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Title: New strategies for the rhodium-catalysed aqueous-biphasic hydroformylation of medium chain alkenes
Author: Desset, Simon L.
ISNI:       0000 0004 2718 7549
Awarding Body: University of St Andrews
Current Institution: University of St Andrews
Date of Award: 2009
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Aqueous-biphasic organometallic catalysis is, as illustrated by the industrial hydroformylation of propene and butene, one of the most promising ways to overcome the intrinsic problem of catalyst separation in organometallic catalysis. However, for poorly water-soluble substrates, mass transfer limitations bring the reaction rate below any that could be economically viable, greatly limiting the scope of this elegant technology. We have studied three different strategies to overcome this limitation. We developed additives that speed up the reaction whilst retaining fast phase separation and good metal retention. Evidence suggests that those additives affect the reaction by forming emulsions with poor stability under the reaction conditions These emulsions increase the interfacial surface area but break after settling for a short time. We also developed ligands that allow the catalyst to be reversibly transported between an aqueous and an organic phase upon addition and removal of carbon dioxide. This allows the reaction to be carried out under homogeneous conditions, only limited by intrinsic kinetics, and the catalyst to be separated by aqueous extraction triggered by carbon dioxide. The catalyst can be returned to a fresh organic phase by flushing out the carbon dioxide. By applying this methodology for the hydroformylation of medium chain length alkenes, very high reaction rates were obtained and the catalyst could be recycle three times with excellent retention of activity and low metal leaching. This methodology could also be reversed with the reaction being carried out in an aqueous phase in the presence of carbon dioxide and extracting the catalyst into an organic solvent using nitrogen flushing. Finally, we briefly investigated the use of an oscillatory baffled reactor as a mean for mass transfer improvement for aqueous-biphasic hydroformylation. This new type reactor did not improve the performance of the system under the investigated conditions, but may require less energy input for equivalent agitation and mixing.
Supervisor: Cole-Hamilton, David J. Sponsor: EaStCHEM ; Sasol Technology UK Ltd
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Homogeneous catalysis ; Rhodium ; Aqueous-biphasic ; Hydroformylation ; Catalyst recycling ; Carbon dioxide ; Mass transfer ; QD505.D4 ; Catalysts--Recycling ; Rhodium catalysts ; Hydroformylation ; Alkenes ; Ligands