JP6233478B2 - Purification method of bismuth - Google Patents

Purification method of bismuth Download PDF

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JP6233478B2
JP6233478B2 JP2016179071A JP2016179071A JP6233478B2 JP 6233478 B2 JP6233478 B2 JP 6233478B2 JP 2016179071 A JP2016179071 A JP 2016179071A JP 2016179071 A JP2016179071 A JP 2016179071A JP 6233478 B2 JP6233478 B2 JP 6233478B2
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bismuth
leaching
solution
sulfuric acid
alkali
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宏 竹之内
宏 竹之内
俊彦 永倉
俊彦 永倉
浅野 聡
聡 浅野
賢二 竹田
賢二 竹田
伸行 加地
伸行 加地
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住友金属鉱山株式会社
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Description

本発明は、ビスマスの精製方法に関する。さらに詳しくは、銅電解精製工程で発生する銅電解スライムから有価金属であるビスマスを回収する精製方法に関するものである。   The present invention relates to a method for purifying bismuth. More specifically, the present invention relates to a purification method for recovering bismuth, which is a valuable metal, from copper electrolytic slime generated in the copper electrolytic purification process.
銅を含有する鉱石から銅を回収する方法として、銅を含有する鉱石を選鉱工程に付して銅を濃縮した銅精鉱を得、次にこの銅精鉱を炉に投入して高温で熔融する乾式製錬に付して粗銅を得、次にこの粗銅をアノードとして硫酸酸性溶液に浸漬し、同時に面対して浸漬したステンレスや銅の板を用いたカソードとの間に電流を流し、アノードから溶解した銅を選択的にカソード上に電析させる電解精製に付すことを経て、高純度な電気銅を得る方法が一般的に用いられてきた。   As a method of recovering copper from ores containing copper, copper concentrates are obtained by subjecting copper-containing ores to a beneficiation process to obtain copper concentrate, and then the copper concentrate is put into a furnace and melted at a high temperature. It is subjected to dry smelting to obtain crude copper, and then this crude copper is immersed in a sulfuric acid acidic solution as an anode, and at the same time, a current is passed between the cathode using a stainless steel plate or a copper plate immersed in the anode. In general, a method for obtaining high-purity electrolytic copper has been generally used by subjecting copper dissolved in the copper to electrolytic purification in which the copper is selectively deposited on the cathode.
上記の銅を含有する鉱石には、目的とする銅のほかに金銀などの貴金属やビスマスやヒ素やアンチモンやセレンや鉛や鉄やテルルなどの有価物でもあり不純物でもある多種多様な成分が含有されることが多い。これらの成分は、上記の乾式製錬でスラグとして分離されたり、電解精製では銅電解スライムとして貴金属とともに電解槽の底に沈積されたりするなどして銅と分離される。   In addition to the target copper, the above ores containing copper contain a wide variety of components that are valuable and impurities such as precious metals such as gold and silver, bismuth, arsenic, antimony, selenium, lead, iron, tellurium, etc. Often done. These components are separated from copper by the above-described dry smelting, or separated from copper by electrolytic refining, such as being deposited as a copper electrolytic slime along with the precious metal at the bottom of the electrolytic cell.
上記の銅電解スライムは、前述するように多種多様な成分が含有されているため、このスライムを精製して目的とする有価物を回収する処理が必要となる。   Since the copper electrolytic slime contains various components as described above, it is necessary to purify the slime and recover the target valuable material.
スライムを精製する方法としてはいくつかの方法が知られているが、その中の一つの方法として、銅電解スライムに硫酸を添加して銅電解スライムに混在する銅を溶解して除去する脱銅工程を行い、次に脱銅して得た脱銅スライムを炉に入れて高温に加熱し、セレン、アンチモンを揮発して分離し、次に酸化して鉛を酸化物として分離し、その後に貴金属とビスマスを分離してする方法がある。   Several methods are known as methods for purifying slime, and one of them is the removal of copper by adding sulfuric acid to copper electrolytic slime to dissolve and remove copper mixed in copper electrolytic slime. Then, the copper removal slime obtained by copper removal is put in a furnace and heated to high temperature, selenium and antimony are volatilized and separated, then oxidized to separate lead as an oxide, and then There is a method of separating noble metal and bismuth.
上記の方法は、大量の物量を取り扱うのには適した方法であるが、一方で大掛かりな設備が必要で、処理に要するエネルギーコストも大きく、また貴金属を回収できるのが工程の後半になるので仕掛り金利がかさむなどの課題があった。   The above method is a suitable method for handling a large amount of material, but on the other hand, a large facility is required, the energy cost required for processing is high, and precious metals can be recovered in the latter half of the process. There were issues such as an in-progress interest rate.
そこで近年では、湿式方法を中心とした新しい処理プロセスが広く実用化されてきた。これら湿式処理プロセスは、セレン分離に湿式還元法を採用するか、焙焼法を採用するかにより、以下の二つの方法に大別される。   Therefore, in recent years, new treatment processes centered on wet methods have been widely put into practical use. These wet treatment processes are roughly classified into the following two methods depending on whether a wet reduction method or a roasting method is adopted for selenium separation.
第一の方法は、非特許文献1や特許文献1あるいは特許文献2に示される方法である。
これらの方法では、銅電解スライムに硫酸と酸素を加えて高温高圧下でテルルの一部と銅を浸出する。次に浸出して得た残渣に塩酸及び過酸化水素あるいは塩素を加えて金、白金族元素、セレン、テルルを浸出する。
つぎに、この浸出液に有機抽出剤であるビス(2-ブトキシエチル)エーテル(以後DBCと表記する)を混合して金を抽出剤中に抽出し、その抽残液を二酸化硫黄で還元してセレン、テルル、白金族元素を回収する。セレン、テルル、白金族元素の混合物はメタル状態のまま蒸留することにより、セレンとテルル及び白金族元素とに分離される。塩素浸出残渣は、アンモニア水にて処理することにより銀を浸出し、この浸出液から銀が粉末として回収される。
The first method is a method disclosed in Non-Patent Document 1, Patent Document 1, or Patent Document 2.
In these methods, sulfuric acid and oxygen are added to copper electrolytic slime, and a portion of tellurium and copper are leached under high temperature and pressure. Next, hydrochloric acid and hydrogen peroxide or chlorine are added to the leaching residue to leach gold, platinum group elements, selenium and tellurium.
Next, bis (2-butoxyethyl) ether (hereinafter referred to as DBC), which is an organic extractant, is mixed with this leachate to extract gold into the extractant, and the extract is reduced with sulfur dioxide. Collect selenium, tellurium and platinum group elements. A mixture of selenium, tellurium, and platinum group elements is separated into selenium, tellurium, and platinum group elements by distillation in a metal state. The chlorine leaching residue is leached with silver by treating with ammonia water, and silver is recovered as a powder from the leaching solution.
第二の方法は、非特許文献2に示す方法である。すわなち、銅電解スライムを硫酸による加圧浸出に付して、脱銅、脱テルルを行なう工程までは上記第一の方法と同じであるが、その後残渣を硫酸と混合し、焙焼してセレンを揮発分離すると同時に、残渣中の銀を硫酸銀に変換する。そして硫酸焙焼残渣は、まず、硝酸カルシウム水溶液を用いて銀を浸出し、この浸出液を電解することにより銀メタルを回収する。   The second method is a method shown in Non-Patent Document 2. In other words, the process until the copper electrolysis slime is subjected to pressure leaching with sulfuric acid to remove copper and tellurium is the same as the first method above, but the residue is then mixed with sulfuric acid and roasted. At the same time, selenium is volatilized and the silver in the residue is converted to silver sulfate. The sulfuric acid roasting residue first leaches silver using an aqueous calcium nitrate solution, and recovers silver metal by electrolyzing the leaching solution.
銀を浸出した残渣は、塩酸及び塩素にて金、白金族、セレン、及び残留しているテルルを浸出する。この浸出液にDBCを混合して金を抽出するが、この原理は第一の方法と同じである。更に、この抽残液をヒドラジン還元することにより、白金族元素とテルルとを金属粉として回収する。   The residue leached from silver leaches gold, platinum group, selenium, and remaining tellurium with hydrochloric acid and chlorine. This leachate is mixed with DBC to extract gold, but the principle is the same as in the first method. Further, the extracted residue is hydrazine reduced to recover platinum group elements and tellurium as metal powder.
なお、上記の第二の方法における硫酸焙焼残渣から銀を回収する法としては、上記第一の方法と同様に、アンモニアを使用する方法、亜硫酸ナトリウムを使用する方法も提案されている。   In addition, as a method for recovering silver from the sulfuric acid roasting residue in the second method, a method using ammonia and a method using sodium sulfite have been proposed as in the first method.
しかるに、上記2つの方法では、いくつかの有価物並びに不純物の分離方法として、例えばビスマスに関しては、湿式工程で回収することは示されていない。ビスマスは従来から行われてきた乾式工程を用いて熔融し、スラグから回収する方法が一般的である。しかし乾式工程を実現するためには炉を設けるための投資や使用するエネルギーなどの投資や費用が大きくなる等の問題があり好ましくなかった。   However, in the above two methods, as a method for separating some valuables and impurities, for example, bismuth is not shown to be recovered in a wet process. Generally, bismuth is melted using a conventional dry process and recovered from slag. However, in order to realize the dry process, there are problems such as an investment for providing a furnace, an investment such as energy to be used, and a cost, which are not preferable.
