n-Heptane and methylcyclohexane transformation over a HMCM-22 zeolite. Origin of the features typical of large-or of medium-pore zeolites

The main features of methylcyclohexane (mch) and n-heptane (n-C7) transformation at 350°C were compared for fresh samples of HMWW, HMFI and HFAU zeolites. With both reactions, the behavior of HMWW was between those of the medium HMFI and large pore HFAU zeolites. Thus, the values of turnover frequency (TOF) and of the TOFmch/n-C7 ratio were similar with HMWW and HMFI and much higher with HFAU. In contrast, small differences were found between product distributions over HMWW and HFAU but large differences between HMWW and HMFI. These observations can be explained by alkane transformation in the large supercages with 10-MR apertures of HMWW: the narrow apertures limit diffusion of the mch within the supercages, but not the diffusion of the products which are therefore typical of the transformation within large cages hence without any steric limitation.