Selectivity of composite thionocarbamate collector in flotation separation of chalcocite from pyrite in low-alkaline pH pulp

Abstract

The flotation separation of high pyrite content secondary copper ores faces challenges including elevated pH levels, poor xanthate selectivity, and higher costs associated with its combination with Z-200. In this work, a composite thionocarbamate collector (TJ-215), with low-cost raw materials and a short synthetic route, showed a better selectivity for chalcocite than Z-200 when pH>8. Zeta potential analysis indicated a stronger interaction between TJ-215 and chalcocite. These results were achieved through the synergistic coordination of NH—C=S and C=N—OH in TJ-215 molecule, compared with the single thiourea group, NH—C=S, in Z-200 molecule. At low-alkaline condition, the NH—C=S in TJ-215 formed Cu—S, Cu—N bonds with Cu atoms, and the C=N—OH combined with Cu to form a Cu—O bond. The results of this study provide guidance on the replacement of Z-200 by TJ-215 in the separation of chalcocite from pyrite in weak alkaline conditions.

Keywords

composite thionocarbamate / chalcocite / pyrite / flotation / adsorption mechanism

References

[1] Bulatovic S MHandbook of flotation reagents: chemistry, theory and practice: Volume 1: flotation of sulfide ores [M], 2007

[2] Owusu C, Zanin M, Fornasiero D, et al.. Influence of pyrite content on the flotation of chalcopyrite after regrinding with Isamill [C]. Chemeca 2011 (39th: 2011: Sydney, NSW): Engineers Australia Barton, 201121-30

[3] Li W-q, Li Y-b, Wu X-y, et al.. Pyrite activation in seawater flotation by copper and lead ions: XPS and in-situ electrochemical investigation [J]. Applied Surface Science, 2025, 680: 161363

[4] Castellón C I, Toro N, Gálvez E, et al.. Froth flotation of chalcopyrite/pyrite ore: A critical review [J]. Materials, 2022, 15(19): 6536

[5] Matsanga N, Nheta W, Chimwani N. A review of the grinding media in ball mills for mineral processing [J]. Minerals, 2023, 13(11): 1373

[6] Chen X-m, Peng Y-j, Bradshaw D. The separation of chalcopyrite and chalcocite from pyrite in cleaner flotation after regrinding [J]. Minerals Engineering, 2014, 58: 64-72

[7] Sun X-s, Yu J-w, Li Y-j, et al.. A novel selective collector MIBATC and its performance on flotation separation of chalcopyrite from sphalerite and pyrite [J]. Minerals Engineering, 2024, 216: 108875

[8] Zou S, Wang S, Ma X, et al.. Highly selective flotation separation of chalcopyrite and pyrite by a novel dithiocarbamate collector with morpholine group [J]. Minerals Engineering, 2023, 202: 108292

[9] Feng Q-c, Yang W-h, Wen S-m, et al.. Flotation of copper oxide minerals: A review [J]. International Journal of Mining Science and Technology, 2022, 32(6): 1351-1364

[10] Liu J, Liu Z-g, Tan J, et al.. Flotation separation of pyrite from chalcopyrite by tetrazinan-thione collectors [J]. Journal of Central South University, 2023, 30(8): 2587-2598

[11] Mkhonto P P, Zhang X-r, Lu L, et al.. Adsorption mechanisms and effects of thiocarbamate collectors in the separation of chalcopyrite from pyrite minerals: DFT and experimental studies [J]. Minerals Engineering, 2022, 176: 107318

[12] Bu Y-j, Hu Y-h, Sun W, et al.. Fundamental flotation behaviors of chalcopyrite and galena using O-isopropyl-N-ethyl thionocarbamate as a collector [J]. Minerals, 2018, 8(3): 115

[13] Xu B, Wu J-t, Dong Z-l, et al.. Flotation performance, structure-activity relationship and adsorption mechanism of a newly-synthesized collector for copper sulfide minerals in Gacun polymetallic ore [J]. Applied Surface Science, 2021, 551: 149420

[14] Yuan-yuan F, Xian-zhong B, Zhao W, Cun-jian W, Xian-ping L. Synergistic Effect of Multi-Component Copper Sulfide Collector in Chalcocite Flotation. Mining and Metallurgical Engineering, 2021, 41: 45-49

