Chromatographic separation and recovery of Zn(Ⅱ)and Cu(Ⅱ)from high-chlorine raffinate of germanium chlorination distillation  

色层分离法回收锗氯化蒸馏高氯残液中的Zn(Ⅱ)和Cu(Ⅱ)

作　　者：Ye-hui-zi WU Kang-gen ZHOU Wei CHEN Qing-yuan LEI Er-jun ZHANG Yu-yao CHENG Yang JIANG Chang-hong PENG Jun JIANG Xue-kai ZHANG 吴业惠子;周康根;陈伟;雷清源;张二军;程钰尧;江洋;彭长宏;江钧;张雪凯(中南大学冶金与环境学院,长沙410083;中南大学国家重金属污染防治工程技术研究中心,长沙410083;中南大学化学化工学院,长沙410083)

机构地区：[1]School of Metallurgy and Environment,Central South University,Changsha 410083,China [2]Chinese National Engineering Research Center for Control&Treatment of Heavy Metal Pollution,Central South University,Changsha 410083,China [3]School of Chemistry and Chemical Engineering,Central South University,Changsha 410083,China

出　　处：《Transactions of Nonferrous Metals Society of China》2022年第4期1336-1350,共15页中国有色金属学报（英文版）

基　　金：financially supported by the Postdoctoral Research Foundation of Central South University,China(No.140050037)。

摘　　要：An anion-exchange-based chromatographic separation approach was developed to selectively recover zinc and copper from the high-chlorine raffinate generated in the process of germanium chlorination distillation using 717 resins based on the coordination difference between Zn^(2+)/Cu^(2+)and Cl^(-).The theoretical calculation and spectroscopic analyses suggested that the coordination between Zn^(2+)and Cl^(-)is much stronger than that between Cu^(2+)and Cl^(-),and the Cl-concentration significantly affects Zn(Ⅱ)and Cu(Ⅱ)species.The factors involving Cl-concentration,resin dosage,shaking speed,and temperature were investigated to determine the optimal condition,and the maximum separation factor of Zn/Cu reached as high as 479.2.The results of the adsorption isotherms,adsorption kinetics,SEM,FTIR,and XPS analyses indicated that the process followed the monolayer uniform chemisorption.Through the continuous adsorption experiments,Zn(Ⅱ)and Cu(Ⅱ)in the high-chlorine raffinate were separately recovered,allowing the reuse of residual waste acid and germanium.基于Zn^(2+)/Cu^(2+)与Cl^(-)配位能力的差异,采用阴离子交换色层分离法和717树脂,选择性回收氯化蒸馏提锗工艺所产生高氯残液中的锌和铜。理论计算和光谱分析表明,Zn^(2+)与Cl^(-)的配位能力远强于Cu^(2+)与Cl^(-)的配位能力,同时Cl^(-)浓度显著影响Zn(Ⅱ)和Cu(Ⅱ)在溶液中的存在形态。此外,考察Cl^(-)浓度、树脂用量、振荡速率及温度等因素的影响,在优化条件下Zn/Cu两者间的分离因子达到479.2。吸附等温线、吸附动力学、SEM、FTIR和XPS等研究结果表明,该过程是均匀的单分子层化学吸附。最后,通过连续吸附柱实验分别回收高氯残液中的Zn(Ⅱ)和Cu(Ⅱ),从而实现残液中废酸和锗的再利用。

关 键 词：chromatographic separation Zn/Cu recovery high-chlorine raffinate anion exchange 717 resin 

分 类 号：TF811[冶金工程—有色金属冶金] TF813[环境科学与工程—环境工程] X703