Electrometallurgy of copper refinery anode slimes

High-selenium copper refinery anode slimes form two separate and dynamically evolving series of compounds with increasing electrolysis time. In one, silver is progressively added to non-stoichiometric copper selenides, both those originally present in the anode and those formed subsequently in the slime layer, and in the other, silver-poor copper selenides undergo a dis-continuous crystallographic sequence of anodic-oxidative transformations. The silver-to-selenium molar ratio in the as-cast anode and the current density of electrorefining can be used to construct predominance diagrams for both series and, thus, to predict the final bulk “mineralogy” of the slimes. Although totally incorrect in detail, these bulk data are sufficiently accurate to provide explanations for several processing problems which have been experienced by Kidd Creek Division, Falconbridge Ltd., in its commercial tankhouse. They form the basis for a computer model which predicts final cathode quality from chemical analyses of smelter feed.     

Tellurium distribution in copper anode slimes smelting

Tellurium is a common minor constituent of copper anode slimes. The distribution of tellurium between the phases during slimes smelting is an important consideration, both in terms of metal quality and the capture of the oxidized tellurium. In this work, the oxidation by oxygen at 1100 °C of a silver-copper selenide matte containing 2 pct tellurium has been examined. The distribution of tellurium between the phases was determined as the extent of oxidation increased, and the system was modeled using a computational thermodynamics package. Oxidized tellurium was found to report to the slag, with none being removed with the gas. The thermodynamic model predicted, to an acceptable level, the tellurium content of all phases as oxidation progressed. It was used to show that oxidation by air rather than oxygen results in higher residual tellurium levels in silver metal and that the lower the smelting temperature, the greater the extent of tellurium elimination from silver to the slag.     

Recovery of selenium from copper anode slimes

Thermogravimetric studies were made on thin layers and spherical pellets of decopperized anode slimes. These have shown that deselenization proceeds initially by the volatilization of the free selenium content at about 360°C. At higher temperatures and under an oxidizing atmosphere, silver selenide is decomposed either directly or via the formation of silver selenite and its subsequent decomposition. The rates of these reactions depend greatly on the concentration of selenium dioxide in the atmosphere over the reacting surface. It has been shown that the deselenization of slime pellets is enhanced when a forced air flow over the reacting particle is provided. This will promote oxidation, remove the selenium dioxide product to minimize the formation of silver selenite from silver and selenium dioxide, and increase the rate of decomposition of the silver selenite formed.     

Extraction of selenium from copper anode slimes in a sealed leaching system

A new method was proposed for extracting selenium from copper anode slimes with a low concentration of nitric acid in a sealed sulfuric acid leaching system. It is performed under an atmosphere of oxygen which allowed for a cyclic utilization of nitric acid. The effects of main parameters on selenium leaching were studied. The mineralogical characterizations of the typical samples were investigated by XRD and SEM. The results showed that the optimal conditions of the process are considered to be total gas pressure of 0.1 MPa, leaching temperature of 388 K, solid-liquid ratio of 0.20 g mL^–1, H₂SO₄ concentration of 2 mol L^–1, HNO₃ concentration of 0.07 mol L^–1 and leaching time of 2 h. The high selenium leaching efficiency of 99.23% was obtained under these conditions. According to the results of XRD and SEM-EDS, Cu–Ag selenide in the raw anode slimes is difficult to be leached with sulfuric acid alone; copper can be leached more easily from Cu-Ag selenide than silver; selenide is oxidized into the solution, undergoing the intermediate product of elemental selenium.     

