Chalcopyrite

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Chalcopyrite
Chalcopyrite-199453.jpg
General
Category Sulfide mineral
Formula
(repeating unit)		CuFeS2
IMA symbol Ccp [1]
Strunz classification 2.CB.10a
Crystal system Tetragonal
Crystal class Scalenohedral (42m)
H-M symbol: (4 2m)
Space group I42d
Unit cell a = 5.289 Å,
c = 10.423 Å; Z = 4
Identification
Formula mass 183.54 g/mol
ColorBrass yellow, may have iridescent purplish tarnish.
Crystal habit Predominantly the disphenoid and resembles a tetrahedron, commonly massive, and sometimes botryoidal.
Twinning Penetration twins
Cleavage Indistinct on {011}
Fracture Irregular to uneven
Tenacity Brittle
Mohs scale hardness3.5–4
Luster Metallic
Streak Greenish black
Diaphaneity Opaque
Specific gravity 4.1–4.3
Optical propertiesOpaque
Solubility Soluble in HNO3
Other characteristicsmagnetic on heating
References [2] [3] [4] [5] [6]

Chalcopyrite ( /ˌkælkəˈpaɪˌraɪt,-koʊ-/ [7] [8] KAL-kə-PY-ryte, -⁠koh-) is a copper iron sulfide mineral and the most abundant copper ore mineral. It has the chemical formula CuFeS2 and crystallizes in the tetragonal system. It has a brassy to golden yellow color and a hardness of 3.5 to 4 on the Mohs scale. Its streak is diagnostic as green-tinged black. [9]

Contents

On exposure to air, chalcopyrite tarnishes to a variety of oxides, hydroxides, and sulfates. Associated copper minerals include the sulfides bornite (Cu5FeS4), chalcocite (Cu2S), covellite (CuS), digenite (Cu9S5); carbonates such as malachite and azurite, and rarely oxides such as cuprite (Cu2O). It is rarely found in association with native copper. Chalcopyrite is a conductor of electricity. [10]

Copper can be extracted from chalcopyrite ore using various methods. The two predominant methods are pyrometallurgy and hydrometallurgy, the former being the most commercially viable. [11]

Etymology

The name chalcopyrite comes from the Greek words chalkos, which means copper, and pyrites', which means striking fire. [12] It was sometimes historically referred to as "yellow copper". [13]

Identification

Chalcopyrite is often confused with pyrite and gold since all three of these minerals have a yellowish color and a metallic luster. Some important mineral characteristics that help distinguish these minerals are hardness and streak. Chalcopyrite is much softer than pyrite and can be scratched with a knife, whereas pyrite cannot be scratched by a knife. [14] However, chalcopyrite is harder than gold, which, if pure, can be scratched by copper. [15] Chalcopyrite has a distinctive black streak with green flecks in it. Pyrite has a black streak and gold has a yellow streak. [16]

Chemistry

The unit cell of chalcopyrite. Copper is shown in pink, iron in blue and sulfur in yellow. Chalcopyrite-unit-cell-3D-balls.png
The unit cell of chalcopyrite. Copper is shown in pink, iron in blue and sulfur in yellow.
Microscopic picture of chalcopyrite Chalcopyrite under polarized light.jpg
Microscopic picture of chalcopyrite

Natural chalcopyrite has no solid solution series with any other sulfide minerals. There is limited substitution of zinc with copper despite chalcopyrite having the same crystal structure as sphalerite.

Minor amounts of elements such as silver, gold, cadmium, cobalt, nickel, lead, tin, and zinc can be measured (at parts per million levels), likely substituting for copper and iron. Selenium, bismuth, tellurium, and arsenic may substitute for sulfur in minor amounts. [17] Chalcopyrite can be oxidized to form malachite, azurite, and cuprite. [18]

Structure

Chalcopyrite is a member of the tetragonal crystal system. Crystallographically the structure of chalcopyrite is closely related to that of zinc blende ZnS (sphalerite). [19] The unit cell is twice as large, reflecting an alternation of Cu+ and Fe3+ ions replacing Zn2+ ions in adjacent cells. In contrast to the pyrite structure chalcopyrite has single S2− sulfide anions rather than disulfide pairs. Another difference is that the iron cation is not diamagnetic low spin Fe(II) as in pyrite.

