FeSO_4-ZnSO_4-H_2O体系中水热赤铁矿法沉铁的研究
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摘要
针对高铁闪锌矿的矿物学特点开发的还原浸出-置换沉铜-中和沉铟-水热赤铁矿法沉铁新工艺可实现该矿物中有价元素的高效浸出与回收,并获得环境友好型赤铁矿法沉铁渣.FeSO_4-ZnSO_4-H_2O体系中Fe(Ⅱ)氧化水热水解赤铁矿法沉铁研究结果表明:温度是影响亚稳态铁矾物相形成和转化的关键因素,升高温度亚稳态铁矾物相的热力学稳定性降低并转变为赤铁矿;增加Zn~(2+)浓度、提高氧分压、添加晶种、增大搅拌转速均会促进Fe(Ⅱ)氧化水热水解为赤铁矿.在反应温度为190℃、锌离子浓度为100 g/L、晶种添加量为20 g/L、反应时间为4 h、氧分压为0.6 MPa、搅拌速度为500 r/min的优化工艺条件下,Fe(Ⅱ)氧化水热水解赤铁矿法沉铁过程中除铁率为95%,获得含铁58.3%大颗粒的纯净沉铁渣.
A new process which contains reductive leaching,copper cementation,indium precipitation and hematite precipitation was presented in this paper. Through this new process,valuable metals were effectively leached and recovered,and an environment-friendly hematite slag was obtained. Hydrothermal oxydrolysis of Fe(Ⅱ) to produce hematite was studied in FeSO_4-ZnSO_4-H_2O system and the research results show that temperature is the key factor affecting the formation and transformation of metastable jarosite phases. The thermodynamic stability of jarosite phase decreases and becomes hematite at elevated temperature. It is advantage for hematite precipitation via hydrothermal oxydrolysis of Fe(Ⅱ) by increasing Zn~(2+) concentration and oxygen partial pressure,addition of Fe_2O_3 seed and strengthening stirring speed. Large particle sized and pure hematite precipitate with iron content of 58. 3% was obtained,and with iron removal efficiency of being 95% under the optimum conditions of temperature of 190 ℃,Zn~(2+) concentration of 100 g/L,hematite seed of 20 g/L,reaction time of 4 h,oxygen partial pressure of 0. 6 Mpa and stirring speed of 500 r/min.
A new process which contains reductive leaching,copper cementation,indium precipitation and hematite precipitation was presented in this paper. Through this new process,valuable metals were effectively leached and recovered,and an environment-friendly hematite slag was obtained. Hydrothermal oxydrolysis of Fe(Ⅱ) to produce hematite was studied in FeSO_4-ZnSO_4-H_2O system and the research results show that temperature is the key factor affecting the formation and transformation of metastable jarosite phases. The thermodynamic stability of jarosite phase decreases and becomes hematite at elevated temperature. It is advantage for hematite precipitation via hydrothermal oxydrolysis of Fe(Ⅱ) by increasing Zn~(2+) concentration and oxygen partial pressure,addition of Fe_2O_3 seed and strengthening stirring speed. Large particle sized and pure hematite precipitate with iron content of 58. 3% was obtained,and with iron removal efficiency of being 95% under the optimum conditions of temperature of 190 ℃,Zn~(2+) concentration of 100 g/L,hematite seed of 20 g/L,reaction time of 4 h,oxygen partial pressure of 0. 6 Mpa and stirring speed of 500 r/min.
引文
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[10]王益昭,李存兄,魏昶,等.湿法炼锌过程中赤铁矿生成及硫的吸附转化[J].中国有色金属学报,2017,27(10):1-9
[11]杨凡,邓志敢,魏昶,等.高铁闪锌矿赤铁矿法除铁中锌离子和镁离子的影响及存在机理[J].中国有色金属学报,2014,24(11):2906-2913.
[12]张帆,魏昶,邓志敢,等.锌中浸渣—硫化锌精矿协同浸出锌和铟[J].有色金属工程,2016,6(3):40-44.
