JP5110421B2 - Bi recovery method - Google Patents
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Description
本発明は、Biの回収方法に関する。
更に詳しくは、粗BiメタルからのBiの回収方法に関するものである。
さらに、Sb,Bi,Cu,Asを含む中和滓からのBi及び又はSbを回収方法に関するものである。
The present invention relates to a method for recovering Bi.
More specifically, the present invention relates to a method for recovering Bi from crude Bi metal.
Furthermore, the present invention relates to a method for recovering Bi and / or Sb from neutralized soot containing Sb, Bi, Cu and As.
Cu品位が低いBiメタルからの脱Cu方法としては、溶融状態のメタルに硫黄を添加することで、Cuを硫化銅のスカムの形にして除去する方法がよく用いられている。 As a method for removing Cu from Bi metal having a low Cu quality, a method of removing Cu in the form of copper sulfide scum by adding sulfur to a molten metal is often used.
Bi-Cuメタルにおいて、Biのみのメタルの融点は２７１℃であるが、Cu品位が３mass％程度であれば融点は約５００℃であるが、Bi品位９０mass％、Cu品位１０mass％のメタルでは融点は約７３０℃に、Bi品位８０mass％、Cu品位２０mass％のメタルでは融点は約８００℃にまで達する。 In Bi-Cu metal, the melting point of Bi-only metal is 271 ° C, but if the Cu grade is about 3 mass%, the melting point is about 500 ° C, but the melting point is Bi grade 90 mass% and Cu grade 10 mass%. Has a melting point of about 800 ° C. with a metal having a Bi grade of 80 mass% and a Cu grade of 20 mass%.
溶融状態にある融点が700〜８７０℃でCu品位が10〜20 mass％のBi-Cuメタル中に硫黄を添加して硫化処理によりメタル中のCuを除去しようとするが、硫黄の沸点が444℃であるために、溶融メタルの温度が700〜８７０℃であると、硫黄を添加すると硫黄がすぐに揮発してしまい、メタルと硫黄との反応が進まないのでスカムが生成せず、メタルの硫化処理ができない。 The melting point in the molten state is 700 to 870 ° C., and Cu is added to Bi-Cu metal having a Cu grade of 10 to 20 mass%, and Cu in the metal is removed by sulfidation, but the boiling point of sulfur is 444. Therefore, when the temperature of the molten metal is 700 to 870 ° C., sulfur is volatilized immediately when sulfur is added, and the reaction between the metal and sulfur does not proceed, so scum is not generated. Can not be sulfurized.
また、溶融状態にある融点が700〜８７０℃でCu品位が10〜20 mass％のBi-Cuメタル中に無水の硫化ナトリウムではなく、一般的な試薬の硫化ナトリウムの水和物を添加すると、水和水中の水の影響からか、反応がうまく進まないためにスカムが生成せず、メタルの硫化処理ができない。
一方特許文献１（特開2006-89809 SbとBiの分離回収方法）では、Biメタル中の銅の除去方法は、開示されていない。
On the other hand, Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2006-89809 Sb and Bi Separation and Recovery Method) does not disclose a method for removing copper in Bi metal.
本発明は、効率的にビスマスメタルから銅を除去する方法を提供すると同時に、アンチモンも効率的に回収することを目的とするものである。 The object of the present invention is to provide a method for efficiently removing copper from bismuth metal, and at the same time to efficiently recover antimony.
（１）溶融状態にある融点が７００〜８７０℃であって、Ｃｕ品位が１０〜２０ｍａｓｓ％のＢｉ−Ｃｕメタルに、無水硫化ナトリウムを添加して脱Ｃｕすることを特徴とするＢｉの回収方法。(1) A Bi recovery method characterized by adding anhydrous sodium sulfide to de-Cu by adding Bi-Cu metal having a melting point of 700 to 870 ° C in a molten state and a Cu grade of 10 to 20 mass% .
（２）Sb,Bi,Cu,Asを含む中間生成物を、炭酸ナトリウムと還元剤とを混合して溶融還元し、
得られた還元メタルを620〜680℃に加熱し、ソーダ処理し脱Asした後、
さらに620〜680℃において、酸素含有ガスを吹き込みSbを酸化揮発して酸化アンチモンとして回収し、
Sb揮発後に残った溶融状態にある融点が700〜８７０℃であり、Cu品位が10〜20 mass％のBi-Cuメタルに対して、
上記（１）に記載の方法を用いて粗Biメタルを得るBiの回収方法。
を提供する。
(2) The intermediate product containing Sb, Bi, Cu, As is melt-reduced by mixing sodium carbonate and a reducing agent,
The resulting reduced metal was heated to 620 to 680 ° C., treated with soda and de-Assed,
Further, at 620 to 680 ° C., oxygen-containing gas was blown to oxidize and volatilize Sb and recovered as antimony oxide,
For Bi-Cu metal with a melting point of 700-870 ° C. remaining after Sb volatilization and a Cu grade of 10-20 mass%,
A Bi recovery method for obtaining crude Bi metal using the method described in (1) above.
