The activity of copper-containing substances in the solution is 10−3 M and the activity of sulphur-containing substances is equal to 10−1 M at a total pressure of 0.1 MPa. Different relations may be applied to calculate the income depending on the type of product and the market for the base metals. Some copper sulfides are economically important ores. Its principal employment is in agriculture, and, up to a generation or so ago, about its only uses in industry were as a mordant for dyeing and for electroplating. Note the sulfate roasting, the precipitation of cobalt hydroxide and the redissolution of the cobalt hydroxide followed by cobalt electrowinning. Whatever their source, copper sulfides vary widely in composition with 0.5 ≤ Cu/S ≤ 2, including numerous non-stoichiometric compounds. A decrease of the total concentration of copper below 0.01 M results in the area of stability of CuCl2−(aq). Zdzisław, in Reference Module in Materials Science and Materials Engineering, 2017. Copper sulfate is used in the preparation of Paris green, to kill mosquito larvae that cause malaria. In this example, the production of a copper concentrate is investigated. The iceman's hair contained high levels of the toxin arsenic, which may indicate the man was exposed to the element during copper … Conductivities range from (10−10…10−8 [Ω cm]−1) with nylon and polyester. Both minerals and synthetic materials comprise these compounds. Precipitation with MgO and redissolution produces cobalt-rich, high-purity electrolyte. Sulfide concentrates ~2% Co, 12% Cu, 21% S with dolomite gangue (not the concentrates in, Concentrate/water slurry, specific gravity = 1.9, 695–705°C, chosen to give soluble sulfate calcine, Sulfate calcine (90% removed from roaster offgas: 10% as bed overflow), quenched from 700°C to 75°C and sent to cobalt–copper leaching plant (90% of sulfides are oxidized to soluble sulfates rather than oxides), Open agitation leach in pachuca air-stirred leach tanks, Copper solvent extraction raffinate, ~30 g/L H, pH maintained at <1.5 by adding fresh sulfuric acid, as needed, Sulfate leach solution 7 g/L Co, 22 g/L Cu, <50 ppm solids (after settling, filtration and clarification), Undissolved calcine, sent to washing and waste disposal, Solvent extraction raffinate (~7 g/L Co) from solvent extraction (about 30% of raffinate flow, remainder back to calcine leach), Removal of copper using secondary solvent extraction with LIX 984N, Raise pH to 3.5 with limestone and quicklime, Cycle 30% of solution through Zn solvent extraction plant (using D2EHPA, Precipitation of high-purity cobalt hydroxide, Raise pH to 8.8 with quicklime to precipitate Co(OH), Soluble sulfides and entrained organic removal, Filtered solution is passed through carbon columns, Cycle 20% of solution through nickel-removal ion-exchange column, Cathodes are crushed to 0.02 m × 0.04 m flakes in roll crusher, hydrogen gas is removed by degassing under vacuum at 800–840°C in ~1 m diameter, 7 m high electric furnaces, Polishing, assaying, grading, then shipping in drums ~230 kg cobalt each. The residuum is removed from the cell and re-melted/cast into fresh anodes and these are placed in the cell. [8][9][10] 25 °C – pH=5.7÷9.2 (∆pH=3.5); Eh=−0.56÷−0.31 (∆Eh=0.25). 8. Pourbaix diagram of the Cu–Fe–S–O–H2O system at 25 °C. The anodes are dissolved to the point at which they start to fall apart. Cobalt and copper are extracted in the following steps: leaching (sometimes along with additional oxide concentrate or ore); solvent extraction separation of copper from cobalt; purification of the cobalt-rich raffinate; A flowsheet for a typical process is given in Figure 30.7 and operating details are given in Tables 30.2–30.6. In the mining industry, the minerals bornite or chalcopyrite, which consist of mixed copper-iron sulfides, are often referred to as "copper sulfides". A black colloidal precipitate of CuS is formed when hydrogen sulfide, H 2 S, is bubbled through solutions of Cu(II) salts. W. G. Mumme, R. W. Gable, V. Petříček, Canadian Mineralogist; (2012); 50; 423-430. General Measures: Remove patient from area of exposure. Copper sulfate is also used in order to help with public health and safety. It has