JP2960652B2 - Method and apparatus for purifying high purity metal - Google Patents
Method and apparatus for purifying high purity metalInfo
- Publication number
- JP2960652B2 JP2960652B2 JP6227095A JP22709594A JP2960652B2 JP 2960652 B2 JP2960652 B2 JP 2960652B2 JP 6227095 A JP6227095 A JP 6227095A JP 22709594 A JP22709594 A JP 22709594A JP 2960652 B2 JP2960652 B2 JP 2960652B2
- Authority
- JP
- Japan
- Prior art keywords
- melting
- metal
- purity
- band
- plasma arc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 85
- 239000002184 metal Substances 0.000 title claims description 85
- 238000000034 method Methods 0.000 title claims description 41
- 238000002844 melting Methods 0.000 claims description 76
- 230000008018 melting Effects 0.000 claims description 74
- 239000012535 impurity Substances 0.000 claims description 62
- 239000010949 copper Substances 0.000 claims description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- 238000000746 purification Methods 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 34
- 229910052802 copper Inorganic materials 0.000 claims description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 238000004857 zone melting Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000007670 refining Methods 0.000 claims description 17
- 150000002739 metals Chemical class 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 13
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 229910052755 nonmetal Inorganic materials 0.000 description 9
- 238000005204 segregation Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000001304 sample melting Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- -1 specifically Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属中に含まれる微量
の非金属不純物（酸素，炭素など）および金属不純物を
除去することによって、高純度の金属を精製する方法お
よびその精製装置に関するものである。とくに本発明
は、帯溶融時の不純物の偏析による分離精製効果とプラ
ズマアーク加熱溶融時の不純物の蒸発除去効果を利用し
て簡便に高純度の金属を精製, 回収する技術について提
案する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying high-purity metal by removing trace amounts of nonmetallic impurities (oxygen, carbon, etc.) and metal impurities contained in the metal, and a purification apparatus therefor. It is. In particular, the present invention proposes a technique for easily purifying and recovering high-purity metals by utilizing the effect of separation and purification by segregation of impurities during zone melting and the effect of evaporation and removal of impurities during plasma arc heating and melting.
【０００２】[0002]
【発明の背景】金属および合金などの金属材料あるいは
各種の金属化合物は、電子材料や機能性材料としての用
途にも使われているが、かかる材料の高性能化に当たっ
ては、素材である金属材料に含まれるガス成分や金属不
純物を極力低減化した高純度金属材料が求められてい
る。このような高純度金属を得るための精製方法として
は、化学的精製法や物理的精製法など多くの手段がある
が、対象金属や除去すべき不純物の種類によって適，不
適があった。そのため、一般に、高純度金属は、いくつ
かの精製法を適宜組み合わせて複雑な精製プロセスを経
て製造されているのが実情である。その結果、高純度金
属および高純度金属を使用した最終材料はきわめて高価
なものとなり、先端技術産業の発展を阻害する一因とも
なっている。こうした背景の下で、近年、多くの不純物
を単一工程の処理で低レベルにまで除去できるような精
製技術の確立が求められていた。BACKGROUND OF THE INVENTION Metal materials such as metals and alloys and various metal compounds are also used as electronic materials and functional materials. However, in order to improve the performance of such materials, the metal materials which are the materials are used. There is a demand for a high-purity metal material in which gas components and metal impurities contained in the steel are reduced as much as possible. As a purification method for obtaining such a high-purity metal, there are many means such as a chemical purification method and a physical purification method. However, there are some suitable and unsuitable methods depending on the target metal and the type of impurities to be removed. Therefore, in general, high-purity metals are generally manufactured through a complicated purification process by appropriately combining several purification methods. As a result, the high-purity metal and the final material using the high-purity metal are extremely expensive, which is a factor that hinders the development of the high-tech industry. Under such a background, in recent years, there has been a demand for the establishment of a purification technique capable of removing many impurities to a low level by a single-step treatment.
【０００３】[0003]
【従来の技術およびその解決課題】さて、Pfanらにより
提案された帯溶融精製法は、溶融金属が凝固する際に、
固−液平衡に基づき、不純物を溶融相（液相）または凝
固相（固相）に分配濃縮する原理を応用する方法であ
り、シリコンを始め多くの高純度金属を精製するための
方法の１つとして有望である。この方法において、帯溶
融部を形成するための加熱源としては、従来、(1) 抵抗
加熱、(2) 高周波誘導加熱、(3) アーク加熱、(4) 電子
ビーム衝撃加熱などが使用されている。2. Description of the Related Art The belt melting and refining method proposed by Pfan et al.
This is a method that applies the principle of partitioning and concentrating impurities into a molten phase (liquid phase) or a solidified phase (solid phase) based on solid-liquid equilibrium. One of the methods for purifying silicon and other high-purity metals is as follows. One promising. In this method, as a heating source for forming a band fusion zone, conventionally, (1) resistance heating, (2) high-frequency induction heating, (3) arc heating, (4) electron beam impact heating, and the like have been used. I have.
【０００４】上記(1),(2) の技術の場合、その帯溶融加
熱が、真空, 不活性ガス雰囲気または還元性ガス雰囲気
で可能であり、雰囲気からの汚染がない状態で金属を精
製することができる。また、目的金属よりも蒸気圧が著
しく高い場合には不純物の蒸発除去も期待できる。しか
しながら、上記各従来技術の精製は主に偏析作用を利用
する方法であり、金属不純物のみならず非金属不純物な
どをも極低濃度まで低減化することは難しいという欠点
があった。[0004] In the case of the techniques (1) and (2), the zone melting and heating can be performed in a vacuum, an inert gas atmosphere or a reducing gas atmosphere, and the metal is refined without contamination from the atmosphere. be able to. When the vapor pressure is significantly higher than that of the target metal, evaporation of impurities can be expected. However, the refining of each of the above prior arts is a method mainly utilizing a segregation effect, and has a drawback that it is difficult to reduce not only metal impurities but also nonmetal impurities to an extremely low concentration.
【０００５】また、上記(3) の従来技術の場合も、その
帯溶融加熱が不活性ガス雰囲気または還元性ガス雰囲気
下で偏析作用を主に利用する精製であるから、上記(1),
(2)の方法と全く同じ欠点があった。Also, in the case of the prior art (3), since the zone melting heating is a purification mainly utilizing a segregation action in an inert gas atmosphere or a reducing gas atmosphere, the above-mentioned (1),
There was exactly the same drawback as the method (2).
