Metavanadates

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. 

The red cake can be further purified by dissolving it in an aqueous solution of Na2C02- The iron, aluminum, and silicon impurities precipitate from the solution upon pH adjustment. Ammonium metavanadate then precipitates upon the addition of NH Cl and is calcined to give vanadium pentoxide of greater than 99.8% purity. 

Some properties of selected vanadium compounds are Hsted in Table 1. Detailed solubiUty data are available (3), as are physical constants of other vanadium compounds (4). Included are the lattice energy of several metavanadates and the magnetic susceptibiUty of vanadium bromides, chlorides, fluorides, oxides, and sulfides (5). 

Vanadium raw materials are processed to produce vanadium chemicals, eg, the pentoxide and ammonium metavanadate (AMV) primary compounds, by salt roasting or acid leaching. Interlocking circuits, in which unfinished or scavenged material from one process is diverted to the other, are sometimes used. Such interlocking to enhance vanadium recovery and product grade became more feasible in the late 1950s with the advent of solvent extraction. 

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 direct precipitation of vanadium from the salt-roast leach Hquor, acidulation to ca pH 1 without the addition of ammonia salts yields an impure vanadic acid when ammonium salts are added, ammonium polyvanadate precipitates. The impure vanadic acid ordinarily is redissolved in sodium carbonate solution, and ammonium metavanadate precipitates upon addition of ammonium salts. Fusion of the directly precipitated ammonium salts can yield high purity V20 for the chemical industry. Amine solvent extraction is sometimes used to recover 1—3 g/L of residual V20 from the directly precipitated tail Hquors. 

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). 

Dissolve 0.6 g anunonium monovanadate (ammonium metavanadate) in 22.5 ml water and carefully add 2.5 ml cone, sulfuric acid and 25 ml acetone. 

AMMO 2.5 EC , cypermetlu-in, 13 Ammonia, 13 Ammonium acetate, 13 Ammonium arsenate, 13 Ammonium benzoate, 13 Ammonium bicarbonate, 13 Ammonium bifluoride, 14 Ammonium bisulfite, 14 Ammonium carbamate, 14 Ammonium carbonate, 14 Ammonium chloride, 14 Ammonium chlorplatmate, 14 Ammonium clu omate, 14 Ammonium citrate, 14 Ammonium diclu omate, 14 Ammonium fluoride, 14 Ammonium fomiate, 15 Ammonium hexafluorosilicate, 15 Ammonium hydroxide, 15 Ammonium metavanadate, 15 Ammonium molybdate, 15 Ammonium nitrate, 15 Ammonium oxalate, 15 Ammonium perfluorooctanoate, 15 Ammonium persulfate, 15 Ammonium phosphate, 15 Ammonium picrate, 16 Ammonium salicylate, 16... 

In gas reforming plants, e.g. the hot potassium carbonate process for CO removal, sodium metavanadate is used to prevent mild-steel corrosion". Banks reports" that this treatment does not reduce the rather high corrosion rate of Cu-30Ni in these plants. 

Determination of vanadium as silver vanadate Discussion. Vanadates are precipitated by excess of silver nitrate solution in the presence of sodium acetate after boiling, the precipitate consists of silver orthovanadate. The following reactions occur with a solution of a metavanadate ... 

It has been stated that the results obtained by precipitation of vanadate as silver orthovanadate Ag3V04 are not altogether satisfactory. Better results are obtained by precipitation at pH 4.5 as silver metavanadate AgV03 the precipitate is weighed after drying at 100-105 °C. 

Sodium metavanadate (Na20 V205), having a MP of approximately 1165 °F (629 °C)... 

In this paper we report (i) the catalytic activity for SCR of VOx/Zr02 samples prepared by various methods (adsorption from aqueous metavanadate solutions at different pH values, dry impregnation, and adsorption from VO(acetylacetonate)2 in toluene), (ii) sample characterization (nuclearity, dispersion and oxidation state) by means of XPS, ESR and FTIR and (iii) the nature and reactivity of the surface species observed in the presence of the reactant mixture. Catalytic results are here reported in full. Characterization data relevant to the discussion of the catalytic activity will be given, whereas details on the catalysts preparation and... 

VOx/ZrOz samples were prepared by three methods (i) adsorption from a solution of ammonium metavanadate (AV) at pH values from 1 to 4, adjusted by nitric acid, (ii) dry impregnation with AV solutions and (iii) adsorption from a solution of VO(acetylacetonate)2 in toluene. 

In a.p. ZV(a) and ZV(i) samples, broad bands arising from hydrated vanadates were detected in the 800-1100 cm-i region. Metavanadate-like species (band at 920 cm i) prevailed on ZV samples with V-content < 1.5 atoms nm 2 and decavanadates (bands at 850-880 cm i and 960-990 cm- ) in the range 1.5-3 atoms nm 2. A.p. ZV(acac) samples showed bands from CH3 and C=0, suggesting the adsorption of VO(acac)2 as such (spectra not reported). 

Usually the nitric acid/amine interaction is more dangerous when impurities that can play a catalytic role are present. This goes for metal oxides such as copper oxides, iron (III) oxide and divanadium pentoxide. Salts such as sodium or ammonium metavanadates, iron trichloride, alkaline chromates and dichromates, cyanoferrates and alkaline or nitrosopentacyanoferrates can also act as catalysts. 

Sodium m-nitrobenzenesulphonate has been proposed as an oxidising agent for vat dyes. It is available as a proprietary product and is claimed to react with leuco compounds more quickly than does peroxide. The solubilised vat leuco esters are most commonly hydrolysed and reoxidised to the insoluble parent dye using sodium nitrite and sulphuric acid. Alternative oxidising agents for vat leuco esters include hydrogen peroxide and ammonium metavanadate (NH4VO3), persulphates and nitric acid [218]. 

The effect of inorganic additives upon ignition delay in anilinium nitrate-red finning nitric acid systems was examined. The insoluble compounds copper(I) chloride, potassium permanganate, sodium pentacyanonitrosylferrate and vanadium(V) oxide were moderately effective promoters, while the soluble ammonium or sodium metavanadates were very effective, producing vigorous ignition. 

The effects of various metal oxides and salts which promote ignition of amine-red fuming nitric acid systems were examined. Among soluble catalysts, copperQ oxide, ammonium metavanadate, sodium metavanadate, iron(III) chloride (and potassium hexacyanoferrate(II) with o-toluidine) are most effective. Of the insoluble materials, copper(II) oxide, iron(III) oxide, vanadium(V) oxide, potassium chromate, potassium dichromate, potassium hexacyanoferrate(III) and sodium pentacyanonitrosylferrate(II) were effective. 

Turpentine and fuming nitric acid do not ignite on contact in absence of added catalysts (fuming sulfuric acid, iron(III) chloride, ammonium metavanadate or copper(II) chloride). 

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