the chemical compound Cu2S. This is cast into slab-like anodes. Column flotation cleaner cells are particularly effective at giving a high Cu grade in the concentrate. At these concentrations of Cu, Fe, and S in ground water the stability regions of cubanite and chalcopyrite are nonexistent, which is accordant with reactions (1) and (2). Both are constructed of acid resistant concrete and contain anodes (connected in parallel) interleaved with anodes (also connected in parallel). Interspersed copper anodes and cathodes are suspended in an electrolyte. The anodes are dissolved to the point at which they start to fall apart. TABLE 30.2. Treatment of copper deficiency 5. Research done by Havlik (2008) and others (Peters, 1977) has demonstrated that cubanite is not stable in a hypergenic environment and in the presence of water and oxygen is converted at a fast rate into chalcopyrite according to reaction equation: whereas the formed chalcopyrite in the same environment will undergo further conversion into bornite according to reaction equation: Bornite is a more stable copper and iron sulphide in a hypergenic environment than cubanite and chalcopyrite. [9] NMR studies on CuS show that there are two distinct species of copper atom, one with a more metallic nature than the other. Ingredient: Copper (II) Sulfide. One typical series of reactions that occur under oxidizing conditions and at high temperatures is shown below: FIGURE 15.4. Antiseptic agent 2. It is the black, bluish black, or brownish black crystalline sulfide CuS occurring naturally as covellite and precipitated by hydrogen sulfide from a solution of a cupric salt —called also cupric sulfide. Different stoichiometric compositions can be obtained by changing the redox atmosphere of the synthetic environment. COPPER SULFIDE . FIGURE 30.7. Further evidence that the assignment of the so-called "valence hole" should be to the S2 units in these two formulae is the length of the S-S bonds, which are significantly shorter in CuS (0.207 nm) and CuS2 (0.203 nm) than in the "classical" disulfide Fe2+(S2)2− (0.218 nm). In addition to the iron sulphate, iron chloride is also used as an oxidation agent, especially because it is a far more efficient leaching agent than the sulphate. After mineralogical examination, we decided to divide the ore into four species for characterization: Cp (100% CuFeS2), CpPy (95% CuFeS2 - 5% FeS2), PyAs (70% FeS2 - 30% AsFeS), and Sc (100% SiO2). INHALATION: Remove to fresh air, keep warm and quiet, give oxygen if breathing is difficult. [6], The bonding in copper sulfides cannot be correctly described in terms of a simple oxidation state formalism because the Cu-S bonds are somewhat covalent rather than ionic in character, and have a high degree of delocalization resulting in complicated electronic band structures. By continuing you agree to the use of cookies. 5.15. In this example, the production of a copper concentrate is investigated. CAS Number: 1317-40-4 / EC Number: 215-271-2 Company: Angstrom Sciences, Inc. Felipe D. Sepulveda, ... Edelmira D. Gálvez, in Computer Aided Chemical Engineering, 2012. Major uses: Preparation of Bordeaux and Burgundy mixtures for use as fungicides: Manufacture of other copper fungicides such as copper-lime dust, tribasic: copper sulphate, copper carbonate and cuprous oxide: Manufacture of insecticides such as copper arsenite and Paris green: Control of fungus diseases (see Table B) Correction of copper deficiency in soils Precious metal impurities in the anode are not oxidized at the anode potentials employed, but fall to the bottom of the cell as an “anode slime” which is occasionally harvested from the cells and sent for recovery of precious metals. Typical concentrate grades are 30% Cu (higher with chalcocite, bornite, and native copper mineralization). Oxidation of iron impurities also occurs at the anodes to produce ferric and ferrous ions in solution. Evans, in Encyclopedia of Materials: Science and Technology, 2003. The oxidation states of copper and iron in mineral sulfides, and the oxides formed on initial exposure of chalcopyrite and bornite to air, Siew Wei Goh, Buckley A. N. Lamb R.N., Rosenberg R. A., Moran D., Geochimica et