Effect of fluoride roasting on copper species transformation on chrysocolla surfaces and its role in enhanced sulfidation flotation

Yingqiang Ma , Xin Huang , Yafeng Fu , Zhenguo Song , Sen Luo , Shuanglin Zheng , Feng Rao , Wanzhong Yin

International Journal of Minerals, Metallurgy, and Materials ›› 2026, Vol. 33 ›› Issue (1) : 165 -176.

PDF
International Journal of Minerals, Metallurgy, and Materials ›› 2026, Vol. 33 ›› Issue (1) :165 -176. DOI: 10.1007/s12613-025-3152-4
Research Article
research-article

Effect of fluoride roasting on copper species transformation on chrysocolla surfaces and its role in enhanced sulfidation flotation

Author information +
History +
PDF

Abstract

It is difficult to recover chrysocolla from sulfidation flotation, which is closely related to the mineral surface composition. In this study, the effects of fluoride roasting on the surface composition of chrysocolla were investigated, its impact on sulfidation flotation was explored, and the mechanisms involved in both fluoride roasting and sulfidation flotation were discussed. With CaF2 as the roasting reagent, Na2S·9H2O as the sulfidation reagent, and sodium butyl xanthate (NaBX) as the collector, the results of the flotation experiments showed that fluoride roasting improved the floatability of chrysocolla, and the recovery rate increased from 16.87% to 82.74%. X-ray diffraction analysis revealed that after fluoride roasting, approximately all the Cu on the chrysocolla surface was exposed in the form of CuO, which could provide a basis for subsequent sulfidation flotation. The microscopy and elemental analyses revealed that large quantities of “pagoda-like” grains were observed on the sulfidation surface of the fluoride-roasted chrysocolla, indicating high crystallinity particles of copper sulfide. This suggests that the effect of sulfide formation on the chrysocolla surface was more pronounced. X-ray photoelectron spectroscopy revealed that fluoride roasting increased the relative contents of sulfur and copper on the surface and that both the Cu+ and polysulfide fractions on the surface of the minerals increased. This enhances the effect of sulfidation, which is conducive to flotation recovery. Therefore, fluoride roasting improved the effect of copper species transformation and sulfidation on the surface of chrysocolla, promoted the adsorption of collectors, and improved the recovery of chrysocolla from sulfidation flotation.

Keywords

sulfidation flotation / chrysocolla / fluoride roasting / copper species transformation / enhanced sulfidation

Cite this article

Download citation ▾
Yingqiang Ma, Xin Huang, Yafeng Fu, Zhenguo Song, Sen Luo, Shuanglin Zheng, Feng Rao, Wanzhong Yin. Effect of fluoride roasting on copper species transformation on chrysocolla surfaces and its role in enhanced sulfidation flotation. International Journal of Minerals, Metallurgy, and Materials, 2026, 33(1): 165-176 DOI:10.1007/s12613-025-3152-4

登录浏览全文

4963

注册一个新账户 忘记密码

References

[1]

Cheje Machaca DM, Botelho AB, de Carvalho TC, Tenório JAS, Espinosa DCR. Hydrometallurgical processing of chalcopyrite: A review of leaching techniques. Int. J. Miner. Metall. Mater., 2024, 31(12): 2537.

[2]

Q.Y. Sheng, W.Z. Yin, B. Yang, H.R. Sun, and J. Yao, Efficiently separating malachite from talc using new collector famciclovir via reverse flotation, Miner. Eng., 174(2021), art. No. 107243.

[3]

Shen ZH, Wen SM, Wang H, et al. . Effect of dissolved components of malachite and calcite on surface properties and flotation behavior. Int. J. Miner. Metall. Mater., 2023, 30(7): 1297.

[4]

Han JW, Xiao J, Qin WQ, Chen DX, Liu W. Copper recovery from Yulong complex copper oxide ore by flotation and magnetic separation. JOM, 2017, 69(9): 1563.

[5]

Feng QC, Lu WM, Wang H, Zhang Q. Mechanistic insights into stepwise activation of malachite for enhancing surface reactivity and flotation performance. Int. J. Miner. Metall. Mater., 2024, 31(10): 2159.

