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The concept of supported ionic liquid phase (SILP) catalysis has been established in recent years by our group and others. Its application in continuous catalytic gas‐phase processes provides a very attractive way to bridge the gap between homogeneous and heterogeneous catalysis. In this contribution, we extend SILP hydroformylation catalysis to reactions with a highly diluted, technical C4 feed containing 1.5 % 1‐butene, 28.5 % 2‐butenes, and 70 % of inert n‐butane. To obtain the desired product, n‐pentanal, the Rh‐biphephos catalyst system was immobilized in the SILP system to allow for consecutive isomerization/hydroformylation activity. The resulting SILP catalyst material converted up to 81 % of the reactive butenes, with a residence time of 155 s in the reactor. An n‐pentanal selectivity greater than 92 % was realized for more than 500 h time‐on‐stream in the continuous gas‐phase reaction. Post‐reaction NMR studies revealed no significant loss of the phosphite ligand through ligand oxidation during the reaction.

Ein besonders aktiver, hochselektiver Diphosphitligand ermöglicht die Titelreaktion unter Bildung linearen n‐Pentanals durch eine Kombination von Isomerisierung und Hydroformylierung. Wird der Wassergehalt des C4‐Substrats verringert, um die Bildung von sauren Abbauprodukten zu unterbinden, lässt sich die Standzeit des SILP‐Katalysators auf >800 h ausdehnen. Ex‐situ‐NMR‐Analysen bestätigen die Langzeitstabilität des Katalysators. Die Gefäße 1–4 enthalten typische SILP‐Katalysatoren.

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