Application and mechanism of calcium hypochlorite in replacing sodium sulfide for the clean separation of low-grade molybdenum-bismuth ore

Abstract

Stemming from the high costs and environmental pollution associated with the use of sodium sulfide in the separation and extraction processes of molybdenum bismuth ore, calcium hypochlorite was introduced as a substitute to facilitate the cleaner production of low-grade molybdenum bismuth ore in this study. The effects of calcium hypochlorite on molybdenite, bismuthinite, and pyrite were investigated through micro-flotation, flotation kinetics, batch flotation, FTIR spectra, Scanning electron microscope energy dispersion spectra (SEM-EDS), and Inductively coupled plasma-optical emission spectra (ICP-OES). The flotation tests results showed that calcium hypochlorite could selectively depress bismuthinite and pyrite. In comparison to sodium sulfide, calcium hypochlorite not only improved the flotation indicators for molybdenum and bismuth concentrates but also reduced the dosage of flotation reagents. Moreover, the chemical oxygen demand (COD) of tailings wastewater significantly decreased when using calcium hypochlorite as a depressant. Mechanism research revealed that the use of calcium hypochlorite as a depressant led to BiOCl precipitation on bismuthinite, which hindered the attachment of the collector. In summary, calcium hypochlorite serves as a more efficient and environmentally friendly depressant compared to sodium sulfide in the industrial production processes of low-grade molybdenum bismuth ore.

Keywords

bismuthinite / molybdenite / selective separation / calcium hypochlorite

References

[1] HasanS N, XuM, AsselinE. Electrodeposition of metallic molybdenum and its alloys–A review [J]. Canadian Metallurgical Quarterly, 2019, 58(1): 1-18

[2] ReddyK J, MunnL C, WangL Chemistry and mineralogy of molybdenum in soils [M], 1997

[3] OjebuobohF K. Bismuth: Production, properties, and applications [J]. JOM, 1992, 44(4): 46-49

[4] LasheenT A, El-AhmadyM E, HassibH B, et al.. Molybdenum metallurgy review: Hydrometallurgical routes to recovery of molybdenum from ores and mineral raw materials [J]. Mineral Processing and Extractive Metallurgy Review, 2015, 36(3): 145-173

[5] LinS-y, LiuR-q, LiW-h, et al.. Clean desulfurization of sulfur - rich tungsten concentrates by reverse flotation [J]. Journal of Cleaner Production, 2020, 244: 118876

[6] LinS-y, WangC-w, LiuR-q, et al.. Surface characterization of molybdenite, bismuthinite, and pyrite to identify the influence of pH on the mineral floatability [J]. Applied Surface Science, 2022, 577: 151756

[7] LinS-y, ZhangH-l, MengX-s, et al.. Selective fabrication of hydrophilic BiOCl deposition layer on bismuthinite surface for efficient molybdenite/bismuthinite separation [J]. Minerals Engineering, 2023, 202: 108235

[8] LinS-y, LiuR-q, SunW, et al.. Effect of H₂O₂ on the separation of Mo-Bi-containing ore by flotation [J]. Minerals, 2018, 8(9): 402

[9] LinS-y, LiuR-q, HuY-h, et al.. Optimize flotation process of Mo - Bi sulfide ore for cleaner production [J]. Journal of Cleaner Production, 2021, 291: 125236

[10] MazurK L, FeuserP E, ValérioA, et al.. Diethyldithiocarbamate loaded in beeswax-copaiba oil nanoparticles obtained by solventless double emulsion technique promote promastigote death in vitro [J]. Colloids and Surfaces B: Biointerfaces, 2019, 176: 507-512

[11] LiuR-q, ZhongC-y, LinS-y, et al.. Depression mechanism of sodium sulfide in flotation separation of molybdenite and bismuthinite [J]. Mineral Processing and Extractive Metallurgy Review, 2022, 43(6): 739-746

[12] KirjavainenV, SchreithoferN, HeiskanenK. Effect of calcium and thiosulfate ions on flotation selectivity of nickel-copper ores [J]. Minerals Engineering, 2002, 15(12): 1-5

[13] BIJçakÖ, EkmekçiZ, CanM, et al.. The effect of water chemistry on froth stability and surface chemistry of the flotation of a Cu - Zn sulfide ore [J]. International Journal of Mineral Processing, 2012, 102: 32-37

[14] QinW-q, WuJ-j, JiaoF, et al.. Mechanism study on flotation separation of molybdenite from chalcocite using thioglycollic acid as depressant [J]. International Journal of Mining Science and Technology, 2017, 27(6): 1043-1049

[15] SuyantaraG P W, HirajimaT, MikiH, et al.. Selective flotation of chalcopyrite and molybdenite using H₂O₂ oxidation method with the addition of ferrous sulfate [J]. Minerals Engineering, 2018, 122: 312-326

[16] RubioJ, SouzaM L, SmithR W. Overview of flotation as a wastewater treatment technique [J]. Minerals Engineering, 2002, 15(3): 139-155

[17] LuoQ-y, ShiQ, LiuD-z, et al.. Effect of deep oxidation of chalcopyrite on surface properties and flotation performance [J]. International Journal of Mining Science and Technology, 2022, 32(4): 907-914

