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Poly(oxymethylene) dimethyl ethers (OME, H3C–O–(CH2O)n–CH3) are promising synthetic diesel fuels. For
designing OME production processes, a model for describing the vapor–liquid equilibrium (VLE) in mixtures of
(formaldehyde + water + methanol + methylal + OME + trioxane) is needed. Building on previous work of
our group, a physico-chemical model for the VLE in these mixtures is developed in the present work. For the
development and the testing of the model, experiments of different types were carried out: VLE measurements in
a thin film evaporator, batch evaporation experiments in an open still, and continuous distillation experiments in
a laboratory column. The model predicts the results of the distillation experiments well. It is shown that OME
with n ≥ 3 can be separated as bottom product from mixtures of formaldehyde, water, methanol, methylal, and
OME with n ≥ 2. This separation is a critical step in a novel OME production process that increases the sustainability
of OME production.
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