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Production and performance evaluation of ZIF-8 based binary and ternary mixed matrix gas separation membranes

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2012
Keser, Nilay
Mixed matrix membranes (MMMs) have gained importance because they combine the desirable properties of the polymers and the organic/inorganic filler materials and they may have a very big potential. In this study polyethersulfone (PES) was used as polymeric material, and Zeolitic Imidazolate Framework-8 (ZIF-8) was used as porous filler material, and 2-hydroxy 5-methyl aniline(HMA), was used as a third component in membrane formulation. In this study, ZIF-8 crystals were synthesized with varying particle sizes, and a novel recycling methodology was developed to improve the efficiency of ZIF-8 production. ZIF-8 nano-crystals were synthesized by a 1-hour stirring method at room temperature and characterized by X-ray diffractometer, scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS) and thermal gravimetric analysis (TGA). In order to investigate the effect of ZIF-8 loading on the membrane performance, different types of membranes were prepared with varying amounts of ZIF-8 between 10-60% (w/w). Moreover, ternary mixed matrix membranes were synthesized consisting of different amounts of ZIF-8 between 10-30% (w/w) and HMA 1-10% (w/w). Gas transport properties of the membranes were investigated by single gas permeation experiments of H2, CO2 and CH4 at 3 bar feed pressure. In order to investigate the effect of feed pressure on the gas transport properties of the membranes, single gas experiments were conducted on 3, 6, 8, 10 and 12 bar feed pressures. Moreover, binary gas permeation experiments of CO2/CH4 pair were conducted through selected membranes at 3 bar and 12 bar feed pressures. In addition to gas permeation experiments, the morphology and thermal characteristics of the membranes were characterized by SEM, TGA and differential scanning calorimetry (DSC) analysis. The incorporation of ZIF-8 crystals into continuous PES matrix resulted in high performance gas separation membranes. The permeabilities of all studied gases increased with ZIF-8 loading while the ideal selectivities showed a slight decrease compared to neat PES membrane. Highly reproducible and repeatable results were obtained up to 30 % w/w ZIF-8 loading, while membrane formulation reproducibility was decreased for higher ZIF-8 contents (>30 w/w %). Addition of HMA improved the gas separation performances of the binary membranes significantly by decreasing permeabilities and increasing ideal selectivities. PES/ZIF-8(%20)/HMA(%7) membrane has the best separation performance for all gases among the ternary membranes. When 7 w/w % HMA was added to PES/ZIF-8(%20) membrane, H2 permeability decreased from 26.3 to 13.7 barrer, while H2/CH4 ideal selectivity increased from 61.8 to 103.7. Increasing feed pressures appreciably increased the separation performances of all membranes. While the H2 permeability is pressure independent, the CO2 and CH4 permeabilities were reduced with increasing feed pressures and the highest selectivity improvement was observed in H2/CH4 pair for all membrane compositions. For instance, when the feed pressure was increased from 3 bar to 12 bar, the percentage improvements in ideal selectivities through PES/ZIF-8(%10)/HMA(%4) membrane were calculated as 26, 69, 113 % for the H2/CO2, CO2/CH4 and H2/CH4 gas pairs; respectively. This results show that working at higher feed pressures will be more advantageous for separation of the studied gas pairs. The ideal selectivities and the separation factors were equal to each other for all membrane compositions both for 3 and 12 bar operating pressures.