Vanadium -oxide

6 Cathode Materials with Monoatomic Ions in a Three-Dimensional Framework 

we observe a continuous decrease of the electrical conductivity, which is also recorded in the far-infrared spectrum by the disappearance of the Drude absorption [137]. 

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Vanadium oxide tribromide, VOBr3. Dark red deliquescent liquid formed by heating V2O3 plus Brj. 

Vanadium oxide dibromide, VOBr2- Yellow powder obtained by heating VOBr3 or Br2 plus S2fir2 over healed V2OS. 

Vanadium oxide trichloride, VOCI3, vanadyl chloride. Readily prepared yellow liquid, b.p. 127 C, formed CK plus heated V2OS plus C. Readily hydrolysed by water. 

Vanadium oxide dichloride, VOCI2. Green crystals VOCI3 plus H2. 

Bell R C, Zemski K A, Kerns K P, Deng H T and Castleman A W Jr 1998 Reactivities and collision-induced dissociation of vanadium oxide duster cations J. Phys. Chem. A 102 1733... 

Patents claiming specific catalysts and processes for thek use in each of the two reactions have been assigned to Japan Catalytic (45,47—49), Sohio (50), Toyo Soda (51), Rohm and Haas (52), Sumitomo (53), BASF (54), Mitsubishi Petrochemical (56,57), Celanese (55), and others. The catalysts used for these reactions remain based on bismuth molybdate for the first stage and molybdenum vanadium oxides for the second stage, but improvements in minor component composition and catalyst preparation have resulted in yields that can reach the 85—90% range and lifetimes of several years under optimum conditions. Since plants operate under more productive conditions than those optimum for yield and life, the economically most attractive yields and productive lifetimes maybe somewhat lower. 

Maleic anhydride and the two diacid isomers were first prepared in the 1830s (1) but commercial manufacture did not begin until a century later. In 1933 the National Aniline and Chemical Co., Inc., installed a process for maleic anhydride based on benzene oxidation using a vanadium oxide catalyst (2). Maleic acid was available commercially ia 1928 and fumaric acid production began in 1932 by acid-catalyzed isomerization of maleic acid. 

Benzene-Based Catalyst Technology. The catalyst used for the conversion of ben2ene to maleic anhydride consists of supported vanadium oxide [11099-11-9]. The support is an inert oxide such as kieselguhr, alumina [1344-28-17, or sUica, and is of low surface area (142). Supports with higher surface area adversely affect conversion of benzene to maleic anhydride. The conversion of benzene to maleic anhydride is a less complex oxidation than the conversion of butane, so higher catalyst selectivities are obtained. The vanadium oxide on the surface of the support is often modified with molybdenum oxides. There is approximately 70% vanadium oxide and 30% molybdenum oxide [11098-99-0] in the active phase for these fixed-bed catalysts (143). The molybdenum oxide is thought to form either a soUd solution or compound oxide with the vanadium oxide and result in a more active catalyst (142). 

The anhydride of 1,8-naphthalenedicarboxyHc acid is obtained in ca 95—116 wt % yield by the vapor-phase air-oxidation of acenaphthene at ca 330—450°C, using unsupported or supported vanadium oxide catalysts, with or without modifiers (96). 

The catalyst combines two essential ingredients found in eadier catalysts, vanadium oxide and titanium dioxide, which are coated on an inert, nonporous carrier in a layer 0.02- to 2.0-mm thick (13,16). Other elements such as phosphoms are also used. Ring-shaped supports are used instead of spherical supports to give longer catalyst life, less pressure drop though the reactor, and higher yields (17,18). Half rings are even better and allow more catalyst to be loaded (18). 

Fixed-Bed Vapor-Phase Oxidation of Naphthalene. A sihca gel or sihcon carbide support is used for catalyst involved in the oxidation of naphthalene. The typical naphthalene oxidation catalyst is a mixture of vanadium oxide and alkali metal sulfate on the siUca support. Some changes, such as the introduction of feed vaporizers, are needed to handle a naphthalene feed (14), but otherwise the equipment is the same. 

