Thermodynamic theory was employed in this study to investigate the feasibility of separating antimony (Sb) from crude arsenic (As) using vacuum sublimation. Ab initio molecular dynamics simulations are used to calculate the structure, stability, and diffusion properties of AsmSbn (m + n ≤ 6) clusters. As4, As3Sb, As2Sb2, and AsSb3 are the possible clusters in this thermodynamic calculation, and the molecular dynamics results confirmed their structural stability and stabilization in the gas phase. As4 had the largest diffusion coefficients, which is the reason it separates from the Sb-containing clusters (As3Sb, As2Sb2, and AsSb3) during gas-phase diffusion and condensation processes. The experimental results show that As vapor was transformed from crystalline to amorphous with increasing subcooling, and the Sb-containing clusters that enter the gas phase were mainly condensed and deposited at the proximal end of the heating zone. Not considering the volatilization rate, the removal rate of Sb in products can reach 99.35% by increasing the condensation disk and expanding the condensation zone; thus, experiments confirmed that industrial crude arsenic can realize deep Sb removal after vacuum sublimation.