【０００６】これに対し、上記(4) の従来技術の場合、
高真空中で帯溶融加熱が行われるので、その精製効果
は、帯溶融時の偏析作用に加えて、高真空溶解による不
純物の蒸発除去作用も発生し、特に高融点金属などに対
して優れた精製効果が得られる。しかし、この技術は、
排気量の大きな高真空排気装置が必要であり、しかも高
真空を長時間保持することが必要になることから、装置
が大掛かりとなる欠点があり、経済的な高純度精製法で
はない。また、この技術は、高真空中での帯溶融精製方
法であることから、蒸気圧が高いホウ素などの精製は不
可能であり、蒸気圧が低い金属を帯溶融精製する場合に
おいても、目的金属自体の蒸発損失が増加するために、
歩留りが低下するという問題があった。On the other hand, in the case of the prior art (4),
Since the zone melting and heating are performed in a high vacuum, its refining effect is not only segregation at the time of zone melting, but also the effect of evaporating and removing impurities due to high vacuum melting. A purification effect is obtained. However, this technology
Since a high-vacuum evacuation device with a large displacement is required, and a high vacuum must be maintained for a long time, there is a drawback that the device becomes large-sized, and it is not an economical high-purity purification method. In addition, since this technique is a method for band melting and refining in a high vacuum, it is impossible to purify boron or the like having a high vapor pressure. Because the evaporation loss of itself increases
There was a problem that the yield was reduced.
【０００７】本発明の目的は、装置の大型化や操業の煩
雑化を招くことなく、金属不純物のみならず非金属不純
物までも容易に除去できる、経済的な高純度金属の精製
・回収技術を提供することにある。An object of the present invention is to economically purify a high-purity metal which can easily remove not only metal impurities but also non-metal impurities without increasing the size of the apparatus and complicating the operation.
・ To provide collection technology.
【０００８】[0008]
【課題を解決するための手段】発明者らは、上記各従来
技術が抱えている解決課題につき鋭意研究した。その結
果、プラズマアークが優れた高温加熱源であり、特にプ
ラズマ作動ガスに水素を使用する水素プラズマアークに
よって金属を溶解処理すると、単一溶解工程の処理で、
酸素などの非金属不純物および目的金属より蒸気圧が高
い金属不純物を容易に分離除去できるという知見を得
た。このように水素プラズマアーク溶解によって非金属
不純物および金属不純物が効果的に除去される理由は、
以下のような機構により生じるものと考えられる。Means for Solving the Problems The present inventors have conducted intensive research on the problems to be solved by the above prior arts. As a result, the plasma arc is an excellent high-temperature heating source, and particularly when the metal is melted by a hydrogen plasma arc using hydrogen as the plasma working gas, a single melting process is performed.
It has been found that nonmetallic impurities such as oxygen and metal impurities having a higher vapor pressure than the target metal can be easily separated and removed. The reason why non-metal impurities and metal impurities are effectively removed by hydrogen plasma arc melting is as follows.
It is thought to be caused by the following mechanism.
【０００９】一般に、プラズマアークの温度は5000〜20
000 ℃程度であり、一方、水素Ｈ2の解離度は5000℃で9
5〜96％に達する。従って、プラズマアークおよびアー
ク高温内に導入された水素Ｈ2 の大部分は、(1) 式のよ
うに解離し活性水素Ｈとして存在する。 Ｈ2 →Ｈ＋Ｈ …(1) この活性水素Ｈは、通常の水素Ｈ2 に比べて反応性、還
元性が著しく優れており、それ故に、この活性水素Ｈを
利用すると優れた精製効果が得られる。すなわち、被溶
解金属に含まれる非金属不純物、例えば、酸素（Ｏ）
は、下記(2) 式に示すように、活性水素Ｈとの反応によ
り還元除去される。同様にして、窒素や炭素なども除去
される。Ｏ ＋ ２Ｈ → Ｈ2 Ｏ …(2) さらに、被溶解金属より蒸気圧が高い金属不純物（蒸
気）は一般に、水素プラズマ相と接する溶融金属表面上
のガス側境界層内において、下記(3）式に示すように、 xＭ［蒸気］＋ yＨ［活性水素］→Ｍx Ｈy ［一次的な緩い結合］…(3) （Ｍ：被溶解金属中の金属不純物）反応し、高い蒸気圧
を有する金属不純物の蒸気と活性水素Ｈとが一次的な緩
い結合を生じ、活性水素Ｈがこれら金属不純物蒸気を捕
捉する形でガス相側に搬出し、その結果、高い蒸気圧を
有する金属不純物の蒸発除去を促進するのである。この
ことによって、高真空を用いない溶解法であるにもかか
わらず、水素プラズマアーク溶解では、被溶解金属中の
非金属不純物および金属不純物を極低濃度にまで除去す
ることができる。[0009] Generally, the temperature of the plasma arc is 5000 to 20
2,000 ° C., while the dissociation degree of hydrogen H 2 is 9
Reaches 5 to 96%. Therefore, most of the hydrogen H 2 introduced into the plasma arc and the high temperature of the arc is dissociated and exists as active hydrogen H as shown in equation (1). H 2 → H + H (1) The active hydrogen H has remarkably excellent reactivity and reducibility as compared with normal hydrogen H 2 , and therefore, if this active hydrogen H is used, an excellent purification effect can be obtained. . That is, non-metal impurities contained in the metal to be dissolved, for example, oxygen ( O 2 )
Is reduced and removed by reaction with active hydrogen H as shown in the following formula (2). Similarly, nitrogen and carbon are removed. O + 2H → H 2 O (2) Further, metal impurities (vapors) having a higher vapor pressure than the metal to be melted generally have the following (3) in the gas-side boundary layer on the surface of the molten metal in contact with the hydrogen plasma phase. As shown in the equation, xM [steam] + yH [active hydrogen] → Mx Hy [primary loose bond] (3) (M: metal impurities in the metal to be dissolved) The impurity vapor and the active hydrogen H form a temporary loose bond, and the active hydrogen H is carried out to the gas phase side in a form capturing these metal impurity vapors. As a result, the metal impurities having a high vapor pressure are removed by evaporation. To promote. As a result, non-metal impurities and metal impurities in the metal to be melted can be removed to an extremely low concentration by the hydrogen plasma arc melting, even though the melting method does not use a high vacuum.
