铅锌混合熔炼提铟过程中铅与锌铟铁间相互作用的研究

【作者】 王文静；

【导师】 邓勇； 崔浩；

【作者基本信息】 昆明理工大学 ， 冶金工程（专业学位）， 2022， 硕士

【摘要】 铟是十分重要的战略资源,是一种稀贵金属,无法从原矿中直接提取,从伴生矿的炼锌副产物中回收铟是铟的主要来源之一。我国高铁闪锌矿储量十分丰富,高铁闪锌矿是铟的主要伴生矿之一,为解决在高铁闪锌矿锌还原熔炼提铟过程中存在的铟回收率低、渣中铟流失多等问题,课题组提出了加铅富集铟的思路,并通过实验证实了铅对铟具有富集效果,铟的回收率得到了一定的提升。为深入了解高铁闪锌矿锌还原熔炼时加铅富集铟过程中各元素间的相互作用行为,本文更为深入系统的对体系中组元间的相互作用,尤其是主要杂质元素铁对体系中其他组元的影响,开展了相应的研究,为继续提高铟回收率提供理论依据。主要的研究内容为:基于密度泛函理论,采用从头算分子动力学的方法在研究In_nZn_n（n=2-10）团簇、Pb_nZn_n（n=2-10）团簇、Pb_nIn_n（n=2-10）团簇结构演化规律及电子性质的同时,增加了对Pb_nFe_n（n=2-12）团簇、In_nFe_n（n=2-12）团簇的研究,并在此基础上,对团簇的平均结合能、自然价键轨道、垂直电子电离能、垂直电子亲和势、HOMO-LUMO能隙、径向分布函数、均方位移、轨道质心距离等性质进行了系统的理论研究,在此基础上,对三元的Pb-In-Zn团簇及熔体、Pb-In-Fe熔体以及四元的Pb-In-Zn-Fe熔体结构进行了AIMD模拟,并首次利用AIMD-Deep-Learning-MD方法对Pb-In-Zn熔体进行了模拟计算,弥补了原有理论工作对团簇及熔体性质研究的不足。随后开展了铅锌铟均匀混熔实验,对所得合金的切面进行了测试分析,验证了计算结果的正确性。主要研究结果如下:（1）对二元In_nZn_n（n=2-10）团簇、Pb_nZn_n（n=2-10）团簇、Pb_nIn_n（n=2-10）团簇、Pb_nFe_n（n=2-12）团簇、In_nFe_n（n=2-12）团簇的研究结果表明,Pb-In之间有较强的相互作用力,Fe聚集在与Pb、In团簇体系的中部,且Fe-In、Fe-Pb体系有变得分散的趋势。（2）不同铅铟配比的三元Zn₁₂In₆Pb₂（In:Pb=3:1）团簇、Zn₁₄In₂Pb₄（In:Pb=1:2）团簇、Zn₁₂In₂Pb₆（In:Pb=1:3）团簇和Zn₁₅In Pb₄（In:Pb=1:4）团簇的研究发现,在铅铟比为3:1时,Zn会最大程度的脱离本体且与Pb、In有明显分界线,铅对铟富集效果最好。（3）三元Pb-In-Zn熔体经过AIMD模拟后,Pb原子与In原子很明显的聚集在一起,利用AIMD方法以及AIMD-Deep-Learning-MD方法计算得到的Pb-In-Zn熔体的径向分布函数（RDF）与均方位移（MSD）分析的结果也证实了Pb对In的富集作用。（4）按照模拟计算的配比合成Pb-In-Zn熔体进行EDS分析结果表明,Pb与In在熔体中明显聚集在一起,共同存在于熔体底层,验证了模拟结果的正确性以及计算机模拟应用于稀贵金属提取方面的可行性。（5）三元Pb-In-Fe、Pb-In-Fe-Zn熔体经过动力学模拟与性质分析后发现Fe对Pb、In有一定的分散作用,因此Fe的存在与含量会对加铅富集铟过程会产生较大的影响,继续提高铟回收率时需考虑控制Fe对铅铟的作用。本文在对体系内Pb、In、Zn、Fe之间相互作用的理论研究在为加铅富集铟方法提高铟回收率提供微观层面分析的同时,也分析了各元素在其他领域可能发挥的作用,为铅、铟、锌、铁元素在各领域发挥作用提供坚实的理论基础。更多还原

