黄铁矿对硫砷铜矿化学浸出的促进作用
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摘要
为了考查黄铁矿对硫砷铜矿浸出的影响,在添加黄铁矿、常压化学浸出条件下研究硫砷铜矿的浸出动力学和电化学。采用自制浸出装置在H_2SO_4-Fe_2(SO_4)_3体系中开展混合矿物化学浸出实验。结果表明:添加黄铁矿后硫砷铜矿的表观活化能降低至48.15kJ/mol;随着黄铁矿加入比例的升高,硫砷铜矿的浸出率逐渐提高,当硫砷铜矿与黄铁矿质量比为1:6时,12天硫砷铜矿的浸出率可达23.6%。通过XPS分析了混合矿物表面化学浸出前后硫和砷形态的变化,加入黄铁矿后促进砷转化为五价砷,降低毒性。电化学工作站测定硫砷铜矿的静止电位为0.48 V,无菌条件下的电化学行为解释了黄铁矿和硫砷铜矿混合化学浸出时形成原电池,促进了硫砷铜矿的溶解。
In order to investigate the effect of pyrite on enargite leaching,the leaching kinetic and electrochemistry of enargite and pyrite mixture by chemical leaching under the condition of atmospheric pressure were studied.Leaching experiments of enargite and pyrite mixture in H_2SO_4-Fe_2(SO_4)_3 system were investigated by leaching experimental device.The results show that the activation energy of enargite is decreased to 48.15 kJ/mol,while enargite leaching is increased by the addition of pyrite.Enargite leaching is increased dramatically up to 25% after 12 days with the proportion of enargite to pyrite equaled to 1:6.The morphological changes of sulfur and arsenic of mixture before and after leaching were demonstrated by XPS.Arsenic is promoted to transfer to pentavalent arsenic,which means less toxic.The rest potential of enargite is detected to 0.48 V by the electrochemical workstation.Electrochemical behavior explains the galvanic effect of chemical leaching of enargite and pyrite mixture,which promotes the dissolution of enargite.
In order to investigate the effect of pyrite on enargite leaching,the leaching kinetic and electrochemistry of enargite and pyrite mixture by chemical leaching under the condition of atmospheric pressure were studied.Leaching experiments of enargite and pyrite mixture in H_2SO_4-Fe_2(SO_4)_3 system were investigated by leaching experimental device.The results show that the activation energy of enargite is decreased to 48.15 kJ/mol,while enargite leaching is increased by the addition of pyrite.Enargite leaching is increased dramatically up to 25% after 12 days with the proportion of enargite to pyrite equaled to 1:6.The morphological changes of sulfur and arsenic of mixture before and after leaching were demonstrated by XPS.Arsenic is promoted to transfer to pentavalent arsenic,which means less toxic.The rest potential of enargite is detected to 0.48 V by the electrochemical workstation.Electrochemical behavior explains the galvanic effect of chemical leaching of enargite and pyrite mixture,which promotes the dissolution of enargite.
引文
[1]伍赠玲,吴智,朱永官.硫砷铜矿化学浸出动力学研究[J].稀有金属,2015,39(8):734-739.WU Zeng-ling,WU Zhi,ZHU Yong-guan.Kinetics of enargite chemical leaching[J].Chinese Journal of Rare Metals,2015,39(8):734-739.
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[3]范道焱,庄荣传,陈水波.硫砷铜矿热压浸出研究现状及进展[J].黄金,2016,37(6):64-67.FAN Dao-yan,ZHUANG Rong-chuan,CHEN Shui-bo.Current situation and progress of the pressure oxidation of enargites[J].Gold,2016,37(6):64-67.
[4]孔维长,伍赠玲,刘金艳.硫砷铜矿浸出技术进展[J].有色金属(冶炼部分),2014,8:14-17.KONG Wei-zhang,WU Zeng-ling,LIU Jin-yan.Technical progress of enargite leaching technology[J].Nonferrous Metals(Extractive Metallurgy),2014,8:14-17.
[5]SAFARZADEH M S,MOATS M S,MILLER J D.Recent trends in the processing of enargite concentrates[J].Mineral Processing and Extractive Metallurgy Review,2014,35(5):283-367.
[6]SAFARZADEH M S,MOATS M S,MILLER J D.An update to“Recent trends in the processing of enargite concentrates”[J].Mineral Processing and Extractive Metallurgy Review,2014b,35(5):390-422.
[7]PADILLA R,ARACENA A,RUIZ M C.Reaction mechanism and kinetics of enargite oxidation at roasting temperatures[J].Metallurgical and Materials Transactions B,2012,43B(5):1119-1126.
[8]RUIZ M C,VERA M V,PADILLA R.Mechanism of enargite pressure leaching in the presence of pyrite[J].Hydrometallurgy,2011,105:290-295.
[9]CANALES C F,ACEVEDO J C.GENTINA.Laboratory-scale continuous bio-oxidation of a gold concentrate of high pyrite and enargite content[J].Process Biochemistry,2002,37:1051-1055.
