JP4216307B2 - Process for electrolytically precipitated copper - Google Patents

Process for electrolytically precipitated copper Download PDF

Info

Publication number
JP4216307B2
JP4216307B2 JP2006262766A JP2006262766A JP4216307B2 JP 4216307 B2 JP4216307 B2 JP 4216307B2 JP 2006262766 A JP2006262766 A JP 2006262766A JP 2006262766 A JP2006262766 A JP 2006262766A JP 4216307 B2 JP4216307 B2 JP 4216307B2
Authority
JP
Japan
Prior art keywords
copper
solution
arsenic
sulfuric acid
precipitate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
JP2006262766A
Other languages
English (en)
Other versions
JP2008081784A (ja
Inventor
幸夫 木村
滋男 桂
Original Assignee
日鉱金属株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日鉱金属株式会社 filed Critical 日鉱金属株式会社
Priority to JP2006262766A priority Critical patent/JP4216307B2/ja
Publication of JP2008081784A publication Critical patent/JP2008081784A/ja
Application granted granted Critical
Publication of JP4216307B2 publication Critical patent/JP4216307B2/ja
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • C22B15/0065Leaching or slurrying
    • C22B15/0067Leaching or slurrying with acids or salts thereof
    • C22B15/0071Leaching or slurrying with acids or salts thereof containing sulfur
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • C22B15/0084Treating solutions
    • C22B15/0086Treating solutions by physical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/045Leaching using electrochemical processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08Sulfuric acid, other sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, by thermal decomposition
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/02Obtaining antimony
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/04Obtaining arsenic
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/06Obtaining bismuth
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Description

本発明は銅の製錬工程で産出する電解沈殿銅の処理方法に関する。より詳細には、本発明は電解沈殿銅から銅、ヒ素、ビスマス、アンチモン等をそれぞれ分離・回収する方法に関する。   The present invention relates to a method for treating electrolytically precipitated copper produced in a copper smelting process. More specifically, the present invention relates to a method for separating and recovering copper, arsenic, bismuth, antimony, and the like from electrolytically precipitated copper.

銅鉱石中には種々の不純物が混入しており、そのような不純物としてはヒ素(As)、ビスマス(Bi)、アンチモン(Sb)等が挙げられる。これら不純物の大部分は銅製錬の乾式工程で高熱によって揮発分離されるが、一部は粗銅に混入して銅の電解精製工程へ持ち込まれることとなる。
粗銅(銅陽極)に含まれるAs、Sb、Bi等は電解液に一部溶出し、未溶出分はアノードスライムとして電解槽底部に沈殿する。また、陰極に析出する銅量よりも陽極から溶出する銅量の方が一般に多いので、電解液中の銅濃度は次第に増大する。そのため、電解液の一部を別の電解槽に抜き出して電解液の品質を制御している。抜き出した電解液に対しては脱銅電解を行い、陰極にCu及び上記不純物を析出させ、また、電解槽底部にこれらを沈殿させることでCu及び上記不純物を分離回収する。斯界では、これら電解槽底部に沈殿するものと陰極に析出するものを併せて電解沈殿銅と呼んでいる。
Various impurities are mixed in the copper ore, and examples of such impurities include arsenic (As), bismuth (Bi), antimony (Sb), and the like. Most of these impurities are volatilized and separated by high heat in the dry process of copper smelting, but some are mixed into the crude copper and brought into the copper electrolytic purification process.
As, Sb, Bi, etc. contained in the crude copper (copper anode) are partly eluted in the electrolytic solution, and the undissolved part is precipitated at the bottom of the electrolytic cell as anode slime. Further, since the amount of copper eluted from the anode is generally larger than the amount of copper deposited on the cathode, the copper concentration in the electrolytic solution gradually increases. Therefore, a part of the electrolytic solution is extracted into another electrolytic cell to control the quality of the electrolytic solution. The extracted electrolytic solution is subjected to copper removal electrolysis, Cu and the impurities are deposited on the cathode, and Cu and the impurities are separated and recovered by depositing them on the bottom of the electrolytic cell. In this field, those precipitated at the bottom of the electrolytic cell and those deposited at the cathode are collectively referred to as electrolytically precipitated copper.

電解沈殿銅は銅製錬工程に繰り返されるのが通常であるが、そのためには電解沈殿銅から不純物を分離しておくのが好ましい。また、As、Sb、Bi等は有価物として利用する道も残されている。従って、電解沈殿銅からCu、As、Sb、Bi等をそれぞれ分離・回収する技術が望まれる。   Electrolytically precipitated copper is usually repeated in the copper smelting process, but it is preferable to separate impurities from the electrolytically precipitated copper. In addition, As, Sb, Bi, etc. still have a way to be used as valuable materials. Therefore, a technique for separating and recovering Cu, As, Sb, Bi, and the like from electrolytically precipitated copper is desired.

例えば、特開2002−249827号公報には湿式法により電解沈殿銅からビスマス及びアンチモンを分離する方法が記載されている。具体的には、酸化銅及びビスマス、アンチモンを含む電解沈殿銅のアルカリ処理物を液温40〜90℃、処理時間2〜5時間、50〜200g/Lの硫酸で浸出し、銅、砒素、ニッケル等を溶出させ、ビスマスとアンチモンを残渣に残すことにより、ビスマス、アンチモンと銅等を分離している。一方、硫酸で浸出された銅、砒素、ニッケルの回収は、例えば中和処理後に銅製錬の乾式工程に繰り返すことができる旨が記載されている。   For example, JP 2002-249827 A describes a method of separating bismuth and antimony from electrolytically precipitated copper by a wet method. Specifically, an alkaline treatment of electrolytically precipitated copper containing copper oxide, bismuth, and antimony was leached with 50 to 200 g / L sulfuric acid at a liquid temperature of 40 to 90 ° C., a treatment time of 2 to 5 hours, copper, arsenic, By eluting nickel and leaving bismuth and antimony in the residue, bismuth, antimony and copper are separated. On the other hand, it is described that the recovery of copper, arsenic and nickel leached with sulfuric acid can be repeated, for example, after the neutralization treatment in the dry process of copper smelting.

また、特許第3212875号公報には製錬中間物からヒ素を回収する方法が記載されている。具体的には、ヒ素を含む水溶液に、銅及び銅酸化物もしくは銅又は銅酸化物を添加し、かつ、酸化によりヒ酸を生成する工程を含むヒ素の回収方法である。ヒ酸は消石灰によってヒ酸カルシウムの沈殿として回収される。
特開2002−249827号公報 特許第3212875号公報
Japanese Patent No. 3212875 describes a method for recovering arsenic from a smelting intermediate. Specifically, it is a method for recovering arsenic, which includes a step of adding copper and copper oxide or copper or copper oxide to an arsenic-containing aqueous solution and generating arsenic acid by oxidation. Arsenic is recovered by slaked lime as calcium arsenate precipitate.
JP 2002-249827 A Japanese Patent No. 3212875

しかしながら、銅製錬工程に繰り返す電解沈殿銅中に不純物が多いと乾式工程や電錬への負担増となることは避けられないことや、ヒ素についてもヒ酸カルシウムよりも長期保存に適した形態で回収することができればより望ましいといった種々の課題が未だ存在する。すなわち、従来提案されてきた電解沈殿銅の処理システムでは分離手順、回収物質の安定性、リサイクル性といった観点から最適なシステムということはできず、改良の余地が未だ存在する。   However, it is unavoidable that there are a lot of impurities in the electrolytically precipitated copper that is repeated in the copper smelting process, which increases the burden on the dry process and electric smelting, and arsenic is also more suitable for long-term storage than calcium arsenate Various problems still exist such that it is more desirable if it can be recovered. That is, the conventionally proposed electrolytic precipitation copper treatment system cannot be an optimal system from the viewpoint of separation procedure, stability of recovered material, and recyclability, and there is still room for improvement.

