Chemical synthetic pharmaceutical wastewater has characteristics of high concentration, high toxicity and poor biodegradability, so it is difficult to directly biodegrade. We used acid modified attapulgite (ATP) supported Fe-Mn-Cu polymetallic oxide as catalyst for multi-phase Fenton-like ultraviolet photocatalytic oxidation (photo-Fenton) treatment with actual chemical synthetic pharmaceutical wastewater as the treatment object. The results showed that at the initial pH of 2.0, light distance of 20 cm, and catalyst dosage and hydrogen peroxide concentration of 10.0 g/L and 0.5 mol/L respectively, the COD removal rate of wastewater reached 65% and BOD5/COD increased to 0.387 when the reaction lasted for 180 min. The results of gas chromatography-mass spectrometry (GC-MS) indicated that Fenton-like reaction with Fe-Mn-Cu@ATP had good catalytic potential and significant synergistic effect, and could remove almost all heterocycle compounds well. 3D-EEM (3D electron microscope) fluorescence spectra showed that the fluorescence intensity decreased significantly during catalytic degradation, and the UV humus-like and fulvic acid were effectively removed. The degradation efficiency of the nanocomposite only decreased by 5.8% after repeated use for 6 cycles. It seems appropriate to use this process as a pre-treatment for actual pharmaceutical wastewater to facilitate further biological treatment.

A simple one-pot method was used to successfully embed manganese ferrite (MnFe2O4) nanoparticles on the nitrogen-doped reduced graphene oxide matrix (NrGO), which was used to activate peroxymonosulfate to treat the landfill leachate nanofiltration concentration (LLNC) with electrochemical enhancement. NrGO-MnFe2O4 and rGO-MnFe2O4 were characterized by various means. This indicates that nitrogen-doped could induce more graphene oxide (GO) spall and reduction to produce more active centers, and was favorable for uniformly loading MnFe2O4 particles. The comparison between electrochemical/peroxymonosulfate/NrGO-MnFe2O4 (EC/PMS/NrGO-MnFe2O4) system and different catalytic systems shows that electrochemical reaction, NrGO and MnFe2O4 can produce synergies, and the chemical oxygen demand (COD) removal rate of LLNC can reach 72.89% under the optimal conditions. The three-dimensional (3D-EEM) fluorescence spectrum shows that the system has a strong treatment effect on the macromolecules with intense fluorescence emission in LLNC, such as humic acid, and degrades into substances with weak or no fluorescence characteristics. Gas chromatography-mass spectrometry (GC-MS) indicates that the complex structure of refractory organic compounds can be simplified, while the simple small molecular organic compounds can be directly mineralized. The mechanism of catalytic degradation of the system was preliminarily discussed by the free radical quenching experiment. Therefore, the EC/PMS/NrGO-MnFe2O4 system has significant application potential in the treatment of refractory wastewater.