A green and moderate approach for the synthesis of methyl formate via dimethoxymethane disproportionation over H-zeolites

Methyl formate (MF) is an important building block in the modern chemical industry, primarily produced through homogeneous carbonylation of methanol under harsh reaction conditions. It is of great interest but remains challenges to develop new heterogeneous catalytic system under mild reaction conditions to replace the homogeneous route. Herein, we report an efficient and green strategy for MF production by dimethoxymethane (DMM) disproportionation over acidic zeolites. Up to nearly100 % DMM conversion and 0.76 g g_cat⁻¹ h⁻¹ of MF space time yield (STY) is achieved over H-SSZ-13 under moderate conditions of 0.1 MPa and 393 K. Moreover, H-SSZ-13 shows superior stability during a 100 h continuous test. Combined with multiple characterizations, formaldehyde (FA) has been proved to be a crucial precursor for the formation of MF and the complete mechanism is proposed. This strategy provides a new and feasible approach for continuous large-scale MF production using acidic zeolite as catalyst by heterogeneous catalytic systems.