JPS6130639A - Metal thermal reduction for rare earth element oxide with calcium metal - Google Patents
Metal thermal reduction for rare earth element oxide with calcium metalInfo
- Publication number
- JPS6130639A JPS6130639A JP14645085A JP14645085A JPS6130639A JP S6130639 A JPS6130639 A JP S6130639A JP 14645085 A JP14645085 A JP 14645085A JP 14645085 A JP14645085 A JP 14645085A JP S6130639 A JPS6130639 A JP S6130639A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- metal
- salt bath
- molten salt
- oxide
- 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.)
- Granted
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
- C22B5/00—General methods of reducing to metals
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
Abstract
Description
【発明の詳細な説明】
本発明は希土類元素酸化物、特に酸化ネオジムを直接還
元して希土類元素金属にするだめの新規な金属熱プロセ
ス（ｍｅｔａｌｌｏｔｈｅｒｍｉｃｐｒｏｅｅ８１１
）に関する。この方法は特にネオジム・鉄・硼素磁石用
のネオジム金属の低コスト製造法に利用される。DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel metal thermal process for the direct reduction of rare earth oxides, particularly neodymium oxide, to rare earth metals.
) regarding. This method is particularly useful for low-cost production of neodymium metal for neodymium-iron-boron magnets.
これまで、商業的に製造される最高の永久磁石はサマリ
ウムとコバルトの合金（ＳｍＣＯ５）の焼結粉末から造
られた。最近更に強力な磁石が軽い希土類元素、特にネ
オジム及びプラセオジム、鉄及び硼素の合金から造られ
ている。上記の合金及びこれらを加工して磁石にする方
法はヨーロッパ特許出願Ｎｎ０１０８４７４．０１２５
７５２．０１３３７５８及び０１４４１１２に述べられ
ている。To date, the best commercially produced permanent magnets have been made from sintered powder of an alloy of samarium and cobalt (SmCO5). Recently even stronger magnets have been made from alloys of lighter rare earth elements, especially neodymium and praseodymium, iron and boron. The above alloys and the method of processing them into magnets are disclosed in European patent application No. 0108474.0125.
752.0133758 and 0144112.
希土類（ＲＥ）元素５周期表中の原子番号５７〜７１並
びに原子番号３９イツトリウムの供給源はバストネス石
及びモナズ石である。The sources of yttrium, atomic number 57-71 and atomic number 39 in the periodic table of rare earth (RE) elements 5, are bastnesite and monazite.
希土類混合物を上記鉱石から幾つかの公知のを溶出及び
液・液抽出などの従来からのプロセスにより相互に分離
出来る。The rare earth mixtures can be separated from each other from the ore by several conventional processes such as leaching and liquid-liquid extraction.
希土類金属を相互に分離ｌ−た後は、これらを酸化物か
ら、永久磁石に役立つ比較的純粋な形（混在物の種類に
よって純度９５原子パーセントか又はそれ以上）の夫々
の金属に還元する必要がある。これまでは上記の最終還
元過程が複雑で費用が掛かシ、希土類金属のコストに大
きな負担となった。After the rare earth metals have been separated from each other, it is necessary to reduce them from their oxides to relatively pure forms of the respective metals (95 atomic percent purity or higher, depending on the type of inclusions) useful in permanent magnets. There is. Up until now, the final reduction process described above has been complicated and expensive, adding to the cost of rare earth metals.
希土類の還元には、電解プロセスと金属熱（非電解）プ
ロセスの両方が採用されて来た。Both electrolytic and metal thermal (non-electrolytic) processes have been employed for the reduction of rare earths.
電解プロセスには（１）溶融アルカリ又はアルカリ土類
塩に溶けた無水希土類塩化物の分解及び（２）溶融弗化
物塩に溶けた希土類酸化物の分解がある。The electrolytic process includes (1) the decomposition of anhydrous rare earth chlorides dissolved in molten alkali or alkaline earth salts and (2) the decomposition of rare earth oxides dissolved in molten fluoride salts.
両方の電解プロセスの欠点には、最終的には消耗する高
価な電極の使用、望ましくないＲＥ・オキシ塩類（例え
ばＮｄＯα）の生成防止のための無水塩化物又は弗化物
塩の使用、高温度の電解槽操作（一般には１０００℃以
上）、高いエネルギーコストを斉らす低電流効率及び塩
から金属への低収率（４０％以下の金属が回収出来るに
過ぎない）が挙げられる。ＲＥ・塩化物還元プロセスで
は腐蝕性の塩素ガスが発生し、又弗化物プロセスでは希
土類金属団塊（ｎｏｄｕｌｅ ）を固化させるため電解
塩槽中の温度勾配を注意深く制御しなければならない。Disadvantages of both electrolytic processes include the use of expensive electrodes that eventually wear out, the use of anhydrous chloride or fluoride salts to prevent the formation of undesirable RE oxysalts (e.g. NdOα), and the high temperature These include electrolyzer operation (generally above 1000° C.), low current efficiency compounded by high energy costs, and low salt-to-metal yields (less than 40% of metal can be recovered). The RE/chloride reduction process generates corrosive chlorine gas, and the fluoride process requires careful control of the temperature gradient in the electrolytic salt bath to solidify rare earth metal nodules.
電解プロセスの利点は、還元された金属を取出し、塩浴
を補給出来る措置が講じられ＼ば、プロセスを連続的に
進めることが出来る事である。An advantage of the electrolytic process is that the process can be run continuously if provision is made to remove the reduced metal and replenish the salt bath.
金属熱（非電解）プロセスには （１）カルシウム金属
粉末によるＲＥ・弗化物の還元Ｃカルシオサ−ミック・
プロセス（ｃａｌｅｉｏｔｈｅｒ −ｍｉｅ ｐｒａｃ
ｅｓｓ ） ）、と（２）水素化カルシウム（Ｃ２Ｈ５
）又はカルシウム金属（Ｃａ）によるＲＥ・酸化物の還
元拡散がある。欠点はいずれのプロセスもバッチ方式で
、非酸化性雰囲気中で実施しなければならず、エネルギ
ー消費量が太きく又還元拡散法の場合の生成物は粉末で
、粉末は使用前に水和して精製しなければならない事で
ある。いずれのプロセスも多くの段階からなっている。Metal thermal (non-electrolytic) processes include (1) RE using calcium metal powder, reduction of fluoride, C calciothermic,
process(caleiother-mie prac
ess ) ), and (2) calcium hydride (C2H5
) or the reduction and diffusion of RE/oxide by calcium metal (Ca). Disadvantages are that both processes are batch-based and must be carried out in a non-oxidizing atmosphere, consume a lot of energy, and in the case of the reduction-diffusion method, the product is a powder, which must be hydrated before use. This is something that must be refined. Both processes consist of many steps.
金属熱還元プロセスの一つの利点は、酸化物又は弗化物
からの金属の収率が一般に９０％より良いことである。One advantage of metal thermal reduction processes is that the yield of metal from oxide or fluoride is generally better than 90%.
ＲＥ弗化物又は塩化物が含まれるプロセスには、ＲＥ・
酸化物を前処理してハロゲン化物にする必要がある。こ
の段階が加わるため、希土類金属の最終コストがその分
多くなる。Processes involving RE fluoride or chloride include
Oxides must be pretreated to form halides. This additional step increases the final cost of the rare earth metal.
軽希土類・鉄永久磁石が発明されたため、低コストで、
比較的高純度の希土類金属に対する需要は大幅に増大し
た。然しなから既存の希土類化合物還元方法のいずれに
も、コストの低減或いは磁石グレードの金属の入手し易
さの増大の面で大きな期待が持てなかった。Since light rare earth/iron permanent magnets were invented, they can be made at low cost.
The demand for relatively high purity rare earth metals has increased significantly. However, none of the existing rare earth compound reduction methods has shown much promise in reducing costs or increasing the availability of magnet-grade metals.
従って新規、効率的でコストの安い希土類金属の製造法
を提供することが本発明の目的の一つである。Accordingly, it is one of the objects of the present invention to provide a new, efficient, and inexpensive method for producing rare earth metals.
