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By Vinay Kumar, Jae-Chun Lee, Rakesh Kumar, Manis Kumar Jha, Archana Kumari, Pankaj Choubey

Present work is a part of developing novel recycling technique for waste printed circuit boards (PCBs) i.e. the liberation of metals from PCBs by organic swelling followed by the treatment of resin to remove/ recover hazardous soldering materials. In order to recover the hazardous metallic constituent lead from the liberated resin, initially the leaching studies were made using fresh solder containing 63.9% Pb and remaining tin. Experimental results obtained in different conditions viz. time, temperature and acidity showed -97.20% of lead dissolution with 6M HNO3 at solid to liquid (S:L) ratio 1:10 (g/mL) and temperature 90°C in 75 minutes. The result of the studies validated with crushed PCBs shows that almost total lead and tin was leached out with 6M HNO3 and 6M HC1 respectively at S:L ratio 1:10 (g/mL) and temperature 90°C within 50 minutes. The results will be useful for the treatment and safe disposal of PCBs resin.

Jan 1, 2011

By M. Wallin

Millions of tons of sludge from different metallurgical processes are produced worldwide annually, and the environmental impact of landfilling these often hazardous sludges stresses the need to understand their role as valuable resources. The current work explores the potential of producing a saleable low-phosphorous ferromanganese alloy by utilizing sludge from the silicomanganese industry together with an iron source. The aim of the project is to explore the feasibility and practical challenges related to reduction and dissolution of manganese and silicon from the sludge to liquid metal and slag. Parameters such as ratio of input material as well as the effect of adding limestone and coke to the mixture were explored by thermodynamic calculations and adapted experimentally. Results show that a ferromanganese alloy, in fact, can be formed, while silicon and calcium forms a complex slag that captures a significant amount of impurities.

By B. J. Jody

At Argonne National Laboratory, we have been developing a potentially economical process to recycle automobile shredder residue (ASR). We identified three potentially marketable materials that can be recovered from ASR and developed technologies to recover and upgrade these materials. We built and tested a field-demonstration plant for recycling polyurethane foam and produced about 2,000 lb (907 kg) of recycled foam. Several 300-lb (I36-kg) samples were sent for evaluation and were found to be of marketable quality. We are also preparing for a large-scale test in which about 200 tons (181 tonnes) of ASR-derived fines «0.25 in. [<0.62 cm]) will be used as a raw material in cement making. A major cement company has evaluated small samples of fines prepared in the laboratory and found that they meet its requirements as a substitute for iron ore or mill scale. We also produced about 50 lb (23 kg) of recycled acrylonitrile butadiene styrene (ABS) from obsolete automobiles and found that it has properties that could be readily upgraded to meet the specifications of the automotive industry. In this paper, we briefly discuss the process as a whole and summarize the results obtained from the field work on foam and fines recycling.

Jan 1, 1996

By Yuanbing Ling

Keywords: Calcium sulfate, Sulfuric acid, Phase transformations, Thermodynamic analysis As part of a boarder research project, seeking the development of a cost-effective process for direct production of the high value material, -calcium sulfate hemihydrate, from sulfuric acid at atmospheric as opposed to elevated pressure conditions, the fundamental work presented here has been undertaken. This includes experimental monitoring of phase transformation reactions and thermodynamic analysis of the relationships among the various phases, namely, calcium sulfate dihydrate, hemihydrate and anhydrite in aqueous sulfuric acid solution at temperatures ranging from 20oC to boiling point.

