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Recovery of Copper and Magnetite from Copper Slag Using Concentrated Solar Power (CSP)

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Recovery of Copper and Magnetite from Copper Slag Using Concentrated Solar Power (CSP) metals Article Recovery of Copper and Magnetite from Copper Slag Using Concentrated Solar Power (CSP) Daniel Fernández-González 1,* , Janusz Prazuch 2 , Íñigo Ruiz-Bustinza 3 , Carmen González-Gasca 4, Cristian Gómez-Rodríguez 5 and Luis Felipe Verdeja 6 1 Nanomaterials and Nanotechnology Research Center (CINN-CSIC), Universidad de Oviedo (UO), Principado de Asturias (PA), Avda. de la Vega, 4-6, 33940 El Entrego, Spain 2 Department of Physical Chemistry and Modelling, Faculty of Materials Science and Ceramics, AGH University of Science and Technology, 30-059 Krakow, Poland; [email protected] 3 Departamento de Ingeniería Geológica y Minera, Escuela Técnica Superior de Ingenieros de Minas y Energía, Universidad Politécnica de Madrid, 28003 Madrid, Spain; [email protected] 4 Vice-Rector’s Office, Universidad Internacional de Valencia, 46002 Valencia, Spain; [email protected] 5 Departamento de Mecánica, Facultad de Ingeniería, Campus Coatzacoalcos, Universidad Veracruzana, Av. Universidad km 7.5 Col. Santa Isabel, Coatzacoalcos 6535, Veracruz, Mexico; [email protected] 6 Department of Materials Science and Metallurgical Engineering, Oviedo School of Mines, Energy and Materials, University of Oviedo, 33004 Oviedo/Uviéu, Spain; [email protected] * Correspondence: [email protected] Abstract: On the one hand, copper slag is nowadays a waste in copper pyrometallurgy despite the significant quantities of iron (>40 wt. %) and copper (1 to 2 wt. %). On the other hand, solar energy, when properly concentrated, offers great potential in high-temperature processes. Therefore, Citation: Fernández-González, D.; concentrated solar power (CSP) could be used in the treatment of copper slag to transform fayalite Prazuch, J.; Ruiz-Bustinza, Í.; into magnetite and copper sulfides and oxides into copper nodules. This is the objective of this paper. González-Gasca, C.; The results show that fayalite was partially decomposed into magnetite and silica. Moreover, copper Gómez-Rodríguez, C.; Verdeja, L.F. nodules (65–85 wt. % Cu) were identified in the treated samples, while the initial slag, analyzed by Recovery of Copper and Magnetite X-ray diffraction, X-ray fluorescence, and SEM-EDX, did not show the presence of metallic copper. from Copper Slag Using µ Concentrated Solar Power (CSP). Finally, the treated copper slag was crushed and grinded down to 40 m, and two fractions were Metals 2021, 11, 1032. https:// obtained by magnetic separation. The magnetic fraction (85%) was mainly comprised of magnetite, doi.org/10.3390/met11071032 while the non-magnetic fraction (15%) had 5–10 wt. % Cu. Considering the experimental results, 7.5–18 kg Cu/t slag might be recovered from the slag. A preliminary economic analysis, considering Academic Editor: Fernando Castro the current copper price, indicates that only the recovery of copper could represent a significant economic benefit (>30 €/t slag). Therefore, CSP might be a potential candidate for the treatment of Received: 31 May 2021 copper slag to recover copper and iron. Accepted: 24 June 2021 Published: 27 June 2021 Keywords: concentrated solar power (CSP); copper slag; copper; environment; sustainable metal- lurgy; solar energy Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affil- iations. 1. Introduction Copper is one of the most mined metals on the Earth due to the applications of this metal in different fields. However, a lot of tailing material, currently unprocessed, is generated in the process, and provides a huge opportunity to use concentrated solar power Copyright: © 2021 by the authors. (CSP). Licensee MDPI, Basel, Switzerland. The pyrometallurgical technique is the most important to produce copper, and the This article is an open access article smelting conversion process is the most widely used within this route [1]. Thus, 80% of distributed under the terms and conditions of the Creative Commons the copper is currently produced by the concentration, smelting, and refining of sulfide Attribution (CC BY) license (https:// ores [2], which include chalcopyrite (CuFeS2), bornite (Cu5FeS4), and chalcocite (Cu2S). creativecommons.org/licenses/by/ Different products are generated in the fusion conversion process (Figure1). These include 4.0/). matte, which is heavy and contains most of the copper as sulfide (it is later treated in the Metals 2021, 11, 1032. https://doi.org/10.3390/met11071032 https://www.mdpi.com/journal/metals Metals 2021, 11, x FOR PEER REVIEW 2 of 18 Metals 2021, 11, 1032 2 of 18 include matte, which is heavy and contains most of the copper as sulfide (it is later treated converter to obtain blister copper, and finally metallic copper is produced after fire refining in the converter to obtain blister copper, and finally metallic copper is produced after fire and electrowinning) and slag, which contains most of the iron as fayalite. refining and electrowinning) and slag, which contains most of the iron as fayalite. FigureFigure 1. 