Immobilization of copper flotation waste using red mud and clinoptilolite

The flash smelting process has been used in the copper industry for a number of years and has replaced most of the reverberatory applications, known as conventional copper smelting processes. Copper smelters produce large amounts of copper slag or copper flotation waste and the dumping of these quantities of copper slag causes economic, environmental and space problems. The aim of this study was to perform a laboratory investigation to assess the feasibility of immobilizing the heavy metals contained in copper flotation waste. For this purpose, samples of copper flotation waste were immobilized with relatively small proportions of red mud and large proportions of clinoptilolite. The results of laboratory leaching demonstrate that addition of red mud and clinoptilolite to the copper flotation waste drastically reduced the heavy metal content in the effluent and the red mud performed better than clinoptilolite. This study also compared the leaching behaviour of metals in copper flotation waste by short-time extraction tests such as the toxicity characteristic leaching procedure (TCLP), deionized water (DI) and field leach test (FLT). The results of leach tests showed that the results of the FLT and DI methods were close and generally lower than those of the TCLP methods.     

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.     

Characterization of the leaching behaviour of concrete mortars and of cement-stabilized wastes with different waste loading for long term environmental assessment

The leaching behaviour of cement-based products-both construction products and cement-stabilized wastes--have been shown to be similar after assessing the leaching characteristics by means of a pH dependence leaching test. This procedure is particularly suited to identifying the chemical speciation of materials. Geochemical modelling has shown a number of solubility controlling phases in this largely inorganic matrix, that can very well explain the observed leaching patterns as a function of pH. Understanding these relationships allows the prediction of leaching behaviour under other exposure conditions and to improve the ultimate quality of products, if so desired. The role of ettringite-type phases for the binding of oxyanions in the pH range above pH 12 has been identified before and confirmed in this work. The order of incorporation follows from the ratio between the maximum leachability at mildly alkaline pH and at high pH. Increased levels of sulfate negatively influence the binding of oxyanions in cement-stabilized waste through site competition.     

Comparison of leaching tests to determine and quantify the release of inorganic contaminants in demolition waste

The changes in waste management policy caused by the massive generation of waste materials (e.g. construction and demolition waste material, municipal waste incineration products) has led to an increase in the reuse and recycling of waste materials. For environmental risk assessment, test procedures are necessary to examine waste materials before they can be reused. In this article, results of column and lysimeter leaching tests having been applied to inorganic compounds in a reference demolition waste material are presented. The results show a good agreement between the leaching behaviour determined with the lysimeter unit and the column units used in the laboratory. In view of less time and system requirements compared to lysimeter systems, laboratory column units can be considered as a practicable instrument to assess the time-dependent release of inorganic compounds under conditions similar to those encountered in a natural environment. The high concentrations of elements in the seepage water at the initial stage of elution are reflected by the laboratory column leaching tests. In particular, authorities or laboratories might benefit and have an easy-to-use, but nevertheless reliable, method to serve as a basis for decision-making.     

Vitrification as an alternative to landfilling of tannery sewage sludge

Due to high content of heavy metals such as chromium, tannery sewage sludge is a material which is difficult to be biologically treated as it is in the case of organic waste. Consequently, a common practice in managing tannery sewage sludge is landfilling. This poses a potential threat to both soil and water environments and it additionally generates costs of construction of landfills that meet specific environment protection requirements. Vitrification of this kind of sewage sludge with the addition of mineral wastes can represent an alternative to landfilling.The aim of this study was to investigate the possibility of obtaining an environmentally safe product by means of vitrification of tannery sewage sludge from a flotation wastewater treatment process and chemical precipitation in order to address the upcoming issue of dealing with sewage sludge from the tannery industry which will be prohibited to be landfilled in Poland after 2016. The focus was set on determining mixtures of tannery sewage sludge with additives which would result in the lowest possible heavy metal leaching levels and highest hardness rating of the products obtained from their vitrification.The plasma vitrification process was carried out for mixtures with various amounts of additives depending on the type of sewage sludge used. Only the materials of waste character were used as additives.One finding of the study was an optimum content of mineral additives in vitrified mixture of 30% v/v waste molding sands with 20% v/v carbonate flotation waste from the zinc and lead industry for the formulations with flotation sewage sludge, and 45% v/v and 5% v/v, respectively, for precipitation sewage sludge. These combinations allowed for obtaining products with negligible heavy metal leaching levels and hardness similar to commercial glass, which suggests they could be potentially used as construction aggregate substitutes. Incineration of sewage sludge before the vitrification process lead to increased hardness of the vitrificates and reduced leaching of some heavy metals.     

