JP2018095965A - Rare earth metal ingot degassing method - Google Patents
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 165
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 120
- 238000007872 degassing Methods 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 158
- 239000002184 metal Substances 0.000 claims abstract description 157
- -1 rare earth hydride Chemical class 0.000 claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000002844 melting Methods 0.000 claims abstract description 34
- 230000008018 melting Effects 0.000 claims abstract description 34
- 239000011261 inert gas Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 96
- 239000007789 gas Substances 0.000 claims description 61
- 229910052786 argon Inorganic materials 0.000 claims description 48
- 230000006698 induction Effects 0.000 claims description 45
- 229910052746 lanthanum Inorganic materials 0.000 claims description 44
- 239000002245 particle Substances 0.000 claims description 42
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052721 tungsten Inorganic materials 0.000 claims description 16
- 239000010937 tungsten Substances 0.000 claims description 16
- 229910052689 Holmium Inorganic materials 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000001603 reducing effect Effects 0.000 abstract description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 34
- 238000000034 method Methods 0.000 description 30
- 239000012535 impurity Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 238000009413 insulation Methods 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- 239000003039 volatile agent Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 238000011109 contamination Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- LCTWRNOEZKTLGG-UHFFFAOYSA-K holmium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ho+3] LCTWRNOEZKTLGG-UHFFFAOYSA-K 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/003—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals by induction
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
Abstract
Description
本発明は、希土類金属精錬技術分野に関し、具体的には希土類金属溶製脱ガス方法に関する。 The present invention relates to the technical field of rare earth metal refining, and more specifically, to a method for melting and degassing a rare earth metal.
希土類金属はハイテク技術分野において広く利用されており、超高純度希土類金属はハイテク材料を研究・開発するための重要な原料であり、高性能磁性材料、発光材料、エネルギー材料等の機能材料に対して材料の保障を提供する。ハイテク産業の発展に伴い、高純度希土類金属へのニーズも高まりつつある。 Rare earth metals are widely used in the high-tech field, and ultra-high-purity rare earth metals are important raw materials for research and development of high-tech materials. For high-performance magnetic materials, light-emitting materials, energy materials, and other functional materials Provide material security. With the development of the high-tech industry, the need for high-purity rare earth metals is also increasing.
金属の純度は希土類機能材料にとって非常に重要な意義を持っている。第一に、高純度金属は、金属の本体の特性及び不純物による材料性能への被害を理解するのに役立つ。第二に、金属材料の構造感受性、不純物の欠陥への影響等の要素を釈明し、且つこれによって、材料性質が予め特定された新材料の設計の条件を作り出すのに役立つ。また、金属の潜在的性能をさらに明らかにし、新たな利用分野を開拓し、ハイテクのさらなる展開の道を開くのに役立つ。希土類金属は、アルカリ金属及びアルカリ土類金属元素に次ぐ化学的活性を有し、マグネシウムに近い還元性を持ち、常温下、空気中で酸化でき、高温下でほとんどの金属及び非金属と作用し、形成される希土類化合物はすべて負の生成自由エネルギーを有するため、希土類金属の調製及び精製は、反応温度を高める(通常、1000℃以上)だけで実現できる。高純度/超高純度希土類金属を調製するための技術は主に、真空溶解、真空蒸留、ゾーンメルト法、電子ビーム溶解法及び固相電解法等の様々な方法を含み、技術の組み合わせによって、希土類金属と不純物との分離を実現させる。しかしながら、希土類金属は気体元素(C、H、O、N等)と極めて強い結合力を有するため、調製及び精製時に不可避的にガス状不純物が希土類金属に混入し、化合物を形成するため除去されにくい。また、気体元素はFe、Al、Ni等金属元素とは電気陰性度が大きく異なるため、気体元素(C、O、N、S)は通常化合物、例えば酸化物、窒化物及び硫化物の形態で希土類金属内部に介在し、このような化合物は融点が高く、蒸気圧が低く、化学的性質が安定している等の特徴を有し、一般の方法により除去することが難しい。 The purity of the metal is very important for rare earth functional materials. First, high purity metals help to understand the properties of the metal body and the damage to material performance due to impurities. Secondly, it explains factors such as the structural sensitivity of metallic materials, the effect of impurities on defects, and this helps to create new material design conditions whose material properties are pre-specified. It also helps to further clarify the potential performance of metals, open up new fields of application, and pave the way for further development of high technology. Rare earth metal has chemical activity next to alkali metal and alkaline earth metal element, has reducibility close to magnesium, can be oxidized in air at room temperature, and works with most metals and non-metals at high temperature. Since all the rare earth compounds formed have negative free energy of formation, the preparation and purification of the rare earth metal can be realized only by increasing the reaction temperature (usually 1000 ° C. or higher). Technologies for preparing high purity / ultra high purity rare earth metals mainly include various methods such as vacuum melting, vacuum distillation, zone melt method, electron beam melting method and solid phase electrolysis method, Realize separation of rare earth metal and impurities. However, rare earth metals have extremely strong bonding strength with gaseous elements (C, H, O, N, etc.), so they are inevitably removed during preparation and purification because gaseous impurities are mixed into rare earth metals to form compounds. Hateful. Also, gas elements (C, O, N, S) are usually in the form of compounds such as oxides, nitrides, and sulfides because the gas elements are significantly different in electronegativity from metallic elements such as Fe, Al, and Ni. Such a compound is present inside the rare earth metal and has such characteristics as a high melting point, a low vapor pressure, and a stable chemical property, and is difficult to remove by a general method.
希土類金属を精製する過程では、ガス状不純物の含有量が単調に低減し、多くの熱力学的性質もそれに伴って変化し、特に深度浄化後期に入ると、その不純物の活量が急低下するため、精製時の物質移動及び反応の推進力が低減し、ユニット操作時の不純物の反応を低下させ、移動速度及び分離効率を低下させる。現在、単純に精製処理温度を上げ、精製時間を延長し、精製ステップ及び回数を増やす等の方法により、希土類純度に所望なガス状不純物の制御指標を満足することしかできないため、エネルギー消費によるコストが高く、生産効率が低く、製品の品質が安定していない。 In the process of refining rare earth metals, the content of gaseous impurities decreases monotonically, and many thermodynamic properties change accordingly. Therefore, the mass transfer during the purification and the driving force of the reaction are reduced, the reaction of the impurities during the unit operation is lowered, and the moving speed and the separation efficiency are lowered. At present, it is only possible to satisfy the control index of the desired gaseous impurities in the rare earth purity by simply increasing the purification temperature, extending the purification time, increasing the number of purification steps and the number of times, etc. Is high, production efficiency is low, product quality is not stable.
現時点では、希土類金属脱ガス方法は、固相電解法、水素プラズマ溶解及びサクション法等が挙げられ、金属中の気体元素を徹底的に除去するには効果があるが、上記の方法は生産効率が極めて低く、歩留まりが低く、コストが高く、量産の要求を満たすことができないため、実用化には至っていない。どのように従来の希土類金属脱酸素法の欠点を克服し、金属中の気体元素を簡単且つ経済的に除去するかは、高純度希土類金属調製分野で解決されるべき肝心な技術問題となっている。 At present, rare earth metal degassing methods include solid phase electrolysis, hydrogen plasma melting and suction methods, etc., which are effective for thoroughly removing gaseous elements in the metal. However, it has not been put into practical use because it is extremely low, yield is low, cost is high, and demand for mass production cannot be satisfied. How to overcome the shortcomings of the conventional rare earth metal deoxygenation method and easily and economically remove gaseous elements in the metal is an important technical problem to be solved in the field of preparing high purity rare earth metals. Yes.
本発明の主な目的は、希土類金属溶製脱ガス方法を提供することで、従来技術における希土類金属精製方法の周期が長く、歩留まりが低く、且つエネルギー消費が高いという問題を解決することにある。 The main object of the present invention is to provide a rare earth metal melting and degassing method to solve the problems that the rare earth metal purification method in the prior art has a long cycle, low yield, and high energy consumption. .
上記の目的を実現するために、本発明の一つの実施形態においては、精製対象である希土類金属を真空環境下で溶融し、溶融金属液を形成するステップS1と、0.01〜0.05MPaの真空度で、上記精製対象である希土類金属の重量に対して、0.5〜10%の重量で希土類水素化物を上記溶融金属液と混合し、5〜30min保温し、脱ガスされた溶融金属及びガス状物質を得るステップS2と、上記ガス状物質と上記脱ガスされた溶融金属とを分離し、且つ上記脱ガスされた溶融金属を不活性ガス中で冷却し、脱ガス希土類金属を得るステップS3と、を含む希土類金属溶製脱ガス方法が提供される。 In order to achieve the above object, in one embodiment of the present invention, step S1 of melting a rare earth metal to be refined in a vacuum environment to form a molten metal liquid, and a degree of vacuum of 0.01 to 0.05 MPa. Then, the rare earth hydride is mixed with the molten metal liquid in a weight of 0.5 to 10% with respect to the weight of the rare earth metal to be purified, and the molten metal and the gaseous substance are degassed and kept warm for 5 to 30 minutes. Separating the gaseous substance and the degassed molten metal, and cooling the degassed molten metal in an inert gas to obtain a degassed rare earth metal; A rare earth metal melt degassing method is provided.
さらに、上記希土類金属は、La、Ce、Pr、Nd、Gd、Tb、Dy、Ho、Er、Lu、Y又はScである。 Furthermore, the rare earth metal is La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu, Y, or Sc.