[15] Tian X-d, Li X-t, Bi P-fei. Effect of O-isobutyl-N-ethyl thionocarbamates on flotation behavior of porphyry copper ore and its adsorption mechanism [J]. Applied Surface Science, 2020, 503: 144313

[16] Ma Y-q, Yang M-y, Tang L-f, et al.. Flotation separation mechanism for secondary copper sulfide minerals and pyrite using novel collector ethyl isobutyl xanthogenic acetate [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 634: 128010

[17] Jefferson M, Yenial-Arslan U, Evans C, et al.. Effect of pyrite textures and composition on flotation performance: A review [J]. Minerals Engineering, 2023, 201: 108234

[18] Suyantara G P W, Berdakh D, Miki H, et al.. Effect of hydrogen peroxide on selective flotation of chalcocite and enargite [J]. International Journal of Mining Science and Technology, 2023, 33(6): 703-716

[19] Reyes-Bozo L, Escudey M, Vyhmeister E, et al.. Adsorption of biosolids and their main components on chalcopyrite, molybdenite and pyrite: Zeta potential and FTIR spectroscopy studies [J]. Minerals Engineering, 2015, 78: 128-135

[20] Xiao J-j, Liu G-y, Zhong H. The adsorption mechanism of N-butoxypropyl-S- [2-(hydroxyimino) propyl] dithiocarbamate ester to copper minerals flotation [J]. International Journal of Mineral Processing, 2017, 166: 53-61

[21] Zou S, Wang S, Ma X, et al.. Highly selective flotation separation of chalcopyrite and pyrite by a novel dithiocarbamate collector with morpholine group [J]. Minerals Engineering, 2023, 202: 108292

[22] Yin Z-g, Hu Y-h, Sun W, et al.. Adsorption mechanism of 4-amino-5-mercapto-1, 2, 4-triazole as flotation reagent on chalcopyrite [J]. Langmuir, 2018, 34(13): 4071-4083

[23] Cao F, Sun D-s, Qiu X-h, et al.. Synthesis of novel thionocarbamate for copper–sulfur flotation separation and its adsorption mechanism [J]. Transactions of Nonferrous Metals Society of China, 2022, 32(8): 2709-2718

[24] Qu X-y, Xiao J-j, Liu G-y, et al.. Investigation on the flotation behavior and adsorption mechanism of 3-hexyl-4-amino-1, 2, 4-triazole-5-thione to chalcopyrite [J]. Minerals Engineering, 2016, 89: 10-17

[25] Krishna D N G, Philip J. Review on surface-characterization applications of X-ray photoelectron spectroscopy (XPS): Recent developments and challenges [J]. Applied Surface Science Advances, 2022, 12: 100332

[26] Khalakhan I, Vorokhta M, Xie X-x, et al.. On the interpretation of X-ray photoelectron spectra of Pt-Cu bimetallic alloys [J]. Journal of Electron Spectroscopy and Related Phenomena, 2021, 246: 147027

[27] Jiang X, Zhang W-j, Fan R-h, et al.. Improved flotation of chalcopyrite from galena and pyrite by employing Cu-affinity phosphate collector [J]. Minerals Engineering, 2023, 197: 108064

[28] Isaacs M A, Davies-Jones J, Davies P R, et al.. Advanced XPS characterization: XPS-based multi-technique analyses for comprehensive understanding of functional materials [J]. Materials Chemistry Frontiers, 2021, 5(22): 7931-7963

[29] Matsuoka H, Mitsuhashi K, Kawata M, et al.. Surface properties of copper-sulfide minerals with sodium-hydrosulfide activation [J]. Minerals Engineering, 2020, 156: 106530

[30] Li W-q, Li Y-b, Wu X-y, et al.. Pyrite activation in seawater flotation by copper and lead ions: XPS and in-situ electrochemical investigation [J]. Applied Surface Science, 2025, 680: 161363

[31] Shen P-l, Liu D-w, Xu X-h, et al.. Effects of ammonium phosphate on the formation of crystal copper sulfide on chrysocolla surfaces and its response to flotation [J]. Minerals Engineering, 2020, 155: 106300

