硫砷铜矿化学浸出动力学研究
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摘要
模拟生物堆浸工艺条件,在硫酸铁酸性介质体系下,进行硫砷铜矿化学浸出动力学实验研究。硫砷铜矿化学性质稳定,在初始Fe3+浓度31 g·L-1,Fe2+浓度0.02 g·L-1,初始p H=1.00±0.05,氧化还原电位恒定在(900±5)m V,30℃条件下浸出96 h,硫砷铜矿的浸出率仅有2.49%。不同电位对硫砷铜矿浸出的影响结果表明,硫砷铜矿的浸出率与电位呈弱正相关,30,45,60,75℃时硫砷铜矿的浸出率与电位的关联指数分别为0.0037,0.0053,0.0062,0.0120。低温下电位对溶解速率影响很小,高温下较显著。研究了温度对硫砷铜矿浸出的影响,氧化还原电位在800 m V时,温度在30~75℃范围,硫砷铜矿硫酸铁酸性化学浸出的表观活化能Ea=57.87 k J·mol-1。实验结果表明,硫酸铁酸性浸出硫砷铜矿符合典型的缩核模型,速率受表面化学反应控制,而非扩散。结合低品位次生硫化铜矿生物堆浸生产实际,为生产实践提出了工艺优化措施。
Simulating the bio-heap leaching,enargite leaching kinetics tests were carried out under the condition of ferric sulfate acid medium. The chemical property of enargite was found to be stable. About 2. 49% of enargite was dissolved after leaching at 30 ℃ for96 h in a solution containing 31 g·L- 1Fe3 +and 0. 02 g·L- 1Fe2 +with p H of 1. 00 ± 0. 05,under the redox potential of( 900 ± 5)m V. The dissolution rate of enargite was weakly dependent on redox potential,with the reaction orders of 0. 0037,0. 0053,0. 0062,0. 0120 respectively at 30,45,60 and 75 ℃. Potential had few effects on the dissolution rate at lower temperature but a significant effect at higher temperature. The effect of temperature was investigated. An apparent activation energy of 57. 87 k J·mol- 1was obtained with Ehof 800 m V in the temperature range of 30 ~ 75 ℃. It indicated that the kinetics of arsenic dissolution were well represented by a shrinking core model for spherical particles,the kinetics of which were controlled by surface reaction,not by diffusion. Based on the bio-heap leaching practice of low-grade secondary copper sulfide,some suggestions were proposed to optimize the process.
Simulating the bio-heap leaching,enargite leaching kinetics tests were carried out under the condition of ferric sulfate acid medium. The chemical property of enargite was found to be stable. About 2. 49% of enargite was dissolved after leaching at 30 ℃ for96 h in a solution containing 31 g·L- 1Fe3 +and 0. 02 g·L- 1Fe2 +with p H of 1. 00 ± 0. 05,under the redox potential of( 900 ± 5)m V. The dissolution rate of enargite was weakly dependent on redox potential,with the reaction orders of 0. 0037,0. 0053,0. 0062,0. 0120 respectively at 30,45,60 and 75 ℃. Potential had few effects on the dissolution rate at lower temperature but a significant effect at higher temperature. The effect of temperature was investigated. An apparent activation energy of 57. 87 k J·mol- 1was obtained with Ehof 800 m V in the temperature range of 30 ~ 75 ℃. It indicated that the kinetics of arsenic dissolution were well represented by a shrinking core model for spherical particles,the kinetics of which were controlled by surface reaction,not by diffusion. Based on the bio-heap leaching practice of low-grade secondary copper sulfide,some suggestions were proposed to optimize the process.
引文
[1]Filippou D,St-Germain P,Grammatikopoulos T.Recovery of metal values from copper-arsenic minerals and other related resources[J].Mineral Processing and Extractive Metallurgy Review,2007,28(4):247.
[2]Da Pelo S,Musu E,Atzei D,Elsener B,Fantauzzi M,Rossi M.Enargite oxidation:a review[J].Earth Science Reviews,2008,86(1-4):62.
[3]Sasaki K,Takatasugi K,Ishikura K,Hirajima T.Spectroscopic study on oxidative dissolution of chalcopyritie,enargite and tennantite at differnt p H values[J].Hydrometallurgy,2010,100(3-4):144.