さらに、上記ステップS1は、上記精製対象である希土類金属を中間周波数誘導炉のるつぼに入れ、且つ上記中間周波数誘導炉の炉内を真空引きし、真空チャンバを形成することと、上記真空チャンバに上記不活性ガスを導入して上記真空チャンバを洗浄し、上記真空チャンバの真空度が10-2Pa未満になった時に、上記真空チャンバを上記精製対象である希土類金属の融点温度よりも50〜100℃高い温度までに昇温し、上記精製対象である希土類金属を溶融し、且つ5〜15min保温した後に、上記溶融金属液を得ることと、を含む。 Further, in the step S1, the rare earth metal to be refined is put into a crucible of an intermediate frequency induction furnace, and the inside of the intermediate frequency induction furnace is evacuated to form a vacuum chamber, and the vacuum chamber The inert gas is introduced to clean the vacuum chamber, and when the vacuum degree of the vacuum chamber becomes less than 10 −2 Pa, the vacuum chamber is 50 to 50 ° C. higher than the melting point temperature of the rare earth metal to be purified. And heating the rare earth metal to be purified to obtain a molten metal liquid after maintaining the temperature for 5 to 15 minutes.
さらに、上記るつぼは、タングステン製るつぼである。 Further, the crucible is a tungsten crucible.
さらに、10〜30kWの電力で上記真空チャンバを昇温する。 Further, the vacuum chamber is heated with electric power of 10 to 30 kW.
さらに、上記ステップS2は、上記中間周波数誘導炉の真空システムの排気バルブを閉じて、且つ上記真空チャンバ内に上記不活性ガスを真空度が0.01〜0.05MPaとなるまでに充填することと、希土類水素化物粒子を上記溶融金属液に添加し、且つ上記真空チャンバの温度を、溶融金属液の表面が凝固状態になった後に5〜30min保温し続け、脱ガスされた溶融金属及びガス状物質を得ることと、を含む。 Further, the step S2 includes closing the exhaust valve of the vacuum system of the intermediate frequency induction furnace and filling the vacuum chamber with the inert gas until the degree of vacuum is 0.01 to 0.05 MPa, The hydride particles are added to the molten metal liquid, and the temperature of the vacuum chamber is kept warm for 5 to 30 minutes after the surface of the molten metal liquid is in a solidified state, and the degassed molten metal and gaseous substances are removed. Obtaining.
さらに、上記希土類水素化物粒子の粒子径は、0.1〜5mmである。 Further, the rare earth hydride particles have a particle size of 0.1 to 5 mm.
さらに、上記ステップS3は、上記真空システムの排気バルブを開け、上記真空チャンバを真空引きすることと、上記真空チャンバの真空度が10-2Pa以下に戻った後に、上記真空チャンバを上記精製対象である希土類金属の融点温度よりも50〜300℃高い温度までに昇温し、5〜20min保温することと、保温終了後に、上記脱ガスされた溶融金属を鋳造し、次いで、上記不活性ガスを利用して保護し、且つ室温までに冷却し、上記脱ガスされた希土類金属を得ることと、を含む。 Further, the step S3 opens the exhaust valve of the vacuum system, evacuates the vacuum chamber, and after the vacuum degree of the vacuum chamber returns to 10 −2 Pa or less, the vacuum chamber is subjected to the purification target. The temperature is raised to a temperature 50 to 300 ° C. higher than the melting point temperature of the rare earth metal, and the temperature is maintained for 5 to 20 minutes. After the temperature is maintained, the degassed molten metal is cast, and then the inert gas. And cooling to room temperature to obtain the degassed rare earth metal.
さらに、上記不活性ガスは、アルゴンガスである。 Furthermore, the inert gas is argon gas.
さらに、上記希土類水素化物及び上記精製対象である希土類金属における希土類元素は同じである。 Furthermore, the rare earth elements in the rare earth hydride and the rare earth metal to be purified are the same.
本発明に係る発明によって、希土類水素化物と溶融金属液を混合し、希土類水素化物の融点温度付近で脱離することで極めて強い還元性を示すH原子が生成され、さらに励起状態の水素原子は過飽和に溶融金属液に溶解することもできれば、溶融金属から放出することもできるため、この溶解‐放出過程は、強い還元性を示す水素原子と溶融金属液中の気体元素との結合を促進し、溶融金属に介在している化合物中の気体元素をH2O、CO2、NH3及びCH4等の気体化合物の形態で貯蔵し、最終的には揮発により除去することができる。また、希土類水素化物の添加量は、精製対象である希土類金属に対して0.5〜10%(重量)であるため、希土類金属の水素化反応を引き起こさないどころか、顕著な脱ガス効果を発揮することができる。本願の脱ガス方法を用いると、低ガス含有量を有する希土類金属を得るために、単独でその後の複数回の蒸留、固相電解法又はサクション法等の方法によって希土類金属を徹底的に脱ガスする必要がない。しかも、該方法は流れが短く、脱ガス効果が顕著で、金属精製ステップが長く、工程が複雑等の要因による希土類金属への二次汚染を回避し、低ネルギー消費で高効率的に脱ガスする目的を達成できる。本願の上記脱ガス方法を、希土類金属の溶融精製及び希土類金属ターゲットの真空溶解に適用することができ、歩留まりが比較的高く、製品の品質が良い。 By the invention according to the present invention, a rare earth hydride and a molten metal liquid are mixed and desorbed near the melting temperature of the rare earth hydride to generate H atoms that exhibit extremely strong reducibility. This dissolution-release process promotes the bond between hydrogen atoms that exhibit strong reducibility and gaseous elements in the molten metal liquid, because it can be dissolved in the molten metal liquid supersaturated or released from the molten metal. The gaseous elements in the compound intervening in the molten metal can be stored in the form of gaseous compounds such as H 2 O, CO 2 , NH 3 and CH 4 and finally removed by volatilization. In addition, since the amount of rare earth hydride added is 0.5 to 10% (weight) based on the rare earth metal to be refined, it exhibits a remarkable degassing effect rather than causing a hydrogenation reaction of the rare earth metal. Can do. Using the degassing method of the present application, in order to obtain a rare earth metal having a low gas content, the rare earth metal is thoroughly degassed by a method such as subsequent distillation, solid phase electrolysis, or suction method alone. There is no need to do. In addition, the method has a short flow, a remarkable degassing effect, a long metal purification step, avoids secondary contamination to rare earth metals due to factors such as complicated processes, and efficiently degass with low energy consumption. Can achieve the purpose. The above degassing method of the present application can be applied to melting and refining rare earth metals and vacuum melting of rare earth metal targets, and the yield is relatively high and the product quality is good.
なお、矛盾していない限り、本願における実施例、及び実施例における要件を組み合わせることができると理解される。以下、実施例を参照しながら、本発明を詳細に説明する。 As long as there is no contradiction, it is understood that the embodiment in the present application and the requirements in the embodiment can be combined. Hereinafter, the present invention will be described in detail with reference to examples.
背景技術にあるように、従来技術における希土類金属精製方法は、周期が長く、歩留まりが低く、且つエネルギー消費が高い。この課題を解決するために、本願の1つの典型的な実施形態においては、精製対象である希土類金属を真空環境下で溶融し、溶融金属液を形成するステップS1と、0.01〜0.05MPaの真空度で、精製対象である希土類金属の重量に対して、0.5〜10%の重量で希土類水素化物を溶融金属液と混合し、5〜30min保温し、脱ガスされた溶融金属及びガス状物質を得るステップS2と、ガス状物質と脱ガスされた溶融金属とを分離し、且つ脱ガスされた溶融金属を不活性ガス中で冷却し、脱ガス希土類金属を得るステップS3と、を含む希土類金属溶製脱ガス方法が提供される。 As in the background art, the rare earth metal refining method in the prior art has a long period, a low yield, and a high energy consumption. In order to solve this problem, in one exemplary embodiment of the present application, a rare earth metal to be purified is melted in a vacuum environment to form a molten metal liquid, and a vacuum of 0.01 to 0.05 MPa. At this time, the rare earth hydride is mixed with the molten metal liquid in a weight of 0.5 to 10% with respect to the weight of the rare earth metal to be refined, and the mixture is kept warm for 5 to 30 minutes. A rare earth metal comprising: obtaining step S2, and separating the gaseous substance and the degassed molten metal, and cooling the degassed molten metal in an inert gas to obtain a degassed rare earth metal. A melt degassing method is provided.
本願の上記脱ガス方法を、希土類金属の溶融精製及び希土類金属ターゲットの真空溶解に適用することができ、歩留まりが比較的高く、製品の品質が良い。希土類水素化物と溶融金属液を混合し、希土類水素化物の融点温度付近で脱離することで極めて強い還元性を示すH原子が生成され、さらに励起状態の水素原子は過飽和に溶融金属液に溶解することもできれば、溶融金属から放出することもできるため、この溶解‐放出過程は、強い還元性を示す水素原子と溶融金属液中の気体元素との結合を促進し、溶融金属に介在している化合物中の気体元素をH2O、CO2、NH3及びCH4等の気体化合物の形態で貯蔵し、最終的には揮発により除去することができる。また、水素化物の希土類金属への脱ガス効果及びコスト要因を考慮し、希土類水素化物の添加量を、精製対象である希土類金属に対して0.5〜10%(重量)とし、顕著な脱ガス効果を発揮できるのみならず、希土類金属中の水素含有量の増加を引き起こすこともない。本願の脱ガス方法を用いると、低ガス含有量を有する希土類金属を得るために、単独でその後の複数回の蒸留、固相電解法又はサクション法等の方法によって希土類金属を徹底的に脱ガスする必要がない。しかも、該方法は流れが短く、脱ガス効果が顕著で、金属精製ステップが長く、工程が複雑等の要因による希土類金属への二次汚染を回避し、低ネルギー消費で高効率的に脱ガスする目的を達成できる。 The above degassing method of the present application can be applied to melting and refining rare earth metals and vacuum melting of rare earth metal targets, and the yield is relatively high and the product quality is good. By mixing the rare earth hydride and the molten metal liquid and desorbing near the melting temperature of the rare earth hydride, H atoms exhibiting extremely strong reducibility are generated, and the excited hydrogen atoms are supersaturated and dissolved in the molten metal liquid. Can be released from the molten metal, so this dissolution-release process promotes the bonding of hydrogen atoms that exhibit strong reducibility and gaseous elements in the molten metal liquid, intervening in the molten metal. The gaseous elements in the compound can be stored in the form of gaseous compounds such as H 2 O, CO 2 , NH 3 and CH 4 and finally removed by volatilization. Considering the degassing effect of hydride on rare earth metals and cost factors, the amount of rare earth hydride added is 0.5-10% (weight) with respect to the rare earth metal to be refined, and the remarkable degassing effect In addition, the hydrogen content in the rare earth metal is not increased. Using the degassing method of the present application, in order to obtain a rare earth metal having a low gas content, the rare earth metal is thoroughly degassed by a method such as subsequent distillation, solid phase electrolysis, or suction method alone. There is no need to do. In addition, the method has a short flow, a remarkable degassing effect, a long metal purification step, avoids secondary contamination to rare earth metals due to factors such as complicated processes, and efficiently degass with low energy consumption. Can achieve the purpose.