[32] Cai J-p, Shen P-l, Liu D-w, et al.. Growth of covellite crystal onto azurite surface during sulfurization and its response to flotation behavior [J]. International Journal of Mining Science and Technology, 2021, 31(6): 1003-1012

[33] Wang C-w, Zhang R-h, Li X-s, et al.. A novel chelating collector with di-minerophilic group 5-methyl butylxanthate-1, 2, 4-triazole-3-thione: Its synthesis and selective flotation mechanism of chalcopyrite from pyrite [J]. Jom, 2024, 76(5): 2478-2490

[34] Buckley A N, Hope G A, Lee K C, et al.. Adsorption of O-isopropyl-N-ethyl thionocarbamate on Cu sulfide ore minerals [J]. Minerals Engineering, 2014, 69: 120-132

[35] Xiao J-jing. Flotation behavior and adsorption mechanism of BOPHPDT to chalcopyrite [J]. The Chinese Journal of Nonferrous Metals, 2021, 31: 2247-2257(in Chinese)

[36] Huang X-p, Huang K-h, Jia Y, et al.. Investigating the selectivity of a xanthate derivative for the flotation separation of chalcopyrite from pyrite [J]. Chemical Engineering Science, 2019, 205: 220-229

[37] Chastain J, King R CHandbook of X-ray photoelectron spectroscopy [M], 1992Eden Prairie, Minn USAPerkin-Elmer Corporation

[38] Qi M-y, Peng W-j, Wang W, et al.. A novel molybdenite depressant for efficient selective flotation separation of chalcopyrite and molybdenite [J]. International Journal of Mining Science and Technology, 2024, 34(8): 1179-1196

[39] Liu J-y, Feng B, Guo W, et al.. Utilizing H₂O₂ for the selective flotation separation of chalcopyrite and galena with their surface pre-adsorbed with Isopropyl Ethyl Thiocarbamate [J]. Separation and Purification Technology, 2024, 330: 125477

[40] Fazal M A, Haseeb A S M A, Masjuki H H. Corrosion mechanism of copper in palm biodiesel [J]. Corrosion Science, 2013, 67: 50-59

[41] Huang X-p, Yuan X-l, Yang H-f, et al.. Evaluating the adsorption mechanism of a novel thiocarbamate on chalcopyrite and pyrite particles [J]. Advanced Powder Technology, 2023, 34(2): 103935

[42] Yang B-q, Yan H, Zeng M-y, et al.. Tiopronin as a novel copper depressant for the selective flotation separation of chalcopyrite and molybdenite [J]. Separation and Purification Technology, 2021, 266: 118576

[43] Mkhonto P P, Zhang X-r, Lu L, et al.. Adsorption mechanisms and effects of thiocarbamate collectors in the separation of chalcopyrite from pyrite minerals: DFT and experimental studies [J]. Minerals Engineering, 2022, 176: 107318

[44] Moimane T, Peng Y-jun. Limitations of conventional sulphidisation in restoring the floatability of oxidised chalcocite [J]. Minerals Engineering, 2022, 185: 107683

[45] Zou S, He G-c, Yu X-y, et al.. Three novel dithiocarbamate surfactants: Synthesis, DFT calculation and flotation mechanism to chalcopyrite [J]. Journal of Molecular Liquids, 2024, 413: 125993

[46] Chen J-h, Wang J-m, Li Y-q, et al.. Effects of surface spatial structures and electronic properties of chalcopyrite and pyrite on Z-200 selectivity [J]. Minerals Engineering, 2021, 163: 106803

[47] He S-x, Huang Y-g, Wang M, et al.. An efficient solid-liquid interface adsorption mode in chalcopyrite flotation with a novel di-minerophilic group surfactant 5-methyl isobutylxanthate-1, 3, 4-oxadiazole-2-thione [J]. Journal of Molecular Liquids, 2022, 345: 118254

[48] Salem N M H, El Sayed L, Haase W, et al.. Synthesis, characterization and molecular structures of copper(II) and nickel(II) complexes derived from diacetylmonooxime thiosemicarbazone and diacetylmonooxime S-benzyl dithiocarbazonate [J]. Journal of Coordination Chemistry, 2015, 68(12): 2147-2166

RIGHTS & PERMISSIONS

Central South University