Vanadium in oxides

E. Cadot, C. Marchal, M. Fournier, A. Teze G. Herve, Role of Vanadium in Oxidation Catalysis by Heteropoly anions, in Polyoxometalates M. T. Pope A. Muller, Ed., Kluwer Academic Publisher 1994, S. 315-326. 

Vanadium-zirconia is another blue stain used often. A mixture consists of zirconia ZrO, silica SiO, and vanadium pentoxide (vanadium in + oxidation state, which is colorless). The blue color is due to the formation of in the calcination process. The V atom in is in the -hIV oxidation that has a characteristic blue color. The formation of scans to be facilitated by the addition of... 

P. Chaurand, J. Rose, V. Briois, M. Salome, O. Proux, V. Nassif, L. Olivi, J. Susini, J.-L. Hazemann, J.-Y. Bottero, New methodological approach for the vanadium K-edge X-ray absorption near-edge structure interpretation application to the speciation of vanadium in oxide phases from steel slag. J. Phys. Chem. B 111(19), 5101-10 (2007)... 

Bradley and Gitlitz (193, 666) via the insertion of carbon disuUide into metal amides, [V(NR2)4]- Dithiocarbamates are now known to stabilize vanadium in oxidation states ranging from +3 to +5. 

In the early 1980s, predse measurements of the acidity of the intracellular fluid in intact vanadocytes by two different methods showed that the pH of blood is very close to the physiological pH, 7.2 (Dingley et al, 1982 Hawkins et al, 1983). Similar results were obtained with lysed vanadocytes of Phallusia julinea in totally anaerobic conditions (pH = 6.5), and strongly addic Henze solutions would be attributable to the action of oxygen (Brand, Hawkins, and Parry, 1987 Taylor et al, 1994). Vanadium in oxidation state (III) would be stabilized by chelation in a... 

Vanadium pentoxide, vanadium(V) oxide, V2O5, is the most important compound in this oxidation state. It is a coloured solid (colour due to charge transfer, p. 60), the colour varying somewhat (red -> brown) with the state of subdivision it is formed when vanadium (or some of its compounds) is completely oxidised, and also by heating ammonium vanadate)V) ... 

This IS the important state of vanadium in aqueous solution it is neither strongly oxidising or strongly reducing and acidic solutions are stable to atmospheric oxidation ... 

Benzoquinone ( quinone ) is obtained as the end product of the oxidation of aniline by acid dichromate solution. Industrially, the crude product is reduced with sulphur dioxide to hydroquinone, and the latter is oxidised either with dichromate mixture or in very dilute sulphuric acid solution with sodium chlorate in the presence of a little vanadium pentoxide as catalyst. For the preparation in the laboratory, it is best to oxidise the inexpensive hydroquinone with chromic acid or with sodium chlorate in the presence of vanadium pent-oxide. Naphthalene may be converted into 1 4-naphthoquinone by oxidation with chromic acid. 

The catalyst used in the production of maleic anhydride from butane is vanadium—phosphoms—oxide (VPO). Several routes may be used to prepare the catalyst (123), but the route favored by industry involves the reaction of vanadium(V) oxide [1314-62-1] and phosphoric acid [7664-38-2] to form vanadyl hydrogen phosphate, VOHPO O.5H2O. This material is then heated to eliminate water from the stmcture and irreversibly form vanadyl pyrophosphate, (V(123,124). Vanadyl pyrophosphate is befleved to be the catalyticaHy active phase required for the conversion of butane to maleic anhydride (125,126). 

Promoters are sometimes added to the vanadium phosphoms oxide (VPO) catalyst during synthesis (129,130) to increase its overall activity and/or selectivity. Promoters may be added during formation of the catalyst precursor (VOHPO O.5H2O), or impregnated onto the surface of the precursor before transformation into its activated phase. They ate thought to play a twofold stmctural role in the catalyst (130). First, promoters facilitate transformation of the catalyst precursor into the desired vanadium phosphoms oxide active phase, while decreasing the amount of nonselective VPO phases in the catalyst. The second role of promoters is to participate in formation of a soHd solution which controls the activity of the catalyst. 