本願の上記脱ガス方法は、現在の一般的な希土類金属、例えば様々な軽希土類、中重希土類、重希土類金属の脱ガスに適用することができる。該希土類金属は、La、Ce、Pr、Nd、Gd、Tb、Dy、Ho、Er、Lu、Y又はScであることが好ましい。 The degassing method of the present application can be applied to the degassing of current general rare earth metals such as various light rare earth, medium heavy rare earth, and heavy rare earth metals. The rare earth metal is preferably La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu, Y, or Sc.
本願の脱ガス方法は、中間周波数誘導炉で実施することで、該方法の利用コストを低減することができ、且つその炉内の密閉性を利用することで処理環境の純潔度を向上させることができる。中間周波数誘導炉で脱ガスする場合、上記ステップS1は、精製対象である希土類金属を中間周波数誘導炉のるつぼに入れ、且つ中間周波数誘導炉の炉内を真空引きし、真空チャンバを形成することと、真空チャンバに不活性ガスを導入して真空チャンバを洗浄し、真空チャンバの真空度が10-2Pa未満になった時に、真空チャンバを精製対象である希土類金属の融点温度よりも50〜100℃高い温度までに昇温し、精製対象である希土類金属を溶融し、且つ5〜15min保温した後に、溶融金属液を得ることと、を含むことが好ましい。 The degassing method of the present application can be carried out in an intermediate frequency induction furnace to reduce the use cost of the method, and to improve the cleanliness of the processing environment by utilizing the hermeticity in the furnace. Can do. When degassing with an intermediate frequency induction furnace, the above step S1 is to put the rare earth metal to be purified into a crucible of the intermediate frequency induction furnace, and evacuate the furnace of the intermediate frequency induction furnace to form a vacuum chamber. When the vacuum chamber is cleaned by introducing an inert gas into the vacuum chamber and the vacuum degree of the vacuum chamber becomes less than 10 −2 Pa, the vacuum chamber is 50 to 50 ° C. higher than the melting point temperature of the rare earth metal to be purified. It is preferable to include the step of raising the temperature to 100 ° C., melting the rare earth metal to be refined, and keeping the temperature for 5 to 15 minutes, and then obtaining the molten metal liquid.
この過程では、真空環境を利用することで、精製対象である希土類金属の溶融時の気体元素の導入による二次汚染を低減させる。また、金属を溶融状態下で5〜15min保温し、且つ真空条件下で保温時間を延長することは、金属液中の揮発性不純物の徹底除去に有利である。しかしながら、保温時間が長すぎると、金属液中のるつぼ不純物による汚染が多くなる。したがって、保温時間を5〜15minとすることが好ましい。 In this process, by using a vacuum environment, secondary contamination due to the introduction of gaseous elements during the melting of the rare earth metal to be purified is reduced. Further, it is advantageous for thorough removal of volatile impurities in the metal liquid to keep the metal in a molten state for 5 to 15 minutes and to extend the heat retention time under vacuum conditions. However, if the heat retention time is too long, the contamination by the crucible impurities in the metal liquid increases. Therefore, it is preferable that the heat retention time is 5 to 15 minutes.
中間周波数誘導炉で使用されるるつぼは、現在の金属精製でよく用いられているるつぼ、例えばタングステン製るつぼ、タンタルるつぼ等であって良い。コスト削減の観点から、上記るつぼはタングステン製るつぼであることが好ましい。 The crucible used in the intermediate frequency induction furnace may be a crucible often used in current metal refining, such as a tungsten crucible, a tantalum crucible, or the like. From the viewpoint of cost reduction, the crucible is preferably a tungsten crucible.
また、希土類金属の融点、蒸気圧等の特性を考慮し、最適な溶製を提供するために、10〜30kWの電力で真空チャンバを昇温することが好ましい。 Further, in consideration of characteristics such as melting point and vapor pressure of rare earth metals, it is preferable to raise the temperature of the vacuum chamber with electric power of 10 to 30 kW in order to provide optimum melting.
本願の1つの好ましい実施例では、上記ステップS2は、中間周波数誘導炉の真空システムの排気バルブを閉じて、且つ真空チャンバ内に不活性ガスを真空度が0.01〜0.05MPaとなるまでに充填することと、希土類水素化物粒子を溶融金属液に添加し、且つ真空チャンバの温度を、溶融金属液の表面が凝固状態になった後に5〜30min保温し続け、脱ガスされた溶融金属及びガス状物質を得ることと、を含む。 In one preferred embodiment of the present application, the above step S2 closes the exhaust valve of the vacuum system of the intermediate frequency induction furnace and fills the vacuum chamber with an inert gas until the degree of vacuum is 0.01 to 0.05 MPa. In addition, the rare earth hydride particles are added to the molten metal liquid, and the temperature of the vacuum chamber is kept warm for 5 to 30 minutes after the surface of the molten metal liquid is in a solidified state. Obtaining a substance.
真空チャンバ内に不活性ガスを導入し、真空チャンバ内の圧力を増やすことで、希土類水素化物の溶融金属中への溶解速度を促進する。真空チャンバの温度下で、希土類水素化物中の水素が脱離して極めて強い還元性を示すH原子を生成し、励起状態の水素原子は過飽和に溶融金属に溶解することもできれば、溶融金属から放出することもできるため、水素のこの溶解‐放出過程は、強い還元性を示す水素原子と溶融金属内の気体元素(C、O、N、S)との結合を促進し、最終的には気体分子の形態で揮発させて除去することができる。 By introducing an inert gas into the vacuum chamber and increasing the pressure in the vacuum chamber, the dissolution rate of the rare earth hydride in the molten metal is promoted. Under the temperature of the vacuum chamber, the hydrogen in the rare earth hydride is desorbed to generate H atoms that exhibit extremely strong reducibility, and the excited hydrogen atoms can be dissolved in the molten metal supersaturated or released from the molten metal. This dissolution-release process of hydrogen also promotes the bonding of highly reducible hydrogen atoms with gaseous elements (C, O, N, S) in the molten metal, and eventually gas It can be removed by volatilization in the form of molecules.
希土類水素化物からの水素原子の放出をより一層迅速化する目的で、その燃焼損失率も考慮しながら、上記希土類水素化物粒子の粒子径は0.1mm〜5mmであることが好ましい。 In order to further expedite the release of hydrogen atoms from the rare earth hydride, the particle size of the rare earth hydride particles is preferably 0.1 mm to 5 mm, taking into account the combustion loss rate.
本願のもう1つの好ましい実施例では、上記ステップS3は、真空システムの排気バルブを開け、真空チャンバを真空引きすることと、真空チャンバの真空度が10-2Pa以下に戻った後に、真空チャンバを精製対象である希土類金属の融点温度よりも50〜300℃高い温度までに昇温し、5〜20min保温することと、保温終了後に、脱ガスされた溶融金属を鋳造し、次いで、不活性ガスを利用して保護し、且つ室温までに冷却し、脱ガスされた希土類金属を得ることと、を含む。 In another preferred embodiment of the present application, the step S3 is performed by opening the exhaust valve of the vacuum system, evacuating the vacuum chamber, and after the vacuum degree of the vacuum chamber returns to 10 −2 Pa or less, Is heated to a temperature 50 to 300 ° C. higher than the melting point temperature of the rare earth metal to be refined, kept warm for 5 to 20 minutes, and after the heat insulation is finished, the degassed molten metal is cast, and then inert. Protecting with gas and cooling to room temperature to obtain degassed rare earth metal.
上記ステップS3では、脱ガスされる物質の脱離効果及び金属のるつぼへの腐食性を考慮し、温度を金属融点よりも50〜300℃高い温度に制御することが好ましい。希土類水素化物による溶融金属の不純物除去が終了した後に、真空チャンバを真空引きすることで、不純物除去時に水素原子と溶融金属内の気体元素(C、O、N、S)とが結合してなるガスがアルゴンガスと共に抽出され、脱ガスされた溶融金属とガス状物質との分離が実現できた。その後に、不活性ガスの保護下で、脱ガスされた溶融金属の冷却を実現させ、高純度の脱ガスされた希土類金属を得ることができる。 In step S3, the temperature is preferably controlled to be 50 to 300 ° C. higher than the metal melting point in consideration of the desorption effect of the substance to be degassed and the corrosiveness of the metal to the crucible. After removing impurities from molten metal with rare earth hydride, the vacuum chamber is evacuated to combine hydrogen atoms and gaseous elements (C, O, N, S) in the molten metal when removing impurities The gas was extracted together with argon gas, and separation of the degassed molten metal and gaseous material could be realized. Thereafter, cooling of the degassed molten metal can be realized under the protection of the inert gas, and a high purity degassed rare earth metal can be obtained.
上記各ステップで使用される不活性ガスは、希ガスから選択される。不活性ガスにかかるコストを削減する観点から、上記不活性ガスはアルゴンガスであることが好ましい。 The inert gas used in each of the above steps is selected from rare gases. From the viewpoint of reducing the cost of the inert gas, the inert gas is preferably argon gas.
単一種類の希土類の純度を高めるために、上記希土類水素化物及び精製対象である希土類金属における希土類元素は同じであることが好ましい。 In order to increase the purity of a single kind of rare earth, the rare earth hydride and the rare earth element in the rare earth metal to be purified are preferably the same.
