The catalytic upgrading of cellulose pyrolysis vapors is one of the effective methods to realize its high value utilization. Tuning the pore structure and acid sites of ZSM-5 (Z5) is a necessary strategy to develop effective catalysts for the production of light aromatics and the inhibition of carbon formation. In this study, a core-shell structure ZSM-5 @MCM-41 was developed and used for the first time in catalytic fast pyrolysis (CFP) of cellulose to prepare light aromatic hydrocarbons. The successful synthesis of the hierarchical core-shell ZSM-5 @MCM-41 was confirmed by nitrogen physisorption, X-ray diffraction (XRD), and transmission electron microscope (TEM) analysis. In aromatic hydrocarbon production, 1.0SH-Z5 @ M41 (1.0 mol/L, ZSM-5 @MCM-41) has the highest relative content of 98.76%. The relative content of BTEX (benzene, toluene, ethylbenzene, and xylene) is up to 89.83%, which is 2.39 times that of traditional microporous Z5. The quadratic polynomials were developed to correlate the Brønsted-to-Lewis acid site strength ratio (BLR) and mesopore-to-micropore volume ratio (MMR) with the relative content of BTEX. The mechanism of in-situ catalytic upgrading of cellulose pyrolysis vapor over ZSM-5 @MCM-41 was revealed. Due to high selectivities and low coke formation, ZSM-5 @MCM-41 offers an improved option for making monocyclic aromatics from cellulosic biomass.
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