Collaborative Research Center/Transregio 63

"Integrated Chemical Processes in Liquid Multiphase Systems"

>Research>Project Area D>Project D3

D3 Development and testing of integrated reaction and catalyst separation for the homogenously catalyzed reductive amination and hydroaminomethylation of long chain alkenes in a miniplant

Sub-Coordinators: Prof. Dr.-Ing. Mirko Skiborowski     Prof. Dr. Dieter Vogt

Researchers: M. Sc. Stefan Schlüter, M. Sc. Kai Künnemann,  M. Sc. Tim Riemer

State of the art

In the first funding period a continuously operated miniplant for the hydroformylation of 1-dodecene was designed, built and tested. To realize an efficient catalyst recycling, a solvent-system with a highly temperature dependent miscibility gap is used. The miniplant contains a continuously stirred tank reactor (CSTR) where the homogeneous catalyzed reaction takes place and a liquid/liquid phase separator in which the product-phase and the catalyst-phase are separated from each other. After phase-separation the catalyst is fed back into the reactor and the product is taken out of the process. It was possible to realize a steady state operation of this miniplant for 200 h with a yield of 63 % of the main product.      
In the second funding period a sophisticated catalyst recycling was tested. Therefore the influence of an organic solvent nanofiltration membrane on the catalyst behaviour was investigated, to expand the miniplant with a nanofiltration-unit and increase the effectiveness of the process. Furthermore the non-polar solvent has to be separated from the product with a distillation unit and reused in the reaction-step. Also an optimal designed reactor (project B1) was successful tested in the miniplant and compared to the CSTR, in order increase the yield. Further scientific investigations on hydroformylation and hydroesterification reactions in the miniplant lead to the processing of renewable materials.

Research goals

The aim of Project Area D3 is to further develop the methods developed in the two previous funding periods in B5 E for the rapid and efficient process development of integrated systems of reaction and separation. The D3 project aims to implement and test the new continuous processes for reductive amination and integrated hydroaminomethylation (HAM) on a miniplant scale. To this end, new concepts for recycling the catalyst and separating the by-product water must be developed. This is to be achieved by membrane separations in conjunction with TMS. Together with D1, the tandem reaction process is to be compared with a conventional process design.As a new reaction, the reductive amination of 1-undecanal is to be processed first. This builds on the work on hydroformylation in the first and second funding periods. Later, the combination of hydroformylation and reductive amination, the hydroaminomethylation (HAM) of 1-decene, will also be realized in a tandem catalysis. The starting point for the realization of reductive amination and HAM on a miniplant scale is the existing combination of reactor, phase separation and organophilic nanofiltration, ONF.

  • Fluid separation
  • Process intensification
  • Homogeneous catalysis
  • Thermomorphic solvent systems
  • Miniplants
Connected projects within Collaborative Research Centre/Transregio 63

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

A11 (Seidensticker, Vogt): Homogeneously catalyzed reductive amination of long-chain aldehydes and hydroaminomethylation of long-chain alkenes with integrated catalyst separation in thermo-regulated solvent systems

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

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

D4 (Engell, Esche): Control and optimal operation of the reductive amination and of the hydroaminomethylation in the demonstration plants

Recent Publications

Huxoll, F.; Schlüter, S.; Budde, R.; Skiborowski, M.; Petzold, M.; Böhm, L.; Kraume, M.; Sadowski, G. Phase Equilibria for the Hydroaminomethylation of 1-Decene. Journal of Chemical & Engineering Data, 66 (12), 4484-4495, 2021. [DOI: 10.1021/acs.jced.1c00561]

Künnemann, K. U.; Weber, D.; Becquet, C.; Tilloy, S.; Monflier, E.; Seidensticker, T.; Vogt, D. Aqueous biphasic hydroaminomethylation enabled by methylated cyclodextrins: sensitivity analysis for transfer into a continuous process. ACS sustainable chemistry & engineering, 9, 273–283, 2021. [DOI:10.1021/acssuschemeng.0c07125]

Schlüter, S.; Künnemann, K. U.; Freis, M.; Roth, T.; Vogt, D.; Dreimann, J. M.; Skiborowski, M. Continuous co-product separation by organic solvent nanofiltration for the hydroaminomethylation in a thermomorphic multiphase system, Chemical Engineering Journal, 409, 128219, 2021. [DOI: 10.1016/j.cej.2020.128219]