本願の1つの好ましい実施例では、上記脱ガス方法は、0.01Pa以下の真空条件下で、精製対象である希土類金属が溶融するように昇温し、溶融金属液を形成し、温度を金属融点より50〜100℃高い温度に制御し、5〜15min保温するステップS1と、真空システムを閉じて、不活性ガスを0.01〜0.05MPaとなるように導入し、精製対象である希土類金属の重量に対して、0.5〜10%の重量で希土類水素化物を溶融金属液に徐々に添加し、金属表面が凝固状態になる臨界的温度までに電力を下げ、且つ5〜30min保温し、脱ガスされた溶融金属及びガス状物質を得るステップS2と、真空システムを改めて開け、再度に電力を上げ、金属の温度を融点より50〜300℃高い温度に上げ、5〜20min保温し、チャンパ内及び金属液に溶解したガス状生成物を除去するステップS3と、脱ガスされた溶融金属を鋳造し、且つ不活性ガス中で冷却し、脱ガスされた希土類金属を得るステップS4と、を含む。 In one preferred embodiment of the present application, the degassing method is performed under a vacuum condition of 0.01 Pa or less so that the rare earth metal to be purified is melted to form a molten metal liquid, and the temperature is set to the metal melting point. Step S1 is controlled at a temperature higher by 50 to 100 ° C and kept for 5 to 15 minutes, and the vacuum system is closed, and an inert gas is introduced so that the pressure becomes 0.01 to 0.05 MPa. On the other hand, rare earth hydride was gradually added to the molten metal liquid at a weight of 0.5 to 10%, the power was lowered to a critical temperature at which the metal surface became solidified, and the temperature was kept for 5 to 30 minutes, and degassed. Step S2 to obtain molten metal and gaseous substances, open the vacuum system again, increase the power again, raise the temperature of the metal to a temperature 50 to 300 ° C. higher than the melting point, keep it warm for 5 to 20 minutes, in the chamber and in the metal liquid Step S3 to remove the gaseous product dissolved in the Been cast molten metal, and cooled in an inert gas, comprising the step S4 to obtain a degassed rare earth metals, the.
以下、実施例及び比較例を参照しながら、本願の有利な効果についてさらに説明する。 Hereinafter, the advantageous effects of the present application will be further described with reference to Examples and Comparative Examples.
実施例1 Example 1
精製対象である希土類金属ランタン2375gを中間周波数誘導炉のタングステン製るつぼに入れ、粒子径が0.1mm〜2mmである水素化ランタン119gをホッパーに入れ、真空引きした。真空チャンバに高純度アルゴンガスを導入し、炉体を2〜3回洗浄し、次いで、真空度が10-2Pa未満になった後に、18kWの電力で昇温し始め、希土類金属をゆっくりと溶融した。金属ランタンが完全に溶融した後に980℃までに昇温し続け、且つ10min保温して溶融ランタン金属液を得た。真空システムのバルブを閉じ、真空度が0.03MPaとなるまでに、高純度アルゴンガスを導入した。ホッパー内のランタン水素化物粒子をランタン金属液に添加し、温度が915℃になるまでに電力を下げ、且つ20min保温して溶液状態を維持した。真空システムの排気バルブを開け、真空チャンバ内の高純度アルゴンガス及びその揮発分を抽出し、真空度が10-2Pa以下に戻った後に、再度電力を上げ、金属の温度を1150℃までに上昇させ、10min保温し続け、脱ガスされた溶融金属を得た。保温終了後に、脱ガスされた溶融金属を直接的に鋳造した後に、高純度アルゴンガスを導入して保護し、且つ中間周波数誘導炉を閉じて、脱ガスされた溶融金属を誘導炉と共に室温までに冷却し、実施例1の高純度ランタン希土類金属を得た。 2375 g of rare earth metal lanthanum to be purified was placed in a tungsten crucible of an intermediate frequency induction furnace, and 119 g of lanthanum hydride having a particle size of 0.1 mm to 2 mm was placed in a hopper and evacuated. High purity argon gas is introduced into the vacuum chamber, the furnace body is cleaned 2 to 3 times, then after the degree of vacuum is less than 10 -2 Pa, the temperature starts to be raised with 18 kW power, and the rare earth metal is slowly Melted. After the metal lanthanum was completely melted, the temperature was continuously raised to 980 ° C. and kept for 10 minutes to obtain a molten lanthanum metal liquid. The valve of the vacuum system was closed and high purity argon gas was introduced until the degree of vacuum reached 0.03 MPa. The lanthanum hydride particles in the hopper were added to the lanthanum metal solution, the power was lowered until the temperature reached 915 ° C., and the solution state was maintained by keeping the temperature for 20 minutes. Open the exhaust valve of the vacuum system, extract high-purity argon gas and its volatiles in the vacuum chamber, and after the vacuum level has returned to 10-2 Pa or less, turn on the power again and bring the metal temperature to 1150 ℃ The temperature was raised and kept warm for 10 minutes to obtain a degassed molten metal. After the heat insulation is completed, the degassed molten metal is directly cast, and then high purity argon gas is introduced and protected, and the intermediate frequency induction furnace is closed, and the degassed molten metal is brought to room temperature together with the induction furnace. To obtain a high-purity lanthanum rare earth metal of Example 1.
実施例2 Example 2
精製対象である希土類金属ランタン2306gを中間周波数誘導炉のタングステン製るつぼに入れ、粒子径が1mm〜3mmである水素化ランタン粒子23gをホッパーに入れ、真空引きした。真空チャンバに高純度アルゴンガスを導入し、炉体を2〜3回洗浄し、次いで、真空度が10-2Pa未満になった後に、25kWの電力で昇温し始め、希土類金属をゆっくりと溶融した。金属ランタンが完全に溶融した後に1020℃までに昇温し続け、且つ15min保温して溶融ランタン金属液を得た。真空システムのバルブを閉じ、真空度が0.03MPaとなるまでに、高純度アルゴンガスを導入した。ホッパー内の水素化ランタン粒子をランタン金属液に添加し、温度が915℃になるまでに電力を下げ、且つ5min保温して溶液状態を維持した。真空システムの排気バルブを開け、真空チャンバ内の高純度アルゴンガス及びその揮発分を抽出し、真空度が10-2Pa以下に戻った後に、再度電力を上げ、金属の温度を1200℃までに上昇させ、20min保温し続け、脱ガスされた溶融金属を得た。保温終了後に、脱ガスされた溶融金属を直接的に鋳造した後に、高純度アルゴンガスを導入して保護し、且つ中間周波数誘導炉を閉じて、脱ガスされた溶融金属を誘導炉と共に室温までに冷却し、実施例2の高純度ランタン希土類金属を得た。 2306 g of rare earth metal lanthanum to be purified was placed in a tungsten crucible of an intermediate frequency induction furnace, and 23 g of lanthanum hydride particles having a particle size of 1 mm to 3 mm were placed in a hopper and evacuated. High purity argon gas is introduced into the vacuum chamber, the furnace body is cleaned 2 to 3 times, then after the degree of vacuum is less than 10 -2 Pa, the temperature starts to be raised with 25 kW power, and the rare earth metal is slowly Melted. After the metal lanthanum was completely melted, the temperature was continuously raised to 1020 ° C. and kept for 15 minutes to obtain a molten lanthanum metal liquid. The valve of the vacuum system was closed and high purity argon gas was introduced until the degree of vacuum reached 0.03 MPa. The lanthanum hydride particles in the hopper were added to the lanthanum metal solution, the power was lowered until the temperature reached 915 ° C., and the solution state was maintained by keeping the temperature for 5 minutes. Open the exhaust valve of the vacuum system, extract high-purity argon gas and its volatiles in the vacuum chamber, and after the vacuum level has returned to 10 -2 Pa or less, turn on the power again and bring the metal temperature to 1200 ° C. The temperature was raised and kept warm for 20 minutes to obtain a degassed molten metal. After the heat insulation is completed, the degassed molten metal is directly cast, and then high purity argon gas is introduced and protected, and the intermediate frequency induction furnace is closed, and the degassed molten metal is brought to room temperature together with the induction furnace. The high-purity lanthanum rare earth metal of Example 2 was obtained.
実施例3 Example 3
精製対象である希土類金属ランタン2315gを中間周波数誘導炉のタングステン製るつぼに入れ、粒子径が3mm〜5mmである水素化ランタン粒子46gをホッパーに入れ、真空引きした。真空チャンバに高純度アルゴンガスを導入し、炉体を2〜3回洗浄し、次いで、真空度が10-2Pa未満になった後に、10kWの電力で昇温し始め、希土類金属をゆっくりと溶融した。金属ランタンが完全に溶融した後に970℃で5min保温して溶融ランタン金属液を得た。真空システムのバルブを閉じ、真空度が0.04MPaとなるまでに、高純度アルゴンガスを導入した。ホッパー内の水素化ランタン粒子をランタン金属液に添加し、温度が915℃になるまでに電力を下げ、且つ30min保温して溶液状態を維持した。真空システムの排気バルブを開け、真空チャンバ内の高純度アルゴンガス及びその揮発分を抽出し、真空度が10-2Pa以下に戻った後に、再度電力を上げ、金属の温度を980℃までに上昇させ、5min保温し続け、脱ガスされた溶融金属を得た。保温終了後に、脱ガスされた溶融金属を直接的に鋳造した後に、高純度アルゴンガスを導入して保護し、且つ中間周波数誘導炉を閉じて、脱ガスされた溶融金属を誘導炉と共に室温までに冷却し、実施例3の高純度ランタン希土類金属を得た。 2315 g of the rare earth metal lanthanum to be purified was placed in a tungsten crucible in an intermediate frequency induction furnace, and 46 g of lanthanum hydride particles having a particle diameter of 3 mm to 5 mm were placed in a hopper and evacuated. High purity argon gas is introduced into the vacuum chamber, the furnace body is cleaned 2 to 3 times, and after the degree of vacuum is less than 10 -2 Pa, the temperature starts to rise with 10 kW power, and the rare earth metal is slowly Melted. After the metal lanthanum was completely melted, it was kept at 970 ° C. for 5 minutes to obtain a molten lanthanum metal solution. The valve of the vacuum system was closed and high purity argon gas was introduced until the degree of vacuum reached 0.04 MPa. The lanthanum hydride particles in the hopper were added to the lanthanum metal solution, the power was lowered until the temperature reached 915 ° C., and the solution state was maintained by keeping the temperature for 30 minutes. Open the exhaust valve of the vacuum system, extract high-purity argon gas and its volatiles in the vacuum chamber, and after the vacuum level returns to 10 -2 Pa or less, turn on the power again and bring the metal temperature to 980 ° C The temperature was raised and kept warm for 5 minutes to obtain a degassed molten metal. After the heat insulation is completed, the degassed molten metal is directly cast, and then high purity argon gas is introduced and protected, and the intermediate frequency induction furnace is closed, and the degassed molten metal is brought to room temperature together with the induction furnace. The high-purity lanthanum rare earth metal of Example 3 was obtained.
