The pore structure of the zeolite is therefore the
main parameter which determines the deactivating effect of coke molecules. Hence, only tridimensional
zeolites without trap cavities could be used as catalysts
for reactions in which coke can be rapidly formed
because of the presence of coke-maker molecules and
operating conditions favouring coke formation. However,
monodimensional zeolites or zeolites with trap
cavities could be stable catalysts for processes in
which the formation of coke is very slow. A typical
example is n-hexane isomerization on a bifunctional
PtHMOR catalyst [26]. Modifications of the pore
structure can also significantly decrease the deactivating
effect of coke molecules. This has been shown, in
particular, for the transformation of methanol to shortchain
olefins on HMOR catalysts; the deactivating
effect of coke molecules is much lower (>10 times) in
dealuminated samples because mesopores created by
dealumination allow a quasi-tridimensional diffusion
of reactant molecules [27].
Besides the pore structure, the operating conditions
can also affect, though indirectly, the deactivating
effect of coke molecules. With operating conditions
favouring a rapid formation of coke, coke molecules
will be formed and deposited in the pores of the outer
part of the zeolite crystallites even if the zeolite is not
monodimensional and has no trap cavities. These coke
molecules block the diffusion of the reactant molecules
to the acid sites of the core of the crystallites,
with a large deactivating effect of coke molecules.
This pore mouth (or shell) blockage [28] was shown in
methylnaphthalene transformation on a USHY zeolite
[11].
Some general rules allowing to minimize the deactivating
effect of coke are indicated in Table 2.