上記及びその他の目的は下記の本発明の好ましい具体例
に依って達成されよう。These and other objects will be achieved by the preferred embodiments of the invention described below.
電気抵抗ヒーター又はその他の加熱手段によって所望の
温度迄加熱出来る反応容器を準備する。容器本体は反応
構成成分に実質上不活性か又は無害な金属又は耐火材料
で造られていることが好ましい。A reaction vessel is prepared that can be heated to the desired temperature by an electric resistance heater or other heating means. Preferably, the container body is constructed of a metal or refractory material that is substantially inert or non-toxic to the reaction components.
予め所定量のＲＥ−酸化物を、約７０重量％以上の塩化
カルシウムと約５〜３０重量係の塩化ナトリウム（Ｎａ
α）の塩混合物を含んだ反応容器内に装入する。塩は還
元反応のための媒体となる。希土類酸化物の量に対して
、化学量論的に過剰のカルシウム金属を添加する。還元
された希土類金属と共融合金を生成させて反応を低目の
温度で行わせ、ＲＥ・金属生成物が液状で得られる様に
、ある量の鉄或いは亜鉛などの別の金属を添加するのが
好都合であろう。A predetermined amount of RE-oxide is mixed in advance with about 70% by weight or more of calcium chloride and about 5 to 30% by weight of sodium chloride (Na
Charge into a reaction vessel containing the salt mixture of α). The salt serves as a medium for the reduction reaction. A stoichiometric excess of calcium metal is added relative to the amount of rare earth oxide. A eutectic alloy is formed with the reduced rare earth metal, the reaction is carried out at a low temperature, and an amount of another metal such as iron or zinc is added so that the RE metal product is obtained in liquid form. It would be convenient.
反応を進めるため、容器を構成成分の融点以上の温度に
迄加熱する（約６７５℃）。反応の進行中に相互の接触
を保つため容器内の溶融構成成分を急速に撹拌する。必
要に応じて塩化カルシウム（Ｃａα２）を浴に補充し、
Ｃａα２とＮａαの合計重量にたいして７０重量％を維
持する。Ｃａ ｃ７！ ２濃度が７０％以下の所で反応
が進むと、収率が急激に低下する。To proceed with the reaction, the vessel is heated to a temperature above the melting point of the components (approximately 675°C). The molten components in the vessel are rapidly stirred to maintain contact with each other during the course of the reaction. Replenish the bath with calcium chloride (Caα2) as necessary,
70% by weight of the total weight of Caα2 and Naα is maintained. Ca c7! If the reaction proceeds at a concentration of 2 or less than 70%, the yield will drop sharply.
容器内では幾つかの異った競争化学反応が起るが、ＲＥ
・酸化物の還元反応は下記の実験反応式に従って進むも
のと考えられるＲＥｎＯｍ ＋ｍＣａ−＋ｍＣａＯ＋ｎ
ＲＥ絃で「ｎ」と「ｍ」は構成成分のモル数で又、ｎ
とｍの関係は希土類元素の酸化状態によって左右される
。Although several different competitive chemical reactions occur within the container, RE
・The reduction reaction of oxides is thought to proceed according to the following experimental reaction formula REnOm +mCa-+mCaO+n
In the RE string, "n" and "m" are the number of moles of the constituent components, and n
The relationship between and m depends on the oxidation state of the rare earth element.
還元された金属の密度は約７グラム／ｅ Ｏで、塩浴の
密度は約１，９グラム／ｃｅである。撹拌を止めると、
還元金属は反応容器の、底に完全な層が出来る。この層
は溶融状態のまま抜き取る事も出来、或いは固化した後
塩層と分離する事も出来る。The density of the reduced metal is approximately 7 grams/e O, and the density of the salt bath is approximately 1,9 grams/ce. When you stop stirring,
The reduced metal forms a complete layer at the bottom of the reaction vessel. This layer can be extracted in its molten state, or it can be solidified and then separated from the salt layer.
この様に、本発明の方法には従来技術の方法にまさる多
数の利点がある。この方法は、特に希土類金属が亜鉛又
は鉄との共融合金の形で回収される場合、約７００℃と
言う比較的低温の所で行われる。この方法には比較的安
価なＲＥ・酸化物、Ｃａα２、Ｎａα及びＣａ金属が反
応物として用いられる。ＲＥ・酸化物を塩化物又は弗化
物に予め変換する必要はなく、高価な還元剤である純Ｃ
ａ又はＣａＨ２を用いる必要もない。電解的な方法では
ないからエネルギー消費量も少く、約７００℃の温度で
大気圧で具合よ〈実施される。この方法は回分式又は連
続式プロセスのいずれの形でも実施出来、副生物Ｃａα
２、Ｎａα及び酸化カルシウム（ＣａＯ）は始末が容易
である。Thus, the method of the present invention has a number of advantages over prior art methods. This process is carried out at relatively low temperatures of about 700° C., especially when the rare earth metals are recovered in the form of eutectic alloys with zinc or iron. This method uses relatively inexpensive RE oxides, Caα2, Naα, and Ca metals as reactants. There is no need to pre-convert RE/oxides to chlorides or fluorides, and pure C, which is an expensive reducing agent, can be used.
There is also no need to use a or CaH2. Since it is not an electrolytic method, it consumes little energy and can be carried out at temperatures of about 700°C and atmospheric pressure. This method can be carried out in either a batch or continuous process, with the by-product Caα
2. Naα and calcium oxide (CaO) are easy to dispose of.
その上希土類金属は、ＲＥ−ｈ、共融合金の形で造られ
る場合は反応容器中に鉄を添加して合金化する事も出来
、或いはその後に高価な精製処理を行うことなしにＲＥ
−Ｆａ磁石用に合金化することも出来る。Moreover, rare earth metals can be alloyed by adding iron to the reaction vessel if they are made in the form of RE-h, eutectic alloys, or RE-h without subsequent expensive refining processes.
It can also be alloyed for -Fa magnets.
本発明は希土類元素の化合物を還元して対応する金属単
体を得る改良された方法に関する。希土類金属には、周
期表の５７〜７１番元素（ランタン、セリウム、プラセ
オジム、ネオジム、プロメチウム、サマリウム、ユーロ
ピウム、ガドリニウム、テルビウム、ジスプロシウム、
ホルミウム、エルビウム、ツリウム、イッテルビウム、
ルテチウム）及び原子番号３９、イツトリウムが含まれ
る。希土類の酸化物は一般に金属分離プロセスで生産さ
れる着色粉末である。絃で「軽希土類」と言う用語はラ
ンタン（Ｌａ ） 、セリウム（Ｃｅ）、プラセオジム
（Ｐｒ）及びネオジム（Ｎｄ）を表わす。The present invention relates to an improved method for reducing compounds of rare earth elements to obtain the corresponding elemental metals. Rare earth metals include elements 57 to 71 of the periodic table (lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium,
Holmium, erbium, thulium, ytterbium,
lutetium) and atomic number 39, yttrium. Rare earth oxides are commonly colored powders produced in metal separation processes. The term "light rare earths" in the strings refers to lanthanum (La), cerium (Ce), praseodymium (Pr) and neodymium (Nd).
本発明の方法に於いて、ＲＥ酸化物は一般に分離器から
出たままの姿で使われるが、■焼して過剰の吸収水分又
は炭酸ガスを除去してもよい。以下の例ではＲＥ・酸化
物は使用に先立ち１０００℃で約２時間炉で乾燥した。In the process of the present invention, the RE oxide is generally used as it comes out of the separator, but may be calcined to remove excess absorbed moisture or carbon dioxide. In the examples below, the RE oxide was oven dried at 1000° C. for approximately 2 hours prior to use.
塩浴用のＣａ Ｃ／ ２とＮａＣｔは試薬グレードのも
ので、使用に先立ち５００℃で約２時間乾燥した。Ca C/2 and NaCt for the salt bath were of reagent grade and dried at 500°C for approximately 2 hours prior to use.
