Coal/NH3 interactions during co-pyrolysis and their effects on the char reactivity for NO-reduction: A ReaxFF MD study

In this work, the interactions between NH3 and coal during co-pyrolysis and their influences on char structure and char reactivity for NO reduction are investigated using reactive molecular dynamic (ReaxFF MD) simulations, revealing that coal promotes the thermal decomposition of NH3 because it provides H radicals to attack the N-H bonds in NH3. The primary pyrolysis reactions (thermal breaking of weak covalent bonds) of coal are inhibited by NH3 center dot NH3 also influences the secondary reactions in coal pyrolysis through two aspects: (1) promotes tar cracking to generate gas, and (2) inhibits the polymerization of tar to form char. Compared with coal pyrolysis, the H/C ratio of char and number of O and N atoms in char decrease more slowly during coal/NH3 copyrolysis. However, NH3 has little influence on the release of H2S. The effect of NH3 on the physicochemical properties of the char is then analyzed. The oxygen atoms are present mainly as hydroxyl, ether, and carbonyl forms, and the nitrogen atoms are present mainly as cyanide and amino forms in both coal pyrolysis char and coal/NH3 co-pyrolysis char. The coal/NH3 co-pyrolysis char has lower helium density, lower graphitization degree, and larger pores compared with coal pyrolysis char. Finally, the reactivity of coal pyrolysis char and coal/NH3 co-pyrolysis char for NO reduction are examined. The coal/NH3 co-pyrolysis char is more conducive to NO chemisorption and N-2 generation. Using a first-order kinetics model, the activation energy of NO reduction reactions on coal pyrolysis char and coal/NH3 co-pyrolysis char are determined as 180 and 123 kJ/mol, respectively.

Automated summary

The interactions between NH3 and coal during co-pyrolysis were investigated using ReaxFF MD simulations. It was found that coal promotes the thermal decomposition of NH3 and NH3 influences the primary and secondary reactions in coal pyrolysis. The physicochemical properties of the char produced from coal/NH3 co-pyrolysis were also analyzed. Finally, the reactivity of the char for NO reduction was examined, showing that coal/NH3 co-pyrolysis char is more conducive to NO chemisorption and N-2 generation than coal pyrolysis char.