ZnSO_(4)-FeSO_(4)溶液120~180℃的矿化沉铁行为及机理  

Behavior and mechanism of iron mineralization precipitation in ZnSO_(4)-FeSO_(4) solution at 120−180℃

作　　者：彭晓华 陆占清 陈国木 周东风 魏昶[1] 李兴彬[1] 杨博 邓志敢[1] PENG Xiaohua;LU Zhanqing;CHEN Guomu;ZHOU Dongfeng;WEI Chang;LI Xingbin;YANG Bo;DENG Zhigan(Faculty of Metallurgical and Energy Engineering,Kunming University of Science and Technology,Kunming 650093,China;Yunnan Chihong Zn&Ge Co.,Ltd.,Qujing 655011,China;Danxia Smelter of Shenzhen Zhongjin Lingnan Nonfemet Co.,Ltd.,Shaoguan 512325,China)

机构地区：[1]昆明理工大学冶金与能源工程学院,昆明650093 [2]云南驰宏锌锗股份有限公司,曲靖655011 [3]深圳市中金岭南有色金属股份有限公司丹霞冶炼厂,韶关512325

出　　处：《中国有色金属学报》2024年第11期3843-3855,共13页The Chinese Journal of Nonferrous Metals

基　　金：国家自然科学基金资助项目(52164039);云南省重大科技专项项目(202302AG050008,202302AB080012)。

摘　　要：针对湿法炼锌含Zn^(2+)130 g/L、Fe^(2+)15 g/L的高锌含铁溶液矿化沉铁过程机理及铁物相转变行为,本文于120~180℃下开展了矿化沉铁行为及机理研究,深入研究了温度、氧分压、搅拌转速和反应时间对亚铁离子矿化沉铁行为的影响。结果表明:温度150℃、氧分压0.3~0.4 MPa、搅拌转速500 r/min以及反应时间180 min为合理的矿化沉铁条件。在此条件下,沉铁率为91.33%,沉铁后液中Fe^(2+)和全Fe浓度分别降至0.10 g/L和1.30 g/L,同时可产出Fe、Zn和S含量分别为61.35%、1.01%和1.61%的高品位赤铁矿。XRD和SEM分析结果表明:当反应温度低于130℃时,沉铁产物物相由针铁矿和羟基氧化铁组成,高于130℃,主要为赤铁矿。Fe^(2+)矿化沉铁伴随着复杂的氧化、水解、脱水、缩合等反应过程。XPS分析结果表明,沉铁产物为羟基氧化铁(Fe_(2-x/3)(OH)_xO_(3-x)),其脱水(H_(2)O)和脱羟基(—OH)不完全导致Fe空位;Zn^(2+)以间隙或原子替代的方式存在于沉铁产物晶体内,并与O^(2-)配位;SO_(4)^(2-)与晶体晶面的Fe(Ⅲ)络合(FeSO_(4)^(+)),以硫酸铁(Fe_(2)(SO_(4))_(3))的形式存在,硫酸根几乎均匀地分布于赤铁矿颗粒内部及表面。In order to solve the problem that the mechanism and the phase transition behavior of Fe^(2+)mineralization precipitation process of high zinc concentration iron-containing solution containing Zn^(2+)130 g/L and Fe^(2+)15 g/L in zinc hydrometallurgy are unclear,the mineralization precipitation behavior of ferrous ion from zinc hydrometallurgical ZnSO_(4)-FeSO_(4) solution at 120-180℃was investigated.The effect of reaction temperature,oxygen partial pressure,agitation speed and reaction time on the mineralization precipitation behavior of ferrous ion was analyzed.The results indicate that the reasonable mineralization conditions as follows:reaction temperature of 150℃,oxygen partial pressure of 0.3-0.4 MPa,agitation speed of 500 r/min and reaction time of 180 min.The iron removal efficiency is 91.33%at the optimal condition.The concentration of Fe^(2+)and total Fe in the solution after Fe precipitation decreases to 0.10 g/L and 1.30 g/L,respectively.At the same time,high-grade hematite containing 61.35%Fe,1.01%Zn and 1.61%S can be produced.XRD and SEM characterization shows that the phase composition of mineralization product consists of goethite and oxyhydroxides at below 130℃,and mainly of hematite at above 130℃.Fe^(2+)mineralization precipitation involves the reaction process of oxidation,hydrolysis,dehydration and dehydroxylation.XPS analysis shows that the mineralization product is oxyhydroxides(Fe_(2-x/3)(OH)_(x)O_(3-x)),with incomplete dehydration(H_(2)O)and dehydroxylation(—OH)leading to Fe vacancies.Zn^(2+)exists in the crystal of mineralization products through interstitial atom or atomic substitution,and coordinates with O_(2)-.Sulfate ions coordinate with Fe(Ⅲ)on the crystal surface(FeSO_(4)^(+))and exist in the form of sulfate(Fe2(SO_(4))_(3)).Sulfate ions are almost uniformly incorporated into mineral particles and distributed evenly on the crystal surface and inner.

关 键 词：湿法炼锌 亚铁离子 矿化沉铁 羟基氧化铁 针铁矿 赤铁矿 

分 类 号：TF813[冶金工程—有色金属冶金]