ESTUDO CINÉTICO DA LIXIVIAÇÃO DE CALCOPIRITA POR SULFATO FÉRRICO E CLORETO DE SÓDIO
A KINETC STUDY OF CHALCOPYRITE LEACHING BY FERRIC SULPHATE AND SODIUM CHLORIDE
Porcaro, Rodrigo Rangel; Resende, Andréia De-Lazzari Bicalho Peixoto; Leão, Versiane Albis
http://dx.doi.org/10.4322/2176-1523.0855
Tecnol. Metal. Mater. Min., vol.13, n1, p.98-105, 2016
Abstract
O presente trabalho objetivou estudar a cinética de lixiviação de uma amostra de calcopirita por ferro férrico na presença de Ãons cloreto. Foram realizados ensaios de bancada com soluções contendo 0,5mol/L de Fe 3+ (como sulfato férrico), variando-se a temperatura desde 60oC até 90oC, enquanto a concentração de NaCl atingiu 2mol/L. A presença de cloreto foi benéfica ao processo e elevou a extração de cobre de 16,4% na ausência para 29,4% na presença de 1mol/L de NaCl. Os dados experimentais foram ajustados ao modelo do núcleo não reagido para partÃculas de tamanho constante. Observou-se que a cinética de lixiviação era controlada por reação quÃmica na superfÃcie da partÃcula com uma energia de ativação de 55,6kJ/mol. Na presença de Ãon cloreto, os valores da constante de velocidade foram entre 1,5 a 2 vezes mais altas do que no sistema sem NaCl, sendo que a ordem da reação em relação ao Ãon cloreto foi de 0,24.
Keywords
Calcopirita, Cloreto, Energia de ativação, Ordem de reação.
Resumo
This work aimed at investigating the kinetics of chalcopyrite leaching by ferric sulphate in the presence of chloride ions. That was accomplished through batch tests performed with 0.5mol/L Fe 3+ solutions, in which the temperature varied from 60oC to 90oC, whereas the NaCl concentration was increased up to 2mol/L. Chloride ions improved copper extractions, which increased from 16.4% in the absence to 29.4% with 1mol/L NaCl. The experimental data were fitted to the shrinking core model for constant particle size. The leaching kinetics was controlled by chemical reaction on the particle surface with activation energy of 55.6kJ/mol. Chloride ions also increased the reaction rate constant, which was about 1.5 to 2 times that in the absence of chloride and the reaction order was 0.24 with respect to NaCl.
Palavras-chave
Chalcopyrite, Chloride, Activation energy, Reaction order.
Referências
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2 Hackl RP, Dreisinger DB, Peters E, King JA. Passivation of chalcopyrite during oxidative leaching in sulfate media. Hydrometallurgy. 1995;39(1-3):25-48. http://dx.doi.org/10.1016/0304-386X(95)00023-A.
3 Córdoba EM, Muñoz JA, Blázquez ML, González F, Ballester A. Passivation of chalcopyrite during its chemical leaching with ferric ion at 68 °C. Minerals Engineering. 2009;22(3):229-235. http://dx.doi.org/10.1016/j.mineng.2008.07.004.
4 Mateos FB, Pérez IP, Mora FC. The passivation of chalcopyrite subjected to ferric sulfate leaching and its reactivation with metal sulfides. Hydrometallurgy. 1987;19(2):159-167. http://dx.doi.org/10.1016/0304-386X(87)90002-8.
5 Munoz PB, Miller JD, Wadsworth ME. Reaction mechanism for the acid ferric sulfate leaching of chalcopyrite. MTB. 1979;10(2):149-158. http://dx.doi.org/10.1007/BF02652458.
6 Busang K, Poole C. Ferric chloride leaching of copper from chalcopyrite. Leeds: University of Leeds; 2009.
7 Lu ZY, Jeffrey MI, Lawson F. The effect of chloride ions on the dissolution of chalcopyrite in acidic solutions. Hydrometallurgy. 2000;56(2):189-202. http://dx.doi.org/10.1016/S0304-386X(00)00075-X.
8 Carneiro MFC, Leão VA. The role of sodium chloride on surface properties of chalcopyrite leached with ferric sulphate. Hydrometallurgy. 2007;87(3-4):73-82. http://dx.doi.org/10.1016/j.hydromet.2007.01.005.
9 Hirato T, Majima H, Awakura Y. The leaching of chalcopyrite with cupric chloride. Metallurgical Transactions. B, Process Metallurgy. 1987;18(1):31-39. http://dx.doi.org/10.1007/BF02658429.
10 Lu ZY, Jeffrey MI, Lawson F. An electrochemical study of the effect of chloride ions on the dissolution of chalcopyrite in acidic solutions. Hydrometallurgy. 2000;56(2):145-155. http://dx.doi.org/10.1016/S0304-386X(00)00068-2.
11 Dutrisac JE, MacDonald RJC, Ingraham TR. The kinetics of dissolution of synthetic chalcopyrite in aqueous acidic ferric sulfate solutions. Transactions of the Metallurgical Society of AIME. 1969;245:955-959.
12 Hirato T, Kinoshita M, Awakura Y, Majima H. The leaching of chalcopyrite with ferric chloride. MTB. 1986;17(1):19-28. http://dx.doi.org/10.1007/BF02670815.
13 Porcaro RR. Estudos cinéticos de lixiviação de calcopirita [Monografia de final de curso]. Ouro Preto: Universidade Federal de Ouro Preto; 2010.