In the crystal structure, each metal ion is tetrahedrally coordinated to 4 sulfur anions. Each sulfur anion is bonded to two copper atoms and two iron atoms. [19]

Paragenesis

Brass-yellow chalcopyrite crystals below large striated pyrite cubes Pyrite-Chalcopyrite-Sphalerite-40297.jpg
Brass-yellow chalcopyrite crystals below large striated pyrite cubes

Chalcopyrite is present with many ore-bearing environments via a variety of ore forming processes.

Chalcopyrite is present in volcanogenic massive sulfide ore deposits and sedimentary exhalative deposits, formed by deposition of copper during hydrothermal circulation. Chalcopyrite is concentrated in this environment via fluid transport. Porphyry copper ore deposits are formed by concentration of copper within a granitic stock during the ascent and crystallisation of a magma. Chalcopyrite in this environment is produced by concentration within a magmatic system.

Chalcopyrite is an accessory mineral in Kambalda type komatiitic nickel ore deposits, formed from an immiscible sulfide liquid in sulfide-saturated ultramafic lavas. In this environment chalcopyrite is formed by a sulfide liquid stripping copper from an immiscible silicate liquid.

Chalcopyrite has been the most important ore of copper since the Bronze Age. [20]

Occurrence

Copper-zinc ore sample from a VMS deposit at Potter Mine in Timmins, Ontario, Canada. The brassy-yellow mineral is chalcopyrite- the primary ore mineral at this mine. Polymetallic massive sulfide (Middle Tholeiitic Unit, Kidd-Munro Assemblage, Neoarchean, 2.711 to 2.719 Ga; Potter Mine, east of Timmins, Ontario, Canada) 2 (47820008922).jpg
Copper-zinc ore sample from a VMS deposit at Potter Mine in Timmins, Ontario, Canada. The brassy-yellow mineral is chalcopyrite- the primary ore mineral at this mine.

Even though Chalcopyrite does not contain the most copper in its structure relative to other minerals, it is the most important copper ore since it can be found in many localities. Chalcopyrite ore occurs in a variety of ore types, from huge masses as at Timmins, Ontario, to irregular veins and disseminations associated with granitic to dioritic intrusives as in the porphyry copper deposits of Broken Hill, the American Cordillera and the Andes. The largest deposit of nearly pure chalcopyrite ever discovered in Canada was at the southern end of the Temagami Greenstone Belt where Copperfields Mine extracted the high-grade copper. [21]

Chalcopyrite is present in the supergiant Olympic Dam Cu-Au-U deposit in South Australia.

Chalcopyrite may also be found in coal seams associated with pyrite nodules, and as disseminations in carbonate sedimentary rocks. [22]

Extraction of copper

Copper flash smelting process, a pyrometallurgical method of copper extraction from chalcopyrite Copper Flash Smelting Process (EN).svg
Copper flash smelting process, a pyrometallurgical method of copper extraction from chalcopyrite

Copper metal is predominantly extracted from chalcopyrite ore using two methods: pyrometallurgy and hydrometallurgy. The most common and commercially viable [11] method, pyrometallurgy, involves "crushing, grinding, flotation, smelting, refining, and electro-refining" techniques. Crushing, leaching, solvent extraction, and electrowinning are techniques used in hydrometallurgy.[ citation needed ] Specifically in the case of chalcopyrite, pressure oxidation leaching is practiced. [23]

Pyrometallurgical processes

The most important method for copper extraction from chalcopyrite is pyrometallurgy. Pyrometallurgy is commonly used for large scale, copper rich operations with high-grade ores. [24] This is because Cu-Fe-S ores, such as chalcopyrite, are difficult to dissolve in aqueous solutions. [25] The extraction process using this method undergoes four stages:

