Surface Enrichment in Malachite Sulfurization Flotation: Adsorption Mechanisms and Performance Optimization | ||
| Journal of Mining and Environment | ||
| مقاله 3، دوره 16، شماره 6، آذر و دی 2025، صفحه 1881-1895 اصل مقاله (1.89 M) | ||
| نوع مقاله: Original Research Paper | ||
| شناسه دیجیتال (DOI): 10.22044/jme.2025.16134.3115 | ||
| نویسندگان | ||
| Ayman M. Ibrahim1، 2، 3؛ Han Wang* 1؛ Nazar Mekawi3؛ Jaber A. Yousif4؛ Emadeldin Adam5؛ Alfarouq Alnoor5؛ Mohammed Kabashi5؛ Dianwen Liu1 | ||
| 1State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Yunnan Key Laboratory of Green Separation and Enrichment of Strategic Metal Resources, Faculty of Land Resources Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, PR China | ||
| 2Department of Mining Engineering, Faculty of Engineering Science, University of Nyala, Nyala 63311, PR Sudan | ||
| 3Department of Mining Engineering, Faculty of Engineering, University of Khartoum, Khartoum 11115, PR Sudan | ||
| 4Department of Mining Engineering, Faculty of Engineering, Eldaein University, Eldaein 63312, PR Sudan | ||
| 5Department of Mining Engineering, Faculty of Engineering Science, Omdurman Islamic University, 14411, Khartoum, PR Sudan | ||
| چکیده | ||
| This work investigates the surface enrichment of malachite during sulfurization flotation to enhance copper recovery. The goal is to improve flotation efficiency by modifying malachite’s surface properties through sulfurization, using sodium sulfide as the sulfurizing agent. The effects of pre-treatment reagents on flotation recovery were evaluated, focusing on their impact on the surface chemistry of malachite. The findings indicated that malachite treated with ammonium sulfate ((NH₄)₂SO₄) exhibited superior flotation recovery compared to ammonium phosphate ((NH₄)₃PO₄), achieving an optimal recovery rate of 87.5%. FESEM-EDS and ToF-SIMS analyses revealed a significant increase in sulfur species on the surface, promoting the formation of copper sulfide (CuS) films and enhancing the mineral's reactivity during flotation. Theoretical solution chemistry calculations corroborated these findings, showing that ammonium salt treatments facilitate the formation of copper-ammonium complexes, stabilizing copper ions in solution and preventing their precipitation as copper hydroxides or carbonates. By maintaining copper in a stable reactive form, these complexes improve flotation efficiency. Both theoretical calculations and experimental observations confirm that stabilizing copper ions is crucial for enhancing flotation, ensuring copper remains available for interaction with flotation reagents and ultimately, improving copper recovery. The integration of theoretical and experimental approaches enhances the understanding of the sulfurization process and provides an optimized method for improving flotation performance and copper recovery. | ||
| کلیدواژهها | ||
| malachite؛ hydrolysis reaction؛ copper–ammonium complex؛ surface enrichment؛ adsorption | ||
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| مراجع | ||
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[1]. Ndoro, T., & Witika, L. (2017). A Review of the Flotation of Copper Minerals. International Journal of Sciences: Basic and Applied Research, 34(2), 145–165.
[2]. Bulatovic, S. (2007). Flotation of oxide copper and copper cobalt ores. Handbook of flotation reagents: chemistry, theory and practice, 2, 47–65.
[3]. Jin, X., Cui, S., Sun, S., Gu, X., Li, H., & Liu, X. (2019). The preparation of a bio-polyelectrolytes based core-shell structure and its application in flame retardant polylactic acid composites. Composites Part A: Applied Science and Manufacturing, 124, 105485.
[4]. Khoso, S., Gao, Z., & Sun, W. (2021). Recovery of high-grade copper concentrate from sulfur-rich porphyry ore using tricarboxystarch micromolecule as pyrite depressant. Minerals Engineering, 168(4), 106916.
[5]. Yuan, Z., Ji, H., Zhang, L., & Liu, L. (2023). Sustaining the United States’ copper resource supply. Journal of Cleaner Production, 429(6), 139636.
[6]. Banza, A., & Gock, E. (2003). Mechanochemical processing of chrysocolla with sodium sulphide. Minerals Engineering, 16(12), 1349–1354.
[7]. Chen, X., Peng, Y., & Bradshaw, D. (2014). The separation of chalcopyrite and chalcocite from pyrite in cleaner flotation after regrinding. Minerals Engineering, 58, 64–72.
[8]. Zhang, Q., Wen, S., Feng, Q., & Zhang, S. (2020). Surface characterization of azurite modified with sodium sulfide and its response to flotation mechanism. Separation and Purification Technology, 242, 116760.