I will provide a.
本発明を実施することにより以下の効果を有する。
（１）粗Biメタル中の銅を、硫黄での脱銅が可能となる融点以下となる、2.6mass％以下まで容易に低減できる。
（２）Sb,Bi,Cu,Asを含む中間性生物から効率的にSb,Biを回収することが
出来る。
By implementing the present invention, the following effects are obtained.
(1) The copper in the crude Bi metal can be easily reduced to 2.6 mass% or less, which is equal to or lower than the melting point at which decoppering with sulfur is possible.
(2) Sb and Bi can be efficiently recovered from intermediate organisms containing Sb, Bi, Cu and As.
本発明の対象は、少なくとも銅を５から３０mass%含むBiメタルである。
又更に、Sb,Bi,Cu,Asを含む中間産物であって、非鉄製錬或いは、非鉄金属リサイクル処理現場で発生する中間産物である。
中間産物は、例えば、Biを10から３５mass%、Sbを１０から３０mass%、Cuを２から１０mass%、Asを３から１５mass%を含むものである。
The object of the present invention is Bi metal containing at least 5 to 30 mass% of copper.
Furthermore, it is an intermediate product containing Sb, Bi, Cu, As, and is an intermediate product generated at non-ferrous smelting or non-ferrous metal recycling treatment sites.
The intermediate product contains, for example, Bi of 10 to 35 mass%, Sb of 10 to 30 mass%, Cu of 2 to 10 mass%, and As of 3 to 15 mass%.
粗Biメタルを処理する場合は、７００から８７０℃に前記メタルに、無水硫化ナトリウムを添加し、攪拌を行いながら、0.5から1.5時間、加熱溶融する。 メタル表面に浮遊しているスカムを除去し、Bi品位９７mass%以上のBiメタルを得ることが出来る。
上記の無水硫化ナトリウムは、フレーク状の物が好ましい。 好ましく溶融メタルと反応するからである。
When processing the crude Bi metal, anhydrous sodium sulfide is added to the metal at 700 to 870 ° C., and the mixture is heated and melted for 0.5 to 1.5 hours while stirring. By removing scum floating on the metal surface, Bi metal with a Bi quality of 97 mass% or more can be obtained.
The anhydrous sodium sulfide is preferably flaky. This is because it preferably reacts with molten metal.
また、上記中間産物を処理する場合は、炭酸ナトリウムと還元剤（コークス等）と混合し、溶融還元する。 Moreover, when processing the said intermediate product, it mixes with sodium carbonate and a reducing agent (coke etc.), and carries out melting reduction.
得られた還元メタルを620から680℃にて溶融し、ソーダ処理を行う。ソーダ処理においては、例えば粒状の水酸化ナトリウムを使用する。この際に、数回に分けて、水酸化ナトリウムを添加する事が望ましい。効率的な反応を促すためである。
メタル表面に浮上するスカムを除き、含有するAsを効率的に除去できる。
The obtained reduced metal is melted at 620 to 680 ° C. and subjected to soda treatment. In the soda treatment, for example, granular sodium hydroxide is used. At this time, it is desirable to add sodium hydroxide in several times. This is to promote an efficient reaction.
The contained As can be removed efficiently except for scum that floats on the metal surface.
更に、ソーダ処理後のメタルを620から680℃にて溶融し、メタル表面及び内部に酸素含有ガス（空気等）を吹き込み、アンチモンを酸化除去する。
一方アンチモンは、酸化アンチモンとして回収される。
アンチモン除去後のCu含有Biメタルは、上記の手法により銅を除去する。
この際、更に、粒状の水酸化ナトリウムを添加し、最後の精製をすることが望ましい。
Further, the soda-treated metal is melted at 620 to 680 ° C., and an oxygen-containing gas (air or the like) is blown into and on the metal surface to oxidize and remove antimony.
On the other hand, antimony is recovered as antimony oxide.
The Cu-containing Bi metal after antimony removal removes copper by the above method.
At this time, it is desirable to further add granular sodium hydroxide for the final purification.
