JPS6277431A - Method for selectively extracting copper and arsenic respectively from decopperizing slime - Google Patents

Abstract

PURPOSE:To respectively selectively extract copper and arsenic contg. less impurities at a high recovery rate form decopperizing slime by treating the decopperizing slime with an aq. alkaline hydroxide soln. in the co-presence of gaseous oxygen and treating the resulted residue of extraction with an aq. sulfuric acid soln. CONSTITUTION:The decopperizing slime is treated with the aq. sodium hydroxide soln, which is kept stirred in the co-presence of the gaseous oxygen. The above- mentioned aq. sodium hydroxide soln. is held at a room temp. or above, more preferably at >=60 deg.C. Only the arsenic-component in the decopperizing slime is thereby selectively extracted as sodium arsenate. The above-mentioned reaction liquid is subjected to a solid-liquid sepn. and the resulted residue of extraction is treated with the aq. sulfuric acid soln. which is kept stirred. The above-mentioned aq. sulfuric acid soln. contains 0.7-1.3 equiv. sulfuric acid with regard to the copper content in the above- mentioned residue of extraction and is preferably held at >=50 deg.C in the co-presence of extraction is thereby selectively extracted as copper sulfate. The above-mentioned reaction liquid is subjected to the solid-liquid sepn. and the residue of extraction is used as a raw material for refining Sb, Bi, etc.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、脱銅スライムから銅及び砒素を選択的に抽出
分離する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for selectively extracting and separating copper and arsenic from decoppered slime.

〔従来の技術〕[Conventional technology]

脱銅スライムとは当業者の呼称であって、銅の電解精製
中に粗銅に含まれている砒素、アンチモン、ビスマス等
が電解液中に溶出するが、これらの不純物が陰極に銅と
一緒に析出しないように、電解液の一部を別の電解槽に
抜き取って所謂脱銅電解を行なうが、脱銅電解の後期に
なると陰極に銅と共に砒素、アンチモン、ビスマス等が
粒状に析出し、又槽底にスライムとして沈殿してくる。Decoppered slime is what those skilled in the art call it. During the electrolytic refining of copper, arsenic, antimony, bismuth, etc. contained in blister copper are eluted into the electrolyte, and these impurities are mixed with copper at the cathode. In order to prevent precipitation, a part of the electrolyte is extracted into a separate electrolytic tank to perform so-called decoppering electrolysis, but in the latter stages of decoppering electrolysis, arsenic, antimony, bismuth, etc. are deposited in granular form along with copper on the cathode. It will settle as slime on the bottom of the tank.

上記陰極から掻き取ることのできるものや、槽底に沈殿
するスライムを合わせ一般に脱銅スライムと呼んでいる
。The slime that can be scraped off from the cathode and the slime that settles on the bottom of the tank is generally called decoppered slime.

この脱銅スライムは鋼製針工程に繰り返させるのが一般
的であるが製錬系内を多量の不純物が循環することにな
るので好ましい方法ではない。This decoppered slime is generally repeated in the steel needle making process, but this is not a preferred method because a large amount of impurities will circulate within the smelting system.

このため従来、脱銅スライム中の不純物を製錬系外に除
去するための乾式法又は湿式法が提案されている。For this reason, conventionally, dry methods or wet methods have been proposed for removing impurities in decoppered slime outside the smelting system.

しかしながら上記乾式法においては、亜砒酸等を含有す
る排ガス処理等コスト高となるだけでなく、作業環境上
から見ても好ましい方法とは云えない。However, the above-mentioned dry method not only increases the cost of treating exhaust gas containing arsenous acid and the like, but also cannot be said to be a preferable method from the viewpoint of the working environment.

一方湿式処理方法としては、例えば特開昭５９−７４２
４５号公報、特開昭５９−８３９３６号公報のように脱
銅スライムを低濃度の硫酸溶液又は酸素ガス共存下硫酸
酸性水溶液と接触させ、銅及び砒素を浸出した後、冷却
により又は浸出液に硫化砒素と過酸化水素水溶液を添加
して、夫々銅と砒素分を分離する方法等があるが、いず
れも分離された水溶液中には相当量の不純物（ｓｂＸＢ
ｉ等）を含有する等問題点の多いものであった。On the other hand, as a wet treatment method, for example, JP-A-59-742
45 and JP-A-59-83936, the decoppered slime is brought into contact with a low-concentration sulfuric acid solution or an acidic sulfuric acid aqueous solution in the presence of oxygen gas to leach out copper and arsenic, and then sulfurized by cooling or in the leachate. There are methods to separate copper and arsenic by adding arsenic and hydrogen peroxide aqueous solutions, respectively, but in either case, a considerable amount of impurities (sbXB
It had many problems, such as containing substances such as i).