当初の作業では、反応容器内に全く水分が導入されない
様に注意を払い、Ｎａ又はＣａと有害な反応が起らない
様にした。Ｎａα・含有浴にカルシウムを添加すると、
下記の反応で、いくらかのナトリウム金属が生ずること
ができる。In the initial work, care was taken to ensure that no moisture was introduced into the reaction vessel to avoid harmful reactions with Na or Ca. When calcium is added to the Naα/containing bath,
Some sodium metal can be produced in the reactions described below.
２Ｎａα十Ｃａ−＋Ｃａｃｔ２ ＋２Ｎａ溶融浴中でＮ
ｄ２Ｏ３にＣａα２が混合されると、下記の反応でオキ
シ塩化物が生成する
ＮｄｚＯｓ ＋Ｃａα２ → ２ＮｄＯα＋ＣａＯこの
種のＲＥ・オキシ塩化物の存在は先行技術電解プロセス
では収率を低下させる事が知られている。然しなから本
発明に於いてはＲＥ酸化物もＲＥ・オキシ塩化物も共に
容易にカルシウム金属で還元される。実際にはＲＥ・オ
キシ酸化物は還元されたＲＥ・金属の溶融層上に浮遊す
るので、その生成は好都合である。一方、ＲＥ・酸化物
の方は還元ＲＥ・金属に近い密度を持っているから、還
元ＲＥ・金属の溶融層中に不純物の形で保持されるおそ
れがあり、ＲＥ金金属磁石用に使う際に不都合を生ずる
おそれがある。本発明に依る方法で還元されたＲＥ金金
属基本的に酸素を含んでいなかった。2Naα+Ca−+Cact2 +2NaN in molten bath
When Caα2 is mixed with d2O3, oxychloride is formed in the following reaction: NdzOs +Caα2 → 2NdOα+CaO The presence of this type of RE oxychloride is known to reduce the yield in prior art electrolytic processes. . However, in the present invention, both RE oxide and RE oxychloride are easily reduced with calcium metal. In reality, the formation of RE oxyoxide is advantageous since it floats on top of the molten layer of reduced RE metal. On the other hand, since RE/oxide has a density close to that of reduced RE/metal, there is a risk that it will be retained in the form of impurities in the molten layer of reduced RE/metal. There is a risk of causing inconvenience. The RE gold metal reduced by the method according to the invention was essentially oxygen-free.
合金化されないＮｄ金属の融点は約１０２５℃である。The melting point of unalloyed Nd metal is about 1025°C.
他の希土類金属も高い融点を持っている。対象とする反
応をこの程度の温度で進めようと思うなら、そうする事
も可能であシ純金属を高収率で得ることも出来よう。然
しなからもつと低い温度で溶融する、回収希土類金属の
合金を生成させるため、還元容器に鉄、亜鉛などの他の
金属、又は他の非希土類金属をある量添加することが好
ましい。例えば鉄はネオジムと低融点共融合金を生成す
る（Ｆｚｌｌ、５重量％ ｅ ｍ−ｐ、約６４０℃）、
亜鉛も同様である（Ｚａｌｌ、９重量％、ｍ、ｐ、約６
３０℃）。Ｎｄ２Ｏ３還元系に十分な鉄が添加されると
、還元された金属は約６４０℃で液状の溜シを生成する
。Ｎｄ−ＦＪＩ共融合金は、鉄及び硼素を添加して合金
化し、前述のヨーロＬ１５ノ
ツバ特許出願に述べられた最適のＮｄ ｆｎ Ｉ４ Ｂ
磁石相を持った磁石にすることが出来る。Other rare earth metals also have high melting points. If you want to proceed with the target reaction at this temperature, it is possible to do so, and the pure metal can be obtained in high yield. However, in order to form an alloy of recovered rare earth metals that melts at lower temperatures, it is preferred to add some amount of other metals such as iron, zinc, or other non-rare earth metals to the reduction vessel. For example, iron forms a low melting point eutectic alloy with neodymium (Fzll, 5 wt% e m-p, about 640 °C),
The same goes for zinc (Zall, 9% by weight, m, p, approx. 6
30℃). When enough iron is added to the Nd2O3 reduction system, the reduced metal forms a liquid reservoir at about 640°C. The Nd-FJI eutectic alloy is alloyed with the addition of iron and boron to produce the optimal Nd fn I4 B described in the aforementioned Euro L15 Notsuba patent application.
It can be made into a magnet with a magnetic phase.
回収希土類金属の融点を引下げることが好ま１−いが、
その様にして添加された金属を残すことが好ましくない
場合は、回収希土類金属の沸点よりもずっと低い沸点を
持つ金属を反応容器に添加してもよい。例えばムは９０
７℃で沸騰し、Ｎｄは３１５０℃で沸騰する。Although it is preferable to lower the melting point of the recovered rare earth metal,
If it is undesirable to leave the metal so added, a metal having a boiling point much lower than that of the recovered rare earth metal may be added to the reaction vessel. For example, MU is 90
It boils at 7°C, and Nd boils at 3150°C.
低融点金属はその後、簡単な蒸留操作で希土類金属から
容易に分離出来る。The low melting point metal can then be easily separated from the rare earth metal by a simple distillation operation.
反応容器又はその内張りに用いる材料は、溶融希土類金
属、特に塩融剤環境中に残った希土類金属に腐蝕性があ
るため慎重に選択されなければならない。イツトリヤ内
張シアルミナや硼素ナイトライドは非反応性である、耐
火材料は一般に許容される。タンタルの様な基本的に不
活性の金属或いは鉄の様な消耗性だが無害の金属で造ら
れた耐火内張）材を用いることも可能である。鉄の内張
シは還元されたＲＥ金金属入れるのに使え、その後磁石
に使うためにＲＥと合金化出来る。The materials used for the reaction vessel or its lining must be carefully selected due to the corrosive nature of molten rare earth metals, especially rare earth metals left in salt flux environments. Ittriya-lined sialumina and boron nitride are non-reactive, refractory materials that are generally acceptable. It is also possible to use refractory linings made of essentially inert metals such as tantalum or consumable but non-hazardous metals such as iron. The iron lining can be used to contain reduced RE gold metal, which can then be alloyed with RE for use in magnets.
本発明に依って、希土類酸化物の還元にカルシウム金属
を用いる新しい方法が発見された。本方法は溶融カルシ
ウムとＲＥ・酸化物を一緒にして下記の反応を起させる
ことをその内容とする
ＲＥｎｏｒｎ、 ＋ ｍ Ｃａ −＋ ｎ ＲＥ十ｍ
ＣａＯ反応容器を加圧しない場合には、ＣａとＮａαの
反応によって生ずるＮａの過大な損失を回避するため、
温度を約９１０℃辺シに保つことが望ましい。最も好ま
しい操業温度範囲は、約６５０℃〜７５０℃の辺りであ
る。この様な温度では、反応容器の損耗は甚だしくはな
い。Ｎｄ−Ｆｉ及びＮｄ −Ｚｎ共融物の溶融温度は７
００℃以下であるから上記の温度範囲はＮｄ２Ｏ，をＮ
ｄ金属に還元するのに好適である。In accordance with the present invention, a new method of using calcium metal for the reduction of rare earth oxides has been discovered. This method involves bringing together molten calcium and RE/oxide to cause the following reaction.
When the CaO reaction vessel is not pressurized, in order to avoid excessive loss of Na caused by the reaction between Ca and Naα,
It is desirable to maintain the temperature at about 910°C. The most preferred operating temperature range is around 650°C to 750°C. At such temperatures, the wear and tear on the reaction vessel is not significant. The melting temperature of Nd-Fi and Nd-Zn eutectic is 7
Since it is below 00℃, the above temperature range is Nd2O,
Suitable for reduction to d metal.
その上約７００℃では塩浴中のＣａ金属の溶解度は約１
．３モルチである。この値は速かにＲＥ酸化物をＲＥ・
金属に還元するのに十分である。Moreover, at about 700°C, the solubility of Ca metal in the salt bath is about 1
．． It is 3 molti. This value quickly converts RE oxide into RE・
sufficient to reduce it to metal.
