cobalt processing

Introduction

      preparation of the metal for use in various products.

      Below 417° C (783° F), cobalt (Co) has a stable hexagonal close-packed crystal structure. At higher temperatures up to the melting point of 1,495° C (2,723° F), the stable form is face-centred cubic. The metal has 12 radioactive isotopes, none of which occurs naturally. The best-known is cobalt-60, which has a half-life of 5.3 years and is used in medicine and industry.

      Of the three common ferromagnetic metals (iron, nickel, and cobalt), cobalt has the highest Curie point (that is, the temperature above which its magnetic properties are weakened). It is unique in that, added in moderate amounts to iron, it raises that metal's saturation magnetization (the limit to which its magnetic properties can be raised). Magnetic alloys form the most important use of cobalt.

      The second most important cobalt outlet is in the making of high-temperature alloys, in which it improves the high-temperature strength and corrosion resistance of alloys based on more common metals, especially nickel and chromium.

History

      Ores containing cobalt have been used since antiquity as pigments (pigment) to impart a blue colour to porcelain and glass. It was not until 1742, however, that a Swedish chemist, Georg Brandt (Brandt, Georg), showed that the blue colour was due to a previously unidentified metal, cobalt.

      In 1874 the output of cobalt from European deposits was surpassed by production in New Caledonia; in about 1905, Canadian ores assumed the leadership. Since 1920 the dominant world producer has been Congo (Kinshasa) (Congo). Other important producers are Russia, Zambia, Australia, Canada, Finland, Cuba, and Germany.

      Prior to World War I, most of the world's production of cobalt was consumed in the ceramic and glass industries. The cobalt, in the form of cobalt oxide, served as a colouring agent. Since that time, increasing amounts have been used in magnetic and high-temperature alloys and in other metallurgical applications; about 80 percent of the output is now employed in the metallic state.

Ores

      Nearly all cobalt is found associated with ores of copper, nickel, or copper-nickel.

      In the copper-cobalt ore bodies of central Africa and Russia, cobalt occurs as sulfides (sulfide mineral) (carrollite, linnaeite, or siegenite), the oxide minerals heterogenite (hydrated cobalt oxide) and asbolite (a mixture of manganese and cobalt oxides), and the carbonate sphaerocobaltite. In the copper-nickel-iron sulfide mines of Canada, Australia, Russia, and other regions, cobalt is present in place of nickel in many minerals.

      Cobalt arsenides (arsenide), such as smaltite, safflorite, and skutterudite, with the sulfoarsenide cobaltite and the arsenate (arsenate mineral) erythrite, are mined in Morocco and on a much smaller scale in many other countries. These are the only primary cobalt ores.

      Huge nickel-containing deposits found in New Caledonia, Cuba, Celebes (Indonesia), and other regions contain a small quantity of cobalt in the form of oxide minerals, such as asbolite.

      A few pyrite (iron disulfide) deposits mined for their sulfur content contain enough cobalt to warrant the extraction of the latter from the roasted residue. Cobalt sulfides occasionally occur in lead-zinc deposits in quantities sufficient to justify their recovery.

Mineral processing

      The most important sulfide sources, the copper-cobalt ores of Congo (Kinshasa) and Zambia, are processed in the conventional manner to produce a copper-cobalt concentrate. This is then treated by flotation to separate a cobalt-rich concentrate for treatment in the cobalt circuit. Separation flotation utilizes pneumatic and mechanical agitation to produce air bubbles that carry the mineral particles to the surface. Different reagents are used to attract the cobalt minerals to the bubbles in preference to copper. Cobalt concentrates, which can contain as much as 15 percent cobalt, are then processed further, using either pyrometallurgical or hydrometallurgical extractive processes.

Extraction and refining

From copper and nickel processing

      Cobalt contained in and smelted with copper concentrate is oxidized along with iron during the final conversion to blister copper. It then enters the slag layer, which can be treated separately, usually in an electric furnace, and the cobalt recovered by reduction with carbon to a copper-iron-cobalt alloy. In nickel smelting, most of the cobalt is recovered during electrolytic refining of the nickel by precipitation from solution, usually as a cobaltic hydroxide. But even in nickel smelting, cobalt starts to oxidize before the nickel and can be recovered from the final converter slag. In the ammonia pressure leaching of nickel, cobalt is recovered from solution by reduction with hydrogen under pressure. In refineries using a chloride leach for nickel matte, solvent extraction is used to remove cobalt directly from the pregnant solution. The resulting concentrated solution, after some purification, is suitable for the recovery of cobalt by electrowinning.

