The low pH of Maotai-flavor Baijiu wastewater (MFBW) adversely affects its anaerobic digestion (AD) performance, resulting in low AD efficiency. Here, coconut shell was used to produce biochar. The characteristics of biochar were regulated through acid, alkali, and magnetic modification, respectively. Biochar and modified biochars were applied to assist the AD of MFBW. The results showed that biochar could significantly increase methane yield by 220.8 %–241.7 % with the corresponding soluble chemical oxygen demand (sCOD) degradation increasing by 52.3 %–57.5 % (p < 0.05). Joint modification could significantly enhance the electron donating capacity from 0.0042 to 0.0095 mmol e−1/g (p < 0.05). The combined modification with magnetic alkali had the best stimulating effect on the AD process, which might be related to the conductive particles (Fe3O4) formed during magnetization processes. The modified biochar featured a high degree of surface roughness, a relatively large aperture, and strong electron donating ability, all of which were beneficial to the colonization and microbial growth. Supplementation with biochar resulted in the enrichment of Proteobacteria, Firmicutes, and Actinobacteria, especially for Syntrophomonas (rising from 0.013 % to 6.74 %–10.93 % of relative abundance). These microorganisms are related to the hydrolysis, acidification, and extracellular electron transfer. The enrichment of electroactive microorganism is a prerequisite for improving the direct interspecies electron transfer pathway. This study provides theoretical support for efficient MFBW treatment.

Biochar accelerates methane production efficiency from Baijiu wastewater: Some viewpoints considering direct interspecies electron transfer