JPH11319752A - Recovery of valued composition from rare earth element-containing substance and alloy powder obtained thereby - Google Patents
Recovery of valued composition from rare earth element-containing substance and alloy powder obtained therebyInfo
- Publication number
- JPH11319752A JPH11319752A JP12871298A JP12871298A JPH11319752A JP H11319752 A JPH11319752 A JP H11319752A JP 12871298 A JP12871298 A JP 12871298A JP 12871298 A JP12871298 A JP 12871298A JP H11319752 A JPH11319752 A JP H11319752A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- earth element
- calcium
- weight
- composition
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、希土類元素含有物
からの有価組成物を回収する方法、および、その回収方
法によって得られた希土類元素含有合金粉末に関する。The present invention relates to a method for recovering a valuable composition from a rare earth element-containing material, and a rare earth element-containing alloy powder obtained by the method.
【０００２】[0002]
【従来の技術】Ｓｍ−Ｃｏ系、Ｎｄ−Ｆｅ−Ｂ系などの
焼結磁石、Ｔｂ−Ｆｅ−Ｃｏ系などのスパッタリング用
ターゲット材は、希土類元素成分を含有している。焼結
磁石は成形体の常圧焼結法によって、ターゲット材はホ
ットプレス法によって主として得られている。これら焼
結体には、製品不良によって発生するスクラップや、組
み込まれた製品が廃棄されたときのスクラップ等が存在
する。特にスパッタリングターゲット材では、ターゲッ
ト材全体をスパッタリングで消費することは困難で、必
ず使用後に一部の焼結体が残存し、これがスクラップと
なる。2. Description of the Related Art Sm-Co based, Nd-Fe-B based sintered magnets, and Tb-Fe-Co based sputtering target materials contain rare earth elements. The sintered magnet is mainly obtained by a normal pressure sintering method of a molded body, and the target material is mainly obtained by a hot pressing method. In these sintered bodies, there are scraps generated due to defective products, scraps when the incorporated products are discarded, and the like. In particular, in the case of a sputtering target material, it is difficult to consume the entire target material by sputtering, and a portion of the sintered body always remains after use, and this becomes scrap.
【０００３】希土類元素は比較的高価であり、また、限
られた資源でもあるので、これらスクラップから有価組
成物を回収し、再使用することは、資源の有効利用とし
て重要である。[0003] Since rare earth elements are relatively expensive and have limited resources, it is important to recover and reuse valuable compositions from these scraps as an effective use of resources.
【０００４】従来、このような目的として、湿式冶金技
術によって含有成分を相互分離する方法が主として行わ
れた。また、溶解用の母合金として再利用する方法もあ
った。Heretofore, for this purpose, a method of mutually separating components contained by hydrometallurgy has been mainly used. There is also a method of reusing as a melting master alloy.
【０００５】[0005]
【発明が解決しようとする課題】従来の方法は公知の冶
金技術を基本とし、条件を適正化することで処理が可能
であったが、複雑な工程を要したり、非常に低価値な産
物が生じるなどの問題があった。The conventional method is based on a known metallurgy technique and can be processed by optimizing the conditions. However, it requires complicated steps and requires a very low-value product. And other problems.
【０００６】例えば、従来方法のひとつである湿式冶金
法の場合は、希土類金属やコバルト金属などの比較的高
価な元素がスクラップの主構成成分であるときは比較的
好ましい方法である。しかし、回収物の形態が酸化物等
の化合物であるため、合金原料として用いる場合は金属
へ還元する工程が必要となる。For example, in the case of hydrometallurgy, which is one of the conventional methods, it is a relatively preferable method when relatively expensive elements such as rare earth metals and cobalt metals are the main components of scrap. However, since the form of the recovered product is a compound such as an oxide, a step of reducing it to a metal is required when used as an alloy raw material.
【０００７】また、従来の他の方法である乾式冶金法の
場合は、不純物精製工程において希土類金属がスラグ中
へ逃げ出し、別途スラグから希土類金属成分を回収する
必要であった。また、溶解用の母原料に利用できるほど
酸素量を十分除去することが困難であった。[0007] In the case of the dry metallurgy method as another conventional method, the rare earth metal escapes into the slag in the impurity refining step, and it is necessary to separately recover the rare earth metal component from the slag. Further, it was difficult to sufficiently remove the amount of oxygen so that it could be used as a base material for dissolution.
【０００８】そこで本発明は、従来の方法のように各構
成元素単体にまで分離精製することなく、適当な調整合
金との配合によって容易に焼結体原料として再利用可能
な粉末状の有価組成物が得られる希土類元素含有物から
の有価組成物の回収方法を提供することを目的とする。Accordingly, the present invention provides a powdery valuable composition which can be easily reused as a raw material for a sintered body by blending with an appropriate adjustment alloy without separating and purifying each constituent element as in the conventional method. It is an object of the present invention to provide a method for recovering a valuable composition from a rare earth element-containing material from which a product is obtained.
【０００９】[0009]
【課題を解決するための手段】上記課題を解決するため
の本発明の有価組成物の回収方法は、希土類元素含有物
を粉砕し、粉砕物を酸洗浄処理後乾燥して有価組成物を
得ることを特徴とする。According to the present invention, there is provided a method for recovering a valuable composition, comprising the steps of: pulverizing a rare earth element-containing substance; washing the pulverized product with an acid washing treatment; and drying to obtain a valuable composition. It is characterized by the following.
【００１０】また、本発明の他の有価組成物の回収方法
は、希土類元素含有物を粉砕し、粉砕物をカルシウム還
元処理し、生成した酸化カルシウム及び残留したカルシ
ウムを除去するための水洗後、乾燥して有価組成物を得
ることを特徴とする。Another method of recovering a valuable composition of the present invention is to pulverize the rare earth element-containing material, reduce the pulverized material with calcium, and wash with water to remove generated calcium oxide and remaining calcium. It is characterized in that a valuable composition is obtained by drying.
【００１１】また、本発明の他の希土類元素含有物から
の有価組成物の回収方法は、希土類元素含有物を粉砕
し、粉砕物を酸洗浄処理し、更にカルシウム還元処理
し、生成した酸化カルシウム及び残留したカルシウムを
除去するための水洗後、乾燥して有価組成物を得ること
を特徴とする。Further, another method of recovering a valuable composition from a rare earth element-containing material according to the present invention is to pulverize the rare earth element-containing material, subject the pulverized material to an acid washing treatment, further perform a calcium reduction treatment, and generate calcium oxide. And washing with water to remove residual calcium, followed by drying to obtain a valuable composition.
