Mixed matrix membranes (MMMs) with nano-fillers dispersed in polymer matrix have been proposed as alternative pervaporation membrane materials. They possess both promising selectivity benefiting from the fillers and economical processing capabilities of polymers. ZIF-67 was synthesized and incorporated into the sulfonated poly (aryl ether sulfone) (SPES) matrix to prepare SPES/ZIF-67 mixed matrix membranes with different ZIF-67 mass fractions. The as-prepared membranes were used for pervaporation separation of methanol/methyl tert-butyl ether mixtures. X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and laser particle size analysis results show that ZIF-67 is successfully synthesized, and the particle size is mainly between 280 nm and 400 nm. The membranes were characterized by SEM, atomic force microscope (AFM), water contact angle, thermogravimetric analysis (TGA), mechanical property testing and positron annihilation technique (PAT), sorption and swelling experiments, and the pervaporation performance was also investigated. The results reveal that ZIF-67 particles disperse uniformly in the SPES matrix. The roughness and hydrophilicity are enhanced by ZIF-67 exposed on the membrane surface. The mixed matrix membrane has good thermal stability and mechanical properties, which can meet the requirements of pervaporation operation. The introduction of ZIF-67 effectively regulates the free volume parameters of the mixed matrix membrane. With increasing ZIF-67 mass fraction, the cavity radius and free volume fraction increase gradually. When the operating temperature is 40 °C, the flow rate is 50 L·h-1 and the mass fraction of methanol in feed is 15%, the mixed matrix membrane with ZIF-67 mass fraction of 20% shows the best comprehensive pervaporation performance. The total flux and separation factor reach 0.297 kg·m-2·h-1 and 2123, respectively.
Keywords: ZIF-67; mixed matrix membrane; pervaporation; separation; sulfonated poly (aryl ether sulfone).