氟盐法净化锰电解液中镁离子的研究
收稿日期: 2023-09-11
网络出版日期: 2024-06-20
基金资助
铜市科研(2021)13号项目(550025);黔科合重大专项[2022]003(550025);黔科合支撑[2022]重点020项目(554300)
Study on purification of magnesium from manganese electrolyte by fluorine salt method
Received date: 2023-09-11
Online published: 2024-06-20
采用电解法制备金属锰,因该工艺制备的金属锰纯度高、污染小而受到广泛应用,而生产过程中镁离子的循环富集会对系统造成很大危害。为降低镁离子的浓度保证电解生产正常进行,以镁离子的质量浓度降至15~20 g/L为研究目的,开展了氟盐法对锰电解液中镁离子的去除研究,考察了沉淀剂种类、用量系数、搅拌时间、温度和pH等因素对镁脱除效果的影响。研究结果表明,使用氟化铵为沉淀剂时,随着沉淀剂用量、搅拌时间、反应温度和体系pH的增加,镁离子浓度均呈现逐渐降低并达到一定水平后趋于稳定,得出较佳除杂条件:温度为50 ℃、搅拌时间为50 min、pH为5~6、沉淀剂用量为理论量(物质的量)的80%,可将溶液中镁离子质量浓度降至15.6 g/L,残余氟质量浓度为1.7 g/L。对除镁后的溶液采用低成本纳米除氟剂进行处理,通过利用EDS和ICP等分析手段可得到以下结果:氟离子质量浓度小于100 mg/L,除氟剂中的铝在硫酸锰溶液中的质量浓度仅为2.51×10-4 g/L,能满足电解锰工业的生产需求。
鲁菊 , 王家伟 , 王海峰 , 裴正清 , 周兴杰 , 郑可欣 , 马德华 . 氟盐法净化锰电解液中镁离子的研究[J]. 无机盐工业, 2024 , 56(6) : 40 -45 . DOI: 10.19964/j.issn.1006-4990.2023-0454
Metal manganese prepared by electrolysis is widely used because of its high purity and small pollution.The cyclic rich accumulation of magnesium ions in the production process will cause great harm to the system.In order to reduce the concentration of magnesium ions and ensure the normal production of electrolysis,the research objective was to reduce the mass concentration of magnesium ions to 15~20 g/L and the removal of magnesium from manganese electrolyte by fluorine salt method was carried out.The effects of precipitant type,dosage coefficient,stirring time,temperature and pH on the removal effect of magnesium were investigated.The results showed that when the ammonium fluoride was used as the precipitant,with the increase of precipitation agent,stirring time,the reaction temperature,and system pH,the concentration of magnesium ions was gradually decreased and reached a certain level,and the optimal conditions for impurity removal using ammonium fluoride as a precipitant were as follows:the temperature was 50 ℃,the stirring time was 50 min,the pH was 5~6,and the amount of precipitant was 80% of the theoretical amount,the concentration of magnesium ions in the solution could be reduced to 15.6 g/L,and the residual fluoride content was 1.7 g/L.The solution after magnesium removal was treated with low-cost nano-fluoride removal agent,and the following results could be obtained by using EDS and ICP analysis:the concentration of fluoride ion was reduced to less than 100 mg/L,and the content of aluminum in the fluoride removal agent in the manganese sulfate solution was only 2.51×10-4 g/L,which could meet the production demand of electrolytic manganese industry.