Validation of Microtox as a first screening tool for waste classification

The Waste Framework Directive (WFD; 2008/98/EG) describes how waste materials are to be classified as hazardous or not. For complex waste materials chemical analyses are often not conclusive and the WFD provides the possibility to assess the hazardous properties by testing on the waste materials directly. As a methodology WFD refers to the protocols described in the CLP regulation (regulation on Classification, Labeling and Packaging of chemicals) but the toxicity tests on mammals are not acceptable for waste materials. The DISCRISET project was initiated to investigate the suitability of alternative toxicity tests that are already in use in pharmaceutical applications, for the toxicological hazard assessment of complex waste materials. Results indicated that Microtox was a good candidate as a first screening test in a tiered approached hazard assessment. This is now further validated in the present study. The toxic responses measured in Microtox were compared to biological responses in other bioassays for both organic and inorganic fractions of the wastes. Both fractions contribute to the toxic load of waste samples. Results show that the Microtox test is indeed a good and practical screening tool for the organic fraction. A screening threshold (ST) of 5 geq/l as the EC₅₀ value in Microtox is proposed as this ST allows to recognize highly toxic samples in the screening test. The data presented here show that the Microtox toxicity response at this ST is not only predictive for acute toxicity in other organisms but also for sub lethal toxic effects of the organic fraction. This limit value has to be further validated. For the inorganic fraction no specific biotest can be recommended as a screening test, but the use of direct toxicity assessment is also preferable for this fraction as metal speciation is an important issue to define the toxic load of elutriate fractions. A battery of 3 tests (Microtox, Daphnia and Algae) for direct toxicity assessment of this fraction is recommended in literature, but including tests for mechanistic toxicity might be useful.     

Effect of exposure test conditions on leaching behavior of inorganic contaminants from recycled materials for roadbeds

Throughout the utilization of recycled materials, weathering factors such as humidity, gas composition and temperature have the potential to change the material properties and enhance the release of inorganic contaminants. In this research, the effects of weathering factors on recycled gravel materials for roadbeds were evaluated by applying three kinds of accelerating exposure tests: freezing–melting cycle test, carbonation test, and dry–humid cycle test. The effects of exposure tests were determined by X-ray diffraction (XRD) analysis and serial batch leaching test, making it possible to identify the change in release mechanisms. Sixteen elements, mainly metals, were investigated. Tested samples were molten slag from municipal solid waste, molten slag from automobile shredded residue, and crushed natural stone.After the exposure tests, the increase of cumulative release in the leaching test was generally less than 2.0 times that of the samples without the exposure test. Among the three test conditions, freezing–melting showed a slightly higher effect of enhancing the release of constituents. XRD analysis showed no change in chemical species. From these results, it was determined that the stony samples were stable enough so that their properties were not significantly changed by the exposure tests.     

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.     

