Insight into the fate of nitrogen during char thermal conversion and the influence mechanism of potassium: A theoretical research.

Nitrogen oxides (NOₓ) are primary pollutants produced during biomass combustion. During the devolatilization stage, char nitrogen (char(N)) is formed. In the subsequent char combustion stage, char(N) can decompose directly into NOx precursors or engage in heterogeneous reactions with O2 or NO to form NO and N2. Nonetheless, a comprehensive understanding of the reaction mechanisms and competitiveness of char(N) migration, especially the influence of the alkali metal potassium (K) present in biomass, remains incomplete. Building on the Zigzag char(N) models, the present study delves into the migration reactions of char(N), assessing their competitive dynamics through the integration of density functional theory, electronic structure analysis, and conventional transition state theory. Furthermore, it examines the impact of K on char(N) conversion. The competitiveness of the heterogeneous reactions follows the sequence: heterogeneous reduction of NO to N2 > heterogeneous oxidation of char(N) to NO > decomposition of char(N) to NOx precursors. Moreover, the formation of HCN is more favorable than NH₃ production. The successive conversion from char(N) to NO and then to N2 is the predominant migration route for char(N), with NO generation as the pivotal step. The less preferred char(N) migration route involves decomposition to NH3/HCN, followed by oxidation to NOx within the main combustion zone, which cannot be mitigated by char. K can accelerate NO generation and sustain the primacy of the heterogeneous NO reduction, consequently enhancing the oxidation-reduction process of char(N). As a result, K plays a constructive role in managing NOx emissions during the thermal conversion of char.