有色金属(冶炼部分)

黑铜电解阳极泥是以含铜电镀污泥、废电子线路板、废杂铜、含铜残渣等含铜杂料火法熔炼得到的黑铜在电解过程中产生的，富集了大量的锡、铜、铅、镍、锑等金属，成分复杂且波动较大。目前，铜阳极泥的回收均需先脱除贱金属，主要方法有常规的硫酸浸出法、焙烧+酸浸法、臭氧强化酸浸法、硝酸氧化酸性浸出法、氯化催化浸出法以及加压氧化浸出法等。对于黑铜电解阳极泥来说，目前的处理工艺存在浸出率低，或处理成本高问题，具有一定的局限性。针对现有工艺存在的不足，利用X射线衍射、X射线光电子能谱等分析手段，分析了黑铜电解阳极泥中铜、镍、锡及铅等的存在形式，并提出以稀硫酸为浸出剂，工业氧(99%)、硫酸铁及氯化钠为助浸剂，常压浸出脱铜镍的工艺。采用单因素试验法，通过改变硫酸浓度、三价铁离子浓度、氯离子浓度、液固比、氧气流量、反应温度、反应时间等浸出参数，研究了黑铜电解阳极泥中铜、镍的浸出行为。研究结果表明，在硫酸浓度130 g/L、三价铁离子浓度8 g/L、氯离子浓度4 g/L、液固比6 mL/g、氧气流速0.3 min/L、反应温度80℃、反应时间6 h的优化条件下，铜、镍的浸出率分别为98.21%、99.59%。该方法实现了黑铜电解阳极泥在硫酸体系中铜镍高效浸出，成本较低，浸出后液经pH调节，其中的铜、镍可分别用Lix984和HBL110萃取剂直接萃取，经后续处理可以分别得到电积铜和硫酸镍。

Black copper electrolytic anode mud is an insoluble product deposited at the bottom of the electrolytic cell during the electrolysis process of black copper(containing 75%— 90% copper) obtained by pyrometallurgical smelting of copper-containing electroplating sludge, waste electronic circuit boards, waste miscellaneous copper, residual copper and other copper-containing miscellaneous materials. These materials enriched with a large number of tin, copper, lead, nickel, antimony and other metals, the composition of which is complex and fluctuates. At present, the recovery of copper anode mud needs to be treated to remove non-precious metals first. Although the conventional sulfuric acid leaching method shows low cost, it is difficult to achieve satisfied pre-treatment effect and hence enhancing the leaching process is necessary.The methods to strengthen the leaching process of copper and nickel mainly includes: roasting+acid leaching, ozone enhanced acid leaching, nitric acid oxidative acid leaching, chlorination catalytic leaching and pressure oxidation leaching methods. For the anode slime of black copper electrolysis, in the current copper-nickel separation process, the conventional sulfuric acid leaching method has a low leaching rate; the enhanced processes generally have high costs, and some processes produce polluting gases, such as the sulfuric acid roasting-acid leaching method generates sulfur dioxide, and the nitric acid oxidation acid leaching method generates nitrogen oxides. In view of the deficiencies of the existing processes, this paper analyzes the existence forms of copper, nickel, tin and lead in black copper electrolytic anode slime by means of scanning electron microscope(SEM), energy dispersive spectroscopy(EDS), X-ray diffraction(XRD), and X-ray photoelectron spectroscopy(XPS), etc., and on this basis, the process of leaching under atmospheric pressure to recover copper and nickel was proposed by using dilute sulfuric acid as the leaching agent, industrial oxygen(99%), iron sulfate and sodium chloride as the leaching-aid reagent. The leaching parameters such as sulfuric acid concentration, ferric ion concentration, chloride ion concentration, liquid-solid ratio, oxygen flow, reaction temperature, and reaction time were changed by using the single factor experimental method. The leaching behavior of copper and nickel in black copper electrolytic anode mud was studied.The results show that the leaching rates of copper and nickel are 98.21% and 99.59%, respectively, under the optimized conditions including sulfuric acid concentration of 130 g/L, ferric ion concentration of 8 g/L, chloride ion concentration of 4 g/L, liquid-solid ratio of 6 mL/g, oxygen flow rate of 0.3 min/L, reaction temperature of 80 °C, and reaction time of 6 h. This method realizes the efficient leaching of copper-nickel in the sulfuric acid system of black copper electrolytic anode mud with low cost, and the leaching solution is pH adjusted, in which the copper and nickel can be directly extracted with Lix984 and HBL110 extractants, respectively. After subsequent processing, electrowinning copper and nickel sulfate can be obtained respectively.