【００１０】本発明は、この水素プラズマアーク溶解の
精製作用に着目して案出した、プラズマアークを加熱源
とした帯溶融精製法およびその精製装置である。すなわ
ち、本発明の要旨構成は次のとおりである。 (1) 公称純度が99.9mass％以上である高純度の金属に含
まれる不純物を単一溶解工程の処理で除去するに当たっ
て、プラズマアーク加熱により、水素含有雰囲気下に解
離した活性水素Ｈを発生させると同時に、帯溶融を行う
ことを特徴とする高純度金属の精製方法である。 (2) 上記(1) に記載の方法において、プラズマアークの
作動ガスとして、アルゴンまたはヘリウムとともに２〜
100 ％の水素を含むガスを使用することが望ましい。 (3) 上記(1) に記載の方法において、プラズマアーク加
熱による帯溶融に当たって、雰囲気中の内圧を３気圧〜
10トルに調整することが好ましい。 (4) プラズマアークを発生させるためのプラズマトー
チ、公称純度99.9mass％以上である被精製金属試料を載
置するための水平方向駆動装置を具える水冷銅ハースお
よび帯溶融用容器を有する帯溶融部と、前記プラズマア
ークの出力制御機構、前記水冷銅ハースの移動速度制御
機構および前記帯溶融用容器内の圧力制御機構を有する
制御系と、高純度ガス精製装置と、から主として構成さ
れることを特徴とする高純度金属の精製装置である。The present invention is a zone melting purification method using a plasma arc as a heating source and a purification apparatus therefor devised by focusing on the purification action of the hydrogen plasma arc melting. That is, the gist configuration of the present invention is as follows. (1) In removing impurities contained in a high-purity metal having a nominal purity of 99.9 mass% or more by a single melting step, active hydrogen H dissociated in a hydrogen-containing atmosphere is generated by plasma arc heating. At the same time, a method for refining a high-purity metal characterized by performing band melting. (2) The method according to (1), as the working gas for the plasma arc, an argon or helium are both 2
It is desirable to use a gas containing 100% hydrogen. (3) In the method according to the above (1), when the zone is melted by plasma arc heating, the internal pressure in the atmosphere is 3 atm.
Preferably adjusted to 10 torr. (4) A plasma torch for generating a plasma arc, a water-cooled copper hearth equipped with a horizontal drive for mounting a metal sample to be purified having a nominal purity of 99.9 mass% or more, and a band melting having a band melting container. Unit, a control system having an output control mechanism of the plasma arc, a movement speed control mechanism of the water-cooled copper hearth, and a pressure control mechanism in the band melting vessel, and a high-purity gas purification device. This is an apparatus for refining high purity metals.
【００１１】[0011]
【作用】ところで、常圧から３気圧程度の加圧下もしく
は10トル程度の減圧下で、高融点金属などを溶解処理す
る場合、従来技術では、金属不純物の除去，低減化が極
めて困難であった。これに対し、溶解雰囲気内に水素を
導入し、プラズマアークを加熱源にして帯溶融処理を実
施する本発明方法では、常圧から３気圧程度の加圧下も
しくは10トル程度の減圧下であっても、金属不純物を迅
速に除去でき、高融点金属などを容易に高純度化できる
ことが判った。When dissolving a high melting point metal or the like under a pressure of about 3 atm or a reduced pressure of about 10 torr from normal pressure, it is extremely difficult to remove and reduce metal impurities with the conventional technology. . On the other hand, in the method of the present invention in which hydrogen is introduced into the melting atmosphere and the band melting treatment is performed using the plasma arc as a heating source, the pressure is reduced from normal pressure to about 3 atm or reduced to about 10 torr. It was also found that metal impurities could be quickly removed, and high melting point metals and the like could be easily purified.
【００１２】すなわち、本発明にかかる精製方法は、帯
域溶融による偏析作用に加えて、プラズマアーク溶解に
よる不純物の蒸発除去作用を兼ね備えたプラズマアーク
帯溶融法であり、被溶解金属に含まれる酸素、炭素、窒
素などの非金属不純物、および金属不純物を効率的に分
離除去し、低減化できる、優れた金属の高純度化法であ
る。また、この方法は、高真空等を用いない精製方法で
あり、しかも、帯溶融時の操作、試料の交換および帯溶
融容器内の清掃等が非常に簡単であることから、装置の
簡略化、操業の簡便化を実現することができる。That is, the refining method according to the present invention is a plasma arc zone melting method having not only the segregation action by zone melting but also the action of evaporating and removing impurities by plasma arc melting. This is an excellent metal purification method capable of efficiently separating and removing non-metal impurities such as carbon and nitrogen, and metal impurities. In addition, this method is a purification method that does not use a high vacuum or the like, and furthermore, the operation at the time of band melting, the exchange of the sample and the cleaning of the inside of the band melting container, etc. are very simple, so that the apparatus can be simplified, Operation can be simplified.
【００１３】なお、プラズマアークは、出力調整によ
り、融点が数百℃から数千℃以上にわたる種々の金属を
加熱溶解することができる。したがって、プラズマアー
クを加熱源として用いる本発明の精製方法は、アルミニ
ウムや銅などの融点が比較的低い金属からニオブやタン
タルなどの高融点金属までの精製、具体的には、Fe,Cu,
Al,Zn,Pbなどの常用金属、Mg,Sc,Y,Ti,Zr,Hf,V,Nb,Ta,C
r,Mo,W,Mn,Re, Ru,Os,Co,Ni,Cd,In,Tl,Rh,Pd,Pt,Ag,Au,
La,Ce,Pr,Nd,Gd,Tb,Dyなどのレアメタル、Si,B,Ge,Biな
どの半金属、等ほぼ全ての金属および半金属の精製が可
能であり、実用的かつ経済的な高純度化法である。The plasma arc can heat and melt various metals whose melting point ranges from several hundred degrees Celsius to several thousand degrees Celsius by adjusting the output. Therefore, the purification method of the present invention using a plasma arc as a heating source, purification from relatively low melting point metal such as aluminum and copper to high melting point metal such as niobium and tantalum, specifically, Fe, Cu,
Common metals such as Al, Zn, Pb, Mg, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, C
r, Mo, W, Mn, Re, Ru, Os, Co, Ni, Cd, In, Tl, Rh, Pd, Pt, Ag, Au,
Almost all metals and semimetals such as rare metals such as La, Ce, Pr, Nd, Gd, Tb, and Dy, and semimetals such as Si, B, Ge, and Bi can be purified, making them practical and economical. It is a high purification method.
