Molecular insights into the catalytic oxidation of methanol-to-olefins wastewater with phosphoric acid modified sludge biochar.

With the development of methanol-to-olefin (MTO) process, the effective disposal of wastewater was one key factor for the long-period and benign development of this technology. Herein, a sludge-based biochar catalyst (GSC-P) was synthesized and used in photo-Fenton reaction for the degradation of MTO wastewater from the outlet of a biological aerated filter. More iron was distributed on the surface of GSC-P catalyst, facilitating the photo-Fenton oxidation of MTO wastewater, with chemical oxygen demand (COD) removal rate of 75.4% and total organic carbon (TOC) removal rate of 62.5%. The 2223 unique molecular formulas assigned by a Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in the original MTO wastewater showed that CHO compounds shared the lowest peak numbers (20.2%) but the highest peak abundance (51.6%) among the four groups. Besides, lipids, unsaturated hydrocarbons, lignins and proteins were the main structural types. After photo-Fenton treatment of 60 min, there were 56.7%-74.0% of compounds removed by the analysis of van Krevelen diagram, indicating that the MTO wastewater was degraded efficiently. Three possible evolution processes of dissolved organic matters during the photo-Fenton reaction were disclosed at the molecular-level.