特開平9−316559号公報JP-A-9-316559 特開平9−316561号公報JP-A-9-316561
本発明は、銅電解スライムから貴金属を回収後に得られる液からビスマスを、湿式工程を主として用い炉等を極力用いずに、効率よく回収し精製す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 efficiently recovering and purifying bismuth from a liquid obtained after recovering a noble metal from copper electrolytic slime, mainly using a wet process and using a furnace as much as possible.
第1発明は、銅と貴金属とビスマスと不純物とを含有する鉱物を製錬して得た粗銅を電解精製に付して銅を回収し、次に電解精製を行うことで生成した電解スライムから湿式法により貴金属を回収する工程において、貴金属を回収後に生成した酸性溶液を以下の工程に付すことを特徴とするビスマスの精製方法である。
1)前記酸性溶液にアルカリを添加してpHを2.0以上3.0以下の範囲に調整し、次いで固液分離して中和濾液と中和澱物を得る中和処理工程
2)前記中和澱物にアルカリを添加してアルカリ浸出液とアルカリ浸出残渣に分離するアルカリ浸出工程
3)前記アルカリ浸出残渣に硫酸を添加して硫酸浸出液と硫酸浸出残渣とに分離する硫酸浸出工程
4)前記硫酸浸出液を冷却し、硫酸ビスマスの結晶を得る冷却工程
5)前記硫酸ビスマスの結晶にアルカリを加え、酸化ビスマスを得るビスマス酸化工程
6)前記酸化ビスマスに酸溶液を添加して溶解し、得た溶解液を電解採取して金属ビスマスを得る電解工程
The first invention is based on an electrolytic slime produced by subjecting crude copper obtained by smelting a mineral containing copper, noble metal, bismuth and impurities to electrolytic purification to recover copper, and then performing electrolytic purification. In the step of recovering a noble metal by a wet method, an acidic solution produced after recovering the noble metal is subjected to the following step, which is a bismuth purification method.
1) Neutralization step of adding an alkali to the acidic solution to adjust the pH to a range of 2.0 to 3.0, and then solid-liquid separation to obtain a neutralized filtrate and a neutralized starch 2) Alkaline leaching step of adding alkali to neutralized starch to separate into alkali leaching solution and alkali leaching residue 3) Sulfuric acid leaching step of adding sulfuric acid to said alkali leaching residue to separate into sulfuric acid leaching solution and sulfuric acid leaching residue 4) Cooling step of cooling the sulfuric acid leachate to obtain bismuth sulfate crystals 5) Bismuth oxidation step of adding alkali to the bismuth sulfate crystals to obtain bismuth oxide 6) Obtaining and dissolving the acid solution in the bismuth oxide Electrolytic process to obtain metal bismuth by electrolyzing the solution
第2発明は、第1発明において、前記不純物が鉄、鉛、ヒ素、テルルの1種以上であることを特徴とするビスマスの精製方法である。
第3発明は、第1発明において、前記アルカリ浸出工程で得たアルカリ浸出液を90℃以上に加熱し、次いで冷却してヒ素を含む結晶を得ることを特徴とするビスマスの精製方法である。
第4発明は、第1発明における前記硫酸浸出工程が、溶液のpHが0〜3.5の低濃度の硫酸を接触させて浸出残渣を浸出して1次浸出液と1次浸出残差とに分離する1次処理を行い得られた1次浸出残渣に溶液のpHが0未満の高濃度の硫酸を接触させて2次浸出液と2次浸出残渣とに分離し、得られた2次浸出液を上記第1の発明の冷却工程に供給する2次処理を行う2段階の浸出処理からなることを特徴とするビスマスの精製方法である。
第5発明は、第1発明における前記電解工程で用いる酸溶液が、硅フッ酸を含む溶液であることを特徴とするビスマスの精製方法である。
第6発明は、第1発明のアルカリ浸出工程において、中和澱物に添加するアルカリとして1mol/l以上5mol/l以下の濃度の水酸化ナトリウム溶液を使用し、スラリー濃度が10g/l以上100g/l以下の範囲になるように混合して溶解し、アルカリ浸出液とアルカリ浸出残渣を得ることを特徴とするビスマスの精製方法である。
第7発明は、第1発明の硫酸浸出工程において、硫酸を添加した後のスラリーのpHを0以上、3.5以下の範囲に調整して浸出し、浸出後に固液分離して硫酸浸出液と硫酸浸出残渣を得ることを特徴とするビスマスの精製方法である。
A second invention is the bismuth purification method according to the first invention, wherein the impurity is one or more of iron , lead, arsenic, and tellurium.
A third invention is a method for purifying bismuth according to the first invention, wherein the alkali leaching solution obtained in the alkali leaching step is heated to 90 ° C. or higher and then cooled to obtain crystals containing arsenic.
According to a fourth aspect of the present invention, the sulfuric acid leaching step according to the first aspect of the present invention is carried out by contacting a low-concentration sulfuric acid whose pH of the solution is 0 to 3.5 to leach out the leaching residue to obtain a primary leaching solution and a primary leaching residual. performs primary processing to separate, resulting primary leaching residue by contacting a high concentration of sulfuric acid of pH of the solution is less than 0 is separated into a secondary leachate and secondary leach residue, secondary leachate obtained This is a bismuth purification method characterized by comprising a two-stage leaching process in which a secondary process is performed to supply the above to the cooling process of the first invention.
The fifth invention is a method for purifying bismuth, characterized in that the acid solution used in the electrolysis step in the first invention is a solution containing hydrofluoric acid.
The sixth invention uses a sodium hydroxide solution having a concentration of 1 mol / l or more and 5 mol / l or less as an alkali to be added to the neutralized starch in the alkali leaching step of the first invention, and a slurry concentration of 10 g / l or more and 100 g. This is a method for purifying bismuth, characterized in that an alkali leaching solution and an alkali leaching residue are obtained by mixing and dissolving so as to be in a range of 1 / l or less.
The seventh invention is the sulfuric acid leaching step of the first invention, wherein the pH of the slurry after adding sulfuric acid is adjusted to a range of 0 or more and 3.5 or less and leached. A method for purifying bismuth characterized in that a sulfuric acid leaching residue is obtained.
第1発明によれば、中和処理工程では、pHが2〜3であることで、不純物を水酸化物の形態で分離でき、ビスマスの濃度を最大化でき、固液分離によりビスマスを含む中和澱物と中和濾液に分離できる。アルカリ浸出工程では、ビスマスが残るアルカリ浸出残渣とアルカリ浸出液に分離できる。硫酸浸出工程ではビスマスを含む硫酸浸出液と硫酸浸出残渣とに分離できる。冷却工程では硫酸ビスマスの結晶を得ることができ、ビスマス酸化工程では酸化ビスマスを得ることができる。電解工程では酸化ビスマスに酸溶液を添加した溶解液を電解採取して、最終的に電析した金属ビスマスを得ることができる。
このように、本発明によれば、銅製錬から高純度な金属ビスマスを湿式工程によって回収でき、乾式では必要な大掛かりな設備を必要としないので、低コストで操業できる
According to the first invention, in the neutralization treatment step, since the pH is 2 to 3, impurities can be separated in the form of hydroxide, the concentration of bismuth can be maximized, and bismuth is contained by solid-liquid separation. It can be separated into Japanese starch and neutralized filtrate. In the alkali leaching step, the alkali leaching residue in which bismuth remains and the alkali leaching solution can be separated. In the sulfuric acid leaching step, it can be separated into a sulfuric acid leaching solution containing bismuth and a sulfuric acid leaching residue. Crystals of bismuth sulfate can be obtained in the cooling step, and bismuth oxide can be obtained in the bismuth oxidation step. In the electrolysis step, a solution obtained by adding an acid solution to bismuth oxide can be electrolytically collected to finally obtain electrodeposited metal bismuth.
As described above, according to the present invention, high-purity metal bismuth can be recovered from a copper smelting process by a wet process, and since it does not require large-scale equipment necessary for a dry process, it can be operated at a low cost.
第2発明によれば、鉄、鉛、ヒ素、テルルの1種以上である不純物であれば、中和や電解精製等におけるビスマスとの挙動はある程度異なるので、本発明の方法を用いることで効率よく分離でき、それだけビスマスを濃縮できるので、ビスマス回収に支障をきたさない。
第3発明によれば、アルカリ浸出液を90℃以上に加熱し、次いで冷却してヒ素を含む結晶を得ることにより、ヒ素を選択的に分離し、ヒ素を再利用しやすくできる。
第4発明によれば、溶液のpHが0〜3.5の低濃度の硫酸を用いる1次処理をした後で、溶液のpHが0未満の高濃度の硫酸を用いる2次処理を行う2段階処理を行うと、ビスマスの溶解度が上昇してより濃縮しやすくなる。
第5発明によれば、硅フッ化ビスマスを含有する電解液を用いるので、不純物を充分に分離した高純度の金属ビスマスが得られる。
第6発明のアルカリ濃度とスラリー濃度によれば、ヒ素を分離する際の分離率を向上させることができ、かつ固液分離時のろ過性の低下の防止などの効率向上が図れる。
第7発明によれば、電解採取することでビスマスが回収できないロスを低減できる。
According to the second invention, if the impurity is one or more of iron , lead, arsenic, and tellurium, the behavior with bismuth in neutralization, electrolytic refining, and the like differs to some extent. Since it can be separated well and bismuth can be concentrated as much, it does not interfere with bismuth recovery.
