铁酸锌选择性还原及其在锌浸出渣处理中的应用（英文）
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摘要
传统湿法炼锌过程产生大量富含有价金属资源的铁酸锌废渣,铁的分离是实现铁酸锌废渣中有价金属资源回收的关键。提出含大量铁酸锌的锌浸出渣选择性还原焙烧-浸出分离铁和锌的新方法。通过热力学分析确定铁酸锌分解过程中Fe3O4和ZnO产物的优势区域,并发现V(CO)/V(CO+CO2)比是控制铁酸锌还原焙烧产物物相的关键因素,在V(CO)/V(CO+CO2)比在2.68%-36.18%范围内,铁酸锌优先分解生成在Fe3O4和ZnO。通过TG分析,确定铁酸锌还原焙烧的最佳条件为焙烧温度700-750°C,CO体积分数6%,V(CO)/V(CO+CO2)30%。基于上述研究结果,对富含铁酸锌的锌浸渣进行还原焙烧处理,焙烧产物经酸浸后,锌的浸出率达70%,铁的浸出率仅为18.4%,实现锌浸渣中锌和铁的有效分离。
The traditional zinc hydro-metallurgy generates a large amount of zinc ferrite residue rich in valuable metals. The separation of iron is crucial for resource recycling of valuable metals in zinc ferrite residue. A novel selective reduction roasting-leaching process was proposed to separate zinc and iron from zinc leaching residue which contains zinc ferrite. The thermodynamic analysis was employed to determine the predominant range of Fe3O4 and ZnO during reduction roasting process of zinc ferrite. Based on the result of thermodynamic calculation, we found that V(CO)/V(CO+CO2) ratio is a key factor determining the phase composition in the reduction roasting product of zinc ferrite. In the range of V(CO)/V(CO+CO2) ratio between 2.68% and 36.18%, zinc ferrite is preferentially decomposed into Fe3O4 and ZnO. Based on thermogravimetric(TG) analysis, the optimal conditions for reduction roasting of zinc ferrite are determined as follows: temperature 700-750 °C, volume fraction of CO 6% and V(CO)/V(CO+CO2) ratio 30%. Based on the above results, zinc leaching residue rich in zinc ferrite was roasted and the roasted product was leached by acid solution. It is found that zinc extraction rate in zinc leaching residue reaches up to 70% and iron extraction rate is only 18.4%. The result indicates that zinc and iron can be effectively separated from zinc leaching residue.
The traditional zinc hydro-metallurgy generates a large amount of zinc ferrite residue rich in valuable metals. The separation of iron is crucial for resource recycling of valuable metals in zinc ferrite residue. A novel selective reduction roasting-leaching process was proposed to separate zinc and iron from zinc leaching residue which contains zinc ferrite. The thermodynamic analysis was employed to determine the predominant range of Fe3O4 and ZnO during reduction roasting process of zinc ferrite. Based on the result of thermodynamic calculation, we found that V(CO)/V(CO+CO2) ratio is a key factor determining the phase composition in the reduction roasting product of zinc ferrite. In the range of V(CO)/V(CO+CO2) ratio between 2.68% and 36.18%, zinc ferrite is preferentially decomposed into Fe3O4 and ZnO. Based on thermogravimetric(TG) analysis, the optimal conditions for reduction roasting of zinc ferrite are determined as follows: temperature 700-750 °C, volume fraction of CO 6% and V(CO)/V(CO+CO2) ratio 30%. Based on the above results, zinc leaching residue rich in zinc ferrite was roasted and the roasted product was leached by acid solution. It is found that zinc extraction rate in zinc leaching residue reaches up to 70% and iron extraction rate is only 18.4%. The result indicates that zinc and iron can be effectively separated from zinc leaching residue.
引文
[1]WANG Ji-ming,PENG Bing,CHAI Li-yuan,LI Mi,PENG Ning.Recovery of iron from zinc leaching residues by reduction roasting and magnetic separation[J].The Chinese Journal of Nonferrous Metals,2012,22(5):1455-1461.(in Chinese)
[2]LI Mi,PENG Bing,CHAI Li-yuan,WANG Ji-ming,PENG Ning,YAN Huan.Element distribution of high iron-bearing zinc calcine in high gradient magnetic field[J].Transactions of Nonferrous Metals Society of China,2012,22(9):2261-2267.
