铜阳极泥复合浸出渣选择性分离硒过程热力学分析  

Thermodynamic analysis on selective separation of Selenium from compound leaching slag of copper anode slime

作　　者：曾颜亮[1] 霍瑞浩 邹建柏 廖春发[1] 刘付朋 ZENG Yanliang;HUO Ruihao;ZOU Jianbai;LIAO Chunfa;LIU Fupeng(Faculty of Materials Metallurgy and Chemistry,Jiangxi University of Science and Technology,Ganzhou 341000,Jiangxi,China;Jiangxi Copper Lead&Zinc Metals Co.,Ltd,Jiujiang 332000,Jiangxi,China)

机构地区：[1]江西理工大学材料冶金化学学部,江西赣州341000 [2]江西铜业铅锌金属有限公司,江西九江332000

出　　处：《有色金属科学与工程》2023年第1期1-7,共7页Nonferrous Metals Science and Engineering

基　　金：国家自然科学基金资助项目(U1802251);江西省科技厅资助项目(20212AEI91003);江西省教育厅科技项目(GJJ180466)。

摘　　要：铜阳极泥复合浸出渣是铜阳极泥采用复合浸出砷锑铋后的产物,采用硫酸化焙烧选择性分离硒。针对其含硒物质在选择性分离过程中的反应历程不明晰,本文利用Factsage数据库中相关热力学数据及Equilib平衡计算模块对含硒物质在不同温度时反应的ΔG^(θ)及反应过程平衡分析,明晰反应过程中的物相变化规律。结果表明:Cu_(2)Se与H_(2)SO_(4)在低温下反应生成固态Se、CuSO_(4)·H_(2)O、SO_(2)及H_(2)SO_(4)吸水形成H_(2)SO_(4)·H_(2)O;然后固态Se融化变成液态Se,同时与H_(2)SO_(4)·H_(2)O反应生成SeO_(2)、SO_(2)和H_(2)O;高温下CuSO_(4)·H_(2)O会脱水生成CuSO_(4)和H_(2)O,CuSO_(4)会进一步分解生成CuSO_(4)·CuO和SO_(3);Ag_(2)Se与H_(2)SO_(4)反应生成固态Se、Ag_(2)SO_(4)、SO_(2)及H_(2)SO_(4)吸水形成H_(2)SO_(4)·H_(2)O;然后固态Se融化变成液态Se,同时与H_(2)SO_(4)·H_(2)O反应生成SeO_(2)、SO_(2)和H_(2)O;另外高温下Ag_(2)SO_(4)会转变形态;Se与H_(2)SO_(4)反应生成SeO_(2)、SO_(2)和H_(2)O。考察了铜阳极泥复合浸出渣在不同焙烧温度、硫酸用量及焙烧时间对蒸硒率的影响,在焙烧温度为500℃、H_(2)SO_(4)加入量为0.2 mL/g、升温速率为10℃/min、反应时间为30 min的焙烧条件下,蒸硒率达到95.4%。The compound leaching slag of copper anode slime is the product of compound leaching of arsenic,antimony and bismuth from copper anode slime,and Selenium (Se) is selectively separated by sulfated roasting.In view of the unclear reaction process of the selenium-containing substances in the selective separation process,relevant thermodynamic data in Factsage and Equilib equilibrium calculation module were used to analyze the ΔG^(θ) of selenium-containing substances reacting at different temperatures and reaction process balance,to clarify the law of phase change in reaction process.The results show that at low temperature Cu_(2)Se reacts with H_(2)SO_(4)to generate solid Se,CuSO_(4)·H_(2)O,SO_(2)and H_(2)SO_(4)absorbs water to form H_(2)SO_(4)·H_(2)O.Solid Se then melts into liquid Se and simultaneously reacts with H_(2)SO_(4)·H_(2)O to form SeO_(2),SO_(2)and H_(2)O.At high temperature,CuSO_(4)·H_(2)O will be dehydrated to produce CuSO_(4)and H_(2)O,and CuSO_(4)will be further decomposed to produce CuSO_(4)·CuO and SO_(3).Ag_(2)Se reacts with H_(2)SO_(4)to generate solid Se,Ag_(2)SO_(4),SO_(2)and H_(2)SO_(4)absorbs water to form H_(2)SO_(4)·H_(2)O,and then solid Se melts into liquid Se and reacts with H_(2)SO_(4)·H_(2)O to form SeO_(2),SO_(2)and H_(2)O.In addition,Ag_(2)SO_(4)will change form at high temperature,and Se reacts with H_(2)SO_(4)to generate SeO_(2),SO_(2)and H_(2)O.Therefore,the Se evaporation rates of compound leaching slag of copper anode slime at different roasting temperatures,with different sulfuric acid dosages and for different roasting time were analyzed.Under the roasting condition of temperature at 500℃,the added quantity of H_(2)SO_(4)of 0.2 mL/g,the warming rate 10℃/min and the reacting time 30 min,Se evaporation rate reached 95.4%.

关 键 词：选择性分离 铜阳极泥 热力学 蒸硒 

分 类 号：TF843.5[冶金工程—有色金属冶金]