Collaborative Research Center/Transregio 63

"Integrated Chemical Processes in Liquid Multiphase Systems"

>Research>Completed Projects>Project A1 E

A1 Transition Metal Catalysed Hydroformylation and Hydroesterification of Petro- and Oleochemical Starting Materials with Temperature Controlled Catalyst Separation in Gas/liquid/liquid Systems (completed)

Sub-Coordinators: Dr. Andreas Vorholt, Prof. Dr. Arno Behr
Researcher: M.Sc. Tom Gaide

State of the art

The hydroformlyation of dodecene in thermomorphic solvents systems was investigated in the first research period. A highly selective catalyst system consisting of Rh(acac)(CO)2 and Biphephos yields >80% aldehydes and linearity’s of 99%.

 

Hydroformylation of 1-dodecene

Different influence parameters of the hydroformylation and the solvent system could be shown to have a distinct influence on yield, selectivity and leaching of the metal catalyst.

Research goals

The project A1 bases on the results of the former period and will transfer this knowledge to other substrates and to other reaction with another catalyst system. Starting from dodecene internal olefins will be tested in the isomerizing hydroformylation. Oleo compounds like undecylenic methyl ester and oleic methyl ester will be employed to investigate the influences of further functional groups in thermomorphic solvent systems. The hydroesterification is an atom economic reaction yielding ester moieties in palladium catalyst systems. This reaction/substrate set puts the project in a position to investigate influences of different reactions types like isomerization, hydroesterification and hydroformylation, different functional moieties and catalysts systems on thermomorphic solvent systems.

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Recent Publications

Dreimann, J. M.; Kohls, E.; Warmeling,  H. F. W.; Stein, M.; Guo,  L. F.; Garland,  M.;  Dinh, T. N.; Vorholt, A. J. In Situ Infrared Spectroscopy as a Tool for Monitoring Molecular Catalyst for Hydroformylation in Continuous Processes. ACS Catal.9, 4308–4319, 2019. DOI: 10.1021/acscatal.8b05066


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.; Fassbach, T. A.; Fuchs, S.; Fuerst, M. R. L.; Geide, T.; Kuhlmann, R.; Ostrowski, K. A.; Stadler, A.; Sidensticker, T.; Vogelsang, D.; Warmeling, H. V. F.; Vorholt, A. J. From Lab Curiosity to a Continuously Operated Process: Development of Thermomorphic Solvent Systems. Chem. Eng. Tech., 89, 252-262, 2017. [doi:10.1002/cite.201600119]

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]

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. ChemPubSoc, 8, 4319-4323, 2017. [https://doi.org/10.1002/cctc.201700965]

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: http://doi.org/10.1016/j.apcata.2016.12.011]

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: http://doi.org/10.1016/j.cej.2016.12.070]

Vogelsang, D.; Dreimann, M., J.; Wenzel, D.; Peeva, L.; Burgal, J.; Livingston,G.A; Behr,A; Vorholt, A. J. Continuously Operated Hydroamination -Toward Highl Catalytic Performance via Nano filtration in a membrane Reactor. Ind. Eng. Chem. Res., 56, 13634-13641, 2017. [doi: 10.1021/acs.iecr.7b03770]


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]

Dissertations

Brunsch, Y. Temperaturgesteuertes Katalysatorrecycling für die homogen katalysierte Hydroformylierung langkettiger Alkene. Technische Universität Dortmund, 2013.
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Last updated:30-04-2019