Insight into the Extractive Metallurgy of Tin from Cassiterite.

This review details both the conventional and emerging methods of extracting tin from cassiterite. The emerging methods reviewed include sulphuric acid leaching of SnO, cooling crystallization of SnO, sulphide leaching, alkaline leaching, and dry chlorination. From these methods, the conventional approach (direct reduction smelting) stands out as the sole method that is suitable for industrial application, with none of the emerging ones being promising enough to be a contender. The thermodynamics involved in the hydrometallurgical extraction of tin from the mineral are also discussed. ΔGo values calculated at 25 °C for the reduction-dissolution of SnO2 using reducing gases revealed feasibility only when carbon monoxide was used. An indication of the possible species produced during the hydrolysis of the oxide of the metal (SnO2 and SnO) as a function of pH (ranging from -2 to 14 and 0 to 14 for SnO2 and SnO, respectively) was noted and highlighted to link a Pourbaix diagram generated from literature data. This diagram suggests that the solubility of SnO2 in both strongly acidic and alkaline media is possible, but with a small dissolution window in each. The purification and recovery routes of the various processing techniques were then envisaged.

Mineral Weathering and Metal Leaching under Meteoric Conditions in F-(Ba-Pb-Zn) Mining Waste of Hammam Zriba (NE Tunisia).

Mining waste is an obvious source of environmental pollution due to the presence of heavy metals, which can contaminate soils, water resources, sediments, air, and people living nearby. The F-(Ba-Pb-Zn) deposit of Hammam Zriba located in northeast Tunisia, 8 km southeast of Zaghouan was intensively exploited from 1970 to 1992. More than 250,000 m3 of flotation tailings were produced and stored in the open air in three dumps without any measure of environmental protection. Thus, in this paper, mineralogical and chemical characterization, especially the sulfide and carbonate phases, were carried out to evaluate the potential for acid mining drainage (AMD) and metal leaching (ML). Conventional analytical methods (XRD, XRF, SEM) have revealed that this mining waste contains on average 34.8% barite-celestine series, 26.6% calcite, 23% quartz, 6.3% anglesite, 4.8% fluorite, 2.1% pyrite, and 0.4% sphalerite. The content of sulfides is less important. The tailing leaching tests (AFNOR NFX 31-210 standard) did not generate acidic leachate (pH: 8.3). The acidity produced by sulfide oxidation was neutralized by calcite present in abundance. Furthermore, the leaching tests yielded leachates with high concentrations of heavy metals, above the authorized thresholds. This high mobilization rate in potential toxic elements (PTE) represents a contamination risk for the environment.

Processing of End-of-Life Materials and Industrial Wastes.

This Special Issue (SI) offered the opportunity to present the latest scientific developments and findings in the field of processing of end-of-life materials and solid industrial wastes. Due to the large quantity of wastes generated and to their complex elemental and mineralogical composition, the approaches, methods and processes proposed for their decontamination, energy beneficiation and high-added-value metal recovery are complex and diverse. Some transversal research investigations using wastes as remediation agents and for synthesis of new materials were also included in the SI. After a brief introduction, the main scientific contributions and findings of each article published in the SI are summarized.

Novel extraction route of lithium from α-spodumene by dry chlorination.

Processing spodumene for lithium is challenging as it requires a high temperature transformation of the natural α-monoclinic form to ß-tetragonal form, usually followed by acid baking and digestion. This three-step extraction process requires significant heat energy, acid, process complexity and residence time, leading to both operating and capital costs. An approach which helps to eliminate this challenge will therefore be a milestone in processing spodumene. This study, thus, investigates a direct chlorination of α-spodumene using calcium chloride followed by water leaching of the residue to recover lithium, which reduces the energy requirement and number of unit operations. HSC Chemistry software was used to simulate the process using both phases (α and ß) of the mineral up to 1100 °C prior to experimental investigation. The α-form was the only polymorph identified in residues after leaching, suggesting that the extraction is directly from the α-phase. However, an initial formation of a metastable ß-form followed by a fast synthesis of lithium chloride from it is also suspected. Under optimal conditions of calcium chloride/spodumene molar ratio of 2.0, and 1000 °C treatment for 60 minutes, almost 90 percent lithium chloride was extracted and 85 percent was recovered to the leach solution with the remainder exiting with the off-gas. An apparent activation energy of about 122 ± 6 kJ mol-1 was obtained at temperatures ranging from 800 to 950 °C during the process.

Physico-Chemical Characteristics of Spodumene Concentrate and Its Thermal Transformations.

