Heliyon 6 (2020) e03135 Contents lists available at ScienceDirect Heliyon journal homepage: www.cell.com/heliyon Research article Enhancing the flotation recovery of copper minerals in smelter slags from Namibia prior to disposal V. Sibanda a, E. Sipunga a, G. Danha b, T.A. Mamvura b,* a School of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, Private Bag 3, Wits, 2050, South Africa b Department of Chemical, Materials and Metallurgical Engineering, Faculty of Engineering and Technology, Botswana International University of Science and Technology, Plot 10071, Boseja Ward, Private Bag 16, Palapye, Botswana ARTICLE INFO ABSTRACT Keywords: Namibia Custom Smelters (NCS) process a range of copper concentrates in their three furnaces, namely; top Metallurgical engineering submerged lance, copper converter and reverberatory furnaces, in order to produce mattes and fayalitic slags. The Materials characterization copper content of the slags range between 0.8 to 5 wt. % and this is considered too high for disposal to the Degradation environment. Currently, the slags are sent to a milling and flotation plant for liberation and recovery of residual Metallurgical process copper. The copper recoveries realized in the plant are much lower than expected and it has been postulated that Metallurgy fi fl fi Materials property some copper minerals may be occurring in forms that are more dif cult to oat like oxides or ne disseminations Top submerged lance in the gangue matrix. Mineralogical analysis of the slag samples was done using X-Ray Diffraction (XRD) and Converter slag Scanning Electron Microscopy (SEM) techniques. The analysis did not reveal the presence of copper oxide min- Reverbetory furnace slag erals, however most scans showed copper sulphide minerals as free grains and some finely disseminated in Copper recovery fayalite gangue. In the first phase of the present experimental studies, the slags were milled to 75% passing 45 Flotation microns, which is the degree of milling done in the existing plant mill-float circuit. A range of commercial Milling and grinding flotation reagents that include xanthates, dithiophosphates, mercaptobenzothiazole, thionocarbamates, fatty acids, sulphides and sulphates were used in the flotation test-work. The copper recoveries obtained in the mill- float stage were between 70 - 80%. In the second phase of the study, the flotation tailings were further milled to 90% passing 45 microns and floated. The cumulative copper recoveries increased markedly to over 90%, which represents a significant improvement in comparison to the recoveries obtained from the mill-float process. Sodium alkyl dithiophosphate, mercaptobenzothiazole (FC7245) was found to be the secondary flotation reagent that gave the best copper recoveries. 1. Introduction Slags are basically formed by fluxing agents used to aid high tem- perature liquid-liquid separation in furnaces. The gangue portion of the Slags that are produced from smelting of both ferrous and non-ferrous ore, with the help of fluxes, is absorbed in the slag phase during smelting metal ores and concentrates together with other metallurgically gener- while the valuable portion is tapped off as matte. Slags have found a wide ated residues like tailings dumps are increasingly becoming a subject of range of applications in civil engineering, fertilizer production, road great environmental and ecological debate. The world now holds the construction, cement production and in landfilling (Ziemkiewicz, 1998). view that economic and ecological considerations have to be integrated Wang et al. (2011) reported that the main constituents of copper smelter into the extraction process design, hence the emergence of the concept of slags found around the world are FeO and SiO2, which are components of sustainable metallurgy (Zander et al., 2013). fayalite, and each is present at about 20–55 wt. %. They also reported Sustainable metallurgy emphasizes on the point that recovery of that the copper content of most smelter slags is normally around 1–2 wt. valuable materials from waste residues, their reuse and recycling have a % while that of the converter slag lies between 2 and 2.5 wt. %. This major advantage of saving the earth's finite resources and reducing the higher content for the latter is due to over-oxidation and entrapment of negative impact that waste has on the environment. metal droplets during the converting process. * Corresponding author. E-mail address: [email protected] (T.A. Mamvura). https://doi.org/10.1016/j.heliyon.2019.e03135 Received 11 November 2019; Received in revised form 11 December 2019; Accepted 24 December 2019 2405-8440/© 2019 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). V. Sibanda et