The shape selectivity in the liquid-phase hydroxylation of aromatic hydrocarbons with hydrogen peroxide has been studied on two kinds of titanosilicate, the large-pore Ti-M with MOR structure and medium-pore TS-1 with MFI structure, and the liquid-phase diffusion of aromatics into both catalysts was compared in the presence of H2O and H2O2 to clarify the origin of the shape selectivity. The hydroxylation rate on TS-1 decreased monotonically with increasing molecular size in the order benzene>toluene. ethylbenzene>cumene, while Ti-M showed the maximum rate for toluene hydroxylation. The apparent diffusivity of aromatics was lowered roughly by 1 order by adding H2O2 to H2O solvent for both titanosilicates but was not affected for their Ti-free derivatives, mordenite and silicalite-1. The reduction in diffusion rate in the presence of H2O2 was more pronounced for TS-1 and for Ti-rich samples. It is concluded that a bulky Ti peroxo species (Ti-OOH) formed by the interaction of Ti site with H2O2 mainly causes a transition-state shape selectivity in the hydroxylation of bulky aromatics in titanosilicate/H2O2 systems.

Disproportionation of toluene has been studied over dealuminated MCM-22 zeolites. The dealumination of MCM-22 was performed by acid reflux and the combination of calcination or steaming with the subsequent acid reflux, These treatments effectively eliminated A1 atoms from the framework site but left most of them in the crystallites as non-acidic extra-framework species. The activity of MCM-22 for the toluene disproportionation measured at relatively low temperatures (473-573K) was comparable to that of mordenite and much higher than that of ZSM-5. Toluene disproportionation was found to occur mainly within the supercages of MCM-22 but not in the 10-membered ring (10-MR) channels of MCM-22 at these temperatures. The fraction ofp-xylene in xylene isomers (para-selectivity) formed on MCM-22 was higher than its equilibrium value, and increased further by the dealumination. p-Xylene formed within the supercages as a primary product would be isomerized to o- and m-xylene by the acid sites not only on the external surface but also within the 10-MR channels. The improvement in para-selectivity by the dealumination resulted from the suppression of isomerization activity probably because the dealumination treatments eliminated framework A1 atoms predominantly on the external surface and inside the 10-MR channels compared with those inside the supercages.