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By Jürgen Antrekowitsch, Thomas Griessacher

"Heavy metal containing residues are typically hazardous wastes because on the one hand, a deposition gets more and more complicated and on the other hand, the large amounts of metals like Zn, Cu, Fe and Pb represent a significant value. Thus, a post-treatment of these materials with the recovery/recycling of the metals and stabilization of the waste is not only ecological but often also economical. The therefore typically applied recycling processes utilize pyrometallurgical steps, where carbon or carbon monoxide from fossil coal and coke is used as a reducing agent, which results in large amounts of CO2 emissions. An alternative option is the application of a hydrogen-rich gas emitted in biomass utilization processes as a carbon-neutral reducing agent. Investigations in a retort process which were done at different temperatures and times showed excellent results concerning the achievable reduction rates and final contents of the heavy metals for various residues.IntroductionNowadays heavy metal containing residues like electric arc furnace dust (EAFD), dust from cupola furnaces, waelz slag, etc. are declared as hazardous wastes in a growing number of countries due to the leachability of the heavy metals in these residues. For that reason it is no longer possible to landfill these materials or use them for road construction or disposal works. Some land filling activities, carried out until now, have only been realizable because of some process modifications or cost intensive post-treatment steps of these residues. But the disposal capacities for such materials are decreasing, therefore increasing the prices. The second point for the growing disposal limitations is the stringent environmental legislations and regulations, which restrict the number and amounts of materials which can be dumped [1 – 5].From the other point of view these heavy metal containing residues usually have high contents of zinc, lead, iron, etc., which represent a significant value and therefore a big potential to recover these metals. This is why in recent years the number of recycling processes and the amount of recycled heavy metal containing residues have continuously increased. These recycling processes have the target to recover the valuable metals from the residual materials in the form of a saleable product as well as the stabilization of the slag produced in these processes [5, 6]."

Jan 1, 2011

By Murali Thirukkonda, Rahul Shah, Srinivas Tangrila, Shankar Rachakonda, Jan Kajuch, Arthur Gurson

"High-temperature superconductors have potential for a variety of applications such as power generators, superconducting magnets for mine sweepers or ship propulsion motors, and magnetic levitation transportation systems. Interest in the use of superconducting wires and tapes increased dramatically after the discovery of high-critical-temperature (high-Tc) oxide superconducting compounds, which offer operating temperatures above that of liquid nitrogen. Several techniques have been proposed to produce commercially viable high-Tc oxide based superconducting wires. One of the promising methods involves multi-pass powder-in-tube (PIT) wire drawing followed by rolling and heat treatment. This work focuses on the development of a numerical model to simulate the PIT drawing process for fabrication of long lengths of silver sheathed Bi-2212 superconducting wires. The finite element based model was used to predict densification of the oxide powder, wire drawing forces, and silver sheath thickness during drawing. A cap-type pressure dependent constitutive equation was implemented in the model to simulate the powder behavior. The model incorporated experimentally obtained material data for the silver and powder. Results indicate that powder densification is increased by decreasing the initial silver thickness and increasing the silver strength. Data from wire drawing experiments were used to verify model predictions. IntroductionSuperconducting wires and tapes can be used to carry large dc currents with no measurable loss due to resistivity. When used in superconducting magnets for power generators, motors, levitation devices, magnetic detectors, or energy storage devices, they could potentially result in significantly reduced energy losses. In the past, most prototypes were tested in liquid helium at 4.2K [1]. However, the necessity to provide liquid-helium cooling systems proved to be a serious limitation in commercialization. In 1986 high-critical-temperature (high-Tc) oxide superconductors were discovered [2], which could allow for higher operating temperatures above liquid nitrogen (77 K). Since then, both academia and industry have concentrated their efforts on the development of high-Tc oxide superconducting wires, tapes and coils. As yet, large scale fabrication of long lengths of these wires with the required current carrying capacity and mechanical properties remains an enormous challenge."

Jan 1, 1994

By Andrew Wessman

Keywords: Recycling, Electrodeposition, Recovery, Dilute, Dissolved Metal Ions In order to facilitate the recovery of pure metals from solutions containing a mixture of dissolved metal ions, a pulsed electrodeposition method was developed. Using this method, it is possible to selectively remove metal ions from solution based upon the electrochemical potential of the particular ion desired. The use of pulsed electrodeposition rather than direct current electrodeposition creates an electrodeposited material with better morphology, increases electrical efficiency of the process, and avoids problems with short circuiting between electrodes. Using this method, it is possible to recover dissolved metal ions in a purified form in one simple step, and therefore maximizes recovery of the metal ions while obtaining them in a saleable form. This method is likely to be useful in improving the recycling process for numerous complex metal mixtures and alloys.

