Collaborative Research Center/Transregio 63

"Integrated Chemical Processes in Liquid Multiphase Systems"

>Research>Project Area A>Project A11

A11 Homogeneously catalyzed reductive amination of long-chain aldehydes and hydroaminomethylation of long-chain alkenes with integrated catalyst separation in thermoregulated phase systems

Sub-Coordinators: Dr. rer. nat. Thomas Seidensticker     Prof. Dr. Dieter Vogt

Researchers: M. Sc. Jonas Bianga, M. Sc. Anna Kampwerth

State of the art

In the last research periods Carbonylation reactions of long chain olefins in thermomorphic solvents systems were investigated in project A1. Different influence parameters of the reactions and the solvent systems could be shown to have a distinct influence on yields, selectivities and leaching of the used metal catalysts.

Research goals

In the third funding period, the knowledge about the physical and chemical properties of temperature-controlled liquid/liquid multiphase systems (TMS) for efficient reaction control and recirculation of the catalyst in A1 will be transferred step by step to a new, untested homogeneous catalytic reaction. To broaden the product range, the introduction of nitrogen into petrochemical and renewable basic chemicals will be investigated in A11.

Fig 1:Reaction scheme from olefine to amine.

The key point will be the reductive amination of 1-undecanal with diethylamine. The Hydroaminomethylation (HAM) as a tandem reaction of hydroformylation and reductive amination of 1-decene leads in one reaction step to the same amine as the two-stage combination of these two reactions. Furthermore, the HAM of 10-undecenoic acid methyl ester will be investigated as an example of an oleochemical building block. The comparison of the single-stage tandem reaction (HAM) with the two-stage reaction approach as an important goal takes place in the second half of the funding period, so that a well-founded decision can finally be made for a single-stage or two-stage continuous process control.

Connected projects within Collaborative Research Centre/Transregio 63

A2 (Schomäcker): Catalytic Upgrading of Long Chain Olefins by Hydroformylation and Hydroesterification in Surfactant Modified Multi Phase Systems

A3 (Hamel, Seidel-Morgenstern): Mechanistic and Kinetic Investigations of the Isomerization, Hydroformylation and Hydroesterification of Petrochemicals and Oleochemicals in Multiphase Fluid Systems

A4 (Sadowski, Stein): Reaction Kinetics and Phase Equilibria in Complex Mixtures

B1 (Sundmacher, Zähringer): Optimal Reactor Design and Operation for Liquid Multiphase Systems

B9 (Kienle Sundmacher): Integrated design of thermomorphic multicomponent systems (TMS) and separation processes for the efficient recovery of homogeneous catalysts and solvents

D1 (Engell, Sadowski, Sundmacher):  Fast model-based design of chemical processes with several liquid phases

D3 (Skiborowski, Vogt): Development and testing of integrated reaction and catalyst separation for the homogeneously catalyzed reductive amination and hydroaminomethylation of long chain alkenes in a miniplant

Recent Publications

Huxoll, F.; Kampwerth, A.; Seidensticker, T.; Vogt, D.; Sadowski, G. Predicting Solvent Effects on Homogeneity and Kinetics of the Hydroaminomethylation: A Thermodynamic Approach Using PC-SAFT. Industrial & Engineering Chemistry Research, 61 (5), 2323-2332, 2022. [DOI: 10.1021/acs.iecr.1c03891]


Bianga, J.; Herrmann, N.; Schurm, L.; Gaide, T.;  Dreimann, J.M.; Vogt, D.; Seidensticker, T. Improvement of Productivity for Aqueous Biphasic Hydroformylation of Methyl 10‐Undecenoate – A Detailed Phase Investigation. Eur. J. Lipid Sci.Technol., 122, 1900317, 2020. []

Bianga, J.; Künnemann, K. U.; Goclik, L.; Schurm, L.; Vogt, D.; Seidensticker, T. Tandem Catalytic Amine Synthesis from Alkenes in Continuous Flow Enabled by Integrated Catalyst Recycling. ACS Catalysis.,  10, 6463–6472, 2020. []

Bianga, J; Kopplin, N.; Hülsmann, J.; Vogt, D.; Seidensticker, T. Rhodium‐Catalysed Reductive Amination for the Synthesis of Tertiary Amines. Adv. Synth. Catal., 362, 4415-4424, 2020. []

Herrmann, N.; Bianga, J.; Palten, M.; Riemer, T.;  Vogt, D.; Dreimann, J.M.;  Seidensticker, T. Improving Aqueous Biphasic Hydroformylation of Unsaturated Oleochemicals Using a Jet‐Loop‐Reactor. Eur. J. Lipid Sci. Technol., 122, 1900166, 2020. []

Herrmann, N.; Köhnke, K.; Seidensticker, T. Selective Product Crystallization for Concurrent Product Separation and Catalyst Recycling in the Isomerizing Methoxycarbonylation of Methyl Oleate. ACS Sustainable Chemistry & Engineering, 8 (29), 10633-10638,2020. [DOI: 10.1021/acssuschemeng.0c03432]

Künnemann, K. U.; Bianga, J.; Scheel, R.; Seidensticker, T.; Dreimann, J.M.; Vogt, D.: Process Development for the Rhodium-Catalyzed Reductive Amination in a Thermomorphic Multiphase System. Organic Process Research & Development. 24 (1), 41-49, 2020. []

Terhorst, M.; Heider, C.; Vorholt, A.; Vogt, D.; Seidensticker, T. Productivity Leap in the Homogeneous Ruthenium-Catalyzed Alcohol Amination through Catalyst Recycling Avoiding Volatile Organic Solvents. ACS Sustainable Chem. Eng., 8, 9962−9967, 2020. []

