Collaborative Research Center/Transregio 63
"Integrated Chemical Processes in Liquid Multiphase Systems"
"Integrated Chemical Processes in Liquid Multiphase Systems"
Collaborative Research Center/Transregio 63
"Integrated Chemical Processes in Liquid Multiphase Systems"
Sub-Coordinator: Prof. Dr. Reinhard Schomäcker
Researchers: M. Sc. Ariane Weber
The project A2 will transfer the achievements of the last funding periods to another catalytic reaction. The objectives are focussed on the reductive amination of 1-undecanal with diethylamine to long-chain amines. This reaction consists of two steps, a condensation reaction followed by a hydrogenation, i.e. a more complex reaction network compared to the earlier studied hydroformylation of long chain olefins (see figure 1).
Figure 1: Reaction network of the reductive amination of 1-undecanal with diethylamine.
Kinetic and mechanistic studies of the reductive amination are done in cooperation with subproject A3. The influence of diethylamine on the phase behaviour of the multiphase system is investigated in order to select a suitable surfactant for the reductive amination. Thus, the impact of the product concentration on reaction performance and phase behaviour is tested. Together with subproject D2 we aim for the development of a continuous mini-plant process in a minimum of time.
Finally, the well-known hydroformylation and the reductive amination will be combined to the hydroaminomethylation reaction. There are different options for this combination, e.g. a one-pot synthesis with one catalyst and the same multiphase system for both reactions or a process with two consecutive reactions using different catalysts, surfactants and/or reaction conditions (see figure 2).
Figure 2: Process scheme for the Hydroaminomethylation. A one-pot synthesis. B uncoupled consecutive reactions.
Stock, S.; Schlander, A.; Kempin, M.; Geisler, R.; Stehl, D.; Spanheimer, K.; Hondow, N.; Micklethwaite, S.; Weber, A.; Schomäcker, R.; Drews, A.; Gallei, M.; von Klitzing, R.The quantitative impact of fluid vs. solid interfaces on the catalytic performance of pickering emulsions, Phys. Chem. Chem. Phys., 23, 2355-2367, 2021. [DOI:10.1039/D0CP06030E]
Weber, A.; Isbrücker, P.; Schmidt, M.; Schomäcker, R. Ionic Liquids as Surfactants in Aqueous Multiphase Systems for the Pd-Catalyzed Hydrocarboxylation. Chem. Ing. Tech. 93 (1-2), 201-207, 2021. [DOI:10.1002/cite.202000165]
Pogrzeba, T., Illner, M., Schmidt, M., Milojevic, N., Esche, E., Repke, J.-U., Schomäcker, R. Kinetics of Hydroformylation of 1‑Dodecene in Microemulsion Systems Using a Rhodium Sulfoxantphos Catalyst. Industrial & Engineering Chemistry Research, 58, 4443-4453, 2019, [doi.org/10.1021/acs.iecr.8b06157]
Stehl, D.; Milojević, N.; Stock, S.; Schomäcker, R.; von Klitzing, R. Synergistic Effects of Rh-catalyst on Particle Stabilized Pickering Emulsions for Hydroformylation of Long Chain Olefins. Industrial & Engineering Chemistry Research, 58(7), 2524-2536, 2019, [DOI: 10.1021/acs.iecr.8b04619]
Bibouche, B.; Peral, D.; Stehl, D.; Söderholm, V.; Schomäcker, R.; von Klitzing, R.; Vogt, D. Multiphasic aqueous hydroformylation of 1-alkenes with micelle-like polymer particles as phase transfer agents. RSC Adv., 8, 23332-23338, 2018. [doi:10.1039/C8RA04022B]
Illner, M.; Schmidt, M.; Pogrzeba, T.; Urban, C.; Esche, E.; Schomäcker, R.; Repke, J.-U. Palladium-Catalyzed Methoxycarbonylation of 1-Dodecene in a Two-Phase System: The Path toward a Continuous Process. Ind. Eng. Chem. Res., 57(27), 8884-8894, 2018. [doi: 10.1021/acs.iecr.8b01537]
Lemberg, M.; Schomäcker, R.; Sadowski, G. Thermodynamic prediction of the solvent effect on a transesterification reaction. Chem. Eng., 176, 264-269, 2018. [doi.org/10.1016/j.ces.2017.10.033]
Peral, D.; Stehl, D.; Bibouche, B.; Yu, H.; Mardoukh, J.; Schomacker, R.; von Klitzing, R.; Vogt, D. Colloidal polymer particles as catalyst carriers and phase transfer agents in multiphasic hydroformylation reactions. J. Colloid Interface Sci., 513, 647-657. 2018. [doi.org/10.1016/j.jcis.2017.11.071]
Schmidt, M.; Deckwerth, J.; Schomäcker, R.; Schwarze, M. Alkaline Hydrolysis of methyl decanoate in surfactant based systems. J. Org. Chem., 83, 7398-7406, 2018. [DOI: 10.1021/acs.joc.8b00247]
Schmidt, M.; Urban, C.; Schmidt, S.; Schomäcker, R. Palladium-Catalyzed Hydroxycarbonylation of 1-Dodecene in Microemulsion Systems: Does Reaction Performance Care about Phase Behavior? ACS Omega, 3(10), 13355-13364, 2018. [doi.org/10.1021/acsomega.8b01708]
