vanadium processing

Introduction

      preparation of the metal for use in various products.

      Vanadium (V) is a grayish silver metal whose crystal structure is a body-centred cubic (bcc) lattice, with a melting point of 1,926° C (3,499° F). The metal is used principally as an alloying addition to high-strength low-alloy (HSLA) steels and, to a lesser extent, in tool steels and iron and steel castings. It is also an important strengthener for titanium alloys. Vanadium alloys are promising candidates for applications in nuclear reactors. The metal is recognized as an industrial hazard, however, as breathing of particulate material with a high vanadium content has been observed to cause an intense, dry cough accompanied by irritation of the nose, eyes, and throat.

History

      The discovery of vanadium was first claimed in 1801 by a Spanish mineralogist, Andrés Manuel del Río, who gave it the name erythronium, after the red colour of one of its chemical compounds (Greek erythros, “red”). In 1830 a Swedish chemist, Nils Gabriel Sefström, rediscovered the element and named it vanadium, after Vanadis, the Scandinavian goddess of beauty, because of the beautiful colours of its compounds in solution. The English chemist Henry Enfield Roscoe first isolated the metal by hydrogen reduction of vanadium dichloride in 1867, and the American chemists John Wesley Marden and Malcolm N. Rich obtained vanadium of 99.7 percent purity by a calcium reduction process in 1925.

      Since the early 1900s, vanadium has been used as an alloying element for steels and iron. In 1905 Antenor Riza Patron discovered a large asphaltite deposit containing rich vanadium ores in Mina Ragra, Peru. Two years later, the American Vanadium Company produced ferrovanadium on a commercial scale for the first time. After titanium became an aerospace construction material in the 1950s, vanadium saw wide use in titanium alloys.

Ores

      The important vanadium minerals are patronite (VS₄), carnotite [K₂(UO₂)₂(VO₄)₂], and vanadinite, [Pb₅(VO₄)₃Cl]. Ore deposits mined solely for vanadium are rare because much of the vanadium in igneous rocks occurs in the relatively insoluble trivalent state, substituting for ferric iron in ferromagnesium silicates, magnetite (an iron ore), ilmenite (a titanium ore), and chromite.

      The world's largest mines of vanadium are from titaniferous magnetite reserves in such regions as the Bushveld of South Africa, the Kachkanar Massif of the Ural Mountains, and China's Szechwan province. Carnotite ores in the sandstones of the Colorado Plateau have been mined for vanadium and uranium. Other sources of vanadium include ash from the combustion of fossil fuel, slag from phosphate ore, the aluminum ore bauxite, and spent catalysts.

Mining

      Because vanadium is essentially the by-product of ores that are mined for other minerals, they are mined by methods peculiar to those ores.

Extraction and refining

Vanadium pentoxide

      Titaniferous magnetite ore is partially reduced with coal in rotary kilns and then melted in a furnace. This produces a slag containing most of the titanium and a pig iron containing most of the vanadium. After removing the slag, the molten pig iron is blown with oxygen to form a new slag containing 12–24 percent vanadium pentoxide (V₂O₅), which is used in the further processing of the metal.

      Vanadium is extracted from carnotite as a coproduct with uranium by leaching the ore concentrate for 24 hours with hot sulfuric acid and an oxidant such as sodium chlorate. After removal of solids, the leachate is fed into a solvent extraction circuit where the uranium is extracted in an organic solvent consisting of 2.5-percent-amine–2.5-percent-isodecanol–95-percent-kerosene. Vanadium remains in the raffinate, which is fed into a second solvent extraction circuit. There vanadium in turn is extracted in the organic phase, stripped with a 10 percent soda ash solution, and precipitated with ammonium sulfate. The ammonium metavanadate precipitate is filtered, dried, and calcined to V₂O₅.

      Most other vanadium-bearing ores or slags are crushed, ground, screened, and mixed with a sodium salt such as sodium chloride or sodium carbonate. This charge is then roasted at about 850° C (1,550° F) to convert the oxides to sodium metavanadate, which can be leached in hot water. With the acidulation of the leachate with sulfuric acid, the vanadium is precipitated as sodium hexavanadate. This compound, known as red cake, can be fused at 700° C (1,300° F) to yield technical-grade vanadium pentoxide (at least 86 percent V₂O₅, or it can be further purified by dissolving it in an aqueous solution of sodium carbonate. In the latter case, the iron, aluminum, and silicon impurities in the red cake precipitate from solution upon adjustment of the acidity. The vanadium is precipitated as ammonium metavanadate by adding ammonium chloride. After filtration, the precipitate is calcined to produce V₂O₅ of a purity greater than 99.8 percent.