（実施例１）
Bi品位が８０mass％、Cu品位が２０mass％のBi-Cuメタルを８５０℃で加熱溶融しているところに、無水硫化ナトリウムを添加して１時間攪拌した後に、メタル表面に浮遊しているスカムを掬い取り除くと、Bi品位が９７mass％、Cu品位が０．６２mass％の粗Biメタルが得られた。
Example 1
Bi-Cu metal with a Bi grade of 80 mass% and Cu grade of 20 mass% is heated and melted at 850 ° C. After adding anhydrous sodium sulfide and stirring for 1 hour, the scum floating on the metal surface is removed. When removed, a crude Bi metal having a Bi grade of 97 mass% and a Cu grade of 0.62 mass% was obtained.
（比較例１）
Bi品位が８０mass％、Cu品位が２０mass％のBi-Cuメタルを８５０℃で加熱溶融しているところに、硫黄を添加すると、即座に硫黄が揮発し、SOxガスが＞100 ppmで発生してしまい、メタルはそのままの状態で未反応のまま残った。
(Comparative Example 1)
When sulfur is added to Bi-Cu metal with a Bi grade of 80 mass% and Cu grade of 20 mass% heated and melted at 850 ° C, the sulfur volatilizes immediately and SOx gas is generated at> 100 ppm. The metal was left unreacted as it was.
（比較例２）
Bi品位が８０mass％、Cu品位が２０mass％のBi-Cuメタルを８5０℃で加熱溶融しているところに、試薬の硫化ナトリウムの９水和物を添加したが、メタルは硫化されず、そのままの品位で残った。
(Comparative Example 2)
Bi-Cu metal with a Bi grade of 80 mass% and a Cu grade of 20 mass% was heated and melted at 8500C, but the reagent sodium sulfide nonahydrate was added. Remained in dignity.
以上のように、本発明では、溶融状態にある融点が700〜８７０℃でCu品位が10〜20 mass％のBi-Cuメタルにおいて、低融点の硫黄を使用する代わりに、高融点の無水硫化ナトリウムを使用することで、融点が700〜８７０℃でCu品位が10〜20 mass％のBi-Cuメタルから脱Cuすることが可能である。
（実施例２）
As described above, in the present invention, in the Bi-Cu metal having a melting point of 700 to 870 ° C. and a Cu grade of 10 to 20 mass% in the molten state, instead of using low melting point sulfur, high melting point anhydrous sulfide By using sodium, it is possible to remove Cu from Bi—Cu metal having a melting point of 700 to 870 ° C. and a Cu grade of 10 to 20 mass%.
(Example 2)
Sb,Bi,Cu,Asを含む中和滓(Bi品位 26 mass％, Cu品位 5.5 mass％, Sb品位 18 mass %, As品位 9.8 mass %) 2579 kgを、炭酸ナトリウム565kgとコークス130kgとともに電気炉に入れて還元し、還元メタル606kgが得られた。その還元メタルのうち、6000gを坩堝内で620〜680℃で溶融して、そこに粒状の水酸化ナトリウム1600gを４回に分けて添加し、メタル表面に浮遊するスカムを掬い取り、ソーダー処理後メタル4562gを得た。 Neutralized soot containing Sb, Bi, Cu, As (Bi grade 26 mass%, Cu grade 5.5 mass%, Sb grade 18 mass%, As grade 9.8 mass%) 2579 kg of electric furnace with 565 kg of sodium carbonate and 130 kg of coke And reduced to 606 kg of reduced metal. Of the reduced metal, 6000 g was melted in a crucible at 620-680 ° C., 1600 g of granular sodium hydroxide was added in four portions, and the scum floating on the metal surface was scooped up, after soda treatment Obtained 4562 g of metal.
そのソーダ処理後メタル4562gを、650℃〜680℃で溶融しながら、メタル表面及びメタル内部に空気を吹き込み、揮発物を回収して酸化アンチモン400gを得た。 After the soda treatment, while 4562 g of metal was melted at 650 ° C. to 680 ° C., air was blown into the metal surface and inside the metal, and volatiles were recovered to obtain 400 g of antimony oxide.
