Acid–Hydrothermal Pretreatment Enhances Methane Production from Pine Nut Shells: Structural Disruption and Derivative-Based Kinetic Landmark Analysis

Anaerobic digestion (AD) of lignocellulosic biomass is often constrained by biomass recalcitrance, limiting methane recovery. This study investigated whether low-temperature dilute-acid hydrothermal pretreatment could enhance methane production from pine nut shells (PNSs), a lignin-rich and underutilized agro-industrial residue, and whether derivative-based kinetic landmarks could provide a more systematic characterization of batch AD performance. Methane production was significantly improved by dilute sulfuric acid and hydrothermal pretreatments. The highest methane yield (201.8 mL CH4 g−1 VS) was achieved under the combined 100 °C hydrothermal and 2.5% H2SO4 condition, representing approximately 1.8-fold and 3.3-fold increases compared with hydrothermal-only and untreated PNSs, respectively. Enhanced performance was attributed to hemicellulose solubilization, lignin disruption, and improved substrate accessibility. In contrast, excessive acid severity resulted in process instability, associated with total volatile fatty acid accumulation and pH reduction. The Modified Logistic Model (MLM) was further used to derive five kinetic landmarks (PAA, PAM, PI, PDM, and PDA) describing phase-specific features of cumulative methane production curves. While these landmarks provide a model-based framework for comparing batch AD kinetics, their nearly constant normalized yields primarily reflect the geometry of the fitted logistic function rather than independent biological invariants. Overall, the results identify 100 °C hydrothermal pretreatment with 2.5% H2SO4 as an effective moderate-severity strategy for enhancing methane recovery from PNSs and demonstrate the utility of MLM-derived landmarks as comparative descriptors of phase-resolved methane production.