【００１４】また、前述した活性水素Ｈを発生させるた
めの溶解雰囲気の温度は、5000℃以上とすることが要求
されるが、この温度は水素分子の解離に必要な温度であ
り、この温度条件であれば、常圧から３気圧程度の加圧
下もしくは10トル程度の減圧下でも、有効な活性水素Ｈ
を得ることができる。Further, the temperature of the dissolving atmosphere for generating the above-mentioned active hydrogen H is required to be 5000 ° C. or higher, which is a temperature required for dissociation of hydrogen molecules. In this case, effective active hydrogen H can be used under normal pressure or about 3 atm or under reduced pressure of about 10 torr.
Can be obtained.
【００１５】したがって、本発明によれば、蒸気圧が高
いホウ素や希土類金属などの精製では、常圧から３気圧
程度の加圧下での帯溶融精製が可能であり、一方、高融
点金属など蒸気圧が低い金属の精製では、高真空を用い
ることなく、10トル程度の減圧下で帯溶融精製すること
ができる。以上のように、本発明は、目的金属の蒸気圧
に合わせて炉内圧を３気圧〜10トル程度に設定し、帯溶
融することが可能であることから、高真空中で行う帯溶
融などに較べ、目的金属の蒸発損失が極めて少なく、高
い歩留りの下に回収することができる。Therefore, according to the present invention, in the refining of boron or rare earth metal having a high vapor pressure, it is possible to purify the molten zone under a pressure of about 3 atm from normal pressure. In the purification of low pressure metals, zone melting and refining can be performed under reduced pressure of about 10 Torr without using high vacuum. As described above, the present invention sets the furnace pressure to about 3 atm to about 10 torr in accordance with the vapor pressure of the target metal, and can perform band melting. In comparison, the evaporation loss of the target metal is extremely small, and the target metal can be recovered at a high yield.
【００１６】次に、本発明の精製装置を説明する。図１
は本発明の精製装置全体を示す構成図である。即ち、本
発明の精製装置は、プラズマアークを発生させるための
プラズマトーチ１、このプラズマトーチ１の下方に位置
し被精製金属試料ａを載置するための水平方向駆動装置
16を具える水冷銅ハース２およびこの水冷銅ハース２を
支持するための帯溶融用容器３を有する帯溶融部と、前
記プラズマアークの出力制御機構、前記水冷銅ハース２
の移動速度制御機構および前記帯溶融用容器３内の圧力
制御機構を有する制御系と、高純度ガス精製装置15と、
から主として構成される。図２は上記帯溶融部を示す部
分断面図であり、図３は上記水冷銅ハース２を示す斜視
図である。Next, the purification apparatus of the present invention will be described. FIG.
FIG. 1 is a configuration diagram showing the entire purification apparatus of the present invention. That is, the refining device of the present invention comprises a plasma torch 1 for generating a plasma arc, and a horizontal driving device for placing a metal sample a to be purified and located below the plasma torch 1.
A water-cooled copper hearth 2 comprising a water-cooled copper hearth 2, a band-melting part having a band-melting vessel 3 for supporting the water-cooled copper hearth 2, an output control mechanism of the plasma arc,
A control system having a moving speed control mechanism and a pressure control mechanism in the zone melting vessel 3;
Mainly composed of FIG. 2 is a partial cross-sectional view showing the above-mentioned fusion zone, and FIG. 3 is a perspective view showing the water-cooled copper hearth 2.
【００１７】これらの図において、上記帯溶融部を構成
するプラズマトーチ１は、上記帯溶融用容器３の筒状胴
部に設けられた容器上蓋４に取り付けられており、プラ
ズマ発生用電源14に接続され、この電源14の出力調整に
より、被精製金属試料ａの帯溶融形成に最適なプラズマ
アークを発生させることができる。なお、前記容器上蓋
４はプラズマトーチ１の清掃または補修のために分解可
能である。In these figures, the plasma torch 1 constituting the band melting section is attached to a container upper lid 4 provided on a cylindrical body of the band melting container 3, and is connected to a plasma generating power supply 14. It is connected, and by adjusting the output of the power supply 14, it is possible to generate a plasma arc that is optimal for forming a molten zone of the metal sample a to be purified. The container upper lid 4 can be disassembled for cleaning or repairing the plasma torch 1.
【００１８】上記帯溶融部を構成する水冷銅ハース２
は、端面にフランジ12を設けて、このフランジ12と帯溶
融用容器３の軸方向の延在位置に外設された水平方向駆
動装置16から容器３内に伸びている移動用シャフト７の
遊端部とを固定することによって、容器３内の所定の位
置に空中保持されている。また、この水冷銅ハース２の
上面には、被精製金属試料ａを置くための溝10（溝幅約
５〜10ｍｍ、溝深さ約３〜６ｍｍ、溝長さ約 150〜200
ｍｍ）が設けてある。そして、水冷銅ハース２の中央部
には、軸方向に沿って穿孔してあり、その孔は前記シャ
フト７に通じており、外部から供給される冷却水を循環
させることができるようになっている。なお、このシャ
フト７と容器側壁とは、Ｏ−リング８などでシールされ
ている。即ち、該帯溶融容器３内を減圧状態にするため
に、水冷銅ハース２の水平方向移動時における外部から
容器３内部への空気の侵入を防ぐために設けたものであ
る。さらに、この水冷銅ハース２は、被精製金属試料ａ
の大きさや長さに対応した帯溶融を可能にすべく、溝10
の幅や長さが異なるものに交換可能である。A water-cooled copper hearth 2 forming the above-mentioned band fusion zone
Is provided with a flange 12 on the end face thereof, and the movement shaft 7 extending into the container 3 from the horizontal driving device 16 provided outside the flange 12 and the axially extending position of the band melting container 3. By fixing the end portion, it is held in the air at a predetermined position in the container 3. A groove 10 (groove width: about 5 to 10 mm, groove depth: about 3 to 6 mm, groove length: about 150 to 200) is provided on the upper surface of the water-cooled copper hearth 2.
mm). A hole is formed in the center of the water-cooled copper hearth 2 along the axial direction, and the hole communicates with the shaft 7 so that cooling water supplied from the outside can be circulated. I have. The shaft 7 and the container side wall are sealed with an O-ring 8 or the like. That is, it is provided to prevent air from entering the inside of the container 3 when the water-cooled copper hearth 2 moves in the horizontal direction in order to reduce the pressure inside the band melting container 3. Further, the water-cooled copper hearth 2 is a metal sample a
Groove 10 to enable band melting corresponding to the size and length of
Can be exchanged for different widths and lengths.