実施例4 Example 4
精製対象である希土類金属ランタン2301gを中間周波数誘導炉のタングステン製るつぼに入れ、粒子径が0.1mm〜2mmである水素化ランタン粒子115gをホッパーに入れ、真空引きした。真空チャンバに高純度アルゴンガスを導入し、炉体を2〜3回洗浄し、次いで、真空度が10-2Pa未満になった後に、20kWの電力で昇温し始め、希土類金属をゆっくりと溶融した。金属ランタンが完全に溶融した後に1000℃で20min保温して溶融ランタン金属液を得た。真空システムのバルブを閉じ、真空度が0.05MPaとなるまでに、高純度アルゴンガスを導入した。ホッパー内の水素化ランタン粒子をランタン金属液に添加し、温度が920℃になるまでに電力を下げ、且つ20min保温して溶液状態を維持した。真空システムの排気バルブを開け、真空チャンバ内の高純度アルゴンガス及びその揮発分を抽出し、真空度が10-2Pa以下に戻った後に、再度電力を上げ、金属の温度を1120℃までに上昇させ、10min保温し続け、脱ガスされた溶融金属を得た。保温終了後に、脱ガスされた溶融金属を直接的に鋳造した後に、高純度アルゴンガスを導入して保護し、且つ中間周波数誘導炉を閉じて、脱ガスされた溶融金属を誘導炉と共に室温までに冷却し、実施例4の高純度ランタン希土類金属を得た。 2301 g of rare earth metal lanthanum to be purified was placed in a tungsten crucible of an intermediate frequency induction furnace, and 115 g of lanthanum hydride particles having a particle size of 0.1 mm to 2 mm were placed in a hopper and evacuated. High purity argon gas is introduced into the vacuum chamber, the furnace body is cleaned 2 to 3 times, then after the degree of vacuum is less than 10 -2 Pa, the temperature starts to rise with 20kW power, and the rare earth metal is slowly Melted. After the metal lanthanum was completely melted, the mixture was kept at 1000 ° C. for 20 minutes to obtain a molten lanthanum metal solution. The valve of the vacuum system was closed, and high-purity argon gas was introduced until the degree of vacuum reached 0.05 MPa. The lanthanum hydride particles in the hopper were added to the lanthanum metal solution, the power was lowered until the temperature reached 920 ° C., and the solution state was maintained by keeping the temperature for 20 minutes. Open the exhaust valve of the vacuum system, extract high-purity argon gas and its volatiles in the vacuum chamber, and after the vacuum level has returned to 10-2 Pa or less, turn on the power again and bring the metal temperature to 1120 ℃ The temperature was raised and kept warm for 10 minutes to obtain a degassed molten metal. After the heat insulation is completed, the degassed molten metal is directly cast, and then high purity argon gas is introduced and protected, and the intermediate frequency induction furnace is closed, and the degassed molten metal is brought to room temperature together with the induction furnace. The high-purity lanthanum rare earth metal of Example 4 was obtained.
実施例5 Example 5
精製対象である希土類金属ランタン2320gを中間周波数誘導炉のタングステン製るつぼに入れ、粒子径が5.5mm〜7mmである水素化ランタン粒子116gをホッパーに入れ、真空引きした。真空チャンバに高純度アルゴンガスを導入し、炉体を2〜3回洗浄し、次いで、真空度が10-2Pa未満になった後に、20kWの電力で昇温し始め、希土類金属をゆっくりと溶融した。金属ランタンが完全に溶融した後に950℃で10min保温して溶融ランタン金属液を得た。真空システムのバルブを閉じ、真空度が0.05MPaとなるまでに、高純度アルゴンガスを導入した。ホッパー内の水素化ランタン粒子をランタン金属液に添加し、温度が915℃になるまでに電力を下げ、且つ20min保温して溶液状態を維持した。真空システムの排気バルブを開け、真空チャンバ内の高純度アルゴンガス及びその揮発分を抽出し、真空度が10-2Pa以下に戻った後に、再度電力を上げ、金属の温度を1250℃までに上昇させ、25min保温し続け、脱ガスされた溶融金属を得た。保温終了後に、脱ガスされた溶融金属を直接的に鋳造した後に、高純度アルゴンガスを導入して保護し、且つ中間周波数誘導炉を閉じて、脱ガスされた溶融金属を誘導炉と共に室温までに冷却し、実施例5の高純度ランタン希土類金属を得た。 2320 g of rare earth metal lanthanum to be purified was placed in a tungsten crucible of an intermediate frequency induction furnace, and 116 g of hydrogenated lanthanum particles having a particle size of 5.5 mm to 7 mm were placed in a hopper and evacuated. High purity argon gas is introduced into the vacuum chamber, the furnace body is cleaned 2 to 3 times, then after the degree of vacuum is less than 10 -2 Pa, the temperature starts to rise with 20kW power, and the rare earth metal is slowly Melted. After the metal lanthanum was completely melted, the mixture was kept at 950 ° C. for 10 minutes to obtain a molten lanthanum metal liquid. The valve of the vacuum system was closed, and high-purity argon gas was introduced until the degree of vacuum reached 0.05 MPa. The lanthanum hydride particles in the hopper were added to the lanthanum metal solution, the power was lowered until the temperature reached 915 ° C., and the solution state was maintained by keeping the temperature for 20 minutes. Open the exhaust valve of the vacuum system, extract high-purity argon gas and its volatiles in the vacuum chamber, and after the vacuum level has returned to 10-2 Pa or less, turn on the power again and bring the metal temperature to 1250 ℃ The temperature was raised and kept warm for 25 minutes to obtain a degassed molten metal. After the heat insulation is completed, the degassed molten metal is directly cast, and then high purity argon gas is introduced and protected, and the intermediate frequency induction furnace is closed, and the degassed molten metal is brought to room temperature together with the induction furnace. The high-purity lanthanum rare earth metal of Example 5 was obtained.
実施例6 Example 6
精製対象である希土類金属ランタン2190gを中間周波数誘導炉のタングステン製るつぼに入れ、粒子径が0.1mm〜2mmである水素化ランタン219gをホッパーに入れ、真空引きした。真空チャンバに高純度アルゴンガスを導入し、炉体を2〜3回洗浄し、次いで、真空度が10-2Pa未満になった後に、18kWの電力で昇温し、希土類金属をゆっくりと溶融した。金属ランタンが完全に溶融した後に980℃までに昇温し続け、且つ10min保温して溶融ランタン金属液を得た。真空システムのバルブを閉じ、真空度が0.03MPaとなるまでに、高純度アルゴンガスを導入した。ホッパー内のランタン水素化物粒子をランタン金属液に添加し、温度が915℃になるまでに電力を下げ、且つ20min保温して溶液状態を維持した。真空システムの排気バルブを開け、真空チャンバ内の高純度アルゴンガス及びその揮発分を抽出し、真空度が10-2Pa以下に戻った後に、再度電力を上げ、金属の温度を1150℃までに上昇させ、10min保温し続け、脱ガスされた溶融金属を得た。保温終了後に、脱ガスされた溶融金属を直接的に鋳造した後に、高純度アルゴンガスを導入して保護し、且つ中間周波数誘導炉を閉じて、脱ガスされた溶融金属を誘導炉と共に室温までに冷却し、実施例6の高純度ランタン希土類金属を得た。 2190 g of rare earth metal lanthanum to be purified was placed in a tungsten crucible in an intermediate frequency induction furnace, and 219 g of lanthanum hydride having a particle size of 0.1 mm to 2 mm was placed in a hopper and evacuated. High purity argon gas is introduced into the vacuum chamber, the furnace body is cleaned 2 to 3 times, and after the degree of vacuum is less than 10 -2 Pa, the temperature is raised with an electric power of 18 kW, and the rare earth metal is slowly melted did. After the metal lanthanum was completely melted, the temperature was continuously raised to 980 ° C. and kept for 10 minutes to obtain a molten lanthanum metal liquid. The valve of the vacuum system was closed and high purity argon gas was introduced until the degree of vacuum reached 0.03 MPa. The lanthanum hydride particles in the hopper were added to the lanthanum metal solution, the power was lowered until the temperature reached 915 ° C., and the solution state was maintained by keeping the temperature for 20 minutes. Open the exhaust valve of the vacuum system, extract high-purity argon gas and its volatiles in the vacuum chamber, and after the vacuum level has returned to 10-2 Pa or less, turn on the power again and bring the metal temperature to 1150 ℃ The temperature was raised and kept warm for 10 minutes to obtain a degassed molten metal. After the heat insulation is completed, the degassed molten metal is directly cast, and then high purity argon gas is introduced and protected, and the intermediate frequency induction furnace is closed, and the degassed molten metal is brought to room temperature together with the induction furnace. The high-purity lanthanum rare earth metal of Example 6 was obtained.