【Abstract】 Indium is a very important strategic resource in China.As a rare metal,it has no primary source and cannot be directly extracted from raw ore.Recovery of indium from zinc smelting by-products of associated ore is one of the main sources of indium.The reserves of marmatite are abundant in China.Marmatite is one of the main associated minerals of indium.In order to solve the problems such as low indium recovery rate and high indium loss from slag in the process of zinc reduction smelting of marmatite,the research group put forward the idea of indium enrichment by adding lead in the preorder research and verified the enrichment effect of lead on indium through experiments,and the indium recovery rate has been improved to a certain extent.However,the theoretical research on this process is not thorough enough in previous studies,and there are few studies on the microstructure and properties of materials involved in this process at home and abroad,which restricts the further development of this technology to a certain extent.For insight into the high iron reduction smelting zinc blende leaded enrichment indium interaction behavior between each element in the process,provide theoretical basis to continue to improve the recovery rate of indium,in this paper,on the basis of studying the former sequence,a more thorough system of the interaction between the components in the system,especially the main impurity element iron in the system the influence of the other groups in the yuan,to carry out the corresponding research,The main research contents are as follows:Based on DFT,ab initio molecular dynamics was used to further study the structural evolution and electronic properties of In_nZn_n（n=2-10）clusters,Pb_nZn_n（n=2-10）clusters and Pb_nIn_n（n=2-10）clusters.The study of Pb_nFe_n（n=2-12）cluster and In_nFe_n（n=2-12）cluster is added.On this basis,the dynamics simulation of ternary Pb-In-Zn cluster and melt,Pb-In-Fe melt and quaternary Pb-In-Zn-Fe melt are carried out.Clusters on the basis of the dynamics of the average binding energy,natural valence orbit,vertical ionization energy,vertical electron affinity,HOMO,LUMO energy gap,radial distribution function,track centroid distance azimuth shift,such as properties of the study of the theory of the system,make up for the original work theory of the properties of clusters and melt.Subsequently,the uniform mixed melting experiment of lead,Zinc and indium was carried out,and the section of the alloy was tested and analyzed,which verified the correctness of the calculated results.The main results are as follows:（1）The results of binary In_nZn_n（n=2-10）cluster,Pb_nZn_n（n=2-10）cluster,Pb_nIn_n（n=2-10）cluster,Pb_nFe_n（n=2-12）cluster,and In_nFe_n（n=2-12）cluster show that there are strong interactions between Pb-In clusters.Fe-In and Fe-Pb cluster systems tend to become dispersed.（2）Studies on Zn₁₂In₆Pb₂（In:Pb=3:1）clusters,Zn₁₄In₂Pb₄（In:Pb=1:2）clusters,Zn₁₂In₂Pb₆（In:Pb=1:3）clusters and Zn₁₅In Pb₄（In:Pb=1:4）clusters with different ratios of Lead and indium found that when the ratio of lead and indium was 3:1,Zn will be separated from the body to the greatest extent and has a clear boundary with Pb and In,so lead has the best enrichment effect on indium under this ratio.（3）After dynamic simulation of ternary Pb-In-Zn melt,Pb atoms and In atoms are obviously clustered together,and the results of RDF and MSD analysis also confirm the enrichment effect of Pb on In.（4）EDS analysis of Pb-In-Zn melt synthesized according to the ratio of simulated calculation shows that Pb and In are obviously clustered together in the melt bottom,which verifies the correctness of the simulation results and the feasibility of computer simulation in the extraction of rare metals.（5）After dynamic simulation and property analysis of terpolymer Pb-In-Fe and Pb-In-Fe-Zn melts,it is found that Fe has a certain dispersion effect on Pb and In.Therefore,the existence and content of Fe will have a great influence on the process of indium enrichment by adding lead,and the effect of Fe on lead indium should be controlled when continuing to improve the recovery of indium.The theoretical study on the interaction between Pb,In,Zn and Fe in the system not only provides a microscopic analysis for improving the recovery rate of indium by adding lead to enrich indium,but also analyzes the possible role of each element in other fields,providing a solid theoretical basis for the role of lead,indium,zinc and Iron in various fields.更多还原