[6]

Raghavan S, Fuerstenau DW. Characterization and pore structure analysis of a copper ore containing chrysocolla. Int. J. Miner. Process., 1977, 4(4): 381.

[7]

Banza AN, Gock E. Mechanochemical processing of chrysocolla with sodium sulphide. Miner. Eng., 2003, 16(12): 1349.

[8]

Tanda BC, Eksteen JJ, Oraby EA. An investigation into the leaching behaviour of copper oxide minerals in aqueous alkaline glycine solutions. Hydrometallurgy, 2017, 167: 153.

[9]

Chen DX, Liu MF, Hu B, et al. . New insights into the promotion mechanism of (NH4)2SO4 in sulfidization flotation: A combined experimental and computational study. Physicochem. Probl. Miner. Process., 2021, 57(5): 57

[10]

Kamariah N, Xanthopoulos P, Binnemans K, Spooren J. Solvometallurgical process for the recovery of copper from chrysocolla in monoethanolamine. Ind. Eng. Chem. Res, 2023, 62(33): 12880.

[11]

G.C. Shi, Y.L. Liao, B.W. Su, Y. Zhang, W. Wang, and J.J. Xi, Kinetics of copper extraction from copper smelting slag by pressure oxidative leaching with sulfuric acid, Sep. Purif. Technol., 241(2020), art. No. 116699.

[12]

Gonzalez G, Soto H. The effect of thermal treatment on the flotation of chrysocolla. Int. J. Miner. Process., 1978, 5(2): 153.

[13]

Fuerstenau DW, Herrera-Urbina R, McGlashan DW. Studies on the applicability of chelating agents as universal collectors for copper minerals. Int. J. Miner. Process., 2000, 58(1–4): 15.

[14]

Barbaro M, Herrera Urbina R, Cozza C, Fuerstenau D, Marabini A. Flotation of oxidized minerals of copper using a new synthetic chelating reagent as collector. Int. J. Miner. Process., 1997, 50(4): 275.

[15]

Hope GA, Numprasanthai A, Buckley AN, Parker GK, Sheldon G. Bench-scale flotation of chrysocolla with n-octanohydroxamate. Miner. Eng, 2012, 36–38: 12.

[16]

Hope GA, Buckley AN, Parker GK, Numprasanthai A, Woods R, McLean J. The interaction of n-octanohydroxamate with chrysocolla and oxide copper surfaces. Miner. Eng, 2012, 36–38: 2.

[17]

D. Liu, D.Q. Wang, Y.J. Xian, X.S. Tian, and S.M. Wen, Enhancement of xanthate adsorption on chrysocolla surface via sodium diethyldithiocarbamate (DDTC) modification, Physicochem. Probl. Miner. Process., 58(2022), No. 6, art. No. 152599.

[18]

G. Han, S.M. Wen, H. Wang, and Q.C. Feng, Surface sulfidization mechanism of cuprite and its response to xanthate adsorption and flotation performance, Miner. Eng., 169(2021), art. No. 106982.

[19]

Q. Zhang, Y.J. Wang, Q.C. Feng, et al., Identification of sulfidization products formed on azurite surfaces and its correlations with xanthate adsorption and flotation, Appl. Surf. Sci., 511(2020), art. No. 145594.

[20]

Liu C, Song SX, Li HQ, Ai GH. Sulfidization flotation performance of malachite in the presence of calcite. Miner. Eng., 2019, 132: 293.

[21]

Masdarian M, Azizi A, Bahri Z. Mechanochemical sulfidization of a mixed oxide-sulphide copper ore by co-grinding with sulfur and its effect on the flotation efficiency. Chin. J. Chem. Eng, 2020, 28(3): 743.

[22]

Raghavan S, Adamec E, Lee L. Sulfidization and flotation of chrysocolla and brochantite. Int. J. Miner. Process., 1984, 12(1–3): 173.

[23]

Park K, Park S, Choi J, Kim G, Tong MP, Kim H. Influence of excess sulfide ions on the malachite-bubble interaction in the presence of thiol-collector. Sep. Purif. Technol., 2016, 168: 1.