  1. Isolating desired elements from ore using froth flotation to create a concentration
  2. Creating a high-Cu sulfide matte by smelting the concentration
  3. Oxidizing/converting the sulfide matte, resulting in an impure molten copper
  4. Refining by fire and electrowinning techniques to increase purity of resultant copper [25]

Chalcopyrite ore is not directly smelted. This is because the ore is primarily composed of non-economically valuable material, or waste rock, with low concentrations of copper. The abundance of waste material results in a lot of hydrocarbon fuel being required to heat and melt the ore. Alternatively, copper is isolated from the ore first using a technique called froth flotation . Essentially, reagents are used to make the copper water-repellent, thus the Cu is able to concentrate in a flotation cell by floating on air bubbles. In contrast to the 0.5–2% copper in chalcopyrite ore, froth flotation results in a concentrate containing about 30% copper. [25]

The concentrate then undergoes a process called matte smelting. Matte smelting oxidizes the sulfur and iron [26] by melting the flotation concentrate in a 1250 °C furnace to create a new concentrate (matte) with about 45–75% copper. [25] This process is typically done in flash furnaces. To reduce the amount of copper in the slag material, the slag is kept molten with an addition of SiO2 flux [26] to promote immiscibility between concentration and slag. In terms of byproducts, matte smelting copper can produce SO2 gas which is harmful to the environment, thus it is captured in the form of sulfuric acid. Example reactions are as follows: [25]

  1. 2CuFeS2 (s) +3.25O2(g) → Cu2S-0.5FeS(l) + 1.5FeO(s) + 2.5SO2(g)
  2. 2FeO(s) + SiO2(s) → Fe2SiO4(l) [25]

Converting involves oxidizing the matte once more to further remove sulfur and iron; however, the product is 99% molten copper. [25] Converting occurs in two stages: the slag forming stage and the copper forming stage. In the slag forming stage, iron and sulfur are reduced to concentrations of less than 1% and 0.02%, respectively. The concentrate from matte smelting is poured into a converter that is then rotated, supplying the slag with oxygen through tuyeres. The reaction is as follows:

2FeS(l)+3O2(g)+SiO2(s) -> Fe2SiO4(l) + 2SO2(g) + heat

In the copper forming stage, the matte produced from the slag stage undergoes charging (inputting the matte in the converter), blowing (blasting more oxygen), and skimming (retrieving impure molten copper known as blister copper). [25] The reaction is as follows:

Cu2S(l) + O2(g) -> 2Cu(l) + SO2(g) + heat [25]

Finally, the blister copper undergoes refinement through fire, electrorefining or both. In this stage, copper is refined to a high-purity cathode. [25]

Hydrometallurgical processes

Chalcopyrite is an exception to most copper bearing minerals. In contrast to the majority of copper minerals which can be leached at atmospheric conditions, such as through heap leaching, chalcopyrite is a refractory mineral that requires elevated temperatures as well as oxidizing conditions to release its copper into solution. [27] This is because of the extracting challenges which arise from the 1:1 presence of iron to copper, [28] resulting in slow leaching kinetics. [27] Elevated temperatures and pressures create an abundance of oxygen in solution, which facilitates faster reaction speeds in terms of breaking down chalcopyrite's crystal lattice. [27] A hydrometallurgical process which elevates temperature with oxidizing conditions required for chalcopyrite is known as pressure oxidation leaching. A typical reaction series of chalcopyrite under oxidizing, high temperature conditions is as follows:

i) 2CuFeS2 + 4Fe2(SO4)3 -> 2Cu2++ 2SO42- + 10FeSO4+4S

ii) 4FeSO4 + O2 + 2H2SO4 -> 2Fe2(SO4)3 +2H2O

iii) 2S + 3O2 +2H2O -> 2H2SO4

(overall) 4CuFeS2+ 17O2 + 4H2O -> 4Cu2++ 2Fe2O3 + 4H2SO4 [27]

Pressure oxidation leaching is particularly useful for low grade chalcopyrite. This is because it can "process concentrate product from flotation" [27] rather than having to process whole ore. Additionally, it can be used as an alternative method to pyrometallurgy for variable ore. [27] Other advantages hydrometallurgical processes have in regards to copper extraction over pyrometallurgical processes (smelting) include:

