The recycling and utilization opportunities for coal fly ash (CFA) have increased in the past two decades. However, limited commercialization of the material is still reported, while disposal and management remain major concerns. CFA utilization is currently commercially feasible in the building and construction industry. Other alternative uses that are being explored involve the extraction of valuable metals and the purification of wastewater. The CFA-produced adsorbent material utilized in wastewater purification processes should be able to generate water that meets the legal quality requirements for reutilization in alternative applications. On the other hand, in the recovery of metallic components such as smelter-grade alumina, high recovery and high purity products are only achievable through the processing of CFA using expensive and energy—intensive processes. Furthermore, most of the current CFA recycling processes tend to generate secondary solid residues (SSR), which can cause environmental pollution, thus requiring further downstream processing. In this context, this paper reviews and discusses current research on CFA recycling methods, challenges and opportunities associated with resource recovery from CFA, and the acceptability of the value-added products, and it therefore proposes sustainable processes for CFA utilization. This review further suggests that to successfully compete with bauxite for production of smelter-grade alumina, other saleable value-added products such as Ti, Fe and the REEs should be recovered by engineering an integrated process design. The generated SSR in each process must also be characterized, recycled and re-used to reduce waste production and advance the circular economy concept. The review concludes that for CFA to become considered as a more attractive commercial resource, there is need for its complete and holistic utilization in high volumes and in different applications to offset its low value.

Miners around Zimbabwe used to supply gold concentrates from sulphide flotation to the Kwekwe Roasting Plant (Zimbabwe) for toll treatment. The concentrates were roasted in Edward’s roasters and the calcine product was leached by cyanidation. Due to inefficient roasting, overall gold recoveries of 75–80% left behind a rich calcine leach residue at the Kwekwe Roasting Plant. The characterization performed to establish a potential process route involved several techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM), fire assaying and inductively coupled plasma (ICP). Assays conducted on samples from the 350,000 tons tailings dam residue, created over the operational years, gave an average Au grade of 8.58 g/t and 12.54 g/t for Ag. The base metals assayed—0.11% Cu, 0.10% Pb, 0.17% Zn and 26.05% Fe. SiO₂ (36.1%), Fe₂O₃ (36.9%), Mg₃Si₄O₁₀ (OH)₂ (8.9%), NaAlSi₃O₈ (6.9%), and Fe₃O₄ (6.4%)—were the major mineral phases in the cyanide leach residue. SEM gold scans on 24 polished sections showed only 2 discrete gold particles of less than 5 µm, with one partially liberated and associated with quartz, while the other was fully liberated. Therefore, the particulate gold in the calcine leach residue was negligible. It was deduced from the analysis after ultrafine milling (P₈₀ < 5 µm) followed by cyanidation that 68.53% of the gold was sub-microscopic. Direct cyanidation using bottle roll resulted in only 2.33% of the total gold being leachable, indicating that the calcine leach residue was highly refractory. Diagnostic leaching by sequential use of acids in order of their strength resulted in HCl leachable phases (CaCO₃, CaMg(CO₃)₂, PbS, Fe1-XS, and Fe₂O₃) freeing 4.2% of the total Au during subsequent cyanidation leach. H₂SO₄ leachable phases (Cu–Zn sulphides, labile FeS₂) released an additional 26.57% during cyanidation, whereas HNO₃ leachable phases (FeS₂, FeAsS) released a further 20.98% of Au. After acid treatment and subsequent cyanidation, hot caustic leach of the residue followed by carbon in pulp resulted 4.43% of the total gold being eluted. Therefore, 4.43% of the total gold was surface bound. From the analysis after diagnostic acid leaching, it was deduced that a total of 54.08% of the gold was in the acid-leachable phase. Due to cost and environmental considerations, H₂SO₄ was selected for the evaluation of acid digestion as a pretreatment stage followed by cyanidation. Increasing the H₂SO₄ strength for the pretreatment of the calcine leach residue increased gold recoveries during cyanidation.

