The effect of introducing Ga on the ZSM-5-catalyzed methanol to aromatics reaction: taking methylcyclopentane to benzene as an example

Naphthenes are key intermediates in the formation of aromatic compounds during the methanol to aromatics (MTA) reaction, and the dehydrogenation process is more important than the hydrogen transfer process. Theoretical studies were performed to investigate the methylcyclopentane, which represents a naphthene, to benzene MTA process catalyzed by ZSM-5 before and after introducing Ga, showing that Ga-ZSM-5 was more favorable for carrying out the reaction than two H-type ZSM-5 (H-Z1 and H-Z2) models. H-Z1 and H-Z2 are favorable for the transfer of H during ring expansion reactions and the reformation of Bronsted acids, but the dehydrogenation reactions involving H-Z1 and H-Z2 require high free-energy barriers to be overcome. Although introducing Ga to ZSM-5 is not conducive to the transfer of H after dehydrogenation, it can reduce the extremely high dehydrogenation free-energy barrier compared with H-Z1 and H-Z2; this is mainly because Ga at dehydrogenation active centers, [GaH]2+, can accept electrons and donate them to the H atoms of [GaH]2+, giving H negative charge and making it easy to combine with positive B-acid H atoms that come from methylcyclopentane, cyclohexene, and cyclohexadiene to produce H2. Also, analysis of the transition state structures of all DH processes shows that Ga-ZSM-5 is more favorable for promoting the combination of H to produce H2 than H-Z1 and H-Z2.