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.

     

Properties of alkali-activated systems with stone powder sludge

This article investigates the effects of stone powder sludge on the microstructure and strength development of alkali-activated fly ash and blast furnace slag mixes. Stone powder sludge produced from a crushed aggregate factory was used to replace fly ash and granulated blast furnace slag at replacement ratios of 0%, 10%, 20%, and 30% by mass. The unit weight and compressive strength of the samples were measured, and scanning electron microscopy/energy dispersive spectroscopy and X-ray diffraction (XRD) analyses were performed. The test results indicated that the compressive strength of alkali-activated blast furnace slag mixes using stone powder sludge was higher than that of the alkali-activated blast furnace slag control mix, but the compressive strength of alkali-activated fly ash mixes decreased with increasing replacement ratio of stone powder sludge. Microscopy results indicated that for alkaliactivated blast furnace slag samples, broken surfaces were more evident than for the alkali-activated fly ash samples. For all XRD diagrams, broad and diffuse peaks were observed around 2θ = 35° (d = 2.96–3.03 Å), implying amorphous or short-ordering structure phases.     

Upgrading of poly(vinyl chloride) by chemical modifications using sodium sulfide

The recycling of poly(vinyl chloride) (PVC) is one of the most important issues in the treatment of waste plastics. To improve PVC recycling, it is necessary to develop new recycling techniques, including new techniques for the dechlorination of chlorine-containing polymers. It has been established that wet dechlorination of PVC in NaOH/ethylene glycol solution is more effective than dry dechlorination. In this study, the wet process was used, and the chemical modification of PVC by nucleophilic substitution was considered for upgrading waste PVC. Chlorine was substituted in solution by several nucleophilic reagents, thus changing the properties of PVC. The reaction of PVC in Na2S/ethylene glycol solution at 170°C resulted in the formation of a mixture comprising 32% elimination and 26% substitution products. The scanning electron microscopy/energy dispersive X-ray spectroscopy mappings and elementary analysis of PVC indicated that this chlorine-substitution process led to cross-linking by sulfur.     

Synthesis of hydrogarnet from molten slag and its hydrogen chloride fixation performance at high temperature

Hydrogarnet was synthesized hydrothermally below 200°C using molten slag obtained from municipal solid waste. For comparison, it was also synthesized using pure-phase CaO–Al₂O₃–SiO₂–H₂O, as reported previously. The structural and textural properties of this material were investigated using various analytical and spectroscopic techniques such as X-ray diffraction, X-ray fluorescence spectrometry, atomic absorption spectrometry (AAS), thermogravimetry/differential thermal analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy. The Cl⁻ fixation ability of hydrogarnet was investigated in the temperature range 500–800°C in a fixed-bed flow reactor using a HCl concentration (1000 p.p.m.v.) similar to that of incinerator exhaust gas. Under these experimental conditions, the hydrogarnet was capable of reducing the HCl gas level to less than 1 p.p.m.v. Analysis of the spent catalyst revealed that the hydrogarnet was being transformed into wadalite and CaCl₂ at high temperatures. The elution test for chromium ions in hydrogarnet obtained from slag was also used, and it was found that chromium ions were not eluted from hydrogarnet. Received: January 27, 2001 / Accepted: October 11, 2001     

进口含锌物料的表征和鉴别

采用X射线荧光光谱(XRF)、X射线衍射光谱(XRD)等分析手段,对4种进口疑似固体废物的含锌物料进行了表征。通过分析含锌物料的主要元素组成、物相组成和常规理化特征,结合外观特征,与含锌矿物、含锌产品及相关文献资料等进行比对,推导出含锌物料的产生来源。然后,参照我国《进口废物管理目录》得出鉴别结论。结果表明:4种含锌物料分别为锌矿、湿法冶炼锌浸出渣、热镀锌灰和固定CO2产物;后3种属于我国目前禁止进口的固体废物。     

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.     

