Metallurgical Solid Waste: Mineralogy, Chemistry and Application/Treatment

From the colonial era to modern times, gold mining has played a crucial role in shaping Brazil’s economy, culture, and landscape, particularly in the Iron Quadrangle region. Therefore, resulting waste has accumulated in tailings structures, either from deactivated circuits or plants still in production. The present study reveals the potential assessed based on a set of metallurgical tests, assuming specific scenarios depending on the occurrence modes of interesting economic elements. For Au, calcination, leaching, and flotation are promising techniques to recover this element. Tests indicated that toxic elements such as Sb and As could be effectively reused in the form of glass. The generation of other products from dry cleaning techniques was not effective but promising since there was an enrichment of elements with Au, Fe, Al, and K in specific fractions. Full article

Crude steel production in China exceeds 1 billion tons per year, and steel slag production accounts for 10%–15% of the crude steel mass. Although slag presents certain hydration activity, it is still difficult to be used as a building material because the particles contain a large amount of active calcium oxide and magnesium oxide, which are easy to hydrate and expand besides presenting low stability. The heap stock is increasing at a rate of 80 Mt/a because of the limitation of application scenarios. Moreover, every 1 ton of crude steel is associated with an emission of 1.8 tons of carbon dioxide (CO₂), which becomes a greenhouse gas, because it cannot be reused at the moment. In this investigation, CO₂ was used to cure steel slag particles, and the coupling mineralization reaction between them was used to convert active calcium oxide and magnesium oxide in steel slag into carbonate forms and, thus, allow the processing of steel slag particles into fine building aggregate. Two particle size ranges of 0.6–2.36 and 2.36–4.75 mm were selected as representative particle sizes. Mineralization was carried out under a temperature of 25 °C, relative humidity of 75%, a CO₂ concentration of 20%, and a time of 24 h. The carbon fixation rate of steel slag was 9.68%. The quality of steel slag fine aggregate as a product met the GB/T 14684-2011 construction sand grade II standard. The application of this technology is expected to improve the stability of steel slag particles, the utilization rate as a building material, and the resource utilization level of CO₂. It is expected to realize the full, high-value-added resource utilization of steel slag and CO₂ absorption and solve the supply shortage problem of fine aggregate for construction in China, which has potential economic and environmental benefits. Full article

In order to investigate the influence of SiC on the composition and structure of mixed slag (blast-furnace slag: steel slag = 1:9), the chemical composition, equilibrium-phase composition, and microscopic morphological characteristics and elemental distribution in the microscopic region of the SiC-reagent-tempered slag samples were analyzed by X-ray diffractometer (XRD), FactSage7.1 thermodynamic analysis software, scanning electron microscope, and energy spectrum analyzer. It was found that the main physical phases of the tempered slag samples were magnesia–silica–calcite (Ca₃Mg(SiO₄)₂, C₃MS₂), calcium–aluminum yellow feldspar (Ca₂Al₂SiO₇, C₂AS), C₂S, and iron alloy. Theoretical calculations suggest that the experimental temperature should be higher than 1500 °C to facilitate the combination of P⁵⁺ with Fe and Mn in the liquid phase to form an alloy, reduce the P5+ content in the tempered slag, and create conditions for the self-powdering of the conditioned slag. The doping of the SiC reagent can increase the liquid phase line temperature and reduce the binary basicity in the liquid phase; the liquid phase line temperatures were 1150 °C, 1200 °C, and 1300 °C and the basicities in the liquid phase were 4.68, 4.13, and 3.10 for the doping amounts of 3%, 4%, and 5% of the SiC reagent, respectively. The mixed slag doped with 4% SiC reagent achieves self-powdering and reduction of ferroalloys during the air-cooling and cooling processes, realizing the purpose of “resource utilization” of blast-furnace slag and steel slag. Full article

Phosphoric acid-based porous geopolymers were prepared by two different foaming agents (H₂O₂ and Al powder) with phosphoric acid as the activator. High-magnesium nickel slag (HMNS) and fly ash (FA) were the precursor combination. The effects of foaming agent types and contents on the properties of HMNS-FA-phosphate-based porous geopolymers were investigated in terms of dry density, pore structure, compressive strength, thermal conductivity, and water absorption. The phase was analyzed by x-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). It was found that both foaming agents could successfully prepare porous geopolymers, and the compressive strength and dry density of porous geopolymers gradually decreased and the low-thermal conductivity and water absorption gradually increased with the increase in foaming agent content. The foaming agents formed porous structures inside porous geopolymers but did not affect the phases of geopolymerization reactions. This study demonstrates that both foaming agents can be used to prepare HMNS-FA-phosphate-based porous geopolymers for the application of phosphate-activated geopolymers in the direction of refractory materials. Full article

