Improvements in recovery of rare earth elements (REEs) from coal via fluidized-bed combustion: Thermal alteration of REE mineralogy and its impact on element extractability

Abstract

The extraction of rare earth elements (REE) from coal ash has attracted significant attention, but satisfactory solutions have not yet been achieved. Indeed, the REE extractability is largely determined by the transformation behavior of REE during coal combustion. This study found that the controlled combustion conditions of circulated fluidized-bed boiler (CFB) can both utilize the heating value and enhance the recovery of REE from coal. Tests were conducted using a bituminous coal with REE concentration of approximately 149 ppm in an industrial 35 t/h CFB boiler with controlled boiler loads and coal sources. Advanced automated image analysis by scanning electron microscopy (AIA-SEM) and sequential leaching procedure were employed to clarify the speciation transformation behavior of REE in boilers and investigate the effects of these transformations on the leachability of REE. Approximately 75 % of REE partitioned into fly ash and enriched in particles < 45 μm (∼710 ppm) after combustion. Acid leaching tests under mild conditions (1 M HCl at 60 ℃ and S/L = 1:25) performed on coal, bulk ashes, and sieved ashes revealed an improvement in REE leaching ratio from coal (21.34 %) to fly ash (71.07 %). Particle size played a crucial role in acid extractability, particularly for middle and heavy REE in cyclone ash but had no influence on those in fly ash. The dominant forms of REE in coal including Ca-REE fluorocarbonates (36.7 %), aluminophosphates (12.0 %), and organic-bound REE (approximately 20 %) significantly decreased, contributing to the formation of leachable rare earth oxides (∼65 %) in ash. Furthermore, the small size of REE mineral grains in coal (over 50 % below 5 μm) and extensive mineral fragmentation occurring in boiler resulted in the enrichment and enhanced REY leachability in fine ash.