Although hydrometallurgy has its advantages, it continues to face challenges in the commercial setting. [28] [27] In turn, smelting continues to remain the most commercially viable method of copper extraction. [28]

See also

Related Research Articles

Bioleaching is the extraction or liberation of metals from their ores through the use of living organisms. Bioleaching is one of several applications within biohydrometallurgy and several methods are used to treat ores or concentrates containing copper, zinc, lead, arsenic, antimony, nickel, molybdenum, gold, silver, and cobalt.

<span class="mw-page-title-main">Smelting</span> Use of heat and a reducing agent to extract metal from ore

Smelting is a process of applying heat and a chemical reducing agent to an ore to extract a desired base metal product. It is a form of extractive metallurgy that is used to obtain many metals such as iron, copper, silver, tin, lead and zinc. Smelting uses heat and a chemical reducing agent to decompose the ore, driving off other elements as gases or slag and leaving the metal behind. The reducing agent is commonly a fossil-fuel source of carbon, such as carbon monoxide from incomplete combustion of coke—or, in earlier times, of charcoal. The oxygen in the ore binds to carbon at high temperatures, as the chemical potential energy of the bonds in carbon dioxide is lower than that of the bonds in the ore.

Extractive metallurgy is a branch of metallurgical engineering wherein process and methods of extraction of metals from their natural mineral deposits are studied. The field is a materials science, covering all aspects of the types of ore, washing, concentration, separation, chemical processes and extraction of pure metal and their alloying to suit various applications, sometimes for direct use as a finished product, but more often in a form that requires further working to achieve the given properties to suit the applications.

<span class="mw-page-title-main">Pentlandite</span> Iron–nickel sulfide

Pentlandite is an iron–nickel sulfide with the chemical formula (Fe,Ni)9S8. Pentlandite has a narrow variation range in nickel to iron ratios (Ni:Fe), but it is usually described as 1:1. In some cases, this ratio is skewed by the presence of pyrrhotite inclusions. It also contains minor cobalt, usually at low levels as a fraction of weight.

<span class="mw-page-title-main">Galena</span> Natural mineral form of lead sulfide

Galena, also called lead glance, is the natural mineral form of lead(II) sulfide (PbS). It is the most important ore of lead and an important source of silver.

<span class="mw-page-title-main">Nickeline</span> Nickel arsenide mineral

Nickeline or niccolite is the mineral form of nickel arsenide. The naturally-occurring mineral contains roughly 43.9% nickel and 56.1% arsenic by mass, but composition of the mineral may vary slightly.

<span class="mw-page-title-main">Copper extraction</span> Process of extracting copper from the ground

Copper extraction refers to the methods used to obtain copper from its ores. The conversion of copper ores consists of a series of physical, chemical, and electrochemical processes. Methods have evolved and vary with country depending on the ore source, local environmental regulations, and other factors.

<span class="mw-page-title-main">Chalcocite</span> Sulfide mineral

Chalcocite, copper(I) sulfide (Cu2S), is an important copper ore mineral. It is opaque and dark gray to black, with a metallic luster. It has a hardness of 2.5–3 on the Mohs scale. It is a sulfide with a monoclinic crystal system.

<span class="mw-page-title-main">Cobaltite</span> Sulfide mineral composed of cobalt, arsenic, and sulfur

Cobaltite is an arsenide and sulfide mineral with the mineral formula CoAsS. It is the naming mineral of the cobaltite group of minerals, whose members structurally resemble pyrite (FeS2).

<span class="mw-page-title-main">Fukuchilite</span>

Fukuchilite, Cu
3FeS
8, is a copper iron sulfide named after the Japanese mineralogist Nobuyo Fukuchi (1877–1934), that occurs in ore bodies of gypsum-anhydrite at the intersection points of small masses of barite, covellite, gypsum and pyrite, and is mostly found in the Hanawa mine in the Akita prefecture of Honshū, Japan where it was first discovered in 1969. It occurs in masses within the third geologic unit of the Kuroko type deposits within the mine.

