Nature of nitrogen specie in coke and their role in NOx formation during FCC catalyst regeneration

NOx emission during the regeneration of coked fluid catalytic cracking (FCC) catalysts is an environmental problem. In order to follow the route to NOx formation and try to find ways to suppress it, a coked industrial FCC catalyst has been prepared using model N-containing compounds, e.g., pyridine, pyrrole, aniline and hexadecane-pyridine mixture. Nitrogen present in the FCC feed is incorporated as polyaromatic compounds in the coke deposited on the catalyst during cracking. Its functionality has been characterized using XPS. Nitrogen specie of different types, namely, pyridine, pyrrolic or quaternary-nitrogen (Q-N) have been discriminated. Decomposition of the coke during the catalyst regeneration (temperature programmed oxidation (TPO) and isothermal oxidation) has been monitored by GC and MS measurements of the gaseous products formed. The pyrrolic- and pyridinic-type N specie, present more in the outer coke layers, are oxidized under conditions when still large amount of C or CO is available from coke to reduced NOx formed to N2. “Q-N” type species are present in the inner layer, strongly adsorbed on the acid sites on the catalyst. They are combusted last during regeneration. As most of the coke is already combusted at this point, lack of reductants (C, CO, etc.) results in the presence of NOx in the tail gas.