Recently proposed pseudoensemble Monte Carlo methods are extended in this work to map out diverse phase diagrams (projections of the phase-coexistence hypersurface) of multicomponent mixtures required to characterize fluid-phase equilibrium phenomena and to design separation processes. Within the pseudoensemble framework the macroscopic models of different equilibrium processes can be readily integrated to the mathematical constraints that specify the thermodynamic state of the system. The proposed Monte Carlo methods allow, for example, the simulation of isopleths and cloud-point lines to compare experimental to simulation data and to test molecular force fields. Applications of this approach include the study of retrograde phenomena in a model natural-gas mixture through simulation of dewlines and coexistence lines at constant vaporization fraction. As demonstrated, pseudoensemble simulations can also be used to generate the thermodynamic data necessary to solve problems encountered in continuous and discontinuous distillation processes.