Role of ball milling during Cs/X catalyst preparation and effects on catalytic performance in side-chain alkylation of toluene with methanol

Abstract

Ball milling modification was performed on Cs/X catalysts before or after cesium ion exchange. Multiple characterization results (such as pyridine-FTIR, XPS, and solid-state NMR) demonstrated that ball milling played a distinct role in these two different preparation procedures of the catalyst. Ball milling performed after the cesium modification has a strong influence on the Cs/X structure and acid–base properties, which results in the enhancement of the catalytic performance for side-chain methylation of toluene with methanol. Detailed studies revealed that ball milling intensified the interactions between oxides and molecular sieves, which not only increased the dispersion of the Cs species but also generated some weaker basic centers. It is proposed that the new basic centers could be Si–O–Cs and Al–O–Cs, which are produced by breaking of the Si–O–Al bonds of the zeolite framework under the synergetic effect of ball milling and alkali treatment. These new active sites may help to promote the side-chain methylation reaction. However, excessive ball milling will lead to the vanishing of zeolite micropores, thus deactivating side-chain methylation activity, which indicates that microporosity plays a key role in side-chain methylation and individual basic centers cannot catalyze this reaction.