Terhorst, M.; Kampwerth, A.; Marschand, A.; Vogt, D.; Vorholt, A.; Seidensticker, T. Facile Catalyst Recycling by Thermomorphic Behaviour Avoiding Organic Solvents – A Reactive Ionic Liquid in the Homogeneously Pd-Catalysed Telomerisation of the Renewable b-Myrcene. Catal. Sci. Technol., 10, 1827, 2020, [DOI:10.1039/C9CY02569C]

Terhorst, M.; Plass, C.; Hinzmann, A.; Guntermann, A.; Jolmes, T.; Rösler, J.; Panke, D.; Gröger, H.; Vogt, D.; Vorholt, A. J.; Seidensticker, T. One-pot synthesis of aldoximes from alkenes via Rh-catalysed hydroformylation in an aqueous solvent system.Green Chem. 22, 7974-7982, 2020. DOI:[]


Bianga, J.; Künnemann K.U.; Gaide, T.; Vorholt, A.J.; Seidensticker, T.; Dreimann, J.M.; Vogt, D.Thermomorphic Multiphase Systems: Switchable Solvent Mixtures for the Recovery of Homogeneous Catalysts in Batch and Flow Processes. Chem. Eur. J., 25, 11586-11608, 2019. []


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]

Hernandez, R.; Dreimann, J.; Vorholt, A.; Behr, A.; Engell, S. Iterative real-time optimization scheme for optimal operation of chemical processes under uncertainty: proof of concept in a miniplan. Ind. Eng. Chem. Res., 57(26), 8750-8770, 2018. [DOI: 10.1021/acs.iecr.8b00615]

Hernandez, R.; Dreimann, J.; Engell, S. Reliable iterative RTO of a continuously operated hydroformylation process. IFAC-papersOnLine, 51(18), 61-66, 2018. []


Furst, M. R. L., Korkmaz, V., Gaide, T., Seidensticker, T., Behr, A., Vorholt, A. J. Tandem reductive hydroformylation of castor oil derived substrates and catalyst recycling by selective product crystallization. ChemCatChem. 9, 4319–4323, 2017. [doi: 10.1002/cctc.201700965]

Dreimann, J. M.; Hoffmann, F.; Skiborowski, M.; Behr, A.; Vorholt, A. J. Merging Thermomorphic Solvent Systems and Organic Solvent Nanofiltration for Hybrid Catalyst Recovery in a Hydroformylation Process. Ind. Eng. Chem. Res., 56(5), 1354-1359, 2017. [doi: 10.1021/acs.iecr.6b04249]

Faßbach, T. A.; Gaide, T.; Terhorst, M.; Behr, A.; Vorholt, A. J. Renewable Surfactants through the Hydroaminomethylation of Terpenes. ChemChatChem, 9(8), 1359-1362, 2017. [doi: 10.1002/cctc.201700097]

Gaide, T.; Bianga, J.; Schlipköter, K.; Behr, A.; Vorholt, A. J. Linear Selective Isomerization/Hydroformylation of Unsaturated Fatty Acid Methyl Esters: A Bimetallic Approach. ACS Catal., 7, 4163-4171, 2017. [doi: 10.1021/acscatal.7b00249]

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:]

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:]

Dreimann, J. M.; Lutze, P.; Zagajewski, M.; Behr, A.; Górak, A.; Vorholt, A. J. Highly integrated reactor–separator systems for the recycling of homogeneous catalysts. Chem. Eng. Process., 99, 124-131, 2016. [doi:10.1016/j.cep.2015.07.019]

Gaide, T.; Behr, A.; Arns, A.; Benski, F.; Vorholt, A. J. Hydroesterification of methyl 10-undecenoate in thermomorphic multicomponent solvent systems - Process development for the synthesis of sustainable polymer precursors. Chem. Eng. Process., 99, 197-204, 2016. [doi:10.1016/j.cep.2015.07.009]

Gaide, T.; Behr, A.; Terhorst, M.; Arns, A.; Benski, F.; Vorholt, A. J. Katalysatorvergleich bei der Hydroesterifizierung von 10-Undecensäure-methylester in thermomorphen Lösungsmittelsystemen. Chem. Ing. Tech., 88(1-2), 158–167, 2016. [doi:10.1002/cite.201500096]

Gaide, T.; Dreimann, J.; Behr, A.; Vorholt, A. J. Overcoming Phase-Transfer Limitations in the Conversion of Lipophilic Oleo Compounds in Aqueous Media-A Thermomorphic Approach. Angew. Chem. Int. Ed., 55(8), 2924-2928, 2016. [doi:10.1002/anie.201510738]

Gaide, T.; Dreimann, J.; Behr, A.; Vorholt, A. J. Überwindung von Phasentransportlimitierungen in der Umsetzung lipophiler Oleoverbindungen in wässrigen Medien – ein temperaturgesteuerter Ansatz. Angew. Chem., 128(8), 2977-2981, 2016. [doi:10.1002/ange.201510738]

McBride, K.; Gaide, T.; Vorholt, A. J.; Behr, A.; Sundmacher, K. Thermomorphic solvent selection for homogeneous catalyst recovery based on COSMO-RS. Chem. Eng. Process., 99, 97-106, 2016. [doi:10.1016/j.cep.2015.07.004]

Seidensticker, T.; Vorholt, A. J.; Behr, A. The mission of addition and fission – catalytic functionalization of oleochemicals. Eur. J. Lipid Sci. Technol., 118(1), 3–25, 2016. [doi:10.1002/ejlt.201500190]


Gaide, T. Sustainable Process Development for Olefin Carbonylation Reactions, TU Dortmund University, 2017


Brunsch, Y. Temperaturgesteuertes Katalysatorrecycling für die homogen katalysierte Hydroformylierung langkettiger Alkene. TU Dortmund University, 2013.



Last updated:28-03-2022