湿法炼锌溶液中锗的配位反应分离规律及萃取机理
Coordination separation pattern and extraction mechanism of germanium in zinc leaching solution by wet process
顾智辉 1李存兄 1李倡纹 1刘强 1王启亮 1宋健清 1王阳波1
作者信息
- 1. 昆明理工大学 冶金与能源工程学院,昆明 650093
- 折叠
摘要
针对湿法炼锌溶液中锗富集回收成本高、工艺复杂等问题,本文深入研究5种不同配合剂对N235-TBP复合萃取体系选择性分离富集锗过程的影响规律及酒石酸配位反应体系的传质机理.结果表明:在有机相构成为30％N235-15％TBP-55％260#溶剂油、相比O:A为1:2、pH 1.5、反应温度25℃,配合剂与锗的摩尔比nL/nGe=5的条件下,5种配合剂对锗的配位能力大小依次为:酒石酸(C4H6O6)>草酸(C2H2O4)>柠檬酸(C6H8O7)>马来酸(C4H4O4)>水杨酸(C7H6O3),酒石酸对Ge4+与共存离子Zn2+、Fe2+的分离效果最佳,在nC4H6O6/nGe=5.5时,分离系数达最大,分别为βGe/Zn2+=2807.23、βGe/Fe2+=3271.43;酒石酸与锗的配位形式为双齿(螯合)配位;N235-TBP复合萃取体系萃取锗的机理是质子化N235中的HSO-4 与料液中的Ge(OH)2Tar2?发生阴离子置换反应,生成萃合物((R3NH+)2·(Ge(OH)2Tar22-)·TBP0.3).
Abstract
In view of the high cost and complicated process of recovery of enrichment of germanium from hydrothermal zinc solution,this paper thoroughly studied the effect of five different coordination agents on the selective separation and enrichment of germanium from the N235-TBP composite extraction system and the mass transfer mechanism of the tartaric acid system.The results show that,under the conditions of organic phase formation of 30％N235-15％TBP-55％260#solvent oil,O:A ratio of 1:2,pH 1.5,reaction temperature of 25℃,and molar ratio of complexing agent to germanium(nL/nGe)of 5,the coordination abilities of the 5.5 coordination agents to germanium are those tartaric acid(C4H6O6)>oxalic acid(C2H2O4)>citric acid(C6H8O7)>maleic acid(C4H4O4)>salicylic acid(C7H6O3).C4H6O6 had the best separation effect on Ge4+and impurity ions Zn2+and Fe2+.When nC4H6O6/nGe=5,the separation coefficients reach their maximum,respectively,βGe/Zn2+=2807.23,βGe/Fe2+=3271.43.The coordination form between C4H6O6 and germanium is bidentate(chelating)coordination.The mechanism of extracting germanium with N235-TBP composite extraction system is that HSO-4 undergoes anion exchange with Ge(OH)2Tar2-in the feed solution,resulting in the extraction coordination((R3 NH+)2·(Ge(OH)2Tar22-)·TBP0.3).
关键词
湿法炼锌/锗/萃取机理/分离系数Key words
zinc hydrometallurgy/germanium/extraction mechanism/separation coefficient引用本文复制引用
基金项目
国家重点研发计划资助项目(2021YFC2902801)
云南省重点研发计划资助项目(202202AB080005)
国家自然科学基金资助项目(52064034)
出版年
2024
NETL
NSTL
万方数据