Thin supported MOF based mixed matrix membranes of Pebax® 1657 for biogas upgrade

This work shows the preparation of thin mixed matrix membranes (MMMs) with a 2-3 m thick Pebax (R) 1657 layer on two different supports: a porous asymmetric polyimide P84 (R) and dense polytrimethylsilylpropyne (PTMSP). Nanoparticles of metal-organic frameworks (MOFs) ZIF-8, MIL-101(Cr), UiO-66 and ZIF-7/8 core-shells were selected as fillers for the Pebax (R) 1657 based MMMs, all of them being MOFs with high CO2 adsorption capacity but different pore size distribution. All the membranes were characterized by SEM, FTIR, Raman, TGA and XRD analyses, showing in all cases a perfect compatibility of the Pebax (R) layer with both supports and also a good dispersion of the fillers in the polymeric matrix. These membranes were applied for the separation of equimolar CO2/CH4 mixtures at 35 degrees C under feed pressures between 3 and 5 bar, where an improvement in the gas separation performance with increasing pressure was noticed, thanks to the favored solubility of CO2. The synergistic compatibility between Pebax (R) 1657 and P84 (R) gave rise to a 470% enhancement in CO2/CH4 selectivity, reaching a maximum value of 114 while the CO2 permeance increased by 40% up to 7.5 GPU. The addition of fillers in the Pebax (R) polymeric phase produced an improvement in the gas separation performance of the membranes, especially in terms of permeance, where the MMMs containing a 10 wt% loading of UiO-66 reached the optimum value of 11.5 GPU of CO2 (together with a CO2/CH4 selectivity of 55.6).