An overview of recovery of metals from slags

Various slags are produced as by-products in metallurgical processes or as residues in incineration processes. According to the origins and the characteristics, the main slags can be classified into three categories, namely ferrous slag, non-ferrous slag and incineration slag. This paper analysed and summarised the generation, characteristics and application of various slags, and discussed the potential effects of the slags on the environment. On this basis, a review of a number of methods for recovery of metals from the slags was made. It can be seen that a large amount of slags is produced each year. They usually contain a quantity of valuable metals except for blast furnace slag and they are actually a secondary resource of metals. By applying mineral processing technologies, such as crushing, grinding, magnetic separation, eddy current separation, flotation and so on, leaching or roasting, it is possible to recover metals such as Fe, Cr, Cu, Al, Pb, Zn, Co, Ni, Nb, Ta, Au, and Ag etc. from the slags. Recovery of metals from the slags and utilisation of the slags are important not only for saving metal resources, but also for protecting the environment.     

Physicochemical properties of slags produced at various amounts of iron addition in lead smelting

In the process of lead production from lead-bearing materials generated in copper metallurgy, a large amount of hazardous waste in the form of slag is produced. To assess the effect of the slag on the environment, its physicochemical properties were determined. In this study, the following methods were used: wavelength dispersive X-ray fluorescence (WD XRF), X-ray diffraction (XRD), and Bunte-Baum-Reerink method to determine softening and melting points, as well as viscosity examination and leaching tests. The measurements were performed on the slag produced with two different amounts of iron addition to the lead smelting process. The resulting slags, an oxide rich phase slag and a sulfide rich phase slag have different compositions and physicochemical properties. It was found that the increase in iron addition causes an increase in the softening melting point of the oxide rich phase slag by about 100 °C, and a twofold increase in the viscosity of both slag phases. The increase in iron addition also results in the decrease in As leachability and increase in Zn, Fe, and Cu leachability from the slags. Slag produced with increased iron addition has a greater impact on the environment.

     

Products of steel slags an opportunity to save natural resources

In Germany, and in the most industrial countries, the use of blast furnace and steel slags as an aggregate for civil engineering, for metallurgical use and as fertiliser has a very long tradition. Since the introduction of the basic oxygen steel making furnace (BOF) process and the electric arc furnace (EAF) process the German steel industry started extensive research on the development of fields of application for BOF and EAF slags. These investigations have been mainly performed by Forschungsgemeinschaft Eisenhüttenschlacken e. V. (FEhS), the Research Association for blast furnace and steel slags. Today steel slags are well characterised and long-term experienced materials mainly used as aggregates for road construction (e.g. asphaltic or unbound layers), as armour-stones for hydraulic engineering constructions (e.g. stabilisation of shores), and as fertiliser for agriculture purposes. These multifarious fields of application could only be achieved because the steelworks influence the quality of slags by a careful selection of raw materials and a suitable process route. Furthermore, subsequent procedures like a treatment of the liquid slag, an appropriate heat treatment and a suitable processing have been developed to ensure that the quality of steel slags is always adequate for the end use. Depending on the respective field of application, the suitability of steel slags has to be proven by determining the technical properties, as well as the environmental compatibility. For this reason test methods have been developed to evaluate the technical properties especially the volume stability and the environmental behaviour. To evaluate the volume stability a suitable test (steam test) has been developed and the results from laboratory tests were compared with the behaviour of steel slags under practical conditions, e.g. in a road. To determine the environmental behaviour leaching tests have been developed. In the meanwhile most of these test methods are drafted or already accepted as a CEN standard and are used for a continuous quality control. Usually the suitability of steel slags is stated by fulfilling the requirements of national and/or international standards and regulations. Based on these standards and regulations in Germany in 1998 about 97% of the produced steel slags have been used as aggregates for road construction (e.g. as surface layer, road base and sub base for high trafficked roads), ways, earthworks, and armourstones for hydraulic structures. Consistent to the successful long-term experience not only products of steel slags but also products of blast furnace slags have been eliminated from the European Waste Catalogue and the European Shipment of Waste Regulation of the European Community, as well as from the lists of OECD for transfrontier movements by the decision of the OECD-Council from 21 September, 1995.     