The current situation of solid waste management in China

With economic development, the quantity of solid waste is increasing rapidly in China; the total quantities of municipal solid waste (MSW), industrial solid waste (ISW), and hazardous waste (HW) in 2002 were 136.5 million tons, 945 million tons, and 10 million tons, respectively. In 2002, the quantity of MSW disposed of was 74.04 million tons, 89.30% of which was landfilled, 3.72% was incinerated, and 6.98% was composted. There are currently 651 disposal facilities for MSW in China. Mining gangue is the largest component of ISW, making up 27.5% of the total. In the Chinese industrial sector, the coal mining and processing industry contributed most to the total quantity of ISW, with 16.0% of the total quantity of ISW generated by this sector. In total, 44% of HW was recycled, 27% was stored, 13.5% was disposed of, and 15.4% was discharged. Of the total HW generated, 40% was produced by the chemical materials and chemical products industry. Five categories of HW, i.e., waste alkali, waste acid, inorganic fluoride waste, copper waste, and inorganic cyanide waste, made up 57.8% of the total HW generated. Solid waste pollution has become a huge challenge faced by those involved in Chinese environmental management, but this can be seen as an opportunity to improve environmental quality. This article introduces the strategies taken to improve solid waste management in China.     

Leaching of inorganic contaminants from cement-based waste materials as a result of carbonation during intermittent wetting

Characterization of the leaching behavior of wastes is a crucial step in the environmental assessment for reuse or disposal scenarios. The release of inorganic contaminants from waste materials is typically evaluated by tank leaching of continuously water-saturated material. However, materials, in many field or management scenarios, experience cyclic wetting and drying under varied environmental conditions (i.e. variable relative humidity, atmospheric CO2 or CO2 from biologic activities). During periods of storage in an unsaturated environment, many processes may occur that can influence the release potential and release rate of inorganic constituents. The research presented here was carried out to examine how the phenomena of carbonation during drying influence the release of inorganic contaminants from Portland cement-based materials during cyclic wetting and storage. Batch equilibrium leaching tests were used to determine constituent solubility as a function of pH. Dynamic leaching tests on monolithic material were carried out to determine the rate of constituent release as a function of leaching time and intermittent storage conditions. This paper presents the results observed for three typical waste constituents, arsenic, cadmium and lead.     

Assessment of two thermally treated drill mud wastes for landfill containment applications.

Offshore oil and gas drilling operations generate significant amounts of drill mud waste, some of which is transported onshore for subsequent thermal treatment (i.e. via thermal remediation). This treatment process results in a mineral waste by-product (referred to as thermally treated drill mud waste; TTDMW). Bentonites are originally present in many of the drill mud products and it is hypothesized that TTDMW can be utilized in landfill containment applications (i.e. cover or base liner). The objective of this paper is to examine the feasibility of this application by performing various physical and chemical tests on two TTDMW samples. It is shown that the two TTDMW samples contained relatively small amounts of clay-sized minerals although hydraulic conductivity values are found to be less than 10(-8) m/s. Organic carbon contents of the samples were approximately 2%. Mineralogy characterization of the samples confirmed varying amounts of smectite, however, peak friction angles for a TTDMW sample was greater than 36 degrees. Chemical characterization of the TTDMW samples show potential leaching of barium and small amounts of other heavy metals. Discussion is provided in the paper on suggestions to assist in overcoming regulatory issues associated with utilization of TTDMW in landfill containment applications.     

Inertization of hazardous dredging spoils

Vitrification and production of ceramics materials starting from sediment excavated from Venice lagoon is described. This sediment is classified as toxic waste because contains several heavy metal ions and organic pollutants and was successfully vitrified at 1200-1350 degrees C. Twenty weight percentage of glass cullet, coming from a community glass recycling program, was added to the raw materials, previously calcined at 900 degrees C, as a way of adjusting the variations of composition of the individual sediment batches. Chemical durability (leaching) tests showed that the optimized glass compositions are inert, and thus not only volume reduction but also inertization of the waste was obtained by this process. Moreover, the economics of the entire process was analysed. The valorization of the waste was accomplished by the subsequent processing of the glass derived from the inertization. Glass ceramic materials were produced by viscous phase sintering of pressed glass powders which crystallized during the densification process. Sintered glass ceramic products had good mechanical characteristics (HV = 7.5 GPa, bending strength 150 +/- 8 MPa), making them suitable for applications in the building industry.     