【００１９】上記帯溶融部を構成する帯溶融用容器３
は、ステンレス製円筒容器を横置きした密閉構造であ
り、その内部表面は電解研磨等によって鏡面仕上げされ
ている。また、この容器３の筒胴部の適所には、被精製
金属試料ａの交換および水冷銅ハース２の脱着を行うた
めの試料取り出し扉６を有し、その扉６を除く胴周部に
は、水冷管５を例えばスパイラル状に巻き付けた態様に
て設ける。さらに、帯溶融時の試料溶融状態を的確に把
握すべく、上記容器３の筒状胴部に設けられた容器上蓋
４には、斜め上から試料溶融状態を直接観察するための
覗窓９を好ましくは２か所、また容器３の水冷銅ハース
２を臨む胴部には、試料溶融状態やプラズマ発生状況を
観察するための覗窓９′を好ましくは１か所、設ける。
そして、このプラズマトーチ１を支持する帯溶融用容器
３は、排気系（図示せず）と制御系が取り付けられた架
台13上に設置されている。The band melting container 3 constituting the above-mentioned band melting section
Is a hermetically sealed structure in which a cylindrical container made of stainless steel is placed horizontally, and its inner surface is mirror-finished by electrolytic polishing or the like. Further, a sample take-out door 6 for exchanging the metal sample a to be purified and attaching / detaching the water-cooled copper hearth 2 is provided at an appropriate position of the cylindrical body of the container 3. The water cooling tube 5 is provided, for example, in a spirally wound manner. Further, in order to accurately grasp the sample melting state at the time of the band melting, a viewing window 9 for directly observing the sample melting state from diagonally above is provided on the container upper lid 4 provided on the cylindrical body of the container 3. Preferably, at two locations, and at the body of the container 3 facing the water-cooled copper hearth 2, there is provided, preferably, one viewing window 9 'for observing a sample melting state and a plasma generation state.
The band melting vessel 3 supporting the plasma torch 1 is installed on a gantry 13 to which an exhaust system (not shown) and a control system are attached.
【００２０】上記制御系は、架台13の前面パネルに、プ
ラズマアークの出力制御盤、水冷銅ハース２の移動速度
制御盤および容器３内の圧力制御盤を取り付けて構成す
る。そして、これらの装置に付帯させる装置としては、
例えば高純度ガス精製装置15および水平方向駆動装置16
がある。高純度ガス精製装置15は、プラズマアーク発生
用の作動ガスであるアルゴン、水素等を、酸素や水分を
除去して精製し、プラズマトーチ１の側面からプラズマ
トーチ内に供給するための付帯装置である。なお、供給
ガスの流量調整は、高純度ガス精製装置15に設けられた
調整器により行われ、毎分３〜10リットル程度に調整さ
れる。水平方向駆動装置16は、移動用シャフト７を介し
て水冷銅ハース２に連結されており、駆動モーター17の
速度を調節することにより、所望の溶融帯移動速度で帯
溶融を行うための付帯装置である。なお、駆動モーター
17は、一定の溶融帯移動速度を左右両方向に毎分 0.5〜
10ｍｍの範囲内で任意に設定できるものを使用する。The control system is constructed by attaching a plasma arc output control panel, a moving speed control panel for the water-cooled copper hearth 2 and a pressure control panel in the vessel 3 to the front panel of the gantry 13. And as a device attached to these devices,
For example, a high-purity gas purification device 15 and a horizontal drive device 16
There is. The high-purity gas purifier 15 is an auxiliary device for purifying argon, hydrogen, and the like, which are working gases for generating a plasma arc, by removing oxygen and moisture, and supplying the purified gas from the side of the plasma torch 1 into the plasma torch. is there. The flow rate of the supplied gas is adjusted by an adjuster provided in the high-purity gas purifying apparatus 15, and is adjusted to about 3 to 10 liters per minute. The horizontal driving device 16 is connected to the water-cooled copper hearth 2 via the moving shaft 7 and adjusts the speed of the driving motor 17 to perform band melting at a desired melting band moving speed. It is. The drive motor
17, the constant melting zone moving speed in both the left and right directions 0.5 ~
Use one that can be set arbitrarily within the range of 10 mm.
【００２１】次に、上述したような本発明の精製装置を
用いて高純度金属を精製する方法について図２にしたが
って説明する。 (1) まず、試料取出扉６を開け、被精製金属試料ａを水
冷銅ハース２の溝10に沿って載せる。ここで、被精製金
属試料ａは、塊状のものあるいは棒状のものいずれも使
用することができる。特に、棒状金属試料の場合は、長
さが100 〜200mm 程度、直径（または幅）が５〜10mm程
度のものが好適であり、試料直径（または幅）と同程度
の溝幅を持つ水冷銅ハース２を使用することが望まし
い。一方、塊状金属試料の場合は、帯溶融後に得られる
棒状試料の横幅および長さを考慮に入れ、これに適した
溝10を有する水冷銅ハース２を使用することが望まし
い。Next, a method for purifying a high-purity metal using the purifying apparatus of the present invention as described above will be described with reference to FIG. (1) First, the sample removal door 6 is opened, and the metal sample a to be purified is placed along the groove 10 of the water-cooled copper hearth 2. Here, as the metal sample a to be purified, either a lump-shaped or rod-shaped metal sample can be used. In particular, in the case of a rod-shaped metal sample, a sample having a length of about 100 to 200 mm and a diameter (or width) of about 5 to 10 mm is preferable, and a water-cooled copper having a groove width substantially equal to the sample diameter (or width). It is desirable to use Haas 2. On the other hand, in the case of a massive metal sample, it is desirable to use a water-cooled copper hearth 2 having a groove 10 suitable for this, taking into account the width and length of the rod-like sample obtained after the band is melted.
【００２２】(2) 次に、水冷銅ハース２に載せた金属試
料の先端（図２の向かって左端）が、プラズマトーチ１
の直下にくるように、水平方向駆動装置16と駆動モータ
ー17とを作動させて、水冷銅ハース２を移動させた後、
回転真空ポンプ（図示せず）を作動して帯溶融容器３内
を減圧する。 (3) 減圧排気した後、帯溶融容器３内を１気圧になるま
で精製アルゴンガスで満たし、その後、アルゴンガスが
一定流速でプラズマトーチ１を通して帯溶融容器３内に
供給される状態とした。 (4) そして、水冷銅ハース２には冷却水を流し、この状
態でプラズマアークを点火し、所定のプラズマ出力に上
げ、水冷銅ハース２上に載せた被精製金属試料ａの先端
（図２の向かって左端）の溶融を開始する。(2) Next, the tip of the metal sample placed on the water-cooled copper hearth 2 (the left end in FIG. 2) is the plasma torch 1
The water-cooled copper hearth 2 is moved by operating the horizontal driving device 16 and the driving motor 17 so as to be directly below the
The inside of the zone melting vessel 3 is depressurized by operating a rotary vacuum pump (not shown). (3) After evacuating under reduced pressure, the inside of the zone melting container 3 was filled with purified argon gas until the pressure reached 1 atm, and then the argon gas was supplied into the zone melting container 3 through the plasma torch 1 at a constant flow rate. (4) Then, cooling water is supplied to the water-cooled copper hearth 2, a plasma arc is ignited in this state, the plasma output is raised to a predetermined value, and the tip of the metal sample a to be purified placed on the water-cooled copper hearth 2 (FIG. (Left end of the glass).
