摘要
针对采用传统火法工艺从加工废料中回收铼存在能耗大、设备要求高、灵活度低等问题,研究了采用电化学强化浸出—沉淀结晶法从该类铼二次资源中回收高纯度KReO_(4)晶体。结果表明:以22%~24%的HNO_(3)溶液作为电解液时,电解过程无明显钝化,能耗稳定在3.0 kWh/kg左右;电解时,阳极表面六方晶格位点处的Re原子失去电子,并与羟基结合,经由低价氧化态Re转变为桥氧连接Re(Ⅱ),与酸反应,最终以ReO^(-)_(4)形式进入电解液;采用钾盐作为沉淀剂回收电解液中Re元素时,在结晶温度25℃、沉淀剂流速6 mL/min、搅拌速率500 r/min及结晶时间30 min条件下,析出的KReO_(4)晶体呈多面体纺锤形,粒度均匀性好,回收率高,纯度为99.95%,可满足氢还原制备金属铼要求。该法可有效回收铼加工废料,具有一定推广应用价值。
In view of the problems of high energy consumption,high equipment requirements and low flexibility in recovering rhenium from processing waste by traditional pyrometallurgical processes,the electrochemical enhanced leaching—precipitation crystallization method was studied to recover high-purity KReO_(4) crystals from rhenium secondary resources.The results show that when 22%~24%HNO_(3) solution is used as the electrolyte,there is no obvious passivation during the electrolysis process,and the energy consumption is stable at about 3.0 kWh/kg.During the electrolysis,Re atoms at the hexagonal lattice sites on the anode surface lose electrons,combine with hydroxyl groups and transform through low-valent oxidation states of Re to bridge oxygen connected Re(Ⅱ),and finally enter the electrolyte in the form of ReO^(-)_(4) after reacting with the acid.When potassium salt is used as the precipitant to recover Re elements in the electrolyte,under the conditions of crystallization temperature of 25℃,precipitant flow rate of 6 mL/min,stirring rate of 500 r/min and crystallization time of 30 min,the precipitated KReO_(4) crystals are in the shape of polyhedral spindle,with good uniformity in particle size,high recovery rate and purity of 99.95%,which can meet the requirements for hydrogen reduction to prepare metallic rhenium.The method can effectively recover rhenium processing waste and has certain promotion value.
作者
刘宇哲
周欣沅
孙元
韩亚磊
刘帅
LIU Yuzhe;ZHOU Xinyuan;SUN Yuan;HAN Yalei;LIU Shuai(Shi-changxu Innovation Center for Advanced Materials,Chinese Academy of Sciences,Shenyang 110016,China;Northeast Yucai School,Shenyang 110051,China;School of Environmental and Chemical Engineering,Shenyang University of Technology,Shenyang 110870,China)
出处
《湿法冶金》
北大核心
2025年第4期512-523,共12页
Hydrometallurgy of China
基金
国家自然科学基金青年基金项目(52401067)。
关键词
铼
废料
二次资源
电化学
浸出
沉淀
结晶
高铼酸钾
rhenium
waste scrap
secondary resources
electrochemical
leaching
precipitation
crystallization
potassium perrhenate
作者简介
第一作者:刘宇哲(1994—),男,博士研究生,助理研究员,主要研究方向为高温合金二次资源循环利用。;通信作者:孙元(1980—),女,博士研究生,研究员,主要研究方向为焊接修复、战略金属二次资源循环再利用。E-mail:yuansun@imr.ac.cn。
