Abstract
The amblygonite-montebrasite group of minerals is the most abundant lithium-bearing phosphate found in phosphorus-rich lithium pegmatites. The separation of montebrasite from spodumene—the primary lithium ore mineral—commonly by flotation, is necessary for effective downstream lithium extraction. Understanding how water molecules interact with the montebrasite surface is necessary to understand its separation from other minerals by flotation. This study examined the interaction between water and montebrasite using dissolution tests, surface charge analysis, and various spectroscopic techniques (UV, FTIR, XPS, and XANES), all supported by density functional theory calculations. We found evidence of amphoteric properties (hydroxylation of surface Al and Li, and protonation of phosphate group) with acid-base reactions, F/OH ion exchange (-142.61 kcal/mol), non-stoichiometric dissolution (F > Li > Al > P), and dissociative chemisorption (-187.06 kcal/mol) at the mineral–water interface. This surface reactivity could impact solution chemistry and influence collector adsorption on the mineral surface during flotation. Surface dissolution and ion exchange may lead to the release of Li to industrial process water, in addition to F, potentially forming LiF in solution. These findings are important in the froth flotation field because the change in solution pH caused by significant amounts of amphoteric minerals, such as montebrasite, can affect flotation results since flotation performance depends on pH, leading to unstable flotation circuits. However, this issue may be managed by achieving and/or maintaining an equilibrium pH through an appropriate conditioning stage. This work builds important knowledge of montebrasite surface properties and the montebrasite-water interface, essential to understanding many natural phenomena and engineering processes. Accordingly, we discussed the implications for montebrasite froth flotation, mineral alteration, environmental impact, and its potential as a promising functional material for heterogeneous catalysis and Li-ion batteries.
Supplementary materials
Title
Supporting information for the surface reactivity of montebrasite
Description
XRD pattern of the montebrasite sample used in this study, showing the presence of trace amounts of hydroxyapatite, UV spectrum of residual solution of 80 g/L montebrasite-water interaction for 120 min, exposed planes (hkl) of the montebrasite sample used in this study, Shift in pH due to water interaction with montebrasite (solid concentration: 1g/L), raw data of FTIR measurements before and after hydration, wide scan XPS results of montebrasite before and after hydration, extended chemical composition and chemical states of the montebrasite surface before and after hydration, FWHM for different energy levels of the overall high-resolution spectra before and after montebrasite hydration, adsorption sites tested before structural relaxation, adsorption energies of 24 starting configurations, Bader charge distribution of the dissociated water molecule as a function of the distance between OH and H, charge density difference on the dissociated water molecule showing charge accumulation and charge depletion.
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