An isothermal equilibrium theory analysis, based on linear isotherms and a binary feed stream, was carried out to evaluate the feasibility of a rectifying PSA process for producing a pure heavy component at high recovery. Analytic expressions were derived to describe the performance of this process at the periodic state. The performance was also analyzed in terms of the different concentration and velocity profiles exhibited during various cycle steps that included the analysis of complex shock and simple wave interactions. Based on a parametric study, periodic behavior was established for a wide range of process conditions; and a design study with the PCB activated carbon–H2–CH4 system at 25°C further demonstrated the feasibility of a rectifying PSA cycle for producing a 100% CH4 stream from a dilute feed stream (y = 0.01) with a respectable recovery (80%), and reasonable process conditions. It also demonstrated the potential usefulness of an actual rectifying PSA process for bulk gas separation and purification.