According to the third invention, the alkali leaching solution is heated to 90 ° C. or higher and then cooled to obtain crystals containing arsenic, whereby arsenic can be selectively separated and arsenic can be easily reused.
According to the fourth aspect of the invention, after the primary treatment using the low-concentration sulfuric acid whose pH is 0 to 3.5, the secondary treatment is performed using the high-concentration sulfuric acid whose pH is less than 0. When the step treatment is performed, the solubility of bismuth increases and it becomes easier to concentrate.
According to the fifth aspect of the invention, since the electrolytic solution containing bismuth fluorofluoride is used, high-purity metal bismuth in which impurities are sufficiently separated can be obtained.
According to the alkali concentration and the slurry concentration of the sixth invention, it is possible to improve the separation rate when separating arsenic, and to improve the efficiency such as prevention of a decrease in filterability during solid-liquid separation.
According to the seventh aspect of the present invention, it is possible to reduce a loss in which bismuth cannot be recovered by electrolytic collection.
本発明に係るビスマス精製方法の工程図である。It is process drawing of the bismuth refinement | purification method which concerns on this invention. 図1のビスマス精製方法の各工程で得られる生成物の説明図である。It is explanatory drawing of the product obtained at each process of the bismuth refinement | purification method of FIG.
本発明に係る湿式法を用いたビスマス精製方法を、以下に説明する。
本発明は、銅と貴金属とビスマスと不純物とを含有する鉱物を製錬して得た粗銅を電解精製に付して銅を回収し、次に電解精製を行うことで生成した電解スライムから湿式法により貴金属を回収する工程において、貴金属を回収後に生成した酸性溶液を以下の工程に付すことを特徴とする。
The bismuth purification method using the wet method according to the present invention will be described below.
The present invention is a method of subjecting crude copper obtained by smelting a mineral containing copper, a noble metal, bismuth and impurities to electrolytic purification to recover copper, and then wet from electrolytic slime produced by electrolytic purification. In the step of recovering the noble metal by the method, the acidic solution produced after recovering the noble metal is subjected to the following step.
図1はビスマス精製の各工程を示しており、図2は図1に示す各工程で得られる生成物の説明図である。下記符号1)〜6)は図中のものと一致している。
1)中和処理工程
貴金属の回収後に生成した前記酸性溶液にアルカリを添加してpHを2.0以上3.0以下の範囲に調整し、次いで固液分離して中和濾液と中和澱物を得る。
2)アルカリ浸出工程
前記中和処理工程で得た中和澱物にアルカリを添加してアルカリ浸出液とアルカリ浸出残渣に分離する。
3)硫酸浸出工程
前記アルカリ浸出工程で得たアルカリ浸出残渣に硫酸を添加して硫酸浸出液と硫酸浸出残渣とに分離する。
4)冷却工程
前記硫酸浸出工程で得た硫酸浸出液を冷却し、硫酸ビスマスの結晶を得る。
5)ビスマス酸化工程
前記冷却工程で得た硫酸ビスマスの結晶にアルカリを加え、酸化ビスマスを得る。
6)電解工程
前記ビスマス酸化工程で得た酸化ビスマスに酸溶液を添加して溶解し、得た溶解液を電解採取して金属ビスマスを得る。
FIG. 1 shows each step of bismuth purification, and FIG. 2 is an explanatory diagram of a product obtained in each step shown in FIG. The following symbols 1) to 6) correspond to those in the figure.
1) Neutralization treatment step An alkali is added to the acidic solution produced after the precious metal is recovered to adjust the pH to a range of 2.0 or more and 3.0 or less, followed by solid-liquid separation and neutralization filtrate and neutralization starch. Get things.
2) Alkaline leaching step An alkali is added to the neutralized starch obtained in the neutralization treatment step to separate into an alkaline leaching solution and an alkaline leaching residue.
3) Sulfuric acid leaching step Sulfuric acid is added to the alkali leaching residue obtained in the alkali leaching step to separate into a sulfuric acid leaching solution and a sulfuric acid leaching residue.
4) Cooling step The sulfuric acid leaching solution obtained in the sulfuric acid leaching step is cooled to obtain bismuth sulfate crystals.
5) Bismuth oxidation step An alkali is added to the bismuth sulfate crystals obtained in the cooling step to obtain bismuth oxide.
6) Electrolysis step An acid solution is added to and dissolved in the bismuth oxide obtained in the bismuth oxidation step, and the resulting solution is electrolyzed to obtain metal bismuth.
本発明が適用される鉱物において、不純物に含まれるものは、鉄、鉛、ヒ素、テルルの1種以上である。これらの不純物であれば、中和や電解精製等におけるビスマスとの挙動がある程度異なるので、本発明の方法を用いることで効率よく分離でき、それだけビスマスを濃縮することができる。そのため、ビスマス回収に支障をきたすことがない。一方、前記以外の例えばアンチモンなどの不純物が高濃度に含まれていると、ビスマスとの挙動が似ているので、効率的に濃縮を図ることが難しくなる不具合が生ずる。   In the mineral to which the present invention is applied, the impurities include one or more of iron, lead, arsenic, and tellurium. If these impurities are used, the behavior with bismuth in neutralization, electrolytic purification, etc. is somewhat different, so that the method of the present invention can be used for efficient separation, and bismuth can be concentrated accordingly. Therefore, there is no hindrance to bismuth recovery. On the other hand, if impurities such as antimony other than the above are contained in a high concentration, the behavior with bismuth is similar, and therefore, it becomes difficult to concentrate efficiently.
以下、本発明の各工程を詳細に説明する。
1).中和工程
電解スライムから前記湿式法により貴金属を回収した後の酸性溶液にアルカリを添加して、酸性溶液を中和する。
中和処理すると、溶解度積とpHの関係からそれぞれの元素に応じて水酸化物などの中和澱物を形成するものと、形成せずに溶解しづつける中和濾液に分離する。そのためpHを細かく調整することで中和濾液と中和澱物とに分離できる。
Hereafter, each process of this invention is demonstrated in detail.
1). Neutralization step An alkaline solution is added to the acidic solution after the noble metal is recovered from the electrolytic slime by the wet method to neutralize the acidic solution.
When the neutralization treatment is performed, the product is separated into a neutralized filtrate that forms a neutralized starch such as a hydroxide according to each element and a neutralized filtrate that dissolves without forming from the relationship between the solubility product and pH. Therefore, it can isolate | separate into a neutralization filtrate and a neutralization starch by adjusting pH finely.
本発明の後工程であるアルカリ浸出工程や硫酸浸出工程では、不純物として含有されたアンチモンや鉄をビスマスから効果的に分離することは難しい。このため、中和工程で前もってアンチモンや鉄を十分に分離することが重要である。   In the alkali leaching step and the sulfuric acid leaching step, which are the subsequent steps of the present invention, it is difficult to effectively separate antimony and iron contained as impurities from bismuth. For this reason, it is important to sufficiently separate antimony and iron in advance in the neutralization step.
この中和工程では、銅や貴金属、ビスマスの外、鉄、鉛、ヒ素、テルル、アンチモン、ニッケルイオン等の不純物を含む酸性溶液を、まずアルカリを用いてpHを2.0〜3.0の範囲に調整し、次いで中和濾液と中和澱物とに固液分離する。pHが2.0未満ではビスマスの分離効率が弱く、またpHが3.0を超えると銅、アンチモン、ヒ素、ニッケル等がビスマスと同時に沈殿し始めるので、得られるビスマスの品位を低下させるなど好ましくない。pHが2.0〜3.0の範囲であると、高い濃度でビスマスのみを分離できる。
鉄やアンチモンなどの不純物は、水酸化物の形態で分離することが取扱いの面で最適であり、pHは2.0以上3.0以下、望ましくは2.4以上2.8以下の範囲に制御することでビスマス濃度を最大化できる。
In this neutralization step, an acidic solution containing impurities such as iron, lead, arsenic, tellurium, antimony, nickel ions in addition to copper, noble metals and bismuth is first adjusted to a pH of 2.0 to 3.0 using an alkali. Adjust to the range, then solid-liquid separate into neutralized filtrate and neutralized starch. If the pH is less than 2.0, the separation efficiency of bismuth is weak, and if the pH is more than 3.0, copper, antimony, arsenic, nickel, etc. start to precipitate simultaneously with bismuth. Absent. When the pH is in the range of 2.0 to 3.0, only bismuth can be separated at a high concentration.
It is optimal in terms of handling that impurities such as iron and antimony are separated in the form of hydroxide, and the pH is in the range of 2.0 to 3.0, preferably 2.4 to 2.8. By controlling it, the bismuth concentration can be maximized.
固液分離には、ヌッチェと濾瓶、遠心分離機、フィルタープレス、デンバー濾過機などの公知の手法を用いることができ、中和状態の濾液と澱物に分けることができる。   For solid-liquid separation, known methods such as Nutsche and filter bottles, centrifuges, filter presses, Denver filters and the like can be used, which can be divided into neutralized filtrates and starches.
