Using ligand regulation, metal replacement, and ligand doping strategies on Zr-FUM to improve methane separation from coalbed gas

Developing adsorbents suitable for industrial applications that can effectively enhance the separation of methane (CH4) from nitrogen (N2) in coalbed gas is crucial to improve energy recovery and mitigate greenhouse gas emissions. In this study, three modification strategies were implemented on Zr-FUM, including ligand regulation, metal replacement, and ligand doping, to synthesize Zr-FDCA, Al-FUM, and Zr-FUM-FA, with the aim of improving the performance of CH4/N2 separation under humid conditions. The results demonstrated that the promotion of robust orbital overlap and strengthened electrovalent bonding on adsorbents can selectively enhance CH4 adsorption. As a result, Zr-FUM-FA achieved a saturated CH4 adsorption capacity of 1.37 mmol/g, a CH4 working window of 307 s, and a CH4/N2 sorbent selection parameter (Ssp) of 47.31, exceeding the performance of most reported adsorbents. Analyses of the pore structure, surface morphology, and functional groups revealed that the presence of an ultramicropore proximity to CH4, reduced static resistance, and enhanced electrovalent bond were key factors for CH4 separation. Grand Canonical Monte Carlo and Density Functional Theory studies indicated that the introduction of -C-H- in FA played a crucial role in enhancing CH4 adsorption. Optimization of adsorption parameters using the Aspen adsorption package showed that in a dual-adsorbent bed system, the recovery and purity of CH4 in Zr-FUM-FA reach 99.5% and 97.3%, respectively, providing important theoretical support for the improvement of CH4 recovery in the pressure swing adsorption process from coalbed gas. [Display omitted] •Using ligand or metal regulation strategies on Zr-FUM to improve CH4/N2 separation.•Increased robust orbital overlap and electrovalent bonding promote CH4 adsorption.•Synergy of both ultramicropore and reduced static resistance promote CH4 separation.•Zr-FUM-FA has 1.37 mmol/g CH4 uptake and 47.31 CH4/N2Ssp, preceding most materials.•The recovery and purity of CH4 for Zr-FUM-FA reach 99.5% and 97.3%, respectively.