From ores

      For copper-cobalt ores, a sulfide concentrate is roasted under controlled conditions to transform most of the cobalt sulfide to a soluble sulfate while minimizing the change of copper and iron to their water-soluble states. The product is leached, the resulting solution is treated to remove copper and iron, and the cobalt is finally recovered by electrolysis. If the copper and cobalt ores are in the oxidized state, copper can be removed by electrolysis in sulfuric acid solution and the cobalt precipitated from the spent electrolyte by adjustment of the acidity of the solution. Cobalt is again eventually obtained in the metallic state by electrolysis.

      Cobalt concentrates from arsenide ores may be roasted in the same manner as sulfide concentrates in order to remove the arsenic as an impure arsenic trioxide. Alternatively, they can be leached and cobalt precipitated with hydrogen, as with nickel sulfide concentrates.

The metal and its alloys

Cemented carbides

      In the production of a so-called cemented carbide, such as tungsten carbide, a briquetted mixture of tungsten carbide and cobalt powder is heated at a temperature above the melting point of cobalt. The latter melts and binds the hard carbides, giving them the toughness and shock resistance needed to make carbides of practical value for machine tools, drill bits, dies, and saws. Cobalt is the most satisfactory matrix metal for this purpose and may be present in amounts from 3 to 25 percent by weight.

Cobalt-60

      A radioactive (radioactive isotope) form of cobalt, cobalt-60, prepared by exposing cobalt to the radiations of an atomic pile, is useful in industry and medical science. Cobalt-60 is used in place of X rays or radium in the inspection of materials to reveal internal structure, flaws, or foreign objects. It is used in cancer therapy and as a radioactive tracer in biology and industry. The advantages of cobalt-60 over radium lie in lower cost, more homogeneous gamma radiation and softer beta radiation, which can be easily filtered out in the absence of contamination, and its ability to be machined or shaped in any form before irradiation to fit special requirements.

Magnetic alloys (alloy)

      About 25 percent of the world's cobalt output goes into magnets (magnetism). The best permanent magnets contain a substantial quantity of cobalt.

      Cobalt steels, containing 2–40 percent cobalt, are used extensively as magnets. Iron-cobalt-vanadium alloys, such as the so-called Vicalloys, are employed for ductile permanent magnets, as are the Cunicos—i.e., alloys of copper, nickel, and cobalt. Another magnet alloy is iron-cobalt-molybdenum, typified by Remalloy or Comol.

      Since 1930 it has been known that a series of alloys, the Alnicos, containing 6–12 percent aluminum, 14–30 percent nickel, 5–35 percent cobalt, and the balance largely iron, with small quantities of copper and titanium, make the best permanent magnets. Cobalt is also used in some soft magnetic alloys such as the Perminvar alloys of nickel-iron-cobalt, the Permendur alloys of iron-cobalt, and the cobalt ferrites. Nearly all these alloys are used in electrical equipment and electronic devices.

      The alloying of rare-earth metals, in particular samarium and praseodymium, with 60–65 percent cobalt results in a range of high-coercivity, fine-powder magnets. These alloys are particularly suited for applications, such as electronics, that require small magnets with precise dimensions and characteristics.

High-temperature alloys

      An important use for cobalt is in the field of high-temperature steel alloys. Required in gas turbines, jet engines, and similar applications, such alloys retain their strength above 650° C (1,200° F); these alloys contain from 5 to 65 percent cobalt.

      Even higher operating temperatures in turbines have resulted in an increased use of cobalt-containing and cobalt-based alloys known generally as superalloys. These can withstand severe operating conditions and temperatures up to 1,150° C (2,100° F). Nimonic 90, for example, is a nickel-based alloy containing 18 percent cobalt, a similar amount of chromium, and some titanium. Waspaloy is another alloy of this type.

Cutting and wear-resistant alloys

      The addition of 2–12 percent cobalt to tool steels enables them to be used more effectively on hard materials for which deep cuts and high speeds are required.

      Cobalt improves the wear resistance of many alloys. Hard-facing materials contain 10–65 percent cobalt, and abrasion-resistant die steels usually have 0.4–4 percent cobalt.

Glass-to-metal sealing alloys

      Alloys, such as Kovar and Fernico, containing 15–25 percent cobalt, are used extensively in glass-to-metal seals because they have expansion characteristics similar to those of certain glasses.