Vanadium—Silicon. Vanadium—shicon ahoy is made by the reduction of vanadium oxides with shicon in an electric furnace. Apphcation is essentiahy the same as that of the titanium ahoys. Vanadium ahoys sometimes offer the most economical way of introducing vanadium into molten steel. 

The Lo-Cat process, Hcensed by US Filter Company, and Dow/Shell s SulFerox process are additional Hquid redox processes. These processes have replaced the vanadium oxidizing agents used in the Stretford process with iron. Organic chelating compounds are used to provide water-soluble organometaHic complexes in the solution. As in the case of Stretford units, the solution is regenerated by contact with air. 

Vanadium metal can be prepared either by the reduction of vanadium chloride with hydrogen or magnesium or by the reduction of vanadium oxide with calcium, aluminum, or carbon. The oldest and most commonly used method for producing vanadium metal on a commercial scale is the reduction of V20 with calcium. Recently, a two-step process involving the alurninotherniic reduction of vanadium oxide combined with electron-beam melting has been developed. This method makes possible the production of a purer grade of vanadium metal, ie, of the quaUty required for nuclear reactors (qv). 

For vanadium solvent extraction, Hon powder can be added to reduce pentavalent vanadium to quadrivalent and trivalent Hon to divalent at a redox potential of —150 mV. The pH is adjusted to 2 by addition of NH, and an oxyvanadium cation is extracted in four countercurrent stages of mixer—settlers by a diesel oil solution of EHPA. Vanadium is stripped from the organic solvent with a 15 wt % sulfuric acid solution in four countercurrent stages. Addition of NH, steam, and sodium chlorate to the strip Hquor results in the precipitation of vanadium oxides, which are filtered, dried, fused, and flaked (22). Vanadium can also be extracted from oxidized uranium raffinate by solvent extraction with a tertiary amine, and ammonium metavanadate is produced from the soda-ash strip Hquor. Fused and flaked pentoxide is made from the ammonium metavanadate (23). 

The general configuration of one system that has reached an advanced stage of development (22) is shown in Figure 1. The negative electrode consists of thin lithium foil. The composite cathode is composed of vanadium oxide [12037-42-2] 6 13 with polymer electrolyte. Demonstration... 

Other sohd cathode systems that have been widely investigated include those containing lithium cobalt oxide [12190-79-3] LiCo02 (51), vanadium pentoxide [1314-62-17, 20, and higher vanadium oxides, eg, 0 3 (52,53). 

Mixed Metal Oxides and Propylene Ammoxidation. The best catalysts for partial oxidation are metal oxides, usually mixed metal oxides. For example, phosphoms—vanadium oxides are used commercially for oxidation of / -butane to give maleic anhydride, and oxides of bismuth and molybdenum with other components are used commercially for oxidation of propylene to give acrolein or acrylonitrile. 

Tin vanadium yeUows are prepared by introducing small amounts of vanadium oxide into the cassiterite stmcture of Sn02 (28). Tin vanadium... 

Porphyrin, octaethyl-, vanadium oxide complex cyclic voltammetry, 4, 399 <73JA5140)... 

Thus vanadium oxide (IV) eould be of interest for sensor systems. 

NaCl, interact with the sulphur and vanadium oxides emitted from the combustion of technical grade hydrocarbons and die salt spray to form Na2S04 and NaV03- These conosive agents function in two modes, either the acidic mode in which for example, the sulphate has a high SO3 thermodynamic activity, of in the basic mode when the SO3 partial pressure is low in the combustion products. The mechanism of coiTosion is similar to the hot coiTosion of materials by gases widr the added effects due to the penetration of tire oxide coating by tire molten salt. 

Investigations carried out within the past few years have revealed that multicomponent metal oxide systems may interact at interfaces by having one component form a two-dimensional metal oxide overlayer on the second metal oxide component. For example, vanadium oxide can be dispersed on Ti02, Zr02, Si02, AI2O3, and... 

Figure 4 Local microstruetures and experimental solid state NMR spectra in crystalline vanadium oxide compounds.

Figure 5 Solid state NMR spectra of Vanadium oxide on y-alumina as a function of vanadium loading (wt.%) and surface coverage 0. Note the gradual emergence of the six-coordinated vanadium site with increased loading.

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