Spodumene concentrate from the Pilbara region in Western Australia was characterized by X-ray diffraction (XRD), Scanning Electron Microscope Energy Dispersive Spectroscopy (SEM-EDS) and Mineral Liberation Analysis (MLA) to identify and quantify major minerals in the concentrate. Particle diameters ranged from 10 to 200 microns and the degree of liberation of major minerals was found to be more than 90%. The thermal behavior of spodumene and the concentration of its polymorphs were studied by heat treatments in the range of 900 to 1050 °C. All three polymorphs of the mineral (α, γ and ß) were identified. Full transformation of the α-phase was achieved at 975 °C and 1000 °C after 240 and 60 min treatments, respectively. SEM images of thermally treated concentrate revealed fracturing of spodumene grains, producing minor cracks initially which became more prominent with increasing temperature. Material disintegration, melting and agglomeration with gangue minerals were also observed at higher temperatures. The metastable γ-phase achieved a peak concentration of 23% after 120 min at 975 °C. We suggest 1050 °C to be the threshold temperature for the process where even a short residence time causes appreciable transformation, however, 1000 °C may be the ideal temperature for processing the concentrate due to the degree of material disintegration and α-phase transformation observed. The application of a first-order kinetic model yields kinetic parameters which fit the experimental data well. The resultant apparent activation energies of 655 and 731 kJ mol-1 obtained for α- and γ-decay, respectively, confirm the strong temperature dependence for the spodumene polymorph transformations.

Some Aspects of the Thermochemical Route for the Valorization of Plastic Wastes, Part I: Reduction of Iron Oxides by Polyvinyl Chloride (PVC).

The mass production of synthetic plastics began in the last century and today they have become one of the most abundant man-made materials. The disposal or the beneficiation of end-of-life plastics represent a great challenge for society especially in the case of polyvinyl chloride (PVC). This study is focused on the use of PVC waste as a useful agent for the direct reduction of hematite (Fe2O3) after a thermal treatment at 300 °C for removing the chlorine contained in PVC. Thermal reduction tests were conducted from 600 °C to 1100 °C with (Fe2O3 + PVC + clay) pellet mixtures in which clay was used as plasticizing and binder agent of the pellets. The starting samples and treatment residues were analyzed by scanning electron microscopy through energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD) to monitor the chemical behavior and reactivity of the pellet constituents during their thermal treatment. The stepwise reduction of hematite up to metallic iron was achieved at temperatures approaching 1000 °C, confirming the capability of using PVC waste for the direct reduction of iron oxides.

New EAF Slag Characterization Methodology for Strategic Metal Recovery.

The grown demand of current and future development of new technologies for high added value and strategic metals, such as molybdenum, vanadium, and chromium, and facing to the depletion of basic primary resources of these metals, the metal extraction and recovery from industrial by-products and wastes is a promising choice. Slag from the steelmaking sector contains a significant amount of metals; therefore, it must be considered to be an abundant secondary resource for several strategic materials, especially chromium. In this work, the generated slag from electric arc furnace (EAF) provided by the French steel industry was characterized by using multitude analytical techniques in order to determine the physico-chemical characteristics of the targeted slag. The revealed main crystallized phases are larnite (Ca2SiO4), magnetite (Fe3O4), srebrodolskite (Ca2Fe2O5), wüstite (FeO), maghemite (Fe2.6O3), hematite (Fe2O3), chromite [(Fe,Mg)Cr2O4], and quartz (SiO2). The collected slag sample contains about 34.1% iron (48.5% Fe2O3) and 3.5% chromium, whilst the vanadium contents is around 1500 ppm. The Mössbauer spectroscopy suggested that the non-magnetic fraction represents 42 wt% of the slag, while the remainder (58 wt%) is composed of magnetic components. The thermal treatment of steel slag up to 900 °C indicated that this solid is almost stable and few contained phases change their structures.

Reactivity of Low-Grade Chromite Concentrates towards Chlorinating Atmospheres.