Cosmochimica Acta, 70, 9, 2006, 2210-2228, Electronic environments in carrollite, CuCo2S4, determined by soft X-ray photoelectron and absorption spectroscopy, http://rruff.geo.arizona.edu/doclib/hom/villamaninite.pdf, Copper sulfides mineral information and data, https://en.wikipedia.org/w/index.php?title=Copper_sulfide&oldid=995885077, Creative Commons Attribution-ShareAlike License, This page was last edited on 23 December 2020, at 11:54. Extraction of Cobalt and Copper from Sulfide and Mixed Sulfide-oxide Ores. Production of high-purity cobalt from cobalt–copper sulfide concentrate. CAS#: 22205-45-4 %: 100. After mineralogical examination, we decided to divide the ore into four species for characterization: Cp (100% CuFeS 2 ), CpPy (95% CuFeS 2 - 5% FeS 2 ), PyAs (70% FeS 2 - 30% AsFeS), and Sc (100% SiO2). Product Name: Copper Sulfide . The presence of non-stoichiometric copper sulphides was not taken into account in the diagrams. A glance at Table 1, shows that there is little tendency for the iron in the electrolyte to co-deposit with the copper; copper deposition is thermodynamically much more favorable. Estimated flotation stage recoveries, feed mass flow rates and global recovery goals. Sulfide concentrate: 40% Cu, 4% Co (80% Cu recovery, 50% Co recovery). CU-FES-02-C , CU-FES-03-C , CU-FES-04-C , CU-FES-05-C CAS #: 1308-56-1 Relevant identified uses of the substance: Scientific research and development Supplier details: American Elements 10884 Weyburn Ave. 7. Copper sulfide ores must be concentrated before they can be economically transported and smelted. Copper sulfides describe a family of chemical compounds and minerals with the formula CuxSy. Therefore, it appears that the application of E–pH diagrams to chloride systems is more complicated than in the case of the sulphate systems owing to the fact that the chloride form a large number of species, electropositive, electronegative and electroneutral. Copper sulfate, also known as bluestone, is an inexpensive herbicide and algaecide with a variety of applications. Flotation is commonly used to concentrate copper sulfide minerals, such as chalcopyrite (CuFeS2). Expert control systems help to optimize the performance of flotation plants. CAS#: 1317-40-4 %: 100. Sulfates occur widely in everyday life. White metal compounds are low reactive and thus useful for bi-component fibre manufacturing. This division of copper into species depends not only on temperature but also on the total activity of copper in the solution. Alternatively stainless steel cathode blanks are used as described above under Copper Electrowinning. Most minerals require the application of both an acidic environment and an oxidizing agent to leach copper as Cu2+. The input is high-purity cobalt sulfate electrolyte ~20 g/L Co2+. There is a resemblance to the cell of Fig. Oxide concentrate: 20% Cu, 1.3% Co (60% Cu recovery, 40% Co recovery). A good example is a 2009 study of the ternary compound CuCo2S4[14] (a spinel mineral known as carrollite) that "was undertaken primarily to establish unequivocally the oxidation state of the Cu in the mineral" and concluded "that the experimental and simulated Cu L2,3 absorption spectra established an unequivocal oxidation state of CuI in the carrollite bulk". Copper sulfide finds applications in the following: Solar cells; Superionic conductors; Photodetectors; Electroconductive electrodes; Photothermal conversion devices; Microwave shielding coating; Active absorbents of radio waves; Gas sensors; Polarizers of infrared radiation; Chemical Properties. In addition, the majority of its members are semiconductors. At very high pressures, a copper disulfide, CuS2, can be synthesized. In order to determine these effects, detailed simulations of the behavior of the main mineral component of the metallic inclusions in the slag, i.e., cubanite, were carried out. A typical structure is cell-core or side-by-side bi-component structure. Cobalt–copper sulfide ores are being exploited in several Democratic Republic of Congo and Zambia mines (Katanga, 2010). Other leaching methods include ammonia leaching, which is used for certain copper oxide ores. Table 5.8. The naturally occurring mineral binary