The steady-state behavior of an industrial reactive distillation column producing propylene oxide from propylene chlorohydrin and calcium hydroxide is studied. The reaction and separation steps are performed simultaneously in order to avoid the hydrolysis of the oxide into propylene glycol. The description of the thermodynamic behavior of the mixture is complicated by the presence of electrolytes in solution and by the existence of salting-out effects. A model of the process is developed using a process simulator. Simulated results appear to be in good agreement with those obtained from measurements performed in the real plant. The model is then used to improve the understanding of the process, to guide the choice of the optimal operation conditions, and to suggest possible changes to the plant layout in order to improve the process performance.