【００２３】(5) プラズマアークが安定した後、精製水
素をプラズマトーチ１に供給し、水素プラズマアーク加
熱に変換する。ここで、プラズマガス中の水素含有量は
２〜100 ％の範囲とする。 (6) その後、所定の移動速度（帯溶融移動速度）で水冷
銅ハース２を図２の向かって左側に動かし、帯溶融を開
始する。 (7) 被精製金属試料ａの先端（図２の向かって左端）か
ら開始した溶融帯が後端（図２の向かって右端）に達す
ると精製は終了する。必要に応じて同様な帯溶融を複数
回繰り返す。(5) After the plasma arc is stabilized, purified hydrogen is supplied to the plasma torch 1 and converted into hydrogen plasma arc heating. Here, the hydrogen content in the plasma gas is in the range of 2 to 100%. (6) Thereafter, the water-cooled copper hearth 2 is moved to the left side in FIG. 2 at a predetermined moving speed (band melting moving speed) to start band melting. (7) When the molten zone starting from the front end (the left end in FIG. 2) of the metal sample a reaches the rear end (the right end in FIG. 2), the purification ends. The same band melting is repeated a plurality of times as necessary.
【００２４】なお、減圧下でプラズマアーク帯溶融を実
施する場合には、排気系に設置されたダイアフラム真空
ポンプまたは油回転真空ポンプ（図示せず）を稼動し、
オリフィスを用いた流量調整器（図示せず）により排気
速度を制御することにより、容器３内部を10〜100 トル
程度の範囲内で一定の減圧状態を保持しながら、上記と
同様な手順で帯溶融を行う。When melting the plasma arc zone under reduced pressure, a diaphragm vacuum pump or an oil rotary vacuum pump (not shown) installed in the exhaust system is operated.
By controlling the pumping speed by a flow controller (not shown) using an orifice, the inside of the container 3 is maintained in a constant reduced pressure within a range of about 10 to 100 torr, and the pressure is controlled in the same procedure as described above. Perform melting.
【００２５】[0025]
【実施例】以下、本発明を実施例により具体的に説明す
る。 （実施例１）レアメタルの１つであり融点の高い Ta の
精製例を以下に示す。公称純度99.9％の比較的高純度の
Ta 約50ｇ（直径約５mm，長さ150mm ）を、プラズマガ
ス；40％H2−Ar、圧力；100 トル、溶融帯移動速度；２
mm／min 、パス回数；10回の条件でプラズマ帯溶融処理
した時の、帯溶融処理前後のTa中の金属不純物および非
金属不純物の濃度を、表１に示す。金属不純物分析には
グロー放電質量分析法を使用し、一方、非金属不純物分
析には不活性ガス融解法および酸素ガス融解法等を使用
した。なお、処理後の不純物濃度は、高純度化部（試料
中央部）の分析値である。この表１に示すとおり、原料
Ta中のAl,Fe,Cu, 酸素等の不純物は、水素プラズマ溶解
の精製作用を経ることで除去低減され、さらに、各金属
不純物は、帯溶融時の偏析作用を経ることで１mass ppm
以下の極微量にまで低減化することができた。すなわ
ち、煩雑で厳密な工程管理が必要となる多段階の工程を
経ることなく、単一の溶解工程により金属不純物および
非金属不純物が極低濃度域まで低減させることが可能で
ある。しかも、帯溶融時の Ta の蒸発損失は小さく、 T
a の歩留りは約98％と良好であった。なお、その他の希
土類金属についても、プラズマ帯溶融処理によって同様
の精製効果が認められた。The present invention will be described below in more detail with reference to examples. (Example 1) An example of the purification of Ta, which is one of the rare metals and has a high melting point, is shown below. Relatively high purity of 99.9% nominal purity
About 50 g of Ta (about 5 mm in diameter and 150 mm in length) were charged with plasma gas; 40% H 2 -Ar, pressure;
Table 1 shows the concentrations of metallic impurities and nonmetallic impurities in Ta before and after the band melting treatment when the plasma band melting treatment was performed under the conditions of mm / min and the number of passes: 10 times. Glow discharge mass spectrometry was used for metal impurity analysis, while inert gas melting and oxygen gas melting were used for non-metallic impurity analysis. The impurity concentration after the treatment is an analysis value of the highly purified part (the center part of the sample). As shown in Table 1, the raw materials
Impurities such as Al, Fe, Cu, and oxygen in Ta are removed and reduced by the purification action of hydrogen plasma dissolution, and each metal impurity is separated by 1 mass ppm through the segregation action during band melting.
It was possible to reduce to the following trace amounts. That is, it is possible to reduce metal impurities and nonmetal impurities to an extremely low concentration region by a single melting step without going through a multi-step process requiring complicated and strict process control. In addition, the evaporation loss of Ta during zone melting is small,
The yield of a was good at about 98%. Similar refining effects were also observed for other rare earth metals by the plasma zone melting treatment.