2).アルカリ浸出工程
元素には、酸性側でもアルカリ側でも溶解するものがあるが、本発明ではアルカリを添加することで、アルカリ浸出液とアルカリ浸出残査に分離する。中和澱物にアルカリを添加すると、ヒ素など両性化合物のようにアルカリ性でも溶解する元素が溶解する現象が生じて、アルカリ浸出液とアルカリ浸出残渣に分けることができる。
2). Alkali leaching process Some elements dissolve on the acid side or the alkali side. In the present invention, the alkali leaching solution and the alkali leaching residue are separated by adding an alkali. When an alkali is added to the neutralized starch, a phenomenon occurs in which an element that dissolves even in an alkaline state, such as an amphoteric compound such as arsenic, is dissolved, and can be divided into an alkaline leaching solution and an alkaline leaching residue.
後工程で硫酸を使った浸出を検討することを考慮すると、上記中和工程で生成され、残渣へ分配される鉄、鉛、ヒ素の割合は、これを50%以下に抑制することが必要となる。   Considering the study of leaching using sulfuric acid in the subsequent process, the ratio of iron, lead, and arsenic produced in the neutralization process and distributed to the residue needs to be suppressed to 50% or less. Become.
添加するアルカリには、消石灰や水酸化ナトリウムを用いることができる。添加方法は消石灰を水に混合しスラリー状態としたり、水酸化ナトリウムを水に溶解した溶解液などの状態で定量ポンプを用いて添加したりする方法などを利用できる。消石灰を用いると硫酸カルシウム(石膏)が生成して回収ビスマスに対して不純物となることがあるので、中和後の生成物が水溶性である水酸化ナトリウムを用いることが好ましい。   As the alkali to be added, slaked lime or sodium hydroxide can be used. As the addition method, a method of mixing slaked lime with water to form a slurry, or adding a solution of sodium hydroxide dissolved in water using a metering pump can be used. When slaked lime is used, calcium sulfate (gypsum) may be generated and become an impurity with respect to the recovered bismuth. Therefore, it is preferable to use sodium hydroxide in which the product after neutralization is water-soluble.
アルカリ浸出工程の一例では、中和澱物に含有されたヒ素を水酸化ナトリウムを用いてアルカリ浸出液中に浸出する。浸出したヒ素は、アルカリ浸出液を90℃以上に加熱し、次いで冷却してヒ素を含む結晶を得る煮沸工程を経ることで分離できる。つまり、高温でヒ素の結晶構造が変ることを利用して、ヒ素を選択的に分離する。この煮沸工程を経ると、ヒ素を再利用しやすくできる利点が得られる。   In an example of the alkaline leaching step, arsenic contained in the neutralized starch is leached into an alkaline leaching solution using sodium hydroxide. The leached arsenic can be separated through a boiling step in which the alkaline leaching solution is heated to 90 ° C. or higher and then cooled to obtain crystals containing arsenic. That is, arsenic is selectively separated by utilizing the change in the crystal structure of arsenic at a high temperature. Through this boiling step, there is an advantage that arsenic can be easily reused.
ヒ素をより多く除去するためには、前記の中和澱物に水酸化ナトリウムの溶液を添加しスラリーとして反応させるとよい。水酸化ナトリウムの濃度や反応開始時のスラリー濃度は、中和澱物中に含有するヒ素の物量に応じて調整すればよい。   In order to remove more arsenic, a solution of sodium hydroxide may be added to the neutralized starch and reacted as a slurry. The concentration of sodium hydroxide and the slurry concentration at the start of the reaction may be adjusted according to the amount of arsenic contained in the neutralized starch.
具体的には、1〜5mol/lの濃度の水酸化ナトリウム溶液を用い、スラリー濃度を10〜100g/lになるように添加することが好ましい。なお水酸化ナトリウム濃度は2mol/l前後の濃度とすることがさらに望ましい。
また反応温度は60℃前後が適当であり、それより低いと反応が遅くなる。一方60℃より高くても反応が過度に促進されることはなくエネルギーコストが余計にかかるなど好ましくない。
Specifically, it is preferable to use a sodium hydroxide solution having a concentration of 1 to 5 mol / l and add the slurry concentration to 10 to 100 g / l. The sodium hydroxide concentration is more preferably about 2 mol / l.
The reaction temperature is suitably around 60 ° C., and if it is lower, the reaction will be slow. On the other hand, even if the temperature is higher than 60 ° C., the reaction is not excessively promoted, and the energy cost is excessive.
水酸化ナトリウムの濃度が1mol/lより低いと、ヒ素が除去しきれず、中和澱物中に一部が残存するなどの不都合がある。
また、水酸化ナトリウムの濃度が5mol/lを超えるなど過剰に高くなると、ヒ素以外のアンチモンや鉄などの不純物も浸出される。この場合、アルカリ浸出残渣に残留するビスマス純度が上昇するメリットがあるものの、水酸化ナトリウムの使用量が増加するためコストが増加し、さらにビスマスの一部までもがアルカリ浸出液中へ浸出されてロスが増加するなどの課題があり好ましくない。
When the concentration of sodium hydroxide is lower than 1 mol / l, arsenic cannot be completely removed, and there is a disadvantage that a part remains in the neutralized starch.
In addition, when the concentration of sodium hydroxide is excessively high such as exceeding 5 mol / l, impurities such as antimony and iron other than arsenic are also leached. In this case, although there is a merit that the purity of bismuth remaining in the alkali leaching residue is increased, the amount of sodium hydroxide used increases, so the cost increases, and even a part of bismuth is leached into the alkali leaching solution and lost. There is a problem such as an increase in the number and is not preferable.
スラリー濃度が10g/lより低いとアルカリ溶液に対する中和澱物の当量が少なすぎるので、相対的に溶解するビスマスの物量が増加してロスが増加するなどの不都合があり、100g/lより高いとアルカリ溶液に対する中和澱物の当量が多すぎるので、ヒ素を十分に溶解して除去できず、その結果ヒ素の除去効果が低下するなどの不都合がある。これに対し、スラリー濃度が10g/l以上100g/l以下であると、ビスマスのロスを抑制しつつ同時に効率よくヒ素が除去できるという利点が得られる。   If the slurry concentration is lower than 10 g / l, the equivalent of the neutralized starch to the alkaline solution is too small, and there is a disadvantage that the amount of bismuth dissolved relatively increases and the loss increases, and is higher than 100 g / l. Since there are too many equivalents of neutralized starch with respect to the alkaline solution, arsenic cannot be sufficiently dissolved and removed, and as a result, the effect of removing arsenic is reduced. On the other hand, when the slurry concentration is 10 g / l or more and 100 g / l or less, there is an advantage that arsenic can be efficiently removed while suppressing loss of bismuth.
また、例えば上記の中和澱物に原料やその処理工程に由来する塩化物(Cl)イオンが含有されている場合、ビスマスがオキシクロロビスマス(BiClO)のような硫酸に対して高い溶解度を持つ化合物として存在し、後述の冷却工程での硫酸ビスマスの析出を阻害することがある。しかし、本発明のアルカリ浸出を用いることでアルカリ浸出残渣中の塩化物イオンの品位を0.1%以下に抑制することができ、その結果、後述の冷却工程でのビスマスのロスを低減できる効果もある。   In addition, for example, when the neutralized starch contains chloride (Cl) ions derived from the raw material and its processing step, bismuth has high solubility in sulfuric acid such as oxychlorobismuth (BiClO). It exists as a compound and may inhibit the precipitation of bismuth sulfate in the cooling step described later. However, by using the alkaline leaching of the present invention, the quality of chloride ions in the alkaline leaching residue can be suppressed to 0.1% or less, and as a result, the effect of reducing the loss of bismuth in the cooling process described later. There is also.
アルカリ浸出液中のヒ素濃度が高すぎると、浸出液中にヒ酸2水素ナトリウムの結晶が発生することがあり、発生に伴ってろ過性が悪化したり、発生した結晶を溶解して除去するために行う洗浄負荷が増加したりするなど好ましくない。   If the concentration of arsenic in the alkaline leachate is too high, crystals of sodium dihydrogen arsenate may be generated in the leachate, and the filterability deteriorates with the generation, or the generated crystals are dissolved and removed. It is not preferable that the cleaning load to be performed is increased.
なお、アルカリ浸出工程で得られる残渣中のヒ素とビスマスはモル比(As/Bi)が0.1以下になるように浸出する。この比率になるように浸出することで、後述の硫酸浸出工程でビスマスを90%以上回収できる。   Arsenic and bismuth in the residue obtained in the alkali leaching step are leached so that the molar ratio (As / Bi) is 0.1 or less. By leaching so as to have this ratio, 90% or more of bismuth can be recovered in a sulfuric acid leaching process described later.
3).硫酸浸出工程
上記のアルカリ浸出工程で得たアルカリ浸出残渣に硫酸を添加して、硫酸濃度により溶解度に差が生じることを利用して硫酸浸出液と硫酸浸出残渣とに分離する。
3). Sulfuric acid leaching step Sulfuric acid is added to the alkaline leaching residue obtained in the above alkaline leaching step, and the sulfuric acid leaching solution and the sulfuric acid leaching residue are separated by utilizing the difference in solubility depending on the sulfuric acid concentration.
