Synthesis of tailored oxymethylene ether (OME) fuels via transacetalization reactions

Abstract

In the field of alternative diesel fuels, so-called oxymethylene ethers (OMEs) are currently intensely investigated. Particularly OMEs of the type CH$_{3}$O(CH$_{2}$O)$_{n}$CH$_{3}$ with n = 3–5 exhibit promising fuel properties and combustion characteristics with strongly reduced particle and NO$_{x}$ emissions. According to their molecular structure, OMEs can be produced from methanol thus enabling sustainable production strategies from CO$_{2}$ and renewable resources. Compared to the methyl derivatives, analogous compounds with higher alkyl groups (oxymethylene dialkyl ethers, OMDAEs) have been investigated to a much lesser extent. Thus, commercially available OMDAEs, i.e. compounds of the type ROCH$_{2}$OR bearing ethyl, propyl, butyl and 2-ethylhexyl groups, have been studied. Furthermore, asymmetric compounds of the type R$^{1}$OCH$_{2}$OR$^{2}$ have been synthesized from the symmetric compounds employing transacetalization reactions catalyzed by zeolite BEA-25. The OMDAEs have been characterized by spectroscopic and spectrometric methods and several physico-chemical, thermodynamic and fuel-related data have been determined and compared. Despite their structural peculiarities, such as the oxygen-containing acetal moiety in the molecular backbone, all OMDAEs exhibit properties similar to conventional diesel fuels. Based on experimental and analytical data, the development of tools for the prediction of properties by a simple regression method is described. Furthermore, the suitability of group contribution modelling is investigated for OMDAE compounds