Conversion of Green Methanol to Methyl Formate

Abstract

Methyl formate is a key component for both defossilized industry and mobility. The current industrial production via carbonylation of methanol has various disadvantages such as high requirements on reactant purity and low methanol conversion rates. In addition, there is a great interest in replacing the conventional homogeneous catalyst with a heterogeneous one, among other things to improve the downstream processing. This is why new approaches for methyl formate are sought. This review summarizes promising approaches for methyl formate production using methanol as a reactant.

Heterogeneity of oxygen reactivity: key for selectivity of partial methanol oxidation on gold surfaces

“…Methyl formate is an important intermediate for a variety of bulk chemicals, such as formic acid, formamide or dimethyl formamide, and more recently was also tested as a possible alternative fuel (additive). 1–4 Apart from the currently applied industrial synthesis (reaction of CO with methanol over sodium or potassium methoxide requiring dry and CO 2 -free feeds), 2,4,5 dehydrogenation and the thermodynamically more favourable partial oxidation of methanol are pursued as alternative routes. 1,2 On nanoporous gold (np-Au), aerobic partial oxidation of methanol to methyl formate shows a temporally stable, high selectivity at high conversion for temperatures below 100 °C.…”

“…1–4 Apart from the currently applied industrial synthesis (reaction of CO with methanol over sodium or potassium methoxide requiring dry and CO 2 -free feeds), 2,4,5 dehydrogenation and the thermodynamically more favourable partial oxidation of methanol are pursued as alternative routes. 1,2 On nanoporous gold (np-Au), aerobic partial oxidation of methanol to methyl formate shows a temporally stable, high selectivity at high conversion for temperatures below 100 °C. 6 Np-Au is a fully metallic catalyst which is prepared by dealloying a gold alloy containing a less noble metal, mostly Ag, resulting in a porosity on the nanometer scale characterized by ligaments exhibiting a large fraction of low coordinated sites as well as low index facets.…”

Selective oxidation conversion of methanol/dimethyl ether

“…Similarly, the selective oxidation of methanol to MF is completed under the synergistic effect of acidic, basic and redox sites, whereas, the formation of DME is due to the presence of strong acid centers. [22][23][24] In this section, we summarize the research progress on the oxidative conversion of methanol to FA, MF and DMM in recent years. Meanwhile, the relationship between the structure of the catalysts and their catalytic performance as well as the corresponding reaction mechanisms has been discussed.…”

“…As already mentioned above by us, methyl formate is an important C1 intermediate, which can be produced via methanol carbonylation, non-oxidative dehydrogenation of methanol, or direct oxidation of methanol. 23 Alternatively, MF can also be obtained directly from selective oxidation of DME because of its similar structure with DME. It is necessary and beneficial to develop a green route for the synthesis of MF from DME oxidation at a low temperature in order to reduce the toxicity of the reaction process.…”

Recent Advances in Aerobic Photo-Oxidation over Small-Sized IB Metal Nanoparticles

“…Methyl formate is one of the important chemicals applied in synthesis intermediates, the solvent for cellulose, and fumigants and fungicides [22][23][24][25][26]. The anatase-TiO 2 was shown to be a poor photocatalyst [27,28]; thus, the CuO/anatase-TiO 2 system was developed [29].…”