Influence of coke heterogeneity and the interaction between different coke species on the emission of toxic HCN and NOx from FCC spent catalyst regeneration.

ABSTRACT

Concerning the emissions of hydrogen cyanide (HCN) and other N-bearing air pollutants from the fluid catalytic cracking (FCC) regeneration units, this paper has conducted a comprehensive testing and surface characterisation of four industrial spent catalysts, aged catalysts and hard coke sample in three different schemes, Ar-TPD, O2 -TPO and rapid heating to elaborate the transformation of N upon the influence of the heterogeneity of coke and N speciation. In the Ar-TPD scheme, the surface N is responsive for the emission of gaseous NH3 from pyrrolic N-5 and HCN from both pyridinic N-6 and quaternary N-Q. The removal of soft coke is beneficial in promoting the surface exposure of hard coke, thereby increasing the HCN emission dramatically. In the O2-TPO scheme, the oxygen accessibility is the principal factor governing the emission of HCN. The external soft coke is able to access the bulk O2 firstly, the combustion of which in turn provides heat back to promote the cracking of internal hard coke from the same and neighbouring particles to release more HCN. The induction effect of bulk O2 is also superior over the spent catalyst properties in formulating a nearly identical trend of HCN emission for all the four spent catalysts tested. Finally, for the use of rapid heating scheme that is typical in a commercial FCC regenerator, it is effective in accelerating the volatilisation of soft coke quickly, thereby promoting the oxygen accessibility to hard coke and the internal N-bearing precursors so as to mitigate the emission of HCN effectively. The use of a large superficial velocity of gas is further effective in sweeping the volatiles including HCN away from the catalyst, promoting their oxidation extent accordingly.