Properties of Glauconite/Polyaniline Composite Prepared in Aqueous Solution of Citric Acid

Hybrid composite made of glauconite and polyaniline was prepared in aqueous solution of citric acid. Scanning electron microscopy combined with energy dispersive X-ray analysis shows uniform aggregates made of glauconite microparticles and polyaniline matrix. The results of X-ray powder diffraction suggest that: (1) citric acid used for the polymerisation of aniline causes formation of emeraldine salt where macromolecular ordering in the amorphous polymer takes place; (2) no chemical interaction between glauconite and emeraldine takes place in the prepared composite. FT-IR spectra of the prepared polymer and composite show features indicating all the functional groups that are present in the diiminoquinone–diaminobenzene state of polyaniline. Thermal stability of the composite was higher than the prepared polymer suggesting the occurrence of an interphase interaction between glauconite and emeraldine. After pyrolysis in purified nitrogen the composite still remained glauconite, and ε-Fe3N together with amorphous and graphitic carbon were found as reaction products. The values of electrical conductivity and magnetization of the composite suggest that optimization of these values might be achieved based upon the relationship between glauconite and polyaniline.     

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 overview on the production of pigment grade titania from titania-rich slag.

To recover pigment grade TiO2, operating plants all over the world use chemical processes. Slag-based technology is considered to be attractive because of low waste generation and low chemical cost due to high titanium content and is poised to replace the conventional technology. This paper provides a review of the slag-based technology with the specific aim to produce leachable slag and achieving high titania yield from recovered wastes. Leachable oxides of the lower oxidation state, such as TiO and Ti2O3, facilitate the leaching process. However, during smelting these oxides increase the viscosity of the slag. Formation of titanium carbide or carbonitride is also not desirable as it leads to resistance to the leaching of titanium. This report highlights the problems and their possible solutions to obtain leachable slag.     

Prioritising objectives for waste reprocessing: a case study in secondary lead refining

Secondary lead refining produces a sulphidic slag that also contains varying quantities of lead. Initially, the objectives of this project were to treat the slag in order to recover the valuable lead as well as to render the slag environmentally benign. However, in keeping with the principles of clean technology and, specifically, the approach of clean production, the project was redefined with the following priorities: waste characterisation; waste minimisation through process improvement; waste modification; identification of slag treatment methods. Characterisation of the waste facilitated an overall process understanding and aided in identifying process deficiencies. Process improvement was aimed at reducing both the quantity of slag produced as well as the lead loss to the slag. Waste characterisation combined with local hazardous waste regulations enabled desirable waste modifications to be identified. These waste adaptations were implemented through process modification. Lastly, treatment methods for the slag were identified.     

Microbial influenced degradation of solidified waste binder

Ordinary cement pastes with water/cement (w/c) ratios of 0.2, 0.4 and 0.5 were used to examine the chemical and physical effects of microbial influenced degradation (MID). Samples were exposed to an active culture of Thiobacillus thiooxidans or to sterile media containing sulphuric acid using an intermittent immersion technique. Acid consumption and Ca, Al and Fe releases are presented for an exposure period of 90 days. Exposed samples were also sectioned and analysed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). All cement paste samples were subject to significant degradation in either sterile acid media or the T. thiooxidans lixiviant. Corrosion depths observed from SEM examination of exposed samples were affected by the w/c ratio of the cement. The extent and rate of degradation were not apparent from the calculated rate of hydrogen ion consumption, or the leaching rates of Ca, Al and Fe. It was not possible to distinguish differences in corrosion due to the chemical and microbial influenced degradation from the results obtained to date and further work is focusing on modified procedures to address this.     

Metallurgical use of glass fractions from waste electric and electronic equipment (WEEE)

Within the European Union, it is estimated that between 8 and 9 million tonnes of waste electric and electronic equipment (WEEE) arises annually, of which television sets and computers account for an important part. Traditionally, Cathode Ray Tubes (CRT) have been used for TVs and computer monitors, but are rapidly being replaced by flat-screen technology. Only part of the discarded CRT glass is being recycled. Primary smelters use large amounts of silica flux to form iron-silicate slag, and can, in most cases, tolerate lead input. Use of discarded CRT glass in copper smelting is a potential alternative for utilization of the glass.The mineralogical composition of a slag sampled during ordinary slag praxis has been compared with that of a mixture of slag and CRT glass when re-melted and slowly cooled. Slag (iron-silicate slag) from Boliden Mineral AB, Sweden, was used for the experiments. Slag and glass have been mixed in various proportions: pure slag, pure glass, 90% slag-10% glass and 65% slag-35% glass, and heated in an inert atmosphere up to 1400 °C in a Netzsch Thermal Analysis (TA) instrument. The re-melted material has been analyzed using X-ray diffraction (XRD) and scanning electron microscopy (SEM) to determine changes in mineralogical composition after mixing with glass.The results show that the main mineralogical component of the slag is fayalite; the CRT glass is amorphous. The main crystalline phases of the slag do not change with addition of glass. An amorphous phase appears when the addition of glass is increased, which gives the sample a different structure.     

