Molecular insights into the role of char-bound hydrogen in char-NO reactions under high pressures: A reactive molecular dynamics simulation study

Abstract In the present work, the role of char-bound hydrogen in char-NO reaction under pressurized oxy-fuel combustion (POFC) conditions was studied using the reactive molecular dynamics (ReaxFF MD) simulations. The effects of char-bound hydrogen on the chemisorption of NO, formation of N2, kinetics of char-NO reaction, and structure of char at different pressures and temperatures were investigated. The results show that the char-bound hydrogen hindered the chemisorption of NO, and inhibited the generation of CN. The role of char-bound hydrogen in the chemisorption of NO weakened with the increase in pressure. Considerable amount of H2O was generated during the reaction of NO with H-containing char, which proves that char-bound hydrogen provided another channel for the conversion of NO to N2, especially at high pressures. The activation energies of the chemisorption of NO and the formation of N2 during the reaction of NO with H-containing char were determined to be 174 and 126 kJ/mol, respectively. The ReaxFF MD simulation results were in good agreement with previous experimental and DFT values. The char-bound hydrogen increased the activation energies of the chemisorption of NO and the formation of N2 by 40% and 29%, respectively. The role of char-bound hydrogen in char gasification and char structure were also examined. The char-bound hydrogen reduced the consumption of char, and CO was the main product from char gasification. The results of the O/C and N/C ratios of char indicate that char-bound hydrogen had little effect on the desorption of CO. By analyzing the dynamic evolution of char structure, it is found that char-bound hydrogen inhibited N-down chemisorption of NO.