【００１２】また、本発明の他の希土類元素含有物から
の有価組成物の回収方法は、希土類元素含有物を粉砕
し、粉砕物を酸洗浄処理し、酸洗浄処理物をカルシウム
還元処理し、生成した酸化カルシウム及び残留したカル
シウムを除去するための水洗後、更に酸洗浄処理し、水
洗後乾燥して有価組成物を得ることを特徴とする。Further, another method of recovering a valuable composition from a rare earth element-containing material according to the present invention is to pulverize the rare earth element-containing material, subject the pulverized material to an acid washing treatment, and subject the acid washed material to a calcium reduction treatment. After washing with water to remove the generated calcium oxide and residual calcium, it is further subjected to an acid washing treatment, washed with water and dried to obtain a valuable composition.
【００１３】本発明の方法により回収される有価組成物
は、例えば、Ｒ−Ｆｅ−Ｂ系合金や、特に、原子比でＮ
ｄ2Ｆｅ14Ｂ組成の相を含む合金などである。The valuable composition recovered by the method of the present invention may be, for example, an R—Fe—B based alloy or, in particular, N in atomic ratio.
An alloy containing a phase having a d 2 Fe 14 B composition is used.
【００１４】[0014]
【発明の実施の形態】本発明の回収方法が扱う希土類元
素含有物は、例えば、希土類元素を含有する金属質焼結
体や、希土類元素を含有する焼結体磁石、例えばＲ−Ｆ
ｅ−Ｂ系焼結体磁石、Ｎｄ−Ｆｅ−Ｂ系焼結体磁石Ｓｍ
−Ｃｏ系焼結磁石、これらの改良組成や、Ｔｂ−Ｆｅ−
Ｃｏ系ターゲット材などである。BEST MODE FOR CARRYING OUT THE INVENTION The rare earth element-containing material handled by the recovery method of the present invention is, for example, a metal sintered body containing a rare earth element or a sintered magnet containing a rare earth element, such as RF
e-B based sintered magnet, Nd-Fe-B based sintered magnet Sm
-Co-based sintered magnets, their improved compositions, and Tb-Fe-
Co-based target materials and the like.
【００１５】本発明では、まず焼結体などの希土類元素
含有物を粉砕する。粉砕は、酸化防止のため不活性雰囲
気中で機械粉砕することが好ましく、例えば粒径約１０
０μｍ以下に粉砕する。In the present invention, first, a rare earth element-containing material such as a sintered body is pulverized. The pulverization is preferably performed by mechanical pulverization in an inert atmosphere to prevent oxidation.
Grind to 0 μm or less.
【００１６】希土類元素含有物の多くは、体積変化を伴
う水素吸蔵放出の性質を有するため、この性質を利用し
て水素吸収処理、あるいは、水素吸収放出処理を行うこ
とで自己崩壊させ、必要に応じて、機械粉砕で所望の粒
度に調整してもよい。Most of the rare earth element-containing materials have the property of storing and releasing hydrogen with a change in volume. Therefore, by utilizing this property, a hydrogen absorption treatment or a hydrogen absorption and release treatment is performed to cause self-disintegration, and Accordingly, the particle size may be adjusted to a desired particle size by mechanical pulverization.
【００１７】焼結体の原料は、酸素含有量が低いことが
必要である。しかし、スクラップ焼結体の酸素含有量
は、通常０．２〜０．８重量％程度もある。It is necessary that the raw material of the sintered body has a low oxygen content. However, the oxygen content of the scrap sintered body is usually about 0.2 to 0.8% by weight.
【００１８】焼結体中で酸素の多い部分は、焼結時に酸
化されやすい粉末表面領域や、焼結後に酸素が集まる組
織の粒界であると考えられる。本発明における粉砕後の
酸洗浄処理では、これら酸素の偏在する粉末表面領域や
組織の粒界に存在する酸化物や酸化膜を溶出除去し、酸
素量を低下させることを目的として行われる。It is considered that the oxygen-rich portion in the sintered body is a powder surface region that is easily oxidized during sintering, or a grain boundary of a structure in which oxygen collects after sintering. The acid cleaning treatment after the pulverization in the present invention is carried out for the purpose of eluting and removing oxides and oxide films present in the powder surface region where the oxygen is unevenly distributed and the grain boundaries of the structure, thereby reducing the amount of oxygen.
【００１９】酸洗浄処理工程によって、酸素のみなら
ず、焼結体に不要な炭素含有量も低下できる。The acid cleaning step can reduce not only oxygen but also unnecessary carbon content in the sintered body.
【００２０】酸洗浄処理の条件は、その対象となる希土
類元素含有物に適していればよく、特に限定するものは
ないが、ｐＨが低いと不用意に希土類成分の溶出を招く
ため、希酸、あるいは、酢酸等のｐＨ緩衝溶液を用い
て、ｐＨを制御することが好ましい。十分な酸素の低減
が達成されない場合でも、カルシウム還元処理を行うこ
とにより、酸素を低下させることができる。The condition of the acid washing treatment is not particularly limited as long as it is suitable for the target rare earth element-containing material. However, if the pH is low, the rare earth component is inadvertently eluted. Alternatively, it is preferable to control the pH using a pH buffer solution such as acetic acid. Even when sufficient reduction of oxygen is not achieved, oxygen can be reduced by performing the calcium reduction treatment.
【００２１】酸洗浄処理後や水洗処理後は、酸化防止等
のため水分を乾燥除去する必要があるが、特にその方
法、装置は限定されない。After the acid washing treatment or the water washing treatment, it is necessary to dry and remove water to prevent oxidation and the like, but the method and apparatus are not particularly limited.
【００２２】粉砕物のカルシウム還元処理では、粒状ま
たはフレーク状の金属カルシウムを用いることが経済的
で取扱も比較的容易である。その他、水素化カルシウム
を用いることも可能である。還元剤としてのカルシウム
の添加量は特に限定されるものではないが、被還元物の
酸素濃度から必要な還元等量以上を用いるとよい。還元
処理は、粉砕物とカルシウムとの混合物を不活性ガス雰
囲気中や真空中でカルシウムの融点温度以上の温度に適
当な時間保持して行う。In the calcium reduction treatment of the pulverized material, it is economical to use granular or flaky metal calcium and the handling is relatively easy. In addition, calcium hydride can be used. The amount of calcium added as a reducing agent is not particularly limited, but it is preferable to use a necessary reduction equivalent or more based on the oxygen concentration of the substance to be reduced. The reduction treatment is performed by keeping the mixture of the ground material and calcium in an inert gas atmosphere or vacuum at a temperature higher than the melting point of calcium for an appropriate time.