Characteristics of steel slag under different cooling conditions

Four types of steel slags, a ladle slag, a BOF (basic oxygen furnace) slag and two different EAF (electric arc furnace) slags, were characterized and modified by semi-rapid cooling in crucibles and rapid cooling by water granulation. The aim of this work was to investigate the effect of different cooling conditions on the properties of glassy slags with respect to their leaching and volume stability. Optical microscopy, X-ray diffraction, scanning electron microscope and a standard test leaching (prEN 12457-2/3) have been used for the investigation. The results show that the disintegrated ladle slag was made volume stable by water granulation, which consisted of 98% glass. However EAF slag 1, EAF slag 2 and the BOF slag formed 17%, 1% and 1% glass, respectively. The leaching test showed that the glass-containing matrix did not prevent leaching of minor elements from the modified slags. The solubility of chromium, molybdenum and vanadium varied in the different modifications, probably due to their presence in different minerals and their different distributions.     

干式还原法处理铬渣的机理及应用

采用干式还原法处理铬渣。在多级还原焙烧炉中于高温条件下,将过量的煤粉和铬渣混合后与O₂反应,经冷却、擦磨、磁分离后可得到铁精砂和处理后铬渣。介绍了干式还原法处理铬渣的机理和工艺参数。以3种铬渣试样进行应用试验,经多级还原焙烧—磁分离后,铬渣中的Cr（Ⅵ）质量浓度为0.05~0.18 mg/L,低于HJ/T301—2007标准中的要求（0.50 mg/L）,可作为建材原料加以利用。磁分离得到的铁精砂产品中铁的质量分数大于50%,铁回收率大于70%。目前设计的多级还原焙烧炉单炉处理铬渣能力为150 kt/a,标煤消耗为35 kg/t,处理成本约为60元/t。     

Resurrection of the iron and phosphorus resource in steel-making slag

 This research focused on the treatment of steel-making slags to recycle and recover iron and phosphorus. The carbothermal reduction behavior of both synthesized and factory steel-making slag in microwave irradiation was investigated. The slags were mixed with graphite powder and heated to a temperature higher than 1873 K to precipitate a lump of Fe–C alloy with a diameter of 2–8 mm. The larger the carbon equivalent (C_eq, defined in the text), the higher the fractional reduction of iron and phosphorus. An increase in the SiO₂ content of slag led to a considerable improvement in the reduction for both iron and phosphorus because of the improvement in the fluidity of the slags and an increase in the activity coefficient of P₂O₅ in the slags. The extraction behavior of phosphorus from Fe–P–C_satd alloy was also investigated at 1473 K by carbonate flux treatment. For all the experiments with a processing time longer than 10 min, the phosphorus in the fluxes could be concentrated to more than 9% (w/w) showing that it could be used as a phosphorus resource. Compared with K₂CO₃ flux treatment, that using Na₂CO₃ was more effective for the extraction of phosphorus, and this was attributed to the lower evaporation of Na₂CO₃. Finally, a recycling scheme for steel-making slag is proposed. Received: March 16, 2001 / Accepted: November 12, 2001     

Management of MSW in Spain and recovery of packaging steel scrap

Packaging steel is more advantageously recovered and recycled than other packaging material due to its magnetic properties. The steel used for packaging is of high quality, and post-consumer waste therefore produces high-grade ferrous scrap. Recycling is thus an important issue for reducing raw material consumption, including iron ore, coal and energy. Household refuse management consists of collection/disposal, transport, and processing and treatment - incineration and composting being the most widely used methods in Spain. Total Spanish MSW production exceeds 21 million tons per year, of which 28.1% and 6.2% are treated in compost and incineration plants, respectively. This paper presents a comprehensive study of incineration and compost plants in Spain, including a review of the different processes and technologies employed and the characteristics and quality of the recovered ferrous scrap. Of the total amount of packaging steel scrap recovered from MSW, 38% comes from compost plants and 14% from incineration plants. Ferrous scrap from incineration plants presents a high degree of chemical alteration as a consequence of the thermal process to which the MSW is subjected, particularly the conditions in which the slag is cooled, and accordingly its quality diminishes. Fragmentation and magnetic separation processes produce an enhancement of the scrap quality. Ferrous scrap from compost plants has a high tin content, which negatively affects its recycling. Cleaning and detinning processes are required prior to recycling.     

Treatment Of Electric Arc Furnace Dust With A Sustained Shockwave Plasma Reactor

In the reprocessing of steel from automotive scrap, lead, cadmium and zinc, which are volatile constituents, vaporize under the extremely high localized temperatures in an electric arc furnace at the points of contact between the graphite electrodes and the charge. These vapors condense to produce a hazardous dust termed electric arc furnace dust (EFD). This study was undertaken to satisfy the need for a mobile system which could be moved from site to site of generators of EFD to avoid transportation of hazardous waste, and to recycle slags and metallic iron products within the plant. A new type of plasma device, the Sustained Shockwave Plasma (SSP) has been developed and tested for treatment of EFD on a laboratory scale (500 g h^-1). Batch tests show that EFD can be treated to produce a non-hazardous slag and metallic zinc and lead to recycle.     

