A robust ethane-selective metal-organic framework with nonpolar pore surface for efficient C2H6/C2H4 separation

Abstract

A robust chiral chain-based microporous MOF with nonpolar pore surface and suitable cavity space was designed and synthesized for C 2 H 6 /C 2 H 4 separation. The MOF shows simultaneously high C 2 H 6 uptake and inverse C 2 H 6 /C 2 H 4 selectivity, affording the one-step purification of C 2 H 4 from C 2 H 6 -C 2 H 4 mixture under ambient condition. • Adopting the methyl-modified ligands afforded a Zn-MOF with nonpolar channels. • The MOF shows excellent stability and uncommon preferential adsorption for C 2 H 6 . • The methyl groups in MOF are crucial for the separation of C 2 H 6 over C 2 H 4 . • The MOF achieves effective one-step purification of C 2 H 4 from C 2 H 6 -C 2 H 4 mixture. Due to similar physical and chemical properties, the separation of ethane (C 2 H 6 ) and ethylene (C 2 H 4 ) is an indispensable and extremely challenging task in petrochemical process. Although traditional C 2 H 4 -selective porous materials realize the separation of C 2 H 6 -C 2 H 4 mixture, but subsequent multiple separation operations are required to produce high-purity C 2 H 4 . Herein, we designed a hydrophobic methyl group-modified metal-organic framework (MOF) for one-step efficient purification of C 2 H 4 from C 2 H 6 -C 2 H 4 mixture. The as-synthesized MOF constructed from inexpensive carboxylic acid and pyrazole mixed linkers shows high thermal stability and chemical stability (water resistance). Cooperative study on the pure-component sorption isotherm, Ideal Adsorbed Solution Theory method, adsorption heat calculation and grand canonical Monte Carlo (GCMC) simulation supports the unique C 2 H 6 -selective feature of the MOF. Breakthrough experiments revealed the one-step C 2 H 4 purification from C 2 H 6 -C 2 H 4 (1/1, 1/10 and 1/15) mixtures through the MOF around room temperature condition with nice recyclability.