[24]

P.L. Shen, D.W. Liu, X.H. Xu, et al., Effects of ammonium phosphate on the formation of crystal copper sulfide on chrysocolla surfaces and its response to flotation, Miner. Eng., 155(2020), art. No. 106300.

[25]

R. Peng, Z. Xie, Q.C. Wei, et al., Co-modification of chrysocolla with ammonia and 1, 2-diaminopropane and its response to flotation, Colloids Surf. A: Physicochem. Eng. Aspects, 698(2024), art. No. 134566.

[26]

Xu MD, Xing YW, Gui XH, Cao YJ, Wang DY, Wang LW. Effect of ultrasonic pretreatment on oxidized coal flotation. Energy Fuels, 2017, 31(12): 14367.

[27]

Li CX, Wei C, Deng ZG, Li XB, Li MT, Xu HS. Hydrothermal sulfidation and flotation of oxidized zinc-lead ore. Metall. Mater. Trans. B, 2014, 45(3): 833.

[28]

Viñals J, Fuentes G, Hernández MC, Herreros O. Transformation of sphalerite particles into copper sulfide particles by hydrothermal treatment with Cu(II) ions. Hydrometallurgy, 2004, 75(1–4): 177.

[29]

Liang YJ, Chai LY, Min XB, et al. . Hydrothermal sulfidation and floatation treatment of heavy-metal-containing sludge for recovery and stabilization. J. Hazard. Mater, 2012, 217–218: 307

[30]

D’yachenko AN, Kraidenko RI. Processing oxide-sulfide copper ores using ammonium chloride. Russ. J. Non Ferr. Met., 2010, 51(5): 377.

[31]

Zheng YX, Liu W, Qin WQ, Han JW, Yang K, Luo HL. Selective reduction of PbSO4 to PbS with carbon and flotation treatment of synthetic galena. Physicochem. Probl. Miner. Process., 2015, 51(2): 535

[32]

Zheng YX, Liu W, Qin WQ, et al. . Sulfidation roasting of lead and zinc carbonate with sulphur by temperature gradient method. J. Cent. South Univ., 2015, 22(5): 1635.

[33]

Zheng YX, Liu W, Qin WQ, Kong Y, Luo HL, Han JW. Mineralogical reconstruction of lead smelter slag for zinc recovery. Sep. Sci. Technol., 2014, 49(5): 783.

[34]

Q. Wei, L.Y. Dong, W.Q. Qin, et al., Efficient flotation recovery of lead and zinc from refractory lead-zinc ores under low alkaline conditions, Geochemistry, 81(2021), No. 4, art. No. 125769.

[35]

Zheng YX, Ning JL, Xie HY, Lv JF, Hu PJ, Pang J. Study on surface modification of cerussite by thermochemical processing with pyrite. Physicochem. Probl. Miner. Process., 2021, 57(1): 156.

[36]

Q. Zhang, Y.S. Sun, G.D. Wu, X.L. Wei, and P. Gao, Pyrite as a sulfidation agent in chrysocolla sulfidation roasting for copper recovery: Thermodynamics, phase transformation, and sulfur migration, Miner. Eng., 215(2024), art. No. 108813.

[37]

Wang MY, Wang XW. Extraction of molybdenum and nickel from carbonaceous shale by oxidation roasting, sulphation roasting and water leaching. Hydrometallurgy, 2010, 102(1–4): 50.

[38]

R. Peng, H.X. Wang, Z.C. Wei, et al., Effects of 1, 2-diaminopropane on the formation of chelated copper on chrysocolla surfaces and its response to flotation, Miner. Eng., 212(2024), art. No. 108705.

[39]

Xia J, Liu D, Guo ZQ, Li JL, Huang SW. Research status on flotation of chrysocolla. Bull. Chin. Ceram. Soc., 2018, 37(2): 496

[40]

Li X, Shang YJ, Chen ZL, et al. . Study of spontaneous combustion mechanism and heat stability of sulfide minerals powder based on thermal analysis. Powder Technol., 2017, 309: 68.

[41]

Feng QC, Wen SM, Bai X, Chang WH, Cui CF, Zhao WJ. Surface modification of smithsonite with ammonia to enhance the formation of sulfidization products and its response to flotation. Miner. Eng., 2019, 137: 1.

