Extractability and mineralogical evaluation of rare earth elements from Waterberg Coalfield run-of-mine and discard coal

This study explores the extraction of rare earth elements (REEs) from high-ash run-of-mine and discard coal sourced from the Waterberg Coalfield. Three distinct methods were employed: (1) ultrasonic-assisted caustic digestion; (2) direct acid leaching; and (3) ultrasonic-assisted caustic-acid leaching. Inductively coupled plasma mass spectrometry was utilized to quantify REEs in both the coals and resultant leachates. Leaching the coals with 40% NaOH at 80 °C, along with 40 kHz sonication, yielded a total rare earth element (TREE) recovery of less than 2%. Notable enrichment of REEs was observed in the run-of-mine and discard coal by 17% and 19%, respectively. Upon employing 7.5% HCl, a recovery of less than 11.0% for TREE was achieved in both coal samples. However, leaching the caustic digested coal samples with 7.5% HCl significantly enhanced the TREE recovery to 88.8% and 80.0% for run-of-mine and discard coal, respectively. X-ray diffraction analysis identified kaolinite and quartz as the predominant minerals. Scanning electron microscopy-energy dispersive microanalysis revealed monazite and xenotime as the REE-bearing minerals within the coal samples. These minerals were found either liberated, attached to, or encapsulated by the clay-quartz matrices. Further mineralogical assessments highlighted the increased REE concentrations in coals post-caustic digestion and subsequent recovery during acid leaching. This increase was attributed to the partial dissolution of kaolinite encapsulating the RE-phosphates and the digestion of REE-bearing minerals. Notably, undissolved REE-bearing elements in the caustic-acid-leached coal indicated the necessity of harsh leaching conditions to augment REE recovery from these coal samples.