Recent developments in separation technology by adsorption have included the development of new structured adsorbents which offer some attractive characteristics compared to a typical packed bed. These improved features include lower energy consumption, higher throughput and superior recovery and purity of product. However, the exact combination of structural, geometric parameters which yields optimum performance is unknown. This study formulates a methodology for comparison based on a variety of analytical and numerical models and uses it to examine the performance of different adsorbent configurations. In particular, monolithic, laminate and foam structures are evaluated and compared to a packed bed of pellets. The effects of physical adsorbent parameters which govern the performance of a PSA process are considered during model development. Comparisons are carried out based on mass transfer kinetics, adsorbent loading and pressure drop of a PSA system for CO2/N-2 separation. The results indicated that structured adsorbents can provide superior throughput to packed beds provided their geometrical parameters exceed certain values. For example, laminate structures can offer superior performance to a packed bed of pellets only if the critical sheet thickness and spacing are less than about 0.2 mm. Each adsorbent structure should be designed to operate at its "optimal" velocity. When operating at velocities higher than the "optimal" value, the increase in pressure drop and length of the mass transfer zone more than offsets gains accrued through reduction in cycle time. (C) 2009 Elsevier Ltd. All rights reserved.