Green Process Design for Reductive Hydroformylation of Renewable Olefin Cuts for Drop‐In Diesel Fuels

CO(2)‐neutral fuels are a way to cleaner and more sustainable mobility. Utilization of bio‐syngas via Fischer‐Tropsch (FT) synthesis represents an interesting route for the production of tailormade biofuels. Recent developments in FT catalyst research led to olefin‐enriched products, enabling the synthesis of alcohol‐enriched fuels by reductive hydroformylation of the C=C bond. Several alcohols have already proven to be suitable fuel additives with favorable combustion behavior. Here, a hydroformylation‐hydrogenation sequence of FT‐olefin‐paraffin mixtures was investigated as a potential route to alcohols. A liquid‐liquid biphasic system with a rhodium/3,3’,3’’‐phosphanetriyltris(benzenesulfonic acid) trisodium salt (TPPTS) catalyst system was chosen for effective catalyst recycling. After optimizing reaction conditions with a model substrate consisting of 1‐octene and n‐heptane the conversion of an actual olefin‐containing C(5)‐C(10) FT product fraction to alcohols in continuously operated processes for 37 h was achieved with a total turnover number of 23679.