また、坩堝内にはBi-Cuメタル（揮発後メタル）が1019g残っていた。このBi-Cuメタル(Bi品位 89 mass％, Cu品位 9.8 mass％)を700℃で溶融し、フレーク状の無水硫化ナトリウム165gを３回に分けて添加し、メタル表面に浮遊するスカムを掬い取った後に、粒状の水酸化ナトリウム10gを添加して浮遊スカムを掬い取り、粗Biメタル506gを得た。この時の粗Biメタルの品位は、Bi 97 mass %、Cu 2.6 mass％であった。この結果により、粗Biメタル中の銅を、硫黄での脱銅が可能となる融点以下となる、2.6mass％以下まで容易に低減できる。
これにより、高価な無水硫化ナトリウムの使用量を低減できる。
各段階でのメタルの品位は、図１(単位：％は、mass％で示す。)に示すとおりである。
In addition, 1019 g of Bi—Cu metal (metal after volatilization) remained in the crucible. This Bi-Cu metal (Bi grade 89 mass%, Cu grade 9.8 mass%) was melted at 700 ° C and 165 g of flaky anhydrous sodium sulfide was added in three portions to scoop off the scum floating on the metal surface. After that, 10 g of granular sodium hydroxide was added and the floating scum was scraped off to obtain 506 g of crude Bi metal. The quality of the crude Bi metal at this time was Bi 97 mass% and Cu 2.6 mass%. As a result, the copper in the crude Bi metal can be easily reduced to 2.6 mass% or less, which is below the melting point at which copper removal with sulfur is possible.
Thereby, the usage-amount of expensive anhydrous sodium sulfide can be reduced.
The quality of the metal at each stage is as shown in FIG. 1 (unit:% is expressed in mass%).
以上のように、本発明では、Sb,Bi,Cu,Asを含む中和滓を、炭酸ナトリウムとコークス等の還元剤とを混合して溶融還元し、そこで得られた還元メタルを620〜680℃でソーダ処理して脱Asし、
さらに620〜680℃で空気を吹き込みSbを酸化揮発して酸化アンチモンとして回収し、Sb揮発後に残った溶融状態にある融点が700〜８７０℃でCu品位が10〜20 mass％のBi-Cuメタルに対して、無水硫化ナトリウムを添加することで脱Cuすることができ、粗Biメタルを得ることが可能である。
As described above, in the present invention, the neutralized soot containing Sb, Bi, Cu, As is melt-reduced by mixing sodium carbonate and a reducing agent such as coke, and the reduced metal obtained there is 620-680. Dispose by soda treatment at ℃,
In addition, air was blown at 620 to 680 ° C to oxidize and volatilize Sb and collect it as antimony oxide. Bi-Cu metal with a melting point of 700 to 870 ° C and Cu grade of 10 to 20 mass% remained after Sb volatilization. On the other hand, it is possible to remove Cu by adding anhydrous sodium sulfide, and it is possible to obtain crude Bi metal.
Claims (2)
得られた還元メタルを620〜680℃に加熱し、ソーダ処理し脱Asした後、
さらに620〜680℃において、酸素含有ガスを吹き込みSbを酸化揮発して酸化アンチモンとして回収し、
Sb揮発後に残った溶融状態にある融点が700〜８７０℃であり、Cu品位が10〜20 mass％のBi-Cuメタルに対して、
請求項１に記載の方法を用いて粗Biメタルを得ることを特徴とするBiの回収方法。
An intermediate product containing Sb, Bi, Cu, As is melt-reduced by mixing sodium carbonate and a reducing agent,
The resulting reduced metal was heated to 620 to 680 ° C., treated with soda and de-Assed,
Further, at 620 to 680 ° C., oxygen-containing gas was blown to oxidize and volatilize Sb and recovered as antimony oxide,
For Bi-Cu metal with a melting point of 700-870 ° C. remaining after Sb volatilization and a Cu grade of 10-20 mass%,
A method for recovering Bi, comprising using the method according to claim 1 to obtain crude Bi metal.
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| JP2007090392A JP5110421B2 (en) | 2007-03-30 | 2007-03-30 | Bi recovery method |
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| JP5110421B2 true JP5110421B2 (en) | 2012-12-26 |
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| JP6480357B2 (en) * | 2016-02-05 | 2019-03-06 | Ｊｘ金属株式会社 | Method for treating Sb-containing residue |
| JP6480358B2 (en) * | 2016-02-05 | 2019-03-06 | Ｊｘ金属株式会社 | Sb recovery method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5480231A (en) * | 1977-12-09 | 1979-06-26 | Sumitomo Metal Mining Co | Separation of bismuth |
| JPS6217140A (en) * | 1985-07-15 | 1987-01-26 | Sumitomo Metal Mining Co Ltd | Method for removing impurity from copper sulfide concentrate |
| JPS63203727A (en) * | 1987-02-20 | 1988-08-23 | Mitsubishi Metal Corp | Treatment of lead electrolysis slime |
| JPH08311575A (en) * | 1995-05-17 | 1996-11-26 | Sumitomo Metal Mining Co Ltd | Production of bismuth crude metal |
| JP2006089809A (en) * | 2004-09-24 | 2006-04-06 | Nippon Mining & Metals Co Ltd | METHOD FOR SEPARATING AND RECOVERING Sb AND Bi |
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