A rapid electrochemical method for measuring the concentration of active glue in copper refinery electrolyte which contains thiourea

Good cathode quality in copper electrorefining depends on maintaining an optimum level of glue and other leveling reagents in the electrolyte. A rapid electrochemical method has been developed for measuring the concentration of active glue in the electrolyte. It is based on the fact that glue strongly influences the polarization (currentvs potential) curve of a copper cathode in such electrolyte. The polarization curve is also influenced by the concentrations of copper, nickel, and thiourea (another leveling reagent) in the solution; the concentrations of these substances also can vary. With the present method a cathodic scan curve of a copper electrode is measured in the fresh, test electrolyte and again after the electrolyte is heated such as to destroy the active glue by hydrolysis; the heating does not affect the thiourea, Cu⁺² or Ni⁺² ions. The glue concentration is determined from the difference in the scan curves for the fresh and heated electrolytes. The difference may be quantified if needed by making standard glue additions to the cooked electrolyte and measuring the corresponding scan curves. The methods given by Refs. 2 and 4 are useful, despited the limitations stated, for tankhouse application in which Ni⁺² and Cu⁺² ion concentrations change very little or are monitored separately.     

硫脲络合火焰原子吸收光谱法同时测定银和铜

本文通过对几种酸的试验研究，提出了在高氯酸介质中，硫脲络合，火焰原子吸收光谱法同时测定银和铜的新方法。本法适用于地质及选冶样品中银和铜的测定．方法的回收率银为９５．８％～１０３．２％，铜为９３．２％～１０８．６％，标准偏差银为６．７４％，铜为２．８２％。     

连续测定银电解液中游离硝酸、铜和银

介绍了以溴甲酚绿为指示剂,用氢氧化钠滴定银电解质中游离硝酸,然后在乙酸-乙酸钠缓冲溶液中以EDTA络合滴定铜 ,再用铁铵矾为指示剂,在稀硝酸介质中以硫氰酸盐滴定银。当电解液中Br 和Fe 的质量浓度分别大于0.40g/L和0.15g/L时,采用在pH1.5～1.7条件下,以钽试剂为指示剂,先用EDTA滴定Br ,Fe 之后,再将溶液调至pH3.5,用EDTA滴定铜,可以很好消除Br 和Fe 的干扰。对同一试样测定10次,硝酸、铜和银的相对标准偏差分别为0.47%,0.72%和0.10%。方法准确,操作简便     

纤维柱分离富集硫脲分光光度法测定铜电解液中铋

提出了高分子胺纤维交换柱快速分离铜基体 ,同时富集铋的新方法。用硫脲洗脱 ,同时显色 ,成功的测定了铜电解液中微量铋。用本方法测定铜电解液中 0.0 0 0 39g/L铋 ,相对标准偏差为 3 .2 4% ,检出限为 0 . 0 0 0 38mg/L。     

N-己基-N′-(对氨基苯磺酸钠)硫脲光度法测定微量铜的研究

研究了显色剂饱和脂肪烃取代基化合物N-己基-N′-(对氨基苯磺酸钠)硫脲(HXPT)和微量Cu(Ⅱ)的显色反应。结果表明:在pH4.8～5.4的HAc-NaAc介质中,Cu(Ⅱ)与HXPT形成摩尔比为1∶3的蓝色水溶性稳定络合物,其最大吸收波长在343.6nm,表观摩尔吸光系数为ε343.6nm=3.26×105L.mol-1.cm-1。25mL显色液中铜在0～12μg范围内符合比尔定律,相关系数r=0.9990。方法已成功应用于铝矿样和生物样品中微量铜的测定,结果满意。     

N-己基-N''''-(对氨基苯磺酸钠)硫脲光度法测定微量铜的研究

研究了显色剂饱和脂肪烃取代基化合物N-己基-N＇-（对氨基苯磺酸钠）硫脲（HXPT）和微量Cu（Ⅱ）的显色反应。结果表明：在pH4．8～5．4的HAc—NaAc介质中，Cu（Ⅱ）与HXPT形成摩尔比为1：3的蓝色水溶性稳定络合物，其最大吸收波长在343．6nm，表观摩尔吸光系数为ε343．6nm=3．26×10^5L·mol^-1·cm^-1。25mL显色液中铜在0～12μg范围内符合比尔定律，相关系数r=0．9990。方法已成功应用于铝矿样和生物样品中微量铜的测定，结果满意。     