融剤から還元ＲＥ金金属うまく分離する必要がある場合
は、反応温度を還元ＲＥ金金属は合金化された即ち他の
金属と一緒に還元された還元ＲＥ金金属融点より高くし
なければならない。上記の比較的密度の高いＲＥ金金属
は合金は、沈降させると反応容器の底に集まる。これで
溶融中にこれらを抜き取り或いは同化後取出すことが出
来る。If successful separation of the reduced RE gold metal from the flux is required, the reaction temperature must be above the melting point of the reduced RE gold metal with which the reduced RE gold metal is alloyed, ie, reduced with other metals. When the relatively dense RE gold metal alloy is allowed to settle, it collects at the bottom of the reaction vessel. This allows them to be extracted during melting or removed after assimilation.
表１に本発明に用いた単体及び化合物の、分子量（ｍ、
ｗ、）、２５℃に於ける密度（μ）Ｃ９７使）、融点（
ｍ、 ｐ、 ）及び沸騰点（ｂ、ｐ、）を示しである。Table 1 shows the molecular weights (m,
w, ), density at 25°C (μ) using C97), melting point (
m, p, ) and boiling point (b, p, ).
表１
ｍ、ｗ・ μ ｍ−ｐ−（６）ｂ、ｐ（６）Ｎｄ
１４４．２４７．００４１０２４３３０ＯＮｄ２０ｓ
３３６．４８７．２８ １９００ −ＮｄＯαｂ
１９５．６９ ５，５Ｑ
Ｃａ ４０．０８１，５５ ８５０１４９４Ｃａ
Ｏ５６，０８３，２５２９２７３５００Ｆａｒ
５５．８５７．８６ １５３７２８７２Ｚｎ ６
５．３７７．１４ ４１９．６９１１Ｃａα２ １１
０．９９２，１５ ７７２１９４ＯＮａα ５８．
４５２．１６４ ８０１１４６５５５ｎ１１０Ｃａα２
−４５ｍ１０Ｎａα１．９０３※Ｎａ Ｃ／
１，５９６※Ｃａα２ ２．１
０４※
ｂ計算値
※１０００’Ｋにおける値、
図１に本発明を実施するのに適当な装置が示しである、
仁の装置で幾つかの実施例に述べである実験操作を行っ
た。Table 1 m, w・μ m-p-(6)b, p(6)Nd
144.247.0041024330ONd20s
336.487.28 1900 -NdOαb
195.69 5,5Q Ca 40.081,55 8501494Ca
O56,083,2529273500Far
55.857.86 15372872Zn 6
5.377.14 419.6911Caα2 11
0.992,15 772194ONaα 58.
452.164 801146555n110Caα2
-45m10Naα1.903*Na C/
1,596*Caα2 2.1
04* b Calculated value * Value at 1000'K, Figure 1 shows an apparatus suitable for carrying out the present invention.
The experimental operations described in some of the examples were carried out using Jin's apparatus.
実験は全てボルト６でドライボックスの床４に取付けら
れた内径が１２．７ｃｍで深さが５４．６ｃｒＩＬの長
い竪型炉２０内で行われた、実験操作中酸素（０２）、
窒素（Ｎ２）及び水分（Ｎ２０）が夫々百万分の一以下
含まれているヘリウム雰囲気が箱内に保持された。All experiments were conducted in a long vertical furnace 20 with an inner diameter of 12.7 cm and a depth of 54.6 cr IL, which was attached to the floor 4 of the dry box with bolts 6. During the experimental operations, oxygen (02),
A helium atmosphere containing less than one part per million of nitrogen (N2) and water (N20) each was maintained within the box.
炉を内径が１３．３（ｍで全長が４５．７ｃＩｒＬの３
個の円筒状電気クラムシェル加熱体８．１０及び１２で
加熱した。炉の側面及び底面を絶縁物１４で完全に取囲
んだ。熱電対１５を竪型炉２０の外壁１６の種々な位置
にその長さ方向にそって取付けた。中央に位置する熱電
対の中の一個を比例帯域温度調節器（図示せず）に接続
して利用し、自動的に中央クラムシェルヒーター１０を
制御した。残シの３つの熱電対をデジタル温度読み取り
装置を用いて監視し、頂部と底部のクラムシェル加熱器
８及び１２は、変圧器を使って手動で調節し炉全体をか
なシ均一な温度に保った。The furnace has an inner diameter of 13.3 m and a total length of 45.7 cIrL.
Heating was carried out with two cylindrical electric clamshell heating elements 8, 10 and 12. The sides and bottom of the furnace were completely surrounded by an insulator 14. Thermocouples 15 were attached to the outer wall 16 of the vertical furnace 20 at various positions along its length. One of the centrally located thermocouples was used to connect to a proportional band temperature controller (not shown) to automatically control the central clamshell heater 10. The remaining three thermocouples are monitored using a digital temperature readout, and the top and bottom clamshell heaters 8 and 12 are manually adjusted using transformers to maintain a uniform temperature throughout the furnace. Ta.
ステンレス鋼竪型炉２０中に保持された外径１０．２６
ＩＩＬ ％深さ１２．７ｆｆｉで厚みが０．１５ｃｍの
ステンレス鋼るつぼ１８に納められた反応容器２２中で
還元反応を行った。実施例中で特に断っていない限シ、
反応容器２２はタンタル金属製であった。External diameter 10.26 held in stainless steel vertical furnace 20
The reduction reaction was carried out in a reaction vessel 22 housed in a stainless steel crucible 18 with a depth of 12.7ffi and a thickness of 0.15 cm. Unless otherwise specified in the examples,
Reaction vessel 22 was made of tantalum metal.
還元プロセス中溶融物の撹拌にタンタル撹拌器２４を用
いた。撹拌器の軸の長さは４８．３２ｃｒＩｌで翼２６
が溶接されていた。撹拌器は７００回転／分迄の速度で
作動出来る１００ｗ速度可変モーター２８で駆動された
。A tantalum stirrer 24 was used to stir the melt during the reduction process. The length of the agitator shaft is 48.32 crIl and the blades are 26.
was welded. The stirrer was driven by a 100W variable speed motor 28 capable of operating at speeds up to 700 rpm.
モーターは、反応容器中の撹拌翼２６の深さを調整出来
る様に、ブラケット３０に取付けられた。軸は瑠状の支
持ブラケット３４に備えられたブシュ３２に通された。The motor was attached to a bracket 30 so that the depth of the stirring blade 26 in the reaction vessel could be adjusted. The shaft was passed through a bushing 32 provided on a support bracket 34 shaped like a glass.
ブラケットはカラー３５で保持され、カラーには竪型炉
２０がボルト３Ｔによって取付けられている。The bracket is held by a collar 35, and the vertical furnace 20 is attached to the collar by bolts 3T.
竪型炉２０の頂部の近くに冷水コイル３６があシ、揮発
性の反応構成成分の凝縮を促進し逸散を防止する。Ｎａ
蒸気を還流させるために円錐形のステンレス鋼邪魔板３
８が用いられた。底の邪魔板４２の筒４０を通って還流
生成物が下に落ちる。A cold water coil 36 is provided near the top of the vertical furnace 20 to promote condensation of volatile reaction components and prevent their escape. Na
Conical stainless steel baffle plate 3 for steam reflux
8 was used. The reflux product falls down through the tube 40 of the bottom baffle 42.
操作の最後に炉内の構成成分の撹拌を止めると、構成成
分は底に希土類合金溜り４３、その上にＲＥ・オキシ塩
化物、塩化カルシウム／ナトリウム塩浴４４、その上に
もしあれば未反応のカルシウム金属４５と言った形で層
状に分離する。At the end of the operation, when the stirring of the components in the furnace is stopped, the components are deposited with the rare earth alloy reservoir 43 at the bottom, the RE oxychloride, calcium chloride/sodium salt bath 44 above, and any unreacted components above. Calcium metal 45 separates into layers.
図２は本発明によるＮｄ２Ｏ３のＮｄ金属への還元の理
想化されたフロー・チャートである。FIG. 2 is an idealized flow chart of the reduction of Nd2O3 to Nd metal according to the present invention.
Ｎｄ２０ｇは適当な比率の塩化カルシウムおよび塩化ナ
トリウムと共に反応容器に添加される。20 g of Nd is added to the reaction vessel along with the appropriate proportions of calcium chloride and sodium chloride.
