CaCO_3存在下高铁硫化锌矿氧化焙烧的相变机理
|
摘要
针对目前湿法炼锌工艺处理高铁硫化锌矿存在浸出率偏低的缺点,提出添加一定量CaCO_3的方式预先氧化焙烧矿样,使ZnS矿相转变为易于浸出的ZnO。结果表明,当高铁硫化锌矿中未添加CaCO_3时,矿石中的ZnS在700℃和1h的焙烧条件下不能被完全氧化为ZnO,焙烧产物中有难以浸出的ZnFe_2O_4生成;当添加一定量的CaCO_3(Ca∶S=1∶1)时,矿石中的ZnS在相同焙烧条件下可以完全氧化为易浸出的ZnO。在焙烧产物中未检测到ZnFe_2O_4,但发现有Ca_2Fe_2O_5生成,同时添加的CaCO_3在氧化焙烧过程中会转化成CaSO_4。因此,高铁硫化锌矿中加入适量的CaCO_3,既能促进闪锌矿(ZnS)和黄铁矿(FeS2)在氧化焙烧过程中的物相转变,又能通过形成Ca2Fe_2O_5来抑制ZnFe_2O_4的生成,并通过形成CaSO_4来固硫,且实验结果与热力学分析相吻合。
In view of the shortcomings of the low leaching rate of high-iron zinc sulfide ore in the hydrometallurgical zinc smelting process,a method of pre-oxidizing roasting ore samples by adding a certain amount of CaCO_3 to transform the ZnS ore into ZnO which is easy to leach is put forward.The results show that when the CaCO_3 is not added to the high-iron zinc sulfide ore,the ZnS in the ore cannot be completely oxidized to ZnO at 700℃ and 1 h,and ZnFe_2O_4 difficult to be leached is produced in the roasted products.When the CaCO_3 is added with Ca∶S=1∶1,the ZnS in the ore can be completely oxidized to easily leached ZnO under the same conditions,and Ca_2Fe_2O_5 is found,but ZnFe_2O_4 is not detected in the roasted products.At the same time,the added CaCO_3 is converted into CaSO_4 during the process of oxidation roasting.Therefore,the addition of a proper amount of CaCO_3 in the high-iron zinc sulfide ore can not only promote the phase transformation of sphalerite(ZnS)and pyrite(FeS_2)in the oxidative roasting process,but also inhibit the production of ZnFe_2O_4 by forming Ca_2Fe_2O_5,and sulfur is fixed by forming CaSO_4.The experimental results are in good agreement with the thermodynamic analysis.
In view of the shortcomings of the low leaching rate of high-iron zinc sulfide ore in the hydrometallurgical zinc smelting process,a method of pre-oxidizing roasting ore samples by adding a certain amount of CaCO_3 to transform the ZnS ore into ZnO which is easy to leach is put forward.The results show that when the CaCO_3 is not added to the high-iron zinc sulfide ore,the ZnS in the ore cannot be completely oxidized to ZnO at 700℃ and 1 h,and ZnFe_2O_4 difficult to be leached is produced in the roasted products.When the CaCO_3 is added with Ca∶S=1∶1,the ZnS in the ore can be completely oxidized to easily leached ZnO under the same conditions,and Ca_2Fe_2O_5 is found,but ZnFe_2O_4 is not detected in the roasted products.At the same time,the added CaCO_3 is converted into CaSO_4 during the process of oxidation roasting.Therefore,the addition of a proper amount of CaCO_3 in the high-iron zinc sulfide ore can not only promote the phase transformation of sphalerite(ZnS)and pyrite(FeS_2)in the oxidative roasting process,but also inhibit the production of ZnFe_2O_4 by forming Ca_2Fe_2O_5,and sulfur is fixed by forming CaSO_4.The experimental results are in good agreement with the thermodynamic analysis.
引文
[1]奚甡.世界铅锌资源开发现状及其利用[J].中国金属通报,2009(37):32-33.XI Sheng.Development and utilization of lead and zinc resources in the world[J].China Metal Bulletin,2009(37):32-33.
[2]刘晓,张宇,王楠,等.我国铅锌矿资源现状及其发展对策研究[J].中国矿业,2015(增刊1):6-9.LIU Xiao,ZHANG Yu,WANG Nan,et al.Pb-Zn metal resources situation and suggestion for Pb-Zn metals industry devolopment[J].China Mining Magazine,2015(s1):6-9.