197Au Mössbauer study of copper refinery anode slimes

Copper refinery anode slimes are abundantly produced during the electrolytic refining of copper. Although the slimes contain significant and economically recoverable amounts of gold and silver, the chemical state of the gold has not been fully identified. In the present work, the chemical form of gold in a copper anode, in a raw slime, and in slimes treated by different leaching procedures has been investigated by Mössbauer spectroscopy with the 77.3 keVγ-rays of¹⁹⁷Au. The Mössbauer spectrum of the anode is typical of a dilute Au:Cu alloy. The spectrum of the raw slime consists of two components, namely, a single, rather broad line with an isomer shift (IS) of about ?0.3 mm/s relative to a Pt metal source and a quadrupole doublet with an IS of + 1.2 mm/s and a quadrupole splitting of 5.0 mm/s. The single line component can be attributed to a gold-rich alloy, with an approximate composition of Au₆₀Ag{n40} or Au₈₀Cu₂₀ if it is a binary alloy, or to a ternary Au-Ag-Cu alloy of appropriate composition. The parameters of the quadrupole doublet match those of Ag₃AuSe₂ (fischesserite) or related Ag_2?xAu_xSe compounds. In these compounds, the gold atoms are coordinated by two selenium atoms in a linear arrangement, as is typical for Au(I). It was found that the ratio between the concentrations of the metallic phase and the selenide strongly depends on the leaching conditions. The measurement of the Lamb-Mössbauer factor of fischesserite is also reported.     

湿法处理铜阳极泥的新方法

开发了一种处理铜阳极泥的新方法.该法的主要步骤是:铜浸出、培烧、银漫出、贵金属浸出及处理溶液中的杂质.新方法使贵金属的精炼既简单又快捷.文章还介绍了某些铜精炼厂目前的情况.     

Mineralogical characterization of a copper anode and the anode slimes from the la caridad copper refinery of mexicana de cobre

A detailed mineralogical study was carried out to characterize a copper anode, the anode-face slimes, the slimes on the bottom of the refining cell, and the autoclave-leached slimes from the La Caridad refinery of Mexicana de Cobre. The objective was to identify possible Pb-Sb-Bi and As-Sb-Bi interactions that could control the Sb and Bi concentrations of the electrolyte. Although some Pb, As, Sb, and Bi can be found in solid solution in the copper crystals of the anode, these elements are mostly present as Cu-Pb-As oxide and Cu-Pb-As-Sb-Bi oxide inclusions at the grain boundaries. During electrorefining, the Pb, As, Sb, and Bi in solid solution dissolve. Part of the Pb, As, Sb, and Bi in the oxide inclusions also dissolves, but part reacts in situ to form PbSO₄ and Pb₅(AsO₄)₃(OH,Cl). Some of the dissolved elements reprecipitate as PbSO₄, SbAsO₄, Sb-As oxide, Sb-As-Bi oxide, Pb₅(AsO₄)₃(OH,Cl), and an oxidate phase of mainly Cu-Ag-AsO₄-SO₄ composition. Thus, high As contents facilitate the precipitation of Sb and Bi from the electrolyte. Although Pb-Sb oxide and Pb-Bi oxide species were only rarely detected, a high Pb content in the anode may retard the dissolution of the Cu-Pb-As-Sb-Bi oxide inclusions, thereby retaining some Sb and Bi in the raw anode slimes. Autoclave leaching dissolves part of As, Sb, and Bi, but the SbAsO₄ and Sb-As-Bi oxide species remain in the leach residue. The Pb is converted almost entirely to PbSO₄, which is present as subhedral crystals in the autoclave leach residue.     

容量法测定阳极泥中金

本文提出了用氢醌容量法测定阳极泥中的金，研究了如何从阳极泥中分离与富集金的方法，本法的精密度与准确度均好，具有流程短，分析速度快，成本低等优点。     

The recovery of osmium from nickel refinery anode slimes

The commencement of pilot-scale production of high-purity osmium in 1965 increased to fifteen the number of elements recovered in marketable form from the Sudbury, Ontario, Ni−Cu ores. Detection of minute quantities of osmium in various plant intermediate products, development of a procedure for recovering and concentrating most of the osmium previously lost in processing, and the techniques for refining it into a metal powder of 99.98 pct purity, are described.     

