Ferric sludge derived pyrolyzed-hydrochar supported iron catalysts for catalytic cracking of toluene

Effective treatment of ferric sludge in an eco-friendly method is key to the feasibility of Fenton technology in pollution treatment, contributing to the realization of the “dual-carbon” strategic objectives. In this study, Fe-loaded pyrolyzed-hydrochar catalysts were prepared using simple one-pot hydrothermal carbonization (HTC) method with ferric sludge as the precursor, which greatly reduced the energy and time consumption on the preparation of the sludge derived catalyst. At 800 °C with a reaction time of 20 min, all catalysts showed high toluene removal performance (>60 %) and produced H2-rich syngas (H2 > 90 %). In particular, the catalyst prepared by HNO3-assisted HTC (HNC) presented the highest toluene removal efficiency and H2 yield, 77.52 ± 3.36 % and 11.12 ± 0.66 mol%, respectively. Additionally, the sources of carbon deposits and the interaction between the active site and carbon deposits were analyzed in detail by DFT to reveal the catalytic activity and deactivation mechanism of catalyst. The results showed that the adsorption energy of C generated from methyl on different Fe phases was lowest (the adsorption energy of C was −8.79 eV for Fe, −5.28 eV for Fe2O3, and −4.70 eV for Fe3O4), suggesting that the adsorption of C on catalyst was the main reason for the formation of carbon deposits. The lowest adsorption energy of the metallic Fe phase for C indicated that Fe0 was coated by carbon deposits during toluene catalytic cracking, which hampered catalytic activity. These results are of great significance for optimizing the preparation of Fe-loaded carbonaceous catalysts and the regulation of Fe active phase.