【００２６】[0026]
【表１】 [Table 1]
【００２７】（実施例２）常用金属の１つである Cu の
精製例を以下に示す。公称純度99.9％の比較的高純度の
Cu 約 100ｇ（直径約10mm，長さ150mm ）を、プラズマ
ガス；20％H2−Ar、圧力；１気圧、溶融帯移動速度；３
mm／min 、パス回数；10回の条件でプラズマ帯溶融処理
した時の、帯溶融処理前後のCu中の金属不純物および非
金属不純物の濃度を、表２に示す。金属不純物分析には
グロー放電質量分析法を使用し、一方、非金属不純物分
析には不活性ガス融解法および酸素ガス融解法等を使用
した。なお、処理後の不純物濃度は、高純度化部（試料
中央部）の分析値である。この表２に示すとおり、原料
Cu中のPb,Ca,Al,S 等の不純物は、水素プラズマ溶解の
精製作用を経ることで低濃度にまで除去低減され、さら
に、水素プラズマ溶解だけでは低減化の難しいFe,Ni,Si
等の各金属不純物も、帯溶融時の偏析作用を経ることで
１mass ppm以下の極微量にまで低減化することができ、
99.999％以上の高純度Cuが得られた。すなわち、単一の
溶解工程により、Cu中の金属不純物および非金属不純物
は極低濃度まで低減でき、高純度Cuを回収することが可
能であることが確かめられた。しかも、帯溶融時の Cu
の蒸発損失は小さく、 Cu の歩留りは約95％と良好であ
った。なお、その他の常用金属についても、プラズマ帯
溶融処理によって同様の精製効果が認められた。(Example 2) An example of purification of Cu, one of the common metals, is shown below. Relatively high purity of 99.9% nominal purity
About 100 g of Cu (about 10 mm in diameter and 150 mm in length) were charged with plasma gas; 20% H 2 -Ar, pressure;
Table 2 shows the concentrations of metallic impurities and nonmetallic impurities in Cu before and after the band melting treatment when plasma band melting treatment was performed under the conditions of mm / min and the number of passes: 10 times. Glow discharge mass spectrometry was used for metal impurity analysis, while inert gas melting and oxygen gas melting were used for non-metallic impurity analysis. The impurity concentration after the treatment is an analysis value of the highly purified part (the center part of the sample). As shown in Table 2, the raw materials
Impurities such as Pb, Ca, Al, and S in Cu are removed and reduced to a low concentration through the purification action of hydrogen plasma dissolution, and further, it is difficult to reduce Fe, Ni, Si by hydrogen plasma dissolution alone.
Each metal impurity such as can also be reduced to an extremely small amount of 1 mass ppm or less by undergoing segregation at the time of band melting.
High purity Cu of 99.999% or more was obtained. That is, it was confirmed that metal impurities and nonmetal impurities in Cu can be reduced to an extremely low concentration by a single melting step, and high-purity Cu can be recovered. In addition, Cu
The evaporation loss was small, and the Cu yield was good at about 95%. In addition, similar refining effects were also recognized for other common metals by the plasma zone melting treatment.
【００２８】[0028]
【表２】 [Table 2]
【００２９】（実施例３）半金属の１つであるシリコン
の精製例を以下に示す。公称純度99.9％の比較的高純度
のシリコン約40ｇ（直径約10mm，長さ200mm ）を、プラ
ズマガス；50％H2−Ar、圧力；70トル、溶融帯移動速
度；１mm／min 、パス回数；10回の条件でプラズマ帯溶
融処理した時の、帯溶融処理前後のシリコン中の金属不
純物および非金属不純物の濃度を、表３に示す。金属不
純物分析にはグロー放電質量分析法を使用し、一方、非
金属不純物分析には不活性ガス融解法および酸素ガス融
解法等を使用した。なお、処理後の不純物濃度は、高純
度化部（試料中央部）の分析値である。この表３に示す
とおり、原料シリコン中のCa,Al,Mn, 酸素等の不純物
は、水素プラズマ溶解の精製作用を経ることで10mass p
pm以下の低濃度にまで除去低減され、さらに、水素プラ
ズマ溶解だけでは低減化の難しいFe,Ti,Cu,V 等の各金
属不純物も、帯溶融時の偏析作用を経ることで10mass p
pm以下の低濃度にまで低減化することができ、99.99 ％
以上の高純度シリコンが得られた。すなわち、単一の溶
解工程により、シリコン中の金属不純物および非金属不
純物は極低濃度まで低減でき、高純度シリコンを回収す
ることが可能であることが確かめられた。しかも、帯溶
融時の Si の蒸発損失は小さく、 Si の歩留りは約90％
と良好であった。なお、その他の半金属についても、プ
ラズマ帯溶融処理によって同様の精製効果が認められ
た。(Example 3) An example of refining silicon, which is one of the metalloids, is shown below. Approximately 40 g (approximately 10 mm in diameter, 200 mm in length) of relatively pure silicon having a nominal purity of 99.9%, plasma gas: 50% H 2 -Ar, pressure: 70 torr, melting zone moving speed: 1 mm / min, number of passes Table 3 shows the concentrations of metallic impurities and nonmetallic impurities in silicon before and after the band melting treatment when the plasma band melting treatment was performed 10 times. Glow discharge mass spectrometry was used for metal impurity analysis, while inert gas melting and oxygen gas melting were used for non-metallic impurity analysis. The impurity concentration after the treatment is an analysis value of the highly purified part (the center part of the sample). As shown in Table 3, impurities such as Ca, Al, Mn, and oxygen in the raw silicon were reduced to 10 mass p
pm or less, and each metal impurity such as Fe, Ti, Cu, V, etc., which is difficult to reduce by hydrogen plasma melting alone, undergoes segregation during band melting to 10 mass p
It can be reduced to low concentration below pm, 99.99%
The above high-purity silicon was obtained. That is, it was confirmed that the metal impurities and nonmetal impurities in silicon can be reduced to an extremely low concentration by a single melting step, and high-purity silicon can be recovered. In addition, the evaporation loss of Si during band melting is small, and the yield of Si is about 90%.
And was good. Similar refining effects were also observed for the other semimetals by the plasma zone melting treatment.
【００３０】[0030]
【表３】 [Table 3]
【００３１】[0031]
【発明の効果】以上説明したように、本発明は、帯域溶
融による偏析作用に加えて、プラズマアーク溶解による
不純物の蒸発除去作用を兼ね備えた精製技術であり、被
溶解金属に含まれる非金属不純物および金属不純物を、
単一溶解工程の処理で効率的に極低濃度にまで除去する
ことができ、金属の高純度化法として有効である。しか
も、本発明は、高真空等を用いない精製技術であり、帯
溶融時の操作、試料の交換および帯溶融容器内の清掃等
が非常に簡単であることから、装置の簡略化、操業の簡
便化を実現することができる。さらに、本発明は粗金属
からの高純度金属の回収法としても効果的であり、産業
上極めて有用と言える。As described above, the present invention is a purification technique having not only the segregation effect due to zone melting but also the effect of evaporating and removing impurities by plasma arc melting. And metal impurities,
It can be efficiently removed to an extremely low concentration by a single dissolution process, and is effective as a method for purifying metals. In addition, the present invention is a purification technique that does not use a high vacuum or the like, and since the operation at the time of band melting, the exchange of the sample and the cleaning of the inside of the band melting container are very simple, the simplification of the apparatus and the operation Simplification can be realized. Furthermore, the present invention is also effective as a method for recovering high-purity metal from crude metal, and can be said to be extremely useful in industry.
