Styrene, from heterogeneous oxidation

Dehydrogenation, Ammoxidation, and Other Heterogeneous Catalysts. Cerium has minor uses in other commercial catalysts (41) where the element s role is probably related to Ce(III)/Ce(IV) chemistry. Styrene is made from ethylbenzene by an alkah-promoted iron oxide-based catalyst. The addition of a few percent of cerium oxide improves this catalyst s activity for styrene formation presumably because of a beneficial interaction between the Fe(II)/Fe(III) and Ce(III)/Ce(IV) redox couples. The ammoxidation of propjiene to produce acrylonitrile is carried out over catalyticaHy active complex molybdates. Cerium, a component of several patented compositions (42), functions as an oxygen and electron transfer through its redox couple. 

To overcome the problems encountered in the homogeneous Wacker oxidation of higher alkenes several attempts have been undertaken to develop a gas-phase version of the process. The first heterogeneous catalysts were prepared by the deposition of palladium chloride and copper chloride on support materials, such as zeolite Y [2,3] or active carbon [4]. However, these catalysts all suffered from rapid deactivation. Other authors applied other redox components such as vanadium pentoxide [5,6] or p-benzoquinone [7]. The best results have been achieved with catalysts based on palladium salts deposited on a monolayer of vanadium oxide spread out over a high surface area support material, such as y-alumina [8]. Van der Heide showed that with catalysts consisting of H2PdCU deposited on a monolayer vanadium oxide supported on y-alumina, ethene as well as 1-butene and styrene... 

Heterogeneous systems have also been developed for the cleavage of olefins with hydrogen peroxide.174,175 Titanium-containing zeolites can be used to cleave olefins.176 Adam and co-workers have recently shown that acetophenone, an oxidation product from the Ti-zeolite catalysed oxidation of a-methyl-styrene, derives from 2-hydroxyperoxy-2-phenylpropan-l-ol as an intermediate (which they detected and isolated) (Figure 3.34).177... 

When using conventional homogeneous Lewis or Br0nsted acidic catalysts only liquid-phase reactions are applicable. With heterogeneous catalysts gas-phase reactions, which are readily performed continuously, can also be realized. The product is readily separated from the catalyst and higher efficiency is usually achieved (space-time yield). The rearrangement of styrene oxides in the gas phase described later in this section [8,15,16] is an example of the improvement of yields by changing the reactor concept from liquid- to gas-phase. 

The isomerization of styrene oxide to phenylacetaldehyde yields 100% using modified ZSM-5 zeolites, thereby the highest target achieved by catalysis has been fulfilled. A new process as well has been found for the heterogeneously-catalysed production of campholenic aldehyde from a-pinene oxide. By using low reaction temperatures of 0 °C and below in combination with HCl-treated H-US-Y zeolites, up to 85% yield is achieved. This process is competitive with the homogeneous ZnBr2 system. 

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