Thermal Conversion of Paulownia tomentosa Leaves into Carbonaceous Materials: Effects on Physicochemical Properties and Sorption of Metribuzin and Tebuconazole from Water
Margita Ščasná, Michal Hebnár, Alexandra Kucmanová, Maroš Sirotiak, Veronika Kvorková, Maroš Soldán, Jan Hajzler, Barbora Ludrovcová, Marián PalcutThis study investigated carbonaceous materials prepared from Paulownia tomentosa leaves by hydrothermal carbonization, slow pyrolysis, and HCl post-treatment for the adsorption of metribuzin and tebuconazole from water. Hydrochars were prepared at 180–220 °C, pyrochars at 400–600 °C, and the pyrochar produced at 600 °C was further treated with HCl. The materials were characterized by yield, ash content, active and exchangeable pH, oxidizable organic carbon content, FTIR, SEM, and CO2-derived surface and pore properties. Increasing processing temperature reduced the yield in both conversion routes. Hydrochars retained more oxygen-containing and oxidizable organic structures, whereas pyrochars showed stronger carbonization, higher ash content, and higher CO2-derived surface area. HCl treatment decreased the ash residue, thereby resulting in improved CO2-accessible surface and pore properties and more fragmented morphology. Metribuzin adsorption was better described by the pseudo-second-order kinetic model across all sorbents, with the highest fitted equilibrium adsorbed amount observed following HCl treatment. Tebuconazole showed higher initial uptake toward most untreated materials, but its kinetic profiles were non-monotonic, with a decrease in the adsorbed amount at longer contact times. Consequently, the conventional PFO and PSO models did not adequately describe its complete kinetic behavior. Nonlinear isotherm modeling showed predominantly Freundlich-type fitting for metribuzin, suggesting heterogeneous adsorption sites, whereas tebuconazole was formally better described by Langmuir-type fitting, although with poorer fit quality for several materials. The results show that Paulownia tomentosa leaves are a suitable precursor for carbonaceous sorbents and that HCl-treated pyrochar is the most promising material for metribuzin adsorption.