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Oligomeric oxymethylene dimethyl ethers (OMEs) of the type CH 3 O-(CH 2 O) n -CH 3 are promising diesel fuels with an enormous potential for the reduction of soot and NO x emissions. Oligomers with n = 3–5 are particularly advantageous, since their physicochemical and combustion properties are similar to conventional diesel. OMEs can be produced from methanol and formaldehyde but a series of byproducts, especially hemiformals, glycols, water and minor amounts of cyclic ethers, are also formed. These need to be separated from the product mixtures, which affects efficiency of this synthesis pathway. To isolate the desired OMEs, a one-step synthesis/extraction procedure is described. It implies highly selective extraction of OMEs from aqueous reaction solutions employing hydrocarbons as extraction agents. If fuel-type hydrocarbons are used, the resulting OME-hydrocarbon blends can be directly used in fuel applications. The corresponding oxymethylene diethyl ethers (OMDEEs) have also been investigated. Compared to OMEs, OMDEEs exhibit an increased solubility in nonpolar media but, as a result, solubility of educts and byproducts also increases. OME blends with hydrogenated vegetable oil and diesel have been prepared containing 10% of OMEs. It could be shown that such blends meet current diesel standards to a large extent. [ABSTRACT FROM AUTHOR]

A catalyst screening comprising zeolites and ion exchange resins for the synthesis of oligomeric oxymethylene dimethyl ethers (OME) from methanol (MeOH) and formaldehyde (FA) has been carried out. All catalysts led to the same product spectrum and parameters for chemical equilibrium have been determined. The ion exchange resin Dowex50Wx2 showed highest activity and reaction kinetics has been investigated employing this catalyst. The influence of the FA:MeOH ratio and water as well as refeeding of OMEs with undesired chain lengths have been considered in the kinetic model, which is based on a hyperbolic approach. Experiments have been carried out in the temperature range between 40 and 120 °C and variable FA:MeOH ratios from 0.5 to 1.5 g/g have been employed. Regarding water, up to 23 wt.% have been added to the reaction mixtures to investigate its influence on yield and reaction rate. Low water contents lead to high OME selectivities. By varying the FA:MeOH ratio, chain lengths of the OMEs can be influenced. Regarding the most active catalyst Dowex50Wx2, 90% of equilibrium conversion is reached after 5 min at 60 °C employing a catalyst loading of 1 wt.%. A study on the long term performance of the catalyst has been carried out and after 17 days the decrease of activity was below 10% while selectivity remained the same. For different Dowex catalysts a general kinetic model could be developed, which is not limited to Dowex50Wx2. [ABSTRACT FROM AUTHOR]

The conversion of biomass for the production of liquid fuels can help reduce the greenhouse gas (GHG) emissions that are predominantly generated by the combustion of fossil fuels. Oxymethylene ethers (OMEs) are a series of liquid fuel additives that can be obtained from syngas, which is produced from the gasification of biomass. The blending of OMEs in conventional diesel fuel can reduce soot formation during combustion in a diesel engine. In this research, a process for the production of OMEs from woody biomass has been simulated. The process consists of several unit operations including biomass gasification, syngas cleanup, methanol production, and conversion of methanol to OMEs. The methodology involved the development of process models, the identification of the key process parameters affecting OME production based on the process model, and the development of an optimal process design for high OME yields. It was found that up to 9.02 tonnes day −1 of OME 3 , OME 4 , and OME 5 (which are suitable as diesel additives) can be produced from 277.3 tonnes day −1 of wet woody biomass. Furthermore, an optimal combination of the parameters, which was generated from the developed model, can greatly enhance OME production and thermodynamic efficiency. This model can further be used in a techno-economic assessment of the whole biomass conversion chain to produce OMEs. The results of this study can be helpful for petroleum-based fuel producers and policy makers in determining the most attractive pathways of converting bio-resources into liquid fuels. [ABSTRACT FROM AUTHOR]