Efficient bio-ethanol recovery by non-contact vapor permeation process using membranes with tailored pore size and hydrophobicity

Vapor permeation seems to be a more suitable separation process than pervaporation in bio-ethanol recovery from fermentation broth because of its non-direct contact trait. The unsatisfactory flux and selectivity of polymeric membranes limit their utilization in industrial application. Here, we tailored the physical and chemical structure of commercial available polyacrylonitrile (PAN) ultrafiltration membrane to serve in vapor permeation. The membrane porosity was reduced till dense enough for separation while preserving an ultra-high flux by hydrolyzing in alkali. The hydrophilicity/hydrophobicity was controlled by grafting fluoroalkyl chains to ensure an acceptable ethanol selectivity. The changes of physical structure and chemical property were systematically characterized by Fourier transform infrared-attenuated total reflectance (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), water contact angle and pure water permeance. Tested at 60 °C, the optimized membrane exhibited a high flux of ca. 10.5 kg m−2 h−1 and a permeate ethanol content similar to vapor-liquid equilibrium curve, which outstripped most polymeric membranes (applied in pervaporation or vapor permeation) in both flux and selectivity.