| 1 | 宋瀚文,张辉,宋达,等.硫酸锰制备工艺研究进展[J].盐科学与化工,2023,52(2):10-12. |
| SONG Hanwen, ZHANG Hui, SONG Da,et al.Research progress on preparation technology of manganese sulfate[J].Journal of Salt Science and Chemical Industry,2023,52(2):10-12. | |
| 2 | ZHANG Wensheng, CHENG Chuyong.Manganese metallurgy review.Part I:Leaching of ores/secondary materials and recovery of electrolytic/chemical manganese dioxide[J].Hydrometallurgy,2007,89(3/4):137-159. |
| 3 | MENDON?A DE ARAUJO J A, REIS DE CASTRO M M,DE FREITAS CUNHA LINS V.Reuse of furnace fines of ferro alloy in the electrolytic manganese production[J].Hydrometallurgy,2006,84(3/4):204-210. |
| 4 | 王晓东,张衡,彭碧君.钙法提钒废水除锰并制备高纯碳酸 锰[J].化工环保,2022,42(3):293-297. |
| WANG Xiaodong, ZHANG Heng, PENG Bijun.Removal of manganese from vanadium extraction wastewater by calcium process and preparation of high-purity manganese carbonate[J].Environmental Protection of Chemical Industry,2022,42(3):293-297. | |
| 5 | TANG Liang, HE Zhaoyi, CHEN Kefan,et al.Study of microscopic properties and heavy metal solidification mechanism of electrolytic manganese residue-based cementitious materials[J].Environmental Science and Pollution Research,2023,30(48):105056-105071. |
| 6 | 李重洋,钱振,时启龙,等.含镁三元系锰电解液理化性能研究[J].矿冶工程,2019,39(4):79-82,88. |
| LI Chongyang, QIAN Zhen, SHI Qilong,et al.Physical-chemical properties of ternary Mg-containing manganese electrolyte[J].Mining and Metallurgical Engineering,2019,39(4):79-82,88. | |
| 7 | 郑子恩.电解金属锰阳极泥还原焙烧-酸浸试验研究[J].稀有金属与硬质合金,2022,50(2):15-18. |
| ZHENG Zien.Experimental research on reduction roasting-acid leaching of electrolytic manganese anode slime[J].Rare Metals and Cemented Carbides,2022,50(2):15-18. | |
| 8 | 钱振,谭杰,李重洋,等.电解锰工业生产过程中镁组分迁移行为研究[J].矿冶工程,2022,42(4):112-115. |
| QIAN Zhen, TAN Jie, LI Chongyang,et al.Migration behavior of magnesium components in industrial production of electrolytic manganese[J].Mining and Metallurgical Engineering,2022,42(4):112-115. | |
| 9 | SHANG Yabo, WANG Yadong, LI Keqian,et al.Nucleation crystallization pelleting process for highly efficient manganese ion recovery in electrolytic manganese wastewater[J].Chemical Engineering Journal,2023,475:146271. |
| 10 | 耿叶静,刘静,周娥,等.富镁软锰矿中镁的预脱除实验研究[J].中国锰业,2012,30(2):29-31,38. |
| GENG Yejing, LIU Jing, ZHOU E,et al.Research on pre-removal of Mg in rich Mg pyrolusite[J].China′s Manganese Industry,2012,30(2):29-31,38. | |
| 11 | 蔡振勇,易清风,刘汉勇,等.废铁屑还原软锰矿制备高纯硫酸锰工艺研究[J].中国锰业,2011,29(3):28-31. |
| CAI Zhenyong, YI Qingfeng, LIU Hanyong,et al.Preparation of high purity manganese sulfate from the reduction of pyrolusite using scrap iron as the reductant[J].China’s Manganese Industry,2011,29(3):28-31. | |
| 12 | 蒋文杰,张昭.硫酸锰溶液中镁离子的沉淀行为研究[J].无机盐工业,2014,46(10):34-38. |
| JIANG Wenjie, ZHANG Zhao.Precipitation behavior of magnesium ion in manganese sulfate solution[J].Inorganic Chemicals Industry,2014,46(10):34-38. | |