【００２３】還元処理後の反応物は水中に投入すると崩
壊する。残留金属カルシウム分は、水中で水素ガスを発
しながら水酸化カルシウムとなり、この反応で水中崩壊
性が良くなり、カルシウム分と有価組成物の分離を良く
する。デカンテーションとレパルプ洗浄とを繰り返すこ
とにより、生成した酸化カルシウムや残留した金属カル
シウム等のカルシウム分を効果的に除去できる。さら
に、必要に応じて塩化カルシウム等の水溶性フラックス
成分を予め混合添加しても崩壊性が向上する。The reaction product after the reduction treatment is disintegrated when poured into water. The residual metal calcium content becomes calcium hydroxide while generating hydrogen gas in water, and this reaction improves the disintegration in water and improves the separation between the calcium content and the valuable composition. By repeating the decantation and the repulping washing, the generated calcium oxide and the remaining calcium such as metallic calcium can be effectively removed. Furthermore, the disintegration is improved even if a water-soluble flux component such as calcium chloride is added in advance as required.
【００２４】カルシウム還元処理しても、水中崩壊時
や、デカンテーションとレパルプ洗浄時に有価組成物の
表面酸化が進行するためと思われる酸素濃度の上昇が生
じる場合がある。このような場合は、粉砕後、カルシウ
ム還元処理、水中崩壊、水洗浄して更に、酸洗浄処理を
行うことが有効である。[0024] Even when the calcium reduction treatment is performed, the oxygen concentration may increase due to the progress of surface oxidation of the valuable composition during disintegration in water or during decantation and repulping washing. In such a case, after the pulverization, it is effective to perform a calcium reduction treatment, disintegration in water, washing with water, and further an acid washing treatment.
【００２５】また、カルシウム還元前において、被還元
物の炭素濃度が高い場合には、還元反応時に溶解度が低
い炭酸カルシウム等の炭酸塩が若干生成するためか、酸
素と炭素の低減が十分に行われない場合がある。このよ
うな場合は、粉砕後、酸洗浄処理、カルシウム還元処
理、再度の酸洗浄処理を行うことで、より十分な低酸素
化が可能になる。In addition, if the carbon concentration of the substance to be reduced is high before the calcium reduction, the reduction of oxygen and carbon is sufficiently performed, probably because carbonates such as calcium carbonate having low solubility are generated during the reduction reaction. May not be. In such a case, by performing an acid washing treatment, a calcium reduction treatment, and a second acid washing treatment after the pulverization, a more sufficient oxygen reduction can be achieved.
【００２６】得られる有価組成物は粉末状であり、この
粉末を所望の組成となるよう別途準備される組成調整用
の合金粉末と配合することで、焼結体製造用の原料粉末
として再利用できる。組成調整用合金粉末は特に限定さ
れるものではないが、本発明の主目的である低酸素化処
理では、希土類成分を酸浸出しているため、組成調整用
粉末の少なくとも一種は希土類元素含有合金粉末とな
る。The obtained valuable composition is in the form of a powder. By mixing this powder with a separately prepared alloy powder for adjusting the composition so as to have a desired composition, it can be reused as a raw material powder for producing a sintered body. it can. Although the composition-adjusting alloy powder is not particularly limited, in the oxygen reduction treatment, which is the main object of the present invention, at least one of the composition-adjusting powders is a rare-earth element-containing alloy because the rare-earth component is acid-leached. It becomes a powder.
【００２７】組成調整用の合金粉末は、溶解鋳造後粉砕
する溶解鋳造粉砕法、溶解後ロール急冷によりリボン状
薄体を得てそれを粉砕する液体急冷粉砕法、溶解後噴霧
冷却して直接粉末を得る水アトマイズあるいはガスアト
マイズなどのアトマイズ法、カルシウム還元により合金
粉末を得る還元拡散法など、公知の各種方法よりに得ら
れた合金粉末を用いることができる。The alloy powder for composition adjustment is prepared by a melt casting and pulverization method of melting and casting and then pulverizing, a liquid quenching and pulverization method of obtaining a ribbon-like thin body by quenching a roll after melting and pulverizing it, and a spraying and cooling after melting to directly powder An alloy powder obtained by various known methods such as an atomizing method such as water atomizing or gas atomizing, or a reduction diffusion method of obtaining an alloy powder by reducing calcium can be used.
【００２８】[0028]
【実施例】以下、実施例により本発明を説明する。The present invention will be described below with reference to examples.
【００２９】実施例１ ・・・ 希土類元素含有物とし
て、還元拡散法による希土類合金粉末を原料としてホッ
トプレス法により焼結された、Ｔｂ―Ｆｅ―Ｃｏ系光磁
気ディスク用スパッタリングターゲット材のスクラップ
品を用いた。これは、取り扱い時に欠けを生じ製品不良
となったものである。Example 1 A scrap product of a sputtering target material for a Tb-Fe-Co magneto-optical disk, which was sintered by a hot press method using a rare earth alloy powder by a reduction diffusion method as a raw material as a rare earth element-containing material. Was used. This is due to chipping during handling, resulting in a product defect.
【００３０】組成は、テルビウム（Ｔｂ）４９．８重量
％、鉄（Ｆｅ）４６．１重量％、コバルト（Ｃｏ）４．
１２重量％、カルシウム（Ｃａ）０．０９重量％、酸素
（Ｏ）０．２５重量％、炭素（Ｃ）０．０１２重量％で
あった。組織は、ＥＰＭＡの定量分析によると、 Ｆｅ
−Ｃｏ相（鉄が約９３〜９６重量％、コバルトが約４〜
７重量％）、低テルビウム濃度Ｔｂ−Ｆｅ−Ｃｏ合金相
（鉄が約６５〜６８重量％、コバルトが約２〜５重量
％、テルビウムが約２３〜２５重量％）、 中テルビウ
ム濃度Ｔｂ−Ｆｅ−Ｃｏ合金相（鉄が約４５〜５２重量
％、コバルトが約３〜４重量％、テルビウムが約４２〜
４９重量％）、高テルビウム濃度Ｔｂ−Ｆｅ−Ｃｏ合金
相（鉄が約３５〜３７重量％、コバルトが約５〜６重量
％、テルビウムが約５７〜６０重量％）から構成されて
いた。The composition was 49.8% by weight of terbium (Tb), 46.1% by weight of iron (Fe), and 4.0% by weight of cobalt (Co).
