盐酸在黄铜矿表面吸附机制的第一性原理计算
收稿日期: 2020-06-08
修回日期: 2020-09-03
网络出版日期: 2021-07-27
基金资助
国家自然科学基金资助项目(51774158);云南省中青年学术技术带头人后备人才培养项目(2011CI013)
First-principles calculation of adsorption mechanism of hydrochloric acid on chalcopyrite surface
Received date: 2020-06-08
Revised date: 2020-09-03
Online published: 2021-07-27
李小亮 , 田国才 . 盐酸在黄铜矿表面吸附机制的第一性原理计算[J]. 过程工程学报, 2021 , 21(7) : 836 -846 . DOI: 10.12034/j.issn.1009-606X.220175
The leaching of chalcopyrite has always been the core of copper sulfide hydrometallurgy, but chalcopyrite is a sulfide mineral that is difficult to be oxidized and decomposed. At present, a large number of macroscopic phenomena are obtained by focusing on experimental research, and the mechanism is mostly inferred. However, the lack of information on atomic or molecular level hinders the clear and effective explanation to these macroscopic phenomena. Therefore, it is necessary to study the surface interaction between liquid medium and chalcopyrite and the influence of medium on the formation of surface products by means of atomic or molecular level calculation and analysis, which are of great significance to reveal the reaction mechanism of leaching process and improve or develop a green hydrometallurgical technology of chalcopyrite. As a common leaching agent, hydrochloric acid can be used in the leaching of chalcopyrite, and it has been widely studied because of its advantages of recyclable leaching agent, high solubility of metal ions, good oxidation reduction performance and fast leaching rate. In this work, the adsorption and reaction mechanism of hydrochloric acid on different sites of chalcopyrite surface were studied with first-principles calculation. It was shown that the reconstructed sulfur terminated chalcopyrite (001) surface [labeled as (001)-S surface] led to the formation of disulphide S22-. Hydrochloric acid was adsorbed on the sulfur terminated surface (001)-S of chalcopyrite in the form of dissociation. In the process of leaching, the adsorption of H+ on sulfur terminated surface (001)-S of chalcopyrite destroyed the S22- formed on the surface. The surface structure of chalcopyrite (001)-S was destroyed by adsorption of chloride ion Cl-. During the adsorption process, the chemical reactions between H+ and Cl- with the surface of chalcopyrite produce the FeCl2 and H2S, which were both beneficial to the leaching of chalcopyrite. The results can provide a theoretical basis and guidance for future research.
Key words： chalcopyrite; hydrochloric acid; surface adsorption; first-principles
| 1 | Al-Harahsheh M, Kingman S, Al-Harahsheh A. Ferric chloride leaching of chalcopyrite: synergetic effect of CuCl2 [J]. Hydrometallurgy, 2008, 91(1/2/3/4): 89-97. |
| 2 | Córdoba E M, Mu?oz J A, Blázquez M L, et al. Leaching of chalcopyrite with ferric ion. part I: general aspects [J]. Hydrometallurgy, 2008, 93(3/4): 81-87. |
| 3 | Klauber C. A critical review of the surface chemistry of acidic ferric sulphate dissolution of chalcopyrite with regards to hindered dissolution [J]. International Journal of Mineral Processing, 2008, 86(1/2/3/4): 1-17. |
| 4 | Hiroyoshi N, Miki H, Hirajima T, et al. Enhancement of chalcopyrite leaching by ferrous ions in acidic ferric sulfate solutions [J]. Hydrometallurgy, 2001, 60(3): 185-197. |