Real time alteration of a nuclear waste glass and remobilization of lanthanide into an interphase

The development of predictive models for the long term evolution of nuclear waste glass requires the complete knowledge of the glass dissolution at the laboratory scale. A new approach was developed to determine the initial reaction during the first steps of experience, a new concept was developed, based on the combination of dynamic leaching test and the characterization of the altered materials. With this experimental set-up it is possible to follow in real time the glass alteration process at a fine temporal scale. The results put in evidence a singular behaviour of the lanthanide, shown by a concentration peak of La, Nd and Ce after 2 h and a quick decrease of their concentration measured on line in the solution during the leaching test. This fact is directly linked to the development of an interphase (altered layer which differs from the initial solid by its texture, structure and chemical composition) at the interface of the glass surface and the leaching solution. This work is an attempt to integrate the formation of the alteration products (here the interphase) during leaching into the dissolution mechanisms of a nuclear waste glass. A model is proposed and discussed.     

Use of mix of clay/solid waste from steel works for civil construction materials.

The present study focuses on the use of solid waste generated by the steel works in Brazil for manufacturing clay-based structural products. The waste sample was characterized regarding chemical composition, X-ray diffraction, particle size, morphology, specific surface and plastic properties. The waste was added in gradual proportions to a kaolinitic clay from zero up to 3 wt.%. Ceramic bodies were formed by vacuum extrusion and fired at 950 degrees C. The physical-mechanical properties (linear shrinkage, water absorption, apparent density and flexural strength) of the resulting clay/solid waste mixtures were determined. In addition, leaching tests were performed according Brazilian Standards as well as a preliminary analysis of gases evolved during the thermal process. It was found that the solid waste is formed by irregular particles, ranging in size from 1 to 500 microm. The test results indicate that solid wastes generated by steel works can be used as filler in construction materials, thereby increasing reuse in an environmentally safe manner.     

Design optimization and standardization of an environmental availability test under both acidic and alkaline conditions

The objective of this study was to design a procedure for an environmental availability test under both acidic and alkaline conditions for solid wastes and recycled materials and products. The procedure was designed on the basis of the Dutch availability test NEN 7371. Bottom ash from a municipal solid waste incinerator and copper slag were used as test materials. The influences of the type and intensity of liquid stirring apparatus and the open area ratio of the top of the leaching vessel were investigated experimentally, and partial least-squares modeling was applied as multivariate data analysis for the simultaneous evaluation of the three leaching conditions. Interlaboratory validation was then carried out with the participation of seven laboratories in accordance with JIS Z 8402-2/ISO 5725-2. Both repeatability and reproducibility were found to be acceptable, but precise calibration of the pH electrode is required. The proposed procedure will provide sufficient accuracy as a standard test method.     

Leaching of heavy metals from E-waste in simulated landfill columns

In recent history the volume of electronic products purchased by consumers has dramatically escalated. As a result this has produced an ever-increasing electronic waste (E-waste) stream, which has generated concerns regarding the E-waste’s potential for adversely impacting the environment. The leaching of toxic substances from obsolete personal computers (PCs) and cathode ray tubes (CRTs) of televisions and monitors, which are the most significant components in E-waste stream, was studied using landfill simulation in columns. Five columns were employed. One column served as a control which was filled with municipal solid waste (MSW), two columns were filled with a mixture of MSW and CRTs, and the other two were filled with MSW and computer components including printed wire boards, hard disc drives, floppy disc drives, CD/DVD drives, and power supply units. The leachate generated from the columns was monitored for toxic materials throughout the two-year duration of the study. Results indicate that lead (Pb) and various other heavy metals that were of environmental and health concern were not detected in the leachate from the simulators. When the samples of the solids were collected from underneath the E-waste in the columns and were analyzed, significant amount of Pb was detected. This indicates that Pb could readily leach from the E-waste, but was absorbed by the solids around the E-waste materials. While Pb was not observed in the leachate in this study, it is likely that the Pb would eventually enter the leachate after a long term transport.     

