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Minerals 2018, 8(5), 208; https://doi.org/10.3390/min8050208

Removal Process of Structural Oxygen from Tetrahedrons in Muscovite during Acid Leaching of Vanadium-Bearing Shale

1,2,3
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1,2,3,4,* , 1,2,3
,
1,2,3
and
1,2
1
Hubei Collaborative Innovation Center for High Efficient Utilization of Vanadium Resources, Wuhan 430081, China
2
Hubei Provincial Engineering Technology Research Center of High Efficient Cleaning Utilization for Shale Vanadium Resource, Wuhan 430081, China
3
School of Resource and Environmental Engineering, Wuhan University of Science and Technology, Wuhan 430081, China
4
College of Resources and Environmental Engineering, Wuhan University of Technology, Wuhan 430070, China
*
Author to whom correspondence should be addressed.
Received: 21 April 2018 / Revised: 4 May 2018 / Accepted: 9 May 2018 / Published: 11 May 2018
(This article belongs to the Special Issue Process Mineralogy of Critical Metals)
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Abstract

Process mineralogy shows that most vanadium in mica-type black shale exists in the octahedral sites of muscovite. The extraction of vanadium mainly occurs in the acid leaching process with participation of H ions. In this work, we firstly analyzed the dissolution rules of elements in acid leaching of muscovite, then adopted the density functional theory (DFT) calculation to accurately visualize the primary process of the surface corrosion of muscovite by H ions. The experimental results show that K releases the fastest and the release of Al is consistent with K. The simulation results find that the H preferentially shifts to the unsaturated structured O of the tetrahedron to form a strong 001 surface hydroxyl after replacing K, as well as relaxing the near Al(Si)–O bonds for the further removal of structural oxygen. Then, the 001 surface hydroxyls more likely participate in the dehydroxylation reaction through the reverse-path mechanism to remove the structural oxygen and break the hexagonal rings of the tetrahedral sheets. Remarkably, the formation and removal of structural water are overall endoergic, meaning that the disintegration of muscovite requires a sustained supply of heat. Further, the octahedral sheets where vanadium exists can be exposed to the acid environment for overall destruction. This detailed atomic migration process in acid leaching of black shale is visualized, which not only illuminates the reaction mechanism of H ions with the muscovite, but also provides guidance for vanadium extraction from black shale and a new concept for the destruction of other minerals. View Full-Text
Keywords: vanadium; muscovite; black shale; hydrogen; acid leaching; DFT vanadium; muscovite; black shale; hydrogen; acid leaching; DFT
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Zheng, Q.; Zhang, Y.; Liu, T.; Huang, J.; Xue, N. Removal Process of Structural Oxygen from Tetrahedrons in Muscovite during Acid Leaching of Vanadium-Bearing Shale. Minerals 2018, 8, 208.

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