Jan 1, 2004

By Shawn A. Cefalu, Matthew J. M. Krane, Kent J. VanEvery

"Segregation during electroslag remelting (ESR) of a nickel-chromium-molybdenum alloy (Ni-8 wt% Cr-25 wt% Mo) has been modeled. Features of the model include species transport and AC electromagnetic effects coupled with fluid flow, heat transfer, and solidification. The effect of varying ingot diameter and melt rate, on macrosegregation patterns, local solidification time, and liquid pool profiles obtained from this model are demonstrated. The results show that the macrosegregation in the ingots correlates to the filling velocity.IntroductionElectroslag remelting (ESR) is a secondary melting process used to refine the chemical composition and the microstructure of metals. Macrosegregation of solute elements causes defects in ESR ingots, including freckles and the maldistribution of phases. These defects are not correctable through heat treatment due to the large length scales over which they occur. However, the frequency and distribution of these defects may be minimized, or even prevented, through process control based on an understanding of the conditions that lead to their formation.In the past, studies have been conducted on the effect of the process parameters on the shape of the melt pool and the thickness of the mushy zone [1-7]. In these studies, the shape of the liquid pool is determined by consideration of the heat and fluid flow induced by electromagnetic (Lorentz) force and thermal buoyancy. The transport of solute and the resultant solutal buoyancy effects were not considered in these macroscopic models. Defect formation is tied to formation of secondary phases (e.g., freckling and white spots in nickel superalloys) [5,8]. In cases where secondary phase formation is calculated (e.g., [6]), phase fractions are determined using a micro-scale model given the local solidification time (LST) and local thermal history from the macroscale model.Using the local thermal history from the macroscopic transport model to predict microstructure increases the importance of the accuracy of those results. This investigation models the macrosegregation of molybdenum during the ESR of a Ni-Cr-Mo alloy. The effect of macrosegregation on pool shape and depth is demonstrated, along with its effect on the local solidification time. By comparing the relative effects of the melt rate and ingot radius, a better understanding of the factors that affect macrosegregation, and ultimately secondary phase formation may be obtained."

Jan 1, 2004

By Meifeng Zhi

Separation of uranium and molybdenum in the alkaline leach solution of a U–Mo ore was studied. A process of acidification-solvent extraction-precipitation uranium and molybdenum was determined. The influences of solution acidity and phase ratio of acidic scrubbing on separation of uranium and molybdenum were examined. The molybdenum extraction equilibrium isotherm was drawn. The results show that the separation of molybdenum and uranium can be achieved by acidifying the alkaline leach solution, solvent extracting molybdenum using trialkylamine at equilibrium pH 2.5, and scrubbing the loaded organic phase using sulfuric acid solution. The strip solution can directly precipitate ammonium molybdate. Uranium can be directly precipitated from the raffinat

By D. C. Azubike

Wolframite (FeWO4) usually having cassiterite (SnO2) as a major impurity is a primary source of tungsten. Its direct reduction/carburisation with carbon in the temperature range 1000-1400°C, and with hydrogen at 600-900°C followed by carburisation with CO at 900°C are described. Depending on the conditions and reactants employed, Fe, Fe2W, B-Sn,WC, W2C, Fe3W3C and Fe6W6C are the products. Tin was found to inhibit the overall reduction and carburisation reactions significantly. The potential for either efficient separation of iron and tungsten or a one-stage production of an iron-based metal carbide composite is discussed.

Jan 1, 1992

By S. N. Monteiro, C. M. F. Vieira, A. P. N. M. de Sa, J. P. D. Vitorino

"This work has as its objective to characterize an ash waste and to evaluate its incorporation into a clay to produce bricks and roofing tiles. The waste is a type of fly-ash resulting from the incineration of a selected part of urban garbage, which is basically constituted of organic matter and plastics. The waste was submitted to mineralogical and chemical characterization. Compositions were prepared with incorporation of the waste in amounts of up to 20wt.% into athe clay. Rectangular specimens were prepared by extrusion and fired in a laboratory furnace at 900°C. The physical and mechanical properties evaluated were: linear shrinkage, water absorption and flexural rupture strength. The results showed that the waste is predominantly composed of quartz and calcium compounds. The incorporation of the ash was deleterious to the evaluated properties of the clay. It is suggested that the incorporation should be made in amounts below 5wt. % to avoid deleterious effect in the mechanical strength and water absorption of the clayey ceramic.IntroductionThe world attention has turned to a subject of great concern today, the production and disposal of large amounts of industrial wastes as well as wastes of various sources. When deposed in an unsuitable place, these wastes can cause considerable harm to human health and to the environment. Our planet suffers with air pollution, groundwater and soil contamination as well as silting of rivers and lakes with the growing amounts of our society wastes.The recycling of waste materials is of great interest to the industries, mainly due to the environmental agencies legislation. One of the practices for correct disposal of these wastes being investigated is to incorporate into red ceramics, such as bricks and roofing tiles. The natural variability of the characteristics of the clays associated with the relatively simple processing techniques and also the low performance required for the products allow the presence of relatively high levels of impurities in clayey ceramics."