Ferrovanadium

      The production of ferrovanadium, containing 35–80 percent vanadium, is carried out in an electric-arc furnace. Scrap iron is first melted, and a mixture of V₂O₅, aluminum, and a flux such as calcium fluoride or calcium oxide is added. In the ensuing reaction, the aluminum metal is converted to alumina, forming a slag, and the V₂O₅ is reduced to vanadium metal, which is dissolved in the molten iron. Since this oxidation-reduction reaction is exothermic, the heat supply need only develop the kindling temperature of 950° C (1,750° F). After kindling, the electrodes are withdrawn until the reaction is completed; they are then reinserted into the molten slag and the furnace reheated to improve settling.

      The aluminothermic process can also be carried out in a refractory-lined steel pot or water-cooled copper crucible. A charge of V₂O₅, iron oxide, and aluminum is ignited with a barium-peroxide fuse or a magnesium ribbon.

Vanadium metal

      In the production of pure metal, V₂O₅ is reduced metallothermically by calcium or aluminum. In the calcium reduction, the exothermic reaction is carried out in a sealed vessel using calcium chloride as a flux. The vanadium metal is recovered in the form of droplets or beads. (A massive regulus can be obtained by using iodine as both a flux and a thermal booster.) The calcium process requires a rather large amount of reductant and gives low metal yields—in the range of 75–80 percent. In the aluminothermic process, V₂0₅, mixed with aluminum powder, is heated in an electric furnace or ignited in a refractory-lined vessel using barium peroxide as the booster. The vanadium regulus thus obtained may be further purified by electron-beam melting.

      To prepare aluminum-vanadium master alloys for the titanium industry, the aluminothermic method is also used. In this case, an amount of aluminum greater than that required for reduction is added to the charge.

The metal and its alloys

      In its pure form, vanadium is soft and ductile. It can be fabricated into mill forms, but it oxidizes readily at temperatures above 663° C (1,225° F) and is liable to pick up interstitial impurities. Because the metal has good corrosion resistance to liquid metal, a low absorption of neutrons, and a short half-life in its radioactive isotopic forms, vanadium-based alloys have potential as structural materials for fusion and liquid-metal fast-breeder fission reactors.

Iron and steel

      The addition of small amounts of vanadium (less than 0.2 percent) to structural steels improves their toughness, ductility, and strength owing to the grain-refining effect of vanadium carbide precipitates. These HSLA steels are used in automotive components, such as hoods and door panels, and in oil and gas pipelines.

      Almost all tool steels contain vanadium in amounts ranging from 0.10 to 5 percent. It is required to ensure the retention of hardness and cutting ability at high temperatures.

      In some cast irons (iron processing), the addition of a small amount of vanadium controls the size and distribution of graphite flakes, thereby improving strength and wear resistance. Steel castings with vanadium additions also exhibit pronounced shock and wear resistance, which makes them useful in heavy-duty equipment and machinery.

titanium

      Vanadium improves the strength of titanium alloys and promotes their thermal stability. Several important commercial titanium alloys contain between 2.5 and 15 percent vanadium. They are used in the undercarriages, wings, and engines of jet aircraft.

Chemical compounds

Catalysts (catalyst)

      Vanadium is used in the contact process for the manufacture of sulfuric acid. In this process, sulfur dioxide is oxidized to a trioxide by exposure to air in the presence of granular V₂O₅ or sodium metavanadate. Vanadium oxytrichloride and vanadium tetrachloride are catalysts in the production of special types of synthetic rubber. Ammonium metavanadate is employed as a catalyst for the synthesis of organic intermediates of nylon, polyester resins, and other synthetics, and it has also been used as a catalyst in the dyeing (dye) of leather and fur.

Pigments (pigment)

      In dye manufacturing, vanadium compounds are used in the production of aniline black. They are also employed as mordants in the dyeing and printing of cotton and for fixing aniline black on silk. Some modern quick-drying inks depend on the addition of ammonium metavanadate for their performance. Vanadium compounds are used in the ceramics industry for glazes and enamels.

Chun Tsin Wang

Additional Reading

Comprehensive and up-to-date information on many aspects of metallurgy, individual metals, and alloys can be found in convenient reference-form arrangement in the following works: Metals Handbook, 9th ed., 17 vol. (1978–89), a massive and detailed source prepared under the direction of the American Society for Metals, with a 10th edition that began publication in 1990; Herman F. Mark et al. (eds.), Encyclopedia of Chemical Technology, 3rd ed., 31 vol. (1978–84), formerly known as Kirk-Othmer Encyclopedia of Chemical Technology, with a 4th edition begun in 1991; and its European counterpart, the first English-language edition of a monumental German work, Ullmann's Encyclopedia of Industrial Chemistry, 5th, completely rev. ed., edited by Wolfgang Gerhartz et al. (1985– ). Ed. H.Y. Sohn, O. Norman Carlson, and J. Thomas Smith (eds.), Extractive Metallurgy of Refractory Metals: Proceedings of a Symposium (1980), gathers together informative papers, with an in-depth treatment of the extraction and reduction processes of vanadium. A convenient single source of reference information on all the refractory metals is Clifford A. Hampel, Rare Metals Handbook, 2nd ed. (1961, reprinted 1971).Chun Tsin Wang Alexander Sutulov

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