Optimal experimental design for the identification of a reaction kinetic model for the hydroaminomethylation of 1-decene in a thermomorphic multiphase system

The transition toward green chemicals production requires new processes which are able to handle sustainable feedstock comprising unsaturated, long-chain hydrocarbons. The homogeneously rhodium-catalyzed tandem hydroaminomethylation (HAM) is able to convert long-chain olefins to amines and, therefore, represents an example reaction of high interest for the next generation of chemical processes. This work improves upon an existing mechanistic reaction kinetic model for 1-decene in a methanol/dodecane thermomorphic multiphase system (TMS) by structural adjustment of the catalyst pre-equilibrium, the investigation of the water influence on the reaction equilibria as well as the re-estimation of kinetic and inhibition parameters to provide accurate predictions under a wide range of operating conditions. This is achieved by pairing model-based optimal experimental design (mbOED) with perturbed-chain statistical associating fluid theory (PC-SAFT)-based phase equilibrium calculations to account for experiment setup-specific limitations while ensuring monophasic operation throughout all experiments. The subsequent model identification is able to substantially improve the prediction quality of the hydroaminomethylation model in edge cases over the previous model while maintaining a quantitative agreement of experimental and simulated concentration profiles under nominal conditions.