Metal-organic frameworks chelated by zinc fluorides for ultra-high affinity to acetylene during C2/C1 separations

• Published in: Fuel (Guildford) 2020-04, Vol.266, p.117037, Article 117037
• Main Authors: Gu, Chenkai, Liu, Jing, Hu, Jianbo, Wu, Dawei
• Format: Article
• Language: English
• Subjects: Acetylene; Affecting factors; C2/C1 separations; Density functional theory; Electrostatic properties; Energy conservation; Fluorides; Gas composition; Hydrocarbons; Metal-organic frameworks; Methane; Monte Carlo simulation; Petrochemicals industry; Selectivity; Separation; Zinc; Zinc fluorides; ZnF2 chelation
• ISSN: 0016-2361; 1873-7153
• DOI: 10.1016/j.fuel.2020.117037

[Display omitted] •Adsorptions of pure gases were calculated with DFT-developed force field.•Separations of C2 over C1 in the ZnF2-chelated MOFs were investigated.•Various factors affecting C2/C1 separation performance were deeply analyzed.•The effects of former adsorbed molecules on the later ones were studied with DFT method. Separations of C2 hydrocarbons from methane (C1) are very important but challenging processes in petrochemical industry. Metal-organic frameworks (MOFs) are considered as energy-saving materials owing to the weak interactions with gas molecules. In this work, the selective C2 adsorptions over C1 hydrocarbon in the ZnF2-chelated MOFs were investigated by grand canonical Monte Carlo (GCMC) methods and compared with those in the parent MOFs. The effects of many factors including pore diameters, isosteric heat differences, gas composition ratios, dispersion and electrostatic interactions were deeply analyzed as well. Besides, the effects of former adsorbed molecules on the later adsorptions of guest molecules were evaluated through comparing the binding energies with density functional theory (DFT) method. The results show that the incorporation of ZnF2 groups can significantly enhance the C2/C1 separation selectivity of MOFs. The C2H2/CH4 selectivity of Zn2(tmbdc)2(ZnF2-bpy) is 5263.05 which is much higher than that of the parent Zn2(tmbdc)2(bpy) (11.25) and close to the record of C2H2/CH4 selectivity in MOFs (NKMOF-1-Ni) at 298 K. In addition, smaller pore sizes and larger isosteric heat differences tend to result in higher C2/C1 separation selectivities. For ZnF2-chelated MOFs, the former adsorbed molecules mainly show competitive effects on the later adsorptions of guest molecules. This is different from the collaborative effects in the case of non-chelated MOFs.