Near-zero-waste processing of low-grade, complex primary ores and secondary raw materials in Europe: technology development trends

With an increasing number of low-grade primary ores starting to be cog-effectively mined, we are at the verge of mining a myriad of low-grade primary and secondary mineral materials. At the same time, mining practices and mineral waste recycling are both evolving towards sustainable near-zero-waste processing of low-grade resources within a circular economy that requires a shift in business models, policies and improvements in process technologies. This review discusses the evolution towards low-grade primary ore and secondary raw material mining that will allow for sufficient supply of critical raw materials as well as base metals. Seven low-grade ores, including primary (Greek and Polish laterites) and secondary (fayalitic slags, jarosite and goethite sludges, zincrich waste treatment sludge and chromium-rich neutralisation sludge) raw materials are discussed as typical examples for Europe. In order to treat diverse and complex low-grade ores efficiently, the use of a new metallurgical systems toolbox is proposed, which is populated with existing and innovative unit operations: (i) mineral processing, (ii) metal extraction, (iii) metal recovery and (iv) matrix valorisation. Several promising novel techniques are under development for these four unit-operations. From an economical and environmental point of view, such processes must be fitted into new (circular) business models, whereby impacts and costs are divided over the entire value chain. Currently, low-grade secondary raw material processing is only economic and environmentally beneficial when the mineral residues can be valorised and landfill costs are avoided and/or incentives for waste processing can be taken into account

Recovery of critical and other raw materials from mining waste and landfills

The transition to a more circular economy is essential to develop a sustainable, low carbon, resource efficient, and competitive economy in the EU. In this context Critical Raw Materials (CRM) are defined as those which are of particularly great importance to the EU economy and at the same time there is a high risk of supply disruptions. First and foremost, improving the circular use of CRM is a key strategy in improving the security of supply and not surprisingly is an objective of various policy documents. This report delivers on action #39 of the Circular Economy Action Plan: "Sharing of best practice for the recovery of critical raw materials from mining waste and landfills". It builds on discussions held during two 2018 workshops and gathers together six examples of existing practices for the recovery of critical, precious, and other materials from extractive waste and landfills, highlighting technological innovation and contributions that have been made to a more comprehensive knowledge-base on raw materials. The report also provides various estimates of potential recovery of certain materials compared to their current demand. Lessons learnt from the practices include awareness that it is very unlikely that recovery processes can target one or just a few specific materials of great interest and disregard other elements or bulk matrixes. Especially in case of very low concentrations, most of the mineral resources and other bulk materials in which they are embedded must be valorised in order to increase economic viability and minimise waste disposal. As recovery processes can be very energy intensive, environmental and land use related aspects are also particularly relevant even though environmental gains may also occur and, moreover, land space can be liberated and reused for new purposes and services. Finally, availability of data and information on secondary materials as well as a harmonized legislative framework within the EU appear to be crucial for the large-scale deployment of recovery practices.JRC.D.3-Land Resource

Multi-Analytical Characterization of Slags to Determine the Chromium Concentration for a Possible Re-Extraction

The CHROMIC project (effiCient mineral processing and Hydrometallurgical RecOvery of by-product Metals from low-grade metal contaIning seCondary raw materials) aims to recover chromium from steelmaking and ferrochrome slags to regain valuable resources and simultaneously reduce potential environmental impacts. To develop the recovery flowsheets and reliably calculate metal recovery, an accurate assessment of chromium concentration and distribution is essential. Therefore, model streams were thoroughly characterized using a combination of analytical techniques. In all materials, chromium is present in distinct but often small spinel phases, intergrown with other minerals and showing a considerable zonation in Cr content with higher amounts in the cores. The small size of the Cr-rich particles makes recovery by mineral processing challenging. Measured chromium content was found to differ largely based on the chemical dissolution method applied. The analysis of insoluble residues and comparison with a standard reference material evidenced that standard acid dissolution procedures based on HCl/HNO3/HBF4 and HNO3/HF/H2O2 are insufficient to fully dissolve spinel structures, leading to severe underestimations of chromium content. A sodium peroxide treatment is required for a full dissolution of spinels. This is noteworthy, since most of the legislation for the reuse of slags is currently based on acid dissolution methods

Up-Concentration of Chromium in Stainless Steel Slag and Ferrochromium Slags by Magnetic and Gravity Separation

