Abstract
AbstractThe Guerbet reaction from two alcohols to a long‐chain alcohol and water requires a redox catalyst and a strong base in homogeneous liquid systems. Especially, the reaction from ethanol to n‐butanol is a challenging example of the reaction that suffers from low yields and selectivities in comparison with reactions of higher alcohols. The most important side reactions are the polymerization of acetaldehyde to C6+‐components and the saponification of ethyl acetate under consumption of the base. This work pursues the systematic kinetic investigation of the Guerbet reaction network by experiments with isolated subsystems of the network. In‐situ‐infrared spectroscopy is applied to determine time‐resolved concentration profiles. Adapted kinetic models of the single steps are integrated into a microkinetic model of the whole network. The simulation of the reaction network reveals dependencies between temperature, hydrogen pressure, initial concentrations and the yield and selectivity of n‐butanol. Finally, it is shown that Ru‐MACHO does not lead to high yields in the reaction, because the dehydrogenation to ethyl acetate exhibits a too low activation barrier.
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