The aim of this study was to evaluate the effect of Sida hermaphrodita harvest timing on biomass composition, properties, and methane fermentation performance. In addition, an energy–economic assessment was performed for biomass obtained at different stages of the growing season. The economic assessment assumed CHP electrical and thermal efficiencies of 38% and 47%, electricity and heat prices of 0.18 and 0.05 EUR/kWh, respectively, month-specific agrotechnical costs, and OPEX equal to 30% of total energy revenue. The biomass exhibited clear seasonal changes, transitioning from a material with high bioavailability during the summer period to a structurally more recalcitrant substrate in the autumn and winter months, as indicated by increasing lignification and fibrous fraction contents. The highest CH4 production yields, ranging from 300 to 320 mL/g VS, and maximum production rates of up to 33.5 mL/g VS·d were obtained between June and August. In December, the CH4 yield decreased to 180 ± 9 mL/g VS, accompanied by a substantial deterioration in kinetic performance. Despite the relatively stable theoretical methane potential, which ranged from 405 to 430 mL/g VS, its conversion efficiency declined from 77.1% in the summer period to 41.9% in the winter period. Regression analysis confirmed the key influence of the C/N ratio and total solids content, with model fits reaching R2 values of 0.74–0.80, while the structure of lignocellulosic complexes had a less pronounced but still relevant effect. The maximum CH4 production per unit cultivation area, approaching 3380 m3/ha, was achieved in July–August, reflecting a balance between high specific methane yield and biomass productivity. At the same time, the results demonstrated that the maximum biomass yield did not translate into the highest energy and economic performance. The highest net economic return, 1789 ± 330 EUR/ha, was obtained in July, despite biomass yield being 13.6% higher in September. These findings indicate a seasonal decoupling between biomass yield and energy performance, highlight biomass quality as a critical determinant of anaerobic digestion efficiency, and support harvest-date optimization as a low-cost strategy for the practical use of S. hermaphrodita in agricultural biogas plants. Further long-term continuous and semi-continuous studies are required to validate process stability and performance under industrial operating conditions.
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