Nickel Sulfide Concentrates

Finally, nickel is electrolytically produced from the purified nickel-bearing solution. In electrowinning of nickel, the hydrogen discharge reaction competes with nickel deposition at the cathode. This counterproductive effect is minimized by keeping the acidic anolyte solution separate from the catholyte by means of a diaphragm cloth. 

Nickel matte Nickel concentrate Exit gas Alloy scrap 

---

It has been mentioned in an earlier chapter that nickel deposits are basically of two types sulfidic and lateritic (oxide). The scenario of nickel extraction from nickel sulfide concentrates and nickeliferrous pyrrho tite (these two are the two products of physical beneficiation of nickel sulfide ores), and from limonitics and gamieritics (these are the common lateritic ores) has been presented in Figure 5.6. It can be seen that nickel is extracted from its various sources by pyro, pyro-hydro and hydroprocessing. The account given here pertains to the latter two processes applied to the various nickel sources. 

Nickel sulfide concentrates are first subjected to an oxidizing treatment and then converted to nickel matte which is processed by hydrometallurgical methods. These methods have been indicated as A, C, and D in Figure 5.6. 

The International Nickel Company developed a method to refine impure nickel sulfide anodes directly to metal, using mixed sulfate-chloride electrolyte [45]. Nickel sulfide (cz-Nf ) anodes can be cast directly from low-copper converter matte or from melted nickel sulfide concentrate produced by the matte separation process. Controlled cooling is necessary to produce anodes with the required mechanical properties. The cooling of anodes can take up to 36 hours. Using nickel sulfide anodes eliminates the intermediate roasting of the sulfide... 

Sherritt ammonia pressure leaching. This hydrometallurgical process was first implemented in 1954 by Sherritt Gordon Mines in Fort Saskatchewan, Alberta, Canada. In this process, the finely ground nickel sulfide concentrates obtained after flotation or the metal matte are reacted at 80 to 95°C in a high-pressure autoclave under 850 kPa with an oxygenated ammonia or ammonia-ammonium sulfate liquor. Ammonia dissolves nickel and, to a lesser extent, cobalt, zinc, and copper by forming soluble ammonia complex cations as follows ... 

Cobalt can be recovered from nickel-sulfide concentrates or nickel matte by the Sherritt-Gordon ammonia leaching process in Fort Saskatchewan, Alberta, Canada, and it is also recovered from sulfuric-acid pressure leaching of laterites. In both cases, cobalt is obtained in nickel-free liquor by reduction with hydrogen under elevated pressure and temperature (Section 2.2). 

Nickel sulfide concentrates can be treated by flesh melting (see Chapter 31 Nickel) to give a matte with for instance 10% Ni, 2% Cu, 0.4% Co, 33% Fe, 30% S. In the Sher-rit-Gordon process (Canada) the matte is leached with ammonia in autoclaves at high temperature and under a pressure of oxygen. This converts the sulfides to sulfates... 

D.Q. Zhu et ah, Mechanism of Improving the Strengthen of Copper-Nickel Sulfide Concentrate Briquetting by Adding Binder , Yunnan Metallurgy, (4)1997 2-5(in Chinese). 

Juvonen, R., Kallio, E., and Lakomaa, T. (1994) Determination of precious metals in rocks by inductively-coupled plasma-mass spectrometry using nickel sulfide concentration - comparison with other pretreatment methods. Analyst, 119(4), 617-21. 

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. 

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. 

It is good practice to keep concentrations of airborne nickel in any chemical form as low as possible and certainly below the relevant standard. Local exhaust ventilation is the preferred method, particularly for powders, but personal respirator protection may be employed where necessary. In the United States, the Occupational Safety and Health Administration (OSHA) personal exposure limit (PEL) for all forms of nickel except nickel carbonyl is 1 mg/m. The ACGIH TLVs are respectively 1 mg/m for Ni metal, insoluble compounds, and fume and dust from nickel sulfide roasting, and 0.1 mg/m for soluble nickel compounds. The ACGIH is considering whether to lower the TLVs for all forms of nickel to 0.05 mg/m, based on nonmalignant respiratory effects in experimental animals. 

