Automotive catalysts are the largest consumption source of platinum group metals (PGMs). When it exceeds its useful life, spent automotive catalysts (SACs) are the most important secondary PGMs resource and are classified as hazardous solid waste. Recycling SAC is a promising solution to alleviate the shortage of PGMs resources for projects and reduce environmental pollution. The technology for recovering PGMs by iron-melting collection can obtain Fe-PGMs alloy and harmless glass slag. In this paper, the spontaneous aggregation and growth behaviour of Fe and PGMs in slag at melting temperature were studied, and the settling velocity of Fe-PGMs particles in the slag was calculated to be 6.68 × 10