Synergistic catalysis effect of micro-mesoscopic channel for enhanced methyl oleate catalytic cracking to BTX: A molecular simulation study

The hierarchical ZSM-5 zeolite exhibits superior catalytic performance for methyl oleate catalytic cracking to BTX, while the promotion mechanism at the molecular level is still unclear. Herein, the adsorption and diffusion behaviors of reaction species in hierarchical ZSM-5 zeolite, including methyl oleate, C3H6, C4H8 and BTX, were theoretically investigated by Monte Carlo combined with Molecular Dynamics simulation. It is found that the introduction of mesopores exposes the strong adsorption sites (Brønsted acid) without a confinement effect, thereby promoting the adsorption and cracking of methyl oleate. Moreover, the as-formed C3H6 and C4H8 rapidly transfer from mesopore into micropore, enhancing the aromatization reaction to form BTX. Finally, thanks to the adjacent mesopore providing sufficient space for molecule rotation, the desired BTX products easily desorbs from the micropore. Such synergistic catalysis effect of micro-mesoscopic channel increases the BTX yield by decreasing the diffusion coefficient of C3H6 and C4H8 from 13.2 × 10-9 m2/s on the traditional to 6.4 × 10-9 m2/s on the hierarchical ZSM-5. We anticipate that this work could enrich our understanding of the microcosmic mechanism of hierarchical zeolites for prolific aromatics.