al. Heliyon 6 (2020) e03135 In the smelting process, the melt bath instability causes entrapment of the rougher cells. The rougher tails are fed to a series of scavenger cells valuable minerals in slags, resulting in slags that are enriched in mineral before exiting the plant as final tailings. Potassium amyl xanthate (~300 values. The mineral entrapment occurs partly due to mechanical g/t) is the primary flotation collector reagent used, and Sodium Dia- entrapment of matte in the form of fine dispersions of metal sulphides lkyldithiophosphate (200 g/t) is added as a secondary collector. The (Herreros et al., 1998; Sun, 2006) or as heavy metals dissolving into slag main concern with the current process is that tailings grade in the excess as oxides chemically bound with silica in fayalite (Curlook and Papan- of 0.9% Cu are consistently produced. This copper content is considered gelakis, 2004; Toscano, 2001; Toscano and Utigard, 2003). These too high to be lost in the final waste stream. Therefore, the scope of the enriched slags are normally cleaned to remove wanted minerals and present work involves an investigation into how the flotation recoveries metals. Slag cleaning can be divided into two types, first being the py- of the copper minerals can be enhanced by studying the mineralogy, rometallurgical reduction and settling of liquid slag, which is performed milling and liberation profile of the slags and the flotation reagent suite in slag-cleaning furnaces, and the second type being the mineral that can be used to optimally recover the copper minerals from the slags. processing-based slag cleaning of solidified or granulated slag by crush- ing and/or grinding followed by gravity concentration or froth flotation 2. Materials and methods (Davenport et al., 2002). Pyrometallurgical cleaning of copper slags involves inducing condi- 2.1. Feed material tions that encourage suspended matte (Cu2S) droplets to settle into the matte layer. The conditions are achieved by creating a low slag viscosity, The feed material used in this investigation was sourced from a low bath turbulence, longer residence time and a thin slag layer (Guo mineral processing plant called the Namibian Custom Smelters (NCS) et al., 2016). These conditions are often difficult to obtain in the main that is situated in a Southern African state called Namibia. Three ho- smelting vessel, particularly the necessary residence time, hence some mogenized samples were obtained from a reverberatory furnace slag, top copper producers construct separate furnaces specifically for cleaning, submerged lance (TSL) slag and a converter slag, respectively. Laboratory smelting and converting slags that have a high residual copper mineral tests were then carried out on these samples as well as on the combined content (Davenport et al., 2002). slag, with the aim of recovering copper minerals. Flotation is a physical and chemical separation process that utilizes the difference in surface properties of the valuable minerals and the 2.2. Mineralogical tests unwanted gangue minerals (Wills, 2006). Recovery of materials during fl otation can be explained by the following three mechanisms: (i) selec- The prepared and homogenized sub-samples of reverberatory, TSL “ fl ” tive attachment to air bubbles ( true otation ); (ii) entrainment in water and converter slags were submitted for mineralogical analyses using X- passing through froth; and (iii) physical entrapment between particles in ray diffraction (XRD) and scanning electron microscope (SEM) tech- “ ” the froth attached to air bubbles ( aggregation ). The majority of the niques. For XRD analysis, the different samples were prepared same as fl recovery takes place via true otation, as it is a highly chemically se- Ettler et al. (2009) by using a backloading preparation method. For SEM fi lective process. The separation ef ciency between gangue and valuable analysis, the procedure followed that in Ettler et al. (2009). mineral is also dependent on the degree of entrainment and physical A chemical analysis was performed on different size classes of milled entrapment. The two are not chemically selective processes, hence samples to determine the copper deportment across the spectrum of the gangue and valuable minerals are both recovered by entrainment and size classes. Three slag samples (converter slag, TSL slag, reverb slag) fi entrapment. Wills (2006) noted that copper sul de (Cu2S) minerals have were submitted to an external laboratory, SGS (South Africa). Mineral- fl good otation response to anionic collectors such as amyl, iso-propyl and ogical analyses on the slags were performed, particularly for the copper butyl xanthates, and the concentrations of collectors added usually