화학공학소재연구정보센터
Chemical Engineering Journal, Vol.366, 223-234, 2019
Co-oxidation effects and mechanisms between sludge and alcohols (methanol, ethanol and isopropanol) in supercritical water
Sludge is a by-product of wastewater treatment process with high organic and nitrogen contents. Supercritical water oxidation (SCWO) rates of refractory species in sludge might be accelerated by reactive alcohols, which is referred to as a co-oxidation phenomenon. In this work, influences of three typical reactive alcohols (methanol, ethanol and isopropanol) on TOC and of NH3-N removal rates of sludge by SCWO were analyzed and their cooxidation products were characterized by GC-MS, FT-IR, EDS and TG-DTG methods. Additionally, to capture the nature of co-oxidation, HO2 center dot and OH center dot radicals released by alcohols were theoretically compared with detailed chemical kinetics models using the Chemkin Software. The results show that methanol, ethanol and isopropanol all exhibited co-oxidation accelerated effects on TOC and NH3-N removal rates of sludge. One reason was that alcohols provided reactive HO2 center dot and OH center dot radicals. The other reason was that adding alcohols not only prevented forming recalcitrant products (non-nitrogen and nitrogen aromatic compounds) but also encouraged producing reactive products (non-nitrogen open chain compounds). Ethanol offered the best co-oxidation promotion effects on the removal of TOC and NH3-N in the liquid products and also gave the lowest organic contents in the solid products, followed by isopropanol and methanol. This order was consistent with the difficulty of how the alcohols themselves could be oxidized in supercritical water since ethanol could support the highest amount of HO2 center dot radicals for sludge in the shortest time.