铜电解液中砷净化及资源化利用新工艺研究  

A new arsenic removal and utilization process of copper electrolyte

作　　者：匡晨 王乾坤 陈杭 王俊娥 钟萍丽 吴星琳 KUANG Chen;WANG Qiankun;CHEN Hang;WANG Jun'e;ZHONG Pingli;WU Xinglin(State Key Laboratory of Utilization of Low-Grade Refractory Gold Ores,Xiamen 361101,China;Zijin Mining Group Xiamen Zijin Mining and Metallurgy Technology Co.Ltd.,Xiamen 361101,China)

机构地区：[1]低品位难处理黄金资源综合利用国家重点实验室,福建厦门361101 [2]厦门紫金矿冶技术有限公司,福建厦门361101

出　　处：《中国有色冶金》2023年第4期34-43,共10页China Nonferrous Metallurgy

摘　　要：现有铜电解液净化的方法虽能实现砷的脱除,但仍存在环境污染,能耗高,锑、铋含量过高等问题。本文基于Ti—As—O化学键结合的机理,开发了“钛基沉淀剂脱砷-载砷渣碱浸再生-再生沉淀剂酸化脱钠-含砷碱浸液水合肼还原制备金属砷”工艺。脱砷工序较佳工艺参数:硫酸氧钛-硫酸水合物添加量为总砷质量的1.2倍、反应温度40℃、反应时间8 h,在该条件下,初次脱砷率达到60%左右;沉砷渣碱浸再生过程较佳工艺参数为液固比20∶1、NaOH浓度25 g/L、反应温度80、反应时间1.5 h,在该条件下,砷的浸出率为65.3%,一次循环脱砷率达到50.6%;再生沉淀剂酸化脱钠,较佳工艺参数为液固比2∶1、溶液终点pH=3.0、反应温度常温、反应时间1 h,该条件下,酸化后液中钠含量为926 mg/L,钛含量为0.21 mg/L;水合肼还原制备金属砷过程较佳工艺参数为水合肼过量系数3倍、稀释倍数5倍、反应温度80℃、溶液pH=7.0、反应时间2 h,在该条件下,砷的还原率为75%左右,获得金属砷纯度为93%左右。该工艺操作简单、对砷、锑的脱除具有较高选择性,脱砷后液可返回铜电解系统,含砷碱浸液经还原后可制备金属砷,实现了含砷物料资源化利用。砷的多次循环脱除率维持在50%左右,并不造成铜等有价金属的损失,后续需对沉砷药剂和还原剂进一步筛选以降低药剂成本。Although the existing copper electrolyte purification method can remove arsenic,but there are still problems such as environmental pollution,high energy consumption,and high content of antimony and bismuth.In this paper,based on the mechanism of Ti-As-O chemical bond bonding,a process of titanium-based precipitant removing arsenic,arsenic-containing slag alkali leaching regeneration,regenerated precipitant acidification removing sodium,preparing metal arsenic was investigated.The better process parameters of arsenic removal process are as follows:the addition amount of titanium oxysulfate-sulfuric acid hydrate is 1.2 times of the total arsenic mass,the reaction temperature is 40℃,and the reaction time is 8 h.Under this condition,the initial arsenic removal rate reaches about 60%.The optimum process parameters of alkali leaching regeneration process of arsenic sediment are as follows:liquid-solid ratio 20:1,NaOH concentration 25 g/L,reaction temperature 80℃,reaction time 1.5 h.Under these conditions,the leaching rate of arsenic is 65.3%,and the arsenic removal rate reaches 50.6%in one cycle.The optimum process parameters for acidizing removing sodium of regenerated precipitant are as follows:liquid-solid ratio 2:1,end-point pH=3.0,room temperature,reaction time 1 h.Under these conditions,the sodium content in the acidized liquid is 926 mg/L,and the titanium content is 0.21 mg/L.The optimum process parameters for the preparation of metal arsenic are as follows:hydrazine hydrate excess coefficient 3 times,dilution multiple 5 times,reaction temperature 80℃,solution pH=7.0,reaction time 2 h.Under these conditions,the reduction rate of arsenic is about 75%,and the purity of metal arsenic is about 93%.The process is simple in operation and has high selectivity for the removal of arsenic and antimony;the solution after arsenic removal can be returned to the copper electrolysis system;the arsenic-containing alkaline leaching solution can be reduced to prepare metal arsenic.The multiple cycle arsenic removal rate is

关 键 词：铜电解液净化 除砷 钛基沉淀剂 碱浸再生 酸化脱钠 砷资源利用 绿色冶金 

分 类 号：TF811[冶金工程—有色金属冶金] TF803.25