Reverse cationic flotation of low-grade phosphate ore using quaternary ammonium salt as a collector and its adsorption mechanism

Abstract

A novel quaternary ammonium salt collector, LH-01, was employed for the reverse cationic flotation of a magnesium-depleted concentrate (P₂O₅ grade of 19.72wt%, SiO₂ content of 44.26wt%). We achieved an outstanding phosphate concentrate with a P₂O₅ grade of 35.16wt%, a SiO₂ content of 6.06wt%, and a P₂O₅ recovery of 75.88%. This process was accomplished through two sequential reverse cationic flotation processes designed for quartz removal. Importantly, the quartz removal by LH-01 reached 94.17%, far superior to that by dodecyltrimethylammonium chloride, achieving highly selective separation of quartz and apatite. To understand the adsorption mechanism and kinetics of the collector LH-01 on quartz and apatite surfaces, various techniques, such as quartz crystal microbalance with dissipation, atomic force microscopy, and X-ray photoelectron spectroscopy, were employed. Results revealed that the adsorption layer of LH-01 on the apatite surface was thin and rigid, with a significantly lower hydrophobic effect than that of the viscoelastic multiple adsorption layer formed by LH-01 on the quartz surface. This disparity was identified as the primary factor contributing to the selective flotation separation of apatite and quartz. Moreover, the adsorption of LH-01 on the quartz surface was the result of multiple forces, including electrostatic adsorption, multiple-hydrogen-bond adsorption, and intermolecular hydrophobic association.

Keywords

Calcareous–siliceous phosphate ore / Quaternary ammonium salt / Quartz / Quartz crystal microbalance with dissipation / Adsorption mechanism

References

[1] R.G. Cui, Y.F. Zhang, J. Guo, Z.H. Guo, Y.P. Xiao, Development strategy of phosphate rock in China under global allocation of resources, Chin. J. Eng. Sci. 21 (1) (2019) 128.

[2] Y.M. Wang, Q.S. Chen, B.B. Dai, D.L. Wang, Guidance and review: Advancing mining technology for enhanced production and supply of strategic minerals in China, Green Smart Min. Eng. 1 (1) (2024) 2-11.

[3] Y.Y. Ruan, D.S. He, R. Chi, Review on beneficiation techniques and reagents used for phosphate ores, Minerals 9 (4) (2019) 253.

[4] M. Derhy, Y. Taha, R. Hakkou, M. Benzaazoua, Review of the main factors affecting the flotation of phosphate ores, Minerals 10 (12) (2020) 1109.

[5] X.B. Li, Q. Zhang, B. Hou, J.J. Ye, S. Mao, X.H. Li, Flotation separation of quartz from collophane using an amine collector and its adsorption mechanisms, Powder Technol. 318 (2017) 224-229.

[6] J. Fang, Y.Y. Ge, J. Yu, Adsorption behavior and mechanism of an ether amine collector on collophane and quartz, Physicochem. Probl. Miner. Process. 55 (1) (2019) 301-310.

[7] W.B. Liu, W.X. Huang, F. Rao, Z.L. Zhu, Y.M. Zheng, S.M. Wen, Utilization of DTAB as a collector for the reverse flotation separation of quartz from fluorapatite, Int. J. Miner. Metall. Mater. 29 (3) (2022) 446-454.

[8] Z.X. Wu, D.P. Tao, P. Zhang, X.J. Jiang, M. Jiang, Synergistic effect of DBP with CTAB on flotation separation of quartz from collophane, Minerals 11 (11) (2021) 1196.

[9] Z.Q. Huang, C. Cheng, K. Li, S.Y. Zhang, J.R. Zhou, W.H. Luo, Z.W. Liu, W.W. Qin, H.L. Wang, Y.J. Hu, G.C. He, X.Y. Yu, T.S. Qiu, W. Fu, Reverse flotation separation of quartz from phosphorite ore at low temperatures by using an emerging Gemini surfactant as the collector, Sep. Purif. Technol. 246 (2020) 116923.

[10] Y.Y. Zhao, W. Xu, G.J. Mei, M.M. Yu, S.Y. Yang, Z. He, Flotation separation of quartz from phosphorite using an imidazole ionic liquid collector and its adsorption mechanism, Physicochem. Probl. Miner. Process. 58 (1) (2022) 159-168.