Pogrzeba, T.; Schmidt, M.; Milojevic, N.; Urban, C.; Illner, M.; Repke, J.-U.; Schomäcker, R. Understanding the Role of Nonionic Surfactants during Catalysis in Microemulsion Systems on the Example of Rhodium-Catalyzed Hydroformylation. Ind. Eng. Chem. Res. 56(36), 9934-9941, 2017. [doi:10.1021/acs.iecr.7b02242]
Pogrzeba, T.; Illner, M.; Schmidt, M.; Repke, J.-U. Microemulsion Systems as Switchable Reaction Media for the Catalytic Upgrading of Long-Chain Alkenes. Chem. Ing. Tech., 89(4), 459-463, 2017. [doi: 10.1002/cite.201600140]
Schmidt, M.; Burgert, B.; Szilvási, T.; Schomäcker, R.; Driess, M. Improving the Catalytic Activity in the Rhodium-Mediated Hydroformylation of Styrene by a Bis(N-heterocyclic silylene) Ligand. Eur. J. Inorg. Chem., 9, 1284-1291, 2017. [doi: 10.1002/ejic.201700148]
Schmidt, M.; Pogrzeba, T.; Hohl, L.; Weber, A.; Kielholz, A.; Kraume, M.; Schomäcker, R.: Palladium catalyzed methoxycarbonylation of 1-dodecene in biphasic systems - Optimization of catalyst recycling. Mol. Catal., 439, 1-8, 2017. [doi:org/10.1016/j.mcat.2017.06.014]
Schwarze, M. Micellar-enhanced ultrafiltration (MEUF) – state of the art. Environ. Sci.: Water Res. Technol., 3, 598-624, 2017. [doi: 10.1039/C6EW00324A]
Illner, M.; Müller, D.; Esche, E.; Pogrzeba, T.; Schmidt, M.; Schomäcker, R.; Wozny, G.; Repke, J. U. Hydroformylation in Microemulsions: Proof of Concept in a Miniplant. Ind. Eng. Chem. Res., 55, 8616-8626, 2016. [doi:10.1021/acs.iecr.6b00547]
Pogrzeba, T.; Müller, D.; Illner, M.; Schmidt, M.; Kasaka, Y.; Weber, A.; Wozny, G.; Schomäcker, R.; Schwarze, M. Superior catalyst recycling in surfactant based multiphase systems – Quo vadis catalyst complex? Chem. Eng. Process., 99, 155-166, 2016. [doi:10.1016/j.cep.2015.09.003]
Pogrzeba, T.; Schmidt, M.; Hohl, L.; Weber, A.; Buchner, G.; Schulz, J.; Schwarze, M.; Kraume, M.; Schomäcker, R. Catalytic reactions in aqueous surfactant-free multiphase emulsions. Ind. Eng. Chem. Res., 2016. [doi:10.1021/acs.iecr.6b03384]
Schmidt, M.; Pogrezba, T.; Stehl, D.; Sachse, R.; Schwarze, M.; von Klitzing, R.; Schomäcker, R. Verteilungsgleichgewichte von Liganden in mizellaren Lösungsmittelsystemen. Chem. Ing. Tech., 88(1-2), 119–127, 2016. [doi:10.1002/cite.201500125]
Stehl, D.; Hohl, L.; Schmidt, M.; Hübner, J.; Lehmann, M.; Kraume, M.; Schomäcker, R.; von Klitzing, R. Characteristics of Stable Pickering Emulsions under Process Conditions. Chem. Ing. Tech., 88(11), 1806-1814, 2016. [doi: 10.1002/cite.201600065]
Von Klitzing, R.; Stehl, D.; Pogrzeba, T.; Schomäcker, R.; Minullina, R.; Panchal, A.; Konnova, S.; Fakhrullin, R. Koetz, J.; Möhwald, H.; Lvov, Y. Halloysites Stabilized Emulsions for Hydroformylation of Long Chain Olefins. Adv. Mater. Interfaces, 2016. [doi: 10.1002/admi.201600435]
Müller, D.; Esche, E.; Pogrzeba, T.; Illner, M.; Leube, F.; Schomäcker, R.; Wozny, G. Systematic Phase Separation Analysis of Surfactant-Containing Systems for Multiphase Settler Design. Ind. Eng. Chem. Res., 54(12), 3205-3217, 2015. [doi:10.1021/ie5049059]
Nguyen, L. A. T.; Schwarze, M.; Schomäcker, R. Adsorption of non-ionic surfactant from aqueous solution onto various ultrafiltration membranes. J. Membr. Sci., 493, 120-133, 2015. [doi:10.1016/j.memsci.2015.06.026]
Pogrzeba, T.; Müller, D.; Hamerla, T.; Esche, E.; Paul, N.; Wozny, G.; Schomäcker, R. Rhodium-Catalyzed Hydroformylation of Long-Chain Olefins in Aqueous Multiphase Systems in a Continuously Operated Miniplant. Ind. Eng. Chem. Res., 54(48), 11953-11960, 2015. [doi:10.1021/acs.iecr.5b01596]
Schwarze, M.; Pogrzeba, T.; Seifert, K.; Hamerla, T.; Schomäcker, R. Recent Developments in Hydrogenation and Hydroformylation in Surfactant Systems. Catal. Today, 247, 55-63, 2015. [doi:10.1016/j.cattod.2014.06.026]
Schwarze, M.; Pogrzeba, T.; Volovych, I.; Schomäcker, R. Microemulsion Systems for Catalytic Reactions and Processes. Catal. Sci. Technol., 5, 24-33, 2015. [doi:10.1039/C4CY01121J]
Hamerla, T. Hydroformylierung langkettiger Olefine mit zweizähnigen Rhodium-Komplexen in mizellaren Lösungen und Mikroemulsionen. Technische Universität Berlin, 2014.
[More]
Rost, Anke Rhodium - katalysierte Hydroformylierung von 1-Dodecen mit zweizähnigen Liganden in Mikroemulsionssystemen. Technische Universität Berlin, 2013. [More]