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Hydroformylation of 1‑Dodecene in the Thermomorphic Solvent System Dimethylformamide/Decane. Phase Behavior–Reaction Performance–Catalyst Recycling
journal contribution
posted on 2012-08-08, 00:00 authored by Elisabeth Schäfer, Yvonne Brunsch, Gabriele Sadowski, Arno BehrAn economically meaningful hydroformylation of long-chain
olefins
requires an efficient combination of both a high-yield reaction step
and efficient catalyst recycling. The application of thermomorphic
multicomponent solvent (TMS) systems allows for optimal reaction as
well as catalyst-recycling conditions. In this work, the TMS concept
was applied to the homogeneously rhodium-catalyzed hydroformylation
of 1-dodecene in the TMS system dimethylformamide (DMF)/decane using
Rh(acac)(CO)2/Biphephos as the catalyst system. Thermodynamic
investigations focused on the influence of the olefin (hydroformulation
educt) and the aldehyde (hydroformylation product) on the phase behavior
of the TMS system. Temperature dependent liquid–liquid equilibrium
(LLE) data were measured for the binary systems DMF/decane and DMF/1-dodecene
and for the ternary systems DMF/decane/1-dodecene and DMF/decane/dodecanal.
Additionally, the corresponding LLE data were modeled applying the
Perturbed Chain Polar Statistical Associating Fluid Theory (PCP-SAFT)
using a heterosegmented approach for modeling the long-chain aldehyde.
On the basis of the LLE data, adequate working points for hydroformylation
experiments in the TMS system were selected. In these experiments,
aldehyde yields of up to 87% with an n/iso ratio of up to 99:1 were
achieved. Moreover, the TMS system was successfully applied to catalyst
recycling in eight recycling runs with a catalyst leaching of 7 ppm
rhodium at lowest.