高氟氯次氧化锌粉多元浸出液中Cl^(-)竞争吸附及迁移行为  

Competitive adsorption and transport behavior of Cl^(-)in multi-leaching solution of high-fluoride and high-chloride secondary zinc oxide powder

作　　者：宋健清 李存兄[1] 陈帮耀 戴兴征 周中华 邱伟佳 张少博 刘自虎 代林晴[1] SONG Jianqing;LI Cunxiong;CHEN Bangyao;DAI Xingzheng;ZHOU Zhonghua;QIU Weijia;ZHANG Shaobo;LIU Zihu;DAI Linqing(Faculty of Metallurgical and Energy Engineering,Kunming University of Science and Technology,Kunming 650093,China;Yunnan Chihong Zn&Ge Co.,Ltd.,Qujing 655011,China;Yunnan Yuntong Zinc Co.,Ltd.,Kunming 650102,China)

机构地区：[1]昆明理工大学冶金与能源工程学院,昆明650093 [2]云南驰宏锌锗股份有限公司,曲靖655011 [3]云南云铜锌业股份有限公司,昆明650102

出　　处：《中国有色金属学报》2025年第4期1337-1351,共15页The Chinese Journal of Nonferrous Metals

基　　金：国家自然科学基金资助项目(52474381);云南省重点研发计划资助项目(202302AB080017,202302AG050008,202403AA080009,yfgrc202404);云南省高校服务重点产业科技项目(FWVCY-2D2024004)。

摘　　要：随着传统锌资源的日益枯竭,复杂二次锌资源的开发利用成为趋势。针对二次锌资源中氟、氯含量普遍较高且脱出成本高,易新增二次危废的行业难题,研发了“可控浸出-靶向脱氯-氯资源化-原位除氟”的氟氯梯级靶向脱出及氯资源化利用的短流程处理工艺,同时实现氟氯高效洗脱富集、氯靶向分离、氯资源化利用、氟原位沉淀等多重目标。本文着重研究了新工艺流程中产出的高氟氯次氧化锌粉多元浸出液离子交换法靶向脱氯时Cl^(-)的迁移行为及锌、氟、砷、锑共存离子的竞争性吸附规律。结果表明:在优化技术参数下,大孔强碱阴离子树脂对Cl~-具有很强的选择性化学吸附能力,树脂饱和吸附容量(N_(max))为108.04 mg/g,Cl^(-)脱除率>98%,硫酸溶液中Cl^(-)解吸率达98.91%;复杂多元高氯溶液的连续吸附过程遵循B-A吸附模型;微量的锌、氟、砷、锑等共存离子具有竞争性吸附能力,其中,F-是与Cl^(-)竞争吸附的主要对象,砷、锑主要以含氧酸根(H_(2)AsO_(3)^(-)、SbO_(4)^(3-)、[SbO(OH)_(2)]^(-))的形式与Cl-竞争部分活性位点,而Zn^(2+)则与Cl^(-)形成ZnCl_(n)^(2-n)(n=3,4)配合物被树脂吸附并固定于树脂表面。With the increasing depletion of traditional zinc resources,the development and utilization of complex secondary zinc resources has become a trend.Aiming at the industry problem of high-fluoride and high-chloride content in secondary zinc resources and high cost of removal,which makes it easy to add new hazardous secondary waste,we have developed a short-flow treatment process of fluorine and chlorine gradient targeted removal and chlorine resource utilization,which is called“controlled leaching-targeted dechlorination-chlorine resource utilization and in-situ fluorine removal”.At the same time,it realizes the multiple objectives of fluorine and chlorine high-efficiency elution and enrichment,chlorine target separation,chlorine resource utilization,fluorine in-situ precipitation,and so on.This paper focused on the migration behavior of Cl^(-)and the competitive adsorption law of zinc,fluorine,arsenic and antimony coexisting ions in the ion exchange method for targeted dechlorination of the poly leaching solution of high-fluoride and high-chloride secondary zinc oxide powder produced in the new process.The results show that,under the optimized technical parameters,the macroporous strong base anion resin has strong selective chemical adsorption capacity for Cl^(-),the saturated adsorption capacity(Nmax)of the resin is 108.04 mg/g,the Cl^(-)removal rate is more than 98%,and the Cl^(-)desorption rate in sulfuric acid solution reaches 98.91%.The continuous adsorption process of the complex multivariate perchloric acid solution follows the B-A adsorption model.Trace amounts of coexisting anions such as zinc,fluorine,arsenic and antimony have competitive adsorption capacity,of which F-is the main object of adsorption in competition with Cl^(-),and arsenic and antimony are mainly in the form of oxygenated acid radicals(H_(2)AsO_^(3-),SbO_(4)^(3-),[SbO(OH)_(2)]-)to compete with Cl^(-)for part of the active site,while Zn^(2+)forms ZnCl_(n)^(2-n)(n=3,4)complexes with Cl^(-)to be adsorbed by the resin and immobilized on

关 键 词：高氟氯次氧化锌 离子交换树脂 多元复杂溶液 氯吸附率 杂质竞争吸附 

分 类 号：X758[环境科学与工程—环境工程]