JPH06173064A - Method for refining ti - Google Patents
Method for refining tiInfo
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- JPH06173064A JPH06173064A JP35154192A JP35154192A JPH06173064A JP H06173064 A JPH06173064 A JP H06173064A JP 35154192 A JP35154192 A JP 35154192A JP 35154192 A JP35154192 A JP 35154192A JP H06173064 A JPH06173064 A JP H06173064A
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- purity
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- electrolysis
- electrodeposited
- molten salt
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、溶融塩電解法によるＴ
ｉの精製法に関する。本発明により得られる高純度Ｔｉ
は、金属不純物が極微量まで低減されており、半導体デ
バイス製造用のタ−ゲット材等として、好適である。BACKGROUND OF THE INVENTION The present invention relates to T by the molten salt electrolysis method.
i purification method. High-purity Ti obtained by the present invention
The metal impurities are reduced to an extremely small amount, and is suitable as a target material for manufacturing semiconductor devices.
【０００２】[0002]
【従来技術】溶融塩電解法によるＴｉの電解精製に用い
られる電解浴として、一般に、塩化物浴（代表例：Ｎａ
Ｃｌ−ＫＣｌ−ＴｉＣｌ2−ＴｉＣｌ3）、塩化物−弗化
物混浴（代表例：ＮａＣｌ−Ｋ2ＴｉＦ6）、弗化物浴
（代表例：ＮａＦ−Ｋ2ＴｉＦ6）等が知られている。As an electrolytic bath used for electrolytic refining of Ti by a molten salt electrolysis method, a chloride bath (typical example: Na) is generally used.
Cl-KCl-TiCl 2 -TiCl 3 ), chloride - fluoride mixed bathing (typical example: NaCl-K 2 TiF 6) , fluoride bath (typical example: NaF-K 2 TiF 6) and the like are known.
【０００３】しかしながら、高純度Ｔｉ製造のための溶
融塩電解精製法においては、一般にバッチ式であり、粗
Ｔｉを浴中にセットし電解を行い、電解浴中の不純物含
有量が多くなった時点で、電解を終了するため連続的に
高純度Ｔｉを得ることができなかった。さらに、この方
法では、浴の寿命が短く、コストが高いという問題点が
あった。However, the molten salt electrolytic refining method for producing high-purity Ti is generally of a batch type, and when crude Ti is set in a bath for electrolysis, the content of impurities in the electrolytic bath becomes large. However, since the electrolysis was completed, high purity Ti could not be continuously obtained. Further, this method has a problem that the life of the bath is short and the cost is high.
【０００４】[0004]
【問題点を解決するための手段】そこで、本発明者等
が、溶融塩電解精製法において、高純度Ｔｉを連続的に
得る方法について鋭意検討して結果、電解精製時にカソ
−ドに電着する高純度Ｔｉ重量と同量以上のアノ−ドで
ある粗Ｔｉを少なくとも間欠的に補加することにより、
上記問題点が解決できることを見出した。従って、本発
明の目的は、高純度Ｔｉを連続的に得ることができる、
溶融塩電解法によるＴｉの精製方法を提供することにあ
る。Therefore, the present inventors diligently studied a method for continuously obtaining high-purity Ti in a molten salt electrolytic refining method, and as a result, electrodeposition on a cathode during electrolytic refining By at least intermittently adding crude Ti, which is an anode of the same amount or more as the high purity Ti weight,
It has been found that the above problems can be solved. Therefore, the object of the present invention is to obtain high-purity Ti continuously,
It is intended to provide a method for purifying Ti by a molten salt electrolysis method.
【０００５】[0005]
【発明の構成】即ち本発明は、溶融塩電解法で粗Ｔｉを
電解精製する方法において、少なくとも間欠的に電着し
たＴｉ重量と同量以上の粗Ｔｉを補加して電解を行うこ
とを特徴とするＴｉの精製方法を提供する。That is, in the present invention, in a method for electrolytically purifying crude Ti by a molten salt electrolysis method, electrolysis is performed by supplementing at least the same amount of crude Ti as the weight of Ti electrodeposited intermittently. A method for purifying characteristic Ti is provided.
