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Kinetic evaluation of the hydroformylation of the post-metathesis product 7-tetradecene using a heterobimetallic rhodium-ferrocenyl Schiff base derived precatalyst

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Abstract

Reaction engineering kinetics for the hydroformylation of the post-metathesis product 7-tetradecene using a heterobimetallic rhodium-ferrocenyl Schiff base derived precatalyst was investigated with variation of reaction temperature (85–105 °C), precatalyst loading (0.25–0.52 mM), carbon monoxide partial pressures (20–40 bar) and hydrogen partial pressures (20–40 bar). The experimental product-time distributions for the parallel hydroformylation and isomerization reaction system are well described by four interdependent pseudo first-order differential mole balance equations. The effects of temperature in the Arrhenius equation, precatalyst concentration, carbon monoxide and hydrogen partial pressures have been incorporated into a phenomenological mechanism-based rate equation. The rate of hydroformylation is first order in alkene, carbon monoxide and hydrogen, with fractional dependence in precatalyst concentration. The activation energy for the hydroformylation reaction was calculated to be 62 kJ mol−1, which is comparable to that determined for the commercialized phosphorus-modified catalyst systems.

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Abbreviations

C14:

7-Tetradecene

2HN:

2-Hexylnonanal

ISOALK:

Isoalkenes

ISOALD:

Isoaldehydes

Rh:

Rhodium

SSE:

Sum of square errors

C:

Concentration (mol L−1)

EA :

Activation energy (kJ mol−1)

K:

Observed reaction rate constant (h−1)

k0 :

Pre-exponential factor (Lx mol−x bar2 h−1/Lx mol−x h−1)

K:

Equilibrium constant (bar−1)

P:

Pressure (bar)

R:

Universal gas constant (J mol−1 K−1)

T:

Temperature (°C/K)

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Acknowledgements

The support of the DST-NRF Centre of Excellence (CoE) in Catalysis towards this research is hereby acknowledged. Opinions expressed and conclusions arrived at, are those of the author and are not necessarily to be attributed to the CoE. The authors also wish to thank the University of Stellenbosch and University of Cape Town for additional financial support towards this research and Shepherd Siangwata for skilled guidance and assistance in preparing the precatalyst used for the study.

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Authors and Affiliations

  1. Department of Process Engineering, University of Stellenbosch, Private Bag X1, Matieland, 7602, South Africa

    Nicholas C. C. Breckwoldt & Neill J. Goosen

  2. Department of Chemistry, University of Cape Town, Rondebosch, South Africa

    Gregory S. Smith

  3. School of Chemical and Minerals Engineering, Research Focus Area for Chemical Resource Beneficiation, Hoffmann Street, Potchefstroom, 2522, South Africa

    Percy Van der Gryp

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  1. Nicholas C. C. Breckwoldt
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  2. Gregory S. Smith
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  3. Percy Van der Gryp
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  4. Neill J. Goosen
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Correspondence to Nicholas C. C. Breckwoldt.

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Breckwoldt, N.C.C., Smith, G.S., Van der Gryp, P. et al. Kinetic evaluation of the hydroformylation of the post-metathesis product 7-tetradecene using a heterobimetallic rhodium-ferrocenyl Schiff base derived precatalyst. Reac Kinet Mech Cat 128, 333–347 (2019). https://doi.org/10.1007/s11144-019-01628-3

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