As,Sb, and Fe removal from industrial copper electrolyte by solvent displacement crystallisation technique

The presence of impurities in the copper electrolyte increases the energy consumption of an electrorefining process and contaminates the deposited copper on cathode. The concentration of impurities increases over time making it necessary to remove them from the solution. This research introduces a fast, effective, and simple method to refine the industrial electrolyte from arsenic, iron and antimony by solvent displacement crystallisation technique. In this method, when alcohol is added to the electrolyte, the impurities precipitate from the solution as amorphous arsenato antimonite phase. Results show that Fe, Sb, and As are removed from the copper electrolyte by 75.2, 96.9 and 99.8%, respectively. Electro winning experiments show that the electric energy consumption for electrodeposition of copper is 15.5% lower when the electrolyte is free of impurities.     

Glue analysis and behavior in copper electrolyte

Animal glue in combination with other chemicals is often used as a leveling agent in the copper electroplating industry. The control of the glue concentration in the electrolyte is critical to the quality of copper produced. A quantitative galvanostatic technique for glue analysis in copper electrolyte containing lignin sulfonate and Cl⁻ was developed. The kinetics of glue hydrolysis in industrial electrolytes was studied and found to follow first-order reaction kinetics, with sulfuric acid acting as a catalyst. The dependence of the glue hydrolysis rate constant on temperature follows the Arrhenius equation. By adding fresh glue to the electrolyte, the glue activity first rises and then falls. This effect can be explained by the presence of long-chain molecules in the glue which are less active but hydrolyze into the more active medium-sized molecules. A mathematical model of this process shows good agreement with experimental data. The bulk of the electrolyte flow in the INCO commercial electrolytic plating cell bypasses the electrodes, probably across the bottom of the cell. The electrolyte circulation between electrodes is not very intense. A simple equation for the glue concentration calculation in the cell inlet and outlet, depending on the glue addition rate, was derived. V.K. Blechta, formerly Section Leader of Process Technology, INCO Limited, is retired. Z.Z. Wang, formerly Research Scientist, INCO Limited, is Researcher, Laurentian University, Sudbury,Canada.     

容量法测定浸金液中的硫脲

本文介绍了容量法测定浸金液中的硫脲，试验了浸取液中各组分对测定的干扰及其消除方法，初步探明了硫脲法浸金过程及从浸出液中回收金的过程中硫脲损耗的情况。     

铜箔电解液中砷的测定

研究了乙基罗丹明B -砷钼杂多酸 -阿拉伯树胶显色体系 ,提出了测定痕量砷的高灵敏分光光度法。由于形成吸附性缔合物 ,表观摩尔吸光系数高达 3.3 2× 10 5。缔合物最大吸收位于 5 88nm ,本法用于铜箔电解液中痕量砷的测定 ,得到满意结果     

Effect of thiourea on the copper cathode polarization behavior in acidic copper sulfate at 65 °C

The effects of different concentrations of thiourea (TU) on the copper cathode polarization behavior in an acidic copper sulfate solution was investigated at 65 °C using potentiodynamic and galvanostatic methods. The results showed that there was a transition current density for each concentration of the fresh TU, below which the TU exhibited a polarizing effect and above which the TU manifested a depolarizing effect on the copper cathode. The depolarizing effect increased with cathodic overpotential. The transition current density increased with TU concentration and decreased with time. Lowering of the electrolyte temperature resulted in diminution of the transition current density considerably. In the modern copper electrorefining conditions (65 °C, 150 to 350 A/m², and using approximately 1 to 4 mg/dm³ of TU), TU produces only a polarizing effect on the copper cathode.     