【０００６】[0006]
【発明の具体的説明】次に本発明の理解を容易にするた
め具体的かつ詳細に説明する。まず、本発明の対象とな
る粗Ｔｉの純度は、特に制限はないが、通常市販されて
いる純度９９〜９９．９９ｗｔ％のものである。カソ−
ドとしては、電着する高純度Ｔｉを汚染しないもの例え
ばＴｉ，Ｎｉ，Ｗ，Ｍｏ等であり、好ましくはＴｉ、よ
り好ましくは通常目的とする純度以上の高純度Ｔｉであ
る。DETAILED DESCRIPTION OF THE INVENTION Next, a specific and detailed description will be given to facilitate understanding of the present invention. First, the purity of crude Ti which is the subject of the present invention is not particularly limited, but it is usually commercially available with a purity of 99 to 99.99 wt%. Caso
As the electrode, those which do not contaminate the high-purity Ti to be electrodeposited, such as Ti, Ni, W, Mo, etc., are preferably Ti, and more preferably high-purity Ti having a purity higher than the intended purity.
【０００７】次に本発明に用いられる溶融塩としては、
塩化物浴（代表例：ＮａＣｌ−ＫＣｌ−ＴｉＣｌ2−Ｔ
ｉＣｌ3）、塩化物−弗化物混浴（代表例：ＮａＣｌ−
Ｋ2ＴｉＦ6）、弗化物浴（代表例：ＮａＦ−Ｋ2Ｔｉ
Ｆ6）等があるが、ここでは、代表的に塩化物浴を例と
して説明する。Next, as the molten salt used in the present invention,
Chloride bath (typical example: NaCl-KCl-TiCl 2 -T
iCl 3), chloride - fluoride mixed bathing (typical example: NaCl-
K 2 TiF 6), fluoride bath (typical example: NaF-K 2 Ti
F 6 ), etc., but here, a chloride bath will be representatively described as an example.
【０００８】まず、アルカリ金属溶融塩の溶媒として
は、例えばＮａＣｌ，ＮａＣｌ−ＫＣｌ（モル比＝４０
〜６０：６０〜４０）、ＬｉＣｌ−ＫＣｌ（モル比＝４
０〜６０：６０〜４０）等があり、溶質として、ＴｉＣ
ｌ2、ＴｉＣｌ3、ＴｉＣｌ4等がある。以上のような塩
は、通常、重金属、高融点金属、放射性元素等の不純物
の少ない純度の高いもの、具体的には、揮発性の不純物
元素除きで純度９９．９ｗｔ％以上、好ましくは純度９
９．９９ｗｔ％以上のものを使用しなければならない。
９９．９ｗｔ％以下のものを用いると、電析したＴｉが
汚染を受けてしまうからである。First, as a solvent of the molten alkali metal salt, for example, NaCl, NaCl-KCl (molar ratio = 40
~ 60: 60-40), LiCl-KCl (molar ratio = 4
0-60: 60-40), etc., and solute as TiC
l 2 , TiCl 3 , TiCl 4 and the like. The salt as described above is usually a high-purity salt containing few impurities such as heavy metals, high-melting-point metals, and radioactive elements, specifically, a purity of 99.9 wt% or more, preferably 9% by weight, excluding volatile impurities.
It must use 9.99 wt% or more.
This is because if 99.9 wt% or less is used, the electrodeposited Ti will be contaminated.
【０００９】これらを用いて粗Ｔｉを電解精製する際
に、少なくとも間欠的に粗Ｔｉを補加するのが本発明の
特徴である。少なくとも間欠的にとは、連続的又はある
一定間隔をおいてということを意味する。この間隔につ
いては、設備、電解条件等により異なり一律に決めるこ
とはできないが、実際には目的とするＴｉの純度と電解
精製により得られるＴｉの純度を考慮に入れて決定され
る。It is a feature of the present invention that the crude Ti is supplemented at least intermittently when the crude Ti is electrolytically refined using these materials. At least intermittently means continuously or at certain intervals. This interval differs depending on the equipment, electrolysis conditions and the like and cannot be uniformly determined, but in practice, it is determined in consideration of the target purity of Ti and the purity of Ti obtained by electrolytic refining.