そこで、本発明の課題の一つは電解沈殿銅から銅、ヒ素、ビスマス、アンチモン等をそれぞれ分離・回収するためのより利便性の高い方法を提供することである。   Accordingly, one of the objects of the present invention is to provide a more convenient method for separating and recovering copper, arsenic, bismuth, antimony and the like from electrolytically precipitated copper.

本発明者は上記課題を解決するために、電解沈殿銅の処理システムを鋭意検討したところ、一連の操作を組み合わせた以下の処理システムが予想以上に電解沈殿銅の処理に効果的であることを見出した。
すなわち、本発明は一側面において、
(1)電解沈殿銅を随意的に水洗処理した後に、硫酸酸性中の電解沈殿銅に酸素含有ガスを導入しながら、電解沈殿銅中に含まれるAs成分の90wt.%以上を5価に酸化するのに充分な液温及び時間で該溶液を撹拌することを含む硫酸浸出を行い、次いでSb成分及びBi成分を含有する浸出残渣と5価のAs成分を含有する硫酸浸出液に固液分離する第一工程と、
(2)該硫酸浸出液に3価の鉄を添加して結晶性スコロダイト(FeAsO4・2H2O)を生成させることによって、該結晶性スコロダイトを含有する残渣と脱砒後液とに固液分離する第二工程と、
(3)該脱砒後液に未反応のFe又は未反応のFe及びAsが残存している場合に、アルカリを添加してFe塩を生成し、As成分が残存している場合はAs成分をFe塩と共沈させ、次いでFe塩及びAs成分(As成分が残存している場合)を含有する沈殿物と脱鉄後液とに固液分離する随意的な第三工程と、
(4)該脱鉄後液にアルカリを添加してCu塩を沈殿させ、次いでCu塩を含有する沈殿物と脱銅後液とに固液分離する随意的な第四工程と、
を含む電解沈殿銅の処理方法である。
In order to solve the above-mentioned problems, the present inventor has eagerly studied a treatment system for electrolytically precipitated copper, and found that the following treatment system combined with a series of operations is more effective than expected for treating electrolytically precipitated copper. I found it.
That is, the present invention in one aspect,
(1) After the electrolytically precipitated copper is optionally washed with water, 90 wt. As of the As component contained in the electrolytically precipitated copper is introduced into the electrolytically precipitated copper in sulfuric acid acid while introducing an oxygen-containing gas. Sulfuric acid leaching including stirring the solution at a temperature and time sufficient to oxidize more than 5% to pentavalent, followed by leaching residue containing Sb component and Bi component and pentavalent As component A first step of solid-liquid separation into sulfuric acid leachate,
(2) By adding trivalent iron to the sulfuric acid leaching solution to produce crystalline scorodite (FeAsO 4 .2H 2 O), solid-liquid separation into a residue containing the crystalline scorodite and a post-arsenic-removed solution A second step to perform,
(3) When unreacted Fe or unreacted Fe and As remain in the solution after de-arsenic, an alkali is added to form a Fe salt, and the As component remains when the As component remains An optional third step of co-precipitation with Fe salt, followed by solid-liquid separation into a precipitate containing Fe salt and an As component (if the As component remains) and a solution after deironing;
(4) An optional fourth step of adding an alkali to the post-deironation solution to precipitate a Cu salt, and then solid-liquid separation into a precipitate containing the Cu salt and a post-decopperization solution;
It is a processing method of the electrolytic precipitation copper containing.

本発明の一実施形態においては、第一工程における硫酸浸出は70〜95℃で4.5〜11時間撹拌することを伴う。   In one embodiment of the invention, sulfuric acid leaching in the first step involves stirring at 70-95 ° C. for 4.5-11 hours.

本発明の一実施形態においては、第一工程における硫酸浸出は外部から加熱せずに行う。   In one embodiment of the present invention, sulfuric acid leaching in the first step is performed without heating from the outside.

本発明の一実施形態においては、第一工程における酸素含有ガスは空気である。   In one embodiment of the present invention, the oxygen-containing gas in the first step is air.

本発明の一実施形態においては、第一工程における酸素含有ガスの導入及び/又は撹拌はジェット噴射により行う。   In one embodiment of the present invention, the introduction and / or stirring of the oxygen-containing gas in the first step is performed by jet injection.

本発明の一実施形態においては、第一工程における硫酸浸出液は0.3〜2.2のpHである。   In one embodiment of the present invention, the sulfuric acid leachate in the first step has a pH of 0.3 to 2.2.

本発明の一実施形態においては、第一工程における硫酸浸出によりAs成分は95wt.%以上が5価に酸化する。   In one embodiment of the present invention, the As component is 95 wt. % Or more is oxidized to pentavalent.

本発明の一実施形態においては、第二工程における結晶性スコロダイトは60〜95℃に加熱することにより生成する。   In one embodiment of the present invention, the crystalline scorodite in the second step is produced by heating to 60-95 ° C.

本発明の一実施形態においては、第二工程における3価の鉄は硫酸第二鉄として提供される。   In one embodiment of the present invention, the trivalent iron in the second step is provided as ferric sulfate.

本発明の一実施形態においては、第二工程における結晶性スコロダイトはpH0.4〜1.2で生成する。   In one embodiment of the present invention, the crystalline scorodite in the second step is generated at a pH of 0.4 to 1.2.

本発明の一実施形態においては、第三工程におけるアルカリは脱砒後液のpHが2.2〜4.0の範囲となるまで添加する。   In one embodiment of the present invention, the alkali in the third step is added until the pH of the dearsenic solution is in the range of 2.2 to 4.0.

本発明の一実施形態においては、第四工程におけるアルカリは脱鉄後液のpHが4.0〜8.0の範囲となるまで添加する。   In one embodiment of the present invention, the alkali in the fourth step is added until the pH of the solution after deironing is in the range of 4.0 to 8.0.

本発明の一実施形態においては、第三工程及び/又は第四工程におけるアルカリは炭酸カルシウムとして提供される。   In one embodiment of the present invention, the alkali in the third step and / or the fourth step is provided as calcium carbonate.

本発明によれば、電解沈殿銅からCu、As、Bi及びSbがそれぞれ分離・回収できる。この際、Asは安定なスコロダイトとして固定される。これは、砒酸カルシウムよりも水に対する溶解性が低く、安定で長期間保管に適した形態である。Cuは不純物が軽減された状態で銅製錬工程に戻すことができ、乾式工程や電錬の浄化能力に起因する繰り返し量の制限も大幅に軽減される。そのため、中間品としての電解沈澱銅中の銅の製錬工程内滞留時間が短縮できる。   According to the present invention, Cu, As, Bi, and Sb can be separated and recovered from electrolytically precipitated copper. At this time, As is fixed as a stable scorodite. This is a form that is less soluble in water than calcium arsenate, is stable and suitable for long-term storage. Cu can be returned to the copper smelting process in a state in which impurities are reduced, and the limitation on the amount of repetition due to the purification process of the dry process and electric smelting is greatly reduced. Therefore, the residence time in the smelting process of copper in the electrolytically precipitated copper as an intermediate product can be shortened.

