Theoretical Investigation of the Acid Catalyzed Formation of Oxymethylene Dimethyl Ethers from Trioxane and Dimethoxymethane

Oxymethylene dimethyl ethers (OMEs) are promising fuel additives that are accessible from renewable resources. We present a mechanistic investigation of the zeolite-catalyzed synthesis of OMEs from trioxane and OME1 based on first-principles calculations. The most favorable mechanism proceeds via direct incorporation of trioxane rather than formaldehyde incorporation after prior trioxane decomposition to formaldehyde. The computed mechanism is in agreement with the experimental kinetics as well as the selectivity after short and long reaction times. The competition between direct incorporation of trioxane and formaldehyde is predicted to depend on the acidity of the catalyst as well as the concentration of protic species in solution.