[3]LI Mi,PENG Bing,CHAI Li-yuan,PENG Ning,XIE Xian-de,YAN Huan.Technological mineralogy and environmental activity of zinc leaching residue from zinc hydrometallurgical process[J].Transactions of Nonferrous Metals Society of China,2013,23(5):1480-1488.
[4]PENG Ning,PENG Bing,CHAI Li-yuan,YUAN Yuan,YAN Huan.Recovery of iron from zinc calcines by reduction roasting and magnetic separation[J].Minerals Engineering,2012,35(8):57-60.
[5]?OPUR M,PEKDEMIR T,?OLAK S,KUMKUL A.Industrial symbiosis:High purity recovery of metals from Waelz sintering waste by aqueous SO2 solution[J].Journal of Hazardous Materials,2007,149(2):303-309.
[6]LIU Zhi-hong.Present situation and development trend of zinc smelting technology in China and foreign countries[J].World Nonferrous Metals,2000:23-26.(in Chinese)
[7]HOLLOWAY P C,ETSELL T H,MURLAND A L.Roasting of la oroya zinc ferrite with Na2CO3[J].Metallurgical and Materials Transactions B,2007,38(5):781-791.
[8]JU Shao-hua,ZHANG Yi-fei,ZHANG Yi,XUE Pei-yi,WANG Yi-hui.Clean hydrometallurgical route to recover zinc,silver,lead,copper,cadmium and iron from hazardous jarosite residues produced during zinc hydrometallurgy[J].Journal of Hazardous Materials,2011,192(2):554-558.
[9]IKENOBU S.Method for processing siliceous zinc ores[M].New Jersey:John Wiley&Sons,Inc,2013:427-436.
[10]XU Hong-sheng,WEI Chang,LI Cun-xiong,FAN Gang,DENG Zhi-gan,LI Min-ting,LI Xing-bin.Sulfuric acid leaching of zinc silicate ore under pressure[J].Hydrometallurgy,2010,105(1-2):186-190.
[11]LI Cun-xiong,WEI Chang,FAN Gang.Pressure acid leaching of high silicon zinc oxide ore[J].The Chinese Journal of Nonferrous Metals,2009,19(9):1678-1683.(in Chinese)
[12]ZHOU Jing-yuan.The present development trend of zinc and lead smelting industry[J].Non-ferrous Metals Industry,2001(5):42-45,47.(in Chinese)
[13]WIRAGI,DEGUIRE M.Treatment of zinc calcines for zinc recovery:USA Patent,4128617[P].1978-12-5.
[14]ISMAEL M,CARVALHO J.Iron recovery from sulphateleach liquors in zinc hydrometallurgy[J].Minerals Engineering,2003,16(1):31-39.
[15]LANGOVA?,RIPLOVA J,VALLOVA S.Atmospheric leaching of steel-making wastes and the precipitation of goethite from the ferric sulphate solution[J].Hydrometallurgy,2007,87(3-4):157-162.
[16]JHA M,KUMAR V,SINGH R.Review of hydrometallurgical recovery of zinc from industrial wastes[J].Resources,Conservation and Recycling,2001,33(1):1-22.
[17]LI Chao,SUN Heng-hu,BAI Jing,LI Long-tu.Innovative methodology for comprehensive utilization of iron ore tailings:Part 1.The recovery of iron from iron ore tailings using magnetic separation after magnetizing roasting[J].Journal of Hazardous Materials,2010,174(1-3):71-77.
[18]LECLERC N,MEUX E,LECUIRE J.Hydrometallurgical recovery of zinc and lead from electric arc furnace dust using mononitrilotriacetate anion and hexahydrated ferric chloride[J].Journal of Hazardous Materials,2002,91(1-3):257-270.
[19]LECLERC N,MEUX E,LECUIRE J.Hydrometallurgical extraction of zinc from zinc ferrites[J].Hydrometallurgy,2003,70(1-3):175-183.