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. []

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. Org. Process Res. Dev. 24, 1, 41-49, 2020. [DOI: 10.1021/acs.oprd.9b00409]

Künnemann, K. U.; Gumbiowski, N.; Müller, P.; Jirmann, Y.; Dreimann, J. M.; Vogt, D. Chemometrics in the Homogeneously Catalyzed Reductive Amination: Combining In Situ Fourier-Transform Infrared Spectroscopy and Band-Target Entropy Minimization. Industrial & Engineering Chemistry Research 59 (19), 9055-9065, 2020. []

Künnemann, K. U.; Schurm, L.; Lange, D.; Seidensticker, T.;  Tilloy, S.; Monflier, E.; Vogt, D.; Dreimann, J. M. Continuous hydroformylation of 1-decene in an aqueous biphasic system enabled by methylated cyclodextrins. Green Chem. 22, 3809, 2020. []

Scharzec, B.; Holtkötter, J.; Bianga, J.; Dreimann, J.M.; Vogt, D.; Skiborowski, M. Conceptual study of co-product separation from catalyst-rich recycle streams in thermomorphic multiphase systems by OSN. Chemical Engineering Research and Design. 157, 65-76, 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. []


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. []

Jokiel, M.; Rätze, K. H. G.; Kaiser, N. M.; Künnemann, K.; Hollenbeck, J. P.; Dreimann, Dreimann J.M., Vogt D. and Sundmacher K.  Miniplant scale evaluation of a semibatch-continuous tandem reactor system for the hydroformylation of long-chain olefins. Ind. Eng. Chem. Res., 58,7, 2471-2480 2019. [DOI: 10.1021/acs.iecr.8b03874]


Bertleff, B.; Göbel, R.;  Claußnitzer, J.; Korth, W.; Skiborowski, M.; Wasserscheid,; Jess, A.; Albert J. Investigations on Catalyst Stability and Product Isolation in the Extractive Oxidative Desulfurization of Fuels Using Polyoxometalates and Molecular Oxygen. ChemCatChem., 10, 4602-4609, 2018. [DOI: 10.1002/cctc.201801081]


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]


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]

Dreimann, J. M.; Skiborowski, M.; Behr, A.; Vorholt, A. J. Recycling Homogeneous Catalysts Simply by Organic Solvent Nanofiltration: New Ways to Efficient Catalysis.ChemCatChem, 8, 3330-3333, 2016. [doi/10.1002/cctc.201601018]

Dreimann, J. M.; Vorholt, A.; Skiborowski, M.; Behr, A. Removal of Homogeneous Precious Metal Catalysts via Organic Solvent Nanofiltration. Chem. Eng. Trans., 47, 343-348, 2016. [doi:0.3303/CET1647058]

Dreimann, J. M.; Warmeling, H.; Weimann, J. N.; Künnemann, K.; Behr, A.; Vorholt, A. J. Increasing selectivity of the hydroformylation in a miniplant: Catalyst, solvent, and olefin recycle in two loops. AIChE J., 62(12), 4377-4383, 2016. [doi:10.1002/aic.15345]

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]

Zagajewski, M.; Dreimann, J.; Thönes, M.; Behr, A. Rhodium catalyzed hydroformylation of 1-dodecene using an advanced solvent system: Towards highly efficient catalyst recycling. Chem. Eng. Process., 99, 115-123, 2016. [doi:10.1016/j.cep.2015.06.014]


Dreimann, J.M. Process Intesification in Homogenous Catalysis – Catalyst Recovery via Thermomorphic Solvent Systems and Organic Solvent Nanofiltration. Technische Universität Dortmund, 2017.


Haßelberg, J. Process development for the synthesis of saturated branched fatty derivatives: Homogeneous and heterogeneous catalysis in miniplant scale. Technische Universität Dortmund, 2016. 


Zagajewski, M. Planung, Bau und Betrieb einer Miniplant zur kontinuierlichen Hydroformylierung von 1-Dodecen in thermomorphen Mehrkomponenten-Lösungsmittelsystemen. Technische Universität Dortmund, 2015. 


Last updated:28-03-2022