【００１０】この様にしないと、電解精製を行っていく
につれ、スライムが発生し、そのことにより溶出電位が
高くなって、不純物の高いスライムからの溶出量が多く
なり、目的とする高純度Ｔｉを連続的に得ることはでき
ない。即ち、新たな粗Ｔｉを補加することにより、補加
した粗Ｔｉのみが溶け、スライムからの溶出がほとんど
なくなるため、溶融塩電解浴中の不純物濃度が増加しな
くなり、より多くの純度９９．９９９９ｗｔ％（以下、
単に６Ｎと記す）以上の高純度Ｔｉを連続的に得ること
がでると共に、浴の寿命も長くなるものと考えられる。If this is not done, slime is generated as the electrolytic refining is carried out. As a result, the elution potential is increased, and the elution amount from the slime containing a large amount of impurities is increased. Cannot be obtained continuously. That is, by supplementing new crude Ti, only the supplemented crude Ti is melted, and elution from slime is almost eliminated, so that the impurity concentration in the molten salt electrolytic bath is not increased, and a higher purity of 99. 9999 wt% (hereinafter,
It is considered that high purity Ti of 6 N or more) can be continuously obtained, and the life of the bath is extended.
【００１１】次にＴｉの溶融塩電解精製例を具体的に示
す。まず、使用する塩は、事前に十分真空乾燥脱水し、
水分等の除去を行なうことが必要である。そして、Ｎｉ
ルツボ中にＮａＣｌ−ＫＣｌ（モル比＝４０〜６０：６
０〜４０）を入れ、アノ−ドである粗ＴｉスポンジをＮ
ｉルツボの内壁に設けたバスケット中に挿入し、そして
カソ−ドとしてＴｉ棒をＮｉルツボの中心に配置する。
これらは全てＡｒ置換された密封容器中に入れられる。Next, a specific example of molten salt electrolytic refining of Ti will be specifically shown. First, the salt to be used is thoroughly vacuum dried and dehydrated in advance,
It is necessary to remove water and the like. And Ni
NaCl-KCl (molar ratio = 40-60: 6 in crucible)
0-40) and put the crude Ti sponge which is an anode into N
Insert into a basket provided on the inner wall of the i crucible, and place a Ti rod as a cathode in the center of the Ni crucible.
All of these are placed in a sealed container with Ar substitution.
【００１２】そして、加熱することにより、ＮａＣｌ−
ＫＣｌを溶融状態にした後、ＴｉＣｌ4を導入する。こ
れにより、浴中で以下の反応を進行せしめ、ＮａＣｌ−
ＫＣｌ浴中にＴｉＣｌ2、ＴｉＣｌ3を生成せしめる。
が主反応である。 ＴｉＣｌ4＋Ｔｉ→２ＴｉＣｌ2 …………… ＴｉＣｌ2＋ＴｉＣｌ4→２ＴｉＣｌ3 ……… これにより、ＮａＣｌ−ＫＣｌ−ＴｉＣｌ2−ＴｉＣｌ3
（モル比：ＮａＣｌ：ＫＣｌ＝４０〜６０：６０〜４
０，Ｔｉ＝１〜４ｗｔ％）の溶融塩電解浴ができる。Then, by heating, NaCl-
After bringing KCl into a molten state, TiCl 4 is introduced. This allows the following reactions to proceed in the bath, NaCl-
TiCl 2 and TiCl 3 are formed in the KCl bath.
Is the main reaction. TiCl 4 + Ti → 2TiCl 2 …………… TiCl 2 + TiCl 4 → 2TiCl 3 ……… As a result, NaCl-KCl-TiCl 2 -TiCl 3
(Molar ratio: NaCl: KCl = 40-60: 60-4
(0, Ti = 1 to 4 wt%) molten salt electrolytic bath can be formed.