電解沈殿銅
本発明に係る処理方法の対象原料は上で説明した通り銅製錬工程で産出される電解沈殿銅を主とするが、電解沈殿銅と実質的に同一の組成を有する物質であれば本発明に係る処理方法を適用することができる。従って、本発明でいう「電解沈殿銅」にはその起源を問わず、電解沈殿銅と実質的に同一の組成を有する化学物質も含まれることとする。例えば、電解沈殿銅はCu:30〜70wt.%、As:20〜50wt.%、Bi:0.1〜6wt.%、Sb:0.5〜8wt.%、Pb:0.1〜10wt.%等を含有するのが一般的であり、このような組成を有する物質は電解沈殿銅として本発明の処理対象となる。
Electrolytically precipitated copper The target raw material of the treatment method according to the present invention is mainly the electrolytically precipitated copper produced in the copper smelting process as described above, but if it is a substance having substantially the same composition as the electrolytically precipitated copper The processing method according to the present invention can be applied. Therefore, “electrolytically precipitated copper” as used in the present invention includes chemical substances having substantially the same composition as electrolytically precipitated copper regardless of its origin. For example, electrolytically precipitated copper is Cu: 30 to 70 wt. %, As: 20 to 50 wt. %, Bi: 0.1 to 6 wt. %, Sb: 0.5 to 8 wt. %, Pb: 0.1 to 10 wt. In general, a substance having such a composition is the subject of the present invention as electrolytically precipitated copper.

水洗処理
第一工程の前には電解沈殿銅に対して水洗処理を随意的に行ってもよい。水洗処理は電解沈殿銅を水でリパルプし、0.5〜6時間撹拌して、電解沈澱銅の製造時に付着した電解液(硫酸銅、Ni、Fe等を含む)や、電解沈殿銅に含まれる微量のNi及びFe等を溶解させた後に、スラリーをろ過し、固液分離することで実施することができる。この工程では電解沈殿銅からFe及びNiの大部分を分離することができる。
しかしながら、この操作は、電解沈澱銅中の銅量の中で、硫酸銅を排除した0価の(水に溶解しない)銅量を明らかにして、次工程で行う電解沈澱銅の硫酸浸出に必要な硫酸量をより正確に求めるために行うことを主目的とする操作である。NiやFe等の微量元素を特に気にしない場合や、硫酸銅の含有量が既知であったり電解沈澱銅への電解液の持込が少なかったりする場合は、この工程を行う必要はない。
Prior to the first washing process, the electrolytically precipitated copper may be optionally washed with water. The washing process involves repulping the electrolytically precipitated copper with water and stirring for 0.5 to 6 hours, and is included in the electrolytic solution (including copper sulfate, Ni, Fe, etc.) attached during the production of the electrolytically precipitated copper and the electrolytically precipitated copper After dissolving a trace amount of Ni, Fe, and the like, the slurry can be filtered and solid-liquid separated. In this step, most of Fe and Ni can be separated from the electrolytically precipitated copper.
However, this operation is necessary for the sulfuric acid leaching of the electrolytically precipitated copper in the next step by clarifying the amount of zero-valent (not dissolved in water) copper excluded from the copper amount in the electrolytically precipitated copper. The main purpose of this operation is to obtain a more accurate amount of sulfuric acid. If trace elements such as Ni and Fe are not particularly concerned, or if the content of copper sulfate is known or the electrolytic solution is not brought into the electrolytically precipitated copper, this step is not necessary.

第一工程
第一工程では硫酸酸性中の電解沈殿銅に酸素含有ガスを導入しながら、電解沈殿銅中に含まれるAs成分の90wt.%以上を5価に酸化するのに充分な液温及び時間で該溶液を撹拌することを含む硫酸浸出を行い、次いでSb成分及びBi成分を含有する浸出残渣と5価のAs成分を含有する硫酸浸出液に固液分離する。
First Step In the first step, 90 wt. As of the As component contained in the electrolytically precipitated copper is introduced while introducing an oxygen-containing gas into the electrolytically precipitated copper in sulfuric acid acidity. Sulfuric acid leaching including stirring the solution at a temperature and time sufficient to oxidize more than 5% to pentavalent, followed by leaching residue containing Sb component and Bi component and pentavalent As component Solid-liquid separation into sulfuric acid leachate.

このときに起きる浸出反応は一般に次式に従い、CuはCu2+まで、AsはAs+5まで酸化される。
Cu + H2SO4 + 1/2O2 → CuSO4 + H2O ・・・・ (1)
2As + 5/2O2 + 3H2O → 2H3AsO4 ・・・・ (2)
硫酸使用量は、Cu量に対し好ましくは1.0〜1.2当量である。1.0当量未満の場合浸出液が弱酸性になり、Cu3AsO4等の沈澱物が生成しCu、Asの浸出率が低下する。1.2当量を超える場合は、Cu、Asの浸出率に影響しないが、使用硫酸量が多くなる。Cu、Asの硫酸溶液中の濃度は特に制限はないが、溶解度を越えるとCu、Asの浸出率が低下するので、Cu2+、As5+の溶解度以下が好ましい。
また、硫酸浸出液のpHとしては、この後、第二工程で生成する結晶性スコロダイトの溶解度がpH0.3以下で急速に増大して、結晶性スコロダイトの生成を阻害する。さらにpH2.2以上では添加した鉄が水酸化鉄となって沈澱してしまい、鉄が有効にスコロダイトの合成に使われない。これらの理由により0.3〜2.2の範囲のpHとするのが好ましく、0.4〜1.2の範囲とするのがより好ましい。
The leaching reaction occurring at this time generally follows the following equation: Cu is oxidized to Cu 2+ and As is oxidized to As +5 .
Cu + H 2 SO 4 + 1 / 2O 2 → CuSO 4 + H 2 O ···· (1)
2As + 5/2 O 2 + 3H 2 O → 2H 3 AsO 4 (2)
The amount of sulfuric acid used is preferably 1.0 to 1.2 equivalents relative to the amount of Cu. When it is less than 1.0 equivalent, the leaching solution becomes weakly acidic, precipitates such as Cu 3 AsO 4 are generated, and the leaching rate of Cu and As decreases. When it exceeds 1.2 equivalents, the leaching rate of Cu and As is not affected, but the amount of sulfuric acid used is increased. The concentration of Cu and As in the sulfuric acid solution is not particularly limited. However, if the solubility is exceeded, the leaching rate of Cu and As decreases, so that it is preferably not more than the solubility of Cu 2+ and As 5+ .
Further, as the pH of the sulfuric acid leaching solution, the solubility of the crystalline scorodite produced in the second step is rapidly increased at pH 0.3 or less, thereby inhibiting the production of crystalline scorodite. Furthermore, when the pH is 2.2 or more, the added iron is precipitated as iron hydroxide, and iron is not effectively used for the synthesis of scorodite. For these reasons, the pH is preferably in the range of 0.3 to 2.2, more preferably in the range of 0.4 to 1.2.