The content was 12% by weight, calcium (Ca) 0.09% by weight, oxygen (O) 0.25% by weight, and carbon (C) 0.012% by weight. According to the quantitative analysis of EPMA, the tissue
-Co phase (about 93 to 96% by weight of iron, about 4 to
7% by weight), low terbium concentration Tb-Fe-Co alloy phase (about 65-68% by weight of iron, about 2-5% by weight of cobalt, about 23-25% by weight of terbium), medium terbium concentration Tb-Fe -Co alloy phase (about 45-52 wt% iron, about 3-4 wt% cobalt, about 42-
49% by weight), and a high terbium-concentrated Tb-Fe-Co alloy phase (about 35-37% by weight of iron, about 5-6% by weight of cobalt, and about 57-60% by weight of terbium).
【００３１】このターゲット材を炉に入れ、炉内の空気
をアルゴンガスで置換し、さらにアルゴンガスを水素ガ
スに置換し、水素ガス気流中で約３００℃まで昇温し、
３０分間保持した。その後炉内の水素ガスをアルゴンガ
スに置換し、室温まで冷却して取り出したところ、粒径
５００μｍ以下の粉末が得られた。The target material is placed in a furnace, the air in the furnace is replaced with argon gas, and the argon gas is further replaced with hydrogen gas, and the temperature is raised to about 300 ° C. in a hydrogen gas stream.
Hold for 30 minutes. Thereafter, the hydrogen gas in the furnace was replaced with argon gas, cooled to room temperature, and taken out. As a result, a powder having a particle size of 500 μm or less was obtained.
【００３２】得られた粉末を脱イオン水に投入して３０
ｇ／リットル濃度のスラリーとし、攪拌しながらこれに
１０倍の酢酸溶液を滴下してｐＨを５に調整し、約５分
間の酸洗浄処理を行なった。次に、脱イオン水で置換洗
浄した後、ろ過し、水分をエタノールで置換し、真空乾
燥し、合金粉末を得た。The obtained powder is put into deionized water and the powder is charged for 30 minutes.
A slurry having a concentration of g / liter was prepared, and a 10-fold acetic acid solution was added dropwise thereto with stirring to adjust the pH to 5, and an acid washing treatment was performed for about 5 minutes. Next, after washing with replacement with deionized water, filtration was performed, the moisture was replaced with ethanol, and vacuum drying was performed to obtain an alloy powder.
【００３３】得られた合金粉末の組成は、テルビウム４
７．８重量％、鉄４７．２重量％、コバルト５．３６重
量％、カルシウム０．０７重量％、酸素０．０７重量
％、炭素０．００８重量％であった。これは、処理前の
ターゲット材組成に比べ、テルビウム品位は２重量％減
少し、酸素品位は０．１８重量％減少した。合金粉末の
組織は、処理前のターゲット材で確認された組織と同じ
であった。The composition of the obtained alloy powder was terbium 4
7.8% by weight, iron 47.2% by weight, cobalt 5.36% by weight, calcium 0.07% by weight, oxygen 0.07% by weight, and carbon 0.008% by weight. The terbium grade was reduced by 2% by weight and the oxygen grade was reduced by 0.18% by weight, as compared with the target material composition before the treatment. The structure of the alloy powder was the same as the structure confirmed in the target material before the treatment.
【００３４】この回収合金粉と金属テルビウム粉末と
を、テルビウム組成４９．８重量％を目的とし、それぞ
れを重量で９８％と２％で配合し、十分に混合した後、
ホットプレス法によりターゲット材を製造した。The recovered alloy powder and the metal terbium powder are blended at 98% and 2% by weight for a terbium composition of 49.8% by weight, and thoroughly mixed.
The target material was manufactured by the hot press method.
【００３５】得られたターゲット材の組成は、テルビウ
ム４９．７重量％、鉄４６．３重量％、コバルト４．１
８重量％、カルシウム０．０７重量％、酸素０．０７重
量％、炭素０．００９重量％であり、合金組織も処理前
のものと同じであった。The composition of the obtained target material was 49.7% by weight of terbium, 46.3% by weight of iron, and 4.1% by weight of cobalt.
The content was 8% by weight, 0.07% by weight of calcium, 0.07% by weight of oxygen and 0.009% by weight of carbon, and the alloy structure was the same as that before the treatment.
【００３６】上記より、取り扱い時に欠けを生じ製品不
良となったＴｂ―Ｆｅ―Ｃｏ系光磁気ディスク用スパッ
タリングターゲット材の組織は有価物として回収され、
さらに、再利用が可能であることがわかる。As described above, the structure of the sputtering target material for the Tb—Fe—Co based magneto-optical disk, which has become defective due to chipping during handling, is recovered as a valuable resource.
Further, it can be seen that reuse is possible.
【００３７】実施例２ ・・・ 希土類元素含有物とし
て、還元拡散法により得られた合金を原料にして製造し
たＳｍＣｏ5系焼結磁石であって、着磁前の磁石化工程
で寸法不良となったスクラップを用いた。組成は、サマ
リウム（Ｓｍ）３４．８重量％、コバルト（Ｃｏ）６
５．１重量％、カルシウム（Ｃａ）０．０６重量％、酸
素（Ｏ）０．１８重量％、炭素（Ｃ）０．０１１重量％
であった。この焼結体を、実施例１と同様の水素処理と
さらにアルゴン雰囲気中のパルベライザー粉砕によって
粒径５００μｍ以下に粉砕し、次に、実施例１と同様に
酸洗浄処理を実施した。得られた粉砕粉の酸素濃度は
０．１６重量％であり、焼結体の酸素濃度より低下して
いたが、焼結原料として用いるには、まだ不十分なもの
であった。Example 2 An SmCo 5 -based sintered magnet manufactured using an alloy obtained by a reduction diffusion method as a rare earth element-containing material, and having a dimensional defect in a magnetizing process before magnetization. Used scrap was used. The composition is 34.8% by weight of samarium (Sm), cobalt (Co) 6
5.1% by weight, calcium (Ca) 0.06% by weight, oxygen (O) 0.18% by weight, carbon (C) 0.011% by weight
Met. This sintered body was pulverized to a particle size of 500 μm or less by hydrogen treatment as in Example 1 and pulverizer pulverization in an argon atmosphere, and then subjected to an acid washing treatment as in Example 1. The oxygen concentration of the obtained pulverized powder was 0.16% by weight, which was lower than the oxygen concentration of the sintered body, but was still insufficient for use as a raw material for sintering.