Mining activities offer clear economic benefits for mineral-rich countries. However, mining operations can produce several environmental impacts. Many of these are associated with generating and managing mining waste known as tailings, which are typically stored in surface facilities. Windblown dust emissions from tailing deposits can cause severe damage to local ecosystems and adverse health effects for the surrounding population. Microbially induced calcite precipitation (MICP) can be used for the superficial biocementation of tailings, thereby preventing such emissions. This research studied the capacity of MICP for the biocementation of tailings. The effect of applying different doses of biocementation reagents and two different methods for their application were evaluated. Results show that a relevant increase in surface strength can be achieved, especially if reagents are mechanically mixed with the tailings to induce a more homogeneous distribution of precipitates. Micrographical and mineralogical analysis by SEM, FTIR and XRD analysis showed the precipitation of calcium in the form of anorthite, calcite or vaterite. Overall results indicate that calcite precipitation can be induced in tailing by microorganisms with urease activity, providing a potential technique for the biocementation of this material. Full article

Annually, hundreds of thousands of tons of slags are involved in the reverberator and flash smelting as well as converting operations of Cu-Fe sulfide concentrates to produce matte in the Sar Cheshmeh copper smelter plant, Iran, disposed in the landfill and cooled in air. Due to their relatively high average copper content (about 1.5 wt%), a mineral processing plant based on the flotation process has recently been established to produce thousands of tons of Cu-sulfide concentrate after slag crushing and fine grinding operation. In order to make the flotation process more efficient, more knowledge is required on the form and origin of the copper losses in the slag. To achieve this, mineralogical studies of the slags using optical microscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM) methods have been carried out. Mineralogical analyses showed the main part of copper losses into the semi- to fully-crystallized magnetite-rich reverberator and flash slags characterized by crystal–glass matrix ratio ≤ 1 is moderate to coarse particles of Cu-Fe sulfides, i.e., chalcopyrite (CuFeS₂) and bornite (Cu₅FeS₄), that are mainly chemically entrapped. In contrast, the mechanically entrapped fine- to coarse-grain (from 20 up to 200 µm) spherical-shaped of high-grade matte particles with chalcocite (Cu₂S) composition containing droplets or veinlets of metallic copper (Cu⁰) are the dominant forms of copper losses into the converter slags characterized by crystal–glass matrix ratio > 1. From the value recovery point of view, our result show that the fully crystallized slags containing moderate- to coarse-grain copper-bearing particles will result in efficient recovery of a significant amount of entrained copper due to better milling response compared to semi-crystallized ones due to locking the fine- to moderate-grain copper particles in the silicate glassy matrix. Laboratory-scale grinding experiments showed that normal (≤74 μm) to fine (≤44 μm) grinding of high- Cu grade slags lead to a significant increase in the liberation degree of copper particles. in contrast, the increase in fine particle fractions (<37 μm) due to re-grinding or ultra-fine grinding of the originally low-Cu grade slags does not lead to the liberation of copper particles, but it will reduce the efficiency of the flotation process. This study suggests that the highest rate of copper recovery of the slag by the flotation process will be obtained at particle size 80% passing 44 µm which has also reached the optimal liberation degree of copper-bearing particles. Full article

Red mud (RM), a byproduct of aluminum production, is used as amendments to increase the pH and reduce the available Cd in soil, but the effects of RM treatments on rice and rhizosphere chemistry changes at different radial-oxygen-loss (ROL) rates and developmental stages remain unclear. To address this concern, a rhizobox trial was conducted to investigate the effect of 0%, 0.5%, and 1.0% RM, on Cd accumulation by rice cultivars differing in ROL rate (‘Zheyou12’ (ZY12), ‘Qianyou1’ (QY1), and ‘Chunjiangnuo2’ (CJN2)) at two growth stages (tillering and bolting). The results showed that mobility factors of Cd in the soil were decreased significantly at both stages. The Cd mobility factor (MF) of CJN2 was decreased by 33.01% under 1% RM treatment at bolting stage. The pH value was increased by 0.39–0.53 units at two stages. RM contains large amounts of metals, which can increase soil iron (Fe) and manganese (Mn) concentrations, reduce redox potential, and transform the available Cd into Fe/Mn oxide-bound Cd. In addition, the Fe plaque further increased to inhibit the transformation of Cd. These changes reduced the available Cd in the soil and further decreased Cd absorption by rice. With the increase in RM concentration, the shoot and root biomass increased, and Cd accumulation in the plant significantly decreased. Compared with that under 0% RM treatment, the shoot Cd concentrations of ZY12, QY1, and CJN2 under 1% RM treatment at the bolting stage decreased by 27.59%, 36.00%, and 46.03%, respectively. The relative Cd accumulation ability of the three rice cultivars was CJN2 < QY1 < ZY12. The ROL promotes Fe plaque formation on the root surface. The Fe plaque is an obstacle or buffer between Cd and rice, which can immobilize Cd in Fe plaque and further reduce Cd absorption by rice. The addition of RM, in combination with a high-ROL rice cultivar, is a potential strategy for the safe production of rice on Cd-contaminated soils. Full article