硫酸浸出では、例えば70〜95℃で4.5〜11時間、好ましくは80〜95℃で7〜11時間撹拌することにより確実にAsの酸化が進み、As成分の90wt.%以上、好ましくは95wt.%以上、より好ましくは98wt.%以上を5価に酸化することができる。硫酸浸出は発熱反応であるため特に外部から加熱しないで行うことも可能である。撹拌時間は更に長く行っても良く、経済性と効果との兼ね合いで適宜決定すればよい。
Asの酸化効率を高めるためには、導入する酸素含有ガスの気泡を細かくして充分な量(例えば銅に対して酸素10当量/7時間)供給した方がよい。そこで、撹拌を激しく行うのが好ましく、例えば酸素含有ガスの導入及び/又は撹拌はジェット噴射により行うのが好都合である。この値は、ジェット噴射(ジェットアジター商品名)場合であり、通常のタービン翼を用いた撹拌機の場合反応効率は低下し、酸素含有ガス量をこの3.5倍以上導入しても、2倍以上の反応時間が必要となる。この段階でAsの価数制御を行うことで、第二工程でのスコロダイト生成が容易となる。また、Cu2+もAsの酸化を促進する効果がある。
In sulfuric acid leaching, for example, by stirring at 70 to 95 ° C. for 4.5 to 11 hours, preferably at 80 to 95 ° C. for 7 to 11 hours, the oxidation of As progressed reliably, and 90 wt. % Or more, preferably 95 wt. % Or more, more preferably 98 wt. % Or more can be oxidized to pentavalent. Since sulfuric acid leaching is an exothermic reaction, it can be performed without heating from the outside. The stirring time may be longer, and may be determined as appropriate in consideration of economy and effect.
In order to increase the oxidation efficiency of As, it is preferable to supply a sufficient amount of oxygen-containing gas bubbles to be introduced (for example, 10 equivalents of oxygen to copper for 7 hours). Therefore, it is preferable to vigorously perform stirring, and for example, introduction of oxygen-containing gas and / or stirring is conveniently performed by jet injection. This value is in the case of jet injection (trade name of jet agitator), and in the case of a stirrer using a normal turbine blade, the reaction efficiency is lowered, and even when the amount of oxygen-containing gas is introduced 3.5 times or more, More than twice the reaction time is required. By controlling the valence of As at this stage, scorodite generation in the second step is facilitated. Cu 2+ also has the effect of promoting As oxidation.

酸素含有ガスとしては上記反応に有意な悪影響を与えない限り特に制限はないが、例えば純酸素、酸素と不活性ガスの混合物を使用することができる。取扱い性やコストの観点からは空気とするのが好ましい。   The oxygen-containing gas is not particularly limited as long as it does not have a significant adverse effect on the above reaction. For example, pure oxygen or a mixture of oxygen and an inert gas can be used. Air is preferable from the viewpoint of handling and cost.

また、電解沈殿銅からSb及びBiを効率的に分離するためには硫酸浸出液へのSb及びBiの溶解度が一定であることから、(1)硫酸浸出時の電解沈澱銅パルプ濃度を増加させる、(2)Sb及びBi品位の高い電解沈澱銅を用いること等が好ましい。電解沈殿銅から分離されたBi及びSbは更に、例えば電気炉処理により個別に分離回収可能である。   Moreover, in order to efficiently separate Sb and Bi from electrolytically precipitated copper, the solubility of Sb and Bi in the sulfuric acid leachate is constant, so (1) increase the electrolytically precipitated copper pulp concentration during sulfuric acid leaching, (2) It is preferable to use electrolytically precipitated copper having high Sb and Bi quality. Bi and Sb separated from the electrolytically precipitated copper can be separately separated and recovered by, for example, electric furnace treatment.

第二工程
第二工程では、第一工程で得られた硫酸浸出液に3価の鉄を添加して結晶性スコロダイト(FeAsO4・2H2O)を生成させ、次いで該結晶性スコロダイトを含有する残渣と脱砒後液とに固液分離する。
Second Step In the second step, trivalent iron is added to the sulfuric acid leachate obtained in the first step to produce crystalline scorodite (FeAsO 4 .2H 2 O), and then the residue containing the crystalline scorodite And solid-liquid separation after de-arsenic.

結晶性スコロダイトは例えば大気圧下で60〜95℃に加熱することにより生成させることができ、例えば8〜72時間反応させることにより充分な量のスコロダイトが生成する。第一工程においてAsを充分に5価まで酸化させているため、3価の鉄と高い反応効率で結晶性のスコロダイトが生成する。スコロダイトは化学的に安定であり、長期保存にも適している。   Crystalline scorodite can be produced, for example, by heating to 60 to 95 ° C. under atmospheric pressure. For example, a sufficient amount of scorodite is produced by reacting for 8 to 72 hours. Since As is sufficiently oxidized to pentavalent in the first step, crystalline scorodite is produced with trivalent iron and high reaction efficiency. Scorodite is chemically stable and suitable for long-term storage.

3価の鉄としては、酸化鉄、硫酸鉄、塩化鉄等が挙げられるが、3価の鉄は水溶液中での反応を行う観点から酸性水溶液の形態で提供されるのが好ましく、脱鉄後液を電錬の電解液に戻す事が最も有効である観点から硫酸第二鉄(Fe2(SO43)の水溶液の形態で提供されるのが好ましい。また、廃水処理等で使用される、ポリ硫酸第二鉄水溶液も使用可能である。この際、該水溶液を添加した硫酸浸出液のpHが0.3〜2.2、好ましくは0.4〜1.2に維持されるようなpHとして添加するのがスコロダイト合成上の観点から有利である。第一工程においてAsを充分に5価に酸化しているため、このように低いpHでもスコロダイトが容易に生成する。また、この段階でpHを上げる必要がないために苛性ソーダ等のアルカリを添加する必要がなくなるメリットもある。従って、本発明に係る電解沈殿銅の処理方法においては、第一工程と第二工程の間で無駄のないスムーズな連携が可能となる。 Examples of the trivalent iron include iron oxide, iron sulfate, and iron chloride. The trivalent iron is preferably provided in the form of an acidic aqueous solution from the viewpoint of performing a reaction in an aqueous solution. It is preferable that the solution is provided in the form of an aqueous solution of ferric sulfate (Fe 2 (SO 4 ) 3 ) from the viewpoint that it is most effective to return the solution to an electrolysis electrolyte. Moreover, the polyferric sulfate aqueous solution used by waste water treatment etc. can also be used. At this time, it is advantageous from the viewpoint of scorodite synthesis that the sulfuric acid leachate to which the aqueous solution is added is added as a pH such that the pH is maintained at 0.3 to 2.2, preferably 0.4 to 1.2. is there. Since As is sufficiently pentavalently oxidized in the first step, scorodite is easily generated even at such a low pH. There is also an advantage that it is not necessary to add an alkali such as caustic soda because it is not necessary to raise the pH at this stage. Therefore, in the method for treating electrolytically precipitated copper according to the present invention, smooth cooperation without waste is possible between the first step and the second step.

3価鉄の使用量はAsを除去するという観点からは、As量に対して1.0当量以上必要であり、経済的な観点から1.1〜1.5当量であるのが好ましい。   The amount of trivalent iron used is required to be 1.0 equivalent or more with respect to the amount of As from the viewpoint of removing As, and is preferably 1.1 to 1.5 equivalents from an economical viewpoint.

第三工程
第三工程は該脱砒後液に未反応のFe又は未反応のFe及びAsが残存している場合に行う随意的な工程であり、アルカリを添加してFe塩を生成し、As成分が残存している場合にはAs成分をこれと共沈させ、次いでFe塩及びAs成分(As成分が残存している場合)を含有する沈殿物と脱鉄後液とに固液分離する。
Third step The third step is an optional step performed when unreacted Fe or unreacted Fe and As remain in the post-dearsenic solution, and an alkali is added to produce an Fe salt. When the As component remains, the As component is co-precipitated with it, and then solid-liquid separation into a precipitate containing the Fe salt and As component (when the As component remains) and a solution after deironing To do.