【００３８】次に、得られた粉砕粉に、１０重量％の金
属カルシウム（Ｃａ、粒度４メッシュ以下）、２０重量
％の無水塩化カルシウム（ＣａＣｌ2、粒度３００メッ
シュ以下）を十分に混合し、ステンレス製容器に入れ、
アルゴンガス雰囲気中で１０００℃で３時間保持すると
いう、カルシウムによる還元処理を行った。Next, 10% by weight of metallic calcium (Ca, particle size of 4 mesh or less) and 20% by weight of anhydrous calcium chloride (CaCl 2 , particle size of 300 mesh or less) were sufficiently mixed with the obtained pulverized powder, Put it in a stainless steel container,
A reduction treatment with calcium was performed in which the mixture was kept at 1000 ° C. for 3 hours in an argon gas atmosphere.
【００３９】冷却後、反応物を約１０ｍｍ大に粉砕し、
スラリー濃度が３０ｇ／リットルになる条件で水中投下
し、攪拌し、水中崩壊させた。デカンテーションにより
カルシウム分を分離除去した後、ｐＨ値が１０以下にな
るまで１０分攪拌し、排水、注水、攪拌のレパルプ洗浄
を繰り返したところ、４回のレパルプ洗浄でｐＨ値は１
０以下となった。このスラリーを実施例１と同様の方法
でアルコール置換し、乾燥後、合金粉末として回収し
た。After cooling, the reaction product was ground to a size of about 10 mm,
The slurry was dropped in water under the condition that the slurry concentration was 30 g / liter, stirred, and disintegrated in water. After the calcium content was separated and removed by decantation, the mixture was stirred for 10 minutes until the pH value became 10 or less, and the repulp washing of drainage, water injection, and stirring was repeated.
0 or less. This slurry was replaced with alcohol in the same manner as in Example 1, dried, and recovered as an alloy powder.
【００４０】得られた合金粉末の酸素濃度は０．０９重
量％であり、焼結原料として十分な酸素濃度であった。
他の成分は、サマリウム３３．１重量％、コバルト６
５．８重量％、カルシウム０．０７重量％、炭素０．０
１３重量％であり、サマリウム濃度が低下し、ＳｍＣｏ
5の化学量論組成に近づいていた。The oxygen concentration of the obtained alloy powder was 0.09% by weight, which was a sufficient oxygen concentration as a raw material for sintering.
The other components were 33.1% by weight of samarium, cobalt 6
5.8% by weight, calcium 0.07% by weight, carbon 0.0
13% by weight, the samarium concentration decreased, and SmCo
A stoichiometry of 5 was approaching.
【００４１】この合金粉末と、還元拡散法で得られた、
サマリウム濃度４０．２％、コバルト濃度５８．９％、
酸素濃度０．０６重量％、カルシウム濃度０．０８重量
％、炭素０．０１０重量％の合金粉末とを、重量比で７
９．２：２１．７で配合し、サマリウム３４．９重量
％、コバルト６４．９重量％、カルシウム０．０７重量
％、酸素０．０８重量％、炭素０．０１２重量％の合金
粉末とし、ＳｍＣｏ5系焼結体を得たところ、サマリウ
ム３４．８重量％、コバルト６４．８重量％、カルシウ
ム０．０６重量％、酸素０．１８重量％、炭素０．０１
２重量％である処理前のスクラップ品と同等の焼結体を
得た。This alloy powder was obtained by the reduction diffusion method.
Samarium concentration 40.2%, cobalt concentration 58.9%,
An alloy powder having an oxygen concentration of 0.06% by weight, a calcium concentration of 0.08% by weight, and a carbon of 0.010% by weight is mixed with a powder having a weight ratio of
9.2: 21.7 blended to form an alloy powder of 34.9% by weight of samarium, 64.9% by weight of cobalt, 0.07% by weight of calcium, 0.08% by weight of oxygen and 0.012% by weight of carbon, When an SmCo 5 sintered body was obtained, 34.8% by weight of samarium, 64.8% by weight of cobalt, 0.06% by weight of calcium, 0.18% by weight of oxygen, and 0.01% of carbon
A sintered body equivalent to 2% by weight of the unprocessed scrap product was obtained.
【００４２】このことより、寸法不良となったＳｍＣｏ
5系磁石用焼結体中のＳｍＣｏ5相は有価物として回収さ
れ、再利用できたことがわかる。As a result, the dimensional defect of SmCo
It can be seen that the SmCo 5 phase in the sintered body for the 5- system magnet was recovered as a valuable material and could be reused.
【００４３】実施例３ ・・・ カルシウム還元後、実
施例１の酸洗浄処理を行うこと以外は実施例２と同じ処
理を実施例２の不良焼結体について実施した結果、得ら
れた合金粉末の酸素濃度は０．０５重量％となり、焼結
原料としてより酸素濃度が低い良好な合金粉末であっ
た。他の成分はサマリウム３３．１重量％、コバルト６
５．９重量％、カルシウム０．０６重量％、炭素０．０
１１重量％であった。Example 3 An alloy powder obtained as a result of performing the same processing as in Example 2 on the defective sintered body of Example 2 except that the acid cleaning treatment of Example 1 is performed after the calcium reduction. Has an oxygen concentration of 0.05% by weight, and is a good alloy powder having a lower oxygen concentration as a sintering raw material. Other components are 33.1% by weight of samarium, cobalt 6
5.9% by weight, calcium 0.06% by weight, carbon 0.0
It was 11% by weight.
【００４４】このことから、カルシウム還元後に酸洗浄
を行うことで、有価物としての品質が向上することがわ
かる。From this, it can be seen that the quality as a valuable resource is improved by performing acid washing after calcium reduction.
【００４５】実施例４ ・・・ カルシウム還元前に、
実施例１の酸洗浄処理を行うこと以外は実施例２と同じ
処理を実施例２の不良焼結体について実施した結果、得
られた合金粉末の酸素濃度は０．０５重量％であった。
他の成分がサマリウム３３．１重量％、コバルト６５．
９重量％、カルシウム０．０６重量％、炭素０．００５
重量％となり、炭素成分が低く品質の良い合金粉末が得
られた。Example 4 Before calcium reduction,
The same process as in Example 2 was performed on the defective sintered body of Example 2 except that the acid cleaning process of Example 1 was performed. As a result, the oxygen concentration of the obtained alloy powder was 0.05% by weight.
