工业硫酸锰深度除钙、镁、铁的试验研究.pdf

第33卷第3期
矿冶工程
2013年06月
MIINING AND METALLURGICAL ENGINEERING
June 2013
工业硫酸锰深度除钙、镁、铁的试验研究
包新军2,王志坚,刘吉波',苏正夫,田思远,周徳壁2,王洪恩
(1.湖南稀土金属材料研究院,湖南长沙410056;2.中南大学化学化工学院,湖南长沙410083;3武汉理工大学材料科学与工程学院,湖北武汉43000)
摘要:研究了工业MnS02净化除去钙、镁和铁的工艺。具体工艺包括:采用先溶成浆再两步加料的方式,向MnSO4溶液中加人
MnF2浆料净化溶液中的Ca2、Mg3'。加人适量的高锰酸钾优先氧化Fe2“后,再氧化溶液中1%的Mn2“生成活性MnO2,从而有效
吸附沉淀CaF2、MgF2和水解产物Fe(OH)3。试验结果表明:控制pH为4,反应温度90℃,搅拌时间2h,当硫酸锰的浓度为300
g/兀L时,钙、镁和铁的净化率分别高达98.8%、97.25%和9.92%。最后以净化除杂后的硫酸锰为锰源,采用液相共沉淀法合成
Mn02。SEM和XRD表征表明,合成的MnO2产品具有球形形貌,行射峰峰型较尖锐,属于四方晶系a-MnO2
关键词:硫酸锰;净化除杂;氟化锰;二氧化锰
中图分类号:TF111
文献标识码;A
doi:10.3969/j.issn.0253-6099.2013.03.024
文章编号:0253-6099(2013)03-0090-04
Exploratory Research on Deep Removal of Ca(Ⅱ)、Mg(Ⅱ) and Fe(Ⅱ)
from Industrial Manganese Sulfate
BAO Xin-jun", WANG Zhi-jian LIU Ji-bo SU Zheng-fu TIAN Si-yuan, ZHOU De-bi, WANG Hong-en
1. Hunan Rare-earth Metal Research Institute, Changsha 410026, Hunan, China; 2. School of Chemistry and Chemical
Engeeg r oh h h410083, 3 chl of Mterals Scence an Engineering
ty of Technology, Wuhan 430070, Hubei, China)
Abstract An investigation was made on a new purification process to remove Ca(I),Mg(I)and Fe(I) from
industrial manganese sulfate. The whole procedure included the following stages: the precipitating agent Mnf was added
Ca and M" through a method of dissolving Mnf, into pulp followed by two-step charging
a certain amount of potassium permanganate was induced to preferentially oxidize F*and then one percent of M2
oxidized into Mn0, which could effectively adsorb and precipitate Mgf and Caf and hydrolyze Fe(OH)a. Experiment
results showed that at PH of 4 temperature of 90 C, with stiring ime of 2 h and Mns concentrate of 300 g/L, the
precipitation rates of Ca, Mg and Fe were 98.8%, 97.25% and 99.92%, respectively. Finally, Mno2 products were
successfully prepared by a chemical co-preipi ation method with pre-purified manganese sulfate as manganese source
X-ray diffraction(XRD and scanning ele ron microscop(EM characterization proved that the obtained Mn2
products had spherical shape and sharp X-ray diffraction peaks, belonging to tetragonal a-mn02
Key words: manganese sulfate; purification; Mni; Mno2
硫酸锰在锰系产品中具有重要的地位,是生产其酸锰的损失率分别为5%和5%~7%?。赵中伟等人
他锰氧化物及锰盐的重要工业中间产品-3]。由低品采用粉体四氧化三锰为吸附剂,对硫酸锰溶液深度除
位的锰矿制备的硫酸锰产品,杂质特别是钙、镁、铁和钼工艺进行了研究,除钼后溶液的残余Mo浓度低于
其他重金属杂质含量高,去除钙、镁、铁、其他重金属杂0.015mg/L,完全达到生产无汞碱性锌锰电池专用电
质,制备高纯硫酸锰产品,一直是硫酸锰生产工业的难解二氧化锰的要求?。罗昌璃等人采用硫化除镍
题68。邱冠周等人提出了控制结晶过程水分蒸发钻,氟化除钙、镁的方法进行深度除杂,生产出的高纯
量,在50℃和90℃时分别结晶析出纯硫酸锰或硫酸硫酸锰达到客户需求,可以进行大批量工业生产叫。
镁的混晶,从而实现硫酸锰和硫酸镁的分离,该过程硫
溯南郴州市某企业生产的硫酸锰产品中钙、镁、铁
①收稿日期:2012-12-19
作者简介:包新军(1983-),男,湖南风凰人,博士研究生,工程师,主要从事有色金属冶金、锂离子电池正极材料研究。