| 13 | 尤晓宇,王家伟,王海峰,等.电解锰生产用硫酸锰、镁、铵复盐体系结晶的研究[J].应用化工,2021,50(9):2353-2356. |
| YOU Xiaoyu, WANG Jiawei, WANG Haifeng,et al.Study on crystallization of manganese sulfate,magnesium sulfate and ammonium sulfate for electrolytic manganese production[J].Applied Chemical Industry,2021,50(9):2353-2356. | |
| 14 | 杨绍泽,任博,王春侠.电解金属锰加工工艺中乙醇循环除镁工艺初探[J].中国锰业,2011,29(2):15-17,24. |
| YANG Shaoze, REN Bo, WANG Chunxia.The study of magnesium removing by ethanol recycling for the technology of electrolytic manganese processing[J].China′s Manganese Industry,2011,29(2):15-17,24. | |
| 15 | 李萌,朱彤,张翔宇,等.纳滤膜处理含锰废水[J].化工环保,2012,32(3):260-263. |
| LI Meng, ZHU Tong, ZHANG Xiangyu,et al.Treatment of man-ganese-containing wastewater using nanofiltration membrane[J].Environmental Protection of Chemical Industry,2012,32(3):260-263. | |
| 16 | 谢子楠,王蛟,沈家国.工业硫酸锰中钙、镁的净化研究[J].无机盐工业,2015,47(5):48-50. |
| XIE Zinan, WANG Jiao, SHEN Jiaguo.Research on purification of Ca(Ⅱ) and Mg(Ⅱ) in industrial manganese sulfate[J].Inorganic Chemicals Industry,2015,47(5):48-50. | |
| 17 | GUIMAR?ES A S, MANSUR M B.Solvent extraction of calcium and magnesium from concentrate nickel sulfate solutions using D2HEPA and Cyanex 272 extractants[J].Hydrometallurgy,2017,173:91-97. |
| 18 | ZHOU Libo, CHEN Ping, HU Cheng,et al.Study on the mechanical properties and hydration behavior of steel slag-red mud-electrolytic manganese residue based composite mortar[J].Applied Sciences,2023,13(10):5913. |
| 19 | 张彭汝,王文磊,杨超,等.硫酸锰溶液氟化沉淀法除镁的研究[J].有色金属(冶炼部分),2012(12):1-4. |
| ZHANG Pengru, WANG Wenlei, YANG Chao,et al.Study on removal of magnesium from manganese sulfate solution with fluorination precipitation[J].Nonferrous Metals(Extractive Metallurgy),2012(12):1-4. | |
| 20 | 刘洪刚,朱国才.氟化锰沉淀脱除还原氧化锰矿浸出液中钙镁[J].矿冶,2007,16(4):25-28,65. |
| LIU Honggang, ZHU Guocai.Removal of Ca(Ⅱ),Mg(Ⅱ) from leaching solution of low-grade manganese ore by precipitation with fluoride[J].Mining and Metallurgy,2007,16(4):25-28,65. | |
| 21 | 秦吉涛.Mg2+在锰电解体系中的分布及其行为研究[D].贵阳:贵州大学,2019. |
| QIN Jitao.Research on distribution and behavior of Mg2+ in manganese electrolysis system[D].Guiyang:Guizhou University,2019. | |
| 22 | 秦吉涛,王家伟,王海峰,等.Mg2+对硫酸锰电解液理化性质的影响[J].有色金属(冶炼部分),2019(1):12-15,30. |
| QIN Jitao, WANG Jiawei, WANG Haifeng,et al.Effect of Mg2+ on physicochemical properties of manganese sulfate electrolyte[J].Nonferrous Metals(Extractive Metallurgy),2019(1):12-15,30. | |
| 23 | 王海峰,王家伟.一种纳米除氟剂及其制备方法和应用:中国,116786097A[P].2023-09-22. |
| 24 | 时海平,王东田,田美玲.活性氧化铝的制备及除氟性能研究[J].苏州科技学院学报(工程技术版),2010,23(3):23-26. |
| SHI Haiping, WANG Dongtian, TIAN Meiling.A research on preparation of activated alumina and its property of fluriode[J].Journal of Suzhou University of Science and Technology(Engineering and Technology),2010,23(3):23-26. |
/
| 〈 |
|
〉 |