Reprocessing of metallurgical slag into materials for the building industry

Several methods of reprocessing metallurgical (blast furnace) slag into materials for the building industry, based on melting aggregates with submerged combustion, were developed and tested. The first method involves melting hot slag with some additives directly in a slag ladle with a submerged gas-air burner, with the objective of producing stabilized slag or glass-ceramic. The second method involves direct draining of melted slag from a ladle into the slag receiver, with subsequent control of the slag draining into the converter where special charging materials are added to the melt, with the objective of producing glass-ceramic. A third method involves melting cold slag with some additives inside a melting converter with submerged gas-air burners, with the objective of producing glass-ceramic fillers for use in road construction. Specific to the melting process is the use of a gas-air mixture with direct combustion inside the melt. This feature provides melt bubbling to help achieve maximum heat transfer from combustion products to the melt, improve mixing (and therefore homogeneity of the melt), and increases the rate of chemical reactions. The experimental data for different aspects of the proposed methods are presented. The reprocessed blast-furnace slag in the form of granules can be used as fillers for concretes, asphalts, and as additives in the production of cement, bricks and other building materials. As well, reprocessed blast-furnace slag can be poured into forms for the production of glass-ceramic tiles.     

Incorporation of gypsum waste in ceramic block production: Proposal for a minimal battery of tests to evaluate technical and environmental viability of this recycling process

Civil engineering-related construction and demolition debris is an important source of waste disposed of in municipal solid waste landfills. After clay materials, gypsum waste is the second largest contributor to the residential construction waste stream. As demand for sustainable building practices grows, interest in recovering gypsum waste from construction and demolition debris is increasing, but there is a lack of standardized tests to evaluate the technical and environmental viability of this solid waste recycling process. By recycling gypsum waste, natural deposits of gypsum might be conserved and high amounts of the waste by-product could be reused in the civil construction industry. In this context, this paper investigates a physical property (i.e., resistance to axial compression), the chemical composition and the ecotoxicological potential of ceramic blocks constructed with different proportions of clay, cement and gypsum waste, and assesses the feasibility of using a minimal battery of tests to evaluate the viability of this recycling process. Consideration of the results for the resistance to axial compression tests together with production costs revealed that the best formulation was 35% of plastic clay, 35% of non-plastic clay, 10% of Portland cement and 20% of gypsum waste, which showed a mean resistance of 4.64 MPa. Energy dispersive X-ray spectrometry showed calcium and sulfur to be the main elements, while quartz, gypsum, ettringite and nacrite were the main crystalline compounds found in this formulation. Ecotoxicity tests showed that leachate from this formulation is weakly toxic toward daphnids and bacteria (EC_20% = 69.0 and 75.0, respectively), while for algae and fish the leachate samples were not toxic at the EC_50% level. Overall, these results show that the addition of 20% of gypsum waste to the ceramic blocks could provide a viable substitute for clay in the ceramics industry and the tests applied in this study proved to be a useful tool for the technical and environmental evaluation of this recycling process, bacterial and daphnid tests being more sensitive than algae and fish tests.     

气化炉渣的重金属浸出特性及化学形态分析

分别采用硫酸硝酸法、水平振荡法和醋酸缓冲溶液法制取气化炉渣的浸出液，考察了不同提取方式对浸出液中重金属质量浓度的影响。采用改进BCR连续提取法对气化炉渣中的重金属Cr，Zn，Cu，Pb，Ni，As，Cd的化学形态进行了分析。实验结果表明：煤气化工艺中的气化炉渣属第Ⅰ类一般工业固体废物;在3种提取方式中，醋酸缓冲溶液法的重金属浸出种类最多，且浸出量最大;Cd和Cr对环境具有较高的潜在危害性，Cu次之，Zn，Pb，Ni，As主要以残渣态形式存在，对环境的直接危害性较低。     

Thermodynamic and experimental studies on condensation behavior of low-boiling-point elements volatilized in the melting process

