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VALERY FUNDED PROJECTS hydrogenation activity, so that a technical application is currently irrelevant. Similarly, photocatalytic dehydrogenation of alkanes to olefins is involved. The dehydrogenation of alkanes is carried out on a large scale by means of heterogeneous catalysis in the gas phase at high temperatures. Due to the high energy requirement and the associated costs, catalytic dehydration is used only occasionally. An alternative energy-efficient process such as pho- tocatalytic dehydration is therefore desirable. As a few publications show, the photocatalytic conversion of alkanes without acceptor is possible in principle. However, the sales are very low, so that the reaction is still far from a large-scale application. 1.5.2 Project description The aim of the „Valery“ project was to develop a new process for the pro- duction of valeraldehyde. Specifically, the hydroformylation of butene and carbon monoxide to valeraldehyde should be replaced by an alternative process by substituting the toxic carbon monoxide with carbon dioxide and by providing butene to butane by energy-efficient dehydration. First of all, n-butane should be photocatalytically dehydrated. The resulting 1-butene should then be converted to valeraldehyde in a hydroformylation with CO2, whereby one of the two equivalents of hydrogen required for hydroformyl- ation with CO2 is provided by photocatalytic dehydrogenation. Within the scope of the project, technically relevant homogeneous catalysts for the photocatalytic dehydrogenation or direct carbonylation of alkanes as well as for the hydroformylation with CO2 were to be developed. The catalyst devel- opment should be supported by computer-chemical calculations in order to enable a targeted catalyst design. In addition, the catalyst systems should be immobilised to ensure a simplified separation of product and catalyst. In ad- dition to the development of the catalysts, kinetic investigations should be carried out at the same time, on the basis of which a corresponding reaction model and the design of the overall process should be carried out. A final life cycle assessment, taking into account the entire process chain, should provide information on the ecological sustainability of the new process, so that a holistic picture of the feasibility of photocatalytic dehydration and subsequent hydroformylation with CO2 to form aldehydes can be obtained. 1.5.3 Results Existing catalyst systems have been optimized for photocatalytic dehydro- genation as well as for hydroformylation with CO2 and new catalyst systems have been developed. In the case of photocatalytic dehydrogenation, the op- timized reaction conditions with the catalyst system Rh (PMe3)2 (CO)Cl-Com- 51PDF Image | Chemical Processes and Use of CO2
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