Cobalt refining

Cobalt. There is no U.S. mine production of cobalt. Refining of imported nickel—cobalt mattes has not occurred since the mid-1980s. About 1600 t of secondary cobalt was recycled from scrap by 13 faciUties in the United States representing - 22% of total U.S. consumption. The price of the metal was around 44/kg. Most is imported from Zaire and Zambia. Increasing quantities are coming from Russia. Historically, the price of cobalt has been quite volatile and dependent on the pohtical environment in those countries. Cobalt is used in superaHoys, 40% catalysts, 14% paint driers, 11% magnetic alloys, 10% and cemented carbides and other uses, 16%. 

Ono, N. Itasako, S. Fukui, I. Sumitomo s cobalt refining process. Proc. Int. Conf. Cobalt Metall. Uses 1981, 1, 63-71. 

Fittock, John E. (2007) Nickel and cobalt refining by QNi Pty Ltd, Yabulu, QLD in Monograph 19 — The Sir Maurice Mawby Memorial Vol 3rd Ed, Australian Institute of Mining and Metallurgy (Melbourne), p. 1-47... 

Germanium tetrachloride refined for use in making optical fibers is usually specified to contain less than 0.5 to 5 ppb of each of eight impurities vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc. Limits are sometimes specified for a few other elements. Also of concern are hydrogen-bearing impurities therefore, maximum limits of 5 to 10 ppm are usually placed on HCl, OH, CH2, and CH contents. 

Other Meta.Is, Although most cobalt is refined by chemical methods, some is electrorefined. Lead and tin are fire refined, but a better removal of impurities is achieved by electrorefining. Very high purity lead is produced by an electrochemical process using a fluosiUcate electrolyte. A sulfate bath is used for purifying tin. Silver is produced mainly by electrorefining in a nitrate electrolyte, and gold is refined by chemical methods or by electrolysis in a chloride bath. 

Ca.rbonylProcess. Cmde nickel also can be refined to very pure nickel by the carbonyl process. The cmde nickel and carbon monoxide (qv) react at ca 100°C to form nickel carbonyl [13463-39-3] Ni(CO)4, which upon further heating to ca 200—300°C, decomposes to nickel metal and carbon monoxide. The process is highly selective because, under the operating conditions of temperature and atmospheric pressure, carbonyls of other elements that are present, eg, iron and cobalt, are not readily formed. 

HydrometallurgicalProcesses. HydrometaHurgical refining also is used to extract nickel from sulfide ores. Sulfide concentrates can be leached with ammonia (qv) to dissolve the nickel, copper, and cobalt sulfides as amines. The solution is heated to precipitate copper, and the nickel and cobalt solution is oxidized to sulfate and reduced, using hydrogen at a high temperature and pressure to precipitate the nickel and cobalt. The nickel is deposited as a 99 wt % pure powder. 

Pressure-acid leaching was used to extract cobalt from Blackbird mine ores before its closing in 1974. The result was a very fine cobalt powder which was subjected to a seeding process to produce cobalt granules. Leaching methods are also used in the refinement of lateritic ores. 

During World War II German scientists developed a method of hydrogenating soHd fuels to remove the sulfur by using a cobalt catalyst (see Coal CONVERSION processes). Subsequently, various American oil refining companies used the process in the hydrocracking of cmde fuels (see CATALYSIS SuLFUR REMOVAL AND RECOVERY). Cobalt catalysts are also used in the Fisher-Tropsch method of synthesizing Hquid fuels (21—23) (see Fuels, synthetic). 

An obvious refinement of the simple theory for cobalt and nickel and their alloys can be made which leads to a significant increase in the calculated value of the Curie temperature. The foregoing calculation for nickel, for example, is based upon the assumption that the uncoupled valence electrons spend equal amounts of time on the nickel atoms with / = 1 and the nickel atoms with J = 0. However, the stabilizing interaction of the spins of the valence electrons and the parallel atomic moments would cause an increase in the wave function for the valence electrons in the neighborhood of the atoms with / = 1 and the parallel orientation. This effect also produces a change in the shape of the curve of saturation magnetization as a function of temperature. The details of this refined theory will be published later. 

As at room temperature Bragg reflections contain both nuclear and magnetic structure factors, the nuclear structure was refined from a combination of polarized and unpolarized neutron data. Contrary to the ideal structure where only three atomic sites are present, it has been shown [11, 12] that some Y atoms were substituted by pairs of cobalt. These pairs, parallel to the c-axis are responsible for a structure deformation which shrinks the cobalt hexagons surrounding the substitutions. The amount of these substituted Y was refined to be 0.046 0.008. Furthermore, the thermal vibration parameter of Coi site appeared to be very anisotropic. The nuclear structure factors Fn were calculated from this refined structure and were introduced in the polarized neutron data to get the magnetic structure factors Fu. 

Chalkley, M. E. Toirac, I. L. The acid pressure leach process for nickel and cobalt laterite. Part I review of operations at Moa. Hydrometallurgy and Refining of Nickel and Cohalt, Annual Hydrometallurgy Meeting of CIM, 27th, Sudbury, Ont., Aug. 17-20, 1997, 341-353. 

Char formation and reduced monomer production are observed for all of these additives upon reaction with PMMA. Char formation increases as a function of temperature, for the hydrido cobalt compound, there is 5% char at 262°, 8.5% at 322°, 15% at 338°, and 19% at 375°C the cobalt(lll) cyanide produces 3% char at 338° and 11% at 375°C the cobalt(ll) cyanide yields 11% char at 375°C. At the highest temperature, 375°C, the amount of monomer formation is 22% for K3Co(CN)5, 11% for K3Co(CN)6, and 10% for HCo[P(OPh)3]4. Ideally one would hope to observe no monomer formation and complete char production. Such is not the case here, these materials probably have no utility as flame retardant additives for PMMA since monomer formation, even at a reduced level, will still permit a propagation of the burning process. While somewhat positive results for these three additives do not prove the validity of the hypothesis, we take this to be a starting point in our search for suitable additives, further work is underway to refine the hypothesis and to identify other potential hydrogenation catalysts and other additives that may prove useful as flame retardants for PMMA... 

The need to include a variety of minerals in experimental diets has already been mentioned this was especially stressed (1920-1930) by Boyd-Orr, the director of the Rowett Institute for Animal Nutrition in Scotland. Increasingly refined food sources led to the identification of large numbers of trace elements (e.g., Cu, Mn, Mo, Zn) whose importance in the diet was suggested from hydroponic experiments with plant seedlings. Cobalt is an example of such a trace element. Vitamin Bj2 is synthesized by bacteria in the rumens of sheep and cattle but is absent from their fodder. In Australia, sheep feeding on cobalt-deficient pastures failed to thrive because vitamin B12 could no longer be made. 

Cobalt is also found in seawater, meteorites, and other ores such as linnaeite, chloanthite, and smaltite, and traces are found mixed with the ores of silver, copper, nickel, zinc, and manganese. Cobalt ores are found in Canada and parts of Africa, but most of the cobalt used in the United States is recovered as a by-product of the mining, smelting, and refining of the ores of iron, nickel, lead, copper, and zinc. 

Two other refining processes are also frequently employed. One involves hydrometallurgical refining in which sulfide concentrates are leached with ammonia solution to convert the copper, nickel, and cobalt sulfides into their complex amines. Copper is precipitated from this solution upon heating. Under such conditions, the sulfide-amine mixture of nickel and cobalt are oxidized to their sulfates. The sulfates then are reduced to metalhc nickel and cobalt by heating with hydrogen at elevated temperatures under pressure. The metals are obtained in their powder form. 

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