【００１３】溶融塩電解浴中のＴｉ濃度は、添加するＴ
ｉＣｌ4により決まるが、上記、の反応を考慮に入
れＴｉ濃度として、１〜４ｗｔ％になるようにＴｉＣｌ
4を添加することが好ましく、より好ましいＴｉ濃度
は、１．５〜３ｗｔ％である。この範囲内では、電流効
率も良く、電析状態は樹枝状となり、粒の大きさも大き
い。しかし、１ｗｔ％未満であると、カソ−ド棒に電着
しなかったり、電流効率が非常に低いものとなってしま
い好ましくない。また、電着したＴｉの粒度も非常に小
さくなる。４ｗｔ％を超えると、電流効率が低くなり、
電析形態もスポンジ状となり、Ｔｉに付着した溶融塩等
の分離が不十分となり、高純度のＴｉが得にくい。The concentration of Ti in the molten salt electrolytic bath depends on the T added.
It depends on iCl 4 , but the Ti concentration should be 1 to 4 wt% in consideration of the above reaction.
4 is preferably added, and a more preferable Ti concentration is 1.5 to 3 wt%. Within this range, the current efficiency is good, the electrodeposition is dendritic, and the size of the particles is large. However, if it is less than 1 wt%, it is not preferable because the cathode rod is not electrodeposited or the current efficiency is very low. Also, the grain size of electrodeposited Ti is very small. If it exceeds 4 wt%, the current efficiency becomes low,
The electrodeposited form also becomes sponge-like, and the separation of the molten salt and the like adhering to Ti becomes insufficient, and it is difficult to obtain high-purity Ti.
【００１４】初期カソ−ド電流密度は、０．０１〜２Ａ
／ｃｍ2が好ましく、より好ましくは０．１〜１．０Ａ
／ｃｍ2である。電流密度が、上記の電流密度より低い
場合は、電流効率が低く、時間もかかるため生産性が低
く、好ましくない。一方、２．０Ａ／ｃｍ2より高い場
合は、粒が小さくなるため、カソ−ドに付着することが
少なく、仮りに得られたとしても、スポンジ状であるた
め好ましくない。The initial cathode current density is 0.01 to 2 A.
/ Cm 2 is preferable, more preferably 0.1 to 1.0 A
/ Cm 2 . When the current density is lower than the above current density, the current efficiency is low and it takes time, so that the productivity is low, which is not preferable. On the other hand, if it is higher than 2.0 A / cm 2 , the particles are small and the particles are less likely to adhere to the cathode, and even if it is obtained, it is spongy, which is not preferable.
【００１５】電解温度は、６００〜９００℃が好まし
く、より好ましくは、６５０〜８５０℃である。上記の
温度より低い場合は、結晶性の良いＴｉが得られにく
く、また電流効率も低く好ましくない。電解温度が９０
０℃よりも高い場合は、浴の蒸発が多くなり、また、電
流効率も低くなるため、好ましくない。The electrolysis temperature is preferably 600 to 900 ° C, and more preferably 650 to 850 ° C. If the temperature is lower than the above temperature, Ti with good crystallinity is difficult to obtain, and the current efficiency is low, which is not preferable. Electrolysis temperature is 90
When the temperature is higher than 0 ° C., the evaporation of the bath increases and the current efficiency also decreases, which is not preferable.
【００１６】そして、上記条件下で電解を行い、一回目
の電解を終了したならば、カソ−ドに電着したＴｉを引
き上げ、冷却後脱着し、水洗を行なう。その後、Ｔｉの
表面をフッ化水素−硝酸で洗浄し、次いでエタノ−ルで
洗浄する。そして最後に、真空乾燥する。Then, electrolysis is carried out under the above-mentioned conditions, and when the first electrolysis is completed, the Ti electrodeposited on the cathode is pulled up, and after cooling, it is desorbed and washed with water. Then, the surface of Ti is washed with hydrogen fluoride-nitric acid and then with ethanol. And finally, it is vacuum dried.
