Vanadium compounds production

Vanadium compounds, including those which may be involved in the production, processing, and use of vanadium and vanadium alloys, are irritants chiefly to the conjuctivae and respiratory tract. Prolonged exposure may lead to pulmonary compHcations. However, responses are acute, never chronic. Toxic effects vary with the vanadium compound involved. For example, LD q (oral) of vanadium pentoxide dust in rats is 23 mg/kg of body weight (24). 

Most U.S. production (20 x 10 lbs ia 1996) of primary vanadium compounds has been as by-products or coproducts of uranium and of ferrophosphoms derived from smelting Idaho phosphates. Most of this processiag was from leaching acids, residues, and spent catalysts. The only domestic commercially mined ore, for its sole production of vanadium, is Arkansas brookite. It has contributed significantly to domestic supply siace ca 1969, however, it has not been mined siace 1992 (25). 

Conversion of fused pentoxide to alloy additives is by far the largest use of vanadium compounds. Air-dried pentoxide, ammonium vanadate, and some fused pentoxide, representing ca 10% of primary vanadium production, are used as such, purified, or converted to other forms for catalytic, chemical, ceramic, or specialty appHcations. The dominant single use of vanadium chemicals is in catalysts (see Catalysis). Much less is consumed in ceramics and electronic gear, which are the other significant uses (see Batteries). Many of the numerous uses reported in the Hterature are speculative, proposed. 

VO(acac)2 < VO(Et-acac)2 VO(Me-acac)2 BMOV. Conversion rates for all hydrolysis products were faster than for the original species. Both EPR and visible spectroscopic studies of solutions prepared for administration to diabetic rats ocumented both a salt effect on the species formed and formation of a new halogen-containing complex. The authors concluded that vanadium compound efficacy with respect to long-term lowering of plasma glucose levels in diabetic rats traced the concentration of the hydrolysis product in the administration solution. 

The initiator formed from VCLt and A1(C2H5)2C1 is one of the most efficient means for syndioselective polymerization of propene, especially in the presence of a Lewis base such as anisole (methoxybenzene) [Doi, 1979a,b Natta et al., 1962 Zambelli et al., 1978, 1980], Other vanadium compounds such as vanadium acetylacetonate and various vanadates [VO(OR)xClp x), where x — 1,2,3] can be used in place of VCI4 but are more limited in their stereoselectivity [Doi et al., 1979]. Trialkylaluminum can also be used as a coinitiator, but only for VCI4. Syndiotacticity increases with decreasing temperature most of these syndioselective polymerizations are carried out below —40°C and usually at —78°C. The initiators must be prepared and used at low temperatures since most of them undergo decomposition at ambient and higher temperatures. There is considerable reduction of V(III) to V(II) with precipitation of ill-defined products that are low in activity and do not produce syndiotactic polymer, when the initiators are prepared at or warmed to temperatures above ambient. 

In general, the direct-oxidation processes employ a redox couple that has sufficient oxidation potential to convert H2S into elemental sulfur but insufficient potential to oxidize sulfur to higher states. Examples of materials that have this redox potential are vanadium compounds, arsenic compounds, iron compounds, and certain organic species. Typically, the redox materials, dissolved in a hot potassium carbonate solution with the species in its oxidized form, contacts the I S-laden gas and the H2S dissolves as the hydrosulfide. This sulfur reacts with the redox couple, forming elemental sulfur and the reduced state of the couple. Airblowing of the solution reoxidizes the couple and removes the elemental sulfur from solution as a product froth. 

In addition to the reactions that produce elemental sulfur, competing reactions also occur that produce undesirable by-products such as sodium thiosulfate. This is detrimental, because the thiosulfate remains in solution, and its concentration can generally be reduced only by bleeding off a portion of the solution inventory. This solution purge waste stream is hazardous, largely because it also contains vanadium compounds. The key to reducing the metal content of the waste stream is to reduce the rate of thiosulfate formation. 

Preparation of Vanadium.—There is no demand for pure vanadium, and the isolation of the metal is therefore not an industrial process. Even on the small scale the operation is attended with considerable difficulty, owing to the very high temperature necessary for the reduction of vanadium compounds and the tendency for reoxidation to take place. The following methods have given products of variable purity —... 

The use of certain vanadium compounds as catalysts has been increasing. Vanadium oxy trichloride is a catalyst in making ediylene-propylene rubber. Ammonium metavanadate and vanadium pentoxide aie used as oxidation catalysts, particularly in the production of polyamides, such as nylon, in the manufacture of H>S04 by the contact process, in the production of phdialic and maleic anhydrides, and in numerous other oxidation reactions, such as alcohol to acetaldehyde, anthracene to anthraquinone, sugar to oxalic acid, and diphenylamine to carbazole. Vanadium compounds have been used for many years 111 die ceramics field for enamels and glazes. Colors are produced by various combinations of vanadium oxide and silica, zirconia, zinc, lead, tin, selenium, and cadmium. Vanadium intermediate compounds also are used in the making of aniline Mack used by the dye industry... 

