| 104 | 0 | 17 |
| 下载次数 | 被引频次 | 阅读次数 |
针对湿法炼锌过程产出的高浓度含铁溶液，研究在高温条件下硫酸亚铁和硫酸锌的结晶行为，利用硫酸亚铁在高温酸性溶液中易结晶的原理，采用高温结晶方法，探索高温结晶分离硫酸亚铁，降低溶液中铁离子浓度的技术工艺.结果表明：在温度为160～180℃的高温酸性(pH值为0.3～0.5)溶液中，硫酸锌的溶解度高于硫酸亚铁的溶解度；锌离子质量浓度为80～90 g/L、亚铁离子质量浓度为25～40 g/L的湿法炼锌溶液，在温度为160℃时进行高温结晶，溶液中亚铁离子质量浓度可降低至25 g/L以下，高温结晶析出的硫酸亚铁纯度可达93%以上.控制适宜的结晶温度，可在尽可能少析出硫酸锌结晶的同时分离析出硫酸亚铁结晶，实现溶液中锌与铁的初步分离，有利于后续采用赤铁矿法除铁工艺进一步分离锌与铁，对实现湿法炼锌过程中铁资源的高值化与除铁渣的减量化具有重要意义.
Abstract：This study investigated the crystallization behavior of ferrous sulfate and zinc sulfate under high-temperature conditions in iron-rich solutions generated during zinc hydrometallurgy.Based on the principle that ferrous sulfate is prone to crystallization in high-temperature acidic solutions, the high-temperature crystallization method is adopted.Aiming to develop a high-temperature crystallization process for separating ferrous sulfate and reducing iron ion concentration.The results demonstrated that in highly acidic solutions(pH 0.3-0.5) at 160-180 ℃,zinc sulfate exhibits higher solubility than ferrous sulfate.When treating a zinc hydrometallurgical solution containing 80-90 g/L Zn2+ and 25-40 g/L Fe2+ at 160 ℃ through high-temperature crystallization, the ferrous ion concentration could be reduced to below 25 g/L,with the precipitated ferrous sulfate achieving over 93% purity.By optimizing the crystallization temperature, selective separation of ferrous sulfate crystals could be achieved while minimizing co-precipitation of zinc sulfate, thereby enabling preliminary Zn/Fe separation.This process facilitates subsequent iron removal via the hematite method and holds significant importance for both iron resource valorization and reduction of iron-containing residues in zinc hydrometallurgy.
[1] PENG X H,YANG B,LI X B,et al.Dissolution behavior of hematite in H2SO4 solution:A kinetic analysis and its importance on the zinc hydrometallurgical hematite process[J].Minerals Engineering,2024,215:108811.
[2] 邹维，刘俊场，付维琴，等.湿法炼锌铁渣源头减量技术[J].有色金属(冶炼部分),2023(7):5-8.ZOU W,LIU J C,FU W Q,et al.Source reduction technology of iron slag in zinc hydrometallurgy[J].Nonferrous Metals (Extractive Metallurgy),2023(7):5-8.
[3] 邓志敢，樊光，魏昶，等.SO2-H2SO4体系中锌浸渣还原浸出锌和铟[J].有色金属(冶炼部分),2020(5):1-9.DENG Z G,FAN G,WEI C,et al.Reduction leaching of Zn and in from zinc leaching residue in SO2-H2SO4 system[J].Nonferrous Metals (Extractive Metallurgy),2020(5):1-9.
[4] FAN Y Y,LIUY,NIU L P,et al.Reductive leaching of indium-bearing zinc ferrite in sulfuric acid using sulfur dioxide as a reductant[J].Hydrometallurgy,2019,186:192-199.
[5] 邓志敢，王希希，林文军，等.湿法炼锌浸出过程铜铁的浸出与沉淀行为[J].昆明理工大学学报(自然科学版),2024,49(3):34-41.DENG Z G,WANG X X,LIN W J,et al.Behavior of leaching and precipitation of copper and iron in the leaching process of hydrometallurgy zinc[J].Journal of Kunming University of Science and Technology (Natural Science),2024,49(3):34-41.
[6] 王振银，高文成，温建康，等.锌浸出渣有价金属回收及全质化利用研究进展[J].工程科学学报，2020,42(11):1400-1410.WANG Z Y,GAO W C,WEN J K,et al.Research progress in the recovery of valuable metals from zinc leaching residue and its total material utilization[J].Chinese Journal of Engineering,2020,42(11):1400-1410.
[7] 李强，刘三平，张学东，等.锌浸出渣挥发锌铅铟试验研究[J].有色金属(冶炼部分),2020(12):27-30.LI Q,LIU S P,ZHANG X D,et al.Study on volatilization of zinc,lead and indium from zinc leaching residue[J].Nonferrous Metals (Extractive Metallurgy),2020(12):27-30.
[8] 李嘉辉，邓志敢，魏昶，等.氧化锌烟尘中铟锗的分离回收工艺[J].有色金属(冶炼部分),2023(4):60-66.LI J H,DENG Z G,WEI C,et al.Separation and recovery process of indium and germanium from zinc oxide dust[J].Nonferrous Metals (Extractive Metallurgy),2023(4):60-66.