The bulk stmcture of the catalyticaHy active phase is not completely known and is under debate in the Hterature (125,131—133). The central point of controversy is whether (Valone or in combination with other phases is the most catalyticaHy active for the conversion of butane to maleic anhydride. The heart of this issue concerns the role of stmctural disorder in the bulk and how it arises in the catalyst (125,134,135). Most researchers agree that the catalysts with the highest activity and selectivity ate composed mainly of (Vthat exhibits a clustered or distorted platelet morphology (125). It is also generaHy acknowledged that during operation of the catalyst, the bulk oxidation state of the vanadium in the catalyst remains very close to the +4 valence state (125). 

Vanadium phosphoms oxide-based catalysts ate unstable in that they tend to lose phosphoms over time at reaction temperatures. Hot spots in fixed-bed reactors tend to accelerate this loss of phosphoms. This loss of phosphoms also produces a decrease in selectivity (70,136). Many steps have been taken, however, to aHeviate these problems and create an environment where the catalyst can operate at lower temperatures. For example, volatile organophosphoms compounds are fed to the reactor to mitigate the problem of phosphoms loss by the catalyst (137). The phosphoms feed also has the effect of controlling catalyst activity and thus improving catalyst selectivity in the reactor. The catalyst pack in the reactor may be stratified with an inert material (138,139). Stratification has the effect of reducing the extent of reaction pet unit volume and thus reducing the observed catalyst temperature (hot... 

Fluidized-bed reactor systems put other unique stresses on the VPO catalyst system. The mixing action inside the reactor creates an environment that is too harsh for the mechanical strength of a vanadium phosphoms oxide catalyst, and thus requires that the catalyst be attrition resistant (121,140,141). To achieve this goal, vanadium phosphoms oxide is usually spray dried with coUoidal siUca [7631-86-9] or polysiUcic acid [1343-98-2]. Vanadium phosphoms oxide catalysts made with coUoidal sUica are reported to have a loss of selectivity, while no loss in selectivity is reported for catalysts spray dried with polysUicic acid (140). 

Vanadium, a typical transition element, displays weU-cliaractetized valence states of 2—5 in solid compounds and in solutions. Valence states of —1 and 0 may occur in solid compounds, eg, the carbonyl and certain complexes. In oxidation state 5, vanadium is diamagnetic and forms colorless, pale yeUow, or red compounds. In lower oxidation states, the presence of one or more 3d electrons, usually unpaired, results in paramagnetic and colored compounds. All compounds of vanadium having unpaired electrons are colored, but because the absorption spectra may be complex, a specific color does not necessarily correspond to a particular oxidation state. As an illustration, vanadium(IV) oxy salts are generally blue, whereas vanadium(IV) chloride is deep red. Differences over the valence range of 2—5 are shown in Table 2. The stmcture of vanadium compounds has been discussed (6,7). 

The chemistry of vanadium compounds is related to the oxidation state of the vanadium. Thus, V20 is acidic and weaMy basic, VO2 is basic and weaMy acidic, and V2O2 and VO are basic. Vanadium in an aqueous solution of vanadate salt occurs as the anion, eg, (VO ) or (V O ) , but in strongly acid solution, the cation (V02) prevails. Vanadium(IV) forms both oxyanions ((V O ) and oxycations (VCompounds of vanadium(III) and (II) in solution contain the hydrated ions [V(H20)g] and [V(H20)g], respectively. 

Vanadium(IV) Oxide. Vanadium(IV) oxide (vanadium dioxide, VO2) is a blue-black solid, having a distorted mtile (Ti02) stmcture. It can be prepared from the reaction of V20 at the melting point with sulfur or carbonaceous reductants such as sugar or oxaUc acid. The dioxide slowly oxidizes in air. Vanadium dioxide dissolves in acids to give the stable (VO) " ions and in hot alkaUes to yield vanadate(IV) species, eg, (HV20 ) . 