[9]. Feng, Q., Zhao, W., Wen, S., & Cao, Q. (2017). Copper sulfide species formed on malachite surfaces in relation to flotation. Journal of Industrial and Engineering Chemistry, 48, 125–132.
[10]. Zuo, Q., Wu, D., Cao, J., Wang, Z., Shi, Y., & Huang, L. (2022). A DFT-based method to determine the ammonium-induced activation and sulfidation pathway of tenorite. Journal of the Taiwan Institute of Chemical Engineers, 132(2), 104221.
[11]. Yin, Z., Sun, Q., Li, D., Tang, Y., Fu, Y., & Yao, J. (2019). Mechanism and application on sulphidizing flotation of copper oxide with combined collectors. Transactions of Nonferrous Metals Society of China (English Edition), 29(1), 178–185.
[12]. Canpolat, G., & Ziyadanoğullari, R. (2023). Recovery of Copper From Complex Copper Oxide Ore by Flotation and Leaching Methods. Advanced Physical Research, 5(2), 103–116.
[13]. Bai, X., Wen, S., Feng, Q., Liu, J., & Lin, Y. (2019). Utilization of high-gradient magnetic separation–secondary grinding–leaching to improve the copper recovery from refractory copper oxide ores. Minerals Engineering, 36, 77–80.
[14]. Zhang, Q., Wen, S., Feng, Q., & Wang, H. (2022). Enhanced sulfidization of azurite surfaces by ammonium phosphate and its effect on flotation. International Journal of Minerals, Metallurgy and Materials, 29(6), 1150–1160.
[15]. Rao, & Ramachandra, S. (2013). Surface chemistry of froth flotation. 2nd ed. Springer Science & Business Media, 385–575.
[16]. Bulatovic, S. (2007). Handbook of flotation reagents: chemistry, theory and practice: Volume 1: flotation of sulfide ores. Elsevier, 1, 45–129.
[17]. Wills, B., & Finch, J. (2015). Wills’ mineral processing technology: an introduction to the practical aspects of ore treatment and mineral recovery. Butterworth-Heinemann, 8, 285–374.
[18]. Rao, X., Zhang, C., Sun, W., Chen, J., & Zhang, H. (2025). Malachite sulfidation flotation mechanism: Cu-S co-deposition insights. Separation and Purification Technology, 364, 132476.
[19]. Cecile, J., Cruz, M., Barbery, G., & Fripiat, J. (1981). Infrared spectral study of species formed on malachite surface by adsorption from aqueous salicylaldoxime solution. Journal of Colloid And Interface Science, 80(2), 589–597.
[20]. Liu, Y., Fu, X., Sun, W., & Yue, T. ( 2025). Application and interaction mechanisms of sodium methyl-phosphonate sulfonate as novel selective depressant in the flotation separation of dolomite from malachite. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 719, 137033.
[21]. Wu, D., Ma, W., Wen, S., Deng, J., & Bai, S. (2017). Enhancing the sulfidation of smithsonite by superficial dissolution with a novel complexing agent. Minerals Engineering, 114, 1–7.
[22]. Yu, X., Yin, Z., Chen, Y., Shen, P., Wang, H., & Mao, Y. (2024). Experimental and DFT study of modified malachite with 2,5-dimercapto-1,3,4-thiadiazole and its response to sulfidization-xanthate behavior. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 693, 134057.
[23]. Shen, P., Liu, D., Zhang, X., Jia, X., Song, K., & Liu, D. (2019). Effect of (NH4)2SO4 on eliminating the depression of excess sulfide ions in the sulfidization flotation of malachite. Minerals Engineering, 137, 43–52.
[24]. Castro, S., Goldfarb, J., & Laskowski, J. (1974). Sulphidizing reactions in the flotation of oxidized copper minerals, I. Chemical factors in the sulphidization of copper oxide. International Journal of Mineral Processing, 1(2), 141–149.
[25]. Castro, S., Soto, H., Goldfarb, J., & Laskowski, J. (1974). Sulphidizing reactions in the flotation of oxidized copper minerals, II. Role of the adsorption and oxidation of sodium sulphide in the flotation of chrysocolla and malachite. International Journal of Mineral Processing, 1(2), 151–161.
[26]. Lee, K., Archibald, D., Mclean, J., & Reuter, M. (2009). Flotation of mixed copper oxide and sulphide minerals with xanthate and hydroxamate collectors. Minerals Engineering, 22(4), 395–401.
[27]. Zhou, R., & Chander, S. (1993). Kinetics of sulfidization of malachite in hydrosulfide and tetrasulfide solutions. International Journal of Mineral Processing, 37(3), 257–272.