[10]CORKHILL C L,WINCOTT P L,LLOYD J R,VAUGHAN D J.The oxidative Dissolution of arsenopyrite and enargite by Leptospirillum ferooxidans[J].Geochimica et Cosmochimica Acta,2008,72:5616-5633.
[11]LEE J,ACAR S,DOERR D L,BRIERLEY J A.Comparative bioleaching and mineralogy of composited sulfide ores containing enatgite,covellite and chalcocite by mesophilic and thermophilic microorganisms[J].Hydrometallurgy,2011,105:213-221.
[12]PLACKOWSKI C,HAMPTON M A,BRUCKARD W J,NGUYEN A V.An XPS investigation of surface species formed by electrochemically induced surface oxidation of enargite in the oxidative potential range[J].Mineral Engineering,2014,55:60-74.
[13]RIVERA-VASQUEZ B F,DIXON D.Rapid atmospheric leaching of enargite in ferric sulfate media[J].Proceedings of the V International Copper Hydrometallurgy Workshop,Antofagasta,Chile,2009:194-204.
[14]GU Guo-hua,SUN Xiao-jun,HU Ke-ting,LI Jian-hua,QIUGuan-zhou.Electrochemical oxidation behavior of pyrite bioleaching by Acidthiobacillus ferrooxidans[J].Transaction of Nonferrous Metals Society of China,2012,22(5):1250-1254.
[15]LIU Hong-chang,XIA Jin-lan,NIE Zhen-yuan,MA Ya-long,MA Chen-yan,ZHENG Lei,HONG Cai-hao,ZHAO Yi-dong.Iron L-edge and sulfur K-edge XANES spectroscopy analysis of pyrite leached by Acidianus manzaensis[J].Transaction of Nonferrous Metals Society of China,2015,25(7):2407-2414.
[16]马骏,汪菊香,武彪,温建康,尚鹤,武名麟.晶体结构对黄铜矿、黄铁矿生物浸出差异性影响[J].中国有色金属学报,2015,25(10):2898-2904.MA Jun,WANG Ju-xiang,WU Biao,WEN Jian-kang,SHANGHe,WU Ming-lin.Effects of crystal structure on differences of chalcopyrite and pyrite bioleaching[J].The Chinese Journal of Nonferrous Metals,2015,25(10):2898-2904.
[17]方芳,钟宏,江放明,罗忠银,孙晓伟,许凯扬.黄铁矿对砷黄铁矿生物浸出的影响[J].中国有色金属学报,2013,23(10):2970-2976.FANG Fang,ZHONG Hong,JIANG Fang-ming,LUOZhong-yin,SUN Xiao-wei,XU Kai-yang.Effect of pyrite on bioleaching of arsenopyrite[J].The Chinese Journal of Nonferrous Metals,2013,23(10):2970-2976.
[18]刘伟,杨洪英,佟琳琳,刘媛媛.活性炭对含钴矿物生物浸出的催化作用[J].中国有色金属学报,2014,14(4):1050-1055.LIU Wei,YANG Hong-ying,TONG Lin-lin,LIU Yuan-yuan.Catalytic effect of activated carbon on bioleaching of cobalt mineral[J].The Chinese Journal of Nonferrous Metals,2014,14(4):1050-1055.
[19]李宏煦,邱冠周,胡岳华,王淀佐.原电池效应对混合硫化矿细菌浸出的影响[J].中国有色金属学报,2003,13(5):1283-1287.LI Hong-xu,QIU Guan-zhou,HU Yue-hua,WANG Dian-zuo.Galvanic effect on mixed sulfide bioleaching[J].The Chinese Journal of Nonferrous Metals,2003,13(5):1283-1287.
[20]ZHONG Shui-ping.Leaching kinetics of gold bearing pyrite in H2SO4-Fe2(SO4)3 system[J].Transactions of Nonferrous Metals Society of China,2015,25:3461-3466.
[2]LATTANZI P,DA PELO S,MUSU E,ATZE,D,ELSENER B,FANTAUZZI M,ROSSI A.Enargite oxidation:A review[J].Earth Science Reviews,2008,86:62-88.
[3]范道焱,庄荣传,陈水波.硫砷铜矿热压浸出研究现状及进展[J].黄金,2016,37(6):64-67.FAN Dao-yan,ZHUANG Rong-chuan,CHEN Shui-bo.Current situation and progress of the pressure oxidation of enargites[J].Gold,2016,37(6):64-67.
[4]孔维长,伍赠玲,刘金艳.硫砷铜矿浸出技术进展[J].有色金属(冶炼部分),2014,8:14-17.KONG Wei-zhang,WU Zeng-ling,LIU Jin-yan.Technical progress of enargite leaching technology[J].Nonferrous Metals(Extractive Metallurgy),2014,8:14-17.
