Unified mechanistic model for Standard SCR, Fast SCR, and NO2 SCR over a

copper chabazite catalyst

M. Bendrich, A. Scheuer, R.E. Hayes, M. Votsmeier
http://dx.doi.org/10.1016/j.apcatb.2017.09.069

The proposed mechanism consists of linear combination of reactions. Each global reaction
comprises of only one single combination. Two site mechanism is assumed for the model:
one site on which all ammonia is adsorbed (regardless ammonia is adsorbed on both bronsted
acid sites and copper sites) and another where Cu site interaction takes place.

After the active sites are saturated with adsorbed ammonia, temperature is increased
gradually thereby increasing its desorption. The model slightly diverts from experimental
data. This discrepancy can be attributed towards single site ammonia adsorption also due to
oxidation of ammonia at high temperature. The adsorption of NO2 takes place in the form of
nitrates and nitrites. Nitrites are crucial intermediates. Oxidation of nitrites takes place via
NO2 producing NO and HNO3. The standard SCR mechanism and NO oxidation is modelled
via nitrite formation pathway. Also the redox reaction of Cu ions which is taken into account
is described by reduction of Cu+2 by NO and its re-oxidation by O2 and H2O.

The model fails to incorporate formation of N2O at high temperature as it labels N2O
formation as undesired reaction of Standard SCR. Ammonia oxidation is modelled at higher
temperature only due to its single site storage mechanism.

NO2 and NH3 conversion can be achieved at low temperature in absence of Cu in zeolite
catalyst.

NO2 SCR

Adsorption of NO2 takes place in the form of nitrates leading to the production of NO.
Adsorbed NH3 reacts with nitrites and nitrates via NO2 decreasing outlet NO2 concentration.
The copper sites are blocked by Cu2+-NO3[NH3], constant reaction takes place between
NO2 and NH3 at ammonia adsorption sites. Due to this blockage of Cu sites NO2 would
breakthrough beacause it cannot get adsorbed on Cu sites. To avoid this Ammonia spillover
reaction is included which describes that Cu2+-NO3[NH3] can be adsorbed on ammonia sites
freeing Cu sites for further reaction

At low temperature minimal decomposition of ammonium nitrate like species is observed

with the addition of NO but at high temperature fair amount is decomposed.

During driving cycle predictions it is seen that very less amount of ammonium nitrate like
species block the sites. Also the surface coverage throughout the driving cycle varies citing
the need to model the transient effects.