【図１】本発明の精製装置全体を示す構成図である。FIG. 1 is a configuration diagram showing the entire purification apparatus of the present invention.
【図２】本発明の精製装置を構成する帯溶融部を示す部
分断面図である。FIG. 2 is a partial cross-sectional view showing a band melting section constituting the refining device of the present invention.
【図３】本発明の精製装置を構成する水冷銅ハースを示
す斜視図である。FIG. 3 is a perspective view showing a water-cooled copper hearth constituting the purifying apparatus of the present invention.
１ プラズマトーチ ２ 水冷銅ハース ３ 帯溶融用容器 ４ 容器上蓋 ５ 水冷管 ６ 試料取り出し扉 ７ 移動用シャフト ８ Ｏ−リング ９，９′覗窓 13 架台 14 プラズマ発生用電源 15 高純度ガス精製装置 16 水平方向駆動装置 17 駆動モーター DESCRIPTION OF SYMBOLS 1 Plasma torch 2 Water-cooled copper hearth 3 Band melting vessel 4 Container top lid 5 Water cooling tube 6 Sample removal door 7 Moving shaft 8 O-ring 9, 9 'viewing window 13 Mounting stand 14 Plasma generation power supply 15 High-purity gas purification equipment 16 Horizontal drive 17 Drive motor
───────────────────────────────────────────────────── フロントページの続き (72)発明者 相澤 憲司 宮城県仙台市太白区向山１丁目４−18 (56)参考文献 特開 平６−88145（ＪＰ，Ａ) 特開 昭64−73028（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C22B 9/00 - 9/22 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kenji Aizawa 1-4-18 Mukaiyama, Taishiro-ku, Sendai City, Miyagi Prefecture (56) References JP-A-6-88145 (JP, A) JP-A 64-73028 (JP) , A) (58) Field surveyed (Int. Cl. 6 , DB name) C22B 9/00-9/22
Claims (4)
金属に含まれる不純物を単一溶解工程の処理で除去する
に当たって、プラズマアーク加熱により、水素含有雰囲
気下に解離した活性水素Ｈを発生させると同時に、帯溶
融を行うことを特徴とする高純度金属の精製方法。1. A method for removing impurities contained in a high-purity metal having a nominal purity of 99.9 mass% or more by a single melting step, in which an activity dissociated in a hydrogen-containing atmosphere by plasma arc heating. A method for purifying a high-purity metal, which comprises simultaneously performing hydrogen melting and band melting.
ゴンまたはヘリウムとともに２〜100 ％の水素を含むガ
スを使用することを特徴とする請求項１に記載の精製方
法。As wherein plasma arc working gas purification method according to claim 1, characterized in that the use of A Le <br/> Gon or helium are both 2-100% of a gas containing hydrogen.
って、雰囲気中の内圧を３気圧〜10トルに調整すること
を特徴とする請求項１または２に記載の精製方法。3. The refining method according to claim 1, wherein the inner pressure in the atmosphere is adjusted to 3 atm to 10 torr during the zone melting by plasma arc heating.
ズマトーチ、公称純度99.9mass％以上である被精製金属
試料を載置するための水平方向駆動装置を具える水冷銅
ハースおよび帯溶融用容器を有する帯溶融部と、前記プ
ラズマアークの出力制御機構、前記水冷銅ハースの移動
速度制御機構および前記帯溶融用容器内の圧力制御機構
を有する制御系と、高純度ガス精製装置と、から主とし
て構成されることを特徴とする高純度金属の精製装置。4. A water-cooled copper hearth comprising a plasma torch for generating a plasma arc, a horizontal driving device for mounting a metal sample to be purified having a nominal purity of 99.9 mass% or more, and a vessel for melting a band. It mainly comprises a band melting section, a control system having an output control mechanism for the plasma arc, a movement speed control mechanism for the water-cooled copper hearth, and a pressure control mechanism in the band melting vessel, and a high-purity gas purification device. An apparatus for refining high-purity metals.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6227095A JP2960652B2 (en) | 1994-09-21 | 1994-09-21 | Method and apparatus for purifying high purity metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6227095A JP2960652B2 (en) | 1994-09-21 | 1994-09-21 | Method and apparatus for purifying high purity metal |
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| Publication Number | Publication Date |
|---|---|
| JPH0892662A JPH0892662A (en) | 1996-04-09 |
| JP2960652B2 true JP2960652B2 (en) | 1999-10-12 |
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| JP2002180112A (en) * | 2000-12-19 | 2002-06-26 | Hitachi Metals Ltd | Method for manufacturing high melting point metal powder material |
| JP5097890B2 (en) * | 2001-03-13 | 2012-12-12 | 株式会社アルバック | Method for producing gold or gold alloy for vacuum deposition or sputtering, and method for producing hearth ingot |
| RU2403953C2 (en) * | 2005-05-17 | 2010-11-20 | Макс-Планк-Гезельшафт Зур Фёрдерунг Дер Виссеншафтен Е.В. | Purification of materials by hydrogen-based plasma |
| KR100751536B1 (en) * | 2006-03-06 | 2007-08-23 | 한국생산기술연구원 | High Purity Copper Manufacturing Equipment Using Horizontal Multi-Zone Melting |
| US8980169B2 (en) | 2007-12-28 | 2015-03-17 | Jx Nippon Mining & Metals Corporation | High-purity lanthanum, sputtering target comprising high-purity lanthanum, and metal gate film mainly comprising high-purity lanthanum |
| JP5456913B2 (en) | 2011-01-21 | 2014-04-02 | Ｊｘ日鉱日石金属株式会社 | Method for producing high purity lanthanum |
| CN102828233A (en) * | 2012-08-17 | 2012-12-19 | 德阳瑞能电力科技有限公司 | Monocrystalline silicon zone melting drawing furnace control system |
| US10494712B2 (en) | 2015-05-21 | 2019-12-03 | Jx Nippon Mining & Metals Corporation | Copper alloy sputtering target and method for manufacturing same |
| CN116083729A (en) * | 2022-12-23 | 2023-05-09 | 武汉拓材科技有限公司 | Metal purifying device and method and application thereof |
| CN115948657B (en) * | 2022-12-26 | 2025-05-09 | 江苏美特林科特殊合金股份有限公司 | A method for purifying and recovering high-temperature alloy return material |
| CN117965927B (en) * | 2024-04-01 | 2024-06-21 | 北京科技大学 | High-temperature alloy return material purifying smelting method based on hydrogen plasma blowing |
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