[3]杨荣林.浅析我国铅锌矿资源开发现状及可持续发展建议[J].世界有色金属,2018(1):148-150.YANG Ronglin.Analysis of current situation of lead and zinc mine resources development and suggestions for sustainable dvelopment in China[J].World Nonferrous Metal,2018(1):148-150.
[4]ZHANG Y,HUA Y,GAO X,et al.Recovery of zinc from a low-grade zinc oxide ore with high silicon by sulfuric acid curing and water leaching[J].Hydrometallurgy,2016,166:16-21.
[5]HAJATI A,KHODADADI A,KOLEINI S M.Flotation of zinc oxide minerals from lowgrade tailings by oxine and dithizone using the taguchi approach[J].Minerals&Metallurgical Processing,2010,27(3):158-165.
[6]张玉梅.氧化锌矿氨性强化浸出新方法的研究[D].长沙:中南大学,2009:13-14.ZHANG Yumei.Study on a new method for enhanced leaching of zinc oxide ore ammonia[D].Changsha:Central South University,2009:13-14.
[7]WEI Z C,FANG J J,LIU D W,et al.Leaching kinetics of low-grade zinc oxide ores in NH3-NH4HCO3-H2Osystem[J].Journal of Kunming University of Science&Technology,2012,37(1):11-15.
[8]陈爱良,赵中伟,贾希俊,等.氧化锌矿综合利用现状与展望[J].矿冶工程,2008,28(6):62-66.CHEN Ailiang,ZHAO Zhongwei,JIA Xijun,et al.Comprehensive utilization status and expectation of zinc oxide ores[J].Mining and Metallurgical Engineering,2008,28(6):62-66.
[9]魏志聪,刘洋,张文彬.我国氧化锌矿直接浸出提锌技术研究现状及进展[J].矿业研究与开发,2011(1):40-42.WEI Zhicong,LIU Yang,ZHANG Wenbin,et al.Current status and progress of direct leaching technology of zinc oxide ore in china[J].Mining Research and Development,2011(1):40-42.
[10]LI C,WEI C,XU H S,et al.Oxidative pressure leaching of sphalerite concentrate with high indium and iron content in sulfuric acid medium[J].Hydrometallurgy,2010,102(1):91-94.
[11]FILIPPOU D.Innovative hydrometallurgical processes for the primary processing of zinc[J].Mineral Processing and Extractive Metallurgy Review,2004,25(3):205-252.
[12]COLLINS M J,MASTERS I M,OZBERK E,et al.Deportment of selected minor elements at the HBMS zinc pressure leach plant[J].Cim Bulletin,1995,88(986):62-67.
[13]丁治英.氧化锌矿物在氨性溶液中的溶解行为研究[D].长沙:中南大学,2011:9-10.DING Zhiying.Study on dissolution behavior of zinc oxide minerals in ammonia solution[D].Changsha:Central South University,2011:9-10.
[14]YIN Z,DING Z,HU H,et al.Dissolution of zinc silicate(hemimorphite)with ammonia-ammonium chloride solution[J].Hydrometallurgy,2010,103(1):215-220.
[15]凌江华,尹周澜,胡慧萍,等.兰坪低品位氧化锌矿NH3-(NH4)2SO4体系浸出[J].中南大学学报(自然科学版),2011,42(9):2577-2583.LING Jianghua,YI Zhoulan,HU Huiping,et al.Leaching process of low grade zinc oxide ore of lanping in NH3-(NH4)2SO4 system[J].Journal of Central South University:Science and Technology,2011,42(9):2577-2583.
[16]高小兵,华一新,王运,等.高钙低品位硫氧混合锌矿氧化焙烧矿相的转变规律[J].过程工程学报,2017(5):1047-1053.GAO Xiaobing,HUA Yixin,WANG Yun,et al.Mineral phase transformation during oxidation roasting of low-grade sulfide and oxide mixed zinc ore with high calcium[J].The Chinese Journal of Process Engineering,2017(5):1047-1053.
[17]GAN M,FAN X H,CHEN X L,et al.Reaction mechanisms of low-grade molybdenum concentrate during calcification roasting process[J].Transactions of Nonferrous Metals Society of China,2016,26(11):3015-3023.
[18]ZHOU Q S,YUN W T,JUN X I,et al.Molybdenitelimestone oxidizing roasting followed by calcine leaching with ammonium carbonate solution[J].Transactions of Nonferrous Metals Society of China,2017,27(7):1618-1626.
[2]刘晓,张宇,王楠,等.我国铅锌矿资源现状及其发展对策研究[J].中国矿业,2015(增刊1):6-9.LIU Xiao,ZHANG Yu,WANG Nan,et al.Pb-Zn metal resources situation and suggestion for Pb-Zn metals industry devolopment[J].China Mining Magazine,2015(s1):6-9.
