Metal-Loaded ZSM-5 Catalysts for Biomass Pyrolysis Denitrogenation: Nitrogen Migration, Catalyst Deactivation, and Sulfur Resistance

Thermochemical conversion of nitrogen- and sulfur-rich biomass-derived wastes, such as sewage sludge, algae, and agricultural residues, is a promising route for renewable fuel production and waste valorization. However, fuel-bound nitrogen can be released as NH3, HCN, and HNCO, while sulfur species such as H2S, SO2, and COS accelerate catalyst deactivation and generate NOx/SOx precursors. Metal-loaded ZSM-5 catalysts are attractive for clean catalytic pyrolysis because they combine the MFI pore confinement and tunable Brønsted/Lewis acidity of ZSM-5 with the hydrogen transfer, dehydrogenation, cracking, redox, and sulfur-tolerance functions of metal species. This review critically summarizes recent advances in metal-loaded ZSM-5 catalysts for catalytic denitrogenation of biomass-derived solid wastes. The formation and migration of NH3, HCN, HNCO, tar-N, and char-N are first discussed to clarify the chemical basis of fuel-N conversion. The effects of ZSM-5 pore structure, acid-site distribution, Si/Al ratio, hierarchical porosity, and synergy on adsorption, diffusion, C-N bond cleavage, heterocyclic-N ring-opening, aromatization, and nitrogen redistribution are then analyzed. Catalyst deactivation under realistic pyrolysis atmospheres is also highlighted, including coke deposition, metal sintering, framework dealumination, mineral poisoning, and H2S/SO2/COS-induced sulfur poisoning. Finally, future directions are proposed for designing multifunctional ZSM-5-based catalysts integrating denitrogenation activity, sulfur resistance, coke resistance, regenerability, and quantitative nitrogen/sulfur mass balance.