The most economically important iron-chromium bearing minerals is chromite. In natural deposits, iron(II) is frequently substituted by magnesium(II) while chromium(III) is replaced by aluminum(III) and/or iron(III) forming a complex chromium bearing material. The majority of mined chromite is intended for the production of ferrochrome which requires a chromite concentrate with high chromium-to-iron ratio. Found mostly in the spinel chromite structure, iron cannot be removed by physical mineral processing methods. In this frame, the present work deals with the reaction of chlorine and chlorine+oxygen with selected samples of chromite concentrates for assessing the reactivity of their components towards chlorinating atmosphere, allowing the preferential removal of iron, hence meeting the chromite metallurgical grade requirements. Isothermal thermogravimetric analysis was used as a reliable approach for the kinetic reactivity investigation. Results indicated a wide difference in the thermal behavior of chromite constituents in a chlorinating atmosphere when considering their respective values of apparent activation energy oscillating from about 60 to 300 kJ/mol as a function of the sample reacted fraction. During the chromite treatment by chlorine in presence of oxygen, chromium was recovered as liquid chromyl chloride by condensation of the reaction gas phase.

Thermochemical Route for Extraction and Recycling of Critical, Strategic and High-Value Elements from By-Products and End-of-Life Materials, Part II: Processing in Presence of Halogenated Atmosphere.

During the treatment of copper anode slime (CAS) under an air atmosphere, several aspects of the interactions of its main components (CuAgSe, Cu2-xSeyS1-y, Ag3AuSe2) with oxygen were described in Part I. As a comparative and complementary study, this work deals with the thermal behavior of CAS under air in the presence of polyvinyl chloride (PVC) between 195 and 770 °C. The preliminary thermal treatment of an e-waste sample containing brominated substances was also performed. The reaction products were systematically analyzed by scanning electron microscopy through energy-dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD) to investigate the thermal behaviors of the studied samples in a halogenated medium. At low temperatures, the copper, silver and selenium compounds of the CAS reacted with the HCl, issued from PVC degradation, leading to the formation of their respective chlorides. Bromides of valuable metals (Cu, Pb, Sn…) were synthesized during the e-waste treatment at 500 °C and they were distributed between the solid residue and gaseous phase. The data obtained give an insight into the reactivity of several metals towards halogenated substances, which may be valuable information for conducting the extraction and recycling of targeted elements from industrial by-products and end-of-life materials by a thermochemical route.

Green Process for Industrial Waste Transformation into Super-Oxidizing Materials Named Alkali Metal Ferrates (VI).

The investigation presented here features the design of a cleaner and greener chemical process for the conversion of industrial wastes into super-oxidizing materials. The waste of interest is the iron sulfate heptahydrate (FeSO4·7H2O) mainly generated through the sulfate route used for titanium dioxide industrial production. The products of this transformation process are alkali ferrates (A2FeO4, A = Na, K) containing iron in its hexavalent state and considered as powerful oxidants characterized by properties useful for cleaning waters, wastewaters, and industrial effluents. The proposed process includes two steps: (i) The first step consisting of the pre-mixing of two solids (AOH with FeSO4·xH2O) in a rotary reactor allowing the coating of iron sulfate in the alkali hydroxides through solid-solid reactions; and (ii) the second step involves the synthesis of alkali ferrates in a fluidized bed by oxidation of the single solid obtained in the first step in diluted chlorine. The chemical synthesis of alkali ferrates can be carried out within a timeframe of a few minutes. The usage of a fluidized bed enhanced the energy and mass transfer allowing a quasi-complete control of the ferrate synthesis process. The alkali ferrate synthesis process described here possesses many characteristics aligned with the principles of the "green chemistry".

Thermochemical Route for Extraction and Recycling of Critical, Strategic and High Value Elements from By-Products and End-of-Life Materials, Part I: Treatment of a Copper By-Product in Air Atmosphere.

Development of our modern society requests a number of critical and strategic elements (platinum group metals, In, Ga, Ge…) and high value added elements (Au, Ag, Se, Te, Ni…) which are often concentrated in by-products during the extraction of base metals (Cu, Pb, Zn…). Further, recycling of end-of-life materials employed in high technology, renewable energy and transport by conventional extractive processes also leads to the concentration of such chemical elements and their compounds in metallurgical by-products and/or co-products. One of these materials, copper anode slime (CAS), derived from a copper electrolytic refining factory, was used for this study. The sample was subjected to isothermal treatment from 225 to 770 °C under air atmosphere and the reaction products were systematically analyzed by scanning electron microscopy through energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD) to investigate the thermal behavior of the treated sample. The main components of the anode slime (CuAgSe, Cu2-xSeyS1-y, Ag3AuSe2) react with oxygen, producing mostly copper and selenium oxides as well as Ag-Au alloys as final products at temperatures higher than 500 °C. Selenium dioxide (SeO2) is volatilized and recovered in pure state by cooling the gaseous phase, whilst copper(II) oxide, silver, gold and tellurium remain in the treatment residue.