〔発明が解決しようとする問題点〕[Problem that the invention seeks to solve]

本発明は、脱銅スライムからアンチモン、ビスマス等を
殆んど含有しない銅と砒酸の水溶液を得る方法を提供す
ることを目的とする。An object of the present invention is to provide a method for obtaining an aqueous solution of copper and arsenic acid containing almost no antimony, bismuth, etc. from decoppered slime.

〔問題点を解決するための手段〕[Means for solving problems]

この目的を達成するために本発明の方法は、脱銅スライ
ムを、酸素ガスの共存下攪拌され好ましくは室温以上望
ましくは６００以上に保持された例えば砒素に対し当量
以上の水酸化す）　ＩＪウムを含む水酸化す）　ＩＪウ
ム水溶液にて処理し、下記の予想式により砒酸ナトリウ
ムとして砒素分のみを選択的に抽出する第一工程と、 Ａｓ　＋　５／４０　＋　３　ＮａＯＨ→Ｎａ　ＡｓＯ
＋３／２ＨＯ第一工程における不溶解残渣を、該残渣中
に含有する銅量に対し好ましくは１．０〜１．３当量の
硫酸を含み攪拌され、好ましくは酸素ガス共存下５０Ｃ
以上に保持されている硫酸水溶液にて処理し、砒素やア
ンチモンを殆んど含有しない硫酸銅水溶液を得る第二工
程とより成るものである。To achieve this objective, the method of the present invention involves hydrating the decoppered slime in an amount equivalent to or more than, for example, arsenic, while stirring in the presence of oxygen gas and maintaining the temperature preferably above room temperature, preferably above 600°C. A first step of selectively extracting only the arsenic component as sodium arsenate according to the following predicted formula by treating with an IJ aqueous solution (As+5/40+3NaOH→NaAsO)
The undissolved residue in the +3/2HO first step is stirred, preferably containing 1.0 to 1.3 equivalents of sulfuric acid relative to the amount of copper contained in the residue, preferably at 50C in the coexistence of oxygen gas.
The second step consists of treatment with the sulfuric acid aqueous solution retained above to obtain a copper sulfate aqueous solution containing almost no arsenic or antimony.

〔作用〕[Effect]

本発明の方法において、第一工程の反応は発熱反応であ
るので室温で反応を開始し成り行きで通常８５％以上の
砒素分を抽出することが可能であるが、６０Ｃ程度に保
持して反応させると砒素の抽出率は９０％を超える。In the method of the present invention, since the reaction in the first step is an exothermic reaction, it is possible to start the reaction at room temperature and normally extract more than 85% of the arsenic content, but the reaction is maintained at about 60C. The extraction rate of arsenic and arsenic exceeds 90%.

しかし砒素の抽出率をより高めようとすれば、アンチモ
ンの溶出も又増加するので注意を要する。However, if you try to increase the arsenic extraction rate, the elution of antimony will also increase, so care must be taken.

酸素ガスは、空気を使用し通常砒素に対し２〜３当量用
いるとよい。この空気量が少な過ぎると砒素の抽出率が
低下する。As the oxygen gas, it is preferable to use air in an amount of 2 to 3 equivalents to arsenic. If this amount of air is too small, the arsenic extraction rate will decrease.

水酸化アルカリ水溶液の濃度は、あまり濃厚でない程度
であれば良く、水酸化アルカリの量は砒素に対し１〜１
．３当量で充分である。砒素の抽出に際し反応容器に空
気を吹き込んでも、別途にプロペラ式攪拌機等で充分攪
拌する必要がある。The concentration of the alkali hydroxide aqueous solution should be not too concentrated, and the amount of alkali hydroxide should be 1 to 1
．． 3 equivalents is sufficient. Even if air is blown into the reaction vessel during the extraction of arsenic, it is necessary to separately sufficiently stir the reaction vessel using a propeller type stirrer or the like.

第一工程の反応が終了し、スラリーを固液分離するとＣ
ｕＳ　５ｂＸＢｉ等を殆んど含まない砒酸ナトリウム水
溶液と抽出残渣が得られる。When the reaction in the first step is completed and the slurry is separated into solid and liquid, C
An aqueous sodium arsenate solution and an extraction residue containing almost no uS 5bXBi etc. are obtained.

