The mechanism of dimethyl carbonate synthesis on Cu-exchanged zeolite Y

摘要

The mechanism of dimethyl carbonate (DMC) synthesis from oxidative carbonylation of methanol over Cu-exchanged Y zeolite has been investigated using in situ infrared spectroscopy and mass spectrometry under transient-response conditions.The formation of DMC is initiated by reaction of molecularly adsorbed methanol with oxygen to form either mono- or di-methoxide species bound to Cu~+ cations.Reaction of themono-methoxide species with CO produces monomethyl carbonate (MMC) species.DMC is formed via two distinct reaction pathways-CO addition to di-methoxide species or by reaction of methanol with MMC.The rate-limiting step in DMC synthesis is found to be the reaction of CO with mono-methoxide or di-methoxide species.The first of these reactions produces MMC,which then reacts rapidly with methanol to produce DMC,whereas the second of these reactions produces DMC directly.Formaldehyde was identified as an intermediate in the formation of dimethoxy methane (DMM) and methyl formate (MF).Both byproducts are thought to form via a hemiacetal intermediate produced by the reaction of methanol with adsorbed formaldehyde at a Cu~+ site.