Diffusion test of 20 kinds of waste molten slags and competitive materials

“Waste molten slag” is a glass-like material produced by the vitrification of solid waste or solid waste incineration residue. When using slags of this kind in a natural environment, their impact is anticipated to be at the same level as competitive or substituted materials. In this study, we made comparative evaluations between waste molten slags and competitive materials, using 20 samples in total. It was proved that release fluxes of metals from molten slags of municipal solid waste were almost at the same level as competitive or substituted materials. However, a larger impact will be caused from some types of slag that contain harmful metals in high concentrations, such as the slag from shredded automobile residues. The results of release flux showed that nearly 80% of the slope of the flux did not fit with the diffusion range. However, the linearity of every flux was extremely high, regardless of the slope.     

Review on the innovative uses of steel slag for waste minimization

Piles of steel slag, a solid waste generated from the iron and steel industry, could be seen due to no utility found for the past century. Steel slag has now gained much attention because of its new applications. The properties of slag greatly influence its use and thus had got varied applications. The chemical composition of steel slag varies as the mineral composition of raw material such as iron ore and limestone varies. This paper reviews the characteristics of steel slag and its usage. The paper reviews recent developments in well-known applications to the steel slag such as aggregate in bituminous mixes, cement ingredient, concrete aggregate, antiskid aggregate, and rail road ballast. This paper also reviews novel uses such as mechanomutable asphalt binders, building material, green artificial reefs, thermal insulator, catalyst and ceramic Ingredient. The review is also done on utilization of solid waste for waste management by the novel methods like landfill daily cover material, sand capping, carbon sequestration, water treatment and solid waste management. Review also shows recovery of pure calcium carbonate and heavy metals from slag, providing opportunity for revenue generation. Steel slag once traded as free to use by steel industries is now sold in the market at some price. Its utilization is of great economic significance as it also contributes to the reduction of solid waste.     

Metallic-phase lead in slag of municipal solid waste incineration ash and leaching characteristics

Metallic phases in slags and their influence on the leaching characteristics were investigated. The proportions of metallic phase in four slags were 0.028%, 0.24%, 1.87%, and 3.05% by weight. The lead content was 10–248 mg/kg in bulk slag after metal removal, while in the metallic phase it was 579–7390 mg/kg. Lead concentrations in the metallic phase were more than ten times higher than in slags after metal removal. Lead was distributed in the metallic phase at 2.0%, 8.3%, 10.3%, and 47.4%. The concentrations of all metallic elements in metallic phases were much higher than in bulk slag. Iron, copper, and nickel had accumulated in magnetic metals, while aluminum and zinc were found in nonmagnetic metals. As regards chromium, manganese, lead, and tin, the proportion of metallic phases depended on the slag samples. By removing metallic phases, both water and pH 4 leachable lead decreased. The basic principles of melting residues containing lead are the separation of lead as a metal in reductive melting, and the containment of lead ions into uniform glassy particles in oxidization melting. Melting slag can be seen to contribute to environmental preservation by facilitating the recycling of materials through the separation of metals from melting slag. Received: February 21, 2000 / Accepted: July 27, 2000     

Changes in mineralogical and leaching properties of converter steel slag resulting from accelerated carbonation at low CO2 pressure

Steel slag can be applied as substitute for natural aggregates in construction applications. The material imposes a high pH (typically 12.5) and low redox potential (Eh), which may lead to environmental problems in specific application scenarios. The aim of this study is to investigate the potential of accelerated steel slag carbonation, at relatively low pCO₂ pressure (0.2 bar), to improve the environmental pH and the leaching properties of steel slag, with specific focus on the leaching of vanadium. Carbonation experiments are performed in laboratory columns with steel slag under water-saturated and -unsaturated conditions and temperatures between 5 and 90 °C. Two types of steel slag are tested; free lime containing (K3) slag and K1 slag with a very low free lime content. The fresh and carbonated slag samples are investigated using a combination of leaching experiments, geochemical modelling of leaching mechanisms and microscopic/mineralogical analysis, in order to identify the major processes that control the slag pH and resulting V leaching. The major changes in the amount of sequestered CO₂ and the resulting pH reduction occurred within 24 h, the free lime containing slag (K3-slag) being more prone to carbonation than the slag with lower free lime content (K1-slag). While carbonation at these conditions was found to occur predominantly at the surface of the slag grains, the formation of cracks was observed in carbonated K3 slag, suggesting that free lime in the interior of slag grains had also reacted. The pH of the K3 slag (originally pH ± 12.5) was reduced by about 1.5 units, while the K1 slag showed a smaller decrease in pH from about 11.7 to 11.1. However, the pH reduction after carbonation of the K3 slag was observed to lead to an increased V-leaching. Vanadium leaching from the K1 slag resulted in levels above the limit values of the Dutch Soil Quality Decree, for both the untreated and carbonated slag. V-leaching from the carbonated K3 slag remained below these limit values at the relatively high pH that remained after carbonation. The V-bearing di-Ca silicate (C2S) phase has been identified as the major source of the V-leaching. It is shown that the dissolution of this mineral is limited in fresh steel slag, but strongly enhanced by carbonation, which causes the observed enhanced release of V from the K3 slag. The obtained insights in the mineral transformation reactions and their effect on pH and V-leaching provide guidance for further improvement of an accelerated carbonation technology.     