実施例7 Example 7
精製対象である希土類金属ランタン2285gを中間周波数誘導炉のタングステン製るつぼに入れ、粒子径が0.1mm〜2mmである水素化ランタン114gをホッパーに入れ、真空引きした。真空チャンバに高純度アルゴンガスを導入し、炉体を2〜3回洗浄し、次いで、真空度が10-2Pa未満になった後に、18kWの電力で昇温し始め、希土類金属をゆっくりと溶融した。金属ランタンが完全に溶融した後に980℃までに昇温し続け、且つ10min保温して溶融ランタン金属液を得た。真空システムのバルブを閉じ、真空度が0.01MPaとなるまでに、高純度アルゴンガスを導入した。ホッパー内のランタン水素化物粒子をランタン金属液に添加し、温度が915℃になるまでに電力を下げ、且つ20min保温して溶液状態を維持した。真空システムの排気バルブを開け、真空チャンバ内の高純度アルゴンガス及びその揮発分を抽出し、真空度が10-2Pa以下に戻った後に、再度電力を上げ、金属の温度を1150℃までに上昇させ、10min保温し続け、脱ガスされた溶融金属を得た。保温終了後に、脱ガスされた溶融金属を直接的に鋳造した後に、高純度アルゴンガスを導入して保護し、且つ中間周波数誘導炉を閉じて、脱ガスされた溶融金属を誘導炉と共に室温までに冷却し、実施例7の高純度ランタン希土類金属を得た。 2285 g of rare earth metal lanthanum to be purified was placed in a tungsten crucible of an intermediate frequency induction furnace, and 114 g of lanthanum hydride having a particle size of 0.1 mm to 2 mm was placed in a hopper and evacuated. High purity argon gas is introduced into the vacuum chamber, the furnace body is cleaned 2 to 3 times, then after the degree of vacuum is less than 10 -2 Pa, the temperature starts to be raised with 18 kW power, and the rare earth metal is slowly Melted. After the metal lanthanum was completely melted, the temperature was continuously raised to 980 ° C. and kept for 10 minutes to obtain a molten lanthanum metal liquid. The valve of the vacuum system was closed, and high purity argon gas was introduced until the degree of vacuum reached 0.01 MPa. The lanthanum hydride particles in the hopper were added to the lanthanum metal solution, the power was lowered until the temperature reached 915 ° C., and the solution state was maintained by keeping the temperature for 20 minutes. Open the exhaust valve of the vacuum system, extract high-purity argon gas and its volatiles in the vacuum chamber, and after the vacuum level has returned to 10-2 Pa or less, turn on the power again and bring the metal temperature to 1150 ℃ The temperature was raised and kept warm for 10 minutes to obtain a degassed molten metal. After the heat insulation is completed, the degassed molten metal is directly cast, and then high purity argon gas is introduced and protected, and the intermediate frequency induction furnace is closed, and the degassed molten metal is brought to room temperature together with the induction furnace. The high-purity lanthanum rare earth metal of Example 7 was obtained.
実施例8 Example 8
精製対象である希土類金属ホルミウム2870gを中間周波数誘導炉のタングステン製るつぼに入れ、粒子径が0.1mm〜2mmである水酸化ホルミウム粒子140gをホッパーに入れ、真空引きした。真空チャンバに高純度アルゴンガスを導入し、炉体を2〜3回洗浄し、次いで、真空度が10-2Pa未満になった後に、20kWの電力で昇温し始め、希土類金属をゆっくりと溶融した。金属ホルミウムが完全に溶融した後に1540℃で10min保温して溶融ホルミウム金属液を得た。真空システムのバルブを閉じ、真空度が0.05MPaとなるまでに、高純度アルゴンガスを導入した。ホッパー内の水酸化ホルミウム粒子をホルミウム金属液に添加し、温度が1450℃になるまでに電力を下げ、且つ20min保温して溶液状態を維持した。真空システムの排気バルブを開け、真空チャンバ内の高純度アルゴンガス及びその揮発分を抽出し、真空度が10-2Pa以下に戻った後に、再度電力を上げ、金属の温度を1600℃までに上昇させ、10min保温し続け、脱ガスされた溶融金属を得た。保温終了後に、脱ガスされた溶融金属を直接的に鋳造した後に、高純度アルゴンガスを導入して保護し、且つ中間周波数誘導炉を閉じて、脱ガスされた溶融金属を誘導炉と共に室温までに冷却し、実施例8の高純度ホルミウム希土類金属を得た。 2870 g of rare earth metal holmium to be purified was placed in a tungsten crucible of an intermediate frequency induction furnace, and 140 g of holmium hydroxide particles having a particle diameter of 0.1 mm to 2 mm were placed in a hopper and evacuated. High purity argon gas is introduced into the vacuum chamber, the furnace body is cleaned 2 to 3 times, then after the degree of vacuum is less than 10 -2 Pa, the temperature starts to rise with 20kW power, and the rare earth metal is slowly Melted. After the metal holmium was completely melted, it was kept at 1540 ° C. for 10 minutes to obtain a molten holmium metal solution. The valve of the vacuum system was closed, and high-purity argon gas was introduced until the degree of vacuum reached 0.05 MPa. The holmium hydroxide particles in the hopper were added to the holmium metal solution, the electric power was lowered until the temperature reached 1450 ° C., and the solution state was maintained by keeping the temperature for 20 minutes. Open the exhaust valve of the vacuum system, extract high-purity argon gas and its volatiles in the vacuum chamber, and after the vacuum level has returned to 10-2 Pa or less, turn on the power again to bring the metal temperature to 1600 ℃ The temperature was raised and kept warm for 10 minutes to obtain a degassed molten metal. After the heat insulation is completed, the degassed molten metal is directly cast, and then high purity argon gas is introduced and protected, and the intermediate frequency induction furnace is closed, and the degassed molten metal is brought to room temperature together with the induction furnace. The high purity holmium rare earth metal of Example 8 was obtained.
実施例9 Example 9
精製対象である希土類金属イットリウム2100gを中間周波数誘導炉のタングステン製るつぼに入れ、粒子径が0.1mm〜2mmである水酸化イットリウム粒子105gをホッパーに入れ、真空引きした。真空チャンバに高純度アルゴンガスを導入し、炉体を2〜3回洗浄し、次いで、真空度が10-2Pa未満になった後に、20kWの電力で昇温し始め、希土類金属をゆっくりと溶融した。金属イットリウムが完全に溶融した後に1580℃で10min保温して溶融イットリウム金属液を得た。真空システムのバルブを閉じ、真空度が0.05MPaとなるまでに、高純度アルゴンガスを導入した。ホッパー内の水酸化イットリウム粒子を希土類金属液に添加し、温度が1510℃になるまでに電力を下げ、且つ20min保温して溶液状態を維持した。真空システムの排気バルブを開け、真空チャンバ内の高純度アルゴンガス及びその揮発分を抽出し、真空度が10-2Pa以下に戻った後に、再度電力を上げ、金属の温度を1600℃までに上昇させ、10min保温し続け、脱ガスされた溶融金属を得た。保温終了後に、脱ガスされた溶融金属を直接的に鋳造した後に、高純度アルゴンガスを導入して保護し、且つ中間周波数誘導炉を閉じて、脱ガスされた溶融金属を誘導炉と共に室温までに冷却し、実施例9の高純度イットリウム希土類金属を得た。 2100 g of rare earth metal yttrium to be refined was placed in a tungsten crucible of an intermediate frequency induction furnace, and 105 g of yttrium hydroxide particles having a particle diameter of 0.1 mm to 2 mm were placed in a hopper and evacuated. High purity argon gas is introduced into the vacuum chamber, the furnace body is cleaned 2 to 3 times, then after the degree of vacuum is less than 10 -2 Pa, the temperature starts to rise with 20kW power, and the rare earth metal is slowly Melted. After the metal yttrium was completely melted, it was kept at 1580 ° C. for 10 minutes to obtain a molten yttrium metal solution. The valve of the vacuum system was closed, and high-purity argon gas was introduced until the degree of vacuum reached 0.05 MPa. The yttrium hydroxide particles in the hopper were added to the rare earth metal liquid, the electric power was lowered until the temperature reached 1510 ° C., and the solution state was maintained by keeping the temperature for 20 minutes. Open the exhaust valve of the vacuum system, extract high-purity argon gas and its volatiles in the vacuum chamber, and after the vacuum level has returned to 10-2 Pa or less, turn on the power again to bring the metal temperature to 1600 ℃ The temperature was raised and kept warm for 10 minutes to obtain a degassed molten metal. After the heat insulation is completed, the degassed molten metal is directly cast, and then high purity argon gas is introduced and protected, and the intermediate frequency induction furnace is closed, and the degassed molten metal is brought to room temperature together with the induction furnace. The high purity yttrium rare earth metal of Example 9 was obtained.
