Vanadium catalysts alkane oxidation

The success of butane selective oxidation inevitably led to testing of vanadium phosphate catalysts for oxidation of other alkanes and alkenes. Pentane has been similarly transformed to phthalic anhydride in addition to MA (91-97). Phthalic anhydride is an important intermediate in the manufacture of plastics. Flowever, the investigation of vanadium... 

Supported vanadium catalysts, whereby vanadium oxide is dispersed on a support such as alumina or titania are of particular importance in, for instance, the oxidative dehydrogenation of alkanes [58-64]. Such materials have attracted considerable interest in the direct dehydrogenation of butane, where a key driver is to identify the relationship between catalytic activity and structural properties [5, 6, 65-68]. In the pure (solid) metal oxides the coordination of vanadium is well defined. However, this is not necessarily true in the case of supported catalysts. Vanadium may be present on the support surface as isolated vanadium ions dimeric or polymeric species one- and two-dimensional chains of vanadium ions ... 

Characteristic features of vanadium containing heteropoly catalysts for the selective oxidation of hydrocarbons have been described. MAA yield ftom isobutyric acid was successfully enhanced by the stabilization of the vanadium-substituted heteropolyanions by forming cesium salts. As for lower alkane oxidation by using vanadium containing heteropoly catalysts, it was found that the surface of (V0)2P207 was reversibly oxidized to the Xi (8) phase under the reaction conditions of n-butane oxidation. The catalytic properties of cesium salts of 12-heteropolyacids were controlled by the substitution with vanadium, the Cs salt formation, and the addition of transition metal ions. By this way, the yield of MAA from isobutane reached 9.0%. Furthermore, vanadium-substituted 12-molybdates in solution showed 93% conversion on H2O2 basis in hydroxylation of benzene to phenol with 100% selectivity on benzene basis. 

It is well established [1-3] that vanadyl pyrophosphate (VO)2P207 is an essential component of the most selective VPO catalysts. For example, structural and chemical characterization studies of "reactor equilibrated" VPO catalysts indicate that the predominate crystalline phase is vanadyl pyrophosphate (VO)2P207 [1-3], that the bulk P/V ratio is close to 1.0, and that the average vanadium oxidation state is close to -1-4.0 [3-5]. A number of studies [2,5] have indicated that alkane oxidation primarily involves oxygen adspecies adsorbed at vanadium surface sites, and relatively little bulk lattice oxygen. 

Most of the catalysts employed in the chemical technologies are heterogeneous. The chemical reaction takes place on surfaces, and the reactants are introduced as gases or liquids. Homogeneous catalysts, which are frequently metalloorganic molecules or clusters of molecules, also find wide and important applications in the chemical technologies [24]. Some of the important homogeneously catalyzed processes are listed in Table 7.44. Carbonylation, which involves the addition of CO and H2 to a C olefin to produce a + 1 acid, aldehyde, or alcohol, uses rhodium and cobalt complexes. Cobalt, copper, and palladium ions are used for the oxidation of ethylene to acetaldehyde and to acetic acid. Cobalt(II) acetate is used mostly for alkane oxidation to acids, especially butane. The air oxidation of cyclohexane to cyclohexanone and cyclohexanol is also carried out mostly with cobalt salts. Further oxidation to adipic acid uses copper(II) and vanadium(V) salts as catalysts. The... 

Solsona, B., Dejoz, A., Vazquez, M., et al (2001). Si02-Supported Vanadium Magnesium Mixed Oxides as Selective Catalysts for the Oxydehydrogenation of Short Chain Alkanes, Appl. Catal. A Gen., 208, pp. 99-110. 

In 1992, Hari Prasad Rao and Ramaswamy reported on the oxyfunctionalization of alkanes with H2O2 using a vanadium silicate molecular sieve s . With this catalyst acyclic and cyclic alkanes were oxidized to a mixture of the corresponding alcohols (primary and secondary ones), aldehydes and ketones. Unfortunately, most of the early attempts were of rather limited success due to low turnover frequencies and radical producing side reactions as observed, for example, by Mansuy and coworkers in 1988. ... 

The catalysts based on vanadium oxide are one of the better studied systems. A V-Mg oxide in which Mg orthovanadate (Mg2(V04)2) and MgO were the only identifiable phases was a rather selective catalyst (27). Since MgO was relatively inactive in alkane activation, Mg orthovanadate was assumed to be the active component. Indeed, Mg orthovanadate prepared as a stoichiometric compound showed high selectivities for the oxidative dehydrogenation of propane (29). In this latter study, it was shown interestingly that Mg orthovanadate was the only alkali or alkali earth orthovanadate that... 

In summary, catalytic C-H transformations in small unfunctionalized alkanes is a technically very important family of reactions and processes leading to small olefins or to aromatic compounds. The prototypical catalysts are chromia on alumina or vanadium oxides on basic oxide supports and platinum on alumina. Reaction conditions are harsh with a typical minimum temperature of 673 K at atmospheric pressure and often the presence of excess steam. A consistent view of the reaction pathway in the literature is the assumption that the first C-H abstraction should be the most difficult reaction step. It is noted that other than intuitive plausibility there is little direct evidence in heterogeneous reactions that this assumption is correct. From the fact that many of these reactions are highly selective toward aromatic compounds or olefins it must be concluded that later events in the sequence of elementary steps are possibly more likely candidates for the rate-determining step that controls the overall selectivity. A detailed description of the individual reactions of C2-C4 alkanes can be found in a comprehensive review [59]. 

Air oxidation of /i-butane to maleic anhydride is possible over vanadium phos(4tate and, remaiicably, a 60% selectivity is obtained at 85% conversion. In the gas phase oxidation, in conffast to the situation found in the liquid, n-allcanes are oxidized more rapidly than branched chain alkanes. This is because secondary radicals are more readily able to sustain a chain for branched alkanes the relatively stable tertiary radical is preferentially formed but fails to continue the chain process. Vanadium(V)/ manganese(II)/AcOH has been used as a catalyst for the autoxidation of cyclohexane to adipic acid, giving 25-30% yields after only 4 h. ... 

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