Evaluation of waste slags produced by zinc industry in bituminous hot mixtures

Owing to the large amount of waste slags produced by zinc industry, it has become necessary to recycle it in some areas. Road construction has significant potential for the use of waste materials because more material is always needed. In this study, the engineering behaviour of asphalt concrete was investigated using mineral aggregates with waste slag, which is a by-product of the zinc–lead production industry. The asphalt concrete tested in this study was fabricated using 25, 50, 75 and 100 % mixing ratios instead of the conventional fine mineral aggregate (11, 22, 33 and 44 % rate of total aggregate mixture) to determine the possibility of using slags in the binder course of bituminous hot mixtures. The asphalt concretes, made of waste slags and conventional asphalt concrete, were evaluated in terms of their fundamental engineering properties such as Marshall stability, flow, Marshall quotient (MQ), bulk specific gravity, air voids and voids filled with bitumen in the total mix characteristics. The results indicate that the addition of waste slag as mineral aggregate improves the engineering characteristic performance and that it can be used in bituminous hot mixtures. In addition, principal component analyses were applied to examine the significance of each Marshall parameter, and a regression model was developed to estimate the MQ value using effective parameters.     

Production of brown and black pigments by using flotation waste from copper slag.

One of the major problems in copper-producing countries is the treatment of the large amount of copper slag or copper flotation waste generated from copper slag which contains significant amounts of heavy metals such as Cu, Zn, Pb and Co. Dumping or disposal of such large quantities of flotation waste from copper slag causes environmental and space problems. In this study, the treatment of flotation waste from copper slag by a thermal method and its use as an iron source in the production of inorganic brown and black pigments that are used in the ceramic industry were investigated. The pigments were produced by calcining different amounts of flotation waste and chromite, Cr2O3, ZnO and CoO mixtures. The pigments obtained were added to transparent ceramic glazes and porcelainized tile bodies. Their colours were defined by L*a*b* measurements with a spectrophotometer. The results showed that flotation waste from copper slag could be used as an iron source to produce brown and black pigments in both ceramic body and glazes.     

Enhancing performance and durability of slag made from incinerator bottom ash and fly ash

This work presents a method capable of melting the incinerator bottom ash and fly ash in a plasma furnace. The performance of slag and the strategies for recycling of bottom ash and fly ash are improved by adjusting chemical components of bottom ash and fly ash. Ashes are separated by a magnetic process to improve the performance of slag. Analytical results indicate that the air-cooled slag (ACS) and magnetic-separated slag (MSS) have hardness levels below 590 MPa, indicating fragility. Additionally, the hardness of crystallized slag (RTS) is between 655 and 686 MPa, indicating toughness. The leached concentrations of heavy metals for these three slags are all below the regulatory limits. ACS appears to have better chemical stability than MSS, and is not significantly different from RTS. In the potential alkali-silica reactivity of slag, MSS falls on the border between the harmless zone and the potentially harmful zone. ACS and RTS fall in the harmless zone. Hence, the magnetic separation procedure of ashes does not significantly improve the quality of slag. However, RTS appears to improve its quality.     

An assessment on the recycling opportunities of wastes emanating from scrap metal processing in Mauritius

This paper presents an assessment on the wastes namely slag, dust, mill scale and sludge resulting from scrap metal processing. The aim of this study is to demonstrate that there are various ways via which scrap metal processing wastes can be reused or recycled in other applications instead of simply diverting them to the landfill. These wastes are briefly described and an overview on the different areas of applications is presented. Based on the results obtained, the waste generation factor developed was 349.3 kg per ton of steel produced and it was reported that slag represents 72% of the total wastes emanating from the iron and steel industry in Mauritius. Finally the suitability of the different treatment and valorisation options in the context of Mauritius is examined.     