Effect of contact time on the release of contaminants from granular waste materials during column leaching experiments

When reusing or disposing of contaminated granular waste materials there is a need to evaluate how the contaminants will interact on the pathway soil–groundwater and the effect this interaction will have on the surrounding environment. While column testing can provide a closer approximation to field percolation conditions than batch testing, there is still a need to develop column testing procedures that consider the requirements of practical testing time frames. This study evaluates the effect of different column contact times (2.5, 5, and 16 h) on the release of inorganic constituents from bottom ash and demolition waste, two commonly reused granular materials. Leaching data for representative constituents of concern, such as copper, chromium, sulfate and chloride, as well as pH and electrical conductivity was compared for all different contact times studied.Results for the materials investigated in this study showed that variations in contact time have no significant effect on the release of the selected constituents and leaching parameters at low liquid to solid ratios. However, after a liquid to solid ratio of 1 L/kg, the effect is more noticeable, and higher contact times show lower pH values as well as a reduction in the release of constituents of concern from bottom ash. In the case of demolition waste, the variation of contact time did not have a strong effect on the leaching behavior.     

草酸钴废料协同浸出水钴矿中的钴和铜

利用草酸钴废料协同浸出水钴矿中的钴和铜,考察了工艺条件对浸出率的影响,并推荐了一种二段浸出及后续生产草酸钴的工艺流程。实验结果表明,在草酸钴废料与水钴矿的质量比为20%、反应时间为120 min、反应温度为85 ℃、初始H2SO4浓度为1.00 mol/L、液固比为4 mL/g的最佳工艺条件下,钴和铜的浸出率分别达到98.82%和96.24%。该工艺应用于水钴矿的还原浸出,在回收利用草酸钴废料的同时,降低了还原剂的消耗,且对浸出液后续处理工艺无影响。     

Recovery of valuable metals from electronic and galvanic industrial wastes by leaching and electrowinning

In the present paper, a study on laboratory scale to perform a treatment for valuable metals recovery from electronic and galvanic industrial wastes, is reported. The characterisation of the waste, performed by XRD, SEM, EDX and chemical analysis, showed a high metals content in the sludge, such as Cu, Ni, Mn, Pb, Sn, W. A leaching process, coupled by electrowinning, is then proposed in order to reduce the volume of the waste material and to recover selectively valuable metals, such as Cu and Ni. During the leaching step, carried out by using H(2)SO(4), several factors were investigated (acid concentration, temperature and time of treatment). The leached liquor has been successfully treated with an electrowinning process, to recover copper and nickel. The copper and nickel depositions, were performed in acid and alkaline conditions, respectively. The Faraday yield was of about 95%. The energy consumption was 2.13 and 4.43 kWh per kg of copper and nickel recovered, respectively. At the end of the process, about 94-99% of the initial content of Cu and Ni was recovered at the cathode. The experimental results obtained, showed the technical feasibility of the process.     

Leaching behavior of some demolition wastes

Demolition wastes may be used in different civil engineering applications as road constructions, concrete, and embankments or landfill. Regardless its application, leaching tests of the waste should be carried out to assess concentrations of pollutants. Concrete, brick and mixture of concrete, bricks, tiles and ceramics wastes were subject to percolation test—CEN/TS 14405, and batch test—SR EN 12457. The leachates were analyzed with respect to concentration of inorganic elements—arsenic, barium, cadmium, chromium, copper, mercury, molybdenum, nickel, lead, selenium, zinc, fluoride, chloride and sulfate, and organic compounds (phenol index). The concentrations of elements in leachates were compared with the limit values of European regulation for the acceptance of inert wastes at landfills. Generally, the releases of inorganic species in leachates were below limits values. Some waste leachates obtained by percolation and batch test had high values for phenol index.