Cleaner extraction of white phosphorus from phosphate rock through molten salt electrolysis

White phosphorus (P4) is an essential raw material for the production of phosphorus chemicals. The conventional carbothermal reduction process used to extract P4 from phosphate rock is known as energy intensive and environmentally polluting, posing obstacles to meeting the urgent global demands for clean production and carbon neutrality. Moreover, the low product purity restricts its application in high-value industries. This paper presents an original approach that is both simple and coke-free for extracting high-purity P4. The method involves electrolyzing dissolved phosphate rock in molten CaCl2 at a mild temperature. We undertake an in-depth investigation into the dissolution behavior of phosphate rock in molten CaCl2 and the electrolysis behavior of the melt. The experiments demonstrate the rapid dissolution of phosphate in the rock when exposed to molten CaCl2, reaching saturation within a short time (e.g., within 10 min at 850 °C). The dissolution of phosphate shows a preference over silicates present in the phosphate rock. The electrochemical reduction of PO43− in molten CaCl2 is electrochemically reversible, as observed at potential scan rates not exceeding 0.20 V·s−1. The obtained P4 product through electrolysis is of higher purity compared to the industrial-grade commercial product produced via carbothermal reduction. The implementation of pre-electrolysis can further improve the purity of the product and the current efficiency of the electrolysis process. The theoretical electricity and carbon consumption in the electrolysis method are estimated to be 9.12 kWh and 0.53 kg, respectively, for every 1 kg of P4 produced. These values are lower than the conventional carbothermal reduction process. This cutting-edge electrolysis method represents a paradigm shift towards a more sustainable development of the phosphorus chemical industry, thereby showcasing its potential for revolutionizing the field.