Metrics for Evaluation and Screening of Metal–Organic Frameworks for Applications in Mixture Separations

[Image: see text] For mixture separations, metal–organic frameworks (MOFs) are of practical interest. Such separations are carried out in fixed bed adsorption devices that are commonly operated in a transient mode, utilizing the pressure swing adsorption (PSA) technology, consisting of adsorption and desorption cycles. The primary objective of this article is to provide an assessment of the variety of metrics that are appropriate for screening and ranking MOFs for use in fixed bed adsorbers. By detailed analysis of several mixture separations of industrial significance, it is demonstrated that besides the adsorption selectivity, the performance of a specific MOF in PSA separation technologies is also dictated by a number of factors that include uptake capacities, intracrystalline diffusion influences, and regenerability. Low uptake capacities often reduce the efficacy of separations of MOFs with high selectivities. A combined selectivity–capacity metric, Δq, termed as the separation potential and calculable from ideal adsorbed solution theory, quantifies the maximum productivity of a component that can be recovered in either the adsorption or desorption cycle of transient fixed bed operations. As a result of intracrystalline diffusion limitations, the transient breakthroughs have distended characteristics, leading to diminished productivities in a number of cases. This article also highlights the possibility of harnessing intracrystalline diffusion limitations to reverse the adsorption selectivity; this strategy is useful for selective capture of nitrogen from natural gas.