【００１７】さらに、次の電解の前に、少なくとも電着
Ｔｉ重量と同量以上の粗ＴｉをＴｉパイプ等を通してア
ノ−ドに装入する。その後前記操作法により、溶融塩電
解精製を行なう。この粗Ｔｉ補加操作を、一回の電解終
了毎に繰り返す。この粗Ｔｉ補加操作は、電解中にＴｉ
の電着量に応じて連続的に行っても良い。この様にし
て、高純度Ｔｉを連続的に得ることができる。Further, before the next electrolysis, at least the same amount of crude Ti as the electrodeposited Ti weight is charged into the anode through a Ti pipe or the like. Then, molten salt electrolytic refining is performed by the above-mentioned operation method. This rough Ti supplementing operation is repeated every time the electrolysis is completed. This coarse Ti addition operation is
It may be continuously performed depending on the amount of electrodeposition. In this way, high purity Ti can be continuously obtained.
【００１８】以下、本発明の実施例及び比較例について
説明する。Examples of the present invention and comparative examples will be described below.
【００１９】[0019]
【実施例】あらかじめ、表１に示すような純度の原料で
ある粗Ｔｉスポンジ６００ｇを含む約７５０℃で溶融状
態のＮａＣｌ−ＫＣｌ（モル比＝４５：５５）浴１０ｋ
ｇ中に、ＴｉＣｌ4４８５ｇを導入する。これにより、
浴中で上記、の反応が進行し、ＮａＣｌ−ＫＣｌ浴
中にＴｉＣｌ2、ＴｉＣｌ3が生成する。この結果、浴中
のＴｉ濃度が、約２．０ｗｔ％となった。EXAMPLE A NaCl-KCl (molar ratio = 45: 55) bath 10 k in a molten state at about 750 ° C. containing 600 g of crude Ti sponge as a raw material having a purity shown in Table 1 in advance.
Into g, 485 g of TiCl 4 are introduced. This allows
The above reaction proceeds in the bath, and TiCl 2 and TiCl 3 are produced in the NaCl-KCl bath. As a result, the Ti concentration in the bath became about 2.0 wt%.
【００２０】この浴を使用し、Ｔｉスポンジをアノ−
ド、Ｔｉ棒をカソ−ドにして、電解温度７２０℃，初期
カソ−ド電流密度０．３Ａ／ｃｍ2の電解条件で、カソ
−ドに高純度のＴｉを電析させた。電析Ｔｉを純水で洗
浄し、フッ酸−硝酸による酸洗及びエタノ−ル洗浄を行
なった。さらに、６０℃で真空乾燥を行った。これによ
り、電析Ｔｉ５０ｇを得た。二回目の電解の前に、粗Ｔ
ｉスポンジ約１００ｇを装入した。この電解操作を７回
繰り返した。得られたＴｉの分析値を、表１に示す。Using this bath, Ti sponge is anodized.
With the cathode and the Ti rod as cathodes, high-purity Ti was electrodeposited on the cathodes under electrolysis conditions of an electrolysis temperature of 720 ° C. and an initial cathode current density of 0.3 A / cm 2 . The electrodeposited Ti was washed with pure water, followed by pickling with hydrofluoric acid-nitric acid and ethanol washing. Further, vacuum drying was performed at 60 ° C. Thereby, 50 g of electrodeposited Ti was obtained. Before the second electrolysis, rough T
About 100 g of i-sponge was charged. This electrolysis operation was repeated 7 times. Table 1 shows the obtained Ti analysis values.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【比較例】各回の電解終了後、粗Ｔｉスポンジを補加し
ない以外は、実施例１と同様に電解を行った。この結果
を、表２に示す。Comparative Example After each electrolysis, electrolysis was performed in the same manner as in Example 1 except that the crude Ti sponge was not added. The results are shown in Table 2.