Dental and surgical alloys

      Materials containing 28–68 percent cobalt, with chromium, nickel, and molybdenum, are used in dentistry and bone surgery. They have excellent resistance to tarnish and abrasion, compatibility with mouth tissues and body fluids, high strength and stiffness, good casting properties, and low cost in comparison with precious metals.

electroplating

      For certain applications requiring smooth, bright films that are hard but relatively ductile, an alloy of cobalt-nickel is deposited instead of the conventional nickel-plating. The plating alloy may contain 1–18 percent cobalt, and the electrolyte contains both cobalt and nickel salts.

Other alloys

      Cobalt-based alloys having 40–50 percent cobalt are often used as springs. Beryllium copper, used for a multitude of applications besides springs, generally contains 0.1–2 percent cobalt.

      An alloy of 54 percent cobalt, 9.5 percent chromium, and 36.5 percent iron changes dimensions very little with changes in temperature. Cobalt-based alloys of 56–63 percent cobalt, with iron and chromium or vanadium, have the advantage in certain applications of very little variation in elasticity regardless of temperature.

      Another alloy, a stainless steel containing 18 percent nickel and 8 percent cobalt, also has some industrial applications.

Important cobalt compounds

Cobalt oxide

      This substance, usually prepared by heating the cobaltic hydroxide that is precipitated from cobalt-containing solutions by sodium hypochlorite, has a number of important uses in the glass and ceramics industries.

      Cobalt oxide additions of 140 to 4,500 grams (5 ounces to 10 pounds) per ton of glass are made to impart a blue colour to structural glass, bottles, and optical filter glasses. To neutralize the yellow tint of iron in plate and window glass, small quantities of cobalt oxide, 1 to 45 grams (0.04 to 1.6 ounces) per ton of glass, are added. In the proportion of about 454 grams (1 pound) per ton of dry clay, cobalt oxide is also employed to neutralize the iron colour in pottery, sanitary ware, and tiles, and in larger quantities to add blue colour. A rich blue is obtained by adding 5 percent cobalt oxide to a glaze of high lead content. Thenard's blue, a turquoise, is characteristic of cobalt aluminate, whereas cobalt silicate gives a unique violet-blue shade. Cobalt oxide in white enamels neutralizes yellow caused by iron; larger amounts give a blue or black colour. In quantities of 0.2–2 percent this compound, used in enamel coats on steel, promotes adherence of the enamel to the metal.

Cobalt salts

      Cobalt salts are usually made by the action of the appropriate acid on cobalt metal or oxide. A number of cobalt salts, particularly organic compounds, are excellent driers of paints, varnishes, and inks. Cobalt linoleates, resinates, oleates, stearates, tallates, and naphthenates, containing 4–12 percent cobalt, are employed.

      Cobalt, usually in the form of a cobalt-thoria-kieselguhr catalyst, is used in the synthesis of liquid hydrocarbons. Many other cobalt catalysts have been used for a wide variety of chemical reactions.

      In many parts of the world, the content of cobalt in the soil and herbage is too low to maintain the health of cattle and sheep. The addition of a small quantity of a cobalt compound to the ration, water, salt lick, or fertilizer has become a well-established practice.

      Vitamin (vitamin B12) B₁₂ contains 4.3 percent cobalt; it is the only vitamin known to contain a heavy metal.

Roland S. Young John Campbell Taylor

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.Cobalt Monograph (1960), prepared by the Centre d'Information du Cobalt in Brussels in collaboration with the Battelle Memorial Institute in Columbus, Ohio, remains a valuable comprehensive source dedicated specifically to cobalt, covering all aspects of cobalt processing as well as its chemistry and physical, mechanical, and thermodynamic properties. W. Betteridge, Cobalt and Its Alloys (1982), in summarizing the occurrence and extraction of cobalt and in providing data on the properties and applications of cobalt, cobalt alloys, and cobalt compounds, is an ideal update and supplement to the older Cobalt Monograph. Joseph R. Boldt, Jr., The Winning of Nickel: Its Geology, Mining, and Extractive Metallurgy (1967), covers geology, mining, mineral processing, and extractive metallurgy of nickel and associated metals such as copper and cobalt. Boldt's work can be updated, but not replaced, by G.P. Tyroler and C.A. Landolt (eds.), Extractive Metallurgy of Nickel & Cobalt (1988), which collects symposium papers on the latest developments in mineral processing, hydrometallurgy and pyrometallurgy, nickel-cobalt health effects, and particular plant operations. John Campbell Taylor

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