[4]Elsener B,Atzei D,Fantauzzi M,Rossi A.Electrochemical and XPS surface analytical studies on the reactivity of enargite[J].E.Schweizerbart'sche Verlagsbuchhandlung,2007,19(3):353.
[5]Fantauzzi M,Elsener B,Atzei D,Lattanzi P,Rossi A.The surface of enargite after exposure to acidic ferric solutions:an XPS/XAES study[J].Surface and Interface Analysis,2007,39(12-13):908.
[6]Watling H R.The bioleaching of sulphide minerals with emphasis on copper sulphides—a review[J].Hydrometallurgy,2006,84:81.
[7]Kong W Z,Wu Z L,Liu J Y.Technical progress of enargite leaching technology[J].Nonferrous Metals(Extractive Metallurgy),2014,8:14.(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.)
[8]Sullivan J D.Chemical and physical features of copper leaching[J].Trans.Am.Inst.Min.Metall.,1933,106:514.
[9]Brown D W,Sullivan J D.Dissolution of various copper minerals[R].U.S.Bureau of Mines Report of Investigation,1934.3228.
[10]Koch S,Grasselly G.Data on the oxidation of sulphide ore deposites[J].Acta Univ.Szeged,Sect.Sci.Nat.,1952,6:23.
[11]Ehrlich H L.Bacterial oxidation of arsenopyrite and enargite[J].Economic Geology,1964,59(7):1306.
[12]Dutrizac J E,Mac Donald J R C.The kinetics of dissolution of enargite in acidified ferric sulphate solutions[J].Canadian Metallurgical Quarterly,1972,11(3):469.
[13]Dutrizac J E,Mac Donald J R C.Ferric iron as a leaching medium[J].Mineral Science Engineer,1974,6(2):59.
[14]Da Pelo S.Mineralogical and Geochemical Environment of Active and Abandoned Mining Area[D].Italy:University of Cagliari,1998.152.
[15]Filipek L H,Plumlee G S.The Environmental Geochemistry of Mineral Deposits,Part B:Society of Economic Geologists[M].Colorado:Littleton,Co.,1999.373.
[16]Fantauzzi M,Atzei D,Elsener B,Lattanzi P,Rossi A.XPS and XAES analysis of the chemical state of copper,arsenic and sulphur in natural and synthetic enargite[J].Surface and Interface Analysis,2006,38(5):922.
[17]Herreros O,Quiroz R,Hernandez M C,Vinals J.Dissolution kinetics of enargite in dilute Cl2/Cl-media[J].Hydrometallurgy,2002,64:153.
[18]Padilla R,Giron D,Ruiz M C.Leaching of enargite in H2SO4-Na Cl-O2media[J].Hydrometallurgy,2005,80:272.
[19]Gupta M Z.An Investigation into the Leaching of Enargite under Atmospheric Conditions[D].Kingston:Queen's University,2010.85.
[20]Csicsovszki G,Gupta M,Peacey J.An investigation into the leaching of enargite under atmospheric conditions[A].Hydro Copper 2011[C].Chile:6th International Seminar on Copper Hydrometallurgy,2011.2.
[21]Li H G.Metallurgical Principle[M].Beijing:Science Press,2005.308.(李洪桂.冶金原理[M].北京:科学出版社,2005.308.)
[22]Zhong S P,Wu Z,Huang Z S,Ruan R M.Oxidation kinetics reaction of gold-bearing pyrite in sulphuric acid[J].Chinese Journal of Rare Metals,2013,37(2):295.(衷水平,吴智,黄中省,阮仁满.硫酸介质中载金黄铁矿的氧化动力学[J].稀有金属,2013,37(2):295.)
[23]Ruan R M,Zou G,Zhong S P,Wu Z L,Chan Brenda,Wang D Z.Why Zijinshan copper bioheapleaching plant works efficiently at low microbial activity-study on leaching kinetics of copper sulfides and its implications[J].Minerals Engineering,2013,48(4):36.
[24]Rivera-Vasquez B F.Electrochemical and Leaching Studies of Enargite and Chalcopyrite[D].Columbia:University of British,2011.65.
[2]Da Pelo S,Musu E,Atzei D,Elsener B,Fantauzzi M,Rossi M.Enargite oxidation:a review[J].Earth Science Reviews,2008,86(1-4):62.