To study the volatilization and condensation behaviors of low-boiling-point elements in the waste melting process, experiments were conducted to collect the dust from a coke-type incineration residue melting furnace. Then, a comparison was made between the experimental results and the calculated values obtained from a thermodynamic equilibrium model in terms of the chemical composition of the dust. The composition of the dust collected from a cylindrical filter in the exhaust gas duct was determined by chemical methods, scanning electron microscopy/energy-dispersive X-ray spectroscopy, and X-ray analysis. As a result, the sampled dust was classified into two different types: fine particles mainly containing Na, K, Pb, and Zn collected from the side face of the cylindrical filter, and large particles containing Ca, Si, and Al collected from the bottom face of the cylindrical filter. From X-ray analysis of the sampled dust, NaCl, KCl, PbS, and ZnS were identified in the fine-particle dust, while CaO, SiO₂, Al₂O₃ were detected in the large-particle dust. From the results of the thermodynamic equilibrium calculation in the gas cooling process from 2000 to 600 K, it was found that Na, K, Pb, and Zn volatilized as metals in the melting furnace were condensed as alkali chlorides such as NaCl and KCl and heavy metal sulfides such as PbS and ZnS. These computational results were in good agreement with the X-ray diffraction results of the sampled dust at a gas temperature of 823 K for the formation of NaCl, KCl, PbS, and ZnS.     

Effect of MgO and CaO/SiO2 on the immobilization of chromium in synthetic slags

This work investigated the chemical and mineralogical properties of CaO–SiO₂–Cr₂O₃–CaF₂–MgO slags. Synthetic slags were prepared and the effect of the slag basicity (mass ratio CaO/SiO₂) and MgO contents on the stability of the mineralogical species formed was analyzed. The morphology and composition of the slags were analyzed by X-ray powder diffraction (XRD) and scanning electron microscope-energy dispersive spectroscopy (SEM–EDS), whilst their chemical stability was evaluated by leaching with an aqueous acetic acid solution. It was found that in slags with CaO/SiO₂?=?1, the main Cr-compound was MgCr₂O₄ spinel, which forms octahedron crystals. Small amounts of CaCr₂O₄ and CaCrO₄ were also observed. It was found that with increasing the slag basicity from 1 to 2 the compounds MgCr₂O₄ and CaCr₂O₄ were formed together with the Cr(V)-containing compound complex Ca₅(CrO₄)₃F which forms hexagonal crystals. The results showed that the highest Cr concentration levels in the leaching liquors corresponded to slags with CaO/SiO₂?=?2, probably owing to the formation of CaCrO₄ and Ca₅(CrO₄)₃F, whilst the lowest chromium concentration levels corresponded to MgO-based slags owing to the stable binding of chromium in spinel with MgO. Additionally, potential–pH diagrams for the Ca–Cr–H₂O and Mg–Cr–H₂O systems at 25?°C were calculated.     

Nutrients and heavy metals distribution in thermally treated pig manure.

Ash from pig manure treated by combustion and thermal gasification was characterized and compared in terms of nutrient, i.e., potassium (K), phosphorus (P) and heavy metal, i.e., cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and zinc (Zn) contents. Total nutrient and metal concentrations were measured using energy dispersive X-ray fluorescence analysis. Acid (HNO3, H2SO4) and water-extractable concentrations were also measured both in non-classified ash and in selected ash particle size fractions using flame atomic absorption spectrometry and colorimetric spectrometry. Results indicate that ash from gasified manure contained more water-extractable K in comparison with combusted manure whereas the opposite was the case with respect to P. Heavy metals Ni, Cr and Cd were present in higher concentrations in the fine particle size fractions (< 30 microm of particle diameter), whereas K, P, Zn and Cu exhibited higher concentrations in the coarser particle size fractions (> 30 microm).     

Vitrification of lead-rich solid ashes from incineration of hazardous industrial wastes

Lead-rich solid industrial wastes were vitrified by the addition of glass formers in various concentrations, to produce non-toxic vitreous stabilized products that can be freely disposed or used as construction materials. Toxicity of both the as-received industrial solid waste and the stabilized products was determined using standard leaching test procedures. The chemically stable vitreous products were subjected to thermal annealing in order to investigate the extent of crystal separation that could occur during cooling of large pieces of glass. Leaching tests were repeated to investigate the relation between annealing process and chemical stability. X-ray, scanning and transmission electron microscopy techniques were employed to identify the microstructure of stabilized products before and after thermal treatment. Relation between synthesis and processing, chemical stability and microstructure was investigated.     

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。