使用するアルカリとしては、不溶性のFe塩(Asが残存している場合にはAsを共沈させることのできる不溶性のFe塩)を生成することのできるものであれば特に制限はないが、例えば炭酸ナトリウム、炭酸カルシウム、水酸化ナトリウム、水酸化カルシウム、水酸化マグネシウム等が挙げられる。
反応後液を電錬の電解液に戻す事が銅製錬工程にとって最も有効であり、その点を考慮すると、電解液中のナトリウムは除去が困難なため、使用は好ましくない。一方カルシウムは、共存する硫酸と石膏を生成して、除去されるため、強い制限を受けない。この観点からアルカリとして炭酸カルシウム、水酸化カルシウム等のカルシウム化合物を使用するのが好ましく、特にpHの制御が容易なことから、炭酸カルシウムが好ましい。
The alkali to be used is not particularly limited as long as it can generate an insoluble Fe salt (an insoluble Fe salt that can co-precipitate As if it remains). Examples thereof include sodium carbonate, calcium carbonate, sodium hydroxide, calcium hydroxide, and magnesium hydroxide.
It is most effective for the copper smelting process to return the solution after the reaction to the electrolytic solution of electrolysis. Considering this point, it is difficult to remove sodium in the electrolytic solution, so that it is not preferable to use it. On the other hand, calcium is not subject to strong restrictions because it produces and removes coexisting sulfuric acid and gypsum. From this point of view, it is preferable to use calcium compounds such as calcium carbonate and calcium hydroxide as alkali, and calcium carbonate is particularly preferable because pH can be easily controlled.

アルカリは、水酸化鉄の沈澱が顕著となるpHが2.2であり、4.0を超えると銅が沈澱し易くなるため、脱砒後液のpHが2.2〜4.0の範囲となるまで添加するのがFe塩の沈殿効率やCu塩の沈殿回避の理由から好ましく、pHが3.0〜3.5の範囲となるまで添加するのがより好ましい。   Alkaline has a pH at which precipitation of iron hydroxide is noticeable at 2.2, and copper tends to precipitate when it exceeds 4.0, so the pH of the solution after de-arsenic is in the range of 2.2 to 4.0. It is preferable to add it until it becomes, for reasons of precipitation efficiency of Fe salt and avoidance of precipitation of Cu salt, and it is more preferable to add until the pH is in the range of 3.0 to 3.5.

この沈殿は、硫酸で溶解させた後に第二工程に戻し、鉄源及び処理対象のAs(As成分が残存している場合)として再利用することができる。また、脱鉄後液に主として含まれるのは硫酸銅であり、不純物が少ないので、電錬の電解液としての利用が可能である。但し、脱鉄後液は更に次の第四工程によってCuを沈殿物として回収してもよい。   This precipitate can be dissolved in sulfuric acid, then returned to the second step, and reused as the iron source and As to be treated (when the As component remains). In addition, copper sulfate is mainly contained in the liquid after deironing and has few impurities, so that it can be used as an electrolytic solution for electric smelting. However, after the iron removal, the Cu may be recovered as a precipitate by the following fourth step.

第四工程
第四工程はCuを沈殿物として回収する場合に実施する随意的な工程であり、脱鉄後液にアルカリを添加してCu塩を沈殿させ、次いでCu塩を含有する沈殿物と脱銅後液とに固液分離する。濾過性を向上させる為には、例えば40〜70℃で30〜90分間加熱して沈澱を熟成することが有効である。
Fourth Step The fourth step is an optional step that is performed when Cu is recovered as a precipitate. An alkali is added to the solution after deironing to precipitate a Cu salt, and then a precipitate containing the Cu salt is added. Solid-liquid separation after the copper removal. In order to improve the filterability, for example, it is effective to age the precipitate by heating at 40 to 70 ° C. for 30 to 90 minutes.

使用するアルカリとしては、不溶性のCu塩を生成することのできるものであれば特に制限はないが、例えば炭酸ナトリウム、炭酸カルシウム、水酸化ナトリウム、水酸化カルシウム、水酸化マグネシウム等が挙げられる。カルシウム塩を用いると石膏が混入し、沈澱中の銅品位が低下するため、沈殿物を少なくするためには、ナトリウム系のアルカリ、コストを重視するならば安価に入手できるカルシウム系のアルカリを使用するのが好ましい。
アルカリは、脱鉄後液のpHが4.0〜8.0の範囲となるまで添加するのが、Cu塩の沈殿効率やアルカリ費用、沈殿物中の銅品位、排水基準等の理由から好ましく、pHを5.0〜7.0の範囲となるまで添加するのがより好ましい。
The alkali to be used is not particularly limited as long as it can generate an insoluble Cu salt, and examples thereof include sodium carbonate, calcium carbonate, sodium hydroxide, calcium hydroxide, and magnesium hydroxide. If calcium salt is used, gypsum is mixed and the copper quality in the precipitation is lowered, so in order to reduce the precipitate, sodium-based alkali is used. It is preferable to do this.
Alkaline is preferably added until the pH of the solution after iron removal is in the range of 4.0 to 8.0 for reasons such as Cu salt precipitation efficiency, alkali cost, copper quality in the precipitate, and drainage standards. It is more preferable to add until the pH is in the range of 5.0 to 7.0.

脱銅後液は中和に使用したカルシウム又はナトリウム及び硫酸根が主成分であり、重金属が除去されているので、一般的な総合排水として処理することができる。   The solution after copper removal is mainly composed of calcium or sodium and sulfate radicals used for neutralization, and since heavy metals are removed, it can be treated as a general integrated waste water.

以下、本発明及びその利点をより良く理解するための実施例を記載するが、本発明はそれらに限定されることはない。
図1に本発明の処理フローの一態様を示す。
Hereinafter, examples for better understanding of the present invention and its advantages will be described, but the present invention is not limited thereto.
FIG. 1 shows one aspect of the processing flow of the present invention.

電解沈澱銅の水洗処理
表1に示す組成を有する電解沈澱銅1000g(湿重量)を2000mlの水でリパルプし、4時間撹拌して、電解沈澱銅の製造時に付着した電解液(硫酸銅、ニッケル、鉄他)を溶解した後に、スラリーをろ過し、固液分離した。得られた残渣は乾燥してから第一工程に導いた。乾燥後の残渣重量は733.2gであった。Ni及びFeはほぼ完全に除去することができた。残渣の分析値もあわせて表1に示す。
Electrolytically Precipitated Copper Washing Treatment 1000 g (wet weight) of electrolytically precipitated copper having the composition shown in Table 1 was repulped with 2000 ml of water, stirred for 4 hours, and an electrolyte solution (copper sulfate, nickel deposited during the production of electrolytically precipitated copper) , Iron, etc.), the slurry was filtered and solid-liquid separated. The obtained residue was dried and led to the first step. The residue weight after drying was 733.2 g. Ni and Fe could be removed almost completely. The analytical value of the residue is also shown in Table 1.