[11] J. Kou, D. Tao, G. Xu, A study of adsorption of dodecylamine on quartz surface using quartz crystal microbalance with dissipation, Colloids Surf. A Physicochem. Eng. Asp. 368 (1-3) (2010) 75-83.

[12] I.G. Sedeva, R. Fetzer, D. Fornasiero, J. Ralston, D.A. Beattie, Adsorption of modified dextrins to a hydrophobic surface: QCM-D studies, AFM imaging, and dynamic contact angle measurements, J. Colloid Interface Sci. 345 (2) (2010) 417-426.

[13] C. Gutig, B.P. Grady, A. Striolo, Experimental studies on the adsorption of two surfactants on solid−aqueous interfaces: Adsorption isotherms and kinetics, Langmuir 24 (23) (2008) 13814.

[14] S. Paul, D. Paul, T. Basova, A.K. Ray, Studies of adsorption and viscoelastic properties of proteins onto liquid crystal phthalocyanine surface using quartz crystal microbalance with dissipation technique, J. Phys. Chem. C. 112 (31) (2008) 11822-11830.

[15] G. Sauerbrey, Verwendung von Schwingquarzen zur Wägung dünner Schichten und zur Mikrowägung, Z. Für Phys. 155 (2) (1959) 206-222.

[16] M.V. Voinova, M. Rodahl, M. Jonson, B. Kasemo, Viscoelastic acoustic response of layered polymer films at fluid-solid interfaces: Continuum mechanics approach, Phys. Scr. 59 (5) (1999) 391-396.

[17] B.D. Vogt, E.K. Lin, W.L. Wu, C.C. White, Effect of film thickness on the validity of the sauerbrey equation for hydrated polyelectrolyte films, J. Phys. Chem. B 108 (34) (2004) 12685-12690.

[18] Y.X. Yu, L.Q. Ma, Z.L. Zhang, L.Y. Wang, L.Y. Yao, Mechanism of entrainment and slime coating on coal flotation, J. China Coal Soc. 40 (3) (2015) 652-658.

[19] D.H. Hoang, A. Hassanzadeh, U.A. Peuker, M. Rudolph, Impact of flotation hydrodynamics on the optimization of fine-grained carbonaceous sedimentary apatite ore beneficiation, Powder Technol. 345 (2019) 223-233.

[20] J. Yao, X.Q. Ban, Y. Xie, W.Z. Yin, Y.L. Wang, F.J. Xue, Research advancement of efficient flotation separation technologies for magnesium-containing minerals, Green. Smart Min. Eng. 1 (2) (2024) 140-156.

[21] D.H. Hoang, N. Kupka, U.A. Peuker, M. Rudolph, Flotation study of fine grained carbonaceous sedimentary apatite ore-Challenges in process mineralogy and impact of hydrodynamics, Miner. Eng. 121 (2018) 196-204.

[22] T. Leistner, U.A. Peuker, M. Rudolph, How gangue particle size can affect the recovery of ultrafine and fine particles during froth flotation, Miner. Eng. 109 (2017) 1-9.

[23] Z.H. Wang, G. Han, Q.C. Feng, Selective flotation of galena and sphalerite using N-(phosphonomethyl) iminodiacetic acid as an eco-friendly depressant, Green Smart Min. Eng. 1 (1) (2024) 96-103.

[24] Z.C. Pan, Y.F. Wang, Q. Wei, X.T. Chen, F. Jiao, W.Q. Qin, Effect of sodium pyrophosphate on the flotation separation of calcite from apatite, Sep. Purif. Technol. 242 (2020) 116408.

[25] X. Liu, H.H. Luo, R.J. Cheng, C.X. Li, J.H. Zhang, Effect of citric acid and flotation performance of combined depressant on collophanite ore, Miner. Eng. 109 (2017) 162-168.

[26] H. Zhang, W.C. Chai, Y.J. Cao, Flotation separation of quartz from gypsum using benzyl quaternary ammonium salt as collector, Appl. Surf. Sci. 576 (2022) 151834.

[27] J.X. Zhang, Y.P. Zheng, P.Y. Yu, L. He, H.N. Wang, R.M. Wang, Synthesis, characterization and surface-activity of a polyoxyethylene ether trimeric quaternary ammonium surfactant, J. Surfactants Deterg. 13 (2) (2010) 155-158.

[28] S.F. Weng, Fourier Transform Infrared Spectroscopy Analysis, Chemical Industry Press, Beijing, 2010.

