摘要
针对氧化锌烟尘中锌资源的高效回收与高值化利用,提出“浸出工艺优化—界面反应机制解析—纳米材料制备”的全流程技术路线。通过系统实验确定硫酸浸出的最优工艺参数,结合XRD与SEM-EDS表征,揭示浸出渣的物相。最后,采用密度泛函理论(DFT)模拟H_(2)SO_(4)在ZnO(110)表面的吸附行为,并通过电子密度差与Mulliken布居分析阐明双路径电子转移机制。研究结果表明:硫酸浸出的最优工艺参数是硫酸浓度为1.5 mol/L、液固比为7 mL/g、温度为60℃、时间为60 min,在此条件下,锌浸出率达99.32%。浸出渣以PbSO_(4)和ZnFe_(2)O_(4)为主相,证实了锌的高效溶出;H_(2)SO_(4)在ZnO(110)表面的吸附能达-10.16 eV。双路径电子转移机制如下:H_(2)SO_(4)中H原子向ZnO供电子,ZnO中Zn原子向H_(2)SO_(4)中O原子供电子,该过程显著弱化了表面Zn—O键,降低了Zn的浸出反应能垒。基于高锌浸出液,通过两级净化与直接沉淀法,以NH_(4)HCO_(3)为沉淀剂合成碱式碳酸锌前驱体,经550℃煅烧获得纯度为98.14%的纳米氧化锌。
A comprehensive technical route of"leaching process optimization—interface reaction mechanism analysis—nanomaterial preparation"was proposed for efficient recovery and high-value utilization of zinc resources from zinc oxide dust.Systematic experiments were conducted to determine the optimal sulfuric acid leaching parameters,combined with XRD and SEM-EDS characterization to reveal the dominant phases in the residue.Finally,density functional theory(DFT)simulations were innovatively applied to model the adsorption behavior of H_(2)SO_(4)on the ZnO(110)surface,and electron density difference and Mulliken population were analyzed elucidated a dual-path electron transfer mechanism.The results show that the optimal sulfuric acid leaching parameters are H_(2)SO_(4)concentration of 1.5 mol/L,liquid-solid ratio of 7 mL/g,temperature of 60℃,time of 60 min,achieving 99.32%zinc leaching efficiency on this condition.PbSO_(4)and ZnFe_(2)O_(4)are dominant phases in the residue,confirming efficient zinc dissolution.The adsorption energy of H_(2)SO_(4)adsorption on ZnO(110)surfaces is-10.16 eV.The dual-path electron transfer mechanism is as follows:H atoms in H_(2)SO_(4)donate electrons to ZnO,while Zn atoms in ZnO donate electrons to O atoms in H_(2)SO_(4).This process significantly weakens surface Zn—O bonds and reduces the reaction energy barrier for Zn leaching.Based on zinc-rich leachate,basic zinc carbonate precursor is synthesized through two-stage purification and direct precipitation using NH_(4)HCO_(3)as precipitant,followed by calcination at 550℃to obtain nano-ZnO with 98.14%purity.
作者
辛椿福
万杨知为
陈波
张一敏
刘建磊
王占昊
包申旭
XIN Chunfu;WAN Yangzhiwei;CHEN Bo;ZHANG Yimin;LIU Jianlei;WANG Zhanhao;BAO Shenxu(Key Laboratory of Green Utilization of Critical Non-metallic Mineral Resources,Ministry of Education,Wuhan University of Technology,Wuhan 430070,China;School of Resources and Environmental Engineering,Wuhan University of Technology,Wuhan 430070,China;Hubei Key Laboratory of Processing of Mineral Resources and Environment,Wuhan University of Technology,Wuhan University of Technology,Wuhan 430070,China;State Environmental Protection Key Laboratory of Mineral Metallurgical Resources Utilization and Pollution Control,Wuhan University of Science and Technology,Wuhan 430081,China)
出处
《中南大学学报(自然科学版)》
北大核心
2025年第8期3302-3311,共10页
Journal of Central South University:Science and Technology
基金
国家重点研发计划项目(2023YFC3903901)
湖北省技术创新计划项目(2024BAA012)
中国博士后科学基金资助项目(2023M742725)。
关键词
氧化锌烟尘
硫酸浸出
密度泛函理论
纳米氧化锌
二次锌资源
zinc oxide dust
sulfuric acid leaching
density functional theory
nano-zinc oxide
secondary zinc resources