[9] 张国华，朱北平，陈先友，等.湿法炼锌中锌铁分离方法与运用探讨[J].有色金属(冶炼部分),2021(2):20-26.ZHANG G H,ZHU B P,CHEN X Y,et al.Discussion on separation method and application of zinc and iron in zinc hydrometallurgy[J].Nonferrous Metals (Extractive Metallurgy),2021(2):20-26.
[10] 杨博，陆占清，周东风，等.ZnSO4-FeSO4溶液氧压水热强化针铁矿法除铁行为与机理[J].中国有色金属学报，2024,34(11):3750-3765.YANG B,LU Z Q,ZHOU D F,et al.Iron removal behavior and mechanism of oxygen pressure hydrothermal enhanced goethite method in ZnSO4-FeSO4 solution[J].The Chinese Journal of Nonferrous Metals,2024,34(11):3750-3765.
[11] 杨荣净，邓志敢，陈沛崟，等.湿法炼锌酸浸液中三价铁的锌精矿还原工艺[J].有色金属(冶炼部分),2023(10):1-6.YANG R J,DENG Z G,CHEN P Y,et al.Reduction process of zinc concentrate with ferric iron in acid leaching solution of zinc hydrometallurgy[J].Nonferrous Metals (Extractive Metallurgy),2023(10):1-6.
[12] 范旷生，何贵香，刘平，等.锌中浸渣中锌和铟的SO2还原浸出研究[J].有色金属工程，2019,9(2):51-54.FAN K S,HE G X,LIU P,et al.SO2 reduction leaching of zinc and indium in zinc neutral leaching residue[J].Nonferrous Metals Engineering,2019,9(2):51-54.
[13] XING Y B,LIU H Y,DENG Z G,et al.Dissolution behavior of ferrous sulfate in the hematite process[J].Hydrometallurgy,2021,200:105561.
[14] 彭晓华，陆占清，陈国木，等.ZnSO4-FeSO4溶液120～180℃的矿化沉铁行为及机理[J].中国有色金属学报，2024,34(11):3843-3855.PENG X H,LU Z Q,CHEN G M,et al.Behavior and mechanism of iron mineralization precipitation in ZnSO4-FeSO4 solution at 120-180℃[J].The Chinese Journal of Nonferrous Metals,2024,34(11):3843-3855.
[15] 杨源，邓志敢，魏昶，等.利用湿法炼锌赤铁矿法沉铁渣制备铁红工艺[J].工程科学学报，2020,42(10):1325-1334.YANG Y,DENG Z G,WEI C,et al.Preparation of iron oxide red by sinking iron slag in zinc smelting hematite process[J].Chinese Journal of Engineering,2020,42(10):1325-1334.
[16] (苏)Е.В.哈姆斯基.化学工业中的结晶[M].古涛，译.北京：化学工业出版社，1984:93-97.
[17] BRUHN G,GERLACH J,PAWLEK F.Solubilities of salts and gasses in water[J].Zeitschrift Für Anorganische Und Allgemeine Chemie,1965,337,68-79.
[18] HASEGAWA F,TOZAWAK,NISHIMURA T.Solubility of ferrous sulfate in aqueous solutions at high temperatures[J].Shigen to Sozai,1996,112(12):879-884.
[19] ELGERSMA F,WITKAMP G J,VAN ROSMALEN G M.Incorporation of zinc in ferrous sulfate monohydrate[J].Hydrometallurgy,1993,33(3):301-311.
[20] 周甫立.七水硫酸锌结晶过程研究[D].天津：天津大学，2017.ZHOU P L.Study on the crystallization process of zinc sulfate heptahydrate[D].Tianjin:Tianjin University,2017.
[21] 刘慧杨，邓志敢，魏昶，等.硫酸亚铁在高温水溶液中的结晶行为[J].中国有色金属学报，2019,29(11):2645-2652.LIU H Y,DENG Z G,WEI C,et al.Crystallization behavior of ferrous sulfate at elevated temperatures in aqueous solution system[J].The Chinese Journal of Nonferrous Metals,2019,29(11):2645-2652.
[22] DENG Z G,YANG F,WEI C,et al.Transformation behavior of ferrous sulfate during hematite precipitation for iron removal[J].Transactions of Nonferrous Metals Society of China,2020,30(2):492-500.
[23] 刘慧杨，邓志敢，魏昶，等.高温水溶液中铁、锌、镁多元硫酸盐体系的结晶行为[J].中国有色金属学报，2020,30(7):1691-1702.LIU H Y,DENG Z G,WEI C,et al.Crystallization behavior of multi-sulfate system of iron,zinc and magnesium in high temperature aqueous solution[J].The Chinese Journal of Nonferrous Metals,2020,30(7):1691-1702.
[24] 邓志敢，魏昶，李兴彬，等.一种湿法炼锌溶液结晶析出硫酸亚铁的方法：CN108085489A[P].2018-05-29.
基本信息:
DOI：10.16112/j.cnki.53-1223/n.2025.04.402
中图分类号:TF813
引用信息:
[1]胡东风,周东风,邓志敢等.湿法炼锌溶液中硫酸亚铁的高温结晶行为与分离技术[J].昆明理工大学学报(自然科学版),2025,50(04):11-16+25.DOI:10.16112/j.cnki.53-1223/n.2025.04.402.
基金信息:
云南省科技人才计划项目（202405AC350015）; 云南省应用基础研究专项（202401BN070001-001,202401BN070001-008）