[29] Y.M. Zhu, J.L. Chen, J.W. Jia, S.A. Liu, Collecting performance and mechanism of a new cation collector to quartz, Met. Mine 5 (2015) 81-84.

[30] W.B. Liu, K.L. Tong, R. Ding, W.G. Liu, P.X. Zhao, W.H. Sun, Q. Zhao, S.K. Zhao, Synthesis of a novel hydroxyl quaternary ammonium collector and its selective flotation separation of quartz from hematite, Miner. Eng. 200 (2023) 108109.

[31] Z.H. Zhang, Z.L. Huang, H.B. Shi, R.A. Chi, J.Q. Li, N. Sun, Synthesis and growth mechanism of carbonated hydroxyapatite whisker from natural collophanite via a template-directed homogeneous precipitation method, J. Alloy. Compd. 486 (1-2) (2009) 415-417.

[32] R. Mathew, R.P. Cooney, J. Malmstrom, C.S. Doyle, Atomic force microscopy and angular-dependent X-ray photoelectron spectroscopy studies of anchored quaternary ammonium salt biocides on quartz surfaces, Langmuir 34 (16) (2018) 4750-4761.

[33] L.O. Filippov, V.V. Severov, I.V. Filippova, Mechanism of starch adsorption on Fe-Mg-Al-bearing amphiboles, Int. J. Miner. Process. 123 (2013) 120-128.

[34] W.G. Liu, W.B. Liu, X.Y. Wang, D.Z. Wei, B.Y. Wang, Utilization of novel surfactant N-dodecyl-isopropanolamine as collector for efficient separation of quartz from hematite, Sep. Purif. Technol. 162 (2016) 188-194.

[35] W.B. Liu, W.G. Liu, D.Z. Wei, M.Y. Li, Q. Zhao, S.C. Xu, Synthesis of N,N-Bis(2-hydroxypropyl)laurylamine and its flotation on quartz, Chem. Eng. J. 309 (2017) 63-69.

[36] W.B. Liu, W.G. Liu, B.Y. Wang, H. Duan, X.Y. Peng, X.D. Chen, Q. Zhao, Novel hydroxy polyamine surfactant N-(2-hydroxyethyl)-N-dodecyl-ethanediamine: Its synthesis and flotation performance study to quartz, Miner. Eng. 142 (2019) 105894.

[37] J. Kou, Y. Guo, T.C. Sun, S.H. Xu, C.Y. Xu, Adsorption mechanism of two different anionic collectors on quartz surface, J. Cent. South Univ. Sci. Technol. 46 (11) (2015) 4005-4014.

[38] J. Kou, S. Xu, T. Sun, C. Sun, Y. Guo, C. Wang, A study of sodium oleate adsorption on Ca²⁺ activated quartz surface using quartz crystal microbalance with dissipation , Int. J. Miner. Process. 154 (2016) 24-34.

[39] H. Jiang, L.H. Xu, Y.H. Hu, D.Z. Wang, C.K. Li, W. Meng, X.J. Wang, Flotation and adsorption of quaternary ammonium cationic collectors on diaspore and kaolinite, Trans. Nonferrous Met. Soc. China 21 (11) (2011) 2528-2534.

[40] Y.M. Zhu, J. Liu, Y.J. Li, Interaction Theory of Flotation Reagents for Non-sulphide Ores, Metallurgical Industry Press, Beijing, 2021.

[41] X.M. Wang, Y. Lu, Development of surface analytical techniques and their application in mineral engineering-Atomic force microscopy, J. Guizhou Univ. Nat. Sci. 35 (6) (2018) 1-12.

[42] P.R.P. Paiva, M.B.M. Monte, R.A. Simão, J.C. Gaspar, In situ AFM study of potassium oleate adsorption and calcium precipitate formation on an apatite surface , Miner. Eng. 24 (5) (2011) 387-395.

[43] X.C. Wang, Q. Zhang, Insight into the influence of surface roughness on the wettability of apatite and dolomite, Minerals 10 (2) (2020) 114.

[44] X.C. Wang, Q. Zhang, Role of surface roughness in the wettability, surface energy and flotation kinetics of calcite, Powder Technol. 371 (2020) 55-63.

[45] X.Y. Peng, W.B. Liu, Q. Zhao, W.G. Liu, K.L. Tong, P.X. Zhao, Development and utilization of a novel hydrogen bonding enhanced collector in the separation of apatite from quartz, Miner. Eng. 180 (2022) 107477.