Coal fly ash (CFA) is a commercially viable source of alumina comparable to traditional bauxite deposits. Due to its high silica content and alumina in the refractory mullite phase, the most suitable processing technique is the sinter-H₂SO₄ leach process. However, this process is energy-intensive, has low selectivity for Al, and generates a secondary solid waste residue. To develop a sustainable process that is economically attractive, Al can be extracted with REEs, Ti, and Fe as saleable products, while secondary solid waste is regenerated for further applications to achieve high-value and high-volume utilisation of CFA. This study focused on the potential extraction of selected REEs (Ce, La, Nd, Y, and Sc), Al, Ti, and Fe, using dry magnetic separation and the sinter-H₂SO₄ leach process. XRD analysis showed that CFA is predominantly amorphous with crystalline mullite, quartz, and magnetite/hematite. Further analysis using SEM-EDS and TIMA showed Al-Si-rich grains as the predominant phase, with discrete REE-bearing grains (phosphates and silicates) and Fe-oxide (magnetite/hematite) grains. Traces of REEs, Ti, Ca, Si, and Fe were also found in the Al-Si-rich grains. Discrete Fe-oxide was recovered using dry magnetic separation, and up to 65.9% Fe was recovered at 1.05 T as the magnetic fraction (MF). The non-magnetic fraction (non-MF) containing quartz, mullite, and amorphous phase was further processed for preliminary leaching studies. The leaching behaviour of Al, Ti, Fe, and the selected REEs was investigated using the direct H₂SO₄ and sinter-H₂SO₄ leaching processes. The maximum extraction efficiency was observed using the sinter-H₂SO₄ leach process at 6 M H₂SO₄, a 1:5 solid-to-liquid ratio, 70 °C, and a residence time of 10 h, yielding 77.9% Al, 62.1% Fe, 52.3% Ti, and 56.7% Sc extractions. The extraction efficiencies for Ce, La, Nd, and Y were relatively lower at 23.2%, 27.6%, 11.3%, and 11.2%, respectively. Overall, the results demonstrate that the extraction of REEs using the sinter-H₂SO₄ leach process is strongly influenced by the complex CFA phase composition and the possible formation of insoluble calcium sulphates. Appreciable extraction of Al, Fe, Ti, and Sc was also observed, suggesting a potential two-step leaching process for the extraction of REEs as a feasible option for the industrial recovery of multiple saleable products.

For over a century, cyanidation has been a highly effective method for extracting gold from gold-bearing sources. However, due to environmental, health, and safety concerns associated with this process, considerable efforts have been devoted to exploring the use of alternative, less toxic, and environmentally friendly reagents. In this study, a comparative cyanide and ethaline deep eutectic solvent (DES) leaching study of gold from the Witwatersrand gold tailings was undertaken. A Statistical Design of Experiments (DOE) was used for the screening and optimization of significant process factors to achieve optimal gold extraction. The factors investigated include the reagent concentration, leaching time, pulp density, and solution temperature. The subsequent gold recovery from leach solutions was undertaken using activated carbon (AC). Mineralogical analysis by X–ray diffraction (XRD) showed that the tailings consisted of quartz (72.13%), muscovite (7.49%), chlorite (2.65%), pyrophyllite (1.50%), clinochlore (1.30%), and other trace minerals. Mineral liberation analysis (MLA) employing the Sparse Liberation–Dual Zoom (SPL-DZ) method showed that gold was associated with iron oxides (Fe₂O₃, Fe₃O₄). Fire assay analysis (FAA) showed that the bulk tailings had a grade of 0.32 g/t Au. Ethaline was found to be the most efficient reagent, achieving up to 71.9% gold extraction, thereby exceeding the 46.9% gold extraction obtained via the cyanidation process. Moreover, gold recovery using AC from ethaline leach solution was 75%. The high gold extraction from tailings using ethaline suggests a potentially feasible alternative to the traditional cyanidation process, particularly for the processing of gold locked in iron oxide phases, offering the advantages of low toxicity, cost-effectiveness, and ease of preparation.