[42]

G. Han, S.M. Wen, H. Wang, and Q.C. Feng, Selective adsorption mechanism of salicylic acid on pyrite surfaces and its application in flotation separation of chalcopyrite from pyrite, Sep. Purif. Technol., 240(2020), art. No. 116650.

[43]

Xu XH, Shen PL, Zhang XL, Han YG, Liu DW. Effects of ethylene diamine phosphate on the flotation of chrysocolla. Bull. Chin. Ceram. Soc., 2018, 37(7): 2291

[44]

Shen PL, Liu DW, Zhang XL, Jia XD, Song KW, Liu D. Effect of (NH4)2SO4 on eliminating the depression of excess sulfide ions in the sulfidization flotation of malachite. Miner. Eng., 2019, 137: 43.

[45]

Feng QC, Zhao WJ, Wen SM, Cao QB. Copper sulfide species formed on malachite surfaces in relation to flotation. J. Ind. Eng. Chem., 2017, 48: 125.

[46]

Li FX, Zhong H, Xu HF, Jia H, Liu GY. Flotation behavior and adsorption mechanism of α-hydroxyoctyl phosphinic acid to malachite. Miner. Eng., 2015, 71: 188.

[47]

Kartio IJ, Basilio CI, Yoon RH. An XPS study of sphalerite activation by copper. Langmuir, 1998, 14(18): 5274.

[48]

Klein JC, Li CP, Hercules DM, Black JF. Decomposition of copper compounds in X-ray photoelectron spectrometers. Appl. Spectrosc., 1984, 38(5): 729.

[49]

Nakai I, Sugitani Y, Nagashima K, Niwa Y. X-ray photoelectron spectroscopic study of copper minerals. J. Inorg. Nucl. Chem., 1978, 40(5): 789.

[50]

Gauzzi A, Mathieu HJ, James JH, Kellett B. AES, XPS and SIMS characterization of YBa2Cu3O7 superconducting high Tc thin films. Vacuum, 1990, 41(4–6): 870.

[51]

Strohmeier BR, Levden DE, Field RS, Hercules DM. Surface spectroscopic characterization of Cu/Al2O3 catalysts. J. Catal, 1985, 94(2): 514.

[52]

B. Yang and J.F. He, New insights into selective depression mechanism of Tamarindus indica kernel gum in flotation separation of fluorapatite and calcite, Sep. Purif. Technol, 354(2025), Part 3, art. No. 128787.

[53]

Y.Q. Ma, M.Y. Yang, L.F. Tang, et al., Flotation separation mechanism for secondary copper sulfide minerals and pyrite using novel collector ethyl isobutyl xanthogenic acetate, Colloids Surf. A: Physicochem. Eng. Aspects, 634(2022), art. No. 128010.

[54]

Feng QC, Zhao WJ, Wen SM. Surface modification of malachite with ethanediamine and its effect on sulfidization flotation. Appl. Surf. Sci., 2018, 436: 823.

[55]

G.B. Cheng, Y.Q. Ma, A. López-Valdivieso, and W.Z. Yin, Selective depression of phenoxyacetyl chloride on magnesite: Implications for effective flotation separation of magnesite from dolomite, Miner. Eng., 218(2024), art. No. 109017.

[56]

Smart RSC, Skinner WM, Gerson AR. XPS of sulphide mineral surfaces: Metal-deficient, polysulphides, defects and elemental sulphur. Surf. Interface Anal., 1999, 28(1): 101.

[57]

Buckley AN, Woods R. An X-ray photoelectron spectroscopic study of the oxidation of galena. Appl. Surf. Sci., 1984, 17(4): 401.

[58]

Feng QC, Wen SM, Deng JS, Zhao WJ. Combined DFT and XPS investigation of enhanced adsorption of sulfide species onto cerussite by surface modification with chloride. Appl. Surf. Sci., 2017, 425: 8.

RIGHTS & PERMISSIONS

University of Science and Technology Beijing

PDF

27

Accesses

0

Citation

Detail

Sections
Recommended

/