Robust zirconia ceramic membrane with exceptional performance for purifying nano-emulsion oily wastewater

While membrane-based oil-water separation has been widely explored, using conventional membranes to treat oily wastewaters remains practically challenging especially when such wastewaters contain more stable nano-sized oil droplets and are of high oil content, and harsh chemical conditions. Herein, we report a novel protocol of efficiently separating both synthetic and real oil nano-emulsions via specially designed robust zirconia membranes. The best-performing zirconia membrane, fabricated at low sintering temperature, has relatively uniform sub-100 nm pores and is underwater superoleophobic. Such zirconia membranes possess not only outstanding separation performance under long-term operation but robust structural stability at harsh conditions. At different cross-flow velocities, a combined model of intermediate pore blocking and cake filtration dominated membrane fouling behavior. Specifically, at high pH value (especially > pH_(IEP)), membrane fouling was effectively mitigated due to a dominant role of electrostatic repulsion interaction at membrane-oil interface. Compared with conventional and commercial ceramic membranes, our zirconia membrane is the first reported in literature that can effectively reject nano-sized oil droplets (∼18 nm) with over 99% rejection. Moreover, the zirconia membrane has also been challenged with real degreasing wastewater with very high oil content (∼4284 mg L^-1) and pH (∼12.4) and delivered consistently high separation performance over many operation cycles.