Toward sustainability: Dual strategies for tungsten and fluorine upcycling from fluorite-scheelite ores via phase-selective transformation

Tungsten and fluorine are critical to clean energy and semiconductor technologies, yet their frequent co-occurrence in complex ores creates long-standing barriers to efficient and sustainable utilization. Current extraction routes are hampered by severe mutual interference, with substantial tungsten losses entrapped in fluorite concentrate and concomitant fluorine losses retained in tungsten products. Here we present two complementary strategies that enable the simultaneous upcycling of fluorine and tungsten through phase-selective transformation. In the first route, fluorogypsum produced during HF synthesis from tungsten-bearing fluorite, is treated with H 2 O 2 , where peroxo coordination selectively leaches tungsten while stabilizing calcium sulfate; this achieves tungsten recoveries above 95 % at 30 °C and converts waste into environmentally benign gypsum. In the second, tungsten-bearing fluorite is directly decomposed in an H 2 SO 4 -H 3 PO 4 system with added F − , which preferentially complexes Si in the feedstock without consuming fluorine from CaF 2 , thereby suppressing CaF 2 dissolution and CaSO 4 ·2 H 2 O formation under acidic conditions and enabling selective tungsten extraction of up to 95 % while producing a high-grade fluorite concentrate (98.6 % CaF 2 ). Mechanistic studies reveal that the selectivity arises from competitive coordination and solubility control between tungsten- and calcium-bearing species. By coupling mineralogical insight with tailored reaction chemistry, this dual-pathway enables co-recovery of tungsten and fluorine from fluorite-scheelite ores, offering an environmentally benign and streamlined route to sustainable processing of coupled critical elements.