Collaborative Research Center/Transregio 63

"Integrated Chemical Processes in Liquid Multiphase Systems"

>Research>Project Area A>Project A3

A3 Kinetics of reductive amination and hydroaminomethylation in reactive multiphase fluid systems

Sub-Coordinators: Prof. Dr.-Ing. Andreas Seidel-Morgenstern     Prof. Dr.-Ing. Christof Hamel
Researcher: M. Sc. Sabine Kirschtowski

State of the art

During the first founding period we identified the reaction network for the hydroformylation of the long-chain olefin 1-decene, catalytic cycles with all main and side reaction were developed and mechanistic kinetic models were derived. These were reduced by subset-selection techniques and validated successfully. The second founding period was characterized by the study of solvent composition effects and the effects of variable chain length of the substrates. Thereby 1-decene, a model substrate for petro and oleo chemicals, was used to investigate the sub network of the isomerisation in detail separately and the tandem reaction consisting of isomerisation and hydroformylation (so called isomerizing hydroformylation). The results were applied for an extension of the catalytic cycle and revision of the mechanistic models, which could be validated in a broad range of temperatures and pressures, successfully. After adjusting the parameters it was also possible to apply the kinetic model to the hydroesterfication reaction.

Research goals

In the third founding period the subproject A3 deals with the experimental and kinetic research concerning the mechanism and the kinetic of the hydroaminomethylation (HAM) as tandem reaction consisting of reductive amination (RA) and hydroformylation (Hyfo). Thus, the gained knowledge and developed methods for the hydroformylation should be used to analyse and quantify the kinetics.

To require detailed knowledge regarding the overall reaction the sub-network of the reductive amination step is analysed separately in a thermomorphic solvent system. The reaction network and the catalytic cycle will be clarified for the RA to formulate and define new kinetic models. Therefore, perturbation experiments, IR spectroscopy, design of experiments and parameter reduction techniques will provide a data basis. Based on an analysis of the sub network of RA, the next step will be the direct coupling of the olefin–hydroformylation and the RA in a tandem reaction in order to formulate mechanistic kinetic models (Figure 1). Additionally, transient studies will be performed by imposed time-varying concentrations, temperatures and catalyst-ligand properties for olefins with internal double bonds. The developed kinetic models for the tandem reaction of the hydroaminomethylation should provide a basis for the design of reactors and processes. Quantitative assessment of catalyst deactivation processes through feed contamination or addition of water as well as the development of general rules for evaluation of tandem reactions (multi-pot vs. single-pot synthesis) will complete this work package.



Figure 1: Hydroamiomethylation as tandem reaction from reductive amination and hydroformylation


Connected projects within Collaborative Research Centre/Transregio 63

A2 (Schomäcker): Influence of catalyst ligand complexes, network analysis of total and sub reaction networks, evaluation of catalyst deactivation

A4 (Sadowski, Stein): Quantification of gas solubility, solvent influence, reaction kinetics and phase equilibria in complex mixtures, quantification of rate determine steps

A11 (Seidensticker, Vogt): Transition metal catalyzed reductive amination of long-chain aldehydes and hydroaminomethylation, starting materials with temperature controlled catalyst separation in gas/liquid/liquid systems, catalyst activity and stability, IR investigations for development of kinetic mechanisms

B1 (Sundmacher, Zähringer): Exchange of kinetic data and models, validation of the optimal solvent system as well as dosing and temperature trajectories on reactor and process level

B9 (Kienle, Sundmacher): Experimental validation of optimal solvent systems, optimal reactor design and operation for liquid multiphase systems

D1 (Engell, Sadowski, Sundmacher): Providing of simplified and mechanistic kinetic models for process development, optimization and evaluation of kinetics in a pilot scale plant, general rules for the evaluation of tandem reactions (multi-pot vs. single-pot synthesis)

D3 (Skiborowski, Vogt): Characterizations of influences of impurities in the process and compensation by controlled dosing of scavengers


Recent Publications

Gerlach, M.; Kirschtowski, S.; Seidel-Morgenstern, A.; Hamel, C. Kinetic Modeling of the Palladium-Catalyzed Isomerizing Methoxycarbonylation of 1-Decene. Chem. Ing. Tech., 90(5), 673-678, 2018. []

Gaide, T.; Jörke, A.; Schlipköter, K.E.; Hamel, C.; Seidel-Morgenstern, A.; Behr, A.; Vorholt, A. J. Isomerization/hydroformylation tandem reaction of a decene isomeric mixture with subsequent catalyst recycling in thermomorphic solvent systems. Appl. Catal., A, 532, 50-56, 2017. [doi:]

