Hydroformylation and tandem isomerization–hydroformylation of n-decenes using a rhodium-BiPhePhos catalyst: Kinetic modeling, reaction network analysis and optimal reaction control

Abstract

The rhodium-BiPhePhos catalyzed hydroformylation of n-decenes, as representative long-chain olefins, was investigated in this study experimentally and theoretically. Besides hydroformylation activity, the used catalyst enables significant double bond isomerization which is an essential side reaction. Because of this property, highly selective tandem isomerization-hydroformylation reactions that convert mixtures of n-decenes with internal double bond position to the desired terminal aldehyde undecanal are possible using the Rh-BiPhePhos catalyst. Experimentally, a reaction network analysis strategy was applied to study the coupled main and side reactions separately. Subsequently, a mechanistic kinetic model based on an extended Wilkinson-mechanism was developed that includes all relevant main and side reactions. Fitting the model to the 23 well planned experiments was possible with low deviations between model and experiment, including the tandem reaction. It was found that the tandem reaction shows completely opposite dependencies regarding temperature and synthesis gas pressure compared to the conventional hydroformylation of 1-decene, which is also covered by the model. Hence, strategies for optimal reaction performance of the (tandem isomerization-)hydroformylation were developed and presented.

Kinetic Modeling of the Palladium‐Catalyzed Isomerizing Methoxycarbonylation of 1‐Decene

“…A reparametrized Arrhenius equation (Eq. ) was used for the reaction rate constants k j to minimize the correlation between the activation energy and the collision factor ( T ref = 85 °C). …”

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

“…In this system, the olefin concentration in the substrate is different for each carbon chain length. Several published kinetic rate expressions for the hydroformylation of long‐chain olefins suggest a first‐order dependence of the reaction rate in regard to olefin concentration [23,25,39–41] …”

“…One major step in the development of hydroformylation processes is represented by the Ruhrchemie‐Rhône‐Poulenc process for the hydroformylation of the short‐chain olefin propene and its effective multiphase recycling of the expensive rhodium catalyst [19–21] . Applying the water‐based recycling concept to higher olefins has been investigated by several research groups in the past [22–29] . These investigations usually focus on a single olefin, predominantly used as pure substrate phase.…”

Forschungsarbeiten am Institut für Verfahrenstechnik der Otto‐von‐Guericke‐Universität Magdeburg

“…Ein Schwerpunkt der Forschungsarbeiten ist die Untersuchung der Kinetik homogen und heterogen katalysierter Reaktionen. Ein in enger Kooperation mit Kollegen der TU Berlin und der TU Dortmund im Rahme des Transregio‐SFB 63 (Integrierte chemische Prozesse in flüssigen Mehrphasensystemen) entstandenes exemplarisches Ergebnis ist die Entwicklung und Parametrisierung eines kinetischen Modells für die durch Rhodium katalysierte Hydroformylierung langkettiger Olefine 6.…”