎｄの溶出率は７０％、Ｄｙの溶出率は７２％、Ｐｒの溶出率は７０％であった。Ｆｅについては、ほとんど溶出しなかった。
次に、電解終了後、溶液中の残渣をろ過除去して、この濾液をシュウ酸添加し、希土類元素を分離して、Ｎｄ、Ｄｙ、Ｐｒの希土類金属を回収した。
以上より、希土類含有スクラップからＮｄ、Ｄｙ、Ｐｒの希土類金属を、効率的に回収することができ、また、良好なろ過性を得ることができた。そして、このＮｄ、Ｄｙ、Ｐｒは再生永久磁石の原料として使用可能であった。
(Example 2)
A rare earth-containing scrap containing Fe (rare earth elements: containing Nd, Dy, Pr) was roasted, and 200 g of the obtained oxide powder was slurried with 1 L of pure water containing sodium sulfate, and electrolysis was performed. At this time, the electrolysis conditions were pH: 4, electrolysis temperature: 60 ° C., current: 5 A, and electrolysis time of 20 hours. As a result, the elution rate of Nd was 70%, the elution rate of Dy was 72%, and the elution rate of Pr was 70%. Fe was hardly eluted.
Next, after the electrolysis was completed, the residue in the solution was removed by filtration, the filtrate was added with oxalic acid, the rare earth elements were separated, and the rare earth metals Nd, Dy, and Pr were recovered.
As described above, Nd, Dy and Pr rare earth metals can be efficiently recovered from the rare earth-containing scrap, and good filterability can be obtained. And this Nd, Dy, Pr could be used as a raw material of a reproduction | regeneration permanent magnet.
（実施例３）
Ｆｅを含有する希土類含有スクラップ(希土類元素：Ｎｄ、Ｄｙ含有)を焙焼して、得られた酸化粉１００ｇを、硝酸アンモニウムを含有する純水１Ｌでスラリー化し、電解を行った。このとき、電解条件は、ｐＨ：７.５、電解温度：９０℃、電流：１０Ａ、電解時間６時間とした。この結果、Ｎｄの溶出率は４５％、Ｄｙの溶出率は３０％であった。Ｆｅについては、ほとんど溶出しなかった。
次に、電解終了後、溶液中の残渣を濾過除去して、この濾液に炭酸ナトリウムを添加して、希土類元素を分離して、Ｎｄ、Ｄｙの希土類金属を回収した。
以上より、希土類含有スクラップからＮｄ、Ｄｙ、Ｐｒの希土類金属を、効率的に回収することができ、また、良好なろ過性を得ることができた。そして、このＮｄ、Ｄｙ、Ｐｒは再生永久磁石の原料として使用可能であった。
(Example 3)
A rare earth-containing scrap containing Fe (rare earth elements: containing Nd and Dy) was roasted, and 100 g of the obtained oxide powder was slurried with 1 L of pure water containing ammonium nitrate for electrolysis. At this time, the electrolysis conditions were pH: 7.5, electrolysis temperature: 90 ° C., current: 10 A, and electrolysis time 6 hours. As a result, the elution rate of Nd was 45%, and the elution rate of Dy was 30%. Fe was hardly eluted.
Next, after completion of electrolysis, the residue in the solution was removed by filtration, sodium carbonate was added to the filtrate to separate rare earth elements, and rare earth metals of Nd and Dy were recovered.
As described above, Nd, Dy and Pr rare earth metals can be efficiently recovered from the rare earth-containing scrap, and good filterability can be obtained. And this Nd, Dy, Pr could be used as a raw material of a reproduction | regeneration permanent magnet.
