Recalcitrant compounds formation, their toxicity, and mitigation: Key issues in biomass pretreatment and anaerobic digestion.

Increasing energy demands and environmental issues have stressed the importance of sustainable methods of energy production. Anaerobic digestion (AD) of the biodegradable waste, i.e., agricultural residues, organic fraction of municipal solid waste (OFMSW), sewage sludge, etc., results in the production of biogas, which is a sustainable and cost feasible technique that reduces the dependence on fossil fuels and also overcomes the problems associated with biomass waste management. To solubilize the organic matter and enhance the susceptibility of hardly biodegradable fraction (i.e., lignocellulosic) for hydrolysis and increase methane production, several pretreatments, including physical, chemical, biological, and hybrid methods have been studied. However, these pretreatment methods under specific operating conditions result in the formation of recalcitrant compounds, such as sugars (xylose, Xylo-oligomers), organic acids (acetic, formic, levulinic acids), and lignin derivatives (poly and mono-phenolic compounds), causing significant inhibitory effects on anaerobic digestion. During the scaling up of these techniques from laboratory to industrial level, the focus on managing inhibitory compounds formed during pretreatment is envisaged to increase because of the need to use recalcitrant feedstocks in anaerobic digestion to increase biogas productivity. Therefore, it is crucial to understand the production mechanism of inhibitory compounds during pretreatment and work out the possible detoxification methods to improve anaerobic digestion. This paper critically reviews the earlier works based on the formation of recalcitrant compounds during feedstocks pretreatment under variable conditions, and their detrimental effects on process performance. The technologies to mitigate recalcitrant toxicity are also comprehensively discussed.