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锌浸渣是锌冶炼行业主要危废，湿法酸浸工艺可实现锌浸渣中多元素的高效回收，但主物相铁酸锌浸出时铁会大量溶出形成低锌高铁溶液(质量比Zn/Fe=2)，需前置除铁以实现有价金属回收。采用单因素试验法考察了不同条件对ZnSO4-FeSO4体系溶液除铁率和沉铁渣晶型结构、微观形貌的影响。结果表明，在硫酸亚铁模拟液中，初始铁浓度20 g/L、氧气流量1.0 L/min、温度90℃、pH=3的条件下反应1 h，溶液除铁率为99.79%，残铁浓度可降至40 mg/L。硫酸锌的引入虽可略微提升除铁率，但不利于反应后期除铁速率。高的初始铁浓度(≥30 g/L)、氧气流量(≥1.0 L/min)、锌离子浓度(≥15 g/L)可促进针铁矿形核，导致晶粒细化并聚集成大颗粒；提高反应温度可促进针铁矿结晶长大。锌浸渣浸出液除铁应用研究发现，采用碱式碳酸锌作为中和剂，可使得锌浸出液中Zn/Fe质量比从2增加至9.7(对应除铁率69.82%)，满足现有锌湿法冶炼除铁工段进料要求(Zn/Fe=8～10)，为高效湿法酸浸锌浸渣的工业应用提供了技术支撑。
Abstract：Zinc leaching residue is the main hazardous solid waste in the zinc smelting industry. It is rich in iron, zinc, lead, copper, cadmium, arsenic, indium, silver and other elements. Resource endowment and environmental risk coexist. The wet acid leaching process emerges as a promising solution, offering the potential for efficient and comprehensive recovery of these diverse valuable elements from zinc leaching residue, thereby simultaneously addressing resource utilization and environmental remediation goals. However, during the leaching of the primary zinc ferrite phase(ZnFe_2O4), a large amount of iron dissolved into the solution, which shows the characteristics of low-zinc and high-iron(Zn/Fe=2) compared with the leaching solution of zinc hydrometallurgy. It's necessary to remove iron in advance to realize the recovery of valuable metals. Significant progress has been made in the study of iron removal by goethite, but the influence of zinc ions on the formation of goethite still needs further study. The effects of different conditions on the iron removal efficiency and the crystal structure/microstructure characteristics of iron precipitation products in simulated ZnSO4-FeSO4 solution were systematically studied by single factor experiment. The test parameters include initial iron concentration(1–40 g/L), pH value(2–4), temperature(70–90 ℃), oxygen flow rate(0.5–1.0 L/min) and reaction time(0–1 h). The results show that under the optimal conditions of initial iron concentration of 20 g/L, oxygen flow rate of 1.0 L/min, reaction temperature of 90 ℃, pH=3 and reaction time of 1 h in ferrous sulfate simulated solution, the iron removal rate reaches 99.79%, with the residual iron concentration reduces to 40 mg/L, while precipitated residues exhibit α-FeOOH as the predominant phase. The formation of the goethite phase is critically dependent on precise control of pH value of the solution. Furthermore, by adding different concentrations of zinc ions to the FeSO4 solution, it is found that the introduction of zinc sulfate can slightly increase the iron removal rate but is not conducive to the iron removal rate in the later stage of the reaction. The increase of initial iron concentration ≥ 30 g/L), oxygen flow rate( ≥ 1.0 L/min), and zinc ion concentration( ≥ 15 g/L) promote the nucleation of goethite, resulting in a greater number of fine crystals that aggregated into larger particles. At the same time, increasing the reaction temperature can promote the growth of goethite crystals. The application of iron removal technology to actual leaching solution of zinc leaching residue was studied. It is found that the high zinc ion concentrations compete with iron for adsorption sites, thereby inhibiting iron precipitation efficiency. This study finds that basic zinc carbonate exhibits fast neutralization speed and strong pH-adjusting ability, which does not lead to premature oxidation of iron during the neutralization process. The removal efficiency of iron is 69.82% by using basic zinc carbonate as neutralization agent, and the Zn/Fe mass ratio of the solution after iron removal is 9.7, which can be cut into the iron removal section of the existing main production process(Zn/Fe=8–10). It provides technical support for the industrial application of high efficiency wet acid leaching zinc leaching residue.
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基本信息:
DOI：10.20237/j.issn.1007-7545.2025.12.001
中图分类号:TF813
引用信息:
[1]余迈新,王云燕,张李敏,等.低锌高铁溶液针铁矿法除铁工艺及应用研究[J].有色金属(冶炼部分),2025(12):1-16.DOI:10.20237/j.issn.1007-7545.2025.12.001.
基金信息:
湖南省科技创新计划项目（2024RC1014）; 云南省重大科技专项计划项目（202302AB080016-01）
2025-07-02
2025
2025-08-11
2025
1
2025-12-02
2025-12-02