1. FlowFlow diagram diagram of ofthe the smelting smelting conversion conversion process process of copper. of copper. TwoTwo slags slags are are produced produced in the in smelting the smelting conversion conversion process: process: first, in the first, smelting in the fur- smelting nace,furnace, and andsecond second in the in converter. the converter. However, However, these slags these contain slags (apart contain from (apart fayalite from and fayalite magnetite,and magnetite, which which are the are main the mainphases) phases) significant significant quantities quantities of copper of copper (sulfide (sulfide (matte) (matte) draggeddragged or or trapped trapped by by the the slag, slag, or oroxide oxide associated associated with with other other oxides oxides of the of slag the [1,3]). slag [1,3]). The slags slags are are reprocessed reprocessed in inthe the smelting smelting furnace furnace or in or the in theslag slagcleaning cleaning furnace furnace (electric (electric furnaces,furnaces, where where carbon carbon and and pyrite pyrite are are used used as additives) as additives) to recover to recover some some of the of copper. the copper. Finally,Finally, the the final final slag slag is isdisposed disposed of ofin ina controlled a controlled landfill landfill when when the copper the copper concentration concentration isis approximately approximately in in the the range range 1 to 1 to2 wt. 2 wt. % Cu. % Cu. CopperCopper slags slags might might be be considered considered a residue/by-product a residue/by-product with withgreat great potential potential due to due to bothboth the the copper (1–2 wt. % Cu) and iron (>40(>40 wt. % [[4–10])4–10]) contents as a secondarysecondary resourcere- sourcefor metal for recoverymetal recovery [11]. A[11]. total A oftotal 20 Mtof 20 of Mt primary of primary copper copper are produced are produced worldwide, world- and wide,this involves and this 45involves Mt of slag45 Mt generated of slag generated in the process in the (2.2–3process tons (2.2–3 of slag/ton tons of slag/ton copper cop- [2,12,13]), perwhich [2,12,13]), would which represent would >20 represent Mt Fe >20 and Mt 0.5–1 Fe and Mt 0.5–1 Cu Mt yearly Cu yearly sent tosent controlled to controlled landfills. landfills.Therefore, Therefore, copper copper slag represents slag represents an environmental an environmental impact impact [4]: [4]: risks risks of of heavy heavy metals metalslixiviation, lixiviation, a visual a visual impact, impact, and sometimesand sometimes occupation occupation of cultivable of cultivable areas. areas. Researchers Re- searchers have tried to find a use for copper slags, but a massive industrial utilization has have tried to find a use for copper slags, but a massive industrial utilization has still not still not been found [14]. Copper slags have been used as abrasives (polishing and clean- been found [14]. Copper slags have been used as abrasives (polishing and cleaning) for ing) for metallic structures [15,16] and mainly in the building industry: concrete manufac- metallic structures [15,16] and mainly in the building industry: concrete manufactured tured with copper slag [5]; copper slags as fine particles in concrete manufacturing [13]; with copper slag [5]; copper slags as fine particles in concrete manufacturing [13]; copper copper slag as a replacement for the sand in cements [9]; copper slag as a filler in glass– epoxyslag as composites a replacement [17]; and for thecopper sand slag in cementsas a construction [9]; copper material slag asin bituminous a filler in glass–epoxy pave- mentscomposites [18]. Research [17]; and has copper also focused slag as on a construction the recovery materialof iron from in bituminousthe slag: by using pavements coke [18]. asResearch reductant has of also the focusedcopper oxide on the and recovery the magnetite of iron from [19]; theby slag:modifying by using the cokemolten as reductantslag withof the the copper purpose oxide of promoting and the magnetite the mineralization [19]; by modifying of recoverable the molten mineral slag phases with and the in- purpose ducingof promoting the growth the mineralization of the mineral ofphases recoverable [20]; by mineral using a phasesmethod and based inducing on coal, the Direct growth of Reductionthe mineral Iron phases (DRI), [20 and]; by magnetic using a method separation based [21]; on by coal, means Direct of Reduction a process Ironbased (DRI), on and magnetic separation [21]; by means of a process based on aluminothermic reduction [22]; by reduction in an electric furnace with the objective of obtaining a Cu-Pb-Fe alloy [23]; by carbothermic reduction to transform the copper slag into pig iron and glassy material [24]; Metals 2021, 11, 1032 3 of 18 by irradiation with a microwave as a support of the carbothermal method [25]; or by reduction with coke powders and magnetic separation [26]. Solar energy has been widely used in materials science and metallurgy [27]. The main types of research in the field of metallurgy carried out with concentrated solar power (CSP) are listed in Table1.
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