なお、上述のように塩化物イオンが含有される場合、前記アルカリ浸出工程と硫酸浸出工程の間に、アルカリ浸出残渣を水で洗浄する洗浄工程(pH調整工程)を設けて残留塩化物品位をさらに低減する処理を行ってもよい。洗浄工程では、アルカリ浸出残渣に水を加えてスラリー状態にし、pHが2.5〜3.5、好ましくは3程度を示すまで洗浄することで、中和澱物中のビスマス成分の分散性が向上し、硫酸に浸出されやすくなる。   In addition, when chloride ions are contained as described above, a washing step (pH adjustment step) for washing the alkaline leaching residue with water is provided between the alkali leaching step and the sulfuric acid leaching step to reduce the residual chloride product level. Further reduction processing may be performed. In the washing step, water is added to the alkali leaching residue to form a slurry, and washing is performed until the pH is 2.5 to 3.5, preferably about 3, so that the dispersibility of the bismuth component in the neutralized starch is increased. It improves and becomes easy to leach into sulfuric acid.
硫酸浸出工程では、硫酸濃度を変えて2段階の浸出処理を行うことが好ましい。つまり、最初に低濃度の硫酸を接触させて浸出残渣を浸出して1次浸出液と1次浸出残渣とに分離する1次処理を行い、次に前述の1次浸出残渣に高濃度の硫酸を接触させて2次浸出液と2次浸出残渣とに分離する2次処理を行うことが好ましい。   In the sulfuric acid leaching step, it is preferable to perform a two-stage leaching process by changing the sulfuric acid concentration. That is, firstly, a primary treatment is performed in which low concentration sulfuric acid is contacted to leach the leaching residue and separate into a primary leaching solution and a primary leaching residue, and then high concentration sulfuric acid is applied to the primary leaching residue. It is preferable to perform a secondary treatment in which contact is made to separate the secondary leaching solution and the secondary leaching residue.
また、前述の2次浸出液は、上記冷却工程に供給することが好ましい。このような2段階の浸出処理を行うことで、ビスマスの溶解度が上昇して、濃縮しやすくなる。   Moreover, it is preferable to supply the above-mentioned secondary leaching solution to the cooling step. By performing such a two-stage leaching process, the solubility of bismuth increases and it becomes easy to concentrate.
本発明で低濃度の硫酸とは、溶液のpHが0〜3.5、好ましくはpH3前後の範囲である弱酸性の濃度の硫酸溶液を言い、高濃度の硫酸とは、pHが0未満となる強酸性の濃度の硫酸溶液のことを指し、具体的には7mol/l以上、好ましくは10mol/l程度の濃度となる。上述の高濃度の硫酸による浸出時は、スラリーの温度は30〜90℃の範囲とすることがよい。   In the present invention, low-concentration sulfuric acid refers to a weakly acidic sulfuric acid solution in which the pH of the solution is in the range of 0 to 3.5, preferably around pH 3, and high-concentration sulfuric acid refers to a pH of less than 0. This is a sulfuric acid solution having a strongly acidic concentration. Specifically, the concentration is 7 mol / l or more, preferably about 10 mol / l. At the time of leaching with the above-described high-concentration sulfuric acid, the temperature of the slurry is preferably in the range of 30 to 90 ° C.
具体的には、前記のアルカリ浸出残渣に硫酸を添加してpHが0〜3.5の範囲に調整したスラリーとし、銅や鉄を浸出する。pH0〜1の硫酸浸出工程において例えばアルカリ浸出残渣に含まれた銅の中で硫酸浸出液への銅の分配(浸出率)は50%以上となることが好ましい。分配が50%未満では、銅の除去が不十分でビスマス製品中の銅品位に悪影響を及ぼす。   Specifically, sulfuric acid is added to the alkali leaching residue to make a slurry adjusted to a pH of 0 to 3.5, and copper and iron are leached. In the sulfuric acid leaching step of pH 0 to 1, for example, among the copper contained in the alkaline leaching residue, the distribution (leaching rate) of copper to the sulfuric acid leaching solution is preferably 50% or more. If the distribution is less than 50%, copper removal is insufficient and the copper quality in the bismuth product is adversely affected.
またビスマスのアルカリ浸出残渣に含まれた中からの硫酸浸出液への分配(浸出率)は2%以下とすることが必要である。2%を超える分配では、処理全体でのビスマスのロスが無視できなくなる。   The distribution (leaching rate) of the bismuth contained in the alkaline leaching residue into the sulfuric acid leaching solution needs to be 2% or less. If the distribution exceeds 2%, the loss of bismuth in the entire process cannot be ignored.
4).冷却工程
前記硫酸浸出工程で得た硫酸浸出液を冷却して硫酸ビスマスの結晶を晶析させて得る。この冷却工程は、溶解度の差を利用するもので、一般に溶解度は温度が下がるほど下がるので、液体で溶けきれなくなる。そのため、冷却することにより硫酸ビスマスの結晶を得ることができる。
4). Cooling step The sulfuric acid leaching solution obtained in the sulfuric acid leaching step is cooled to crystallize bismuth sulfate crystals. This cooling step uses a difference in solubility. Generally, the solubility is lowered as the temperature is lowered, so that it cannot be completely dissolved by the liquid. Therefore, bismuth sulfate crystals can be obtained by cooling.
冷却方法には、例えば上記の硫酸浸出液を満たした反応槽(冷却槽)の外部にジャケットを設けたり、反応槽内に蛇管を設置したりし、反応槽内を撹拌しつつジャケットや蛇管の中に水等の冷媒を流すことで行える。なお、冷却時に予め得た硫酸ビスマスの結晶を種として浸出液に添加してもよい。
冷却は低い温度まで行う方がよいが、冷却に要するコストや効率などを考えると、30℃未満の室温程度まで冷却するのがよい。また、冷却に要する時間は1時間程度とすることがよい。
For the cooling method, for example, a jacket is provided outside the reaction tank (cooling tank) filled with the sulfuric acid leachate, or a serpentine tube is installed in the reaction tank. This can be done by flowing a coolant such as water. Note that bismuth sulfate crystals obtained in advance during cooling may be added as seeds to the leachate.
Cooling is preferably performed to a low temperature, but considering the cost and efficiency required for cooling, it is preferable to cool to a room temperature of less than 30 ° C. The time required for cooling is preferably about 1 hour.
5).ビスマス酸化工程
前記冷却工程で得た硫酸ビスマスの結晶にアルカリを加える。アルカリを加えると、ビスマス以外を溶解するので、酸化ビスマスを得ることができる。
具体的には、例えば1〜2mol/l程度の濃度の水酸化ナトリウム溶液をスラリー濃度が25g/l程度になるように上記の硫酸ビスマスの結晶と混合し、温度を60℃程度に維持しながら1時間程度撹拌すると、水酸化ビスマス(Bi(OH))が得られ、これを乾燥すると酸化ビスマス(Bi)が得られる。
5). Bismuth oxidation step An alkali is added to the crystals of bismuth sulfate obtained in the cooling step. When alkali is added, other than bismuth is dissolved, so that bismuth oxide can be obtained.
Specifically, for example, a sodium hydroxide solution having a concentration of about 1 to 2 mol / l is mixed with the above bismuth sulfate crystals so that the slurry concentration is about 25 g / l, and the temperature is maintained at about 60 ° C. When stirred for about 1 hour, bismuth hydroxide (Bi (OH) 3 ) is obtained, and when dried, bismuth oxide (Bi 2 O 3 ) is obtained.
6).電解工程
前記ビスマス酸化工程で得た酸化ビスマスに酸溶液を添加して溶解する。このように酸溶液を加えると、ビスマスがイオンとして溶解するが、得た溶解液を電解採取すると、つまり溶解液に電極を入れて通電するとビスマスイオンが電子を受けてカソード上に単体の金属ビスマスとして電析する。
6). Electrolysis step An acid solution is added to and dissolved in the bismuth oxide obtained in the bismuth oxidation step. When an acid solution is added in this manner, bismuth dissolves as ions. However, when the obtained solution is electrolyzed, that is, when an electrode is placed in the solution and energized, the bismuth ions receive electrons and form a single metal bismuth on the cathode. Electrodeposit as
電解に用いる酸溶液には塩酸なども用いることができるが、ビスマスの溶解度が十分に高く電解に好都合なビスマス濃度が確保でき、しかも共存する不純物との分離性が高いことから硅フッ酸溶液が好ましい。硅フッ酸を含有する溶液を用いた電解浴とすることで、硅フッ化ビスマスの形で存在する電解液中から不純物を充分に分離した金属ビスマスが得られる。   Hydrochloric acid or the like can be used for the acid solution used for the electrolysis. However, since the solubility of bismuth is sufficiently high and a bismuth concentration favorable for electrolysis can be secured and the separability from coexisting impurities is high, the hydrofluoric acid solution is used. preferable. By using an electrolytic bath using a solution containing 硅 hydrofluoric acid, metal bismuth in which impurities are sufficiently separated from the electrolyte present in the form of bismuth fluorinated fluoride can be obtained.
