Vanadium fused

The principal vanadium-bearing ores are generally cmshed, ground, screened, and mixed with a sodium salt, eg, NaCl or Na2C02- This mixture is roasted at ca 850°C and the oxides are converted to water-soluble sodium metavanadate, NaVO. The vanadium is extracted by leaching with water and precipitates at pH 2—3 as sodium hexavanadate, Na V O, a red cake, by the addition of sulfuric acid. This is then fused at 700°C to yield a dense black product which is sold as technical-grade vanadium pentoxide. This product contains a minimum of 86 wt % V20 and a maximum of 6—10 wt % Na20. 

Refining of Vanadium. In addition to the purification methods described above, vanadium can be purified by any of three methods iodide refining (van Arkel-deBoer process), electrolytic refining in a fused salt, and electrotransport. 

An electrolytic process for purifying cmde vanadium has been developed at the U.S. Bureau of Mines (16). It involves the cathodic deposition of vanadium from an electrolyte consisting of a solution of VCI2 in a fused KCl—LiCl eutectic. The vanadium content of the mixture is 2—5 wt % and the operating temperature of the cell is 650—675°C. Metal crystals or flakes of up to 99.995% purity have been obtained by this method. 

For solvent extraction of pentavalent vanadium as a decavanadate anion, the leach solution is acidified to ca pH 3 by addition of sulfuric acid. Vanadium is extracted in about four countercurrent mixer—settler stages by a 3—5 wt % solution of a tertiary alkyl amine in kerosene. The organic solvent is stripped by a soda-ash or ammonium hydroxide solution, and addition of ammoniacal salts to the rich vanadium strip Hquor yields ammonium metavanadate. A small part of the metavanadate is marketed in that form and some is decomposed at a carefully controlled low temperature to make air-dried or fine granular pentoxide, but most is converted to fused pentoxide by thermal decomposition at ca 450°C, melting at 900°C, then chilling and flaking. 

For solvent extraction of a tetravalent vanadium oxyvanadium cation, the leach solution is acidified to ca pH 1.6—2.0 by addition of sulfuric acid, and the redox potential is adjusted to —250 mV by heating and reaction with iron powder. Vanadium is extracted from the blue solution in ca six countercurrent mixer—settler stages by a kerosene solution of 5—6 wt % di-2-ethyIhexyl phosphoric acid (EHPA) and 3 wt % tributyl phosphate (TBP). The organic solvent is stripped by a 15 wt % sulfuric acid solution. The rich strip Hquor containing ca 50—65 g V20 /L is oxidized batchwise initially at pH 0.3 by addition of sodium chlorate then it is heated to 70°C and agitated during the addition of NH to raise the pH to 0.6. Vanadium pentoxide of 98—99% grade precipitates, is removed by filtration, and then is fused and flaked. 

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). 

Most foreiga vanadium is obtained as a coproduct of iron and titanium. South Africa, Norway, and Finland are suppHers. Chile produces slag from an iron operation. AustraUa s first vanadium operation started produciag fused pentoxide flake from a vanadium mine ia 1980. Russia and the People s Repubhc of china produce slag and pentoxide from iron—titanium ores. 

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. 

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). 

The usual extraction procedure is to roast the crushed ore, or vanadium residue, with NaCl or Na2C03 at 850°C. This produces sodium vanadate, NaV03, which is leached out with water. Acidification with sulfuric acid to pH 2-3 precipitates red cake , a polyvanadate which, on fusing at 700°C, gives a black, technical grade vanadium pentoxide. Reduction is then necessary to obtain the metal, but, since about 80% of vanadium produced is used as an additive to steel, it is usual to effect the reduction in an electric furnace in the presence of iron or iron ore to produce ferrovanadium, which can then be used without further refinement. Carbon was formerly used as the reductant, but it is difficult to avoid the formation of an intractable carbide, and so it has been superseded by aluminium or, more commonly, ferrosilicon (p. 330) in which case lime is also added to remove the silica as a slag of calcium silicate. If pure vanadium metal is required it can... 