[2]LI Mi,PENG Bing,CHAI Li-yuan,WANG Ji-ming,PENG Ning,YAN Huan.Element distribution of high iron-bearing zinc calcine in high gradient magnetic field[J].Transactions of Nonferrous Metals Society of China,2012,22(9):2261-2267.
[3]LI Mi,PENG Bing,CHAI Li-yuan,PENG Ning,XIE Xian-de,YAN Huan.Technological mineralogy and environmental activity of zinc leaching residue from zinc hydrometallurgical process[J].Transactions of Nonferrous Metals Society of China,2013,23(5):1480-1488.
[4]PENG Ning,PENG Bing,CHAI Li-yuan,YUAN Yuan,YAN Huan.Recovery of iron from zinc calcines by reduction roasting and magnetic separation[J].Minerals Engineering,2012,35(8):57-60.
[5]?OPUR M,PEKDEMIR T,?OLAK S,KUMKUL A.Industrial symbiosis:High purity recovery of metals from Waelz sintering waste by aqueous SO2 solution[J].Journal of Hazardous Materials,2007,149(2):303-309.
[6]LIU Zhi-hong.Present situation and development trend of zinc smelting technology in China and foreign countries[J].World Nonferrous Metals,2000:23-26.(in Chinese)
[7]HOLLOWAY P C,ETSELL T H,MURLAND A L.Roasting of la oroya zinc ferrite with Na2CO3[J].Metallurgical and Materials Transactions B,2007,38(5):781-791.
[8]JU Shao-hua,ZHANG Yi-fei,ZHANG Yi,XUE Pei-yi,WANG Yi-hui.Clean hydrometallurgical route to recover zinc,silver,lead,copper,cadmium and iron from hazardous jarosite residues produced during zinc hydrometallurgy[J].Journal of Hazardous Materials,2011,192(2):554-558.
[9]IKENOBU S.Method for processing siliceous zinc ores[M].New Jersey:John Wiley&Sons,Inc,2013:427-436.
[10]XU Hong-sheng,WEI Chang,LI Cun-xiong,FAN Gang,DENG Zhi-gan,LI Min-ting,LI Xing-bin.Sulfuric acid leaching of zinc silicate ore under pressure[J].Hydrometallurgy,2010,105(1-2):186-190.
[11]LI Cun-xiong,WEI Chang,FAN Gang.Pressure acid leaching of high silicon zinc oxide ore[J].The Chinese Journal of Nonferrous Metals,2009,19(9):1678-1683.(in Chinese)
[12]ZHOU Jing-yuan.The present development trend of zinc and lead smelting industry[J].Non-ferrous Metals Industry,2001(5):42-45,47.(in Chinese)
[13]WIRAGI,DEGUIRE M.Treatment of zinc calcines for zinc recovery:USA Patent,4128617[P].1978-12-5.
[14]ISMAEL M,CARVALHO J.Iron recovery from sulphateleach liquors in zinc hydrometallurgy[J].Minerals Engineering,2003,16(1):31-39.
[15]LANGOVA?,RIPLOVA J,VALLOVA S.Atmospheric leaching of steel-making wastes and the precipitation of goethite from the ferric sulphate solution[J].Hydrometallurgy,2007,87(3-4):157-162.
[16]JHA M,KUMAR V,SINGH R.Review of hydrometallurgical recovery of zinc from industrial wastes[J].Resources,Conservation and Recycling,2001,33(1):1-22.
[17]LI Chao,SUN Heng-hu,BAI Jing,LI Long-tu.Innovative methodology for comprehensive utilization of iron ore tailings:Part 1.The recovery of iron from iron ore tailings using magnetic separation after magnetizing roasting[J].Journal of Hazardous Materials,2010,174(1-3):71-77.
[18]LECLERC N,MEUX E,LECUIRE J.Hydrometallurgical recovery of zinc and lead from electric arc furnace dust using mononitrilotriacetate anion and hexahydrated ferric chloride[J].Journal of Hazardous Materials,2002,91(1-3):257-270.
[19]LECLERC N,MEUX E,LECUIRE J.Hydrometallurgical extraction of zinc from zinc ferrites[J].Hydrometallurgy,2003,70(1-3):175-183.