[28]. Park, K., Park, S., Choi, J., Kim, G., Tong, M., & Kim, H. (2016). Influence of excess sulfide ions on the malachite-bubble interaction in the presence of thiol-collector. Separation and Purification Technology, 168, 1–7.
[29]. Yu, X., Yu, B., Wang, H., Shen, P., & Liu, D. (2024). Evolution of sulfur species on malachite surfaces in the presence of calcium and magnesium ions and implications for xanthate flotation. Advanced Powder Technology, 35(7), 104538.
[30]. Zhang, Q., Wen, S., Zuo, Q., & Feng, Q. (2023). Density functional theory calculation of catalytic sulfidization on the azurite (0 1 1) surface by ammonium salts and its effect on flotation. Separation and Purification Technology, 309, 122993.
[31]. Liu, R., Liu, Z., Li, J., Ao, S., Pei, B., & Liu, D. (2020). Reexamining the Role of Ammonium Ions in the Sulfidization, Xanthate-Flotation of Malachite. Minerals, 10(6), 537.
[32]. Qiu, Z., Fang, J., Liu, D., He, H., Peng, L., & Qin, S. (2024). Flotation activation mechanism of trithiocyanuric acid to malachite. Advanced Powder Technology, 35(6), 104469.
[33]. Cai, J., Su, C., Yu, X., Peng, R., Liu, R., Zhang, X., Shen, P., & Liu, D. (2022). Understanding the mechanism for promoting azurite sulfurization with ammonium sulfate. Minerals Engineering, 177, 107368.
[34]. Shen, P., Liu, D., Xu, X., Jia, X., Zhang, X., & Song, K. (2020). Effects of ammonium phosphate on the formation of crystal copper sulfide on chrysocolla surfaces and its response to flotation. Minerals Engineering, 155, 106300.
[35]. Ibrahim, AM., Jia, X., Su, C., Cai, J., Shen, P., & Liu, D. (2022). Effect of Ammonium Sulfide on Sulfidization Flotation of Malachite. Minerals, 12(10), 1–14.
[36]. Cai, J., Su, C., Ma, Y., Yu, X., Peng, R., Li, J., Shen, P., & Liu, D. (2022). Role of ammonium sulfate in sulfurization flotation of azurite: Inhibiting the formation of copper sulfide colloid and its mechanism. International Journal of Mining Science and Technology, 32(3), 575–584.
[37]. Lu, W., Wen, S., Liu, D., Wang, H., & Feng, Q. (2023). A novel method for improving sulfidization xanthate flotation of malachite: Copper–ammonium synergistic activation. Applied Surface Science, 618, 156660.
[38]. Jia, X., Song, K., Cai, J., Su, C., Xu, X., Ma, Y., & Liu, D. (2023). Effect of oxygen and sodium sulfide on flotation of cuprite and its modification mechanism. Transactions of Nonferrous Metals Society of China (English Edition), 33(4), 1233–1243.
[39]. Ibrahim, AM., Wang, H., Yousif, J., Elhadi, M., Shen, P., & Liu, D. (2025). Improved activation of malachite sulfurization flotation by thiourea’s (CS(NH2)2): Performance and mechanism study. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 705, 135643.
[40]. Liu, R., Liu, D., Li, J., Li, J., Liu, Z., Jia, X. (2020). Sulfidization mechanism in malachite flotation: A heterogeneous solid-liquid reaction that yields CuxSy phases grown on malachite. Minerals Engineering, 154, 106420.
[41]. Ibrahim, AM., Jia, X., Cai, J., Su, C., Yu, X., Zheng, Q., & Liu, D. (2023). Role of ammonium phosphate in improving the physical characteristics of malachite sulfidation flotation. Physicochemical Problems of Mineral Processing, 59(1), 1–13.
[42]. Yu, X., Shen, P., Yin, Z., Wang, L., Wang, H., & Liu, D. (2023). Surface modification of malachite using DMTD and its effect on xanthate adsorption. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 679, 132560.
[43]. Shen, P., Dan, L., Zhang, X., Jia, X., Song, K., & Liu, D. (2019). Effect of (NH4)2SO4 on eliminating the depression of excess sulfide ions in the sulfidization flotation of malachite. Minerals Engineering, 137, 43–52.
[44]. Wang, C., Sun, L., Wang, Q., Wang, Y., Cao, Y., & Wang, X. (2022). Adsorption mechanism and flotation behavior of ammonium salt of N-Nitroso-N-phenylhydroxyamine on malachite mineral. Applied Surface Science, 583, 152489.
[45]. Margl, P., & Ziegler, T. (1999). Solvation of Cu2+ in Water and Ammonia. Insight from Static and Dynamical Density Functional Theory. The Journal of Physical Chemistry A, 103(48), 9693–9701. | ||
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