In ore deposit geology, supergene processes or enrichment are those that occur relatively near the surface as opposed to deep hypogene processes. Supergene processes include the predominance of meteoric water circulation (i.e. water derived from precipitation) with concomitant oxidation and chemical weathering. The descending meteoric waters oxidize the primary (hypogene) sulfide ore minerals and redistribute the metallic ore elements. Supergene enrichment occurs at the base of the oxidized portion of an ore deposit. Metals that have been leached from the oxidized ore are carried downward by percolating groundwater, and react with hypogene sulfides at the supergene-hypogene boundary. The reaction produces secondary sulfides with metal contents higher than those of the primary ore. This is particularly noted in copper ore deposits where the copper sulfide minerals chalcocite (Cu2S), covellite (CuS), digenite (Cu18S10), and djurleite (Cu31S16) are deposited by the descending surface waters.

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<span class="mw-page-title-main">Copper mining in the United States</span>

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Leaching is a process widely used in extractive metallurgy where ore is treated with chemicals to convert the valuable metals within the ore, into soluble salts while the impurity remains insoluble. These can then be washed out and processed to give the pure metal; the materials left over are commonly known as tailings.

<span class="mw-page-title-main">Cubanite</span> Copper iron sulfide mineral

Cubanite is a copper iron sulfide mineral that commonly occurs as a minor alteration mineral in magmatic sulfide deposits. It has the chemical formula CuFe2S3 and when found, it has a bronze to brass-yellow appearance. On the Mohs hardness scale, cubanite falls between 3.5 and 4 and has a orthorhombic crystal system. Cubanite is chemically similar to chalcopyrite; however, it is the less common copper iron sulfide mineral due to crystallization requirements.

<span class="mw-page-title-main">Cobalt extraction</span>

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<span class="mw-page-title-main">Manhès–David process</span>

The Manhès–David process is a refining process of the copper mattes, invented in 1880 by the French industrialist Pierre Manhès and his engineer Paul David. Inspired by the Bessemer process, it consists of the use of a converter to oxidise with air the undesirable chemical elements contained in the matte, to transform it into copper.

Mineral processing and extraction of metals are very energy-intensive processes, which are not exempted of producing large volumes of solid residues and wastewater, which also require energy to be further treated and disposed. Moreover, as the demand for metals increases, the metallurgical industry must rely on sources of materials with lower metal contents both from a primary and/or secondary raw materials. Consequently, mining activities and waste recycling must evolve towards the development of more selective, efficient and environmentally friendly mineral and metal processing routes.