金属ビスマスを得る具体的な電解条件としては、例えば、硅フッ酸濃度が300〜350g/lの溶液を用いて酸化ビスマスを溶解し、ビスマス濃度が80〜100g/lの電解始液を得、この電解始液をカソードにハステロイ、アノードにカーボンを用いた電解槽に供給し、液温を40〜50℃、好ましくは50℃以下、に維持しつつ、80〜120A/mのカソード電流密度で通電することで、カソード上に金属ビスマスを電析させることができる。電流密度が200A/mを超えると電着表面の状態が荒れて粒上析出物が生じやすく電解液が巻き込まれるなど好ましくない。
電解の終了は例えば電解液中のビスマス濃度が20〜30g/l程度まで低下した時点とすれば、析出するビスマスの表面状態の悪化を抑止でき、電解液の巻き込みなどの影響のない表面平滑なビスマスメタルを得ることができて好ましい。
Specific electrolysis conditions for obtaining metal bismuth include, for example, dissolving bismuth oxide using a solution having a hydrofluoric acid concentration of 300 to 350 g / l to obtain an electrolytic starting solution having a bismuth concentration of 80 to 100 g / l. This electrolytic starting solution is supplied to an electrolytic cell using Hastelloy for the cathode and carbon for the anode, and the cathode current density of 80 to 120 A / m 2 is maintained while maintaining the liquid temperature at 40 to 50 ° C., preferably 50 ° C. or less. By energizing at, metal bismuth can be electrodeposited on the cathode. If the current density exceeds 200 A / m 2 , the state of the electrodeposition surface becomes rough and precipitates on the grains are likely to be formed, which is undesirable.
When the electrolysis is finished, for example, when the bismuth concentration in the electrolytic solution is reduced to about 20 to 30 g / l, the deterioration of the surface state of the deposited bismuth can be suppressed, and the surface smoothness without influence of the electrolytic solution is suppressed. Bismuth metal can be obtained and is preferable.
なお、電解始液にビスマスメタルを添加し、浸漬させて電解始液に含有された銀イオンをビスマスメタル上に析出させるセメンテーション反応に付した後の液を電解に付すとビスマスメタル中の銀品位を低減することができて好ましい。セメンテーション反応は、電解始液の酸化還元電位(ORP)が銀・塩化銀電極を参照電極とする値で400〜518mVの範囲あるいはそれ以下に低減するように、ビスマスメタルを添加して行うことがよい。   In addition, when bismuth metal is added to the electrolytic starting solution and immersed in a cementation reaction in which silver ions contained in the electrolytic starting solution are deposited on bismuth metal, the solution is subjected to electrolysis. It is preferable because the quality can be reduced. The cementation reaction should be carried out by adding bismuth metal so that the oxidation-reduction potential (ORP) of the electrolytic starting solution is reduced to a value in the range of 400 to 518 mV or less with a silver / silver chloride electrode as a reference electrode. Is good.
また、電解終了後はカソードを引き上げて電着したビスマスを剥ぎ取り、水で洗浄し、ついで炉の中に入れて不活性雰囲気下でビスマスの融点(271℃)を若干上回る300℃くらいの温度で熔解することで、不純物や酸化物を取り除き、インゴット等の形状のビスマスメタルを得ることができる。   After the electrolysis is finished, the cathode is pulled up, the electrodeposited bismuth is peeled off, washed with water, then placed in a furnace, and the temperature is about 300 ° C., slightly higher than the melting point of bismuth (271 ° C.) in an inert atmosphere. By melting with, impurities and oxides can be removed and bismuth metal having a shape such as an ingot can be obtained.
(実施例1)
銅精鉱を炉に入れて高温で熔解して不純物を分離した粗銅を鋳造して得たアノードを硫酸酸性溶液が張られた電解槽中に浸漬し、同時に面対して装入された銅ないしステンレス製のカソードとの間に通電し、カソード表面上に電気銅を電着させる公知の銅の電解精製方法を用いて、金や銀などの貴金属などを含有する銅電解スライムを得、この銅電解スライムに公知の方法を用いて塩素ガス等の酸化剤を作用させて銅電解スライムから浸出された貴金属が含有された酸性溶液を用意した。
Example 1
An anode obtained by casting copper concentrate in a furnace and melting crude copper separated from impurities by high temperature immersion is immersed in an electrolytic cell filled with a sulfuric acid solution, and at the same time, the copper or A copper electrolytic slime containing a noble metal such as gold or silver is obtained by using a known copper electrolytic purification method in which a current is passed between a cathode made of stainless steel and electrolytic copper is electrodeposited on the cathode surface. An acidic solution containing a noble metal leached from the copper electrolytic slime was prepared by allowing an oxidizing agent such as chlorine gas to act on the electrolytic slime using a known method.
次にこの酸性溶液に常温で水酸化ナトリウムを添加し、pHを2.6に調整したスラリーを得た。次いで、このスラリーをヌッチェと濾瓶を用い、5Cのろ紙を使用して中和澱物と中和濾液とに固液分離した(中和処理工程)。元液に含有されたビスマス、鉄、鉛、ヒ素の各成分が中和澱物に分配した割合を求めると、ビスマス;90%、鉄;40%、鉛;40%、ヒ素;40%となり、ビスマス以外の成分の半分以上の量を分離できた。   Next, sodium hydroxide was added to this acidic solution at room temperature to obtain a slurry adjusted to pH 2.6. Next, this slurry was subjected to solid-liquid separation into a neutralized starch and a neutralized filtrate using 5C filter paper using a Nutsche and a filter bottle (neutralization treatment step). When the proportion of each component of bismuth, iron, lead, and arsenic contained in the original solution was distributed to the neutralized starch, bismuth; 90%, iron; 40%, lead; 40%, arsenic; 40%, More than half of the components other than bismuth could be separated.
(実施例2)
上記実施例1と同じ貴金属を含有する銅電解スライムから貴金属を浸出した酸性溶液を使用し、水酸化ナトリウム溶液を添加してpHを2.6に調整し、実施例1と同じ方法で中和澱物と中和濾液を得た(中和処理工程)。
(Example 2)
Using an acidic solution obtained by leaching a noble metal from a copper electrolytic slime containing the same noble metal as in Example 1 above, adding sodium hydroxide solution to adjust the pH to 2.6, and neutralizing in the same manner as in Example 1 A starch and a neutralized filtrate were obtained (neutralization treatment step).
次に、中和澱物に濃度2mol/lの水酸化ナトリウムを添加して浸出しアルカリ浸出残渣を得た(アルカリ浸出工程)。得たアルカリ浸出残渣にさらに低濃度の硫酸を添加しスラリー濃度を100g/lに調整し1時間撹拌して硫酸浸出液を得た(硫酸浸出工程)。硫酸添加後のスラリーのpHを0.8に調整した。
硫酸浸出液への銅の浸出率は53%となった。一方、ビスマスの浸出は0.7%に抑制でき目標を達成できた。
Next, sodium hydroxide having a concentration of 2 mol / l was added to the neutralized starch and leached to obtain an alkali leaching residue (alkali leaching step). A lower concentration of sulfuric acid was added to the obtained alkali leaching residue to adjust the slurry concentration to 100 g / l and stirred for 1 hour to obtain a sulfuric acid leaching solution (sulfuric acid leaching step). The pH of the slurry after addition of sulfuric acid was adjusted to 0.8.
The leaching rate of copper in the sulfuric acid leaching solution was 53%. On the other hand, the leaching of bismuth was suppressed to 0.7%, and the target was achieved.
得られた残渣に10mol/L濃度の硫酸を添加してスラリーとし温度を60℃に維持して残渣中のBiを浸出した。
残渣を分離後、浸出液を室温まで冷却し、硫酸ビスマスの結晶を得た(冷却工程)。得られた結晶をpH14の苛性ソーダ溶液に投入後撹拌し、酸化ビスマスの結晶を得た。得た結晶を濃度が336g/lの硅フッ酸溶液に溶解してビスマス濃度が100g/lになるように調整し、またこの溶解液に別途用意したビスマスメタルを浸漬してセメンテーション反応により溶解液の銀濃度を13mg/lから分析下限の5mg/l未満まで脱銀した液を電解始液とした(ビスマス酸化工程)。
To the obtained residue, 10 mol / L sulfuric acid was added to form a slurry, and the temperature was maintained at 60 ° C. to leach Bi in the residue.
After separating the residue, the leachate was cooled to room temperature to obtain bismuth sulfate crystals (cooling step). The obtained crystals were added to a caustic soda solution having a pH of 14 and stirred to obtain bismuth oxide crystals. The obtained crystals are dissolved in a hydrofluoric acid solution having a concentration of 336 g / l to adjust the bismuth concentration to 100 g / l, and separately prepared bismuth metal is immersed in this solution to dissolve by a cementation reaction. A solution obtained by desilvering the silver concentration of the solution from 13 mg / l to less than 5 mg / l, which is the lower limit of analysis, was used as an electrolytic starting solution (bismuth oxidation step).
次にこの電解始液を電解槽に入れ、液温度を45〜50℃に維持した。電解槽にハステロイ製のカソードとカーボン製のアノードを面間距離が50mmになるように並べた。次に電解槽から排出される電解液をポンプを用いて電解槽に再度給液することで循環させながら、100A/mとなるカソード電流密度で通電した(電解工程)。電解槽から排出される電解液のビスマス濃度を分析し、ビスマス濃度が25g/l以下まで低下した時点で、通電を止めた。
次いでカソードを引揚げ、電着したビスマスメタルをカソードから剥ぎ取り、ビスマスメタルを水で洗浄し、乾燥させた。
得られたビスマスメタルの量を通電電流量から算出した理論電着量で除した電流効率は99.6%だった。
Next, this electrolytic starting solution was put in an electrolytic cell, and the solution temperature was maintained at 45 to 50 ° C. In the electrolytic cell, a Hastelloy cathode and a carbon anode were arranged so that the distance between the surfaces was 50 mm. Next, current was supplied at a cathode current density of 100 A / m 2 while circulating the electrolytic solution discharged from the electrolytic cell by supplying the electrolytic solution again to the electrolytic cell using a pump (electrolytic process). The bismuth concentration of the electrolyte discharged from the electrolytic cell was analyzed, and when the bismuth concentration dropped to 25 g / l or less, the energization was stopped.
