高铋高砷铅阳极泥有价金属提取的组元相互作用规律与调控机制

According to the characteristics of bismuth-rich and arsenic-rich lead anode slimes containing arsenic,antimony,lead,gold and silver, the following research ideas as the removal of arsenic,antimony and lead by means of pressure oxidation alkaline leaching - crude bismuth alloy casting - bismuth electrolysis, were presented in order to realize the separation of arsenic, antimony and lead, the clean extraction of bismuth and enrichment of gold and silver from bismuth-rich and arsenic-rich lead anode slimes. The component interaction mechanism, law of selective leaching, the reaction pathway and reaction limit can be obtained during the course of the removal of arsenic, antimony and lead by means of pressure oxidation alkaline leaching.The restricted links of the extraction and crystallization separation of arsenic, antimony and lead can be ascertained, and the reaction dynamic equations can be established, which will enrich the theory of extraction and crystallization separation.The basis for the selective oxidation and reduction of the leaching slags during the crude bismuth alloy anode casting can be provided, and the thermodynamics impetus and metallurgical reaction conditions will be obtained. Reaction dynamic behavior of cathode and anode can be verified in the bismuth electrolysis and the online control between additive regulation and cathode active potential will be realized, and the synergetic mechanism of deep removal of copper for activity bismuth powder and sulfur powder in hydrochloric acid and bismuth chloride solutions can be revealed. Above research achievements will enrich the theoretical system of the secondary resources comprehensive recovery for the nonferrous metal, and it will also provide the theoretical basis and technical support for the valuable metal clean extraction with high efficiency-low energy consumption from bismuth-rich and arsenic-rich lead anode slimes.

针对高铋高砷铅阳极泥富含砷、锑、铅、金、银等特点，提出采用“加压氧化碱浸脱砷锑铅–熔铸粗铋合金–铋电解精炼”的研究思路，在分离砷锑铅的同时，实现铋的清洁提取及金银的高度富集。通过研究，获得高铋高砷铅阳极泥加压氧化碱浸脱砷锑铅过程的组元相互作用机制、选择性溶出规律、反应途径与反应限度。确定碱浸液中砷锑铅萃取及结晶分离的限制性环节，建立反应过程动力学方程，丰富萃取与结晶分离理论；获得浸出渣熔铸粗铋合金阳极过程的选择性氧化还原依据，确定热力学推动力与冶金反应条件。探明铋电解的阴阳极反应动力学行为，实现添加剂用量调控与阴极活性电位的在线控制，揭示活性铋粉与单质硫粉在盐酸氯化铋溶液中深度净化除铜的协同机制。研究结果能够进一步丰富我国复杂有色金属二次资源综合回收的理论体系，同时为高铋高砷铅阳极泥中多组份有价金属高效率-低能耗的清洁回收提供理论依据和技术支撑。

针对高铋高砷型铅阳极泥富含砷、锑、铅、铋、金、银等特点，确定了“水热氧化碱浸脱砷锑铅–碱浸渣熔铸粗铋合金–粗铋合金电解提铋”的火-湿法联合处理新工艺，在高效分离砷、锑、铅的基础上，实现了铋的电解清洁提取与金银的高度富集。.通过研究，确定了高铋高砷型铅阳极泥水热氧化碱浸脱砷锑铅过程的组元相互作用机制、反应途径与反应限度；探明了Pb、Sb在NaOH-NaNO3溶液中的电化学氧化溶出机制；通过精确控制NaNO3用量，实现了As、Sb、Pb与Bi在碱性溶液中的选择性氧化浸出分离。As的浸出率>95%，Sb的浸出率>72%，Pb的浸出率>62%，铋以单质、Bi2O3形式留在碱浸渣中；提出了一种添加焦锑酸铅晶种实现碱浸液中Sb、Pb与As高效分离的新方法，利用硝酸钠将碱浸液中的Sb(III)氧化为Sb(V)后，添加焦锑酸铅晶种冷却结晶以焦锑酸铅形式除去Sb、Pb，之后再添加CaO沉砷净化，净化后液返回水热浸出流程循环利用效果好；揭示了铋、锑、铅、锡、铜等氧化物碳还原的初始温度，碱浸渣中的铋氧化物在800℃以上能够获得足够大的还原热力学推动力；提出了一种盐酸-氯化铋溶液净化除铜的新方法，通过活性铋粉与单质硫粉的协同作用使除铜反应过程中生成Cu2S沉淀，净化后液中的铜含量降至3mg/L以下，沉淀物中的铜铋质量比>0.70，实现了深度净化除铜；探明了阴极活性过电位与添加剂用量调控之间的关系控制。在HCl-NaCl-BiCl3溶液中，木质素磺酸钠能明显优化阴极界面条件，促进铋离子的还原沉积和生长方向，降低晶粒尺寸。与铅阳极泥原料中的金、银含量相比，铋电解阳极泥中的金、银含量分别被富集到10.13倍、9.54倍。研究成果能进一步丰富我国复杂有色金属二次资源综合回收理论体系，同时为高铋高砷型铅阳极泥中多组份有价金属高效率-低能耗的清洁回收提供依据和支撑。.在本项目执行期内，出版学术专著1部；发表学术论文7篇。其中，SCI检索5篇；申请国家发明专利1件，获授权国家发明专利2件；培养毕业博士1名、在读硕士1名；举办国际学术会议1次、国内学术会议3次。