[3]Sasaki K,Takatasugi K,Ishikura K,Hirajima T.Spectroscopic study on oxidative dissolution of chalcopyritie,enargite and tennantite at differnt p H values[J].Hydrometallurgy,2010,100(3-4):144.
[4]Elsener B,Atzei D,Fantauzzi M,Rossi A.Electrochemical and XPS surface analytical studies on the reactivity of enargite[J].E.Schweizerbart'sche Verlagsbuchhandlung,2007,19(3):353.
[5]Fantauzzi M,Elsener B,Atzei D,Lattanzi P,Rossi A.The surface of enargite after exposure to acidic ferric solutions:an XPS/XAES study[J].Surface and Interface Analysis,2007,39(12-13):908.
[6]Watling H R.The bioleaching of sulphide minerals with emphasis on copper sulphides—a review[J].Hydrometallurgy,2006,84:81.
[7]Kong W Z,Wu Z L,Liu J Y.Technical progress of enargite leaching technology[J].Nonferrous Metals(Extractive Metallurgy),2014,8:14.(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.)
[8]Sullivan J D.Chemical and physical features of copper leaching[J].Trans.Am.Inst.Min.Metall.,1933,106:514.
[9]Brown D W,Sullivan J D.Dissolution of various copper minerals[R].U.S.Bureau of Mines Report of Investigation,1934.3228.
[10]Koch S,Grasselly G.Data on the oxidation of sulphide ore deposites[J].Acta Univ.Szeged,Sect.Sci.Nat.,1952,6:23.
[11]Ehrlich H L.Bacterial oxidation of arsenopyrite and enargite[J].Economic Geology,1964,59(7):1306.
[12]Dutrizac J E,Mac Donald J R C.The kinetics of dissolution of enargite in acidified ferric sulphate solutions[J].Canadian Metallurgical Quarterly,1972,11(3):469.
[13]Dutrizac J E,Mac Donald J R C.Ferric iron as a leaching medium[J].Mineral Science Engineer,1974,6(2):59.
[14]Da Pelo S.Mineralogical and Geochemical Environment of Active and Abandoned Mining Area[D].Italy:University of Cagliari,1998.152.
[15]Filipek L H,Plumlee G S.The Environmental Geochemistry of Mineral Deposits,Part B:Society of Economic Geologists[M].Colorado:Littleton,Co.,1999.373.
[16]Fantauzzi M,Atzei D,Elsener B,Lattanzi P,Rossi A.XPS and XAES analysis of the chemical state of copper,arsenic and sulphur in natural and synthetic enargite[J].Surface and Interface Analysis,2006,38(5):922.
[17]Herreros O,Quiroz R,Hernandez M C,Vinals J.Dissolution kinetics of enargite in dilute Cl2/Cl-media[J].Hydrometallurgy,2002,64:153.
[18]Padilla R,Giron D,Ruiz M C.Leaching of enargite in H2SO4-Na Cl-O2media[J].Hydrometallurgy,2005,80:272.
[19]Gupta M Z.An Investigation into the Leaching of Enargite under Atmospheric Conditions[D].Kingston:Queen's University,2010.85.
[20]Csicsovszki G,Gupta M,Peacey J.An investigation into the leaching of enargite under atmospheric conditions[A].Hydro Copper 2011[C].Chile:6th International Seminar on Copper Hydrometallurgy,2011.2.
[21]Li H G.Metallurgical Principle[M].Beijing:Science Press,2005.308.(李洪桂.冶金原理[M].北京:科学出版社,2005.308.)
[22]Zhong S P,Wu Z,Huang Z S,Ruan R M.Oxidation kinetics reaction of gold-bearing pyrite in sulphuric acid[J].Chinese Journal of Rare Metals,2013,37(2):295.(衷水平,吴智,黄中省,阮仁满.硫酸介质中载金黄铁矿的氧化动力学[J].稀有金属,2013,37(2):295.)
[23]Ruan R M,Zou G,Zhong S P,Wu Z L,Chan Brenda,Wang D Z.Why Zijinshan copper bioheapleaching plant works efficiently at low microbial activity-study on leaching kinetics of copper sulfides and its implications[J].Minerals Engineering,2013,48(4):36.
[24]Rivera-Vasquez B F.Electrochemical and Leaching Studies of Enargite and Chalcopyrite[D].Columbia:University of British,2011.65.