Formaldehyde (FA) is a key intermediate in the chemical industry and is increasingly gaining importance for biomass-based value chains, for example, in the production of polyoxymethylene dimethyl ethers (OME) as cleaner diesel fuel additives. For decentralized OME synthesis concepts, compact and structured reactors are highly attractive, which require robust kinetic models for the upstream methanol-to-formaldehyde process. The established industrial route is the partial oxidation of methanol over iron molybdate catalysts. Existing kinetic models for this reaction are restricted in temperature range or reaction network completeness, limiting their predictive capability for reactor and process design. In this study, an extended and statistically validated kinetic model for methanol partial oxidation was developed based on intrinsic kinetic data obtained in a Berty-type reactor across a broad temperature range of 250–350 °C. Based on experimental observations and literature analysis, a detailed reaction network comprising seven reactions was established. The kinetics of the oxidation reactions were described using a Mars–van Krevelen mechanism, while the formation of dimethyl ether was modeled as an equilibrium reaction of first order in methanol. With the developed kinetic model, excellent agreement with experimental data is achieved. Validation with independent data sets confirmed the model’s predictive capability for both major and minor components, with deviations below 15–20% for most species. The resulting kinetic framework provides a robust tool for predicting formaldehyde yield and selectivity across a broad range of conditions, including those needed for the design and optimization of compact, structured reactors for efficient, small-scale methanol-to-formaldehyde conversion processes.
Littwin et al. (Thu,) studied this question.