The use of waste basic oxygen furnace slag and hydrogen peroxide to degrade 4-chlorophenol

A new treatment method is developed to degrade 4-chlorophenol (4-cp) and its oxidation intermediates. The experimental results of this research demonstrate that 4-cp and its oxidation intermediates can be decomposed completely by basic oxygen furnace slag (BOF slag) with hydrogen peroxide (H₂O₂) in an acid solution. The factors that effect the treatment efficiency were studied including initial concentration of 4-cp, pH of the solution, concentration of H₂O₂ and amount of BOF slag. The BOF slags are final waste materials in the steel making process. The major components of BOF slag are CaO, SiO₂, Fe₂O₃, FeO, MgO and MnO. As the BOF slag in an acid solution, FeO and Fe₂O₃ can be dissociated to produce ferrous ion and ferric ion. Ferrous ion reacts with hydrogen peroxide to form “Fenton's reagent” which can produce hydroxyl radicals (OH^.). Hydroxyl radical possession of high oxidation ability can oxidize organic chemicals effectively. Results show that 100 mg/l of 4-cp is decomposed completely within 30 min by 438.7 g/l BOF slag with 8.2 mM hydrogen peroxide in pH=2.8±0.2 solution. The COD value of the solution is reduced from 290 to 90 mg/l. The factors studied which affect the 4-cp decomposition efficiency were the hydrogen peroxide concentration, BOF slag concentration, pH of the solution and initial concentration of 4-cp. Because large amounts of Fe₂O₃ and FeO are present in the BOF slag, the BOF slag not only has a high treatment efficiency, but also can be used repeatedly.     

Reuse of residues arising from lead batteries recycle: a feasibility study

The performance of products arising from the stabilization/solidification of slags from lead batteries recycle into a Portland cement matrix has been evaluated not only in order to get a stabilized waste to be disposed of according to the current legislation, but also to obtain a recyclable material, with both economic and environmental benefits. Under this respect a detailed characterization of raw slags has been performed and different slag-cement samples have been prepared by varying the slag content. The parameters related to the cementation process have been evaluated and a series of tests on the final waste forms have been carried out, aimed at assessing both mechanical performance and leaching behaviour. In spite of the acceptable values for flexural, compressive and tensile strength, however, the high release of lead from the solidification products seems to be a limiting factor for a reusable material. While explanations of such phenomenon are given (high alkalinity of Portland cement; early "doping" of cementitious components by lead in the amorphous state), the main conclusion of the research work is that further efforts should be addressed to the adoption of a different or a modified incorporation matrix.     

Strength properties of concrete incorporating coal bottom ash and granulated blast furnace slag

Coal bottom ash (CBA) and fly ash (FA) are by-products of thermal power plants. Granulated blast-furnace slag (GBFS) is developed during iron production in iron and steel plants. This research was conducted to evaluate the compressive strength property and some durability characteristics of concrete incorporating FA, CBA, and GBFS. FA is used as an effective partial cement replacement; CBA and GBFS are used as partial replacement for fine aggregate without grinding. Water absorption capacity, unit weight and compressive strengths in 7, 28, and 90-day ages were assessed experimentally. For these experiments, concrete specimens were produced in the laboratory in appropriate shapes. The samples are divided into two main categories: M1, which incorporated CBA and GBFS; and M2, which incorporated FA, CBA, and GBFS. Remarkable decreases are observed in compressive strength and water absorption capacity of the concrete; bulk density of the concrete is also decreased. It can be concluded that if the content of CBA and GBFS is limited to a reasonable amount, the small decreases in strength can be accepted for low strength concrete works.     

Kinetics of steel slag leaching: Batch tests and modeling

Reusing steel slag as an aggregate for road construction requires to characterize the leaching kinetics and metal releases. In this study, basic oxygen furnace (BOF) steel slag were subjected to batch leaching tests at liquid to solid ratios (L/S) of 10 and 100 over 30 days; the leachate chemistry being regularly sampled in time. A geochemical model of the steel slag is developed and validated from experimental data, particularly the evolution with leaching of mineralogical composition of the slag and trace element speciation. Kinetics is necessary for modeling the primary phase leaching, whereas a simple thermodynamic equilibrium approach can be used for secondary phase precipitation. The proposed model simulates the kinetically-controlled dissolution (hydrolysis) of primary phases, the precipitation of secondary phases (C-S-H, hydroxide and spinel), the pH and redox conditions, and the progressive release of major elements as well as the metals Cr and V. Modeling indicates that the dilution effect of the L/S ratio is often coupled to solubility-controlled processes, which are sensitive to both the pH and the redox potential. A sensitivity analysis of kinetic uncertainties on the modeling of element releases is performed.