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Eingeladener Vortrag
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Although catalytic reductions, cross-couplings, metathesis, and oxidation of C=C double bonds are well established, the corresponding catalytic hydroxylations of C–H bonds in alkanes, arenes, or benzylic (allylic) positions, particularly with O2, the cheapest, 'greenest', and most abundant oxidant, are severely lacking. Certainly, some promising examples in homogenous and heterogenous catalysis exist, as well as enzymes that can perform catalytic aerobic oxidations on various substrates, but these have never achieved an industrial-scale, owing to a low space-time-yield and poor stability. This review illustrates recent advances in aerobic oxidation catalysis by discussing selected examples, and aims to stimulate further exciting work in this area. Theoretical work on catalyst precursors, resting states, and elementary steps, as well as model reactions complemented by spectroscopic studies provide detailed insight into the molecular mechanisms of oxidation catalyses and pave the way for preparative applications. However, O2 also poses a safety hazard, especially when used for large scale reactions, therefore sophisticated methodologies have been developed to minimize these risks and to allow convenient transfer onto industrial scale.
A method for the determination of safety properties for micro reactors and micro structured components is presented.
Micro structured reactors are not inherently safe but the range of safe operating conditions of micro reactors are
extended since the explosion region is reduced. The λ/3 rule was demonstrated to be applicable to micro scale
tubes for stoichiometric mixtures of ethane–oxygen and ethane–nitrous oxide. Furthermore first results from an investigation concerning detonation propagation through a micro reactor of non-ideal geometry are shown. Initial
pressure investigated is ranging from low pressure up to 100 kPa.
The present contribution reports on specific aspects of safety engineering in heterogeneously catalysed oxidation reactions. Results for ethene-oxygen-mixtures in a continuous-flow micro reactor are reported related to the safety issues of the ethylene oxide process. Initial pressure is ranging from below 1 bar up to 10 bar at initial temperatures ranging from room temperature up to 673 K. Micro structured reactors offer an extended range of operating conditions. The key issue to be discussed in the present contribution is how to safely operate a micro reactor at conditions in conventional devices to be characterised as inside the explosion region. Within certain limits suppression of explosion inside a micro reactor can be achieved.
This holds true for chain reactions as well as runaway reactions. Nevertheless it is not possible to safely operate micro structured reactors at any condition. Therefore, explosion propagation through a Micro structured reactor and initiation of gas phase explosions by hot spots inside the reactor were investigated.
The investigation methods applied are subject to actual standardization.
Es wird eine Methode zur sicherheitstechnischen Untersuchung von Mikroreaktoren und mikrostrukturierten Komponenten, die im Explosionsbereich betrieben werden sollen, vorgestellt. Mikrostrukturierte Reaktoren sind nicht inhärent sicher, wenngleich der Bereich der sicheren Betriebsbedingungen gegenüber konventionellen Reaktoren erweitert ist. Der Explosionsbereich kann durch die Mikrostrukturen eingeengt werden. Am Beispiel von Ethylen/Sauerstoff-Gemischen und Ethylen/N2O-Gemischen wird hinsichtlich der Ausbreitung von Detonationen durch Kapillarrohre gezeigt, dass die sogenannte λ/3-Regel angewandt werden kann. Darüber hinaus werden erste Ergebnisse der Untersuchung der Ausbreitung von Explosionen durch einen Mikroreaktor mit rechteckigem Strömungskanal vorgestellt.
The interaction of TS-1 with gaseous hydrogen peroxide at temperatures above 373 K has been investigated by in situ EPR measurements. Treatment of TS-1 with hydrogen peroxide in the gas phase leads to a strong EPR signal, assigned to the Ti(IV)-superoxide species. In contrast to investigations with liquid hydrogen peroxide,
here only one Ti(IV)-superoxide species could be detected in the EPR spectrum. The time constant of the reaction of the Ti(IV)-superoxide species detected by in situ EPR measurements was much larger than that observed for the rate of consumption of propane or propene via gas chromatographic analysis. Thus, we conclude that the Superoxide species may take part in the oxidation reaction (via side reactions or the formation of unselective products), but is probably not the main responsible species in the oxidation of propane or propene.