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Pyrometallurgy is the primary technique for the production of many nonferrous metals such as copper, lead, and zinc. The phase equilibrium information of smelting slags plays an important role in the efficient extraction of metals and energy consumption. The experimental technologies used in phase equilibrium studies are compared. The presentation and applications of the pseudo-ternary and pseudo-binary phase diagrams are demonstrated in the Fe–Si–Ca–Zn–Mg–Al–Cu–S–O system. Experimental results are also compared with the predictions of FactSage to evaluate the accuracy of the current thermodynamic database. This review paper provides comprehensive information for the operation of nonferrous metals and optimization of the thermodynamic database.