第一工程:電解沈澱銅の硫酸浸出
水洗処理を行った電解沈澱銅200g(乾重量)に98%の濃硫酸を228.6g(電解沈澱銅に含まれる銅に対して1.1当量)加え、更に水を加えて、スラリー量を2000mlとした(反応開始前pH0.07)。
700ml/分で空気を導入しながら、7時間撹拌して浸出した。空気の導入、撹拌にはジェットアジター(SHIMAZAKI社製 JET AJITER)を使用した。尚、液温は特に制御しなかったが、硫酸浸出が、発熱反応であるため、浸出開始4時間後には88℃まで液温は上昇し、その後徐々に低下し、7時間後には70℃であった。反応により、液の色は黒から青に変化した(反応終了後pH0.85)。硫酸浸出後に、浸出物をろ過し、固液分離した。残渣は、水で洗浄し、その洗浄水は、硫酸浸出液に加えた。得られた硫酸浸出液、硫酸浸出残渣の物量を表2に示す。
残渣の物量から見ると、電解沈澱銅中の87.1%のビスマスが残渣として、浸出液から除去できた。また、1.6%のヒ素、0.4%の銅しか残渣に残存していないことから、反応効率は高い。
First step: 228.6 g of 98% concentrated sulfuric acid (1.1 equivalent to the copper contained in the electrolytically precipitated copper) was added to 200 g (dry weight) of the electrolytically precipitated copper which had been subjected to the sulfuric acid leaching and washing treatment of the electrolytically precipitated copper. Further, water was added to make the slurry amount 2000 ml (pH 0.07 before starting the reaction).
While introducing air at 700 ml / min, the mixture was stirred and leached for 7 hours. A jet agitator (JET AJITER manufactured by SHIMAZAKI) was used for air introduction and stirring. Although the liquid temperature was not particularly controlled, sulfuric acid leaching is an exothermic reaction, so the liquid temperature rose to 88 ° C. 4 hours after the start of leaching, then gradually decreased, and after 7 hours, the temperature was 70 ° C. there were. Due to the reaction, the color of the liquid changed from black to blue (pH 0.85 after completion of the reaction). After leaching with sulfuric acid, the leachate was filtered and solid-liquid separated. The residue was washed with water, and the washing water was added to the sulfuric acid leachate. Table 2 shows the amounts of the obtained sulfuric acid leaching solution and sulfuric acid leaching residue.
In view of the amount of the residue, 87.1% bismuth in the electrolytically precipitated copper could be removed from the leachate as a residue. Moreover, since only 1.6% arsenic and 0.4% copper remain in the residue, the reaction efficiency is high.

第二工程:スコロダイトの合成
第一工程で得られた硫酸浸出液425mlに硫酸第2鉄液(硫酸第2鉄試薬(n水塩、第2鉄含有率21.3%)43gを温水で溶解した液、硫酸浸出液に含まれるヒ素に対して第2鉄が1.45当量)225mlを加え、液量を650mlとした後、95℃まで加熱し、24時間スコロダイトの合成を行った。
硫酸浸出液と硫酸第2鉄溶液を室温で混ぜ合わせた直後は、反応は進行しないが、加熱に伴い、60℃前後でスコロダイトの沈澱が観察された。合成液のpHは反応開始前で0.63(室温)であったが、反応終了後は0.58(室温)であった。スコロダイトの合成後に、スコロダイト結晶をろ過し、固液分離した。
スコロダイト結晶は、水で洗浄し、その洗浄水は、脱砒後液に加えた。得られたスコロダイト結晶、脱砒後液の物量を表3に示す。得られたスコロダイト結晶のXRDを図2に示す。ヒ素の溶出が少なく、安定な結晶性スコロダイトが得られている。
尚、この合成によって得られたスコロダイトからのヒ素の溶出は0.2mg/L(TCLP pH5の酢酸緩衝溶液使用)であり、ヒ素が安定であることが確認された。スコロダイト結晶の物量から見ると、98.0%のヒ素がスコロダイト結晶に分配していることから、反応効率は高い。
3価のヒ素がスコロダイト合成に寄与しないことを考えれば、電解沈澱銅の硫酸浸出によって、溶解したヒ素の98%以上が5価となっていると言える。電解沈澱銅の硫酸浸出液をスコロダイト合成の原料とすることが有効であることを示した。
Second step: Synthesis of scorodite In 425 ml of sulfuric acid leachate obtained in the first step, 43 g of ferric sulfate solution (ferric sulfate reagent (n-hydrate, ferric content 21.3%)) was dissolved in warm water. 225 ml of ferric iron with respect to arsenic contained in the liquid and sulfuric acid leachate) was added to make the liquid volume 650 ml, heated to 95 ° C., and scorodite was synthesized for 24 hours.
Immediately after mixing the sulfuric acid leachate and the ferric sulfate solution at room temperature, the reaction did not proceed, but precipitation of scorodite was observed at around 60 ° C. with heating. The pH of the synthesis solution was 0.63 (room temperature) before the start of the reaction, but was 0.58 (room temperature) after the completion of the reaction. After the scorodite synthesis, the scorodite crystals were filtered and solid-liquid separated.
The scorodite crystals were washed with water, and the washing water was added to the solution after dearsenization. Table 3 shows the amounts of the obtained scorodite crystals and the liquid after dearsenization. The XRD of the obtained scorodite crystal is shown in FIG. A stable crystalline scorodite with little arsenic elution is obtained.
The elution of arsenic from the scorodite obtained by this synthesis was 0.2 mg / L (using an acetate buffer solution of TCLP pH 5), and it was confirmed that arsenic was stable. From the viewpoint of the quantity of scorodite crystals, the reaction efficiency is high because 98.0% of arsenic is distributed to the scorodite crystals.
Considering that trivalent arsenic does not contribute to scorodite synthesis, it can be said that 98% or more of dissolved arsenic is pentavalent due to sulfuric acid leaching of electrolytically precipitated copper. It was shown that the sulfuric acid leaching solution of electrolytically precipitated copper was effective as a raw material for scorodite synthesis.

第三工程:脱鉄中和
第二工程で得られた脱砒後液1370mlに炭酸カルシウム26.6g(Ca量で10.64g)を加え、pH3.48まで中和して、ヒ素および鉄は水酸化鉄として共沈させた。その後ろ過性を向上させる為に60℃、30分間加熱して沈澱を熟成した。この沈澱には、ヒ素を共沈させた水酸化鉄及び、中和の際に加えた炭酸カルシウムと硫酸根によって生成した石膏が含まれる。
この沈殿物をろ過して、固液分離した。沈殿物は水で洗浄し、その洗浄水は脱鉄後液に加えた。得られた沈殿物(以降、脱鉄泥と呼ぶ。)、脱鉄後液の物量を表4に示す。脱鉄後液からは、ヒ素は検出されず、効率よく除去されている。一方脱鉄泥中の銅は、0.3%しか分配しておらず、脱鉄後液に残存していることを示している。
なお、pH依存性を調べるためにpHを変えて脱鉄中和を行ったときの結果を図3に示す。
Third step: Neutralization of iron removal Add 26.6 g of calcium carbonate (10.64 g of Ca) to 1370 ml of the dearsenic solution obtained in the second step, neutralize to pH 3.48, and arsenic and iron Co-precipitated as iron hydroxide. Thereafter, in order to improve filterability, the precipitate was aged by heating at 60 ° C. for 30 minutes. This precipitation includes iron hydroxide co-precipitated with arsenic and gypsum produced by calcium carbonate and sulfate radicals added during neutralization.
The precipitate was filtered and separated into solid and liquid. The precipitate was washed with water, and the washing water was added to the solution after deironation. Table 4 shows the amount of the obtained precipitate (hereinafter referred to as deironed mud) and the liquid after deironing. Arsenic is not detected from the solution after iron removal and is efficiently removed. On the other hand, only 0.3% of the copper in the iron removal mud is distributed, indicating that it remains in the liquid after the iron removal.
In addition, in order to investigate pH dependence, the result when changing pH and carrying out deiron neutralization is shown in FIG.