カルシウム金属と、共融Ｎｄ合金に近いものを生成させ
るために十分な量の鉄又は亜鉛の様な共融物生成金属が
添加される。少くとも１時間約７００℃の温度において
約３００〜７００回転／分で急速に撹拌しながら反応が
進められる。ヘリウムの様な不活性ガス雰囲気を反応容
器上に保持することが好ましい。Calcium metal and a sufficient amount of a eutectic metal, such as iron or zinc, is added to form something close to a eutectic Nd alloy. The reaction is allowed to proceed for at least 1 hour at a temperature of about 700 DEG C. with rapid stirring at about 300-700 revolutions per minute. Preferably, an inert gas atmosphere, such as helium, is maintained over the reaction vessel.
Ｎｄ２Ｏ３が還元された後、約１時間１００回転／分に
速度を下げて撹拌を継続し次いで撹拌を止めて容器中の
種々の液体を層状に分離させる。還元Ｎｄ共融合金は、
その密度が最も大きいため底に集まる。残シの塩類及び
未反応のＣａはＮｄ合金上に集まシ、容器が冷えて構成
成分が固化した後容易に壊わして取出すことが出来る。After the Nd2O3 has been reduced, stirring is continued at a reduced speed to 100 revolutions per minute for approximately one hour, and then stirring is stopped to allow the various liquids in the vessel to separate into layers. The reduced Nd eutectic alloy is
It gathers at the bottom because it has the highest density. The remaining salts and unreacted Ca collect on the Nd alloy, and after the container has cooled and the constituent components have solidified, they can be easily broken and taken out.
この様にして造られたＮｄ−Ｐｇ合金は追加元素と合金
化して、永久磁石組成物に仕上げることが出来る。この
磁石合金はメルト・スピニング法で加工する事が出来又
摩砕して粉末冶金法で加工して磁石にすることも出来る
。The Nd-Pg alloy thus produced can be alloyed with additional elements to form a permanent magnet composition. This magnetic alloy can be processed by melt spinning, or it can be ground and processed into a magnet by powder metallurgy.
実施例Ｉ
純度９９％のＮｄ金属塊２６５グラムと９９．９％純度
Ｚｎ金属５０グラムを共融合金に近いもの３１５グラム
を造るためタンタル反応容器中に入れた。容器を炉内に
入れ、８００℃に加熱してＮｄ とＺｎを合金化させた
。Example I 265 grams of 99% pure Nd metal ingot and 50 grams of 99.9% pure Zn metal were placed in a tantalum reactor to produce 315 grams of near-eutectic alloy. The container was placed in a furnace and heated to 800°C to alloy Nd and Zn.
炉の温度を約７２０℃に下げ７０重量％のＣａα２の塩
浴を造るためＮａα１５０グラムとＣａα２３５０グラ
ムを添加した。Ｎｄ２Ｏ３２３４グラム（０，７モル）
を添加した。Ｃａ金属１０４グラム（２，６モル）をる
つぼに添加しこれを約２時間３００回転／分の速度で撹
拌し次いで更に１時間６０回転／分の速度で撹拌した。The temperature of the furnace was lowered to about 720° C. and 150 grams of Naα and 2350 grams of Caα were added to create a salt bath of 70% by weight Caα2. 234 grams of Nd2O3 (0,7 mol)
was added. 104 grams (2.6 moles) of Ca metal were added to the crucible, which was stirred for about 2 hours at a speed of 300 revolutions/minute and then for an additional hour at a speed of 60 revolutions/minute.
るつぼを炉から取出し、ドライボックスの床の上で冷や
した。The crucible was removed from the furnace and cooled on the floor of a dry box.
容器の底に集まったＮｄ−Ｚａ金合金蒸留して純度が９
９％以上のＮｄ金属１８９グラム（はじめに加えたＮｄ
金属２６５グラムを除く）を回収した。酸化物からのＮ
ｄ金属の収率は約９４％であった。The Nd-Za gold alloy collected at the bottom of the container was distilled to a purity of 9.
189 grams of Nd metal with 9% or more (Nd added at the beginning)
(excluding 265 grams of metal) was recovered. N from oxides
The yield of d metal was about 94%.
実施例■
４１４グラムの共融合金に近いものを造るため、純度９
９チのＮｄ金属塊３５０グラムと電解鉄６４グラムを厚
さ６龍の軟鋼製反応容器中に入れた。容器を炉内に入れ
８００℃に加熱してＮｄと鉄を合金化させた。Example ■ Purity 9 to produce something close to 414 grams of eutectic alloy.
350 g of Nd metal ingot of 9 mm and 64 g of electrolytic iron were placed in a mild steel reaction vessel of 6 mm thick. The container was placed in a furnace and heated to 800°C to alloy Nd and iron.
炉の温度を約７２０℃に下げてＣａα２が７０重量％の
塩浴を造るため、Ｎａα３００グラムとＣａα２７００
グラムを添加した。Ｎｄ２０ａ １１７グラム（０，３
５モル）を添加した。Ｃａ金属４６グラム（１，１５モ
ル）とＮａ１Ｏ１８グラム（０，４７モル）をるつぼに
添加し約１３５分間３００回転／分の速度でこれらを撹
拌した。この時点で更に、ＮｄｚＯｓ １１７グラム（
０，３５モル）、Ｃａ金属４６グラム（１，１５モル）
及びＮａ１Ｏ，８グラム（０，４７モル）を添加した。In order to lower the furnace temperature to about 720°C and create a salt bath containing 70% by weight of Caα2, 300 grams of Naα and 2700 grams of Caα2 were added.
grams were added. Nd20a 117 grams (0,3
5 mol) was added. 46 grams (1.15 mol) of Ca metal and 18 grams (0.47 mol) of Na1O were added to the crucible and these were stirred at a speed of 300 revolutions/min for about 135 minutes. At this point, 117 grams of NdzOs (
0,35 mol), Ca metal 46 grams (1,15 mol)
and NaIO, 8 grams (0.47 mol) were added.
反応物を更に１１４分間、３００ｒｐｍで撹拌し次いで
もう１時間６０ ｒｐｍの撹拌速度で撹拌した。反応容
器を炉から取出しドライボックスの床の上で冷やした。The reaction was stirred for an additional 114 minutes at 300 rpm and another hour at a stirring speed of 60 rpm. The reaction vessel was removed from the furnace and cooled on the floor of a dry box.
塩層の上に未反応のＣａ−Ｎａ合金の層が出来た。A layer of unreacted Ca--Na alloy was formed on top of the salt layer.
純度９７チのＮｄ −Ｆｎ合金、５９４グラムが回収さ
れた。この合金から、回収後直ちに、鉄及び硼素を結合
させて、永久磁石製造用の理想的なＮｄ−Ｆｉ−Ｂ合金
を造ることができる。594 grams of Nd-Fn alloy with a purity of 97% was recovered. Immediately after recovery, this alloy can be combined with iron and boron to create an ideal Nd-Fi-B alloy for permanent magnet production.
Ｎ ｄ −Ｆａ金合金形で９９−以上の純度のＮｄ金属
１８０グラムが回収された。この実施例はＣａα２−Ｎ
ａα融剤浴中でカルシウム及びナトリラム溶融物が、希
土類酸化物を還元出来ることを示している。180 grams of Nd metal in the form of Nd-Fa gold alloy with a purity greater than 99- was recovered. In this example, Caα2-N
It has been shown that calcium and natrirum melts in an aα flux bath can reduce rare earth oxides.
実施例ｍ
実施例■に述べたプロセスを用いて、但し反応物を４時
間３００回転／分で撹拌した後更に６０ ｒｐｍで１時
間撹拌してＣａ金属を用いてＮｄ２Ｏ３約２３４グラム
を金属熱還元した時の種々の構成成分の使用量を表■に
掲げである。Example M Using the process described in Example ■ except that the reactants were stirred at 300 rpm for 4 hours and then at 60 rpm for an additional hour, approximately 234 grams of Nd2O3 was thermally reduced using Ca metal. The amounts of the various constituent ingredients used are listed in Table 3.