Gerlach, M.; Wajid, D. A.; Hilfert, L.; Edelmann, F. T.; Seidel-Morgenstern, A.; Hamel, C. Impact of minor amounts of hydroperoxides on rhodium-catalyzed hydroformylation of long-chain olefins. Catal. Sci. Technol., 7, 1465-1469, 2017. [doi: 10.1039/C7CY00244K]

Janiga, G.; Stucht, D.; Bordás, R.; Temmel, E.; Seidel-Morgenstern, A.; Thévenin, D.; Speck, O. Non-invasive 4D flow characterization in a stirred tank via phase-contrast magnetic resonance imaging. Chem. Eng. Tech., 40, 1370–1327, 2017. [doi: 10.1002/ceat.201700067]

Jörke, A.; Gaide, T.; Behr, A.;Vorholt, A. J.; Seidel-Morgenstern, A.; Hamel, C. Hydroformylation and tandem isomerization–hydroformylation of n-decenes using a rhodium-BiPhePhos catalyst: Kinetic modeling, reaction network analysis and optimal reaction control. Chem. Eng.J., 313, 382-397, 2017. [doi:]

Jörke, A.; Seidel-Morgenstern, A.; Hamel, C. Rhodium-BiPhePhos catalyzed hydroformylation studied by operando FTIR spectroscopy: Catalyst activation and rate determining step. J. Mol. Catal. A: Chem., 426, 10-14, 2017. [doi:]

Lemberg, M.; Sadowski, G.; Gerlach, M.; Kohls, E.; Stein, M.; Hamel, C.; Seidel-Morgenstern, A. Predicting solvent effects on the 1-dodecene hydroformylation reaction equilibrium. AIChE J., Advance Article, 2017. [doi: 10.1002/aic.15782]

Gao, K.; Yang, J.; Seidel-Morgenstern, A.; Hamel, C. Methane Dehydro-Aromatization: Potential of a Mo/MCM-22 Catalyst and Hydrogene-Selective Membranes. Chem. Ing. Tech., 88(1-2), 168–176, 2016. [doi:10.1002/cite.201500139]

Jörke, A.; Kohls, E.; Triemer, S.; Seidel-Morgenstern, A.; Hamel, C.; Stein, M. Resolution of Structural Isomers of Complex Reaction Mixtures in Homogeneous Catalysis. Chem. Eng. Process., 102, 229-237, 2016. [doi:10.1016/j.cep.2016.01.001]

Kiedorf, G.; Wolff, T.; Seidel-Morgenstern, A.; Hamel, C. Kinetic Analysis oft he Hydrocarbon Total Oxidation Using Individually Measured Adsorption Isotherms. Chem. Ing. Tech., 88(11), 1746-1760, 2016. [doi: 10.1002/cite.201600043]

Chauhan, G.; Stein, M.; Seidel-Morgenstern, A.; Pant, K. K.; Nigam, K. D. P. The thermodynamics and biodegradability of chelating agents upon metal extraction. Chem. Eng. Sci., 137, 768-785, 2015. [doi:10.1016/j.ces.2015.07.02]

Hentschel, B.; Kiedorf, G.; Gerlach, M.; Hamel, C.; Seidel-Morgenstern, A.; Freund, H.; Sundmacher, K. Model-Based Identification and Experimental Validation of the Optimal Reaction Route for the Hydroformylation of 1-Dodecene. Ind. Eng. Chem. Res., 54(6), 1755-1765, 2015. [doi:10.1021/ie504388t]

Jörke, A.; Seidel-Morgenstern, A.; Hamel, C. Isomerization of 1-decene: Estimation of Thermodynamic Properties, Equilibrium Composition Calculation and Experimental Validation Using a Rh-Biphephos Catalyst. Chem. Eng. J., 260, 513-523, 2015. [doi:10.1016/j.cej.2014.09.015]

Jörke, A.; Triemer, S.; Seidel-Morgenstern, A.; Hamel, C. Kinetic Investigation Exploiting Local Parameter Subset Selection: Isomerization of 1-Decene using a Rh-Biphephos Catalyst. Chem. Ing. Tech., 87(6), 1-14, 2015. [doi:10.1002/cite.201400148]



Kiedorf, G. Mechanistic and kinetic analysis of homogeneously and heterogeneously catalyzed reactions. Otto-von-Guericke-Universität Magdeburg, 2018.

Jörke, A. Mechanisms and kinetics of petro- and oleochemicals in complex hydroformylation reaction networks. Otto-von-Guericke-Universität Magdeburg, 2018.

Temmel, E. Design of continuous crystallization processes. Otto-von-Guericke-Universität Magdeburg, 2016.

Hoang Minh, D. A simultaneous optimization approach to optimal experimental design.Technische Universität Berlin, 2014.

Last updated:11-02-2019