电解重量法测定阳极铜中铜

先用恒电流电解重量法测定阳极铜中铜,然后通过原子吸收光谱法(AAS)测定电解残余液中铜,电感耦合等离子体原子发射光谱法(ICP-AES)测定沉积在铂阴极上的金、银等杂质元素,对电解重量法的测定结果进行修正。分别考察了电解条件、铂阴极干燥时间对分析结果的影响,结果表明,在设定电流为1.5A时电解3.0~3.5h后取出铂阴极,干燥3~5min,可以获得较好的测定结果。按照实验方法测定阳极铜中铜,结果的相对标准偏差(RSD,n=11)小于0.05%。方法用于铜合金标准物质IARM 71B中铜量的测定,测定值与认定值相一致。     

X射线荧光光谱法测定阳极铜各成分

研究了X射线荧光光谱法测定阳极铜时样品表面处理的方法,程序设计过程中基体、谱线干扰,分析低含量元素时谱线背景的扣除等问题;对基体铜的测定采用了标准归一法;测定了阳极铜标样中20种元素,测定结果与推荐值一致,RSD为0.1%～6.0%;实测了阳极铜熔炼过程中不同阶段的5个样品,结果满意。     

铜阳极炉溜槽的技术改造

对阳极炉溜槽进行技术改进,采用溜槽预制件和保温结构,溜槽的使用寿命从5h延长到1500h,效果十分显著。     

碘量法测定铜阳极泥中铜的方法改进

使用行业标准方法 YS/T 745.1—2010碘量法测定铜阳极泥中铜时,采用氢溴酸除去试样中硒、砷、锑、锡等干扰元素,溶样过程操作繁琐,耗时长,易发生溅跳而造成无效结果,且检测效率低,因此不适用于冶炼企业大批量样品同时快速分析检测。试验使用盐酸分解试样,用硝硫混酸初步除硒等杂质、再用溴进一步除杂,替代氢溴酸除去试样中的杂质元素,从而对YS/T 745.1—2010碘量法测定铜阳极泥中铜的方法进行了改进。通过试验确定硝硫混酸用量为15mL,而后加入3mL盐酸溶解至溶液体积剩余约0.5mL时能完全溶解盐类。按照实验方法测定铜阳极泥试样中铜,测定结果的相对标准偏差(RSD,n=7)小于0.50%;各试样测定结果与行业标准方法 YS/T 745.1—2010结果一致,且两种方法间不存在显著性差异,可用于冶炼企业大批量快速分析检测铜阳极泥中铜量。     

铜阳极泥处理生产实践

针对阳极泥成分变化及其影响，介绍了各工序优化操作条件和相应的增产措施以及实施效果。     

铜阳极板中的氧对电解生产的影响

分析了铜阳极板中的氧对电铜生产的影响,探讨了火法精炼过程中阳极板氧含量的控制.     

铜阳极板中的氧对电解生产的影响

分析了铜阳极板中的氧对电铜生产的影响,探讨了火法精炼过程中阳极板氧含量的控制。     

铜电解阳极钝化及漂浮阳极泥控制技术研究进展

阳极钝化和漂浮阳极泥是影响铜电解精炼稳定生产的主要因素,会造成生产能力的损失、电耗增加、阴极铜质量下降等问题,其形成的主要原因是阳极铜和电解液中含有杂质.目前文献表述中关于阳极钝化的形成机理包括:砷含量对阳极钝化有促进或抑制作用;阳极铜表面生成CuSO4盐膜引起钝化;氧化亚铜与锌粉共同作用引起钝化;氧化亚铜和硫酸铜晶体...     

碘量法测定阳极铜中铜含量的不确定度评定

本文对碘量法测定阳极铜中铜含量进行了不确定度评定,分析了该方法测定过程中的不确定度来源,包括称样质量、标准溶液的配制、标准滴定液的标定和样品滴定等.通过建立数学模型对各不确定度分量进行了计算,然后按方根和得到的不确定度评定结果,合成标准不确定度为0.20％,扩展不确定度为0.40％.该实验及结果表明,碘量法测定阳极铜中...     

从铜阳极泥高压釜浸出液中回收碲和硒的新工艺

在铜阳极泥加压氧化浸出过程中,超过65％的碲在脱铜过程中同时析出.在浸出条件恶劣的情况下,大约10％ ～15％的硒也会同时溶解.目前对浸出液的处理方式是让浸出液通过一层铜屑进行循环.浸出液经沉积形成碲化铜和硒化铜,溶液再经过滤进行分离.为了提高反应效率,降低工艺成本,尽量减少铜的加入量,缩短停留时间,降低能耗,在实验室中研究了一种化学还原剂,并进行了沉积工艺试验.本文给出了试验结果,并对工艺化学进行了探讨.