[5]SAFARZADEH M S,MOATS M S,MILLER J D.Recent trends in the processing of enargite concentrates[J].Mineral Processing and Extractive Metallurgy Review,2014,35(5):283-367.
[6]SAFARZADEH M S,MOATS M S,MILLER J D.An update to“Recent trends in the processing of enargite concentrates”[J].Mineral Processing and Extractive Metallurgy Review,2014b,35(5):390-422.
[7]PADILLA R,ARACENA A,RUIZ M C.Reaction mechanism and kinetics of enargite oxidation at roasting temperatures[J].Metallurgical and Materials Transactions B,2012,43B(5):1119-1126.
[8]RUIZ M C,VERA M V,PADILLA R.Mechanism of enargite pressure leaching in the presence of pyrite[J].Hydrometallurgy,2011,105:290-295.
[9]CANALES C F,ACEVEDO J C.GENTINA.Laboratory-scale continuous bio-oxidation of a gold concentrate of high pyrite and enargite content[J].Process Biochemistry,2002,37:1051-1055.
[10]CORKHILL C L,WINCOTT P L,LLOYD J R,VAUGHAN D J.The oxidative Dissolution of arsenopyrite and enargite by Leptospirillum ferooxidans[J].Geochimica et Cosmochimica Acta,2008,72:5616-5633.
[11]LEE J,ACAR S,DOERR D L,BRIERLEY J A.Comparative bioleaching and mineralogy of composited sulfide ores containing enatgite,covellite and chalcocite by mesophilic and thermophilic microorganisms[J].Hydrometallurgy,2011,105:213-221.
[12]PLACKOWSKI C,HAMPTON M A,BRUCKARD W J,NGUYEN A V.An XPS investigation of surface species formed by electrochemically induced surface oxidation of enargite in the oxidative potential range[J].Mineral Engineering,2014,55:60-74.
[13]RIVERA-VASQUEZ B F,DIXON D.Rapid atmospheric leaching of enargite in ferric sulfate media[J].Proceedings of the V International Copper Hydrometallurgy Workshop,Antofagasta,Chile,2009:194-204.
[14]GU Guo-hua,SUN Xiao-jun,HU Ke-ting,LI Jian-hua,QIUGuan-zhou.Electrochemical oxidation behavior of pyrite bioleaching by Acidthiobacillus ferrooxidans[J].Transaction of Nonferrous Metals Society of China,2012,22(5):1250-1254.
[15]LIU Hong-chang,XIA Jin-lan,NIE Zhen-yuan,MA Ya-long,MA Chen-yan,ZHENG Lei,HONG Cai-hao,ZHAO Yi-dong.Iron L-edge and sulfur K-edge XANES spectroscopy analysis of pyrite leached by Acidianus manzaensis[J].Transaction of Nonferrous Metals Society of China,2015,25(7):2407-2414.
[16]马骏,汪菊香,武彪,温建康,尚鹤,武名麟.晶体结构对黄铜矿、黄铁矿生物浸出差异性影响[J].中国有色金属学报,2015,25(10):2898-2904.MA Jun,WANG Ju-xiang,WU Biao,WEN Jian-kang,SHANGHe,WU Ming-lin.Effects of crystal structure on differences of chalcopyrite and pyrite bioleaching[J].The Chinese Journal of Nonferrous Metals,2015,25(10):2898-2904.
[17]方芳,钟宏,江放明,罗忠银,孙晓伟,许凯扬.黄铁矿对砷黄铁矿生物浸出的影响[J].中国有色金属学报,2013,23(10):2970-2976.FANG Fang,ZHONG Hong,JIANG Fang-ming,LUOZhong-yin,SUN Xiao-wei,XU Kai-yang.Effect of pyrite on bioleaching of arsenopyrite[J].The Chinese Journal of Nonferrous Metals,2013,23(10):2970-2976.
[18]刘伟,杨洪英,佟琳琳,刘媛媛.活性炭对含钴矿物生物浸出的催化作用[J].中国有色金属学报,2014,14(4):1050-1055.LIU Wei,YANG Hong-ying,TONG Lin-lin,LIU Yuan-yuan.Catalytic effect of activated carbon on bioleaching of cobalt mineral[J].The Chinese Journal of Nonferrous Metals,2014,14(4):1050-1055.
[19]李宏煦,邱冠周,胡岳华,王淀佐.原电池效应对混合硫化矿细菌浸出的影响[J].中国有色金属学报,2003,13(5):1283-1287.LI Hong-xu,QIU Guan-zhou,HU Yue-hua,WANG Dian-zuo.Galvanic effect on mixed sulfide bioleaching[J].The Chinese Journal of Nonferrous Metals,2003,13(5):1283-1287.
[20]ZHONG Shui-ping.Leaching kinetics of gold bearing pyrite in H2SO4-Fe2(SO4)3 system[J].Transactions of Nonferrous Metals Society of China,2015,25:3461-3466.
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