Probing Metal–Organic Framework Design for Adsorptive Natural Gas Purification

Abstract

Parent and amine-functionalized analogues of metal-organic frameworks (MOFs), UiO-66(Zr), MIL-125(Ti), and MIL-101(Cr), were evaluated for their hydrogen sulfide (H₂S) adsorption efficacy and post-exposure acid gas stability. Adsorption experiments were conducted through fixed-bed breakthrough studies utilizing multicomponent 1% H₂S/99% CH₄ and 1% H₂S/10% CO₂/89% CH₄ natural gas simulant mixtures. Instability of MIL-101(Cr) materials after H₂S exposure was discovered through powder X-ray diffraction and porosity measurements following adsorbent pelletization, whereas other materials retained their characteristic properties. Linker-based amine functionalities increased H₂S breakthrough times and saturation capacities from their parent MOF analogues. Competitive CO₂ adsorption effects were mitigated in mesoporous MIL-101(Cr) and MIL-101-NH₂(Cr), in comparison to microporous UiO-66(Zr) and MIL-125(Ti) frameworks. This result suggests that the installation of H₂S binding sites in large-pore MOFs could potentially enhance H₂S selectivity. In situ Fourier transform infrared measurements in 10% CO₂ and 5000 ppm H₂S environments suggest that framework hydroxyl and amine moieties serve as H₂S physisorption sites. Results from this study elucidate design strategies and stability considerations for engineering MOFs in sour gas purification applications.