[13]朱北平,邓志敢,张帆,等.富铟锌铁渣中锌和铟的浸出与铁的同步还原[J].矿冶,2016,25(4):36-40.
[14]陈先友,邓志敢,魏昶,等.锌焙砂中性浸出渣还原酸浸试验研究[J].矿冶,2015,24(2):55-59.
[15]朱北平,邓志敢,张帆,等.热酸浸出富铟锌浸渣提取锌铟的研究[J].矿冶,2016,25(3):46-49.
[16]邓志敢,魏昶,张帆,等.湿法炼锌赤铁矿法除铁及资源综合利用新技术[J].有色金属工程,2016,6(5):38-43.
[17]冯强,魏昶,邓志敢,等.高铁硫酸锌浸出液中铟的富集[J].稀有金属,2014,38(4):687-692.
[18]Cheng T C M.Production of hematite in acidic zinc sulfate media[D].Montreal:Materials Engineering Mc Gill University,2002:246-252.
[2]Zhang F,Wei C,Deng Z,et al.Reductive leaching of indium-bearing zinc residue in sulfuric acid using sphalerite concentrate as reductant[J].Hydrometallurgy,2016,161:102-106.
[3]Zhang F,Wei C,Deng Z,et al.Reductive leaching of zinc and indium from industrial zinc ferrite particulates in sulphuric acid media[J].Transactions of Nonferrous Metals Society of China,2016,26(9):2495-2501.
[4]彭兵,林冬红,刘恢,等.高铁锌焙砂还原焙烧-碱浸工艺[J].中国有色金属学报,2017,27(2):424-429.
[5]刘洋,谭军,刘常青,等.碳还原锌浸出渣炼铁过程的热力学分析[J].中国有色金属学报,2015,25(7):1979-1986.
[6]陈家镛,余淑秋,伍志春.湿法冶金中铁的分离与利用[M].北京:冶金工业出版社,1991:112-135.
[7]Umetsu V,Tozawa K,Sasaki K.The hydrolysis of ferric sulphate solutions at elevated temperatures[J].Canadian Metallurgical Quarterly,1977,16(1):111-117.
[8]Dutrizac J E,Sunyer A.Hematite formation from jarosite type compounds by hydrothermal conversion[J].Canadian Metallurgical Quarterly,2012,51(1):11-23.
[9]Claassen J O,Sandenbergh R F.Particle growth parameters in the precipitation of metastable iron phases from zinc-rich solutions[J].Hydrometallurgy,2006,84(3):165-174.
[10]王益昭,李存兄,魏昶,等.湿法炼锌过程中赤铁矿生成及硫的吸附转化[J].中国有色金属学报,2017,27(10):1-9
[11]杨凡,邓志敢,魏昶,等.高铁闪锌矿赤铁矿法除铁中锌离子和镁离子的影响及存在机理[J].中国有色金属学报,2014,24(11):2906-2913.
[12]张帆,魏昶,邓志敢,等.锌中浸渣—硫化锌精矿协同浸出锌和铟[J].有色金属工程,2016,6(3):40-44.
[13]朱北平,邓志敢,张帆,等.富铟锌铁渣中锌和铟的浸出与铁的同步还原[J].矿冶,2016,25(4):36-40.
[14]陈先友,邓志敢,魏昶,等.锌焙砂中性浸出渣还原酸浸试验研究[J].矿冶,2015,24(2):55-59.
[15]朱北平,邓志敢,张帆,等.热酸浸出富铟锌浸渣提取锌铟的研究[J].矿冶,2016,25(3):46-49.
[16]邓志敢,魏昶,张帆,等.湿法炼锌赤铁矿法除铁及资源综合利用新技术[J].有色金属工程,2016,6(5):38-43.
[17]冯强,魏昶,邓志敢,等.高铁硫酸锌浸出液中铟的富集[J].稀有金属,2014,38(4):687-692.
[18]Cheng T C M.Production of hematite in acidic zinc sulfate media[D].Montreal:Materials Engineering Mc Gill University,2002:246-252.