【００２３】[0023]
【表２】 [Table 2]
【００２４】表１及び表２から明らかなように、実施例
においては、７回の電解を行った後でも不純物であるＦ
ｅ、Ｃｒ、Ｎｉ、Ｃｕが０．０５ｐｐｍ（分析下限以
下）未満なのに対し、比較例においては、２回目以降で
Ｃｕ、そして４回目以降でＦｅ、Ｃｒ、７回目でＮｉが
検出されていることが判る。As is clear from Tables 1 and 2, in the examples, F which is an impurity even after seven times of electrolysis.
e, Cr, Ni, and Cu are less than 0.05 ppm (below the lower limit of analysis), whereas in the comparative example, Cu is detected after the second time, Fe, Cr after the fourth time, and Ni after the seventh time. I understand.
【００２５】[0025]
（１）本発明により、極めて高純度のＴｉ（６Ｎ以上）
を連続的にかつ容易に得ることができる。 （２）得られた高純度Ｔｉは、半導体デバイス製造用の
タ−ゲット材等として好適に用いられる。(1) According to the present invention, extremely high purity Ti (6N or more)
Can be obtained continuously and easily. (2) The obtained high-purity Ti is suitably used as a target material for manufacturing semiconductor devices.
Claims (1)
法において、少なくとも間欠的に電着したＴｉ重量と同
量以上の粗Ｔｉを補加して電解を行うことを特徴とする
Ｔｉの精製方法。1. A method for electrolytically refining crude Ti by a molten salt electrolysis method, characterized in that electrolysis is performed by supplementing at least the same amount or more of crude Ti as electrodeposition of intermittently electrodeposited Ti. Purification method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35154192A JPH06173064A (en) | 1992-12-09 | 1992-12-09 | Method for refining ti |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35154192A JPH06173064A (en) | 1992-12-09 | 1992-12-09 | Method for refining ti |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06173064A true JPH06173064A (en) | 1994-06-21 |
Family
ID=18417985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35154192A Pending JPH06173064A (en) | 1992-12-09 | 1992-12-09 | Method for refining ti |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06173064A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1031734C2 (en) * | 2006-05-03 | 2007-11-06 | Girasolar B V | Process for purifying a semiconductor material using an oxidation-reduction reaction. |
| WO2013065511A1 (en) * | 2011-11-04 | 2013-05-10 | 住友電気工業株式会社 | Molten salt electrolysis metal fabrication method and apparatus for use in same |
| JP2013117063A (en) * | 2011-11-04 | 2013-06-13 | Sumitomo Electric Ind Ltd | Method of producing metal by molten salt electrolysis |
| JP2013147731A (en) * | 2011-12-22 | 2013-08-01 | Sumitomo Electric Ind Ltd | Molten salt electrolysis metal fabrication method |
| US10309022B2 (en) | 2011-08-10 | 2019-06-04 | Sumitomo Electric Industries, Ltd. | Element recovery method and element recovery apparatus |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02213490A (en) * | 1989-02-15 | 1990-08-24 | Nippon Mining Co Ltd | Production of high-purity titanium and equipment thereof and high-purity titanium target material |
-
1992
- 1992-12-09 JP JP35154192A patent/JPH06173064A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02213490A (en) * | 1989-02-15 | 1990-08-24 | Nippon Mining Co Ltd | Production of high-purity titanium and equipment thereof and high-purity titanium target material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1031734C2 (en) * | 2006-05-03 | 2007-11-06 | Girasolar B V | Process for purifying a semiconductor material using an oxidation-reduction reaction. |
| WO2007126309A3 (en) * | 2006-05-03 | 2008-04-03 | Girasolar B V | Method for the purification of a semiconductor material by application of an oxidation-reduction reaction |
| US10309022B2 (en) | 2011-08-10 | 2019-06-04 | Sumitomo Electric Industries, Ltd. | Element recovery method and element recovery apparatus |
| WO2013065511A1 (en) * | 2011-11-04 | 2013-05-10 | 住友電気工業株式会社 | Molten salt electrolysis metal fabrication method and apparatus for use in same |
| JP2013117063A (en) * | 2011-11-04 | 2013-06-13 | Sumitomo Electric Ind Ltd | Method of producing metal by molten salt electrolysis |
| JP2013147731A (en) * | 2011-12-22 | 2013-08-01 | Sumitomo Electric Ind Ltd | Molten salt electrolysis metal fabrication method |
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