compounds of copper and sulfur are listed below. The flotation is made selective by using reagents, which make the Cu-sulfide minerals water-repellant (hydrophobic) while leaving the other minerals wetted (hydrophilic). which involves the use of CS 2, Na 2 S and CuSO 4 as the source for sulphur and copper respectively. In contrast, recycling copper typically uses 90% less energy. However, even though the use of seawater in mineral process ROASTING OF SULFIDE MINERALS In addition to common metals like copper, lead, zinc, and nickel a number of other metals such as antimony, bismuth, cadmium, cobalt, mercury, and molybdenum occur as sulfide minerals. Species diagrams should be applied to these purposes, as discussed later. The copper ions are distributed in a complicated manner over interstitial sites with both trigonal as well as distorted tetrahedral coordination and are rather mobile. Typical operating conditions for copper electrorefining cells are (Habashi 1998): 100–200 Amps m−2 at a cell voltage of 0.3 V with an electrolyte of 40 g L−1 of copper and 150–200 g l of sulfuric acid. The leaching of copper sulfide and copper oxide ores entails partial dissolution to cupric sulfate with sulfuric acid and iron sulfate. Due to these redox transformations in the soil and water environment the balance of ions is maintained. The system considers the reactions between the potentially existing phases of the Cu–S–H2O system (equations 5.185–5.208) and ions and substances containing chlorine, Table 5.8. ∗(Adham et al., 2010). Some copper sulfides are economically important ores. The common route for turning copper sulfide ores into metal is high temperature oxidation of sulfides to produce an impure liquid copper that is cast into slab-like anodes. [Cu] = 0.01 M; [Fe] = [S] = 0.1 M. (Peters, 1976). The copper sulfide is oxidized by Fe3+. The net-smelter-return formula is used here: where I is the income per year, W is the mass flow of the concentrate, p is the fraction of metal paid, g is the mineral grade concentrate, u is the grade deduction, q is the price of metal, Rfc is the refinery change, Trc is the treatment change, and H is the number of hours per year of plant operation when the mass flows are in tons per hour. Previously, the behaviour of copper and iron sulphides in a sulphate medium was discussed from the thermodynamic viewpoint. The stability of bornite is determined by a relatively narrow range of pH values and very narrow range of Eh values, nearly irrespective of the seasonal temperature (Figure 2): Figure 2. pH–Eh diagrams for Cu–Fe–S–H2O system. The copper content of the solution varies from less than 1 g/L to several grams per liter. Precious metal impurities in the anode are not oxidized, at the anode potentials employed, but fall to the bottom of the cell as an ‘anode slime’ which is occasionally harvested from the cells and sent for recovery of precious metals. New Window. Copper sulphate is a very versatile chemical with as extensive a range of uses in industry as it has in agriculture. Stanislav S. Naboychenko, ... Oleg D. Neikov, in Handbook of Non-Ferrous Metal Powders, 2009. Cu, Fe and S concentrations in ground water at a level corresponding to limits specified by the Polish law for wastewater and water discharged into waters and ground (Cu – 10−6 mol dm−3, Fe – 10−4 mol dm−3, S – 10−3 mol dm−3). Both minerals and synthetic materials comprise these compounds. Most of the copper ores mined today are oxide or sulfide ores. The universal technique for this concentration is froth flotation of finely ground ore. Froth flotation entails attaching fine Cu-sulfide mineral particles to bubbles and floating them out of a water–ore mixture. Cooled roaster calcine (~75°C) is leached in aqueous sulfuric acid solution to give a leach sulfate solution of ~22 g/L Cu and 7 g/L Co. A glance at Table 1 shows that there is little tendency for the iron in the electrolyte to co-deposit with the copper; copper deposition is thermodynamically much more favorable. Details of Industrial Leaching of Copper–Cobalt Sulfate Roaster Calcine, Figure 30.7∗. Industrial Cobalt Electrowinning Details∗. Deposition of slags of the presented mineral composition in