In recent years, the steel industry has accumulated approximately 100 million tons of dust annually, severely threatening the environment. Rotary kiln technology is one of the main industrial methods used to process this dust. However, some substances in flue gas congeal on the cooling wall of the gas duct and seriously affect production. In this study, the properties and formation mechanisms of the coagulum were investigated on the basis of experimental and thermodynamic analyses. The experimental results showed that the coagulum is mainly composed of chlorides (KCl, NaCl, and ZnCl2), oxides (ZnO, FeO), and carbon, with three structures: lumps, fibers, and particles. Based on a thermodynamic analysis, a reasonable explanation was proposed to clarify the formation mechanism. The liquid phase (a eutectic system of KCl–NaCl–ZnCl2), dendrites (KCl, NaCl), and particles (ZnO, FeO, C) were found to act as binders, stiffeners, and aggregates in the coagulum, respectively, constituting a composite structure. Liquids acting as binders are essential for coagulum formation, and dendrites and particles strengthen this effect. Furthermore, the eutectic system of chlorides plays a crucial role in coagulum formation. The results of the present study offer a theoretical understanding of gas-duct coagulation and will provide guidance for adopting alleviation measures.