A novel sulfonated polyphenylsulfone (sPPSU)/polyphenylsulfone (PPSU)-based dual-layer hollow fiber membrane with a nanometric thin skin layer has been designed for biofuel dehydration via pervaporation. The thickness of skin selective layer is in the range of 15–90 nm under different spinning conditions measured by positron annihilation spectroscopy (PAS) coupled with a mono-energetic positron beam. The effects of outer-layer dope properties, coagulation temperature, and dope flow rate during spinning were systematically investigated. By tuning these spinning parameters, a high performance sPPSU/PPSU-based dual-layer hollow fiber membrane with desirable morphology was successfully obtained. Particularly owing to its nanometric thin skin layer, a high flux of 3.47 kg/m2h with a separation factor of 156 was achieved for dehydration of an 85 wt % isopropanol aqueous solution at 50°C. After post thermal treatment at 150°C for 2 h, the separation factor was dramatically improved to 687 while flux dropped to 2.30 kg/m2h, which make it comparable to the inorganic membranes. In addition, excellent correlations were found among the results from field emission scanning electron microscopy, PAS spectra, and separation performance. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2943–2956, 2013
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