Jan 1, 2011

By John L. H. Patterson

Handheld XRF has become the favorite way of measuring the content and identity of alloys in the field. This is because of the very portable nature of the instrumentation and its simple operation. However, these analyzers have been unable to determine the concentration of the light elements like Mg and Si due to the very low energy of the x-rays produced by these elements. In the past accessories such as vacuum and He flush have given some analyzers the ability to determine these light elements with modest detection limits. The introduction of the Silicon Drift Detector (SDD) into this class of instrumentation has added a new level of analysis capability to portable XRF instrumentation. X-ray fluorescence is achieved by exciting a sample with a beam of x-rays, which in recent portable equipment are generated by a small tube. This results in the emission of characteristic x-rays from the sample under test. By measuring the energy of each x-ray it is possible to determine what element generated it. By counting the number of x-rays at each energy it is possible to determine the concentration of each element. The detection limit for each element is dependent upon the number of x-rays which reach the detector. As the number of x-rays increases the detection limit will improve. One of the major factors in an x-ray reaching the detector is the energy of the x-ray. As the energy of an x-ray increases the probability of that x-ray reaching the detector increases. The energy of an x-ray is inversely proportional to the atomic number (AN) of the element generating the x-ray. For example, an iron x-ray (AN=26) is 6.40 keV while an aluminum x-ray (AN=13) is 1.49 keV. As the energy decreases, the detection of the x-ray becomes less and less probable because the x-ray may be absorbed by the windows which are part of the instrument and detector or the air in the path between the sample and detector. In SiPIN based portable XRF analyzers, the lowest element which is detected with acceptable detection limits is normally considered to be Ti (AN=22). The detection limits for 60 second measurements on typical SiPIN XRF analyzer are given in Table I. Thus, portable analyzers have not been useful for measurement of aluminum and titanium alloys as major components of these alloys are Mg (AN=12), Al (AN=13) and Si (AN=14).

Jan 1, 2009

By I. D. Reznik

The flowsheets of converter matte production from sulphide copper - nickel and oxide nickel ores on Severonickel and Yuzhuralnickel integrated ,;corks are given. The cobalt behaviour in electrosmelting and autogenous ore smelting, converting and converter slag cleaning is observed. A list of acticles published in the 80 th is given.

Jan 1, 1993

By S. A. Shuey

The present industrial practice used to separate aqueous cobalt from nickel is multistage solvent extraction processing. This paper describes a different but simpler treatment technology. The proposed technology has been applied to cobalt/nickel hydroxide intermediate solids produced from the treatment of Electrochemical Machining (ECM) waste sludge, The process consists of dissolving the cobalt/nickel hydroxides in basic cyanide solutions. Cobalt and nickel form aqueous .solution metal cyanide complexes. Nickel can be selectively precipitated from the solution as a nickellic hydroxide solid. Cobalt can be recovered from the leach solution by precipitation of a cobaltous/cobaltic cyanide double salt. The double salt product can then be subsequently treated to produce an appropriate cobalt product. The process chemistry, proposed fiowsheet and preliminary reagent costs are presented and discussed.

