Chemical Engineering Science, Vol.115, 31-48, 2014
Kinetics of 1-dodecene hydroformylation in a thermomorphic solvent system using a rhodium-biphephos catalyst
The hydroformylation of 1-dodecene on a rhodium-biphephos catalyst complex exploiting a thermomorphic multicomponent solvent system was studied experimentally in a batch reactor in order to describe the kinetics of the main and the most relevant side reactions. The formation of the active catalyst was studied in preliminary experiments. Based on a postulated catalytic cycle mechanistic kinetic models were developed considering isomerization, hydrogenation and hydroformylation reactions as well as the formation of not catalytically active Rh-species. The complex overall network was decomposed to support parameter estimation. The isomerization of 1-dodecene, the hydrogenations of iso- and 1-dodecene and the hydroformylations of iso-dodecene and 1-dodecene were investigated as a function of temperature, total pressure and partial pressures of carbon monoxide and hydrogen, respectively. These four sub-networks of increasing size and the total network were analyzed sequentially in order to identify kinetic models and to estimate the corresponding parameters applying model reduction techniques based on singular value decomposition combined with rank revealing QR factorization. (C) 2013 Elsevier Ltd. All rights reserved.
Keywords:Homogeneous Rhodium catalysis;Hydroformylation of 1-dodecene;Network analysis and kinetics;Model reduction;Singular value decomposition;Parameter estimation