Direct conversion of dimethyl ether and CO to acetone via coupling carbonylation and ketonization

Abstract

Acetone is currently produced by large amount of propylene and benzene, and its synthesis from a cheap and non-petroleum material has not yet been reported. Here, we present a new method for acetone production, which involves the carbonylation of dimethyl ether (DME) to methyl acetate and its subsequent ketonization to acetone over pyridine-modified H-mordenite. This convenient approach offers an acetone selectivity of 73% (CO2 excluded) and a DME conversion of 100% at 553 K. Spectral and isotopic studies revealed that the ketonization of methyl acetate was promoted by carbonylation, while the formation of a ketene intermediate was demonstrated by the formation of CH2DCOOD and two types of pyrones. A ketene-based ketonization mechanism was also proposed based on the kinetic isotope effect of CH2=13CO, indicating that the acetyl moiety contributed to the acyl part of acetone, while the ketene moiety was responsible for the alkyl part of acetone and the generation of CO2.