离子膜电解法制备4N级高纯金属锰的工艺优化和杂质控制  

Process Optimization and Impurity Control for 4N-Grade High-Purity Metallic Manganese via Ion-Exchange Membrane Electrolysis

作　　者：杨文梅 马立华 陆帅 王仕成 马林 王星凯 虎大勇 YANG Wenmei;MA Lihua;LU Shuai;WANG Shicheng;MA Lin;WANG Xingkai;HU Dayong(Ningxia Tianyuan Manganese Industry Group Co.,Ltd.,Zhongwei,Ningxia 755100,China;School of Civil and Hydraulic Engineering,Ningxia University,Yinchuan,Ningxia 750021,China)

机构地区：[1]宁夏天元锰业集团有限公司,宁夏中卫755100 [2]宁夏大学土木与水利工程学院,宁夏银川750021

出　　处：《中国锰业》2025年第1期83-87,共5页China Manganese Industry

摘　　要：为满足市场对4N(99.99%)级高纯度金属锰的需求,提出了一种基于硫酸盐体系的离子膜电解新工艺,旨在优化3N(99.9%)级金属锰提纯至4N级的工业化流程。通过碱液清洗、硫酸酸溶制备硫酸锰溶液,并采用硫化钡、聚合硫酸铁和二氧化锰多级净化工艺去除锌、钴、镍等杂质;结合离子膜电解技术,系统探究了电解液COD含量、亚硫酸铵添加方式及剂量对产物纯度的影响。结果表明,碱洗30 min可有效降低铁、钙及硫杂质;深度净化后电解液中锌、钴、镍含量降至≤1 mg/L,钙、镁含量≤10 mg/L;当COD含量≤2 mg/L时,锰片纯度达99.99%;电解槽内点滴添加100~200 mg/L亚硫酸铵可稳定工况并抑制杂质引入。该工艺成功制备出符合4N级标准的高纯金属锰,为规模化生产提供了技术支撑。To meet the market demand for 4N-grade(99.99%purity)high-purity metallic manganese,this study proposed a novel ion-exchange membrane electrolysis process based on a sulfate system,aiming to optimize the industrial purification process from^(3)N-grade(99.9%purity)to 4N-grade metallic manganese.The process involved alkali washing and sulfuric acid dissolution for manganese sulfate solution preparation,followed by multi-stage purification using barium sulfide(BaS),polymeric ferric sulfate(PFS),and manganese dioxide(MnO 2)to remove impurities such as Zn,Co,and Ni.Combined with ion-exchange membrane electrolysis,the effects of electrolyte chemical oxygen demand(COD)content,ammonium sulfite[(NH 4)2SO 3]addition methods,and dosage on product purity were systematically investigated.Results showed that 30 min alkali washing effectively reduced Fe,Ca,and S impurities.After deep purification,the electrolyte exhibited Zn,Co,and Ni concentrations≤1 mg/L and Ca,Mg≤10 mg/L.When COD was maintained at≤2 mg/L,the purity of manganese sheets reached 99.99%.Stepwise addition of 100-200 mg/L ammonium sulfite stabilized cell operation and suppressed impurity introduction.This process successfully produced 4N-grade(99.99%purity)high-purity metallic manganese,providing technical support for industrial-scale production.

关 键 词：离子膜电解 高纯金属锰 硫酸锰溶液 净化除杂 电解添加剂 

分 类 号：TF111[冶金工程—冶金物理化学]