この抽出残渣を、該残渣中の銅量に対し好ましくはｉ、
ｏ〜１．３当量の硫酸を含有する硫酸水溶液で処理する
のは、これ以下では銅の抽出率が低下し、１．３当量以
上ではｓｂの抽出率が増加するがらである。This extraction residue is preferably i, relative to the amount of copper in the residue.
The reason why the treatment is performed with an aqueous sulfuric acid solution containing sulfuric acid in an amount of 0 to 1.3 equivalents is that if the amount is less than this, the copper extraction rate decreases, and if it is 1.3 equivalents or more, the sb extraction rate increases.

岨　／７′１　油虫ｔ、−呟　１　轟わ妻　ゼ　７　九
　丑プＶ　セル　ＺＬ　　相小各り黒率が上昇する傾向
を示すが、処理温度は反応熱により、液温か上昇するた
めか高湿でも顕著な効果は認められない。岨 /7'1 Yumushit, -Mutsu 1 Todorowa Tsuma Ze 7 9 Ushipu V Cell ZL Each phase shows a tendency for the black rate to increase, but the processing temperature is high, probably because the liquid temperature rises due to reaction heat. No significant effect was observed even in humid conditions.

本発明法によれば、Ｓｂ、Ｂｉを殆んど含まない砒酸水
溶液と、同様に不純物の少ない硫酸銅水溶液及びそのま
−５ｂＳＥｉ回収工程に利用しうる不溶解残渣とを効率
よく分離することができる。又、本発明法は他の０ｕＳ
Ａｓ　、　Ｓｂ含有物にも適用することができる。According to the method of the present invention, it is possible to efficiently separate an arsenic acid aqueous solution that contains almost no Sb or Bi from a copper sulfate aqueous solution that also has few impurities and an undissolved residue that can be used in the 5bSEi recovery process. can. In addition, the method of the present invention can be applied to other 0uS
It can also be applied to materials containing As and Sb.

〔実施例〕〔Example〕

以下実施例について説明する。 Examples will be described below.

実施例１ 第１表に示す脱銅スライム１２８ｇを反応槽に取り、こ
れにＡｓに対し１．０〜１．８当量の水酸化ナトリウム
を含有する水酸化ナトリウム水溶液１．５ノを室温で添
加し、プロペラ式攪拌機で軽く攪拌しながら８２０〜１
２４０　ｍ幻の流速で空気を吹き込み３時間、処理温度
成り行きで反応させた後、放冷し吸す［濾過し抽出液と
一次不溶解残渣を得た。Example 1 128 g of decoppered slime shown in Table 1 was placed in a reaction tank, and 1.5 g of an aqueous sodium hydroxide solution containing 1.0 to 1.8 equivalents of sodium hydroxide relative to As was added at room temperature. 820~1 while stirring lightly with a propeller type stirrer.
After blowing air at a flow rate of 240 m and allowing the reaction to proceed at the treatment temperature for 3 hours, it was allowed to cool and sucked [filtered to obtain an extract and a primary undissolved residue.

次に一次不溶解残渣を別の容器に移し、この残渣中のＣ
ｕに対して０．７〜２．０当量の硫酸を含むように調製
した水溶液１．５１を加え、所定の温度に保持しプロペ
ラ式攪拌機で攪拌しながら、空気を０〜１２４０ｍ１！
／分の流速で吹き込み１時間処理したのち真空濾過しＯ
ｕ抽出液と二次不溶解残渣とを得た。Next, transfer the primary undissolved residue to another container, and remove the C in this residue.
1.51 of an aqueous solution prepared to contain 0.7 to 2.0 equivalents of sulfuric acid per u is added, and while maintaining the predetermined temperature and stirring with a propeller type stirrer, 0 to 1240 ml of air is added.
After blowing at a flow rate of /min and treating for 1 hour, vacuum filtration was performed.
A u extract and a secondary undissolved residue were obtained.

その結果を第２〜第５表に、各元素の分配率を第６表に
示す。The results are shown in Tables 2 to 5, and the distribution ratio of each element is shown in Table 6.