Other components are 33.1% by weight of samarium and 65.
9% by weight, calcium 0.06% by weight, carbon 0.005
% By weight, and a high-quality alloy powder having a low carbon content was obtained.
【００４６】このことから、この磁石用ＳｍＣｏ5系焼
結体では、カルシウム還元前に酸洗浄を行うことで炭素
濃度が低減された品質が向上した有価物となることがわ
かる。From this, it can be seen that this SmCo 5 -based sintered body for magnets is a valuable material having reduced carbon concentration and improved quality by performing acid washing before calcium reduction.
【００４７】実施例５ ・・・ ネオジウム（Ｎｄ）３
１．２重量％、ディスプロシウム（Ｄｙ）１．１重量
％、ホウ素（Ｂ）１．１重量％、酸素（Ｏ）０．５８重
量％、炭素（Ｃ）０．４１重量％からなる、欠けを生じ
たＮｄ−Ｆｅ−Ｂ系磁石用焼結体を、実施例２と同様の
粉砕方法で粒径１００μｍ以下の粉末を得た。Example 5 Neodymium (Nd) 3
1.2% by weight, dysprosium (Dy) 1.1% by weight, boron (B) 1.1% by weight, oxygen (O) 0.58% by weight, carbon (C) 0.41% by weight, The Nd-Fe-B-based sintered body for a magnet having a chip was obtained by the same pulverization method as in Example 2 to obtain a powder having a particle size of 100 µm or less.
【００４８】この粉末をｐＨ値を４とすること以外は実
施例１と同様の方法で酸洗浄処理して粉末を回収したと
ころ、酸素濃度は０．４３重量％、炭素濃度０．０３１
重量％であった。Ｎｄ―Ｆｅ−Ｂ系合金原料として炭素
濃度は十分低いが、酸素は高い数値であった。This powder was subjected to acid washing in the same manner as in Example 1 except that the pH value was changed to 4, and the powder was recovered. The oxygen concentration was 0.43% by weight and the carbon concentration was 0.031%.
% By weight. Although the carbon concentration was sufficiently low as an Nd—Fe—B-based alloy raw material, oxygen was a high value.
【００４９】この合金粉末に対し、１０重量％の金属カ
ルシウム（粒度４メッシュ以下）、２０重量％の無水塩
化カルシウム（粒度３００メッシュ以下）を十分に混合
し、ステンレス製容器に入れ、アルゴンガス雰囲気中で
１０００℃で３時間保持し、カルシウムによる還元処理
を行った。冷却後、反応物を約１０ｍｍ大に粉砕し、ス
ラリー濃度が３０ｇ／リットルになる条件で水中投下
し、攪拌し、水中崩壊させた。デカンテーションにより
カルシウム分を分離除去した後、ｐＨ値が１０以下にな
るまで攪拌１０分、排水、注水、攪拌のレパルプ洗浄を
繰り返したところ、７回のレパルプ洗浄でｐＨ値は１０
以下となった。To this alloy powder, 10% by weight of metallic calcium (particle size of 4 mesh or less) and 20% by weight of anhydrous calcium chloride (particle size of 300 mesh or less) are sufficiently mixed, put in a stainless steel container, and placed in an argon gas atmosphere. And kept at 1000 ° C. for 3 hours in order to perform a reduction treatment with calcium. After cooling, the reaction product was pulverized to a size of about 10 mm, dropped into water under the condition of a slurry concentration of 30 g / liter, stirred, and disintegrated in water. After the calcium content was separated and removed by decantation, the repulp washing of drainage, water injection and stirring was repeated for 10 minutes until the pH value became 10 or less.
It was as follows.
【００５０】この工程までに得られた合金粉末の一部を
エタノール置換し、真空乾燥を経て回収したところ、ネ
オジウム２６．５重量％、ディスプロシウム１．１２重
量％、ホウ素１．０２重量％、酸素濃度０．２７重量％
であり、酸素濃度は、やや高いものであった。A part of the alloy powder obtained up to this step was replaced with ethanol, and recovered by vacuum drying. 26.5% by weight of neodymium, 1.12% by weight of dysprosium, 1.02% by weight of boron , Oxygen concentration 0.27% by weight
And the oxygen concentration was somewhat high.
【００５１】さらに、カルシウム還元前の酸洗浄処理と
同じ処理を実施し、エタノール置換し、真空乾燥を経て
回収したところ、ネオジウム２６．２重量％、ディスプ
ロシウム１．１３重量％、ホウ素１．０１重量％、酸素
濃度０．１４重量％となり、酸素濃度は、十分低かっ
た。また、炭素濃度０．０１８重量％、カルシウム濃度
０．０３重量％となり、これらの不純物濃度も低かっ
た。合金粉末は、大部分がＮｄ−Ｆｅ−Ｂ系磁石の磁気
発現相である、Ｎｄ2Ｆｅ14Ｂ1主相からなる合金粉末で
あった。Further, the same treatment as the acid washing treatment before the calcium reduction was carried out, the mixture was replaced with ethanol, and recovered by vacuum drying. As a result, 26.2% by weight of neodymium, 1.13% by weight of dysprosium and 1. The oxygen concentration was 01% by weight and the oxygen concentration was 0.14% by weight, and the oxygen concentration was sufficiently low. In addition, the carbon concentration was 0.018% by weight and the calcium concentration was 0.03% by weight, and these impurity concentrations were also low. The alloy powder was an alloy powder mainly composed of Nd 2 Fe 14 B 1 main phase, which is a magnetic manifestation phase of the Nd—Fe—B-based magnet.
【００５２】この合金粉末に、ネオジウム濃度８５．４
重量％で、Ｎｄ相とＮｄ2Ｆｅ14相の共晶組織を有する
Ｎｄ−Ｆｅ合金粉末とを、重量比で９４：６に配合し、
常法の粉末冶金法により焼結磁石を作製したところ、得
られた磁石の特性は、最大磁気エネルギー密度、（Ｂ
Ｈ）maxが４３．２ＭＧＯｅ、保磁力、Ｈｃｊが１４．
０ｋＯｅの高性能を示した。The alloy powder was added with a neodymium concentration of 85.4.
