Selective Methanol Oxidation to Green Oxygenates—Catalyst Screening, Reaction Kinetics and Performance in Fixed-Bed and Membrane Reactors

Abstract

Experimental and simulation-based investigations are carried out for the selective oxidation of green methanol to the oxygenates dimethoxymethane (DMM) and methyl formate (MF), including an initial catalyst screening, the derivation of a reaction kinetic model, and a feasibility study of a fixed-bed and a membrane reactor with oxygen distribution. The catalyst screening of different supports and loading of vanadium revealed a 6.6 wt.-% VOx/TiO2 catalyst offering the highest potential to the formation for the target products. Kinetic experiments performed in a broad range of operation conditions, e.g., residence time, temperature, and oxygen concentration, are used for the postulation of a reaction network, providing the basis for mathematical modeling of the individual five reaction rates with a reduced mechanistic approach. A simulation study based on the derived reaction kinetics and parameters revealed the high potential of a distributed oxygen dosing at high residence times, outperforming the conventional fixed-bed reactor by up to 6% in the yield of DMM and up to 19% in the yield of MF. The formation of DMM is favored at low temperatures, whereas the formation of MF is supported by high temperatures.