Jan 1, 1998

By John E. Dutrizac, Tzong T. Chen

"Laboratory experiments were undertaken to ascertain the behaviour of various ""impurity"" species during the precipitation of hematite directly from ferric sulphate solutions at 225°C and in the presence of 40 or 50 g/L of hematite seed. Copper, nickel and zinc are not significantly incorporated in hematite precipitates. Although the nickel contents increase to 0.22% as the Ni concentration increases to 60 g/L, the solid solution Ni contents are low relative to the bulk Ni contents. Thus, part of the Ni may be present as tiny particles of poorly soluble NiS04.H20. Increasing germanium concentrations to 2,000 mg/L result in products containing up to 0.59% Ge. The Ge occurs either in solid solution in the hematite or is adsorbed on the nanometer-size hematite crystallites. Increasing As(V) concentrations to 10 g/L increase the AsO4 contents of the products up to 16%. However, the products consist of hematite together with As04-containing Fe(SO4)(OH) and an unknown Fe-AsO4 species. All the hematite products contain - 1% SO4 which appears to be adsorbed on the nanometer-size hematite crystallites.IntroductionDissolved iron is a common impurity in most hydrometallurgical processing circuits and, generally, the iron must be eliminated prior to the subsequent recovery of the sought after metals. Simple neutralization of iron-rich solutions yields slurries which are difficult to thicken and filter. To address these concerns, the jarosite, goethite and hematite processes have been developed, and these technologies are able to reject the dissolved iron in a readily filterable form [1]. Despite its higher cost, the hematite process offers several potential advantages. Because hematite is an iron-rich, high-density compound, its formation would reduce the mass of residue and the size of a residue storage pond. Hematite is the thermodynamically stable form of iron under ambient conditions, and this stability would facilitate the impoundment of hematite precipitates. Furthermore, hematite has some market potential for cement manufacture and even for iron making [2]. In all the commercial hematite processes, the dissolved ferric ions are first reduced to the ferrous state. Subsequently, the pH of the solution is adjusted and the solution is then oxidized. The ferric ions gradually generated during solution oxidation hydrolyze and precipitate mostly as hematite, although commercial hematite products also contain trace or minor amounts of jarosite-type compounds. However, there are potential advantages in precipitating hematite directly from ferric ion solutions, as the reduction and subsequent oxidation of the iron are not required. Although the precipitation of hematite directly from relatively concentrated ferric sulphate solutions (up to 0.5 M Fe(SO4)is) was recently demonstrated [3], the behaviour of impurity species during hematite precipitation is largely unknown. To address this issue, systematic laboratory experiments were undertaken to ascertain the behaviour of a number of ""impurity"" species during the precipitation of hematite directly from ferric sulphate solutions at 225°C, and the results are presented in this paper."

Jan 1, 2012

By Suguru Kohno, Yoshihiro Momose, Masakazu Honma, Tokirou Kamosawa

Copper metal surfaces have been examined by an extremely sensitive surface analysis technique called temperature programmed photoelectron emission (TPPE). The surfaces were ultrasonically cleaned and subsequently abraded by a screw in organic solvents and water. The TPPE apparatus is composed of a Geiger counter with Q gas (He+ iso-C4H10). The curve of photoelectron emission (PE) intensity vs. wavelength from 300 to 170 nm, termed PE spectrum, was repeatedly measured at different temperatures in the temperature- increase process from 25 to 350°C. The number of emitted electrons in a PE spectrum (PE total count) increased, reached a maximum at-250°C, and decreased with increasing temperature. With the surfaces cleaned alone in the liquids the maximum PE total count decreased in the order C3H70H > (CH3) 2CHOH > C2HpH > CHPH > H2O. With the mechanically abraded surfaces in the liquids the maximum PE total count changed as a function of the abrasion period and the maximum tended to appear at higher temperature with increasing abrasion period; the maximum value at 10-min abrasion decreased in the order H2O > CHpH > C2HPH > (CH3) 2CHOH > n-C3HpH. It was suggested that the TPPE behavior can be related to the acid-base interaction between the alcohols and the abraded metal surfaces and the presence of a contaminant over layer on the surface. From the XPS analysis of the 01 s spectra it was suggested that the chemical change of the adsorbed oxygen to oxide oxygen with temperature plays a substantial role in the appearance of the maximum PE total count.

Jan 1, 2000

By Willem P. C. Duyvesteyn

A novel hydrometallurgical process for Escondida copper concentrates has been developed by The Minerals Laboratory of BHP. The Escondida Process consists of concentrate leaching, solution purification, electrowinning and residue flotation. Part of the copper will be sold as high grade concentrate and part as high purity SX-EW copper. Contrary to previous efforts for the development of a hydrometallurgical process for copper concentrates, this patented process does not advocate the total dissolution of copper. It only aims for the copper that is readily soluble in a mildly oxidizing environment with an ammoniacal or acidic lixiviant. Both lixiviants were studied, but ammonia was preferred because of fast kinetics at ambient temperatures and pressures. By controlling the oxidation potential, the formation of sulfate ions and, consequently, of an ammonium sulfate byproduct, is precluded. These mild leaching conditions also prevent the dissolution of unwanted impurities and result in the production of ultra-high purity electrowon copper. Solution purification is carried out by solvent extraction with LIX-54. The very high loading capacity of this organic results in a compact SX circuit, consisting of two loading, one scrubbing, and one stripping stage. As the organic is selective for simple copper ions, the copper amine complex is broken down and free ammonia is regenerated and recycled for leaching. High purity copper cathodes are produced in a conventional sulfuric acid based electrowinning system. One scrubbing step is needed to separate the ammoniacal circuit from the acid circuit. Limiting copper dissolution to less than 50% also provides an opportunity to produce high grade concentrates by residue flotation. Copper recoveries in excess of 98% with precious metal values reporting to the final concentrate can readily be obtained. Complete breakdown of the copper mineral- pyrite middlings results in a final concentrate grade that can be even higher than the original feed material. The Escondida Process also provides an opportunity to accept lower grade copper concentrates producing improved copper recoveries in the mill and yet high quality concentrates for marketing. The Paul E. Queoeau International

