Biodiesel as a Sustainable Platform Chemical Enabled by Selective Partial Hydrogenation: Compounds Outplace...

The hydrogenation of polyunsaturated fatty acids (PUFAs) in vegetable oils and their derivatives is essential for their use in many areas, such as biofuels and food chemistry. However, no attempts have been made to adapt this technology to the requirements of further chemical utilization of fatty acid methyl esters as molecular building blocks, especially for particularly promising double-bond reactions. In this work, we, therefore, use three homogeneous catalytic model reactions (hydroformylation, isomerizing methoxycarbonylation, and ethenolysis) to show, firstly, that it is already known from the literature that high PUFA contents have a negative impact on activity and selectivity. Subsequently, using the example of soybean and canola biodiesel, we demonstrate that these key figures can be drastically improved by a preceding selective partial hydrogenation. This makes it possible to first reduce the share of PUFAs to <1 w % without causing significant overhydrogenation and then to carry out hydroformylation, methoxycarbonylation, and ethenolysis with significantly increased activity (up to twentyfold) and selectivity (up to 80 % increase). With these findings, we hope to convince the scientific and industrial world of the potential of selective partial hydrogenation as a key technology for utilizing renewable raw materials and to encourage its effective use in future work.