Cobalt and Nickel

Nickel and Cobalt. Often present with copper in sulfuric acid leach Hquors are nickel [7440-02-0] and cobalt [7440-48-4]. Extraction using an organophosphoric acid such as D2EHPA at a moderate (3 to 4) pH can readily take out the nickel and cobalt together, leaving the copper in the aqueous phase, but the cobalt—nickel separation is more difficult (274). In the case of chloride leach Hquors, separation of cobalt from nickel is inherently simpler because cobalt, unlike nickel, has a strong tendency to form anionic chloro-complexes. Thus cobalt can be separated by amine extractants, provided the chloride content of the aqueous phase is carefully controUed. A successhil example of this approach is the Falcon-bridge process developed in Norway (274). 

Goal Upgrading via Fischer-Tropsch. The synthesis of methane by the catalytic reduction of carbon monoxide and hydrogen over nickel and cobalt catalysts at atmospheric pressure was reported in 1902 (11). 

Density is a particularly important characteristic of alloys used in rotating machinery, because centrifugal stresses increase with density. Densities of the various metals in Table 1 range from 6.1 to 19.3 g/cm. Those of iron, nickel, and cobalt-base superaHoys fall in the range 7-8.5 g/cm. Those alloys which contain the heavier elements, ie, molybdenum, tantalum, or tungsten, have correspondingly high densities. 

Appllca.tlons. The principal appHcations of nickel-base superalloys are in gas turbines, where they are utilized as blades, disks, and sheet metal parts. Abcraft gas turbines utilized in both commercial and military service depend upon superalloys for parts exposed to peak metal temperatures in excess of 1000°C. Typical gas turbine engines produced in the United States in 1990 utilized nickel and cobalt-base superalloys for 46% of total engine weight (41). However, programs for future aerospace propulsion systems emphasize the need for lightweight materials having greater heat resistance. For such apphcations, intermetallics matrix composites and ceramic composites are expected to be needed. 

Table 13 is a representative Hst of nickel and cobalt-base eutectics for which mechanical properties data are available. In most eutectics the matrix phase is ductile and the reinforcement is britde or semibritde, but this is not invariably so. The strongest of the aHoys Hsted in Table 13 exhibit ultimate tensile strengths of 1300—1550 MPa. Appreciable ductiHty can be attained in many fibrous eutectics even when the fibers themselves are quite britde. However, some lamellar eutectics, notably y/y —5, reveal Htde plastic deformation prior to fracture. 

Nickel and cobalt are recovered by processes that employ both pressure leaching and precipitation steps. The raw materials for these processes can be sulfide concentrates, matte, arsenide concentrates, and precipitated sulfides. Typically, acidic conditions are used for leaching however, ammonia is also effective in leach solutions because of the tendency for soluble cobalt and nickel ammines to form under the leach conditions. 

Gas Reduction. The use of a gaseous reduciag agent is attractive because the metal is produced as a powder that can easily be separated from the solution. Carbon dioxide, sulfur dioxide, and hydrogen can be used to precipitate copper, nickel, and cobalt, but only hydrogen reduction is appHed on an iadustrial scale. In the Sherritt-Gordon process, the excess ammonia is removed duting the purification to achieve a 2 1 ratio of NH iNi ia solution. Nickel powder is then precipitated by... 

Fig. 5. Flow sheet foi Sheiiitt-Goidon process for production of nickel and cobalt metals from sulfide ore.

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. 

In the acid-leaching process, the oxide ore is leached with sulfuric acid at elevated temperature and pressure, which causes nickel, but not iron, to enter into solution. The leach solution is purified, foHowed by reaction with hydrogen sulfide and subsequent precipitation of nickel and cobalt sulfides. 

G. P. Tyroler and C. A. Landolt, Txtractive Metallurgy of Nickel and Cobalt, The Metallurgical Society, Inc., Warrendale, Pa., 1988. 

The electro deposition of tungsten aUoys of iron, nickel, and cobalt is commercially feasible but has remained largely experimental. The properties of these aUoys should, however, be of sufficient interest for engineering appHcations. 

Ref 2. The brazing filler metal is analyzed for those specific elements for which values are shown. If the presence of other elements is the amount of those elements is deterrnined to ensure that the maximum total of each is <0.15 wt%. Remainder of material is Cu. Value represents maximum. Remainder of material is Mn. Table 7. Chemical Composition Requirements for Nickel and Cobalt Filler Metals indicated in the analysis. ... 

At room temperature, sulfur unites readily with copper, silver, and mercury and vigorously with sodium, potassium, calcium, strontium, and barium to form sulfides. Iron, chromium, tungsten, nickel, and cobalt react much less readily. In a finely divided state, zinc, tin, iron, and aluminum react with sulfur on heating (19). 

In metallurgy, hydrogen sulfide is used to precipitate copper sulfide from nickel—copper-containing ore leach solutions in Alberta, Canada, or to precipitate nickel and cobalt sulfides from sulfuric acid leaching oflaterite ores in Moa Bay, Cuba (120) (see Metallurgy, extractive metallurgy). 