Jan 1, 1993

By J. Phillip Mackey

A whole new group of non-ferrous pyrometallurgical processes with the ability to utilize tonnage oxygen and capture sulphur dioxide were developed and commercialized over the period 1940s–1980s. Many of these earlier process developments were undertaken with limited knowledge of the process chemistry and influence of key process variables; in many cases, piloting helped provide much new physico-chemical data, but gaps remained. The second generation versions of these technologies of today provide all the primary copper, nickel and lead produced worldwide by pyro-metallurgical smelting. Further, process development has continued and a new generation of copper and lead smelting technologies have also been developed in China since the 1990s. The older reverberatory and blast furnaces have been progressively replaced by the newer technologies—a good example being the introduction in 1992 of the copper IsaSmelt technology at the Mt. Isa smelter in Australia where the former fluid bed roaster and reverberatory furnaces were replaced by a single new smelting unit, together with an acid plant for sulphur dioxide collection. The development of these new technologies was made possible by investment in fundamental and applied research. The lesson for the future is, in order to sustain these improvements, continued investment in research and development capability is required—to do otherwise is to risk obsolescence and lack of competiveness in the world market. Dr. Peter Hayes at The University of Queensland is one of the many researchers and process engineers who have contributed to the fundamental understanding of metallurgical processes over this period of rapid change in technologies. The present paper briefly outlines some of the many contributions Peter Hayes has made to the understanding of kinetics, mechanisms and phase equilibria in metallurgical systems, and metallurgical process development.

By Tailoka F.

Various metallurgical residues from iron and steel making processes have been treated by chlorination in excess air with hydrogen chloride gas generated from the combustion of scrap polyvinyl chloride (PVC). The residues include dust from both the electric arc and blast &maces, hydrocyclone overflow, zinc - lead blast furnace slags and dust rich in zinc and copper from copper refining. Chlorination is achieved either directly by mixing the residues with scrap PVC or indirectly in a two furnace system. In the latter, scrap PVC is combusted between 523 and 573 K in a horizontal furnace and the resulting gases are then reacted with metallurgical residues in a vertical furnace at 1166 to 1329 K. Gas chromatography, thermogravimetric measurements, XRD and AAS have been utilised to study the reactions. The recovery of non ferrous metals is as high as 80 to 90 % and only a negligible amount of iron is carried over. The optimum temperature for combustion is between 518 and 573 K. Above 600 K, the evolution of HCI is so fast that sufficient chlorination is not achieved. Analysis showed that no dioxins were present in the gases, the residues or the chlorides.

Jan 1, 1997

By Ross W. Smith

Microorganisms are increasingly finding use in mineral processing and hydrometallurgy both for the enhancement of mineral engineering operations and for the remediation of mineral industry wastes. Some of the applications, such as biologically assisted leaching of sulfide ores and biooxidation of refractory sulfide gold ores, are established commercial processes. Others, such as the use of organisms for the removal of heavy metal ions from dilute aqueous streams, are nearing commercial application. Other uses of microorganisms are potentially possible. These include use of microorganisms in leaching non-sulfide ores, the flocculation or flotation of minerals and remediation of toxic chemicals discharged from mineral engineering operations.