电感耦合等离子体原子发射光谱法同时测定锌电解液中铜镉钴

研究了用电感耦合等离子体原子发射光谱法（ICP-AES）直接同时测定锌电解液中的铜、镉、钴含量的方法。试样不经预处理,在3%（V/V）的HNO₃介质中,以327.393 nm、226.502 nm、228.616 nm波长的谱线分别作为铜、镉、钴的分析线,通过选择分析线和调扣背景点来消除或减少背景干扰和重叠干扰,采用基体匹配方法克服基体效应,用ICP-AES测定了冶炼厂锌电解液中的铜、镉、钴含量。该法操作简单,分析快速、可靠,样品的测定值与极谱法的测定值相符,相对标准偏差在0.7%～1.3%之间,可用于锌电解液中杂质元素含量的控制分析。     

Hydrogen reduction of spent copper electrolyte

The recovery of copper powder and the removal of arsenic from spent copper electrolyte by means of hydrogen reduction aimed at purifying the spent copper electrolyte were studied. About 90% of the copper in the electrolyte could be recovered in the form of pure copper powder after 20 min reduction at 180° at a hydrogen pressure of 20 kg cm^?2 (2.0 MPa). An induction period, due to slow hydrogen reduction of As⁵⁺ to As³⁺, could be eliminated as a result of the addition of copper powder as a reductant. Arsenic, antimony and bismuth in the liquor have been found to catalyze the hydrogen reduction of copper. When the copper concentration in the treated solution reached a certain low level, copper arsenide, Cu₃As₁ was formed on the surface of copper through hydrogen reduction of As³⁺ ions. This reaction was very slow and a long reaction time was required for complete removal of arsenic. Therefore, in order to purify spent copper electrolyte, some arsenic removal technique (e.g., solvent extraction) should be combined with hydrogen reduction.     

含铜原矿石中铜物相的快速分离与测定

经分相后的溶液不需用硝硫混酸处理,直接加入盐酸,调节酸度后即可用空气-乙炔原子吸收法测定,方法操作简便,测定速度快,结果满意.     

铜电解液自净化研究进展

在铜电解过程中,粗铜中的有害杂质(主要是As、Sb、Bi)通过电化学溶解进入电解液并不断富集,从而严重危害阴极铜的质量及电解生产,电解液及时净化对阴极铜质量有着重要的意义.针对现行的铜电解液净化工艺中存在的能耗高、污染大、除杂效率低等缺点,对铜电解液自净化工艺进行了评述,详细介绍了目前国内外自净化除杂的实验室研究、工业应用及自净化机理的研究现状,并对其发展前景进行了展望.     

分子识别技术(MRT)在铜精炼中的应用—从铜电解液中除铋

在世界经济中,高纯电解铜是一种重要的商品,主要用来生产铜线。全球冶炼厂处理来自不同产地的矿石,生产出高纯电解铜。这些铜精矿通常含有0.1%的铋。如果最终产品中的铋含量超过2×10^-6,会导致产品出现脆性,使得铜产品不适合用于拉丝生产。IBC先进技术有限公司开发出一种有效的除铋系统,用于分离铜电解液中溶解的铋,使铋含量达到一个理想的水平。该系统与铜生产系统一体化,可实现连续作业。IBC采用一种分子识别技术（MRT）工艺来进行分离作业。在该工艺中,专门设计的螯和剂或配位体与固体骨架（例如硅胶）进行化学结合,产生一种称为SuperLig^的固相系统。这套除铋系统已经用于几家电解厂的铜精炼生产中。本文介绍了从铜电解液中分离和回收铋的工艺步骤,这些工艺步骤包括:吸收、一段洗涤、预解吸、主要解吸、后解吸、二段洗涤、铋沉淀,给出了每个步骤控制和监测的项目。本文讨论了采用其它技术控制铋的局限性。作者还介绍了MRT系统为铜电解厂带来的经济效益,这些铜电解厂都存在铋的问题。     

PLC在铜电解液循环系统中的应用

叙述了PLC在电解液循环系统高位槽液位、温度、流量控制中的应用,详细介绍了控制原理、系统结构和网络拓扑结构、重要控制回路以及现场仪表的选型。