Cooperativity of Bronsted and Lewis acid sites on zeolite for glycerol dehydration

Selective dehydration of glycerol, a byproduct from the biodiesel industry, on solid acids is an important reaction in the production of the value-added chemical acrolein for economic-sustainable biorefinery. Most efforts have been made on the development of strong Brønsted acid sites (BAS) to improve the production of acrolein, because the Lewis acid sites (LAS) generally promote the generation of the byproduct acetol. However, exclusively tuning the properties of BAS or LAS did not well-promote the acrolein production from glycerol as indicated in this work. We provide a new route for efficient and selective glycerol transformation to acrolein via the cooperative dehydration between the BAS and LAS. The role of LAS (extra-framework aluminum species on zeolites) was altered from competition with BAS to generate the byproduct acetol to cooperation with the neighboring BAS. It is very beneficial for the sequential two-step dehydration of the internal and terminal hydroxyl groups of glycerol to value-added acrolein. This cooperativity of BAS and LAS significantly improved the yield of acrolein from the selective glycerol dehydration.