Titanium alloy systems have been extensively studied. A single company evaluated over 3000 compositions in eight years (Rem-Cm sponsored work at BatteUe Memorial Institute). AHoy development has been aimed at elevated-temperature aerospace appHcations, strength for stmctural appHcations, biocompatibiHty, and corrosion resistance. The original effort has been in aerospace appHcations to replace nickel- and cobalt-base alloys in the 250—600°C range. The useful strength and corrosion-resistance temperature limit is ca 550°C. 

The important (3-stabilizing alloying elements are the bcc elements vanadium, molybdenum, tantalum, and niobium of the P-isomorphous type and manganese, iron, chromium, cobalt, nickel, copper, and siUcon of the P-eutectoid type. The P eutectoid elements, arranged in order of increasing tendency to form compounds, are shown in Table 7. The elements copper, siUcon, nickel, and cobalt are termed active eutectoid formers because of a rapid decomposition of P to a and a compound. The other elements in Table 7 are sluggish in their eutectoid reactions and thus it is possible to avoid compound formation by careful control of heat treatment and composition. The relative P-stabilizing effects of these elements can be expressed in the form of a molybdenum equivalency. Mo (29) ... 

Assay of beryUium metal and beryUium compounds is usuaUy accompHshed by titration. The sample is dissolved in sulfuric acid. Solution pH is adjusted to 8.5 using sodium hydroxide. The beryUium hydroxide precipitate is redissolved by addition of excess sodium fluoride. Liberated hydroxide is titrated with sulfuric acid. The beryUium content of the sample is calculated from the titration volume. Standards containing known beryUium concentrations must be analyzed along with the samples, as complexation of beryUium by fluoride is not quantitative. Titration rate and hold times ate critical therefore use of an automatic titrator is recommended. Other fluotide-complexing elements such as aluminum, sUicon, zirconium, hafnium, uranium, thorium, and rate earth elements must be absent, or must be corrected for if present in smaU amounts. Copper-beryUium and nickel—beryUium aUoys can be analyzed by titration if the beryUium is first separated from copper, nickel, and cobalt by ammonium hydroxide precipitation (15,16). 

I. G. Wright, Oxidation of Iron-, Nickel-, and Cobalt-Base Alloys, MCIC Report 72-07, BatteUe-Columbus Laboratories, BatteUe Memorial Institute, 1972. 

Future Sources. Lateritic ores (7) are becoming increasingly important as a source of nickel, and cobalt is a by-product. In the United States, laterites are found in Minnesota, California, Oregon, and Washington. Deposits also occur in Cuba, Indonesia, New Caledonia, the Philippines, Venezuela, Guatemala, AustraUa, Canada, and Russia (see Nickel and nickel alloys). 

Lateritic Ores. The process used at the Nicaro plant in Cuba requires that the dried ore be roasted in a reducing atmosphere of carbon monoxide at 760°C for 90 minutes. The reduced ore is cooled and discharged into an ammoniacal leaching solution. Nickel and cobalt are held in solution until the soflds are precipitated. The solution is then thickened, filtered, and steam heated to eliminate the ammonia. Nickel and cobalt are precipitated from solution as carbonates and sulfates. This method (8) has several disadvantages (/) a relatively high reduction temperature and a long reaction time (2) formation of nickel oxides (J) a low recovery of nickel and the contamination of nickel with cobalt and (4) low cobalt recovery. Modifications to this process have been proposed but all include the undesirable high 760°C reduction temperature (9). 

A similar process has been devised by the U.S. Bureau of Mines (8) for extraction of nickel and cobalt from United States laterites. The reduction temperature is lowered to 525°C and the hoi ding time for the reaction is 15 minutes. An ammoniacal leach is also employed, but oxidation is controlled, resulting in high extraction of nickel and cobalt into solution. Mixers and settlers are added to separate and concentrate the metals in solution. Organic strippers are used to selectively remove the metals from the solution. The metals are then removed from the strippers. In the case of cobalt, spent cobalt electrolyte is used to separate the metal-containing solution and the stripper. MetaUic cobalt is then recovered by electrolysis from the solution. Using this method, 92.7 wt % nickel and 91.4 wt % cobalt have been economically extracted from domestic laterites containing 0.73 wt % nickel and 0.2 wt % cobalt (8). 

Metals in the platinum family are recognized for their ability to promote combustion at lowtemperatures. Other catalysts include various oxides of copper, chromium, vanadium, nickel, and cobalt. These catalysts are subject to poisoning, particularly from halogens, halogen and sulfur compounds, zinc, arsenic, lead, mercury, and particulates. It is therefore important that catalyst surfaces be clean and active to ensure optimum performance. 

Metal salts in alkaline solution Cuprammonium complex Nickel and cobalt ammonia complex Cyanides (q.v.) Copper pyrophosphates Plumbites Zincates... 

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