Like the refining of the PGMs, the analysis is compHcated by the chemical similarity of the metals. The techniques used depend on the elements present and their concentration in the sample. For some low grade samples, analysis is preceded by a concentration stage using fire assay with collection into a lead or nickel sulfide button. The individual metals can then be determined. 

Direct l eaching of Concentrates. Sherri tt Gordon Mines, Ltd., has adapted the process first used on nickel sulfide ores to zinc sulfide oxidation with air in aqueous slurry under pressure (42,43). The concentrates are leached direcdy with return acid from the cells and the sulfide is converted to free sulfur ... 

It is well established that sulfur compounds even in low parts per million concentrations in fuel gas are detrimental to MCFCs. The principal sulfur compound that has an adverse effect on cell performance is H2S. A nickel anode at anodic potentials reacts with H2S to form nickel sulfide. Chemisorption on Ni surfaces occurs, which can block active electrochemical sites. The tolerance of MCFCs to sulfur compounds is strongly dependent on temperature, pressure, gas composition, cell components, and system operation (i.e., recycle, venting, and gas cleanup). Nickel anode at anodic potentials reacts with H2S to form nickel sulfide. Moreover, oxidation of H2S in a combustion reaction, when recycling system is used, causes subsequent reaction with carbonate ions in the electrolyte [1]. Some researchers have tried to overcome this problem with additional device such as sulfur removal reactor. If the anode itself has a high tolerance to sulfur, the additional device is not required, hence, cutting the capital cost for MCFC plant. To enhance the anode performance on sulfur tolerance, ceria coating on anode is proposed. The main reason is that ceria can react with H2S [2,3] to protect Ni anode. 

The slime is recovered and heated in a brick-lined tank to melt the sulfur. The molten sulfur is filtered in a heated stainless-steel pressure filter to separate remaining nickel sulfide pieces and insoluble precious metals, and cast into moulds. The residue is remelted and cast into anodes, the resulting anode slime is now a relatively concentrated precious metal residue and is treated for the extraction of individual metals. 

The effects of H2S on cell voltage are reversible if H2S concentrations are present at levels below that required to form nickel sulfide. 

Based on the present understanding of the effect of sulfur on MCFCs, and with the available cell components, it is projected that long-term operation (40,000 hr) of MCFCs may require fuel gases with sulfur " levels of the order 0.01 ppm or less, unless the system is purged of sulfur at periodic intervals or sulfur is scrubbed from the cell burner loop (76). Sulfur tolerance would be approximately 0.5 ppm (see Table 6-3) in the latter case. Considerable effort has been devoted to develop low-cost techniques for sulfur removal, and research and development are continuing (80,81). The effects of H2S on cell voltage are reversible if H2S concentrations are present at levels below which nickel sulfide forms. 

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. 

Nickel sulfide melts at 797°C and is insoluble in water (3.6 mg/L at 18°C soluble in concentrated nitric acid and potassium hydrogen sulfide solution slightly soluble in alcohol. 

Little is known concerning the chemistry of nickel in the atmosphere. The probable species present in the atmosphere include soil minerals, nickel oxide, and nickel sulfate (Schmidt and Andren 1980). In aerobic waters at environmental pHs, the predominant form of nickel is the hexahydrate Ni(H20)g ion (Richter and Theis 1980). Complexes with naturally occurring anions, such as OH, SO/, and Cf, are formed to a small degree. Complexes with hydroxyl radicals are more stable than those with sulfate, which in turn are more stable than those with chloride. Ni(OH)2° becomes the dominant species above pH 9.5. In anaerobic systems, nickel sulfide forms if sulfur is present, and this limits the solubility of nickel. In soil, the most important sinks for nickel, other than soil minerals, are amorphous oxides of iron and manganese. The mobility of nickel in soil is site specific pH is the primary factor affecting leachability. Mobility increases at low pH. At one well-studied site, the sulfate concentration and the... 

In natural waters, nickel primarily exists as the hexahydrate. While nickel forms strong, soluble complexes with OH, S04 , and HCQ, these species are minor compared with hydrated in surface water and groundwater with pH <9 (Rai and Zachara 1984). Under anaerobic conditions, such as may exist in deep groundwater, nickel sulfide would control aqueous nickel concentrations to low levels. 

---