表 ■
サンカレＣａα２ Ｎａα総塩量Ｃａ Ｎａ 共融物
中 Ｎｄ Ｎｄ１※ ６５．５ ３４．５ ７４
０ ６６．７− ８８．９ ６５．２ ６５．２
２ ９０ １０ ７８６ ９１．７− ８８．
２ １７０．５ ８５．３３ ９０ １０ １１
７８１０４．２− ９０．２ １９５．７ ９７，
８※ＮｄｚＯａ １１７グラム
Ｃａα２が６５．５重量％でＮａαが３４．５重量％の
塩浴比の時、収率は６５．２％になる。Table ■ Sankare Caα2 Naα total salt amount Ca Na Nd in eutectic Nd1* 65.5 34.5 74
0 66.7- 88.9 65.2 65.2
2 90 10 786 91.7- 88.
2 170.5 85.33 90 10 11
78104.2- 90.2 195.7 97,
8*117 grams of NdzOa When the salt bath ratio is 65.5% by weight of Caα2 and 34.5% by weight of Naα, the yield will be 65.2%.
ＣａＱ！’２が７０重量％又はそれ以上になると、夫々
の場合のＮｄの収率は８５％より高く一般的に９５％以
上である。図３はＣａ金属を還元剤に用いたＮａα−Ｃ
ａα２二成分系出発塩浴中のＣａα２の重量％に対して
Ｎｄ２Ｏ５からのＮｄ金属の収率をプロットしたもので
ある。CaQ! When '2 is 70% by weight or more, the Nd yield in each case is greater than 85% and generally greater than 95%. Figure 3 shows Naα-C using Ca metal as a reducing agent.
Figure 3 is a plot of the yield of Nd metal from Nd2O5 versus the weight percent of Caα2 in the aα2 binary starting salt bath.
表■及び図３に示されるように、高収率を得るには、塩
浴中のＣａ Ｃ／ ２の量を約７０重量−以上に保つ必
要がある事が分った。又ＲＥ・酸化物の分散に適当な融
剤を得るには、塩とＲＥ・酸化物の容積比を少くとも２
：１にすることが望ましい。塩浴のＲＥ・酸化物にたい
する容積比が増すに伴って、成る決まった時間内に同じ
収率を得るのに撹拌速度を引下げられることができると
言う事が認められた。As shown in Table 1 and FIG. 3, it was found that to obtain a high yield, it was necessary to maintain the amount of Ca C/2 in the salt bath at about 70 wt. In addition, in order to obtain a suitable flux for dispersing RE/oxide, the volume ratio of salt to RE/oxide should be at least 2.
: It is desirable to set it to 1. It has been observed that as the volume ratio of the salt bath to RE/oxide increases, the stirring speed can be reduced to obtain the same yield within a given time period.
Ｃａｃｔ２含有浴は本発明の重要な特徴である。The Cact2-containing bath is an important feature of the invention.
幾つかのサンプルを一緒にして真空蒸留によってＺｎ金
属を除去した。得られた合金を分析して純度が９９チ以
上でアルミニウム０．４チ、珪素０．１チ、カルシウム
０．０１％で痕跡量の亜鉛、マグネシウム及び鉄が混在
している事が分った。この様にして得られたＮａ金属を
真空炉中で電解鉄及びフェロ硼素と溶融して名目組成が
Ｎｄｏ、ｔｓ ｎｏ、。５Ｆｎｏ０ｇｏ の合金を造
った。この合金を上述のヨーロッパ特許出願１’１＆１
Ｌｏ１０８４７４に述べられている様にしてメルト・ス
ピニングし、急冷時の保持力が約１０メガ脅ガウス争エ
ルステツドの非常に細かい結晶性リボンを造った。Several samples were combined to remove Zn metal by vacuum distillation. Analysis of the resulting alloy revealed that the purity was 99% or higher, and that it contained 0.4% aluminum, 0.1% silicon, 0.01% calcium, and trace amounts of zinc, magnesium, and iron. . The Na metal thus obtained is melted with electrolytic iron and ferroboron in a vacuum furnace to give a material with a nominal composition of Ndo, ts no. An alloy of 5Fno0go was made. This alloy was described in the above-mentioned European patent application 1'1&1.
Melt spinning was performed as described in Lo 108474 to produce a very fine crystalline ribbon with a retention strength of approximately 10 M Gaussian Oersted during quenching.
本発明はＮｄ ２０’３’の還元に就いて詳しく述べで
あるが、他の単独の希土類単体の酸化物又は希土類酸化
物の組合せ物の還元にも同様に適扇出来る。これはＣａ
Ｏがいずれの希土類の酸化物よりも安定であると言う事
実に基いている。この分野に精通した人ならこれまでＲ
Ｅ酸化物とＣａＯの相対的自由エネルギーを求めること
が出来たであろうが、本発明以前は、ＲＥ・酸化物が非
電解液相プロセスでＣａ金属で還元出来る事は知られて
いなかった。Although the present invention is described in detail with respect to the reduction of Nd 20'3', it is equally applicable to the reduction of other single rare earth oxides or combinations of rare earth oxides. This is Ca
It is based on the fact that O is more stable than any rare earth oxide. If you are familiar with this field, you can
It would have been possible to determine the relative free energy of E oxide and CaO, but prior to the present invention it was not known that RE oxide could be reduced with Ca metal in a non-electrolytic liquid phase process.
望むなら、ｈやＣｏの様な遷移金属の酸化物を、本発明
のプロセスでＲＥ酸化物と一緒に還元出来る。If desired, oxides of transition metals such as h and Co can be reduced together with RE oxides in the process of the present invention.
要するに、希土類酸化物を希土類金属に還元する新しい
効率がよくコストの安い方法が開発された。本方法は、
適当な溶融Ｃａα２ベース浴を造り、その中そ希土類酸
化物を、それを還元するに十分な量のカルシウム金属と
撹拌することをその内容とする。撹拌を止めると、構成
成分は明確な層に分かれ、この層は冷却し固化した後こ
わして除くことが出来る。別の方法では、還元された液
状の希土類金属を反応容器の底から抜き取ることが出来
る。ＲＥ金金属抜き取った後、融浴に補給して次のバッ
チに移シ、プロセスを基本的に連続的なものにすること
が出来る。In summary, a new efficient and low cost method for reducing rare earth oxides to rare earth metals has been developed. This method is
The procedure consists of preparing a suitable molten Caα2-based bath and stirring the rare earth oxide therein with an amount of calcium metal sufficient to reduce it. When stirring is stopped, the components separate into distinct layers that can be broken off after cooling and solidification. Alternatively, the reduced liquid rare earth metal can be withdrawn from the bottom of the reaction vessel. After the RE gold metal is extracted, the melt bath can be refilled and transferred to the next batch, making the process essentially continuous.
図１は本発明によってＲＥ・酸化物をＲＥ金金属還元す
る方法を実施するのに適した装置を側面から見た断面図
である。
図２は酸化ネオジム（Ｎｄ２０ａ）をカルシウムで還元
してネオジム共融合金を造る際のフロー・チャートであ
る。
図３はＮｄ２Ｏ３からのネオジム（Ｎｄ）金属の収率を
、本発明で用いた融剤浴中のＣａ Ｃｌ ２の百分率に
対してプロットしたものである。FIG. 1 is a sectional side view of an apparatus suitable for carrying out the method of RE gold metal reduction of RE oxides according to the present invention. FIG. 2 is a flow chart for producing a neodymium eutectic alloy by reducing neodymium oxide (Nd20a) with calcium. FIG. 3 is a plot of the yield of neodymium (Nd) metal from Nd2O3 versus the percentage of CaCl2 in the flux bath used in the present invention.
