A fundamental dynamic model was successfully used in the implementation of multiple control methodologies via a novel inferential control strategy using HYSYS to treat missing process measurements. Results from steady state and dynamic testing of an azeotropic distillation system of methanol, normal pentane, and cyclohexane were obtained. Steady-state equilibrium and nonequilibrium models were developed and validated with experimental data from a packed distillation unit operated at finite reflux. Dynamic multicomponent distillation experiments were also carried out, and experimental process data were collected using the pilot scale experimental unit. Two different variable pairings were studied, and the results from individual control loop configurations were compared with a multivariable control strategy using the model predictive control (MPC) software Predict Pro.