Solid-state dealumination of zeolites for use as catalysts in alcohol dehydration

• Dealuminated zeolites presented lower coke formation and higher amount of acid sites.
• All catalysts showed 100% selectivity in the developed pulsed microreactor.
• Mechanisms for all dehydrations were related to the presence of Brønsted acid sites.
• Dealuminated zeolites showed better activity in alcohol dehydration than the parents.
• XRD, SEM and FT-IR demonstrated structural maintenance of dealuminated zeolites.

The dealumination of zeolites has been studied to tune acidity, resulting in enhanced catalytic efficiency. MOR, FER, and ZSM-5 were dealuminated to remove 5, 10, 15, or 20 mol% of Al with (NH4)2SiF6 (solid-state reaction at 80 °C). XRD, SEM, and FT-IR showed structural maintenance. Aluminum removal was confirmed by the total Si/Al ratio (XRF and AAS) and 27Al MAS NMR. The dealuminated samples were tested in the dehydration of different alcohols and compared to the protonic parent zeolites. Dealuminated MOR samples exhibited a decrease in coke formation (maximum decrease of 18.3%, 18.2%, and 6.1% for methanol, ethanol, and 1-propanol dehydration, respectively), and an increase in conversion values (maximum increase of 29.0%, 13.9%, and 6.2% for methanol, ethanol, and 1-propanol dehydration). H-FER/20% showed an improvement in methanol (19.9%) and ethanol (3.8%) conversions and a reduction of coke (decrease of 8.6% and 5.6%, respectively), corroborating the highest value of acid sites (0.73 mmol g−1). All catalysts showed 100% selectivity to each desired product. The mechanisms for all dehydrations were related to the presence of Brønsted acid sites. Methanol dehydration might involve the generation of methoxonion ion, and ethoxy groups might be formed for ethanol conversion. For ZSM-5, Lewis acid sites may also participate in the elimination mechanism. High reaction temperature (300 °C) favored intramolecular dehydration to ethylene, avoiding formation of diethyl ether and oligomers. Structural defects on H-ZSM-5/15% could facilitate the access of 1-propanol to active sites, leading to the best combination of TON (0.67), conversion (100%), and coke formation (0.35%).

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