第四工程:脱銅中和
第三工程で得られた脱鉄後液2315mlに炭酸カルシウム9.2g(Ca量で3.68g)を加え、pH5.59まで中和して、水酸化銅として沈澱させた。その後ろ過性を向上させる為に60℃、30分間加熱して沈澱を熟成した。この沈殿物をろ過して、固液分離した。得られた沈殿物(以降、脱銅泥と呼ぶ。)、脱銅後液の物量を表5に示す。銅は高い回収率と共に、ビスマス、ヒ素から良く分離できている。
なお、pH依存性を調べるためにpHを変えて脱銅中和を行ったときの結果を図4に示す。
Fourth step: Neutralization of copper removal Add 9.2 g of calcium carbonate (3.68 g of Ca) to 2315 ml of the post-deironation solution obtained in the third step, and neutralize to pH 5.59 to obtain copper hydroxide. Precipitated. Thereafter, in order to improve filterability, the precipitate was aged by heating at 60 ° C. for 30 minutes. The precipitate was filtered and separated into solid and liquid. Table 5 shows the amount of the obtained precipitate (hereinafter referred to as decoppered mud) and the post-decopperized liquid. Copper is well separated from bismuth and arsenic with high recovery.
In addition, in order to investigate pH dependence, the result at the time of performing copper removal neutralization by changing pH is shown in FIG.

本発明の処理フローの一態様を示す。An aspect of the processing flow of the present invention is shown. 実施例で得られたスコロダイト結晶のXRDである。It is XRD of the scorodite crystal obtained in the Example. 脱鉄中和のpH依存性を表す図である。It is a figure showing the pH dependence of iron removal neutralization. 脱銅中和のpH依存性を表す図である。It is a figure showing the pH dependence of copper removal neutralization.

Claims (13)

  1. (1)電解沈殿銅を随意的に水洗処理した後に、硫酸酸性中の電解沈殿銅に酸素含有ガスを導入しながら、電解沈殿銅中に含まれるAs成分の90wt.%以上を5価に酸化するのに充分な液温及び時間で該溶液を撹拌することを含む硫酸浸出を行い、次いでSb成分及びBi成分を含有する浸出残渣と5価のAs成分を含有する硫酸浸出液に固液分離する第一工程と、
    (2)該硫酸浸出液に3価の鉄を添加して結晶性スコロダイト(FeAsO4・2H2O)を生成させることによって、該結晶性スコロダイトを含有する残渣と脱砒後液とに固液分離する第二工程と、
    (3)該脱砒後液に未反応のFe又は未反応のFe及びAsが残存している場合に、アルカリを添加してFe塩を生成し、As成分が残存している場合はAs成分をFe塩と共沈させ、次いでFe塩及びAs成分(As成分が残存している場合)を含有する沈殿物と脱鉄後液とに固液分離する随意的な第三工程と、
    (4)該脱鉄後液にアルカリを添加してCu塩を沈殿させ、次いでCu塩を含有する沈殿物と脱銅後液とに固液分離する随意的な第四工程と、
    を含む電解沈殿銅の処理方法。
    (1) After the electrolytically precipitated copper is optionally washed with water, 90 wt. As of the As component contained in the electrolytically precipitated copper is introduced into the electrolytically precipitated copper in sulfuric acid acid while introducing an oxygen-containing gas. Sulfuric acid leaching including stirring the solution at a temperature and time sufficient to oxidize more than 5% to pentavalent, followed by leaching residue containing Sb component and Bi component and pentavalent As component A first step of solid-liquid separation into sulfuric acid leachate,
    (2) By adding trivalent iron to the sulfuric acid leaching solution to produce crystalline scorodite (FeAsO 4 .2H 2 O), solid-liquid separation into a residue containing the crystalline scorodite and a post-arsenic-removed solution A second step to perform,
    (3) When unreacted Fe or unreacted Fe and As remain in the solution after de-arsenic, an alkali is added to form a Fe salt, and the As component remains when the As component remains An optional third step of co-precipitation with Fe salt, followed by solid-liquid separation into a precipitate containing Fe salt and an As component (if the As component remains) and a solution after deironing;
    (4) An optional fourth step of adding an alkali to the post-deironation solution to precipitate a Cu salt, and then solid-liquid separation into a precipitate containing the Cu salt and a post-decopperization solution;
    A method for treating electrolytically precipitated copper comprising:
  2. 第一工程における硫酸浸出は70〜95℃で4.5〜11時間撹拌することを伴う請求項1に記載の処理方法。   The processing method according to claim 1, wherein the sulfuric acid leaching in the first step involves stirring at 70 to 95 ° C for 4.5 to 11 hours.
  3. 第一工程における硫酸浸出は外部から加熱せずに行う請求項1又は2に記載の処理方法。   The treatment method according to claim 1 or 2, wherein the sulfuric acid leaching in the first step is performed without heating from the outside.
  4. 第一工程における酸素含有ガスは空気である請求項1〜3の何れか一項に記載の処理方法。   The processing method according to any one of claims 1 to 3, wherein the oxygen-containing gas in the first step is air.
  5. 第一工程における酸素含有ガスの導入及び/又は撹拌はジェット噴射により行う請求項1〜4の何れか一項に記載の処理方法。   The processing method according to any one of claims 1 to 4, wherein the introduction and / or stirring of the oxygen-containing gas in the first step is performed by jet injection.
  6. 第一工程における硫酸浸出液は0.3〜2.2のpHである請求項1〜5の何れか一項に記載の処理方法。   The treatment method according to any one of claims 1 to 5, wherein the sulfuric acid leachate in the first step has a pH of 0.3 to 2.2.
  7. 第一工程における硫酸浸出によりAs成分は95wt.%以上が5価に酸化する請求項1〜6の何れか一項に記載の処理方法。   As component was 95 wt. % Or more is oxidized to pentavalent, The processing method as described in any one of Claims 1-6.
  8. 第二工程における結晶性スコロダイトは60〜95℃に加熱することにより生成する請求項1〜7の何れか一項に記載の処理方法。   The processing method according to any one of claims 1 to 7, wherein the crystalline scorodite in the second step is produced by heating to 60 to 95 ° C.
  9. 第二工程における3価の鉄は硫酸第二鉄として提供される請求項1〜8の何れか一項に記載の処理方法。   The treatment method according to any one of claims 1 to 8, wherein the trivalent iron in the second step is provided as ferric sulfate.
  10. 第二工程における結晶性スコロダイトはpH0.4〜1.2で生成する請求項1〜9の何れか一項に記載の処理方法。   The processing method according to any one of claims 1 to 9, wherein the crystalline scorodite in the second step is generated at a pH of 0.4 to 1.2.
  11. 第三工程におけるアルカリは脱砒後液のpHが2.2〜4.0の範囲となるまで添加する請求項1〜10の何れか一項に記載の処理方法。   The treatment method according to any one of claims 1 to 10, wherein the alkali in the third step is added until the pH of the solution after dearsenic is in the range of 2.2 to 4.0.
  12. 第四工程におけるアルカリは脱鉄後液のpHが4.0〜8.0の範囲となるまで添加する請求項1〜11の何れか一項に記載の処理方法。   The treatment method according to any one of claims 1 to 11, wherein the alkali in the fourth step is added until the pH of the solution after iron removal is in the range of 4.0 to 8.0.
  13. 第三工程及び/又は第四工程におけるアルカリは炭酸カルシウムとして提供される請求項1〜12の何れか一項に記載の処理方法。   The treatment method according to any one of claims 1 to 12, wherein the alkali in the third step and / or the fourth step is provided as calcium carbonate.
JP2006262766A 2006-09-27 2006-09-27 Process for electrolytically precipitated copper Active JP4216307B2 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2006262766A JP4216307B2 (ja) 2006-09-27 2006-09-27 Process for electrolytically precipitated copper

