A molecular level mechanism ofn-butane oxidation to maleic anhydride over vanadyl pyrophosphate

A molecular level mechanism is proposed for the highly selective 14-e^– oxidative transformation ofn-butane to maleic anhydride on the surface of vanadyl pyrophosphate. The mechanism suggests that the dimeric active sites assume at any given time, one of four possible interconvertible states which differ from each other in the number of available oxygen atoms and the formal oxidation states of the individual vanadium atoms. The relative ratios of active sites in each of the four possible states are dictated by the reaction conditions, the redox properties of the reacting gases and the structure of the vanadyl pyrophosphate active surface. A crucial feature of the mechanism is a pseudo-ozonide surface species formed by the interaction of a chemisorbed dioxygen molecule and an adjacent metal-oxo group. This unusual species is responsible for the initial activation of then-butane, which occurs when the chemisorbed dioxygen abstracts an H-atom from the alkane and the adjacent metal-oxo group reacts with the incipient alkyl radical to form an alkoxy group. The proposed mechanism is entirely consistent with literature reports describing the behaviour of (VO)₂P₂O₇ in flow, pulse and TAP reactors.     

Possible effects of site isolation in antimony oxide-modified vanadia/titania catalysts for selective oxidation of o-xylene

Titania-supported vanadia catalysts were modified by addition of antimony oxide for application in o-xylene selective oxidation to phthalic anhydride. It was shown that active and selective catalysts can be prepared by ball-milling mixtures of powders of TiO₂, V₂O₅and Sb₂O₃followed by calcination. X-ray photoelectron spectroscopy proves the formation of highly dispersed overlayers of vanadium oxide and antimony oxide, in which V⁵⁺is partially reduced to lower oxidation states and Sb³⁺is partially oxidized to Sb⁵⁺. Antimony oxide segregated into the outermost surface layers. It is therefore inferred that the presence of the antimony oxide modifier spatially separates V–O species and leads to site isolation which may be responsible for the positive effect of the modifier for the catalyst's selectivity.     

A comparison between classical robust stability conditions

The paper is focused on the comparison between some classical robust stability conditions for continuous‐time linear time‐invariant systems. Such conditions are given as lemmas in the paper, since their statements include some generalizations, needed in order to better compare (and use) them. The analysis is carried out by comparing pairwise the families of systems whose stabilization through a given compensator is guaranteed by each of the considered robust stability conditions. Some properties of the families are formally derived and stated, and some very simple examples arc exhibited in order to illustrate the presented properties and comparisons. A theorem, representing an extension of one of the considered conditions, is proposed in order to overcome some difficulties arising in the use of the classical result. Copyright © 2004 John Wiley & Sons, Ltd.     

Active centers, catalytic behavior, symbiosis and redox properties of MoV(Nb,Ta)TeO ammoxidation catalysts

Selective as well as waste forming active centers were defined for MoVNbTeO and MoVTaTeO catalysts in the ammoxidation of propane to acrylonitrile and all catalytic functionalities were assigned to specific elements at the respective active centers. Symbiosis between M1 and M2 phases of these catalysts was observed, with phase cooperation being more extensive in the Nb than Ta containing compositions. The difference in catalytic effectiveness arises most likely because contact and surface area exposure of the two respective, cooperating phase pairs are not equal. The M1 phase of the catalysts is reducible by propane and ammonia in the absence of dioxygen and is regenerable to its original, fully oxidized state by dioxygen (air). No structural collapse is observed even after 120 C₃H₈ + NH₃ reduction pulses. The so induced reduction of the catalyst extends up to 70 layers deep. The product distribution over the first few pulses is very similar to that under catalytic conditions, supporting the concept that lattice oxygen is involved in the catalytic ammoxidation process. Therefore, the ammoxidation of paraffins is a redox process, as is of course the well-known olefin ammoxidation process.     

Effect of α and γ polymorphs of alumina on the preparation of MgAl2O4-spinel-containing refractory cements

The use of aluminous refractory materials containing MgAl₂O₄-spinel has led to a major breakthrough in the service life of refractory coatings applied in the industries and in the quality of the products.Many researches have been conducted to improve the synthetic procedures in order to reduce the production cost of these materials. In this way, refractory cements involving in situ generated spinel phase have been obtained from mixtures of active alumina and dolomites. Other investigations have demonstrated that γ alumina is advantageous in comparison with the α polymorph in the synthesis and sintering properties of pure MgAl₂O₄-spinel.In this article, the performance of both polymorphs of alumina, used as raw materials in the preparation of the refractory cements, along with dolomite proceeding from Olavarría, in the centre of Buenos Aires Province (Argentine), is compared.The thermal and structural changes which take place during the firing of the batches up to 1450 °C were studied by the combination of diffractometric and infrared spectroscopy data, at the most remarkable reaction steps.According to these results, the study of phase changes within the investigated thermal range allowed to establish the main differences in the composition of both mixtures in each firing step. Independently of the type of alumina used, a mixed phase product consisting of spinel, as a major phase, accompanied by CaAl₂O₄ (CA) and CaAl₄O₇ (CA₂), as secondary phases, was obtained. In addition, it was found that the formation of these phases at lower temperature is favoured by γ-Al₂O₃.     

Catalytic behaviour of M1, M2, and M1/M2 physical mixtures of the Mo–V–Nb–Te–oxide system in propane and propene ammoxidation

Essentially pure orthorhombic M1 and pseudo-hexagonal M2 phases were prepared using the precursor method. Consistent with literature the M1 phase was shown to be effective for propane ammoxidation to acrylonitrile while the M2 phase was essentially inert for propane activation. Both phases convert propene efficiently to acrylonitrile. Both phases show a significant selectivity dependence on the ammonia and oxygen concentrations in the feed, revealing thereby additional insights into the reaction mechanism.

Physical mixtures of the two separately prepared phases exhibited symbiosis in the ammoxidation of propane when finally divided (5 μm), thoroughly mixed and brought into intimate contact with each other. Acrylonitrile yields significantly higher than those obtained with the M1 phase alone were demonstrated with a 50 wt.% M1/50 wt.% M2 physical mixture having a corresponding surface area ratio of about 4:1. The phase cooperation effect is particularly large at high propane conversions and non-existent when the particle size of the phases is too large (e.g. >250 μm) and the inter-particle contact is poor.