Jan 1, 1993

By A. Shemi

Tungsten carbide scrap (WC–Co) is material generated from the tungsten carbide manufacturing process and worn out or used carbide parts from industry. Tungsten (W) ores contain about 3 wt% WO3 and their W concentrates about 10– 75 wt% WO3. Tungsten carbide scrap typically contains 40–95 wt% W. The high intrinsic value of W and the fact that the least valuable scrap contains more W than the average tungsten ore makes tungsten carbide scrap a worthy material for re-use. This study has investigated the selective dissolution of the cobalt (Co) binder phase, and recovery of tungsten monocarbide (WC) and Co using an acid leach process. The Co component was selectively leached leaving the WC solid particles intact. Further investigation using a complexing agent-aided acid leach process that takes advantage of organic chelating agents that form a soluble tungsten complex in place of the passive insoluble tungsten oxide is envisaged. The optimal dissolution of the Co binder phase using an inorganic acid in conjunction with an organic complexing agent is a novel approach with the potential of reduced leaching times and possibility of regenerating the unreacted organic acid.

By Mingming Zhang, Mallikharjuna R. Bogala, Ramana G. Reddy

Steelmaking desulfurization slag samples were characterized using chemical, X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) methods. The objective of this work is to investigate the occurrence of sulfur and phosphorus components in the slag samples and to identify their origin and associations with the iron phases. Thermodynamic calculations results confirm the presence of phosphorus and sulfur components in the slag sample at high temperatures (1400 to 1800oC). The main constituents of slag include Ca3SiO5 (28.1%), MgO (9.31%), Ca3(PO4)2 (9.18%), CaS (8.39%) and CaO (5.68%). The major phosphorus and sulfur components of the slag are Ca3PO4 (99.2%) and CaS (79.3%) respectively. Characterization studies indicate the presence of microparticles of different sizes and shapes in the slag sample. Elemental analysis of these particles confirm the presence of major elements (O, Mg, Al, Si, S, Ca and Fe) in the slag sample.

Jan 1, 2015

By R. Boom, Y. V. Meteleva-Fischer, B. Kraaijveld, H. Kuntzel

"Segregation of impurities during refining of metallurgical grade silicon (MG-Si) is an option to produce solar grade silicon (SG-Si). Directional solidification is a last step in production of SG-Si effective for removal of metallic impurities. The possibility is investigated to use metallic impurities originally present in MG-Si for removing boron and phosphorus. MG-Si has been treated using two methods: 1) alloying with calcium and 2) refining with Na2O-CaO-SiO2 slag, both by controlled cooling. The microstructure of silicon and the impurities distribution have been studied before and after the treatments. Using EPMA phosphorus and boron have been detected in 1-2 wt% concentration range in several intermetallic compounds in grain boundaries after both treatments. This observation points to a different possible mechanism of silicon refining from boron and phosphorus. Controlled cooling improves migration of phosphorus and boron to the silicide phases in grain boundaries, which can be removed by acid leaching treatment.2. IntroductionStandards for silicon solar cells and growing demand on “green” energy require economical and efficient route to the production of solar grade silicon. Refining of cheap metallurgical grade silicon is one of the promising options, where application of existing metallurgical approaches can result in cost-efficient production on industrial scale. Focus in refining is on impurities, which are most difficult to remove: B, P, Al, Ti, due to their large segregation coefficient in silicon and low vapour pressure [1]. Moreover, more environmentally friendly technology in comparison to the traditional Siemens process [2] will be in accordance with societal needs. Based on properties of common impurities in metallurgical grade silicon, alloying refining and slag refining are suggested as competitive techniques having potential effect on removal of impurities harmful for conversion of solar energy [3, 4]. Alloying with Ca followed by acid leaching was found to be effective for removal of Fe and Ti from silicon [5] and to enhance also removal of boron [6] and phosphorus [7, 8]. In the work of Inoue et al. [8] drastically increasing removal of phosphorus from silicon has been observed with an increase of Ca content and a thermodynamics-based explanation was provided. Since phosphorus has been found to condense in the secondary precipitate mainly composed of CaSi2, it can be removed together with iron and titanium by consecutive acid leaching treatment. Slag refining is one of the metallurgical methods proposed to be effective for refining of metallurgical grade silicon from boron [9, 10]. Slags with additions of the following oxides to silica have shown positive effect on removal of boron: CaO [11-13], Na2O [11,14]. Mechanism of slag refining from boron is based on oxidation of boron followed by its incorporation in the slag network [9,11]; the same mechanism is suggested for refining from phosphorus taking into account that oxides of boron and phosphorus are known as network-formers [15]."

Jan 1, 2012