比較例1 Comparative Example 1
精製対象である希土類金属ランタン2280gを中間周波数誘導炉のタングステン製るつぼに入れ、粒子径が0.1mm〜2mmである水素化ランタン粒子114gをホッパーに入れ、真空引きした。真空チャンバに高純度アルゴンガスを導入し、炉体を2〜3回洗浄し、次いで、真空度が10-2Pa未満になった後に、20kWの電力で970℃までに昇温し始め、希土類金属をゆっくりと溶融した。金属ランタンが完全に溶融した後に980℃で10min保温して溶融ランタン金属液を得た。真空システムのバルブを閉じ、真空度が0.008MPaとなるまでに、高純度アルゴンガスを導入した。ホッパー内の希土類水素化物粒子を希土類金属液に添加し、温度が915℃になるまでに電力を下げ、且つ20min保温して溶液状態を維持した。真空システムの排気バルブを開け、真空チャンバ内の高純度アルゴンガス及びその揮発分を抽出し、真空度が10-2Pa以下に戻った後に、再度電力を上げ、金属の温度を1150℃までに上昇させ、10min保温し続け、脱ガスされた溶融金属を得た。保温終了後に、脱ガスされた溶融金属を直接的に鋳造した後に、高純度アルゴンガスを導入して保護し、且つ中間周波数誘導炉を閉じて、脱ガスされた溶融金属を誘導炉と共に室温までに冷却し、比較例1の高純度希土類金属を得た。 2280 g of rare earth metal lanthanum to be purified was placed in a tungsten crucible of an intermediate frequency induction furnace, and 114 g of lanthanum hydride particles having a particle size of 0.1 mm to 2 mm were placed in a hopper and evacuated. High purity argon gas was introduced into the vacuum chamber, the furnace body was cleaned 2 to 3 times, and after the degree of vacuum became less than 10 -2 Pa, the temperature started to 970 ° C with 20kW power, The metal melted slowly. After the metal lanthanum was completely melted, it was kept at 980 ° C. for 10 minutes to obtain a molten lanthanum metal liquid. The valve of the vacuum system was closed and high purity argon gas was introduced until the degree of vacuum reached 0.008 MPa. The rare earth hydride particles in the hopper were added to the rare earth metal liquid, the electric power was lowered until the temperature reached 915 ° C., and the solution state was maintained by keeping the temperature for 20 minutes. Open the exhaust valve of the vacuum system, extract high-purity argon gas and its volatiles in the vacuum chamber, and after the vacuum level has returned to 10-2 Pa or less, turn on the power again and bring the metal temperature to 1150 ℃ The temperature was raised and kept warm for 10 minutes to obtain a degassed molten metal. After the heat insulation is completed, the degassed molten metal is directly cast, and then high purity argon gas is introduced and protected, and the intermediate frequency induction furnace is closed, and the degassed molten metal is brought to room temperature together with the induction furnace. The high purity rare earth metal of Comparative Example 1 was obtained.
比較例2 Comparative Example 2
還元後に調製された精製対象である希土類金属ランタン2310gを中間周波数誘導炉のタングステン製るつぼに入れ、粒子径が0.1mm〜2mmである水素化ランタン粒子9gをホッパーに入れ、真空引きした。真空チャンバに高純度アルゴンガスを導入し、炉体を2〜3回洗浄し、次いで、真空度が10-2Pa未満になった後に、20kWの電力で昇温し始め、希土類金属をゆっくりと溶融した。金属ランタンが完全に溶融した後に980℃で10min保温して溶融ランタン金属液を得た。真空システムのバルブを閉じ、真空度が0.05MPaとなるまでに、高純度アルゴンガスを導入した。ホッパー内の水素化ランタン粒子を希土類金属液に添加し、温度が915℃になるまでに電力を下げ、且つ20min保温して溶液状態を維持した。真空システムの排気バルブを開け、真空チャンバ内の高純度アルゴンガス及びその揮発分を抽出し、真空度が10-2Pa以下に戻った後に、再度電力を上げ、金属の温度を1130℃までに上昇させ、10min保温し続け、脱ガスされた溶融金属を得た。保温終了後に、脱ガスされた溶融金属を直接的に鋳造した後に、高純度アルゴンガスを導入して保護し、且つ中間周波数誘導炉を閉じて、脱ガスされた溶融金属を誘導炉と共に室温までに冷却し、比較例2の高純度希土類金属を得た。 2310 g of rare earth metal lanthanum to be purified prepared after reduction was placed in a tungsten crucible of an intermediate frequency induction furnace, and 9 g of lanthanum hydride particles having a particle size of 0.1 mm to 2 mm were placed in a hopper and evacuated. High purity argon gas is introduced into the vacuum chamber, the furnace body is cleaned 2 to 3 times, then after the degree of vacuum is less than 10 -2 Pa, the temperature starts to rise with 20kW power, and the rare earth metal is slowly Melted. After the metal lanthanum was completely melted, it was kept at 980 ° C. for 10 minutes to obtain a molten lanthanum metal liquid. The valve of the vacuum system was closed, and high-purity argon gas was introduced until the degree of vacuum reached 0.05 MPa. The lanthanum hydride particles in the hopper were added to the rare earth metal liquid, the electric power was lowered until the temperature reached 915 ° C., and the solution state was maintained by keeping the temperature for 20 minutes. Open the exhaust valve of the vacuum system, extract the high purity argon gas and its volatiles in the vacuum chamber, and after the vacuum level returns to 10-2 Pa or less, turn on the power again and bring the metal temperature to 1130 ℃ The temperature was raised and kept warm for 10 minutes to obtain a degassed molten metal. After the heat insulation is completed, the degassed molten metal is directly cast, and then high purity argon gas is introduced and protected, and the intermediate frequency induction furnace is closed, and the degassed molten metal is brought to room temperature together with the induction furnace. The high purity rare earth metal of Comparative Example 2 was obtained.
実施例1〜9、比較例1及び2における精製対象である希土類金属及び脱ガスされた希土類金属の不純物含有量について測定した。測定方法として、パルス赤外線吸収法によって金属中の酸素、窒素、水素の含有量を測定し、電気伝導度法によって金属中の炭素、硫黄の含有量を測定し、誘導結合プラズマ発光分光法によって金属中のタングステンの含有量を測定した。測定結果を表1に示す(単位:重量ppm)。 The impurities content of the rare earth metal to be purified and the degassed rare earth metal in Examples 1 to 9 and Comparative Examples 1 and 2 were measured. As a measuring method, the content of oxygen, nitrogen and hydrogen in the metal is measured by the pulsed infrared absorption method, the content of carbon and sulfur in the metal is measured by the electrical conductivity method, and the metal is measured by inductively coupled plasma emission spectroscopy. The content of tungsten was measured. The measurement results are shown in Table 1 (unit: ppm by weight).
表1 table 1
表1における実施例1〜5と比較例1及び2とのデータを比較すれば明らかなように、希土類水素化物を使用して脱ガスし、且つ真空度、保温時間及び希土類水素化物の使用量を制御することによって、不純物ガスの除去効果が顕著であった。実施例1と実施例4との対比から、希土類金属溶融時の保温時間を適切に延長することは、不純物ガスの除去に有利であるが、るつぼ不純物による汚染も引き起こすため、15min超は望ましくないと分かる。実施例1と実施例5との対比から分かるように、希土類水素化物粒子の粒子径は精製効果にある程度の影響を与えるが、現在の一般の希土類水素化物の粒子サイズでは、すべて優れた不純物ガスの除去効果を実現できた。 As is clear from comparison of the data of Examples 1 to 5 and Comparative Examples 1 and 2 in Table 1, the gas was degassed using rare earth hydride, the degree of vacuum, the heat retention time, and the amount of rare earth hydride used. By controlling this, the effect of removing impurity gas was significant. From the comparison between Example 1 and Example 4, appropriately extending the heat retention time during melting of the rare earth metal is advantageous for removing the impurity gas, but also causes contamination by the crucible impurity, so that more than 15 minutes is not desirable. I understand. As can be seen from the comparison between Example 1 and Example 5, the particle size of the rare earth hydride particles has some influence on the purification effect, but with the current general rare earth hydride particle size, all are excellent impurity gases. The removal effect was realized.
以上の説明から分かるように、本発明の上記実施例は、以下のような効果を実現した。 As can be seen from the above description, the above-described embodiment of the present invention achieves the following effects.
本願の上記脱ガス方法を、希土類金属の溶融精製及び希土類金属ターゲットの真空溶解に適用することができ、歩留まりが比較的高く、製品の品質が良い。希土類水素化物と溶融金属液を混合し、希土類水素化物の融点温度付近で脱離することで極めて強い還元性を示すH原子が生成され、さらに励起状態の水素原子は過飽和に溶融金属液に溶解することもできれば、溶融金属から放出することもできるため、この溶解‐放出過程は、強い還元性を示す水素原子と溶融金属液中の気体元素との結合を促進し、金属液に介在している化合物中の気体元素をH2O、CO2、NH3及びCH4等気体化合物の形態で貯蔵し、最終的には揮発により除去することができる。また、希土類水素化物の添加量は、精製対象である希土類金属に対して0.5〜10%(重量)であり、水素化反応が生じて粉末化することがないどころか、顕著な脱ガス効果を発揮することができる。本願の脱ガス方法を用いると、低ガス含有量を有する希土類金属を得るために、単独でその後の複数回の蒸留、固相電解法又はサクション法等の方法によって希土類金属を徹底的に脱ガスする必要がない。しかも、該方法は流れが短く、脱ガス効果が顕著で、金属精製ステップが長く、工程が複雑等の要因による希土類金属への二次汚染を回避し、低ネルギー消費で高効率的に脱ガスする目的を達成できる。 The above degassing method of the present application can be applied to melting and refining rare earth metals and vacuum melting of rare earth metal targets, and the yield is relatively high and the product quality is good. By mixing the rare earth hydride and the molten metal liquid and desorbing near the melting temperature of the rare earth hydride, H atoms exhibiting extremely strong reducibility are generated, and the excited hydrogen atoms are supersaturated and dissolved in the molten metal liquid. This dissolution-release process promotes the bonding between hydrogen atoms that exhibit strong reducibility and gaseous elements in the molten metal liquid, and can intervene in the metal liquid. The gaseous elements in the compound can be stored in the form of gaseous compounds such as H 2 O, CO 2 , NH 3 and CH 4 and finally removed by volatilization. The amount of rare earth hydride added is 0.5 to 10% (weight) with respect to the rare earth metal to be refined, and it exhibits a remarkable degassing effect, rather than causing hydrogenation reaction and powdering. can do. Using the degassing method of the present application, in order to obtain a rare earth metal having a low gas content, the rare earth metal is thoroughly degassed by a method such as subsequent distillation, solid phase electrolysis, or suction method alone. There is no need to do. In addition, the method has a short flow, a remarkable degassing effect, a long metal purification step, avoids secondary contamination to rare earth metals due to factors such as complicated processes, and efficiently degass with low energy consumption. Can achieve the purpose.