Next, the cathode was lifted, and the electrodeposited bismuth metal was peeled off from the cathode, and the bismuth metal was washed with water and dried.
The current efficiency obtained by dividing the amount of the obtained bismuth metal by the theoretical electrodeposition amount calculated from the amount of energized current was 99.6%.
次に、得たビスマスメタルをGDMS(グロー放電質量分析装置)を用いて分析した。その結果、主な不純物である銀が70ppm程度で、セメンテー所の反応を行わなかった場合の1300ppmに比べて大幅に低減でき、ビスマス品位として99.993%に達する高純度なビスマスメタルが得られた。   Next, the obtained bismuth metal was analyzed using GDMS (glow discharge mass spectrometer). As a result, silver, the main impurity, is about 70 ppm, which can be significantly reduced compared to 1300 ppm when the cementite reaction is not performed, and a high-purity bismuth metal having a bismuth quality of 99.993% is obtained. It was.
また、アルカリ浸出工程で得た、浸出液並びに洗浄液を90℃の温度に煮沸したところ、ヒ酸2水素ナトリウムの結晶を得られ、ろ過することでヒ素を固体として分離し回収できた。   Moreover, when the leaching solution and the washing solution obtained in the alkali leaching step were boiled to a temperature of 90 ° C., crystals of sodium dihydrogen arsenate were obtained, and arsenic was separated and recovered as a solid by filtration.
(実施例3)
上記実施例1および2と同じ酸性溶液を用い、この酸性溶液に常温で水酸化ナトリウムを添加し、pHを2.6に調整したスラリーを得、次いで、実施例1および2と同じ方法を用いて中和澱物と中和濾液とに固液分離した(中和処理工程)。この中和澱物中に含有されたビスマス品位は19重量%、塩化物イオンの品位は11重量%だった。
(Example 3)
Using the same acidic solution as in Examples 1 and 2 above, sodium hydroxide was added to this acidic solution at room temperature to obtain a slurry adjusted to pH 2.6, and then the same method as in Examples 1 and 2 was used. The solid was separated into a neutralized starch and a neutralized filtrate (neutralization treatment step). The bismuth grade contained in the neutralized starch was 19% by weight, and the grade of chloride ions was 11% by weight.
次にこの中和澱物に濃度2mol/lの水酸化ナトリウム溶液を加えてスラリー濃度を100g/lとし、スラリーの温度を60℃に維持しつつ1時間撹拌した(アルカリ浸出工程)。次に撹拌終了後のスラリーを固液分離し、得たアルカリ浸出残渣を水で洗浄し、再度固液分離した洗浄後のアルカリ浸出残渣を分析した。その結果、ビスマス品位が28.1重量%に対して塩化物イオンの品位は0.01重量%と塩化物を大幅に低減できた。   Next, a sodium hydroxide solution having a concentration of 2 mol / l was added to the neutralized starch to make the slurry concentration 100 g / l, and the slurry was stirred for 1 hour while maintaining the temperature of the slurry at 60 ° C. (alkali leaching step). Next, the slurry after the completion of stirring was subjected to solid-liquid separation, the obtained alkaline leaching residue was washed with water, and the washed alkaline leaching residue obtained by solid-liquid separation again was analyzed. As a result, the bismuth grade was 28.1% by weight, and the chloride ion grade was 0.01% by weight, which significantly reduced chloride.
次に上記の洗浄後のアルカリ浸出残渣を上記実施例2と同様の処理を行い、10mol/l濃度の硫酸で浸出してビスマス濃度3.7g/lの浸出液を得、この浸出液を60℃から室温(25℃)まで冷却し、固液分離するとビスマス濃度1.0g/lの濾液が得られ、浸出液中に含まれたビスマスの73%を回収することができた。   Next, the alkaline leaching residue after washing was treated in the same manner as in Example 2 above, and leached with sulfuric acid having a concentration of 10 mol / l to obtain a leachate having a bismuth concentration of 3.7 g / l. After cooling to room temperature (25 ° C.) and solid-liquid separation, a filtrate having a bismuth concentration of 1.0 g / l was obtained, and 73% of the bismuth contained in the leachate could be recovered.
(実施例4)
上記実施例3と同じ方法でアルカリ浸出残渣を得、このアルカリ浸出残渣に濃度が8mol/lの硫酸を加えてビスマスを浸出した浸出液を得た。次いで得た浸出液を実施例3と同じ方法で冷却すると浸出液に含まれたビスマスの80%を回収することができた。
Example 4
An alkaline leaching residue was obtained by the same method as in Example 3 above, and a leaching solution in which bismuth was leached by adding sulfuric acid having a concentration of 8 mol / l to the alkaline leaching residue was obtained. Next, when the obtained leachate was cooled by the same method as in Example 3, 80% of the bismuth contained in the leachate could be recovered.
(実施例5)
上記実施例2と同じ方法でアルカリ浸出残渣を得、このアルカリ浸出残渣にスラリー濃度が100g/lとなるように硫酸と水を添加してpHを3.0に調整し、1時間撹拌を継続した。固液分離後、得た残渣に濃度10mol/lの硫酸と水を添加してスラリーとし、60℃に維持しつつ2時間浸出した。得た浸出液のビスマス濃度は3.0g/lと十分に浸出されたことが確認された。
(Example 5)
An alkali leaching residue was obtained in the same manner as in Example 2 above, and sulfuric acid and water were added to the alkali leaching residue so that the slurry concentration was 100 g / l to adjust the pH to 3.0, and stirring was continued for 1 hour. did. After solid-liquid separation, sulfuric acid and water having a concentration of 10 mol / l were added to the obtained residue to form a slurry, which was leached for 2 hours while maintaining at 60 ° C. It was confirmed that the obtained leaching solution was sufficiently leached with a bismuth concentration of 3.0 g / l.
(比較例1)
pHを3.8に調整した以外は、上記実施例1と同じ装置及び同じ酸性溶液を用い、同じ方法で中和した。中和澱物へ分配した割合は、ビスマスは95%と良好だったものの、鉄;80%、鉛;60%、ヒ素40%となりビスマス品位は52%程度のものしか得られなかった。
(Comparative Example 1)
Except for adjusting the pH to 3.8, the same apparatus and the same acidic solution as in Example 1 were used to neutralize in the same manner. The proportion of bismuth distributed to the neutralized starch was as good as 95%, but iron: 80%, lead: 60%, arsenic 40%, and a bismuth grade of only about 52% was obtained.
(比較例2)
上記実施例2と同様に作成した中和澱物を、アルカリ浸出することなく、実施例1と同条件で硫酸浸出を行ったところ、ビスマスの浸出率は60%だった。浸出液中のビスマス濃度は4.0g/lとなった。しかし、浸出後の残渣を再度同じ条件で硫酸浸出したが、ビスマスは殆ど浸出しなかった。また、浸出液を冷却しても硫酸ビスマスの結晶を得ることはほとんどできなかった。
(Comparative Example 2)
When the neutralized starch prepared in the same manner as in Example 2 was subjected to sulfuric acid leaching under the same conditions as in Example 1 without leaching with alkali, the bismuth leaching rate was 60%. The bismuth concentration in the leachate was 4.0 g / l. However, the leaching residue was again leached with sulfuric acid under the same conditions, but bismuth hardly leached. Further, even when the leachate was cooled, bismuth sulfate crystals could hardly be obtained.
(比較例3)
上記実施例2と同様に作成した中和澱物を、水酸化ナトリウムでpH3.5に調整してアルカリ浸出し、その硫酸溶液を添加してpHを1.2に調整した以外は、上記実施例2と同等の方法で処理した。液中へのビスマスの分配は1.5%と十分な範囲だったが、銅の分配(浸出率)は45%と不足した。
(Comparative Example 3)
Except that the neutralized starch prepared in the same manner as in Example 2 was adjusted to pH 3.5 with sodium hydroxide and alkali leached, and the sulfuric acid solution was added to adjust the pH to 1.2. Treated in the same manner as Example 2. The distribution of bismuth into the liquid was a sufficient range of 1.5%, but the distribution (leaching rate) of copper was insufficient at 45%.
(比較例4)
上記実施例2と同様に作成した中和澱物を、水酸化ナトリウムでpHを3.5に調整してアルカリ浸出し、その後pHが0未満となる高濃度の硫酸を用いた以外は、実施例2と同等の方法で処理した。その結果、液中への銅の溶出は55%で満足する結果だったが、ビスマスが3%も浸出され、目標のビスマスの浸出率に抑えることが出来なかった。
(Comparative Example 4)
The neutralized starch prepared in the same manner as in Example 2 above was adjusted to 3.5 with sodium hydroxide, and alkaline leaching was performed, except that high-concentration sulfuric acid with a pH of less than 0 was used. Treated in the same manner as Example 2. As a result, the dissolution of copper into the solution was satisfactory at 55%, but 3% of bismuth was leached, and the target bismuth leaching rate could not be suppressed.
