Abstract
Coking nanofiltration (NF) concentrates, as typical wastewater with high salinity and refractory organics, have become one of the greatest challenges for "near-zero emission" processes. In our study, an advanced oxidation technology based on ferrous iron/persulfate (Fe(ii)/PS) and polyferric sulfate (PFS) coagulation coupled with ultrafiltration (UF) was used to treat NF concentrates and mitigate membrane fouling. Based on batch experiments, the optimal parameters of Fe(ii)/PS were obtained, during which we discovered that the slow reaction stage of total organic carbon (TOC) removal followed first-order degradation kinetics. Under the optimal reaction conditions, Fe(ii)/PS could efficiently mineralize 69% of organics in coking NF concentrates. In order to eliminate the iron floc generated in the Fe(ii)/PS step, a small amount of PFS (0.05 mM) was added to coagulate the iron floc, which could further improve the effluent quality so that the turbidity, iron content and TOC were significantly reduced by 79.18%, 98% and 21.79% respectively. Gas chromatography coupled with time-of-flight mass spectrometry (GC × GC-TOFMS) and fluorescence excitation-emission matrix spectrometry (EEM) were performed to characterize the removal of phenols, PAHs, quinolines and humic acids in NF concentrates which were responsible for UF membrane fouling. Moreover, scanning electronic microscopy (SEM) and atomic force microscopy (AFM) were conducted to study the surface of the UF membrane after treatment of NF concentrates. The result exhibited that the organic pollutants deposited on the UF membrane surface were reduced by Fe(ii)/PS-PFS pretreatment, and UF membrane flux was thus enhanced. Our results show the potential of the approach of applying Fe(ii)/PS-PFS-UF in NF concentrate treatment.