以上は、本発明の好適な実施例に過ぎず、本発明はこれらに制限されるものではない。当業者であれば、本発明に対して様々な変更および変形を行うことができることが理解されるであろう。本発明の精神及び範囲から逸脱することなく、様々な修正例、置換例、改良例等がすべて本発明に包含される。 The above are only preferred embodiments of the present invention, and the present invention is not limited thereto. Those skilled in the art will appreciate that various changes and modifications can be made to the present invention. Various modifications, substitutions, improvements, and the like are all encompassed by the present invention without departing from the spirit and scope of the present invention.
Claims (10)
0.01〜0.05MPaの真空度で、前記精製対象である希土類金属の重量に対して、0.5〜10%の重量で希土類水素化物を前記溶融金属液と混合し、5〜30min保温し、脱ガスされた溶融金属及びガス状物質を得るステップS2と、
前記ガス状物質と前記脱ガスされた溶融金属とを分離し、且つ前記脱ガスされた溶融金属を不活性ガス中で冷却し、脱ガス希土類金属を得るステップS3と、
を含むことを特徴とする希土類金属溶製脱ガス方法。 Step S1 for melting a rare earth metal to be purified in a vacuum environment to form a molten metal liquid;
A rare earth hydride is mixed with the molten metal solution at a weight of 0.5 to 10% with a vacuum degree of 0.01 to 0.05 MPa and with respect to the weight of the rare earth metal to be purified, and is kept degassed for 5 to 30 minutes. Obtaining a molten metal and a gaseous substance,
Separating the gaseous substance and the degassed molten metal, and cooling the degassed molten metal in an inert gas to obtain a degassed rare earth metal; and
A rare earth metal melt degassing method comprising:
前記精製対象である希土類金属を中間周波数誘導炉のるつぼに入れ、且つ前記中間周波数誘導炉の炉内を真空引きし、真空チャンバを形成することと、
前記真空チャンバに前記不活性ガスを導入して前記真空チャンバを洗浄し、前記真空チャンバの真空度が10-2Pa未満になった時に、前記真空チャンバを前記精製対象である希土類金属の融点温度よりも50〜100℃高い温度までに昇温し、前記精製対象である希土類金属を溶融し、且つ5〜15min保温した後に、前記溶融金属液を得ることと、
を含むことを特徴とする請求項1に記載の脱ガス方法。 Step S1 includes
Putting the rare earth metal to be purified into a crucible of an intermediate frequency induction furnace and evacuating the furnace of the intermediate frequency induction furnace to form a vacuum chamber;
The inert gas is introduced into the vacuum chamber to clean the vacuum chamber, and when the degree of vacuum of the vacuum chamber is less than 10 −2 Pa, the vacuum chamber is melted at a melting point temperature of the rare earth metal to be purified. Raising the temperature to 50 to 100 ° C. higher than that, melting the rare earth metal to be purified, and keeping the temperature for 5 to 15 minutes, obtaining the molten metal liquid,
The degassing method according to claim 1, comprising:
前記中間周波数誘導炉の真空システムの排気バルブを閉じて、且つ前記真空チャンバ内に前記不活性ガスを真空度が0.01〜0.05MPaとなるまでに充填することと、
希土類水素化物粒子を前記溶融金属液に添加し、且つ前記真空チャンバの温度を、溶融金属液の表面が凝固状態になった後に5〜30min保温し続け、脱ガスされた溶融金属及びガス状物質を得ることと、
を含むことを特徴とする請求項3に記載の脱ガス方法。 Step S2 includes
Closing the exhaust valve of the vacuum system of the intermediate frequency induction furnace and filling the vacuum chamber with the inert gas until the degree of vacuum is 0.01 to 0.05 MPa;
The rare earth hydride particles are added to the molten metal liquid, and the temperature of the vacuum chamber is kept warm for 5 to 30 minutes after the surface of the molten metal liquid is in a solidified state. And getting
The degassing method according to claim 3, characterized by comprising:
前記真空システムの排気バルブを開け、前記真空チャンバを真空引きすることと、
前記真空チャンバの真空度が10-2Pa以下に戻った後に、前記真空チャンバを前記精製対象である希土類金属の融点温度よりも50〜300℃高い温度までに昇温し、5〜20min保温することと、
保温終了後に、前記脱ガスされた溶融金属を鋳造し、次いで、前記不活性ガスを利用して保護し、且つ室温までに冷却し、前記脱ガスされた希土類金属を得ることと、
を含むことを特徴とする請求項6に記載の脱ガス方法。 Step S3 includes
Opening the exhaust valve of the vacuum system and evacuating the vacuum chamber;
After the vacuum degree of the vacuum chamber returns to 10 −2 Pa or less, the vacuum chamber is heated to a temperature 50 to 300 ° C. higher than the melting point temperature of the rare earth metal to be purified, and kept for 5 to 20 minutes. And
Casting the degassed molten metal after the heat retention, then protecting using the inert gas and cooling to room temperature to obtain the degassed rare earth metal;
The degassing method according to claim 6, comprising:
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114657420A (en) * | 2022-04-08 | 2022-06-24 | 包头稀土研究院 | Light rare earth-zinc alloy, preparation method and application thereof, and application of smelting container |
CN114752814A (en) * | 2022-04-08 | 2022-07-15 | 包头稀土研究院 | Heavy rare earth zinc alloy, manufacturing method and application thereof, and application of tungsten-containing container |
CN115821087A (en) * | 2022-11-30 | 2023-03-21 | 上海大学 | Rare earth metal plasma deoxidation method and low-oxygen-content rare earth metal |
Families Citing this family (2)
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---|---|---|---|---|
CN110983076B (en) * | 2019-12-31 | 2022-02-18 | 包头市中鑫安泰磁业有限公司 | Preparation device and preparation method of high-purity rare earth |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS619533A (en) * | 1984-06-22 | 1986-01-17 | Showa Denko Kk | Manufacture of rare earth metal |
CN102465210A (en) * | 2010-11-02 | 2012-05-23 | 北京有色金属研究总院 | Method for preparing high purity rare earth metal and its apparatus |
CN102465209A (en) * | 2010-11-02 | 2012-05-23 | 北京有色金属研究总院 | Method and vacuum distillation device for preparing high-purity neodymium |
CN103409650A (en) * | 2013-07-25 | 2013-11-27 | 北京大学 | Novel method for utilizing hydrogen plasma electric arc melting technology to prepare high-purity rare earth gadolinium elementary substance |
JP2014105359A (en) * | 2012-11-28 | 2014-06-09 | Jx Nippon Mining & Metals Corp | Method for producing high purity neodymium, high purity neodymium, sputtering target produced by using high purity neodymium, permanent magnet including high purity neodymium as component |
WO2014206748A1 (en) * | 2013-06-24 | 2014-12-31 | Siemens Aktiengesellschaft | Method for synthesising a rare earth element by means of a redox reaction |
KR20150042018A (en) * | 2013-10-10 | 2015-04-20 | 공주대학교 산학협력단 | Refining method of rare-earth metals by vacuum molten process and apparatus for the manufacturing |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2102513C1 (en) * | 1993-03-22 | 1998-01-20 | Виталий Евгеньевич Дьяков | Method of preparing metal scandium |
CN101665909B (en) * | 2009-10-23 | 2012-08-22 | 宁波江丰电子材料有限公司 | Method for preparing target material |
CN103589874B (en) * | 2013-09-27 | 2016-01-27 | 北京大学 | A kind of method of material of purifying metals under the temperature difference |
-
2016
- 2016-12-16 CN CN201611175185.5A patent/CN108203766B/en active Active
-
2017
- 2017-12-12 MY MYPI2017704771A patent/MY186742A/en unknown
- 2017-12-14 JP JP2017239364A patent/JP6491304B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS619533A (en) * | 1984-06-22 | 1986-01-17 | Showa Denko Kk | Manufacture of rare earth metal |
CN102465210A (en) * | 2010-11-02 | 2012-05-23 | 北京有色金属研究总院 | Method for preparing high purity rare earth metal and its apparatus |
CN102465209A (en) * | 2010-11-02 | 2012-05-23 | 北京有色金属研究总院 | Method and vacuum distillation device for preparing high-purity neodymium |
JP2014105359A (en) * | 2012-11-28 | 2014-06-09 | Jx Nippon Mining & Metals Corp | Method for producing high purity neodymium, high purity neodymium, sputtering target produced by using high purity neodymium, permanent magnet including high purity neodymium as component |
WO2014206748A1 (en) * | 2013-06-24 | 2014-12-31 | Siemens Aktiengesellschaft | Method for synthesising a rare earth element by means of a redox reaction |
CN103409650A (en) * | 2013-07-25 | 2013-11-27 | 北京大学 | Novel method for utilizing hydrogen plasma electric arc melting technology to prepare high-purity rare earth gadolinium elementary substance |
KR20150042018A (en) * | 2013-10-10 | 2015-04-20 | 공주대학교 산학협력단 | Refining method of rare-earth metals by vacuum molten process and apparatus for the manufacturing |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114657420A (en) * | 2022-04-08 | 2022-06-24 | 包头稀土研究院 | Light rare earth-zinc alloy, preparation method and application thereof, and application of smelting container |
CN114752814A (en) * | 2022-04-08 | 2022-07-15 | 包头稀土研究院 | Heavy rare earth zinc alloy, manufacturing method and application thereof, and application of tungsten-containing container |
CN114752814B (en) * | 2022-04-08 | 2023-10-20 | 包头稀土研究院 | Heavy rare earth zinc alloy, method for producing same, use thereof, and use of tungsten-containing container |
CN114657420B (en) * | 2022-04-08 | 2023-10-20 | 包头稀土研究院 | Light rare earth-zinc alloy, preparation method and application thereof and application of smelting container |
CN115821087A (en) * | 2022-11-30 | 2023-03-21 | 上海大学 | Rare earth metal plasma deoxidation method and low-oxygen-content rare earth metal |
CN115821087B (en) * | 2022-11-30 | 2024-06-04 | 上海大学 | Rare earth metal plasma deoxidation method and low-oxygen-content rare earth metal |
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