the environment may produce certain effects in surface and/or ground waters. Otzi the Iceman (3300 BCE) was found with an axe that had a head consisting of nearly pure copper. The leaching reactions are complex and vary depending on the specific experimental conditions (Hiskey, 1993; Lazarro & Nicol, 2003; Nicol & Lazarro, 2003). Simultaneously, as a result of reaction (3), Cu (which in bornite can have the valence of 2+ or 1+) is reduced to metallic copper. With increasing temperature the amount of the copper complexes in the system varies. Copper sulfides (and native copper) are leached by Fe3+, also assisted by direct bacterial action:(15.11a)2FeS2+7O2+2H2O→2Fe2++2SO42−+2H2SO4(15.11b)O2+4Fe2++4SO42−+2H2SO4→4Fe3++6SO42−+2H2O(15.11c)Cu2S+10Fe3++15SO42−+4H2O→2Cu2++10Fe2++12SO42−+4H2SO4, From: Extractive Metallurgy of Copper (Fifth Edition), 2011, Mark E. Schlesinger, ... William G. Davenport, in Extractive Metallurgy of Copper (Fifth Edition), 2011. Most of us realize that mining sulfide ores to source copper threatens clean water and public health. Copper sulfate CuSO 4 found its application in various fields of human activity. Copper sulfides can be classified into three groups: Monosulfides, 1.6 ≤ Cu/S ≤ 2: their crystal structures consist of isolated sulfide anions that are closely related to either hcp or fcc lattices, without any direct S-S bonds. Typical Cu sulfide recoveries to concentrate are 85–90%. Prominent copper sulfide minerals include Cu2S and CuS. Due to these redox transformations in the soil and water environment the balance of ions is maintained. We use cookies to help provide and enhance our service and tailor content and ads. Copper Sulfide is a crystalline solid used as a semiconductor and in photo optic applications. [13] This apparent discrepancy with the X-ray photo-electron spectrum data simply highlights the problem that NMR has in assigning oxidation states in a mixed-valence compound. world, some projects consider the use of seawater to process coper ores by flotation in countries such as Chile, Australia and Indonesia [8]. Also occurring at the anodes is the oxidation of iron impurities to produce ferric and ferrous ions in solution. DATE OF LAST REVISION: 07/09/15. CuS is a moderate conductor of electricity. TABLE 30.4. The residuum is removed from the cell and re-melted/cast into fresh anodes and fresh anodes are placed in the cell. The system shows this behaviour also with a decrease of the total concentration of chlorides in the solution. It is designed to give soluble sulfate calcine rather that insoluble oxide calcine. Substances containing chlorine in the equilibrium system Cu-S-Cl-H2O. Sketch of a copper electrorefining cell from (Evans and DeJonghe 2002). 5 °C – pH=5.9÷10.3 (∆pH=4.4); Eh=−0.58÷−0,30 (∆Eh=0.28). Antifungal agent for topical use 4. Etching - Copper sulfate is also used to etch zinc plates for intaglio printmaking. Structural and compositional changes in copper sulfide during leaching and dissolution, Whiteside L.S, Goble R.J, The Canadian Mineralogist; (1986);. Section 1: Identification . Both are constructed of acid resistant concrete and contain cathodes (connected in parallel) interleaved with anodes (also connected in parallel). In electroplating processes. Principal impurities are iron and precious metals (gold and silver). IDENTIFICATION. Copper sulfate is an eff… Their crystal structures usually consist of alternating hexagonal layers of monosulfide and disulfide anions with Cu cations in trigonal and tetrahedral interstices. The estimated flotation stage recoveries and the feed mass flow rates are given in Table 1. Salts, acid derivatives, and peroxides of sulfate are widely used in industry. J.W. SECTION 1. The product is electrowon cobalt metal, 99.65–99.7% Co. Cobalt recovery from concentrate to metal is ~62%. It is widely used in agriculture as a fungicide in fruit and vegetable farming.It is available as a dust, wettable powder, and as a liquid. Copper /is/ essential for erythropoiesis in rats fed a milk-based diet. A typical benefit of the solution is markedly textile-fibre-like properties with reasonable conductivity. The presence of pyrites in many ore deposits, and its reaction