| 5 | Acero P, Cama J, Ayora C. Kinetics of chalcopyrite dissolution at pH=3 [J]. European Journal of Mineralogy, 2007, 19(2): 173-182. |
| 6 | Li Y, Yao Y, Wang B, et al. New insights into chalcopyrite leaching enhanced by mechanical activation [J]. Hydrometallurgy, 2019, 189: 105131-105137. |
| 7 | Córdoba E M, Mu?oz J A, Blázquez M L, et al. Leaching of chalcopyrite with ferric ion. part II: effect of redox potential [J]. Hydrometallurgy, 2008, 93(3/4): 88-96. |
| 8 | Hackl R P, Dreisinger D B, Peters E, et al. Passivation of chalcopyrite during oxidative leaching in sulfate media [J]. Hydrometallurgy, 1995, 39(1/2/3): 25-48. |
| 9 | Shin D, Ahn J, Lee J. Kinetic study of copper leaching from chalcopyrite concentrate in alkaline glycine solution [J]. Hydrometallurgy, 2019, 183: 71-78. |
| 10 | Ruiz M C, Montes K S, Padilla R. Chalcopyrite leaching in sulfate-chloride media at ambient pressure [J]. Hydrometallurgy, 2011, 109(1/2): 37-42. |
| 11 | Li J, Kawashima N, Kaplun K, et al. Chalcopyrite leaching: the rate controlling factors [J]. Geochimica et Cosmochimica Acta, 2010, 74(10): 2881-2893. |
| 12 | Hall S R, Stewart J M. The crystal structure refinement of chalcopyrite, CuFeS2 [J]. Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry, 1973, 29(3): 579-585. |
| 13 | Harmer S L, Pratt A R, Nesbitt W H, et al. Sulfur species at chalcopyrite (CuFeS2) fracture surfaces [J]. American Mineralogist, 2004, 89(7): 1026-1032. |
| 14 | Klauber C. Fracture-induced reconstruction of a chalcopyrite (CuFeS2) surface [J]. Surface and Interface Analysis, 2003, 35(5): 415-428. |
| 15 | Harmer S L, Thomas J E, Fornasiero D, et al. The evolution of surface layers formed during chalcopyrite leaching [J]. Geochimica et Cosmochimica Acta, 2006, 70(17): 4392-4402. |
| 16 | Petrovic S J, Bogdanovic G D, Antonijevic M M. Leaching of chalcopyrite with hydrogen peroxide in hydrochloric acid solution [J]. Transactions of Nonferrous Metals Society of China, 2018, 28(7): 1444-1455. |
| 17 | Lu Z Y, Jeffrey M I, Lawson F. An electrochemical study of the effect of chloride ions on the dissolution of chalcopyrite in acidic solutions [J]. Hydrometallurgy, 2000, 56(2): 145-155. |
| 18 | Velásquez-Yévenes L, Nicol M, Miki H. The dissolution of chalcopyrite in chloride solutions: part 1: the effect of solution potential [J]. Hydrometallurgy, 2010, 103(1/2/3/4): 108-113. |
| 19 | Velásquez-Yévenes L, Miki H, Nicol M. The dissolution of chalcopyrite in chloride solutions: part 2: effect of various parameters on the rate [J]. Hydrometallurgy, 2010, 103(1/2/3/4): 80-85. |
| 20 | Nicol M, Miki H, Velásquez-Yévenes L. The dissolution of chalcopyrite in chloride solutions: part 3: mechanisms [J]. Hydrometallurgy, 2010, 103(1/2/3/4): 86-95. |
| 21 | Miki H, Nicol M. The dissolution of chalcopyrite in chloride solutions: part IV: the kinetics of the auto-oxidation of copper (I) [J]. Hydrometallurgy, 2011, 105(3/4): 246-250. |
| 22 | Watling H R. Chalcopyrite hydrometallurgy at atmospheric pressure: review of acidic chloride process options [J]. Hydrometallurgy, 2014, 146: 96-110. |
| 23 | Martínez-Gómez V J, Fuentes-Aceituno J C, Pérez-Garibay R, et al. A study of the electro-assisted reductive leaching of a chalcopyrite concentrate in HCl solutions. part I: kinetic behavior and nature of the chalcopyrite reduction [J]. Hydrometallurgy, 2018, 181: 195-205. |
