Three binary vapor-liquid equilibrium (VLE) data were measured : tertbutanol-ethanediol, tertbutanol-KAc, and ethanediol-KAc. Experimental data were correlated with the salt-containing local composition model (SCLCM). For the multicomponent system, VLE data predicted by SCLCM are in agreement with the data in the literature. An industrial plant (3500T/Y) of salt-containing extractive distillation for the tertbutanol/water/ethanediol/potassium acetate system was simulated by SCLCM and improved the Rose relaxation method. Simulation results agree well with industrial data.