High-Throughput Computational Screening of Metal–Organic Frameworks for the Separation of Methane from Ethane and Propane

Abstract

Efficient separation of mixtures of light hydrocarbons is an industrially demanding but challenging process. In this study, we present a high-throughput computational screening of ∼12,000 experimentally realizable metal–organic framework (MOF) structures in order to identify the best candidate that can separate methane from ethane and propane at ambient conditions. We calculated several performance metricsadsorption selectivity, working capacity, and regenerability to assess the performance of the MOFs in the database. The MOFs were screened based on high adsorbent performance score and regenerability >80%. MOFs AZIVAI and BEWCUD were found to be performing the best for the separation of methane from its binary and ternary mixtures with ethane and propane. We looked at various structure–property correlations of selectivity and working capacity that reveal a generic trade-off relation between these two metrics. Selectivity correlates strongly with the heat of adsorption in a linear fashion, whereas working capacity exhibits an increasing and then decreasing behavior with the heat of adsorption complementing the trade-off relation between selectivity and working capacity. We have also screened out few promising MOFs that are thermally and chemically stable and discussed their experimental stability conditions in detail.

Engineering metal–organic frameworks for adsorption-based gas separations: from process to atomic scale

“…203,159,204 This method involves the simulation of adsorption properties for the desired target gases, with the aim to single out those materials that are predicted to provide the best separation performance, evaluated using metrics such as selectivity, working capacity, energy penalty or composite metrics derived therefrom. The focus of these studies used to be primarily on CO2 separations, 102,131,[205][206][207][208][209][210][211][212][213][214][215][216][217][218][219] but recent years have seen a broadening in scope, to cover also hydrocarbons separation, [220][221][222] acetylene purification 91 and Xe/Kr separation. [223][224][225] These computation-based approaches provide a large amount of information that can, in principle, be very valuable to chemists at the sorbent development stage, allowing to make better decisions about the type of material to target for a certain gas separation.…”

High-Throughput Screening of Anion-Pillared Metal–Organic Frameworks for the Separation of Light Hydrocarbons

“…On the basis of the CoRE MOF 2019, Solanki and Borah presented a high-throughput screening based on adsorption selectivity, working capacity, regenerability, and adsorbent performance score to identify candidate materials for propane/propene separations, reporting BOLZIN (NU-1100) as the best performing MOF. Ponraj and Borah performed similar high-throughput screening for the separation of methane from ethane and propane and found that the MOFs AZIVAI and BEWCUD performed well.…”

Combined GCMC, MD, and DFT Approach for Unlocking the Performances of COFs for Methane Purification

“…Borah and Ponraj screened about 12 000 MOFs for C 2 H 6 /CH 4 separation and highlighted that MOFs with the Zr 4+ cation are promising candidates for purification of CH 4 . 25 MOFs have also been investigated for membrane-based CH 4 /C 2 H 6 and CH 4 /H 2 separations, 26 , 27 and all of these works have highlighted the high potential of MOFs for CH 4 purification.…”

“…Yan et al used molecular simulations to examine CH 4 /N 2 mixture separation potentials of 5109 MOFs and revealed that MOFs with pore-limiting diameters (PLDs) in the range of 3.8–4.7 Å achieve high selectivities. Borah and Ponraj screened about 12 000 MOFs for C 2 H 6 /CH 4 separation and highlighted that MOFs with the Zr 4+ cation are promising candidates for purification of CH 4 . MOFs have also been investigated for membrane-based CH 4 /C 2 H 6 and CH 4 /H 2 separations, , and all of these works have highlighted the high potential of MOFs for CH 4 purification.…”

“…Borah and Ponraj screened about 12 000 MOFs for C 2 H 6 /CH 4 separation and highlighted that MOFs with the Zr 4+ cation are promising candidates for purification of CH 4 . 25 MOFs have also been investigated for membrane-based CH 4 /C 2 H 6 and CH 4 /H 2 separations, 26,27 and all of these works have highlighted the high potential of MOFs for CH 4 purification. Covalent organic frameworks (COFs) have recently been considered as an emerging class of porous materials and have become alternatives to MOFs with their immense chemical and thermal stabilities due to the strong covalent bonds holding the structure, low densities, high porosities, and high gas separation performances.…”