| 24 | Biegler T. Reduction kinetics of a chalcopyrite electrode surface [J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1977, 85(1): 101-106. |
| 25 | Biegler T, Swift D A. The electrolytic reduction of chalcopyrite in acid solution [J]. Journal of Applied Electrochemistry, 1976, 6(3): 229-235. |
| 26 | Tesinsky M, Balaz P. Copper leaching from chalcopyrite: mechanochemical approach [J]. In?ynieria Mineralna, 2017, 18(1): 1-5. |
| 27 | 陈建华, 王进明, 龙贤灏, 等. 硫化铜矿物电子结构的第一性原理研究 [J] 中南大学学报(自然科学版), 2011, 42(12): 16-21. |
| 27 | Chen J H, Wang J M, Long X H, et al. First-principle theory on electronic structure of copper sulfides [J]. Journal of Central South University (Science and Technology), 2011, 42(12): 16-21. |
| 28 | de Oliveira C, de Lima G F, de Abreu H A, et al. Reconstruction of the chalcopyrite surfaces: a DFT study [J]. The Journal of Physical Chemistry C, 2012, 116(10): 6357-6366. |
| 29 | de Lima G F, de Oliveira C, de Abreu H A, et al. Water adsorption on the reconstructed (001) chalcopyrite surfaces [J]. The Journal of Physical Chemistry C, 2011, 115(21): 10709-10717. |
| 30 | de Lima G F, de Oliveira C, de Abreu H A, et al. Sulfuric and hydrochloric acid adsorption on the reconstructed sulfur terminated (001) chalcopyrite surface [J]. International Journal of Quantum Chemistry, 2012, 112(19): 3216-3222. |
| 31 | Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple [J]. Physical Review Letters, 1996, 77(18): 3865-3868. |
| 32 | de Oliveira C, Duarte H A. Disulphide and metal sulphide formation on the reconstructed (001) surface of chalcopyrite: a DFT study [J]. Applied Surface Science, 2010, 257(4): 1319-1324. |
| 33 | Li K, Zhao Y, Zhang P, et al. Combined DFT and XPS investigation of iodine anions adsorption on the sulfur terminated (001) chalcopyrite surface [J]. Applied Surface Science, 2016, 390: 412-421. |
| 34 | Li Y, Chandra A P, Gerson A R. Scanning photoelectron microscopy studies of freshly fractured chalcopyrite exposed to O2 and H2O [J]. Geochimica et Cosmochimica Acta, 2014, 133: 372-386. |
| 35 | Li Y, Kawashima N, Li J, et al. A review of the structure, and fundamental mechanisms and kinetics of the leaching of chalcopyrite [J]. Advances in Colloid and Interface Science, 2013, 197: 1-3. |
| 36 | Benedek R, Thackeray M M, Low J J, et al. Simulation of aqueous dissolution of lithium manganate spinel from first principles [J]. Journal of Physical Chemistry C, 2012, 116(6): 4050-4059. |
| 37 | Leung K. First-principles modeling of Mn(II) migration above and dissolution from Li x Mn2O4 (001) surfaces [J]. Chemistry of Materials, 2017, 29(6): 2550-2562. |
| 38 | Stack A G, Raiteri P, Gale J D, et al. Accurate rates of the complex mechanisms for growth and dissolution of minerals using a combination of rare-event theories [J]. Journal of the American Chemical Society, 2012, 134(1): 11-14. |
| 39 | Ionescu A, Allouche A, Aycard J P, et al. Study of γ-alumina surface reactivity: adsorption of water and hydrogen sulfide on octahedral aluminum sites [J]. Journal of Physical Chemistry B, 2002, 106(36): 9359-9366. |
| 40 | Lectez S, Roques J, Salanne M, et al. Car-Parrinello molecular dynamics study of the uranyl behaviour at the gibbsite/water interface [J]. Journal of Chemical Physics, 2012, 137(15): 154705-154713. |
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