On the geometry and material stability of tubular PVDF-TiO2 static mixer membrane contactors for photocatalytic ozonation of micropollutants

The prevention of ozone hotspots in ozonation reactors for wastewater treatment is essential for effective degradation of micropollutants without forming harmful by-products. Membrane contactors can provide a bubble-free ozonation process that is able to decrease by-product formation, e.g., bromate formation in bromide-charged wastewater. Furthermore, the geometry of the reactor influences the distribution of dissolved ozone in a membrane contactor. Turbulence promoters can significantly decrease ozone hotspots and increase ozone mass transfer into wastewater. This work presents a fabrication methodology to produce PVDF-TiO2 helical static mixer membranes using the rotation-in-a-spinneret technology. Static mixer membranes combine the functionality of a membrane contactor and a static mixer in a single component. Furthermore, the PVDF matrix is doped with TiO2 particles as photocatalyst. Thus, we present a membrane-based photocatalytic ozonation process to increase the concentration of hydroxyl radicals for degradation of micropollutants under UV radiation. Static mixer membranes increase the ozone mass transfer coefficient by 70 % compared to conventional hollow fiber membranes. Furthermore, the specific photocatalytic degradation rate of methylene blue increases by 50 % using static mixer membranes. However, this work also reveals a lack of long-term stability of PVDF-TiO2 membranes in the corrosive environment of photocatalytic ozonation. The molecular weight of PVDF decreases by 11 % after use in photocatalytic ozonation resulting in a loss of mechanical stability of the membranes. Similar material concepts are required based on ceramic materials which avoid wetting of the porosity.