The elements of Group 5 are in many ways similar to their predecessors in Group 4. They react with most non-metals, giving products which are frequently interstitial and nonstoichiometric, but they require high temperatures to do so. Their general resistance to corrosion is largely due to the formation of surface films of oxides which are particularly effective in the case of tantalum. Unless heated, tantalum is appreciably attacked only by oleum, hydrofluoric acid or, more particularly, a hydrofluoric/nitric acid mixture. Fused alkalis will also attack it. In addition to these reagents, vanadium and niobium are attacked by other hot concentrated mineral acids but are resistant to fused alkali. 

Niobium and tantalum also form various oxide phases but they are not so extensive or well characterized as those of vanadium. Their pentoxides are relatively much more stable and difficult to reduce. As they are attacked by cone HF and will dissolve in fused alkali, they may perhaps... 

Sulphates, which form part of the ash from the combustion of many fuels, are not harmful to high-alloy steels, but can become so if reduction to sulphide occurs. This leads to the formation of low melting point oxide-sulphide mixtures and to sulphide penetration of the metal. Such reduction is particularly easy if the sulphate can form a mixture of low melting point with some other substance. Reduction can be brought about by bad combustion, as demonstrated by Sykes and Shirley , and it is obviously important to avoid contact with inefficiently burnt fuels when sulphate deposits may be present. Reduction can also be brought about in atmospheres other than reducing ones and the presence of chlorides or vanadium pentoxide has been shown to be sufficient to initiate the reaction. It has also been shown that it can be initiated by prior cathodic polarisation in fused sodium sulphate. The effect of even small amounts of chloride on oxidation in the presence of sulphate is illustrated in Fig. 7.33 . 

Vanadium metal is prepared from pentoxide, V2O5, by reduction with calcium at elevated temperatures. Presence of iodine lowers calcium reduction temperature to 425°C because of heat of formation of calcium iodide. Pentoxide also may be converted to the trichloride, VCI3, and the trichloride reduced with magnesium metal or magnesium-sodium mixture at high temperatures to form high purity ductile metal. Alternatively, a fused mixture of vanadium chloride, sodium chloride, and hthium chloride may be electrolyzed to produce the metal in high purity. 

Vanadium reacts with fused caustic soda and caustic potash to form water soluble vanadates with hberation of hydrogen. The metal, however, is stable in alkaline solutions. 

Nineteenth Century Robert Hare fuses platinum. Two years later he volatilizes it. Del Rio recognizes the presence of a new metal erythronium (vanadium) in a lead ore from Zimapan, Mexico. He afterward confuses it with chromium. 

The /3-diketonates are usually thermally stable and may be fused or volatilized with little or no decomposition. These complexes were tested by gas-liquid chromatography without evidence for on-column degradation.252 However, some retention of fluorodiketonato complexes was due to reaction in the stationary phase or with active sites.253 The sublimation enthalpy of tris(trifluoroacetylacetonate)vanadium(III) is 118 2kJmol-1 and the evaporation enthalpy is 77.8 0.8 kJ mol-1.254 At 300-470°C there is decomposition of [V(acac)3] acetone, CO and CO2 are the products.255... 

The passivity of vanadium is referred to on p. 23, and the electrolytic decomposition of anhydrous fused vanadium salts on p. 17. 

V02.V206 also results as deep blue crystals on heating ammonium metavanadate which has previously been fused and cooled. It is stated that the fused substance does not furnish vanadium pentoxide on being decomposed.10 The residue is extracted with concentrated ammonium hydroxide solution and the oxide precipitated by addition of water. 

The red, amorphous form of vanadium pentoxide is the form most frequently met with in the laboratory. Its preparation has been described above. It melts at 658°10 or 675° C.u to a dark red liquid, but is not volatile even at high temperatures it can be vaporised only in the electric furnace.18 The fused solid conducts electricity, with formation of hypovanadic oxide, V02 18 the electrical conductivity has been measured.14 The oxide absorbs water on exposure to the air, the... 

Molten vanadium pentoxide is a corrosive substance and attacks most containers even when made of platinum, fused silica, or graphite.10... 

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