(参考例1)
上記実施例4と同じ方法でアルカリ浸出残渣を得、このアルカリ浸出残渣に濃度が6mol/lの硫酸を加えてビスマスを浸出した浸出液を得た。次いで得た浸出液を実施例4と同じ方法で冷却すると浸出液に含まれたビスマスの45%しか回収できなかった。
(Reference Example 1)
An alkali leaching residue was obtained by the same method as in Example 4 above, and a leaching solution was obtained in which bismuth was leached by adding sulfuric acid having a concentration of 6 mol / l to the alkali leaching residue. Subsequently, when the obtained leachate was cooled by the same method as in Example 4, only 45% of the bismuth contained in the leachate could be recovered.
(参考例2)
上記実施例5と同じ方法でアルカリ浸出残渣を得、このアルカリ浸出残渣をpH調整することなく濃度10mol/lの硫酸と水を添加してスラリーとし、60℃に維持しつつ2時間浸出した。得た浸出液のビスマス濃度は1.2g/lと不十分な浸出しか得られなかった。
(Reference Example 2)
An alkali leaching residue was obtained in the same manner as in Example 5 above, and sulfuric acid and water having a concentration of 10 mol / l were added to the alkali leaching residue without adjusting the pH to form a slurry, which was leached for 2 hours while maintaining at 60 ° C. The obtained leaching solution had a bismuth concentration of 1.2 g / l, which was insufficient leaching.
(参考例3)
上記実施例5と同じ方法でアルカリ浸出残渣を得、このアルカリ浸出残渣にスラリー濃度が100g/lとなるように硫酸と水を添加してpHを5に調整し、1時間撹拌を継続した。固液分離後、得た残渣に濃度10mol/lの硫酸と水を添加してスラリーとし、60℃に維持しつつ2時間浸出した。得た浸出液のビスマス濃度は2.5g/lと不十分な浸出にとどまった。
(Reference Example 3)
An alkali leaching residue was obtained in the same manner as in Example 5, and sulfuric acid and water were added to the alkali leaching residue so that the slurry concentration was 100 g / l to adjust the pH to 5 and stirring was continued for 1 hour. After solid-liquid separation, sulfuric acid and water having a concentration of 10 mol / l were added to the obtained residue to form a slurry, which was leached for 2 hours while maintaining at 60 ° C. The obtained leaching solution had a bismuth concentration of 2.5 g / l, which was insufficient.
(参考例4)
上記実施例5と同じ方法でアルカリ浸出残渣を得、このアルカリ浸出残渣にスラリー濃度が100g/lとなるように硫酸と水を添加してpH0に調整し、1時間撹拌を継続した。固液分離後、得た残渣に濃度10mol/lの硫酸と水を添加してスラリーとし、60℃に維持しつつ2時間浸出した。得た浸出液のビスマス濃度は2.5g/lと不十分な浸出にとどまった。
(Reference Example 4)
An alkali leaching residue was obtained in the same manner as in Example 5, and sulfuric acid and water were added to the alkali leaching residue so that the slurry concentration would be 100 g / l to adjust to pH 0, and stirring was continued for 1 hour. After solid-liquid separation, sulfuric acid and water having a concentration of 10 mol / l were added to the obtained residue to form a slurry, which was leached for 2 hours while maintaining at 60 ° C. The obtained leaching solution had a bismuth concentration of 2.5 g / l, which was insufficient.
1 中和処理工程
2 アルカリ浸出工程
3 硫酸浸出工程
4 冷却工程
5 ビスマス酸化工程
6 電解工程

DESCRIPTION OF SYMBOLS 1 Neutralization process 2 Alkali leaching process 3 Sulfuric acid leaching process 4 Cooling process 5 Bismuth oxidation process 6 Electrolytic process

Claims (7)

  1. 銅と貴金属とビスマスと不純物とを含有する鉱物を製錬して得た粗銅を電解精製に付して銅を回収し、次に電解精製を行うことで生成した電解スライムから湿式法により貴金属を回収する工程において、貴金属を回収後に生成した酸性溶液を以下の工程に付す
    ことを特徴とするビスマスの精製方法。
    1)前記酸性溶液にアルカリを添加してpHを2.0以上3.0以下の範囲に調整し、次いで固液分離して中和濾液と中和澱物を得る中和処理工程
    2)前記中和澱物にアルカリを添加してアルカリ浸出液とアルカリ浸出残渣に分離するアルカリ浸出工程
    3)前記アルカリ浸出残渣に硫酸を添加して硫酸浸出液と硫酸浸出残渣とに分離する硫酸浸出工程
    4)前記硫酸浸出液を冷却し、硫酸ビスマスの結晶を得る冷却工程
    5)前記硫酸ビスマスの結晶にアルカリを加え、酸化ビスマスを得るビスマス酸化工程
    6)前記酸化ビスマスに酸溶液を添加して溶解し、得た溶解液を電解採取して金属ビスマスを得る電解工程
    Crude copper obtained by smelting a mineral containing copper, noble metal, bismuth and impurities is subjected to electrolytic purification to recover copper, and then the noble metal is obtained from the electrolytic slime produced by electrolytic purification by a wet method. A method for purifying bismuth, characterized in that, in the step of recovering, an acidic solution produced after recovering the precious metal is subjected to the following step.
    1) Neutralization step of adding an alkali to the acidic solution to adjust the pH to a range of 2.0 to 3.0, and then solid-liquid separation to obtain a neutralized filtrate and a neutralized starch 2) Alkaline leaching step of adding alkali to neutralized starch to separate into alkali leaching solution and alkali leaching residue 3) Sulfuric acid leaching step of adding sulfuric acid to said alkali leaching residue to separate into sulfuric acid leaching solution and sulfuric acid leaching residue 4) Cooling step of cooling the sulfuric acid leachate to obtain bismuth sulfate crystals 5) Bismuth oxidation step of adding alkali to the bismuth sulfate crystals to obtain bismuth oxide 6) Obtaining and dissolving the acid solution in the bismuth oxide Electrolytic process to obtain metal bismuth by electrolyzing the solution
  2. 前記不純物が鉄、鉛、ヒ素、テルルの1種以上である
    ことを特徴とする請求項1記載のビスマスの精製方法。
    The method for purifying bismuth according to claim 1, wherein the impurity is at least one of iron , lead, arsenic, and tellurium.
  3. 前記アルカリ浸出工程で得たアルカリ浸出液を90℃以上に加熱し、次いで冷却してヒ素を含む結晶を得る煮沸工程を有する
    ことを特徴とする請求項1記載のビスマスの精製方法。
    The method for purifying bismuth according to claim 1, further comprising a boiling step of heating the alkali leaching solution obtained in the alkali leaching step to 90 ° C or higher and then cooling to obtain crystals containing arsenic.
  4. 前記硫酸浸出工程が、溶液のpHが0〜3.5の低濃度の硫酸を接触させて浸出残渣を浸出して1次浸出液と1次浸出残差とに分離する1次処理を行い得られた1次浸出残渣に溶液のpHが0未満の高濃度の硫酸を接触させて2次浸出液と2次浸出残渣とに分離する2次処理を行う2段階の浸出処理からなり、得られた前記2次浸出液を前記冷却工程に供給する
    ことを特徴とする請求項1記載のビスマスの精製方法。
    The sulfuric leaching step is subjected to primary processing pH of the solution is separated into a primary leachate and the primary leach residue was leached leaching residue by contacting a low concentration of sulfuric acid of 0 to 3.5, resulting It was the primary leach residue consists leaching of two-step pH performs secondary processing by contacting a high concentration of sulfuric acid of less than 0 is separated into a secondary leachate and secondary leach residue of the solution, the resulting The method for purifying bismuth according to claim 1, wherein the secondary leachate is supplied to the cooling step.
  5. 前記電解工程で用いる酸溶液が硅フッ酸を含む溶液である
    ことを特徴とする請求項1記載のビスマスの精製方法。
    The method for purifying bismuth according to claim 1, wherein the acid solution used in the electrolysis step is a solution containing hydrofluoric acid.
  6. 前記アルカリ浸出工程において、中和澱物に添加するアルカリが1mol/l以上5mol/lモル以下の濃度の水酸化ナトリウム溶液であり、該水酸化ナトリウム溶液を使用してスラリー濃度が10g/l以上100g/l以下の範囲になるように混合して溶解し、アルカリ浸出液とアルカリ浸出残渣を得る
    ことを特徴とする請求項1記載のビスマスの精製方法。
    In the alkali leaching step, the alkali added to the neutralized starch is a sodium hydroxide solution having a concentration of 1 mol / l or more and 5 mol / l mol or less, and the slurry concentration is 10 g / l or more using the sodium hydroxide solution. 2. The method for purifying bismuth according to claim 1, wherein the alkali leaching solution and the alkali leaching residue are obtained by mixing and dissolving in a range of 100 g / l or less.
  7. 前記硫酸浸出工程において、硫酸を添加した後のスラリーのpHが0以上、1以下の範囲に調整し、固液分離して硫酸浸出液と硫酸浸出残渣を得る
    ことを特徴とする請求項1記載のビスマスの精製方法。
    2. The sulfuric acid leaching step and the sulfuric acid leaching residue are obtained by adjusting the pH of the slurry after adding sulfuric acid to a range of 0 to 1 and solid-liquid separation in the sulfuric acid leaching step. Bismuth purification method.
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