Several physical and chemical detection methods were used to study the basic properties of sintering dust (ESP dust) collected from Baogang Steel Corporation. The result shows that the major constituents of the ESP dust are KCl, NaCl, Fe2O3 and Fe3O4. Water leaching experiment on the sintering dust shows that KCl in the ESP dust can be separated and recovered by water leaching and fractional crystallization. Component analysis of leaching solution indicates that the massive calcium sulfate in the leaching solution should be removed first in order to obtain the pure potassium salt. In order to provide theoretical guidance to inhibit the dissolution of calcium ions from the sintering dust, the water leaching experiment of ESP dust and the dissolution behavior of CaSO4 in the potassium chloride, sodium chloride, potassium sulfate and their mixed salt solution were studied. It is found that, a lower liquid–solid ratio should be chosen in the leaching process to inhibit the dissolution of calcium sulfate dehydrate. Using sodium carbonate solution as a precipitating agent, the influences of the concentration of sodium carbonate solution, reaction temperature, stirring speed and equilibrium time on the preparation of the spherical calcium carbonate were studied. Spherical calcium carbonate with good dispersing performance and grain size distribution in nanometer range of less than 10 μm was obtained. Furthermore, a potassium recovery process with joint production of spherical calcium carbonate was designed. This process is technically viable and considerable in economic benefit.