Anaerobic digestion (AD) was utilized to treat the ever-growing amount of organic fraction of municipal solid waste (OFMSW) generated due to population growth and the expansion of the global economy. The widespread application of AD has led to a continuous increase in residual solid digestate that necessarily requires further disposal. Improving AD efficiency and reducing the large amount of digestate is necessary. This study investigated the chemical and physical characteristics of biochar derived from digestate at different pyrolysis temperatures (300 ◦C, 500 ◦C, and 700 ◦C), as well as corn stover biochar at 500 ◦C, and their effects on AD performance. The pH value of the biochar increased with an increase in pyrolysis temperature while the electrical conductivity decreased. Macropores dominated the biochar’s pore size, and decreased with an increased pyrolysis temperature. The biochar preparation temperature significantly influenced the AD efficiency. Biochar prepared at 700 ◦C outperformed the other groups, improving the biogas production yields by 10.0%, effectively shortening the lag time, and increasing the average chemical oxygen demand (COD) degradation rate by 14.0%. The addition of biochar (700 ◦C) and corn stover biochar increased the relative abundance of the volatile fatty acid (VFAs)-oxidizing bacteria Syntrophomonadaceae, which expedited the acid conversion in AD systems. Biochar facilitated direct interspecies electron transfer between DMER64 and Trichococcus with Methanosaeta, enhancing the biogas production performance. These findings confirmed that the biochar derived from digestate promoted biogas production and acid conversion in the AD system of OFMSW. Furthermore, biochar has an improved AD stability, which represents a promising approach to recycling digestate.
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