A cooperative adsorbent for the switch-like capture of carbon dioxide from crude natural gas

• Published in: Chemical science (Cambridge) Vol. 13; no. 4; pp. 11772 - 11784
• Main Authors: Siegelman, Rebecca L, Thompson, Joshua A, Mason, Jarad A, McDonald, Thomas M, Long, Jeffrey R
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 19.10.2022; Royal Society of Chemistry (RSC); The Royal Society of Chemistry
• Subjects: Adsorbents; Adsorption; Carbon dioxide; Carbon sequestration; Chemistry; Diamines; Gas pipelines; Isobars; Metal-organic frameworks; Natural gas; Natural gas reserves; Performance enhancement; Purification
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d2sc03570g

Natural gas constitutes a growing share of global primary energy due to its abundant supply and lower CO 2 emission intensity compared to coal. For many natural gas reserves, CO 2 contamination must be removed at the wellhead to meet pipeline specifications. Here, we demonstrate the potential of the diamine-appended metal-organic framework ee-2-Mg 2 (dobpdc) (ee-2 = N , N -diethylethylenediamine; dobpdc 4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) as a next-generation CO 2 capture material for high-pressure natural gas purification. Owing to a cooperative adsorption mechanism involving formation of ammonium carbamate chains, ee-2-Mg 2 (dobpdc) can be readily regenerated with a minimal change in temperature or pressure and maintains its CO 2 capacity in the presence of water. Moreover, breakthrough experiments reveal that water enhances the CO 2 capture performance of ee-2-Mg 2 (dobpdc) by eliminating "slip" of CO 2 before full breakthrough. Spectroscopic characterization and multicomponent adsorption isobars suggest that the enhanced performance under humid conditions arises from preferential stabilization of the CO 2 -inserted phase in the presence of water. The favorable performance of ee-2-Mg 2 (dobpdc) is further demonstrated through comparison with a benchmark material for this separation, zeolite 13X, as well as extended pressure cycling. Overall, these results support continued development of ee-2-Mg 2 (dobpdc) as a promising adsorbent for natural gas purification. Diamine-appended metal-organic frameworks can be optimized as adsorbents for pressure-swing purification of crude natural gas. A cooperative CO 2 binding mechanism enables high CO 2 swing capacities and enhanced performance under humid conditions.