Separation of Hexane Isomers on Rigid Porous Metal Carboxylate-Based Metal—Organic Frameworks

• Published in: Adsorption science & technology Vol. 32
• Main Authors: Patricia A. P. Mendes, Alírio E. Rodrigues, Patricia Horcajada, Jarrod Eubank, Thomas Devic, Christian Serre, José A. C. Silva
• Format: Journal Article
• Language: English
• Published: SAGE Publications 01-06-2014
• ISSN: 0263-6174; 2048-4038
• DOI: 10.1260/0263-6174.32.6.475

Screening separation studies with equimolar quaternary mixtures of hexane isomers, namely, n -hexane/3-methylpentane/2,3-dimethylbutane/2,2-dimethylbutane ( n -HEX/3MP/23DMB/22DMB), in the temperature range of 343–423 K and partial pressures up to 10 kPa have been performed using three rigid porous metal (III/IV) carboxylate-based metal–organic frameworks (MOFs) with different composition and topology. These carboxylate-based MOFs are denoted as MIL-100(Cr), MIL-125(Ti)-NH 2 and MIL-127(Fe). Adsorption study results revealed that all the isomers were adsorbed on MIL-100(Cr) and MIL-125(Ti)-NH 2 with adsorption amounts reaching 24 and 12 wt%, respectively, and the order of adsorption being similar to the normal boiling point of the compounds, that is, n -HEX > 3MP > 23DMB > 22DMB, with selectivity of adsorption never exceeding three (i.e. selectivities between the extreme compounds n -HEX and 22DMB). It is worth noting that adsorption of branched isomers is practically excluded on MIL-127(Fe), which exhibits a strong molecular sieve effect of the adsorbed n -HEX with the loading capacity reaching a maximum of 7 wt%. Finally, an alternative strategy, which involved probing the effect of post-synthetic functionalization on the coordinatively unsaturated metal sites of the MIL-100(Cr) using functional group ethylamine or N -methylethylenediamine showed no significant differences in terms of separation.