第　　１　　表　　（重量％） 第　２　表　実験条件 表註※　Ａ６に対し約３当量相当量 第　３　表　ＮａＯＨ抽出液 第　５　表　抽出残渣 第６表　分配率（％） 第６表の分配率を見て明らかなように、ＮａＯＨ水溶液
による抽出液には、Ｃ！ｕｓＢｉは全く抽出されず、僅
かに微（Ｈのｓｂが含まれるが、高純度のＡｓ又はＡｓ
　Ｏの原料として好適なものが得られ、又硫酸によるＣ
ｕ抽出液中にも微量のＡＳｓＳｂが含まれる程度で、そ
のま＼電気銅の原料に供し得るものが得られた。Table 1 (wt%) Table 2 Experimental conditions Notes* Approximately 3 equivalents to A6 Table 3 NaOH extract Table 5 Extraction residue Table 6 Distribution ratio (%) See the distribution ratio in Table 6 As is clear, the extract with NaOH aqueous solution contains C! usBi is not extracted at all, and contains only a small amount of H (sb), but high purity As or As
A material suitable as a raw material for O is obtained, and C
The u extract contained only a trace amount of ASsSb, and could be used as a raw material for electrolytic copper as it was.

ＣｕＸＡｓを分離した残渣中には、Ｓｂ、Ｂｉが高濃度
に含まれ（第３表参照）、これらの回収工程原料とする
ことができる。The residue after separating CuXAs contains Sb and Bi at high concentrations (see Table 3), and can be used as raw materials for the recovery process.

一方回収率としては、ＡＢは９０％弱、Ｃｕは９８％強
程度であるが、残りはそのまま棄却するものではないの
で満足すべき結果ということができる。On the other hand, the recovery rate is a little less than 90% for AB and a little more than 98% for Cu, but since the rest is not rejected as is, these results can be said to be satisfactory.

尚、抽出に際し空気吹込みをしなかった実験ＡＩＯは、
Ｃｕの抽出率が約９５％にとまった。In addition, the experimental AIO in which air was not blown during extraction was
The extraction rate of Cu remained at about 95%.

〔発明の効果〕〔Effect of the invention〕

同族で分離が困難なＳｂ、Ｂｉを、Ａｓから効率良く分
離し、且つＣｕを不純物の少ない形で回収することがで
きる。Sb and Bi, which are homologous and difficult to separate, can be efficiently separated from As, and Cu can be recovered in a form with less impurities.

脱銅スムイムからの有価物回収法としては、操作が簡単
で回収率が高い等の利点がある。The method of recovering valuables from decoppered Sumuimu has the advantages of easy operation and high recovery rate.

出願人　　住友金属鉱山株式会社 〆乙−、Applicant: Sumitomo Metal Mining Co., Ltd. 〆Otsu-,

Claims (3)

【特許請求の範囲】[Claims] （１）脱銅スライムを、酸素ガスの共存下攪拌されてい
る水酸化アルカリ水溶液にて処理したのち固液分離する
第一工程と、第一工程で得られた抽出残渣を、攪拌され
ている硫酸水溶液で処理し、固液分離する第二工程とよ
り成ることを特徴とする脱銅スライムから銅及び砒素を
夫々選択的に抽出する方法。(1) A first step in which the decoppered slime is treated with an aqueous alkali hydroxide solution that is stirred in the presence of oxygen gas, and then solid-liquid separated, and the extraction residue obtained in the first step is stirred. A method for selectively extracting copper and arsenic from decoppered slime, which comprises a second step of treatment with an aqueous sulfuric acid solution and solid-liquid separation. （２）第一工程で用いられる水酸化アルカリ水溶液は、
６０℃以上に保持することを特徴とする特許請求の範囲
（１）項に記載の脱銅スライムから銅及び砒素を夫々選
択的に抽出する方法。(2) The aqueous alkali hydroxide solution used in the first step is
A method for selectively extracting copper and arsenic from decoppered slime according to claim (1), wherein the temperature is maintained at 60° C. or higher. （３）第二工程で用いられる硫酸水溶液は、第一工程で
得られた抽出残渣中の銅量に対し０．７〜１．３当量の
硫酸を含み、酸素ガスの共存下５０℃以上に保持するこ
とを特徴とする特許請求の範囲（１）項又は（２）項に
記載の脱銅スライムから銅及び砒素を夫々選択的に抽出
する方法。(3) The sulfuric acid aqueous solution used in the second step contains 0.7 to 1.3 equivalents of sulfuric acid based on the amount of copper in the extraction residue obtained in the first step, and is heated to 50°C or higher in the presence of oxygen gas. A method for selectively extracting copper and arsenic from decoppered slime according to claim (1) or (2), wherein the copper and arsenic are respectively retained.