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One‐Pot Selective Synthesis of Renewable p ‐Xylene by Completely Biomass‐Based Ethanol and Dimethylfuran with Functionalized Mesoporous MCM‐41
Author(s) -
Zhao Rongrong,
Zhang Lige,
Xu Lulu,
Zhang Weiping
Publication year - 2021
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.202100121
Subject(s) - zeolite , catalysis , thermogravimetric analysis , selectivity , mesoporous material , chemistry , cycloaddition , xylene , sulfonic acid , organic chemistry , materials science , nuclear chemistry , toluene
One‐pot direct synthesis of renewable p ‐xylene (PX) via Diels‐Alder cycloaddition of completely bio‐based ethanol and 2,5‐dimethylfuran (DMF) was studied comparatively over dealuminated HBeta zeolite and functionalized mesoporous MCM‐41. The sulfonic group‐functionalized MCM‐41 had better catalytic performances. Under the optimized conditions, an ethanol conversion of ∼100 %, 2,5‐DMF conversion of 79 % and PX selectivity of 80 % were obtained over NH 3 ‐Silylated‐MCM‐41‐10 %SO 3 H catalyst with 0.8 wt % N content, which is much better than HBeta zeolite catalyst. X‐ray diffraction (XRD), thermogravimetric analysis (TGA), 29 Si cross‐polarization magic‐angle spinning (CP/MAS) NMR and infared (IR) characterizations showed that sulfonic and silylated groups have been successfully grafted onto MCM‐41. Quantitative 1 H MAS NMR with d5 ‐pyridine adsorption unambiguously demonstrated that silylated MCM‐41‐SO 3 H with NH 3 pre‐treatment has much higher amount and stronger strength of Brönsted acid than zeolite catalyst. This is the vital factor to catalyze the dehydration of ethanol to ethylene and speed up the Diels‐Alder cycloaddition reaction, ultimately increase PX selectivity and reduce much less soft‐coke deposit on MCM‐41‐SO 3 H (∼4 wt %) than on HBeta zeolite (∼12 wt %). This work demonstrates a simple and economical strategy to further improve the potential for the production of sustainable chemicals from complete biomass.