Vanadium Sulfates. Sulfate solutions derived from sulfuric acid leaching of vanadium ores are industrially important in the recovery of vanadium from its raw materials. Vanadium in quadrivalent form may be solvent-extracted from leach solutions as the oxycation complex (VO) ". Alternatively, the vanadium can be oxidized to the pentavalent form and solvent-extracted as an oxyanion, eg, (V O ) . Pentavalent vanadium does not form simple sulfate salts. 

Borides are inert toward nonoxidizing acids however, a few, such as Be2B and MgB2, react with aqueous acids to form boron hydrides. Most borides dissolve in oxidizing acids such as nitric or hot sulfuric acid and they ate also readily attacked by hot alkaline salt melts or fused alkaU peroxides, forming the mote stable borates. In dry air, where a protective oxide film can be preserved, borides ate relatively resistant to oxidation. For example, the borides of vanadium, niobium, tantalum, molybdenum, and tungsten do not oxidize appreciably in air up to temperatures of 1000—1200°C. Zirconium and titanium borides ate fairly resistant up to 1400°C. Engineering and other properties of refractory metal borides have been summarized (1). 

MetaUic conduction occurs in transition-metal oxides such as ReO, vanadium(II) oxide [12035-98-2] VO, titanium(II) oxide [12137-20-17,... 

In this work ion-exchange and gel-permeation chromatography coupled with membrane filtration, photochemical oxidation of organic metal complexes and CL detection were applied to the study of the speciation of cobalt, copper, iron and vanadium in water from the Dnieper reservoirs and some rivers of Ukraine. The role of various groups of organic matters in the complexation of metals is established. 

Eosin Flavonoids Morin Flavonol, fisetin, robinetin Quercetin Rutin condensation products of urea, formaldehyde and methanol [126], pesticide derivatives [127] sweetening agents [128, 129] anion-active and nonionogenic surface-active agents [130] steroids, pesticides [29,132, 133] pesticides [134—137] vanadium in various oxidation states [138] uracil derivatives [139]... 

The modem process uses a potassium-sulfate-promoted vanadium(V) oxide catalyst on a silica or kie,selguhr support. The SO2 is obtained either by burning pure sulfur or by roasting sulfide minerals (p. 651) notably iron pyrite, or ores of Cu, Ni and Zn during the production of these metals. On a worldwide basis about 65% of the SO2 comes from the burning of sulfur and some 35% by the roasting of sulfide ores but in some countries (e.g, the UK) over 95% conies from the former. 

Niobium and tantalum provide no counterpart to the cationic chemistry of vanadium in the -t-3 and -t-2 oxidation states. Instead, they form a series of cluster compounds based... 

The group oxidation state of +5 is too high to allow the formation of simple ionic salts even for Nb and Ta, and in lower oxidation states the higher sublimation energies of these heavier metals, coupled with their ease of oxidation, again militates against the formation of simple salts of the oxoacids. As a consequence the only simple oxoanion salts are the sulfates of vanadium in the oxidation states +3 and +2. These can be crystallized from aqueous solutions as hydrates and are both strongly... 

A new process for the partial oxidation of n-butane to maleic anhydride was developed by DuPont. The important feature of this process is the use of a circulating fluidized bed-reactor. Solids flux in the rizer-reactor is high and the superficial gas velocities are also high, which encounters short residence times usually in seconds. The developed catalyst for this process is based on vanadium phosphorous oxides... 

Vanadium in the feed poisons the FCC catalyst when it is deposited on the catalyst as coke by vanadyl porphydrine in the feed. During regeneration, this coke is burned off and vanadium is oxidized to a oxidation state. The vanadium oxide (V O ) reacts with water vapor in the regenerator to vanadic acid, HjVO. Vanadic acid is mobile and it destroys zeolite crystal through acid-catalyzed hydrolysis. Vanadic acid formation is related to the steam and oxygen concentration in the regenerator. 

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