Dehydrogenation with other oxidants

The pulse experiments using orthovanadates and V/y-AFCb catalysts showed that high selectivity for dehydrogenation of butane could be obtained by reaction of butane with lattice oxygen. This has also been demonstrated with other oxides, including Mg-Mo oxide (43, 44). 

Styrene. Commercial manufacture of this commodity monomer depends on ethylbenzene, which is converted by several means to a low purity styrene, subsequendy distilled to the pure form. A small percentage of styrene is made from the oxidative process, whereby ethylbenzene is oxidized to a hydroperoxide or alcohol and then dehydrated to styrene. A popular commercial route has been the alkylation of benzene to ethylbenzene, with ethylene, after which the cmde ethylbenzene is distilled to give high purity ethylbenzene. The ethylbenzene is direcdy dehydrogenated to styrene monomer in the vapor phase with steam and appropriate catalysts. Most styrene is manufactured by variations of this process. A variety of catalyst systems are used, based on ferric oxide with other components, including potassium salts, which improve the catalytic activity (10). 

Cycloaddition reactions of nitrile oxides continue to be the source of new isoxazoles and dihydroisoxazoles. The oxidation of a-hydroxyimino acids 1 by ammonium hexanitratocerium(IV) has provided a new method of generation of benzonitrile oxide and other nitrile oxides on the other hand the oxime 2 is simply dehydrogenated by this oxidant to produce benzoylnitrile oxide <99BSJ2277>. Manganese dioxide has also been used to oxidise aldoximes to nitrile oxides the reaction is most efficient with methyl (hydroxyimino)acetate <99TL5605>. ... 

The low cost of light alkanes and the fact that they are generally environmentally acceptable because of their low chemical reactivity have provided incentives to use them as feedstock for chemical production. A notable example of the successful use of alkane is the production of maleic anhydride by the selective oxidation of butane instead of benzene (7). However, except for this example, no other successful processes have been reported in recent years. A potential area for alkane utilization is the conversion to unsaturated hydrocarbons. Since the current chemical industry depends heavily on the use of unsaturated hydrocarbons as starting material, if alkanes can be dehydrogenated with high yields, they could become alternate feedstock. 

In order to assess the synthetic potential of enzymatic oxidations for organosilicon chemistry, the (hydroxyalkyl)silanes 95, 97 and 99 have been studied for their oxidation (dehydrogenation) with horse liver alcohol dehydrogenase (HLADH E.C. l.l.l.l)79. For this purpose, these compounds were incubated with HLADH in a TRIS-HC1 buffer/THF system in the presence of NAD+. As monitored spectrophotometrically (increase of absorbance of the NADH formed), the (2-hydroxyethyl)silane 97 and the (3-hydroxypropyl)silane 99 were better substrates for HLADH than ethanol, whereas the related (hydroxymethyl)silane 95 was not a substrate under the experimental conditions used. Interestingly, the corresponding carbon analogue 101 was found to be accepted by HLADH. On the other hand, the (2-hydroxyethyl)silane 97 was found to be a better... 

Lanthanum oxide is well-known as an active isomerization (406) and hydrogenation catalyst (407), and it has attracted much attention recently (along with other basic oxides, such as MgO and CaO) as a catalyst for the oxidative dehydrogenation and coupling of methane to C2 hydrocarbons (408-410). Its activity for selective NO reduction of CH4 in excess oxygen has also been demonstrated (411, 412). 

Smits, Seshan and Ross have studied the selective oxidative dehydrogenation of propane to propylene over Nb20s and Nb2C>5 supported on alumina.32 Vanadia supported on MgO has typically been used in these reactions, although reduced surface vanadyl ions can give rise to decreasing selectivity to propylene. Niobia on the other hand, is much more difficult to reduce than vanadyl but there have been few studies with this oxide in such reactions. 

Lanthanides as modifiers to other oxides in aluminas In zirconias In iron oxide Lanthanide oxides in mixed oxides With aluminas With iron oxides With other transition metal oxides To maintain surface area To increase oxidation rates To increase methanation rates For conduction in electrocatalysis For ammonia synthesis promotion To provide sulfur oxides (SO.,) control For dehydrogenation in carbon monoxide reactions For oxidation... 

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