14 Majima H, Awakura Y, Hirato T, Tanaka T. The leaching of chalcopyrite in ferric chloride and ferric sulfate solutions. Canadian Metallurgical Quarterly. 1985;24(4):283-291. http://dx.doi.org/10.1179/cmq.1985.24.4.283.
15 Gbor PK, Jia CQ. Critical evaluation of coupling particle size distribution with the shrinking core model. Chemical Engineering Science. 2004;59(10):1979-1987. http://dx.doi.org/10.1016/j.ces.2004.01.047.
16 Levenspiel O. Chemical reaction engineering. 1. ed. New York: John Wiley & Sons; 1962.
17 Hiroyoshi N, Kuroiwa S, Miki H, Tsunekawa M, Hirajima T. Synergistic effect of cupric and ferrous ions on active-passive behavior in anodic dissolution of chalcopyrite in sulfuric acid solutions. Hydrometallurgy. 2004;74(1-2):103-116. http://dx.doi.org/10.1016/j.hydromet.2004.01.003.
18 Tshilombo AF, Dixon DG. Kinetic Study of Chalcopyrite Passivation During Electrochemical and Chemical Leaching. In: Doyle FM, Kelsall GH, Woods R, editores. Electrochemistry in mineral and metal. processing. Proceedings of the VI International Symposium; 2003; Pennington, New Jersey; 2003. p. 108-119.
2 Hackl RP, Dreisinger DB, Peters E, King JA. Passivation of chalcopyrite during oxidative leaching in sulfate media. Hydrometallurgy. 1995;39(1-3):25-48. http://dx.doi.org/10.1016/0304-386X(95)00023-A.
3 Córdoba EM, Muñoz JA, Blázquez ML, González F, Ballester A. Passivation of chalcopyrite during its chemical leaching with ferric ion at 68 °C. Minerals Engineering. 2009;22(3):229-235. http://dx.doi.org/10.1016/j.mineng.2008.07.004.
4 Mateos FB, Pérez IP, Mora FC. The passivation of chalcopyrite subjected to ferric sulfate leaching and its reactivation with metal sulfides. Hydrometallurgy. 1987;19(2):159-167. http://dx.doi.org/10.1016/0304-386X(87)90002-8.
5 Munoz PB, Miller JD, Wadsworth ME. Reaction mechanism for the acid ferric sulfate leaching of chalcopyrite. MTB. 1979;10(2):149-158. http://dx.doi.org/10.1007/BF02652458.
6 Busang K, Poole C. Ferric chloride leaching of copper from chalcopyrite. Leeds: University of Leeds; 2009.
7 Lu ZY, Jeffrey MI, Lawson F. The effect of chloride ions on the dissolution of chalcopyrite in acidic solutions. Hydrometallurgy. 2000;56(2):189-202. http://dx.doi.org/10.1016/S0304-386X(00)00075-X.
8 Carneiro MFC, Leão VA. The role of sodium chloride on surface properties of chalcopyrite leached with ferric sulphate. Hydrometallurgy. 2007;87(3-4):73-82. http://dx.doi.org/10.1016/j.hydromet.2007.01.005.
9 Hirato T, Majima H, Awakura Y. The leaching of chalcopyrite with cupric chloride. Metallurgical Transactions. B, Process Metallurgy. 1987;18(1):31-39. http://dx.doi.org/10.1007/BF02658429.
10 Lu ZY, Jeffrey MI, Lawson F. An electrochemical study of the effect of chloride ions on the dissolution of chalcopyrite in acidic solutions. Hydrometallurgy. 2000;56(2):145-155. http://dx.doi.org/10.1016/S0304-386X(00)00068-2.
11 Dutrisac JE, MacDonald RJC, Ingraham TR. The kinetics of dissolution of synthetic chalcopyrite in aqueous acidic ferric sulfate solutions. Transactions of the Metallurgical Society of AIME. 1969;245:955-959.
12 Hirato T, Kinoshita M, Awakura Y, Majima H. The leaching of chalcopyrite with ferric chloride. MTB. 1986;17(1):19-28. http://dx.doi.org/10.1007/BF02670815.
13 Porcaro RR. Estudos cinéticos de lixiviação de calcopirita [Monografia de final de curso]. Ouro Preto: Universidade Federal de Ouro Preto; 2010.
14 Majima H, Awakura Y, Hirato T, Tanaka T. The leaching of chalcopyrite in ferric chloride and ferric sulfate solutions. Canadian Metallurgical Quarterly. 1985;24(4):283-291. http://dx.doi.org/10.1179/cmq.1985.24.4.283.
15 Gbor PK, Jia CQ. Critical evaluation of coupling particle size distribution with the shrinking core model. Chemical Engineering Science. 2004;59(10):1979-1987. http://dx.doi.org/10.1016/j.ces.2004.01.047.
16 Levenspiel O. Chemical reaction engineering. 1. ed. New York: John Wiley & Sons; 1962.
17 Hiroyoshi N, Kuroiwa S, Miki H, Tsunekawa M, Hirajima T. Synergistic effect of cupric and ferrous ions on active-passive behavior in anodic dissolution of chalcopyrite in sulfuric acid solutions. Hydrometallurgy. 2004;74(1-2):103-116. http://dx.doi.org/10.1016/j.hydromet.2004.01.003.
18 Tshilombo AF, Dixon DG. Kinetic Study of Chalcopyrite Passivation During Electrochemical and Chemical Leaching. In: Doyle FM, Kelsall GH, Woods R, editores. Electrochemistry in mineral and metal. processing. Proceedings of the VI International Symposium; 2003; Pennington, New Jersey; 2003. p. 108-119.
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