with water and oxygen to form iron sulfate and sulfuric acid, creates an important source of acid. Its crystal structure is analogous to that of pyrite, with all sulfur atoms occurring as S-S units. Siew Wei Goh, Buckley A.N., Lamb R.N: Copper(II) sulfide?, Min. E–pH diagram of the Cu-S-Cl-H2O system for 100 °C, the activity of sulphur-containing substances of 10−1 M, the activity of copper-containing substances of 10−1 and 10−2 M at the unit activity of chlorides. The anodes are electrolytically refined in cells sketched in Fig. In the mining industry, the minerals bornite or chalcopyrite, which consist of mixed copper-iron sulfides, are often referred to as … Extraction of sulfide ores is covered in more detail in Copper Mining and Extraction: Sulfide Ores (11–14), but is introduced here because an important by-product of this process is used for the extraction of oxide ores. Depending on their composition, these copper sulfides are either semiconductors or metallic conductors. Sketch of a copper electrorefining cell from Evans and DeJonghe (2002). The starting solution is solvent extraction raffinate, containing approximately 7 g/L Co. Advance electrolyte is prepared from the raffinate by purification, precipitation of cobalt hydroxide then redissolution of the cobalt hydroxide in recycle spent electrolyte from cobalt sulfate electrowinning. In dump leaching, the pH of the solution is maintained between 1.5 and 3.0, partly to preserve bacteria that promote and accelerate the oxidation of purity and copper sulfate minerals and also to prevent hydrolysis of iron salts. Adjacent cells are connected in series and several hundred cells would be contained in a typical electrorefining tankhouse. EC#: 215-271-2. ScienceDirect ® is a registered trademark of Elsevier B.V. ScienceDirect ® is a registered trademark of Elsevier B.V. URL: https://www.sciencedirect.com/science/article/pii/B9780080967899100046, URL: https://www.sciencedirect.com/science/article/pii/B9780080967899100150, URL: https://www.sciencedirect.com/science/article/pii/B9780080968094100309, URL: https://www.sciencedirect.com/science/article/pii/B9781856174220000161, URL: https://www.sciencedirect.com/science/article/pii/B9781845690052500139, URL: https://www.sciencedirect.com/science/article/pii/B9780128035818036079, URL: https://www.sciencedirect.com/science/article/pii/B9781845694074500050, URL: https://www.sciencedirect.com/science/article/pii/B008043152601888X, URL: https://www.sciencedirect.com/science/article/pii/B9780128035818035943, URL: https://www.sciencedirect.com/science/article/pii/B9780444595195501258, Extractive Metallurgy of Copper (Fifth Edition), 2011, Production of Cu Concentrate from Finely Ground Cu Ore, Mark E. Schlesinger, ... William G. Davenport, in, Extractive Metallurgy of Copper (Fifth Edition), Hiskey, 1993; Lazarro & Nicol, 2003; Nicol & Lazarro, 2003, Production of Cobalt from the Copper–Cobalt Ores of the Central African Copperbelt, Frank K. Crundwell, ... William G. Davenport, in, Extractive Metallurgy of Nickel, Cobalt and Platinum Group Metals, Based on a Site Visit to the Nkana in 2008, Production of Copper and Copper Alloy Powders, Stanislav S. Naboychenko, ... Oleg D. Neikov, in, Slags of the Imperial Smelting Process for Zn and Pb Production, Reference Module in Materials Science and Materials Engineering, Thermodynamic Studies of Heterogeneous Systems in an Aqueous Medium, Encyclopedia of Materials: Science and Technology, Introduction and the Significance of Electrometallurgy, 22nd European Symposium on Computer Aided Process Engineering, Felipe D. Sepulveda, ... Edelmira D. Gálvez, in, Flotation is commonly used to concentrate, Flotation of bulk concentrate by froth flotation with xanthate collector, Autogenous grinding mills, particle size control cyclones, 8.5 m, 45% Cu, 4% Co concentrate. Copper sulfate is an inorganic compound made by combining two elements, sulfur and copper. Typical operating conditions for copper electrorefining cells are (Habashi, 1998): 100–200 A m-2 at a cell voltage of 0.3 Vwith an electrolyte of 40 g l-1 of copper and 150–200 g l-1 of sulfuric acid. It has a narrow range of stoichiometry ranging from Cu1.997S to Cu2.000S.