[18] PengW-j, LiuS-g, CaoY-j, et al.. A novel approach for selective flotation separation of chalcopyrite and molybdenite-Electrocatalytic oxidation pretreatment and its mechanism [J]. Applied Surface Science, 2022, 597: 153753

[19] FengB, JiaoX-k, WangH-h, et al.. Improving the separation of chalcopyrite and galena by surface oxidation using hydroxyethyl cellulose as depressant [J]. Minerals Engineering, 2021, 160: 106657

[20] RanJ-c, QiuX-y, HuZ, et al.. Enhance flotation separation of arsenopyrite and pyrite by low-temperature oxygen plasma surface modification [J]. Applied Surface Science, 2019, 480: 1136-1146

[21] DingZ, BiY-x, LiJ, et al.. Flotation separation of chalcopyrite and pyrite via Fenton oxidation modification in a low alkaline acid mine drainage (AMD) system [J]. Minerals Engineering, 2022, 187: 107818

[22] LiuR-q, GuoY-z, WangL, et al.. Effect of calcium hypochlorite on the flotation separation of galena and jamesonite in high-alkali systems [J]. Minerals Engineering, 2015, 84: 8-14

[23] LinS-y, LiuR-q, BuY-j, et al.. Oxidative depression of arsenopyrite by using calcium hypochlorite and sodium humate [J]. Minerals, 2018, 8(10): 463

[24] LiuR-q, GuoY-z, WangL, et al.. Effect of calcium hypochlorite on the flotation separation of galena and jamesonite in high-alkali systems [J]. Minerals Engineering, 2015, 84: 8-14

[25] BayatO, UcurumM, PooleC. Effects of size distribution on flotation kinetics of Turkish sphalerite [J]. Mineral Processing and Extractive Metallurgy, 2004, 113(1): 53-59

[26] XuM-qiu. Modified flotation rate constant and selectivity index [J]. Minerals Engineering, 1998, 11(3): 271-278

[27] AgarG E. The optimization of flotation circuit design from laboratory rate data [C]. Proceedings of the Congrès international de minéralurgie 15, F, 1985

[28] SripriyaR, RaoP V T, ChoudhuryB R. Optimisation of operating variables of fine coal flotation using a combination of modified flotation parameters and statistical techniques [J]. International Journal of Mineral Processing, 2003, 68(1–4): 109-127

[29] BaiS-j, YuP, LiC-l, et al.. Depression of pyrite in a low-alkaline medium with added calcium hypochlorite: Experiment, visual MINTEQ models, XPS, and ToF-SIMS studies [J]. Minerals Engineering, 2019, 141: 105853

[30] WangC-t, LiuR-q, Ahmed KhosoS, et al.. Combined inhibitory effect of calcium hypochlorite and dextrin on flotation behavior of pyrite and galena sulphides [J]. Minerals Engineering, 2020, 150: 106274

[31] YinW-z, YangB, FuY-f, et al.. Effect of calcium hypochlorite on flotation separation of covellite and pyrite [J]. Powder Technology, 2019, 343: 578-585

[32] PalatyS, DeviP V, HoneyJ. Studies on the optimisation of the preparation method and the characterisation of zinc butyl xanthate [J]. Progress in Rubber, Plastics and Recycling Technology, 2009, 25(3): 187-197

[33] PalatyS, DeviP V, JosephR. Use of sodium and potassium butyl xanthate as accelerator for room temperature prevulcanization of natural rubber latex [J]. Journal of Applied Polymer Science, 2011, 122(2): 1325-1332

[34] HanG, WenS-m, WangH, et al.. Identification of copper-sulfide species on the cuprite surface and its role in sulfidization flotation [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 624: 126854

[35] PalatyS, JosephR. Xanthate accelerators for low temperature curing of natural rubber [J]. Journal of Applied Polymer Science, 2000, 78(10): 1769-1775

[36] ZHONG M. Flotation separation of molybdenite and talc by xanthan gum [J]. Powder Technology: An International Journal on the Science Technology of Wet Dry Particulate Systems, 2021, 388(1).

[37] PengW-j, LiuS-g, CaoY-j, et al.. A novel approach for selective flotation separation of chalcopyrite and molybdenite - Electrocatalytic oxidation pretreatment and its mechanism [J]. Applied Surface Science, 2022, 597: 153753

[38] JiangS-h, ZhouK-q, ShiY-q, et al.. In situ synthesis of hierarchical flower-like Bi₂S₃/BiOCl composite with enhanced visible light photocatalytic activity [J]. Applied Surface Science, 2014, 290: 313-319

[39] CaoJ, XuB-y, LinH-l, et al.. Novel Bi₂S₃-sensitized BiOCl with highly visible light photocatalytic activity for the removal of rhodamine B [J]. Catalysis Communications, 2012, 26: 204-208

[40] LuY, SongJ-m, LiW-f, et al.. Preparation of BiOCl/Bi₂S₃ composites by simple ion exchange method for highly efficient photocatalytic reduction of Cr⁶⁺ [J]. Applied Surface Science, 2020, 506: 145000

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