By weight, Nd-Fe alloy powder having a eutectic structure of Nd phase and Nd 2 Fe 14 phase is blended in a weight ratio of 94: 6,
When a sintered magnet was manufactured by a conventional powder metallurgy method, the characteristics of the obtained magnet were the maximum magnetic energy density, (B
H) max is 43.2 MGOe, coercive force, Hcj is 14.
It exhibited a high performance of 0 kOe.
【００５３】このことから、この磁石用Ｎｄ−Ｆｅ−Ｂ
系焼結体から回収される低酸素主相合金粉末は、有価物
となるとともに、それを用いて組成調整した合金粉を用
いた磁石は実用レベルの磁石特性を有するものであるこ
とがわかる。From the above, it is clear that Nd-Fe-B for magnets
It can be seen that the low-oxygen main phase alloy powder recovered from the system sintered body is a valuable material, and that the magnet using the alloy powder whose composition has been adjusted using the same has practical-level magnet characteristics.
【００５４】[0054]
【発明の効果】本発明は、 Ｓｍ系やＮｄ系などの希土
類永久磁石や、Ｔｂ−Ｆｅ−Ｃｏ系などのスパッタリン
グ用ターゲット材等の希土類元素含有物から有価組成物
を回収する方法と、回収物の再利用方法を提供するもの
であり、従来法のように各構成元素レベルに分離精製す
ることなく有価組成物としてその大部分を回収するた
め、経済性が高い。また、適当な組成調整合金との配合
により容易に焼結体原料として再生でき、さらに得られ
る製品は十分な特性を発現する。The present invention provides a method of recovering a valuable composition from rare earth element-containing materials such as rare earth permanent magnets such as Sm-based or Nd-based and sputtering target materials such as Tb-Fe-Co-based. The present invention provides a method for reusing materials and recovers most of the valuable composition as a valuable composition without separating and refining to the level of each constituent element as in the conventional method. In addition, it can be easily regenerated as a raw material of a sintered body by blending with an appropriate composition adjusting alloy, and the obtained product exhibits sufficient characteristics.
Claims (11)
洗浄処理後乾燥して有価組成物を得ることを特徴とする
希土類元素含有物からの有価組成物の回収方法。1. A method for recovering a valuable composition from a rare earth element-containing material, wherein the rare earth element-containing material is pulverized, and the pulverized material is subjected to an acid washing treatment and then dried to obtain a valuable composition.
ルシウム還元処理し、生成した酸化カルシウム及び残留
したカルシウムを除去するための水洗後、乾燥して有価
組成物を得ることを特徴とする希土類元素含有物からの
有価組成物の回収方法。2. A rare earth element-containing substance is pulverized, the pulverized substance is subjected to calcium reduction treatment, washed with water to remove generated calcium oxide and residual calcium, and then dried to obtain a valuable composition. A method for recovering a valuable composition from a rare earth element-containing material.
洗浄処理し、更にカルシウム還元処理し、生成した酸化
カルシウム及び残留したカルシウムを除去するための水
洗後、乾燥して有価組成物を得ることを特徴とする希土
類元素含有物からの有価組成物の回収方法。3. The rare earth element-containing substance is pulverized, the pulverized substance is subjected to an acid washing treatment, further subjected to a calcium reduction treatment, washed with water to remove generated calcium oxide and residual calcium, and then dried to obtain a valuable composition. A method for recovering a valuable composition from a rare earth element-containing material, comprising:
洗浄処理し、酸洗浄処理物をカルシウム還元処理し、生
成した酸化カルシウム及び残留したカルシウムを除去す
るための水洗後、更に酸洗浄処理し、水洗後乾燥して有
価組成物を得ることを特徴とする希土類元素含有物から
の有価組成物の回収方法。4. A pulverized material containing a rare earth element, an acid-cleaning treatment of the pulverized material, a calcium reduction treatment of the acid-washed material, water washing for removing generated calcium oxide and residual calcium, and further acid washing. A method for recovering a valuable composition from a rare earth element-containing material, comprising treating, washing with water, and drying to obtain a valuable composition.
る金属質焼結体である請求項１〜請求項４いずれかに記
載の有価組成物の回収方法。5. The method for recovering a valuable composition according to claim 1, wherein the rare earth element-containing material is a metallic sintered body containing a rare earth element.
る焼結体磁石である請求項１〜請求項４いずれかに記載
の有価組成物の回収方法。6. The method for recovering a valuable composition according to claim 1, wherein the rare earth element-containing material is a sintered magnet containing a rare earth element.
体磁石である請求項１〜請求項４いずれかに記載の有価
組成物の回収方法。7. The method for recovering a valuable composition according to claim 1, wherein the rare earth element-containing material is an R—Fe—B based sintered magnet.
結体磁石である請求項１〜請求項４いずれかに記載の有
価組成物の回収方法。8. The method for recovering a valuable composition according to claim 1, wherein the rare earth element-containing material is an Nd—Fe—B-based sintered magnet.
合金である請求項１〜請求項８いずれかに記載の希土類
元素含有物からの有価組成物の回収方法。9. The method for recovering a valuable composition from a rare earth element-containing material according to claim 1, wherein the valuable composition to be recovered is an R—Fe—B-based alloy.
2Ｆｅ14Ｂ組成の相を含む合金である請求項１〜請求項
８いずれかに記載の希土類元素含有物からの有価組成物
の回収方法。10. The recovered valuable composition is Nd in atomic ratio.
Method of recovering valuable compositions from rare earth-containing composition according to any one of claims 1 to 8 are alloys comprising phase 2 Fe 14 B composition.