The presence of tumor necrosis factor a directly leads to apoptosis via interaction with the tumor necrosis factor receptor, one of a class of receptors referred to as death receptors. NF-kB, which must enter the nucleus to initiate apoptosis, is a transcription factor sequestered in the cytoplasm by inhibitor of kB (IkB). The binding of TNFa to its receptor leads to the ubiquitin-dependent proteolysis of IkB, allowing NF-kB to enter the nucleus. The activation of apoptosis results directly from the stimulation of NF-kB, a transcription factor whose phosphorylation is controlled by vanadium compounds. In a global gene expression study, it was found that diabetes increased the formation of IkB, whereas vanadium compound treatment lowered the production of this inhibitor [101]. The activation of the TNFR also activates the caspase proteins, a class of proteases that cleave proteins after specific aspartate residues. 

The polymerization of conjugated dienes to products with a controlled structure usually occurs in the presence of alkylaluminium compounds. The choice not only the transition metal but also of its ligands is of importance. Some systems produce a certain kind of stereochemical structure irrespective of external conditions. So, for example, vanadium compounds yield predominantly the trans-1,4 structure whereas cobalt salts yield the c -1,4 structure. Other catalysts are very sensitive, and a small external effect completely changes their stereochemical activity [267b] [e. g. Cr(acetylacetona-te)3-R3Al]. Examples of several catalytic systems are summarized in Table 7. 

Diabetes mellitus (DM) is an increasingly common disease of sugar metabolism. Juvenile-onset diabetes, also known as Type I or insulin-dependent diabetes (IDDM), is an autoimmune disease that results in decreased release of insulin by the pancreas. Late-onset diabetes, also known as Type II or non-insulin-dependent diabetes (NIDDM), results from reduced sensitivity of cells to the insulin signal. A convenient animal model for studying diabetes and testing alternative therapies is the streptozotocin-freated diabetic rat. Streptozotocin (STZ) attacks the pancreas and decreases insulin production and release, thus, mimicking many aspects of the human disease. Since insulin is not orally absorbed, the oral administration of vanadium compounds that are insuhn-mimetic or insulin-enhancing would be a very attractive therapy ... 

On a commercial scale uranous oxide is prepared by fusing at red heat a mixture of 35 parts of common salt and 20 parts of sodium uranate with 1 part of powdered charcoal, the heating being continued until the escape of gas ceases. After cooling, the mass is lixiviated with water, and the residue of uranous oxide is washed by decantation. By washing with 5 per cent, hydrochloric acid, any iron, aluminium, or vanadium compounds may be removed, and a commercial product of purity equivalent to 97 per cent. U3O3 is obtained. If the uranous oxide is required for the production of ferro-uranium, the complete removal of iron is not necessary. 

Vanadium plays an important role in many industrial catalysts used extensively in a variety of applications including the production of SO3 from SO2, selective oxidation of hydrocarbons, reduction of nitrogen oxides with ammonia, and in the manufacture of many chemicals and chemical intermediates. Such catalysts typically consist of vanadium compounds supported on oxides such as silica, alumina, titania, etc., and their activity depends on factors such as the chemical form and crystalline environment... 

Homogeneous vanadium-based catalysts formed by the reaction of vanadium compounds and reducing agents such as organoaluminum compounds [10-12] are used industrially for the production of elastomers by ethylene/propene copolymerization (EP rubber) and ethylene/propene/diene terpolymerization (EPDM rubber). The dienes are usually derivatives of cyclopentadiene such as ethylidene norbomene or dicyclopentadiene. Examples of catalysts are Structures 1-4. Third components such as anisole or halocarbons are used to prevent a decrease in catalyst activity with time which is observed in the simple systems. 

The sulfoxidation of alkanes to alkane sulfonic acids using a combination of sulfur dioxide and dioxygen and catalyzed by vanadium compounds has been reported [20]. The mechanism involves intermediacy of alkyl radicals which are trapped by sulfur dioxide and then further oxidized to the product. 

Environmental aspects of vanadium chemistry include vanadium chemistry in solution, gaseous, and solid states, and thus span a wide range of the properties of vanadium compounds. The recent compendium of reviews of the environmental chemistry of vanadium has shown that this area does have many contributors (contributed to and edited by Nriagu). Vanadium is a side product from refining coal, because vanadyl porphyrins are very stable (their stability is exceeded only by the nickel porphyrins). 

The element was named by Nils Gabriel Sefstrom (1787-1845) after the Scandinavian goddess of beauty Vanadis. In 1801, Andres Manuel del Rio (1764-1849) identified a new metal he called erythronium (from the Greek for red) that seemed related to uranium and chromium, but he was advised that it was actually lead chromate. In 1830, Sefstrom rediscovered the element and named it, finding out a year later that it was the same material as described by del Rio. Vanadium compounds are found in trace amounts in nature. The majority of vanadium is used as an alloy in steel production. 

Of phenolic oxidations using vanadium compounds, intramolecular oxidative phenolcoupling reactions are quite attractive from the viewpoint of natural products synthesis. A number of benzylisoquinoline alkaloids, lignans and neolignans are well known to be produced, in a key step, by oxidative radical coupling of open phenolic precursors. 

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