Abstract
Fluidized catalytic cracking (FCC) units in refineries process heavy feedstock obtained from crude oil distillation. While cracking feed, catalysts get deactivated due to coke deposition. During catalyst regeneration by burning coke in air, nitrogen oxides (NO
x
) are formed. The increase in nitrogen content in feed over time has resulted in increased NO
x
emissions. To predict NO
x
concentration in flue gas, a reliable model for FCC regenerators is needed that requires comprehensive understanding and accurate kinetics for NO
x
formation. Based on the nitrogen-containing functional groups on coke, model molecules are selected to study reactions between coke-bound nitrogen and O
2
to form NO and NO
2
using density functional theory. The reaction kinetics for the proposed pathways are evaluated using transition state theory. It is observed that the addition of O
2
on coke is favored only when the free radical is present on the carbon atom instead of nitrogen atom. Thus, NO
x
formation during coke oxidation does not result from the direct attack by O
2
on N atoms of coke, but from the transfer of an O atom to N from a neighboring site. The low activation energies required for NO formation indicate that it is more likely to form than NO
2
during coke oxidation. The favorable pathways for NO
x
formation that can be used in FCC models are identified.