Slags coming from stainless steel (SS) and ferrochromium (FeCr) production generally contain between 1 and 10% Cr, mostly present in entrapped metallic particles (Fe–Cr alloys) and in spinel structures. To recover Cr from these slags, magnetic and gravity separation techniques were tested for up-concentrating Cr in a fraction for further processing. In case of SS slag and low carbon (LC) FeCr slag a wet high intensity magnetic separation can up-concentrate Cr in the SS slag (fraction <150 µm) from 2.3 wt.% to almost 9 wt.% with a yield of 7 wt.%, and in the LC FeCr slag from 3.1 wt.% to 11 wt.% with a yield of 3 wt.%. Different behavior of Cr-containing spinel’s in the two slag types observed during magnetic separation can be explained by the presence or absence of Fe in the lattice of the Cr-containing spinel’s, which affects their magnetic susceptibility. The Cr content of the concentrates is low compared to chromium ores, indicating that additional processing steps are necessary for a recovery process. In the case of high carbon (HC) FeCr slag, a Cr up-concentration by a factor of more than three (from 9 wt.% to 28 wt.%) can be achieved on the as received slag, after a single dry low intensity magnetic separation step, due to the well-liberated Cr-rich compounds present in this slag. After gravity separation of the HC FeCr slag, a fraction with a Cr content close to high grade Cr ores (≥50% Cr2O3) can be obtained. This fraction represents 12 wt.% of the HC FeCr slag, and can probably be used directly in traditional smelting processes

Geochemical and mineralogical study of a site severely polluted with heavy metals (Maatheide, Lommel, Belgium)

The former zinc smelter site ‘de Maatheide’ in Lommel (Belgium) was severely polluted with heavy metals and the pollution spread into the surroundings by rain water leaching and wind transportation. This study focuses on the processes of immobilization and natural attenuation that took place on the site. Three important factors were found. Firstly, the high pH values (pH 7–8) in the topsoil influence the mobility of heavy metals. Secondly, the spodic horizons below the polluted top layer seem to accumulate heavy metals, thereby slowing down their release into the environment. Finally, the glassy phases and iron oxi/hydroxides that are present can encapsulate heavy metals during their formation/recrystallization, thereby immobilizing them. An additional shielding effect results from the reaction rims of goethite around the contaminant phases, which partially inhibit the weathering process and release of contaminants. This shielding effect is an important factor to take into account when modelling contaminant release.status: publishe

Rentention and release of Zn and Cd in spodic horizons as determined by pHstat analysis and single extractions

In the northern Campine in Belgium, large areas are contaminated by heavy metals such as Zn and Cd due to the (former) nonferro metal industry. In the sandy soils, the heavy metal adsorption/attenuation in the spodic horizon represents the main retention mechanism of leached pollutants from the contaminated topsoils. In this study, the pH-dependent behaviour of the elements in these spodic horizons was tested by pHstat experiments and compared to sandy loam soils. Extractions with CaCl2 0.01 M and EDTA 0.05 M provided a further insight into the binding mechanisms. The results indicate that organic matter is the main factor responsible for the mobility of Cd, Zn and Ca in the spodic horizons. The binding of elements is not very strong, however, and highly dependent on pH. A slight decrease in pH can cause a significant release of metals from the spodic horizons, with up to 60% of Cd and 90% of Zn being released within a 1.5 unit change in pH (starting from the naturally occurring pH). This pH change can happen rapidly in these soils, due to the low buffering capacity, and is realistic given the acidification in Flanders. For the sandy loam soils, a pH decrease of 3 units is needed to release 40% of Cd and 20% of Zn, and the acid neutralization capacity is exhausted more gradually, suggesting that slower buffering mechanisms take place. For the sandy loam soils, Cd retention is mainly governed by organic matter, while for Zn other factors such as the clay minerals also play an important role. Despite the high potential mobility and pH dependence of the heavy metal retention in the spodic horizons, the actual risk for groundwater pollution is limited. For the diffusely contaminated areas, where traditional remediation is not an option, spodic horizons may therefore contribute to a natural attenuation of the soil contamination.status: publishe

Detoxified Spent Pot Lining from Aluminum Production as (Alumino-)Silicate Source for Composite Cement and AutoClaved Aerated Concrete

New sources of supplementary cementitious materials (SCMs) are needed to meet the future demand. A potential new source of SCM is spent pot lining, a residue from aluminum production. The present work showed that the refined aluminosilicate part of spent pot lining (SPL) has a moderate chemical reactivity in a cementitious system measured in the R3 calorimetry test, comparable to commercially used coal fly ash. The reaction of SPL led to the consumption of Ca(OH)2 in a cement paste beyond 7 days after mixing. At 28 and 90 days a significant contribution to strength development was therefore observed, reaching a relative strength, which is similar to composite cements with coal fly ash. At early age a retardation of the cement hydration is caused by the SPL, which should most likely be associated with the presence of trace amounts of NH3. The spent pot lining is also investigated as silica source for autoclaved aerated concrete blocks. The replacement of quartz by spent pot lining did not show an adverse effect on the strength-density relation of the lightweight blocks up to 50 wt% quartz substitution. Overall, spent pot lining can be used in small replacement volumes (30 wt%) as SCM or as replacement of quartz (50 wt%) in autoclaved aerated concrete blocks