In this study, molecular dynamics simulation was used to study the effect of SiO₂/Al₂O₃ mass ratio on the structural properties and viscosity of molten fused red mud. The stability of various T–O bonds in the melt was elucidated by analyzing the bond angle and coordination number; the degree of polymerization, and the stability of the melt were explored by analyzing the number of T–O–T bridging oxygen (BO) and the distribution of $Q_{Si}^n$ and $Q_{Al}^n$ of [SiO₄]⁴⁻ as well as that of $Q_{Si}^n$ and $Q_{Al}^n$ of [AlO₄]⁵⁻; the self-diffusion coefficient of each atom was determined by mean square displacement (MSD) analysis; and the trend of the melt viscosity was analyzed according to the relationship between diffusion and viscosity. The results show that as the ratio of SiO₂/Al₂O₃ increases, the viscosity of molten fused red mud first increases, then decreases, and finally increases. This is because Ti⁴ and Fe³⁺ combine with O²⁻ to form [TiO₆]⁸⁻ octahedron and [FeO₄]⁵⁻ tetrahedra, which increase the degree of depolymerization of the melt. Full article

Four industrial wastes, i.e., blast furnace slag, steel slag, desulfurization ash, and phosphoric acid sludge, were used to prepare a low-carbon binder, metallurgical slag-based cementitious material (MSCM). The feasibility of solidification/stabilization of municipal solid waste incineration (MSWI) fly ashes by MSCM were evaluated, and the immobilization mechanisms of heavy metals were proposed. The MSCM paste achieved 28-day strength of 35.2 MPa, showing its high-hydration reactivity. While the fly ash content was as high as 80 wt.%, the 28-day strength of MSCM-fly ash blocks reached 2.2 MPa, and the leaching concentrations of Pb, Zn, Cr, and Hg were much lower than the limit values of the Chinese landfill standard (GB 16889-2008). The immobilization rates of each heavy metal reached 98.75–99.99%, while four kinds of MSWI fly ashes were solidified by MSWI at fly ash content of 60 wt.%. The 28-day strength of binder-fly ash blocks had an increase of 104.92–127.96% by using MSCM to replace ordinary Portland cement (OPC). Correspondingly, the lower leachability of heavy metals was achieved by using MSCM compared to OPC. The mechanisms of solidification/stabilization treatment of MSWI fly ash by MSCM were investigated by XRD, SEM, and TG-DSC. Numerous hydrates, such as calcium silicate hydrate (C-S-H), ettringite (AFt), and Friedel’s salt, were observed in hardened MSCM-fly ash pastes. Heavy metals from both MSWI fly ash and MSCM could be effectively immobilized via adsorption, cation exchange, precipitation, and physical encapsulation. Full article

The carbothermic co-reduction of nickel laterite ore and red mud realized the simultaneous reduction of nickel, iron in laterite ore, and iron in red mud at high efficiency. Nickel and iron in nickel laterite ore and iron in red mud were recovered in the form of ferronickel. The size characteristics of ferronickel particles and grindability of carbothermic reduction products are essential for obtaining good technical indicators. The influence of co-reduction conditions on ferronickel particle size and relative grindability was investigated by a carbothermic reduction test, particle size analysis, and relative grindability determination. The mean size of ferronickel particles increased and the proportion of coarse particles grew with improving carbothermic reduction temperature, increasing appropriately anthracite dosage, and prolonging carbothermic reduction time. However, the relative grindability of carbothermic reduction products deteriorated when reduction temperature was improved and the reduction time was extended. The relative grindability was negatively correlated to the ferronickel particle size. The carbothermic reduction temperature had the most dominant effect on the ferronickel particle size and relative grindability, followed by the anthracite dosage and reduction time. More nickel-bearing and iron-bearing minerals were reduced to metallic state with raising reduction temperature and increasing appropriate anthracite dosage. The fine ferronickel particles agglomerated and merged into bulk ferronickel grains with a prolonged reduction time. The results will provide theoretical guidance for the recovery of nickel and iron by co-reduction of nickel laterite ore and red mud. Full article