Small pore zeolites, containing 8-rings as the largest, are widely employed as catalysts in the process of methanol-to-olefins （MTO）. Reactants and products dif- fuse with constraints through 8-rings and this is one...Small pore zeolites, containing 8-rings as the largest, are widely employed as catalysts in the process of methanol-to-olefins （MTO）. Reactants and products dif- fuse with constraints through 8-rings and this is one of the reaction bottlenecks related to zeolite micropore topology. Small pore zeolites and silicon-aluminophosphates （SAPOs） containing cavities, where olefins are mainly formed through the hydrocarbon pool （HP） mechanism, are frequently tested for MTO. Shape selectivity of transition states within the side-chain methylation will be reviewed as this is one of the controlling steps of the MTO process, with particular attention to the role of hexam- ethylbenzene （HMB） and heptamethylbenzenium cation （HeptaMB~）, which are the most tipically detected reaction intermediates, common to the paring and side-chain routes within the HP mechanism. The relative stability of these and other species will be reviewed in terms of confinement effects in different cage-based zeolites. The role of the different alkylating agents, methanol, dimethyl ether （DME）, and surface methoxy species （SMS） will also be reviewed from the computational viewpoint.展开更多
文摘Small pore zeolites, containing 8-rings as the largest, are widely employed as catalysts in the process of methanol-to-olefins （MTO）. Reactants and products dif- fuse with constraints through 8-rings and this is one of the reaction bottlenecks related to zeolite micropore topology. Small pore zeolites and silicon-aluminophosphates （SAPOs） containing cavities, where olefins are mainly formed through the hydrocarbon pool （HP） mechanism, are frequently tested for MTO. Shape selectivity of transition states within the side-chain methylation will be reviewed as this is one of the controlling steps of the MTO process, with particular attention to the role of hexam- ethylbenzene （HMB） and heptamethylbenzenium cation （HeptaMB~）, which are the most tipically detected reaction intermediates, common to the paring and side-chain routes within the HP mechanism. The relative stability of these and other species will be reviewed in terms of confinement effects in different cage-based zeolites. The role of the different alkylating agents, methanol, dimethyl ether （DME）, and surface methoxy species （SMS） will also be reviewed from the computational viewpoint.