References

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  3. ↑ Palache, C., H. Berman, and C. Frondel (1944) Dana’s system of mineralogy, (7th edition), v. I, 219–224
  4. ↑ "Chalcopyrite". Mindat.org.
  5. ↑ Chalcopyrite data on Webmineral.com
  6. ↑ Chalcopyrite in the Handbook of Mineralogy
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  8. ↑ "chalcopyrite". Merriam-Webster.com Dictionary . Merriam-Webster. Retrieved 2016-01-21.
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  10. ↑ Havlík, Tomáš (2008-01-01), Havlík, Tomáš (ed.), "Chapter 10 - Effect of The Electronic Structure on leaching of Sulphide Semiconductors", Hydrometallurgy, Woodhead Publishing Series in Metals and Surface Engineering, Woodhead Publishing, pp. 294–308, doi:10.1533/9781845694616.294, ISBN   978-1-84569-407-4 , retrieved 2023-02-10
  11. 1 2 Daehn, Katrin E.; Stinn, Caspar; Rush, Lucas; Benderly-Kremen, Ethan; Wagner, Mary Elizabeth; Boury, Charles; Chmielowiec, Brian; Gutierrez, Carolina; Allanore, Antoine (2022-08-29). "Liquid Copper and Iron Production from Chalcopyrite, in the Absence of Oxygen". Metals. 12 (9): 1440. doi: 10.3390/met12091440 . hdl: 1721.1/145313 . ISSN   2075-4701.
  12. ↑ "Chalcopyrite". www.esci.umn.edu. Minerals. University of Minnesota. Retrieved 2019-12-20.
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  15. ↑ "Hardness". Earth's Minerals. LearnBPS: Bismarck Public School's Blended Spaces. Retrieved 2019-12-20.
  16. ↑ "Fool's gold and real gold – How to tell the difference". geology.com. Retrieved 2019-12-20.
  17. ↑ Dare, Sarah A.S.; Barnes, Sarah-Jane; Prichard, Hazel M.; Fisher, Peter C. (2011). "Chalcophile and platinum-group element (PGE) concentrations in the sulfide minerals from the McCreedy East deposit, Sudbury, Canada, and the origin of PGE in pyrite". Mineralium Deposita. 46 (4): 381–407. Bibcode:2011MinDe..46..381D. doi:10.1007/s00126-011-0336-9. S2CID   129382712.
  18. ↑ "Chalcopyrite". www.esci.umn.edu. Minerals. University of Minnesota. Retrieved 2019-12-20.
  19. 1 2 Li, Y.; Kawashima, N.; Li, J.; Chandra, A. P.; Gerson, A. R. (2013-09-01). "A review of the structure, and fundamental mechanisms and kinetics of the leaching of chalcopyrite". Advances in Colloid and Interface Science. 197–198: 1–32. doi:10.1016/j.cis.2013.03.004. ISSN   0001-8686. PMID   23791420.
  20. ↑ "Chalcopyrite". Department of Geology. University of Minnesota. Retrieved 18 February 2021.
  21. ↑ Barnes, Michael (2008). More than Free Gold. Renfrew, Ontario: General Store Publishing House. p. 31. ISBN   978-1-897113-90-5 . Retrieved 2015-08-02.
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  23. ↑ Schlesinger, Mark E. (2011). Extractive Metallurgy of Copper. Amsterdam: Elsevier. pp. 281–317. ISBN   978-0-08-096789-9. OCLC   742299078.
  24. ↑ Nassaralla, C. L. (2001-01-01), "Pyrometallurgy", in Buschow, K. H. Jürgen; Cahn, Robert W.; Flemings, Merton C.; Ilschner, Bernhard (eds.), Encyclopedia of Materials: Science and Technology, Oxford: Elsevier, pp. 7938–7941, Bibcode:2001emst.book.7938N, doi:10.1016/b0-08-043152-6/01429-7, ISBN   978-0-08-043152-9 , retrieved 2023-03-23
  25. 1 2 3 4 5 6 7 8 9 10 Schlesinger, Mark E. (2011). Extractive Metallurgy of Copper. Amsterdam: Elsevier. pp. 281–317. ISBN   978-0-08-096789-9. OCLC   742299078.
  26. 1 2 Chamveha, Pimporn; Chaichana, Kattiyapon; Chuachuensuk, Anon; Authayanun, Suthida; Arpornwichanop, Amornchai (2008-10-09). "Performance Analysis of a Smelting Reactor for Copper Production Process". Industrial & Engineering Chemistry Research. 48 (3): 1120–1125. doi:10.1021/ie800618a. ISSN   0888-5885.
  27. 1 2 3 4 5 6 7 8 Schlesinger, Mark E. (2011). Extractive Metallurgy of Copper. Amsterdam: Elsevier. pp. 281–317. ISBN   978-0-08-096789-9. OCLC   742299078.
  28. 1 2 3 Daehn, Katrin E.; Stinn, Caspar; Rush, Lucas; Benderly-Kremen, Ethan; Wagner, Mary Elizabeth; Boury, Charles; Chmielowiec, Brian; Gutierrez, Carolina; Allanore, Antoine (2022-08-29). "Liquid Copper and Iron Production from Chalcopyrite, in the Absence of Oxygen". Metals. 12 (9): 1440. doi: 10.3390/met12091440 . hdl: 1721.1/145313 . ISSN   2075-4701.
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