Sulfur-Based Composite Fillers Enable Adaptive Autotrophic Denitrification for Nitrogen Removal in Photovoltaic Wastewater: From Laboratory to Pilot Scale

Sulfur-based autotrophic denitrification (SAD) is limited by low efficiency and poor stability in carbon-deficient photovoltaic (PV) wastewater treatment. This study developed four sulfur-based composite fillers (S0-CFs) comprising 75% elemental sulfur and mineral additives (boron mud, magnesite, and/or siderite) fabricated via melt mixing–jet granulation. Lab-scale operation showed that at a hydraulic retention time (HRT) of 1 h, all S0-CFs achieved high TN removal (89.1–93.8%) with effluent NO3−-N below 1.5 mg/L (>93% nitrate removal efficiency) and stable pH. Although effluent COD increased with a short HRT (1 h) due to biofilm detachment, no leaching of organic or inorganic pollutants from the fillers was observed, and TP was consistently removed. 16S rRNA sequencing confirmed enrichment of autotrophic denitrifiers Thiobacillus and Sulfurimonas, verifying SAD as the dominant pathway. In a 270-day pilot-scale operation, nitrate removal varied with temperature (7.3–27.2 °C) and HRT, reaching 88.2% on average (range: 86.6–90.0%) at 1 h HRT during warm periods (25.8–27.2 °C), dropping to 13.5–38.1% under cold conditions (7.3–16.0 °C) at 0.5 h HRT, and then stabilizing at 64.1% by adjusting HRT to 1 h. Fluoride was removed at 0.51–1.49 mg/L. Additionally, operational cost was 34.5% lower than heterotrophic denitrification. These results demonstrated that S0-CF enabled efficient, stable, and cost-effective nitrogen removal, making SAD more suitable for low-carbon industrial wastewater treatment.