[3]杨荣林.浅析我国铅锌矿资源开发现状及可持续发展建议[J].世界有色金属,2018(1):148-150.YANG Ronglin.Analysis of current situation of lead and zinc mine resources development and suggestions for sustainable dvelopment in China[J].World Nonferrous Metal,2018(1):148-150.
[4]ZHANG Y,HUA Y,GAO X,et al.Recovery of zinc from a low-grade zinc oxide ore with high silicon by sulfuric acid curing and water leaching[J].Hydrometallurgy,2016,166:16-21.
[5]HAJATI A,KHODADADI A,KOLEINI S M.Flotation of zinc oxide minerals from lowgrade tailings by oxine and dithizone using the taguchi approach[J].Minerals&Metallurgical Processing,2010,27(3):158-165.
[6]张玉梅.氧化锌矿氨性强化浸出新方法的研究[D].长沙:中南大学,2009:13-14.ZHANG Yumei.Study on a new method for enhanced leaching of zinc oxide ore ammonia[D].Changsha:Central South University,2009:13-14.
[7]WEI Z C,FANG J J,LIU D W,et al.Leaching kinetics of low-grade zinc oxide ores in NH3-NH4HCO3-H2Osystem[J].Journal of Kunming University of Science&Technology,2012,37(1):11-15.
[8]陈爱良,赵中伟,贾希俊,等.氧化锌矿综合利用现状与展望[J].矿冶工程,2008,28(6):62-66.CHEN Ailiang,ZHAO Zhongwei,JIA Xijun,et al.Comprehensive utilization status and expectation of zinc oxide ores[J].Mining and Metallurgical Engineering,2008,28(6):62-66.
[9]魏志聪,刘洋,张文彬.我国氧化锌矿直接浸出提锌技术研究现状及进展[J].矿业研究与开发,2011(1):40-42.WEI Zhicong,LIU Yang,ZHANG Wenbin,et al.Current status and progress of direct leaching technology of zinc oxide ore in china[J].Mining Research and Development,2011(1):40-42.
[10]LI C,WEI C,XU H S,et al.Oxidative pressure leaching of sphalerite concentrate with high indium and iron content in sulfuric acid medium[J].Hydrometallurgy,2010,102(1):91-94.
[11]FILIPPOU D.Innovative hydrometallurgical processes for the primary processing of zinc[J].Mineral Processing and Extractive Metallurgy Review,2004,25(3):205-252.
[12]COLLINS M J,MASTERS I M,OZBERK E,et al.Deportment of selected minor elements at the HBMS zinc pressure leach plant[J].Cim Bulletin,1995,88(986):62-67.
[13]丁治英.氧化锌矿物在氨性溶液中的溶解行为研究[D].长沙:中南大学,2011:9-10.DING Zhiying.Study on dissolution behavior of zinc oxide minerals in ammonia solution[D].Changsha:Central South University,2011:9-10.
[14]YIN Z,DING Z,HU H,et al.Dissolution of zinc silicate(hemimorphite)with ammonia-ammonium chloride solution[J].Hydrometallurgy,2010,103(1):215-220.
[15]凌江华,尹周澜,胡慧萍,等.兰坪低品位氧化锌矿NH3-(NH4)2SO4体系浸出[J].中南大学学报(自然科学版),2011,42(9):2577-2583.LING Jianghua,YI Zhoulan,HU Huiping,et al.Leaching process of low grade zinc oxide ore of lanping in NH3-(NH4)2SO4 system[J].Journal of Central South University:Science and Technology,2011,42(9):2577-2583.
[16]高小兵,华一新,王运,等.高钙低品位硫氧混合锌矿氧化焙烧矿相的转变规律[J].过程工程学报,2017(5):1047-1053.GAO Xiaobing,HUA Yixin,WANG Yun,et al.Mineral phase transformation during oxidation roasting of low-grade sulfide and oxide mixed zinc ore with high calcium[J].The Chinese Journal of Process Engineering,2017(5):1047-1053.
[17]GAN M,FAN X H,CHEN X L,et al.Reaction mechanisms of low-grade molybdenum concentrate during calcification roasting process[J].Transactions of Nonferrous Metals Society of China,2016,26(11):3015-3023.
[18]ZHOU Q S,YUN W T,JUN X I,et al.Molybdenitelimestone oxidizing roasting followed by calcine leaching with ammonium carbonate solution[J].Transactions of Nonferrous Metals Society of China,2017,27(7):1618-1626.