(実施例４)
Ｆｅを含有する希土類含有スクラップ(希土類元素：Ｎｄ、Ｄｙ、Ｐｒ含有)を焙焼し得られた酸化粉５０ｇを、塩化ナトリウムを含有する純水１Ｌでスラリー化し、電解を行った。このとき、電解条件はｐＨ：１とし、その他の条件は実施例１と同様にした。この結果、Ｎｄの溶出率は７０％、Ｄｙの溶出率は６５％、Ｐｒの溶出率は６０％であったが、Ｆｅも４０％程度溶出していた。
このように、希土類含有スクラップからＮｄ、Ｄｙ、Ｐｒの希土類金属を、効率的に回収することができたが、一方で、ｐＨが低すぎるとＦｅも溶出していまい、ろ過性が低下することとなった。
Example 4
50 g of oxidized powder obtained by roasting rare earth-containing scrap containing Fe (containing rare earth elements: Nd, Dy, Pr) was slurried with 1 L of pure water containing sodium chloride, and electrolysis was performed. At this time, the electrolysis conditions were pH: 1, and other conditions were the same as in Example 1. As a result, the elution rate of Nd was 70%, the elution rate of Dy was 65%, and the elution rate of Pr was 60%, but Fe was also eluted by about 40%.
Thus, Nd, Dy, and Pr rare earth metals could be efficiently recovered from the rare earth-containing scrap, but on the other hand, if the pH is too low, Fe will not be eluted and the filterability will be reduced. It became.
(実施例５)
Ｆｅを含有する希土類含有スクラップ(希土類元素：Ｎｄ、Ｄｙ、Ｐｒ含有)を焙焼し得られた酸化粉５０ｇを、塩化ナトリウムを含有する純水１Ｌでスラリー化し、電解を行った。このとき、電解条件はｐＨ：９とし、その他の条件は実施例１と同様にした。この結果、Ｎｄの溶出率は４５％、Ｄｙの溶出率は３０％、Ｐｒの溶出率は３０％であった。Ｆｅについては、ほとんど溶出しなかった。
このように、希土類含有スクラップからＮｄ、Ｄｙ、Ｐｒの希土類金属を回収することができ、また、良好なろ過性を得ることができた。そして、このＮｄ、Ｄｙ、Ｐｒは再生永久磁石の原料として使用可能であった。一方で、ｐＨが高すぎると希土類元素が溶出し難いこととなった。
(Example 5)
50 g of oxidized powder obtained by roasting rare earth-containing scrap containing Fe (containing rare earth elements: Nd, Dy, Pr) was slurried with 1 L of pure water containing sodium chloride, and electrolysis was performed. At this time, the electrolysis conditions were pH: 9, and the other conditions were the same as in Example 1. As a result, the elution rate of Nd was 45%, the elution rate of Dy was 30%, and the elution rate of Pr was 30%. Fe was hardly eluted.
Thus, Nd, Dy, and Pr rare earth metals could be recovered from the rare earth-containing scrap, and good filterability could be obtained. And this Nd, Dy, Pr could be used as a raw material of a reproduction | regeneration permanent magnet. On the other hand, if the pH is too high, the rare earth element is difficult to elute.
（比較例１）
Ｆｅを含有する希土類含有スクラップ(希土類元素：Ｎｄ、Ｄｙ、Ｐｒ含有)を、塩酸を用いて酸浸出を行った。その結果、Ｎｄ，Ｄｙ，Ｐｒの溶出率は７０〜８０％であったが、Ｆｅも８０％溶出していた。このように酸浸出では残渣のろ過性が非常に悪く、また、溶け出したＦｅの処理も問題となった。
(Comparative Example 1)
A rare earth-containing scrap containing Fe (rare earth elements: containing Nd, Dy, Pr) was acid leached using hydrochloric acid. As a result, the elution rate of Nd, Dy, and Pr was 70 to 80%, but Fe was also eluted by 80%. Thus, in acid leaching, the filterability of the residue is very poor, and the treatment of dissolved Fe has also become a problem.
本発明は、使用済みの永久磁石又は製造時に発生する端材等のスクラップを焙焼等により作製した酸化粉使用し、これをアノードにおいて電解するだけなので、希土類元素を極めて簡便かつ効率良く回収することができる点で、大きな産業上の利点がある。 The present invention uses oxide powder produced by roasting scraps such as used permanent magnets or scraps generated during production, and this is simply electrolyzed at the anode, so that rare earth elements are recovered very simply and efficiently. There are significant industrial advantages in that it can.
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