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006262766A JP4216307B2 (ja) 2006-09-27 2006-09-27 Process for electrolytically precipitated copper
KR20070033389A KR100866824B1 (ko) 2006-09-27 2007-04-04 전해 침전 구리의 처리 방법
AU2007216890A AU2007216890B2 (en) 2006-09-27 2007-09-20 Process for treating electrolytically precipitated copper
CL2007002747A CL2007002747A1 (es) 2006-09-27 2007-09-24 Proceso para tratar cobre obtenido por precipitacion electrolitica que comprende una primera etapa de lixiviacion con acido sulfurico, agregar oxigeno, agitar la solucion, y luego separar la solucion lixiviada que contiene as pentavalente y una segun

Publications (2)

Publication Number Publication Date
JP2008081784A JP2008081784A (ja) 2008-04-10
JP4216307B2 true JP4216307B2 (ja) 2009-01-28

Family

ID=39310943

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2006262766A Active JP4216307B2 (ja) 2006-09-27 2006-09-27 Process for electrolytically precipitated copper

Country Status (4)

Country Link
JP (1) JP4216307B2 (ja)
KR (1) KR100866824B1 (ja)
AU (1) AU2007216890B2 (ja)
CL (1) CL2007002747A1 (ja)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5299809B2 (ja) * 2006-12-12 2013-09-25 合同資源産業株式会社 非鉄金属製錬残渣からの金属回収方法
JP2009242223A (ja) * 2007-07-13 2009-10-22 Dowa Metals & Mining Co Ltd 三酸化二砒素の処理方法
JP4717917B2 (ja) 2008-10-06 2011-07-06 Jx日鉱日石金属株式会社 スコロダイトの製造方法及び洗浄方法
JP2010285322A (ja) * 2009-06-12 2010-12-24 Dowa Metals & Mining Co Ltd 砒素を含有する溶液から結晶性スコロダイトを得る方法
JP5334120B2 (ja) * 2009-09-25 2013-11-06 独立行政法人産業技術総合研究所 超電導材料、超電導薄膜及びその製造方法
JP2011168467A (ja) * 2010-02-22 2011-09-01 Dowa Metals & Mining Co Ltd 結晶性スコロダイトの生成方法
CN105039713A (zh) * 2015-08-25 2015-11-11 中南大学 一种硫化砷渣一步浸出固砷富集有价金属的方法
CN105838905A (zh) * 2016-04-20 2016-08-10 江西铜业股份有限公司 一种从低品位含锑物料中富集锑的方法
CN106673069B (zh) * 2016-12-20 2017-12-19 中南大学 一种黑色砷酸铁晶体及其合成方法
KR102062502B1 (ko) * 2019-09-18 2020-02-11 건국대학교 산학협력단 전해정련을 이용하여 구리 함유 폐질산으로부터 초고순도 구리를 획득하는 방법

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2548620C2 (ja) 1975-10-30 1977-12-22
JPS6158530B2 (ja) 1983-07-12 1986-12-12 Nippon Mining Co
CA2167026C (en) 1995-01-12 2004-08-17 Atsushi Fukui Method of recovering antimony and bismuth from copper electrolyte
JP3756687B2 (ja) * 1999-01-29 2006-03-15 同和鉱業株式会社 砒素含有溶液からの砒素の除去および固定方法
CA2511662C (en) * 2002-12-31 2017-01-17 Intec Ltd Recovering metals from sulfidic materials
JP4478585B2 (ja) 2005-01-17 2010-06-09 日鉱金属株式会社 飛灰からの有価物回収方法
FI119438B (fi) * 2005-05-03 2008-11-14 Outokumpu Oy Menetelmä arvometallien ja arseenin talteenottamiseksi liuoksesta

Also Published As

Publication number Publication date
CL2007002747A1 (es) 2008-08-22
AU2007216890B2 (en) 2009-07-30
KR100866824B1 (ko) 2008-11-04
AU2007216890A1 (en) 2008-04-10
KR20080028745A (ko) 2008-04-01
JP2008081784A (ja) 2008-04-10

Similar Documents

Publication Publication Date Title
TW561191B (en) Chloride assisted hydrometallurgical extraction of metal from sulphide or laterite ores
CA2856341C (en) Method for producing high-purity nickel sulfate
CN104379778B (zh) 从复杂氧化物矿和硫化物矿回收铟、银、金和其它稀有金属、贵金属和贱金属的方法
JP3756687B2 (ja) 砒素含有溶液からの砒素の除去および固定方法
US9322104B2 (en) Recovering lead from a mixed oxidized material
CN100558918C (zh) 从溶液中回收有价值金属和砷的方法
AU2002346762B2 (en) A method for precipitating iron from a zinc sulphate solution as hematite
JP4895454B2 (ja) 含ニッケルラテライト鉱石の浸出法
US7326390B2 (en) Production of titania
JP3999805B1 (ja) 砒素含有溶液の処理方法
JP5954350B2 (ja) スカンジウム回収方法
JP4525428B2 (ja) ニッケル酸化鉱石の湿式製錬方法
JP4180655B2 (ja) 塩化物で補助される金属の湿式冶金的抽出方法
FI117389B (fi) Menetelmä useampia arvometalleja sisältävän sulfidirikasteen hydrometallurgiseksi käsittelemiseksi
CN101351567B (zh) 在锌浸出过程中回收稀有金属的方法
EP0013098B1 (en) Removal of manganese ions from zinc and manganese containing solutions
EP2546203B1 (en) Method for wastewater treatment for wastewater containing aluminum, magnesium and manganese
EP2174912B1 (en) Method of removing arsenic from smelting residues comprising copper-arsenic compounds
TWI530567B (zh) 回收鋅及/或二氧化鋅的方法
US4891067A (en) Processes for the treatment of smelter flue dust
KR101160752B1 (ko) 비소를 포함한 비철 제련 중간 산물의 처리 방법
RU2023728C1 (ru) Способ извлечения цинка, меди, свинца и серебра из цинкжелезосодержащего сульфидного сырья
AU2009262352A1 (en) Iron precipitation
US9322105B2 (en) Recovering lead from a lead material including lead sulfide
JP5967284B2 (ja) 高純度スカンジウムの回収方法

Legal Events

Date Code Title Description
A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20081023

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20081104

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20081105

R150 Certificate of patent or registration of utility model

Ref document number: 4216307

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20111114

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20111114

Year of fee payment: 3

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313111

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20111114

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20111114

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20121114

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20121114

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20131114

Year of fee payment: 5

S533 Written request for registration of change of name

Free format text: JAPANESE INTERMEDIATE CODE: R313533

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250