【作者】 李丹；

【导师】 邬建辉； 白猛；

【作者基本信息】 中南大学 ， 资源与环境（专业学位）， 2025， 硕士

【摘要】 黑铜电解阳极泥是以含铜废料经过火法熔炼处理形成黑铜,不经吹炼和精炼直接电解形成的难溶性产物,该物质富含铜、镍、锡、铅等多种有价金属元素。针对黑铜电解阳极泥的现有处理技术,普遍存在金属浸出效果差或处理成本高等问题,本研究基于黑铜电解阳极泥的物相分析与成分表征,采用了“常压氧化酸浸-Lix984萃取分离铜-HBL110萃取分离镍”新工艺,实现了铜、镍的高效分离回收。主要研究成果如下:（1）采用了H₂SO₄-O₂-Fe₂（SO₄）₃-NaCl复合浸出体系。在阳极泥质量20 g、硫酸浓度130 g/L、Fe³⁺浓度8 g/L、Cl^-浓度4 g/L、浸出温度80℃、氧气通量0.3 L/min、液固比6:1、浸出时间6 h的优化条件下,铜、镍浸出率分别为98.21%和99.59%,浸出渣中铜、镍残留量仅为0.39 wt%和0.04 wt%。（2）采用Lix984对复合浸出体系的浸出液进行铜的萃取。在浸出液初始p H值2.2、Lix984浓度35%、混合时间8 min、相比4:3的优化条件下,铜单级萃取率为91.02%,在单级萃取实验的优化条件下,铜三级萃取率提升至99.91%;负载铜有机相在经过洗涤预处理后,分别考察了硫酸溶液体系和模拟工业贫铜电解液体系两种反萃介质的反萃效果:采用硫酸溶液体系为反萃剂时,在硫酸浓度2 mol/L、相比1:1、混合时间6 min的优化实验条件下,铜反萃率为98.79%;采用模拟工业贫铜电解液体系（Cu 30 g/L,H₂SO₄2 mol/L）为反萃剂时,在相比1:1、混合时间6 min的优化实验条件下,铜反萃率为98.44%,反萃液Cu²⁺浓度达43.19 g/L,可直接用于电积铜;再生有机相对铜离子的单级萃取效率达到90.84%,展现出优异的循环性能。（3）采用HBL110对萃铜后液进行镍的萃取。在HBL110皂化率80%、料液p H值2.2、萃取相比1.1/1、萃取时间7 min的优化条件下,镍单级萃取率为87.31%,在单级萃取实验的优化条件下,镍三级萃取率提升至97.35%;负载镍有机相在经过洗涤预处理后,采用硫酸溶液作为反萃剂,在硫酸浓度1.5 mol/L、反萃时间6 min、反萃相比6:1的优化条件下,镍单级反萃率仅为74.53%,在此条件下镍的四级反萃率达97.17%;采用5 mol/L氢氧化钠溶液皂化再生后的有机相对镍单级萃取率可达到87.11%,展现出优异的循环性能。图48幅,表13个,参考文献151篇更多还原

【Abstract】 Black copper electrolytic anode slime is an insoluble product formed by directly electrolyzing black copper,which is produced from copper-containing waste through pyrometallurgical smelting without blowing and refining.This substance is rich in various valuable metal elements such as copper,nickel,tin,and lead.The existing treatment technologies for black copper electrolytic anode slime generally suffer from poor metal leaching efficiency or high processing costs.Based on the phase analysis and composition characterization of black copper electrolytic anode slime,this study adopted a new process of"atmospheric pressure oxidation acid leaching-Lix984 extraction and separation of copper-HBL110 extraction and separation of nickel",achieving efficient separation and recovery of copper and nickel.The main research results are as follows:（1）A composite leaching system of H₂SO₄-O₂-Fe₂（SO₄）₃-NaCl was adopted.Under the optimized leaching conditions of 20 g anode slime,130 g/L sulfuric acid concentration,8 g/L Fe³⁺concentration,4 g/L Cl^-concentration,80℃leaching temperature,0.3 L/min oxygen flow rate,6:1 liquid-to-solid ratio,and 6 h leaching time,the leaching rates of copper and nickel were 98.21%and 99.59%,respectively,and the residual amounts of copper and nickel in the leaching residue were only0.39 wt%and 0.04 wt%.（2）Lix984 was used to extract copper from the leaching solution of the composite leaching system.Under the optimized conditions of an initial p H value of 2.2 for the leaching solution,35%Lix984concentration,8 min mixing time,and a phase ratio of 4:3,the single-stage extraction rate of copper was 91.02%.Under the optimized conditions of the single-stage extraction experiment,the three-stage extraction rate of copper increased to 99.91%.After the copper-loaded organic phase was washed and pretreated,the stripping effects of two stripping media,a sulfuric acid solution system and a simulated industrial lean copper electrolyte system（Cu 30 g/L,H₂SO₄2 mol/L）,were investigated.When the sulfuric acid solution system was used as the stripping agent,under the optimized experimental conditions of 2 mol/L sulfuric acid concentration,a phase ratio of 1:1,and 6 min mixing time,the copper stripping rate was 98.79%.When the simulated industrial lean copper electrolyte system was used as the stripping agent,under the optimized experimental conditions of a phase ratio of 1:1 and 6 min mixing time,the copper stripping rate was 98.44%,and the copper ion concentration in the stripping solution reached 43.19 g/L,which could be directly used for copper electrowinning.The single-stage extraction efficiency of the regenerated organic phase for copper ions reached90.84%,demonstrating excellent cycling performance.（3）HBL110 was used to extract nickel from the solution after copper extraction.Under the optimized conditions of 80%saponification rate of HBL110,a p H value of 2.2 for the feed solution,a phase ratio of 1.1/1,and a leaching time of 7 min,the single-stage extraction rate of nickel was 87.31%.Under the optimized conditions of the single-stage extraction experiment,the three-stage extraction rate of nickel increased to 97.35%.After the nickel-loaded organic phase was washed and pretreated,sulfuric acid solution was used as the stripping agent.Under the optimized conditions of 1.5 mol/L sulfuric acid concentration,6 min stripping time,and a phase ratio of 6:1,the single-stage stripping rate of nickel was only 74.53%,and under these conditions,the four-stage stripping rate of nickel reached 97.17%.The single-stage extraction rate of nickel by the organic phase regenerated through saponification with 5mol/L sodium hydroxide solution could reach 87.11%,demonstrating excellent cycling performance.更多还原