Claims (1)
融塩浴よりも少ない容量の希土 類酸化物を分散せしめ、存在する希土類金 属イオンにたいして化学量論的に過剰のカ ルシウム金属を溶融塩浴中に加え、該溶融 塩浴を撹拌し、反応式 ＲＥｎＯ＿ｍ＋ｍＣａ→ｎＲＥ＋ｍＣａＯ 〔式中ＲＥは原子価２、３または４をもつ １種または複類の希土類元素を表わし、Ｏ は酸素を表わし、Ｃａはカルシウムを表わ し、ＣａＯは酸化カルシウムを表わし、ｎとｍは希土類
元素の原子価のｎ倍が酸素の原 子価のｍ倍に等しくなるような整数を表わ す。〕に従つて還元が行われることを特徴 とする希土類酸化物の希土類金属への金属 熱非電解還元法。 ２、反応式 Ｎｄ＿２Ｏ＿３＋３Ｃａ→２Ｎｄ＋３ＣａＯによつて溶
融塩浴中で酸化ネオジムがネオ ジム金属に還元される特許請求範囲第１項 に記載の金属熱非電解還元法。 ３、方法が、塩化カルシウムより成る溶融塩浴を造るこ
と；上記の溶融塩浴に予め決め られた量の希土類酸化物を添加すること； 存在する希土類酸化物の量を基準にして化 学量論的に過剰のカルシウム金属を上記の 溶融塩浴に添加すること；上記の溶融塩浴 を溶融状態に保つて撹拌し、カルシウム金 属が希土類酸化物を希土類金属に還元する こと、より成ることを特徴とする特許請求 範囲第１項に記載の金属熱非電解還元法。 ４、酸化ネオジムがネオジム金属に還元される特許請求
範囲第３項に記載の還元法。 ５、方法が、塩化カルシウムの重量％が少くとも７０％
より成る溶融塩浴を造ること； 上記の溶融塩浴に予め決められた量の希土 類酸化物を添加すること；存在する希土類 酸化物の量を基準にして化学量論的に過剰 のカルシウム金属を上記の溶融塩浴に添加 すること；上記の溶融塩浴を溶融状態に保 ちカルシウム金属が希土類酸化物を希土類 金属に還元する迄撹拌すること；次いで撹 拌を中止し溶融塩浴中に希土類金属を含ん だ明確な層を生成させること、より成る特 許請求範囲第１項に記載の金属熱非電解還 元法。 ６、希土類酸化物が、酸化ランタン、酸化セリウム、酸
化プラセオジム及び酸化ネオジ ムより成る群から選ばれる１種又はそれ以 上の希土類酸化物である特許請求範囲第５ 項に記載の金属熱非電解還元法。 ７、方法が、塩化カルシウムの重量％が少くとも７０％
で残りが塩化ナトリウムである 溶融塩浴を造る段階；溶融塩浴の容積の ５０％以下の容積の酸化ネオジムＮｄ＿２Ｏ＿３を溶融
塩浴に添加する段階；その中の酸化ネ オジムの量をベースにして化学量論的に過 剰のカルシウム金属を溶融塩浴に添加する 段階；溶融塩浴をその溶融温度より高い温 度に保つ段階；上記の溶融塩浴を撹拌し構 成成分を互いに混合し、大部分の酸化ネオ ジムがネオジム金属に還元される迄その撹 拌を継続する段階；その後構成成分を溶融 状態に保つたまま撹拌を中止し、溶融塩浴 中に基本的に酸化ネオジムを含まない、還 元されたネオジム金属を含む明確な層を生 成させる段階、より成る特許請求範囲第１ 項に記載の金属熱非電解還元法。 ８、方法が、塩化カルシウムが少くとも７０重量％で、
残りが塩化ナトリウムである溶 融塩浴を造る段階；溶融塩浴の容積の５０ ％以下の容積の希土類酸化物を溶融塩浴に 添加する段階；存在する希土類酸化物を還 元するに十分な量のカルシウム金属を溶融 塩浴に添加する段階；溶融塩浴をその溶融 温度以上の温度に保持する段階；溶融塩浴 を撹拌して構成成分を相互に混ぜ合わせ、 大部分の希土類酸化物が希土類金属に還元 される迄上記の撹拌を継続する段階；次い で構成成分を溶融状態に保つたまま撹拌を 中止し、溶融塩浴中に還元された希土類金 属を含んだ明確な層を生成させる段階、よ り成る特許請求範囲第１項に記載の金属熱 非電解還元法。 ９、方法が、塩化カルシウムの重量％が少くとも７０で
塩化ナトリウムの重量％が０〜 ３０である溶融塩浴を造ること；上記の溶 融塩浴に予め決められた量の希土類酸化物 を添加すること；溶融塩浴に希土類酸化物 の量を基準にして化学量論的に過剰のカル シウム金属を添加すること；上記の溶融塩 浴を溶融状態に保ち撹拌してカルシウム金 属が希土類酸化物を希土類金属に還元する 様にすること；希土類金属の溶融温度より 遥かに低い溶融温度を持つた希土／非希土 金属合金を生成するに十分な量の非希土類 金属を上記の溶融液浴に添加すること；次 いで撹拌を中止し上記の溶融塩浴中に希土 ／非希土金属合金を明確な層の形で集める 様にすること、より成る特許請求範囲第１ 項に記載の金属熱非電解還元法。 １０、希土類酸化物が、酸化ランタン、酸化セリウム、
酸化プラセオジム及び酸化ネ オジムより成る群から選ばれた１種又 はそれ以上の希土類酸化物であることを特 徴とする特許請求範囲第９項に記載の金属 熱非電解還元法。 １１、希土類酸化物が酸化ネオジムである特許請求範囲
第９項に記載の金属熱非電解還元 法。 １２、非希土類金属が鉄である特許請求範囲第９項ない
し第１１項のいずれか一項に記載の金属熱非電解還元法
。 １３、非希土類金属が亜鉛である特許請求範囲第９項な
いし第１１項の中のいずれか一項 に記載の金属発熱非電解還元法。[Claims] 1. A rare earth oxide having a smaller volume than the molten salt bath is dispersed in a molten salt bath in which calcium chloride accounts for the majority, and a stoichiometric excess of calcium with respect to the rare earth metal ions present is dispersed. The metal is added into a molten salt bath, the molten salt bath is stirred, and the reaction formula is REnO_m+mCa→nRE+mCaO [wherein RE represents one or more rare earth elements with a valence of 2, 3, or 4, and O is oxygen , Ca represents calcium, CaO represents calcium oxide, and n and m represent integers such that n times the valence of the rare earth element is equal to m times the valence of oxygen. ] A metal thermal non-electrolytic reduction method of a rare earth oxide to a rare earth metal, characterized in that the reduction is carried out according to the following method. 2. The metal thermal non-electrolytic reduction method according to claim 1, wherein neodymium oxide is reduced to neodymium metal in a molten salt bath according to the reaction formula Nd_2O_3+3Ca→2Nd+3CaO. 3. The method includes creating a molten salt bath consisting of calcium chloride; adding a predetermined amount of rare earth oxide to said molten salt bath; stoichiometric based on the amount of rare earth oxide present; adding an excess of calcium metal to the molten salt bath; maintaining and stirring the molten salt bath in a molten state, and causing the calcium metal to reduce the rare earth oxide to the rare earth metal. A metal thermal non-electrolytic reduction method according to claim 1. 4. The reduction method according to claim 3, wherein neodymium oxide is reduced to neodymium metal. 5. The method is such that the weight percent of calcium chloride is at least 70%
creating a molten salt bath consisting of; adding a predetermined amount of rare earth oxide to said molten salt bath; adding a stoichiometric excess of calcium metal based on the amount of rare earth oxide present; Add to the above molten salt bath; Keep the above molten salt bath in a molten state and stir until the calcium metal reduces the rare earth oxide to the rare earth metal; Then stop stirring and add the rare earth metal to the molten salt bath. 2. A process as claimed in claim 1, comprising producing a distinct layer comprising: 6. The metal thermal non-electrolytic reduction method according to claim 5, wherein the rare earth oxide is one or more rare earth oxides selected from the group consisting of lanthanum oxide, cerium oxide, praseodymium oxide, and neodymium oxide. . 7. The method is such that the weight percent of calcium chloride is at least 70%
creating a molten salt bath with the remainder being sodium chloride; adding neodymium oxide Nd_2O_3 to the molten salt bath in a volume not more than 50% of the volume of the molten salt bath; Adding a stoichiometric excess of calcium metal to the molten salt bath; Maintaining the molten salt bath above its melting temperature; Stirring the molten salt bath to mix the components together and remove most of the oxidation. Continuing the agitation until the neodymium is reduced to neodymium metal; then, discontinuing the agitation while keeping the components in a molten state, leaving the reduced neodymium metal essentially free of neodymium oxide in the molten salt bath. A method according to claim 1, comprising the step of producing a distinct layer comprising: 8. The method comprises at least 70% by weight of calcium chloride;