の回収方法によって得られた希土類元素含有合金粉末。11. A rare earth element-containing alloy powder obtained by the recovery method according to any one of claims 1 to 10.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12871298A JPH11319752A (en) | 1998-05-12 | 1998-05-12 | Recovery of valued composition from rare earth element-containing substance and alloy powder obtained thereby |
| CN99106463A CN1077603C (en) | 1998-05-12 | 1999-05-12 | Recovering method of valuable composition from rare earth element-containing material and alloy powder obtained therefrom |
| DE1999122144 DE19922144C2 (en) | 1998-05-12 | 1999-05-12 | Process for the preparation of a material composition from material containing rare earth elements |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12871298A JPH11319752A (en) | 1998-05-12 | 1998-05-12 | Recovery of valued composition from rare earth element-containing substance and alloy powder obtained thereby |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11319752A true JPH11319752A (en) | 1999-11-24 |
Family
ID=14991573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12871298A Pending JPH11319752A (en) | 1998-05-12 | 1998-05-12 | Recovery of valued composition from rare earth element-containing substance and alloy powder obtained thereby |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH11319752A (en) |
| CN (1) | CN1077603C (en) |
| DE (1) | DE19922144C2 (en) |
Cited By (4)
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|---|---|---|---|---|
| JP2004068082A (en) * | 2002-08-06 | 2004-03-04 | Chiba Inst Of Technology | Method for recovering rare-earth metal |
| JP2010042346A (en) * | 2008-08-12 | 2010-02-25 | Jfe Mineral Co Ltd | Pretreatment method for recovering rare earth element from disposed fluorescent lamp and method of recovering rare earth element using solid matter obtained by the pretreatment method |
| CN103103361A (en) * | 2013-02-28 | 2013-05-15 | 包头稀土研究院 | Method for preparing rare earth oxide from rare earth polishing powder waste |
| KR101414967B1 (en) * | 2012-03-22 | 2014-07-04 | 한국생산기술연구원 | Nd Extraction Metod From Rare Earth element |
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| JPH11329811A (en) * | 1998-05-18 | 1999-11-30 | Sumitomo Special Metals Co Ltd | Raw material powder for r-fe-b magnet and manufacture of r-fe-b based magnet |
| DE19843883C1 (en) * | 1998-09-24 | 1999-10-07 | Vacuumschmelze Gmbh | Method for recycling of permanent magnets forming part of scrap material |
| JP4240679B2 (en) * | 1999-09-21 | 2009-03-18 | ソニー株式会社 | Method for producing sputtering target |
| US8118906B2 (en) | 2007-10-29 | 2012-02-21 | Heraeus Inc. | Methodology for recycling Ru and Ru-alloy deposition targets and targets made of recycled Ru and Ru-based alloy powders |
| EP2857547B1 (en) * | 2013-01-28 | 2017-08-23 | JX Nippon Mining & Metals Corp. | Method for making a rare-earth magnet sputtering target |
| CN103343234B (en) * | 2013-07-19 | 2015-01-14 | 北京工业大学 | Method for preparing neodymium and iron oxides by using neodymium iron boron oil sludge through regeneration and co-precipitation |
| WO2017034009A1 (en) | 2015-08-26 | 2017-03-02 | 日立金属株式会社 | Useful method for separating light rare earth elements and heavy rare earth elements |
| EP3807913A1 (en) * | 2018-06-18 | 2021-04-21 | ABB Schweiz AG | Method for producing a magnetic powder |
| CN109847892A (en) * | 2019-03-20 | 2019-06-07 | 兰州大学 | A kind of reduction-diffusion process prepares the deimpurity device of terres rares-transition metal alloy |
| CN111876787B (en) * | 2020-07-22 | 2022-03-15 | 宁波江丰电子材料股份有限公司 | Treatment process of copper phosphorus evaporation material |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2818997C2 (en) * | 1978-02-17 | 1980-02-07 | Schweizerische Aluminium Ag, Chippis (Schweiz) | Process for the recovery and separation of gadolinium and gallium from scrap |
| DE2857381C2 (en) * | 1978-04-20 | 1982-02-25 | Fa. Hermann Wegener, 3000 Hannover | Extraction of lanthanides in the manufacture of filter materials |
| DE3211286A1 (en) * | 1981-04-02 | 1982-10-21 | Hermann C. Starck Berlin, 1000 Berlin | Process for recovering mineral acid compounds free from radiation from mineral-acid ores containing, in complex form, uranium, thorium, titanium and rare earths |
| JPS58193331A (en) * | 1982-05-04 | 1983-11-11 | Hitachi Metals Ltd | Treatment of alloy power of rare earth element-cobalt |
| US4578242A (en) * | 1984-07-03 | 1986-03-25 | General Motors Corporation | Metallothermic reduction of rare earth oxides |
| DD240756A1 (en) * | 1985-09-04 | 1986-11-12 | Akad Wissenschaften Ddr | PROCESS FOR OBTAINING RARE EARTH |
| FR2600081A1 (en) * | 1986-03-19 | 1987-12-18 | Rhone Poulenc Chimie | PROCESS FOR SEPARATING RARE EARTHS |
| CN1062232A (en) * | 1990-12-04 | 1992-06-24 | 北京科技大学 | Produce the method for rare-earth iron-boron permanent magnetic material with the rare-earth iron-boron waste material |
| US5314526A (en) * | 1990-12-06 | 1994-05-24 | General Motors Corporation | Metallothermic reduction of rare earth fluorides |
| BR9104844A (en) * | 1991-11-06 | 1993-05-11 | Solvay | PROCESS FOR THE SELECTIVE EXTRACTION OF CERIO FROM AN Aqueous SOLUTION OF ELEMENTS FROM RARE LANDS |
| CN1119216A (en) * | 1994-09-22 | 1996-03-27 | 泰兴市君泰稀土实业有限公司 | Process for preparing neodymium and neodymium-dysprosium compounds by recovering waste neodymium-iron-boron |
| JP3777226B2 (en) * | 1995-09-27 | 2006-05-24 | 株式会社三徳 | Method for recovering reusable rare earth-containing compounds |
-
1998
- 1998-05-12 JP JP12871298A patent/JPH11319752A/en active Pending
-
1999
- 1999-05-12 CN CN99106463A patent/CN1077603C/en not_active Expired - Fee Related
- 1999-05-12 DE DE1999122144 patent/DE19922144C2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004068082A (en) * | 2002-08-06 | 2004-03-04 | Chiba Inst Of Technology | Method for recovering rare-earth metal |
| JP2010042346A (en) * | 2008-08-12 | 2010-02-25 | Jfe Mineral Co Ltd | Pretreatment method for recovering rare earth element from disposed fluorescent lamp and method of recovering rare earth element using solid matter obtained by the pretreatment method |
| KR101414967B1 (en) * | 2012-03-22 | 2014-07-04 | 한국생산기술연구원 | Nd Extraction Metod From Rare Earth element |
| CN103103361A (en) * | 2013-02-28 | 2013-05-15 | 包头稀土研究院 | Method for preparing rare earth oxide from rare earth polishing powder waste |
| CN103103361B (en) * | 2013-02-28 | 2014-11-26 | 包头稀土研究院 | Method for preparing rare earth oxide from rare earth polishing powder waste |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19922144A1 (en) | 1999-11-25 |
| DE19922144C2 (en) | 2001-11-15 |
| CN1237643A (en) | 1999-12-08 |
| CN1077603C (en) | 2002-01-09 |
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