Sustainable Valorization of Brassica napus: A Circular Approach to Enhance Biomethane Recovery via Electrohydrolysis

The circular valorization of biomass for sustainable energy recovery is a strategic priority in the transition toward low-carbon systems. In the last decade, anaerobic digestion (AD) has emerged as an efficient technology to produce an energetic vector to replace natural gas with biomethane and reduce waste; however, the hydrolysis of refractory fractions remains the main rate-limiting step. This study investigates an innovative electro-assisted pretreatment of biomass to promote the first rate-limiting hydrolysis step of refractory compounds in biomethane production. Lignocellulosic residues are employed not only as feedstock for the AD process but also as substrates in electrohydrolysis (EH) pretreatment using an Ir-Ta mixed metal oxide (MMO) anode coupled with advanced biomass-derived carbon felt cathodes. Two cathodes were functionalized with Phragmites Australis (PhA) hydrochars, untreated (PA) and KOH-activated (PA-KOH), to enhance the in situ generation of reactive oxygen species (ROS). Brassica napus (Bn) was chosen as the other biomass selected as a feedstock of AD, and was subjected to EH at varying energy inputs (500–5000 kJ·kg−1), evaluating structural and biochemical shifts. The results demonstrate that EH effectively modifies the biomass matrix; the PA-KOH-CF cathode exhibited good selectivity to degrade lignocellulosic structures, but higher biomethane production was achieved at 2500 kJ·kg−1 TS using PA-CF, reaching an increase of 52% compared with untreated samples. Kinetic analysis of the biomethane potential was performed using the modified Gompertz model. The model accurately captured the asymmetric sigmoidal transitions of methane production with different electrode configurations, and finally, energy balance assessment identified 2500 kJ·kg−1 TS as the optimal operational threshold. These findings suggest that an excess of applied energy is critical to the availability of soluble organic matter and the presence of refractory compounds that reduce efficiency. This electro-assisted approach offers a robust strategy for intensifying AD, aligning with circular bioenergy objectives.