creating a molten salt bath with the balance being sodium chloride; adding a volume of rare earth oxide to the molten salt bath that is not more than 50% of the volume of the molten salt bath; adding a sufficient amount of rare earth oxide to reduce the rare earth oxide present; Adding calcium metal to the molten salt bath; Maintaining the molten salt bath at a temperature above its melting temperature; Stirring the molten salt bath to mix the components together such that most of the rare earth oxide is a rare earth metal. continuing the agitation as described above until the rare earth metal is reduced; then discontinuing the agitation while keeping the components in a molten state to form a distinct layer containing the reduced rare earth metal in the molten salt bath; A metal thermal non-electrolytic reduction method according to claim 1, comprising: 9. The method is to create a molten salt bath in which the weight percent of calcium chloride is at least 70 and the weight percent of sodium chloride is between 0 and 30; adding a predetermined amount of rare earth oxide to the above molten salt bath; Adding a stoichiometric excess of calcium metal based on the amount of rare earth oxide to the molten salt bath; Keeping the above molten salt bath in a molten state and stirring it, the calcium metal converts the rare earth oxide. a non-rare earth metal in sufficient quantity to form a rare earth/non-rare earth metal alloy having a melting temperature much lower than that of the rare earth metal; and then discontinuing the stirring to allow the rare earth/non-rare earth metal alloy to collect in the form of a distinct layer in the molten salt bath. Non-electrolytic reduction method. 10. The rare earth oxide is lanthanum oxide, cerium oxide,
10. The metal thermal non-electrolytic reduction method according to claim 9, wherein the metal oxide is one or more rare earth oxides selected from the group consisting of praseodymium oxide and neodymium oxide. 11. The metal thermal non-electrolytic reduction method according to claim 9, wherein the rare earth oxide is neodymium oxide. 12. The metal thermal non-electrolytic reduction method according to any one of claims 9 to 11, wherein the non-rare earth metal is iron. 13. The metal exothermic non-electrolytic reduction method according to any one of claims 9 to 11, wherein the non-rare earth metal is zinc.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62773684A | 1984-07-03 | 1984-07-03 | |
| US627736 | 1984-07-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6130639A true JPS6130639A (en) | 1986-02-12 |
| JPS6137341B2 JPS6137341B2 (en) | 1986-08-23 |
Family
ID=24515917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14645085A Granted JPS6130639A (en) | 1984-07-03 | 1985-07-03 | Metal thermal reduction for rare earth element oxide with calcium metal |
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| Country | Link |
|---|---|
| EP (1) | EP0170372B1 (en) |
| JP (1) | JPS6130639A (en) |
| KR (1) | KR910001581B1 (en) |
| AT (1) | ATE36560T1 (en) |
| AU (1) | AU575965B2 (en) |
| BR (1) | BR8503140A (en) |
| DE (1) | DE3564451D1 (en) |
| ES (1) | ES8702508A1 (en) |
| MX (1) | MX173880B (en) |
| ZA (1) | ZA854474B (en) |
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| AT389899B (en) * | 1986-08-19 | 1990-02-12 | Treibacher Chemische Werke Ag | METHOD FOR THE PRODUCTION OF SE METALS AND ALLOYS CONTAINING SE |
| JPH01138119A (en) * | 1987-11-24 | 1989-05-31 | Mitsubishi Metal Corp | Recovery of samarium and europium from electrolytic slag of rare-earth element |
| DE3817553A1 (en) * | 1988-05-24 | 1989-11-30 | Leybold Ag | METHOD FOR PRODUCING TITANIUM AND ZIRCONIUM |
| US4917724A (en) * | 1988-10-11 | 1990-04-17 | General Motors Corporation | Method of decalcifying rare earth metals formed by the reduction-diffusion process |
| KR100373109B1 (en) * | 1999-09-30 | 2003-02-25 | 해 남 현 | Extraction method of soil exchangeable K with salt solution and analytical method of the K in the solution |
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| CN103436718B (en) * | 2013-08-16 | 2015-06-17 | 宁夏东方钽业股份有限公司 | High-purity lanthanum metal preparation method |
| AU2019278903A1 (en) | 2018-05-30 | 2021-01-07 | HELA Novel Metals, LLC | Methods for the production of fine metal powders from metal compounds |
| KR102153737B1 (en) * | 2019-12-12 | 2020-09-09 | 한국지질자원연구원 | Method of recovery rare earth elements from a ferrite-rare earth-based permanent magnet using selective chlorination |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59177346A (en) * | 1983-03-25 | 1984-10-08 | Sumitomo Special Metals Co Ltd | Alloy of rare earth metal for magnet material |
| JPS6077943A (en) * | 1983-10-03 | 1985-05-02 | Sumitomo Special Metals Co Ltd | Manufacture of raw material alloy for rare earth magnet |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB190923215A (en) * | 1909-10-11 | 1910-09-29 | Hans Kuzel | Process for the Production of Zirconium and other Rare Metals. |
| US2950962A (en) * | 1957-03-28 | 1960-08-30 | Carlson Oscar Norman | Reduction of fluoride to metal |
| GB1040468A (en) * | 1964-10-26 | 1966-08-24 | Dow Chemical Co | Preparation of rare earth metal, yttrium, or scandium |
| GB1579978A (en) * | 1977-07-05 | 1980-11-26 | Johnson Matthey Co Ltd | Production of yttrium |
| SU1027232A1 (en) * | 1982-01-15 | 1983-07-07 | Научно-исследовательский институт металлургии | Method for producing master alloy |
| DE3379131D1 (en) * | 1982-09-03 | 1989-03-09 | Gen Motors Corp | Re-tm-b alloys, method for their production and permanent magnets containing such alloys |
| US4578242A (en) * | 1984-07-03 | 1986-03-25 | General Motors Corporation | Metallothermic reduction of rare earth oxides |
-
1985
- 1985-06-07 DE DE8585304046T patent/DE3564451D1/en not_active Expired
- 1985-06-07 EP EP85304046A patent/EP0170372B1/en not_active Expired
- 1985-06-07 AT AT85304046T patent/ATE36560T1/en not_active IP Right Cessation
- 1985-06-13 ZA ZA854474A patent/ZA854474B/en unknown
- 1985-06-28 MX MX026616A patent/MX173880B/en unknown
- 1985-06-28 BR BR8503140A patent/BR8503140A/en not_active IP Right Cessation
- 1985-07-01 KR KR1019850004710A patent/KR910001581B1/en not_active IP Right Cessation
- 1985-07-02 ES ES544799A patent/ES8702508A1/en not_active Expired
- 1985-07-02 AU AU44488/85A patent/AU575965B2/en not_active Ceased
- 1985-07-03 JP JP14645085A patent/JPS6130639A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59177346A (en) * | 1983-03-25 | 1984-10-08 | Sumitomo Special Metals Co Ltd | Alloy of rare earth metal for magnet material |
| JPS6077943A (en) * | 1983-10-03 | 1985-05-02 | Sumitomo Special Metals Co Ltd | Manufacture of raw material alloy for rare earth magnet |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0170372A1 (en) | 1986-02-05 |
| AU4448885A (en) | 1986-01-09 |
| MX173880B (en) | 1994-04-07 |
| KR910001581B1 (en) | 1991-03-16 |
| DE3564451D1 (en) | 1988-09-22 |
| JPS6137341B2 (en) | 1986-08-23 |
| ZA854474B (en) | 1986-03-26 |
| BR8503140A (en) | 1986-03-18 |
| KR860001203A (en) | 1986-02-24 |
| ES8702508A1 (en) | 1987-01-01 |
| ES544799A0 (en) | 1987-01-01 |
| EP0170372B1 (en) | 1988-08-17 |
| ATE36560T1 (en) | 1988-09-15 |
| AU575965B2 (en) | 1988-08-11 |
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