An original set of nanometer-scale mineralogical analyses of cookeite and the implications for Li enrichment: No. 21 coal, Mengjin Mine, western Henan

Abstract

Critical elements in coal deposits, such as lithium (Li), have attracted attention recently due to their economic value. Many studies have suggested that the high enrichment of Li in coals is predominantly associated with cookeite, a Li–bearing chlorite mineral of hydrothermal origin. However, the identification of cookeite in coal has primarily relied on indirect methods, owing to the low atomic number of Li, which presents significant challenges for precise observation. The Shanxi Formation No. 2₁ coal in North China is enriched in Li. This study established a nanometer–scale mineralogical analytical technique (including high–resolution transmission electron microscopy (HR–TEM), fast Fourier transformation (FFT), and standard mineral simulation single-crystal diffraction (SSCD)) for the identification of the cookeite and evaluated the Li enrichment mechanism and recovery in this coal (low–volatile bituminous to semi–anthracite) based on a model for the Li mineralization. The Li content of the No. 2₁ coal ranges from 25.2 to 203 ppm. The Li content shows a strong correlation with the ash yield, Al₂O₃, SiO₂, and detrital elements, indicating a dominant aluminosilicate affinity and detrital origin. The major aluminosilicate minerals in coal are kaolinite, chlorite, and illite. The geochemical indicators (the Al₂O₃/TiO₂ ratio and its relationships with the Zr/TiO₂, Nb/Y, and Nb/Yb ratios) indicate that the sediment sources are determined to be intermediate–felsic igneous rocks, probably the Mesoproterozoic moyite (a type of K– feldspar granite) in the Yinshan Oldland. Additionally, the coal can be divided vertically into three sections (Sections I, II, and III), corresponding to three stages of peat formation. Overall, from Section I to Section III, the degree of detrital input increased, and the groundwater and marine influences strengthened and weakened, respectively. Section II exhibits anomalous Li enrichment mainly associated with reducing environments and the geochemical barrier caused by the interaction between infiltrating seawater and groundwater. The detrital kaolinite assemblage with authigenic minerals such as secondary REE–rich minerals (bastnasite), chamosite, and quartz, as well as the REY enrichment patterns, suggests that the No. 2₁ coals, mainly Section II, may have existed the hydrothermal alteration. Cookeite is identified primarily in Section II and coexists with kaolinite based on TEM observations, suggesting that the cookeite is of hydrothermal origin and formed from pre–existing Li–rich kaolinite. Most samples from Section II meet the mining grade of Be–Li–Nb–Ta ore deposits (Li₂O > 0.2%). Thus, this study offers valuable insights into the extraction and recovery of Li from coal combustion residues, particularly when cookeite is the primary Li–bearing mineral.