Jan 1, 2005

By J. R. Donald

Electric arc furnace (EAF) dust, which can be considered as a by-product of the steel recycling process, contains significant quantities of recoverable zinc and iron, as well as hazardous elements such as cadmium, lead and chromium, which can be leached by ground water. The zinc in the EAF dust is found almost entirely in the form of either zinc oxide or zinc ferrite, the latter accounting for 20 to 50 percent of the total zinc. It is important that an efficient process be developed which renders the dust inert, while reclaiming the valuable metals to off-set processing costs. During the conventional carbothermic reduction processes, iron is formed, and this iron can participate in the reduction of the zinc oxide in zinc ferrite. In the present work, the reduction of the zinc oxide in zinc ferrite by iron according to the following reaction: ZnO-Fe2O3(s,s) + 2 Fe(s) = Zn(g) + 4 FeO(s) was studied in an argon atmosphere using a thennogravimetric technique. First, a thermodynamic analysis was performed using the F*A*C*T computational system. Then, the effects of briquette aspect ratio (lid), temperature, zinc ferrite particle size, amount of iron added, as well as additions such as lime, sodium chloride, and calcium fluoride were investigated. It was found that, initially, the reaction was chemically controlled with an activation energy of 178.1 kJ/mol. Then, after a product layer had formed on the outer surface of the briquette, the reaction was restricted by the diffusion of zinc gas away from the reaction interface. The parabolic rate law was fitted to the experimental data, and the parabolic rate constant was found to be: = -6.2275 + 0.0054 T (K)

Jan 1, 1995

By Xiaofei Guan, Adam C. Powell, Uday B. Pal, Srikanth Gopalan

This paper reports a solid oxide membrane (SOM) electrolysis experiment using an LSM– Inconel inert anode current collector for production of Mg and O2 at 1423K. The electrochemical performance of the SOM cell was evaluated by using various electrochemical techniques including electrochemical impedance spectroscopy, potentiodynamic scans, and potentiostatic electrolysis. The effects of Mg solubility in the flux on the current efficiency and the YSZ membrane stability during SOM electrolysis were discussed and examined through experiment and modeling. The electronic transference number of the flux were measured to assess the Mg dissolution in the flux during SOM electrolysis. A negative correlation between the electronic transference number of the flux and the current efficiency of the SOM electrolysis was observed.

Jan 1, 2014

By N. L. Piret

Primary and secondary copper smelting dusts are being generated in varying quantities with very dissimilar characteristics due to the different compositions of feed materials and the type of process utilized. After categorizing the multitude of dust types, the criteria for on-site and off-site recycling of smelter dust in terms of type and concentrations of the accompanying elements are established. Thereby, consideration is given to the important aspects of: ? optimization of copper recovery ? quality of copper product ? valorization of accompanying elements ? elimination and disposal of deleterious impurities ? minimization of impact on operation ? effects on operating costs ? environmental impact of dust treatment on overall process Existing commercial, emerging and proposed copper smelting dusts, pyrometallurgical as well as hydrometallurgical, treatment schemes are reviewed and evaluated technically, economically and environmentally in an attempt to streamline the vast number of proposed options. Thereby, the high selectivity achievable in hydrometallurgical dust processing due to it being complementary to the smelting process is expected to be given increased consideration.

Jan 1, 1995

By Sasa Djokic

In developed countries, the difference between demanded and produced quantities of non-ferrous and rare metals are compensated by secondary raw materials recycling and reprocessing of by-products from both ferrous and non-ferrous extractive metallurgy. Utilization of non-ferrous and rare metals from the metallic secondary raw materials is very significant, both for recovery of the metal value and contribution to the environment protection. Similar to all non-developed countries, the extractive metallurgy in Serbia was based on available natural resources and not so strict environment protection regulations, which was either insufficient or completely absent. Today, Serbia is at the beginning of development of efficient and economical technical and technological solutions in order to ?ecologize? technogenic systems by waste materials, secondary raw materials and degraded soils regeneration (by recycling and revitalization). Several metallurgical technogenic systems in Serbia, together with secondary raw materials classification according to their potentiality for metal extraction by using the existing technologies and expected economical and ecological effects of recycling, are discussed in this paper.

Jan 1, 2005

By Scott A. Shuey

Keywords: E-Waste, Pyrometallurgy Many might think addressing the issue of e-waste is a new area of study. Electronics disposal has been discussed in some circles for at least the past 25 years. The recycling of electronic waste (e-waste) tends to be a rather complex undertaking when considering the intimate bonding of materials in the average printed circuit board. The development of a recycling process is further complicated when considering the wide variety of products being generated under the heading of ?electronics.? Focusing only on the primary constituents (polymers, Cu, Al, Fe, etc.) tends to lead one to fairly simple flowsheets. Ignoring trace elements, and the various halide species generated, will lead process engineers down a development path that is sure to cause material handling issues. Researchers at Colorado School of Mines are modeling the complex chemistry that exists within the body of e-waste?comprising 39 of the known elements. An understanding of the systems thermodynamic behavior will result in the development of a more robust, long-term process for the recovery of valuable materials from the e-waste stream.

Jan 1, 2005

By Chen Song

Keywords: Mixed extractant, Copper, Cobalt, Nickel, Synergistic effect During separation process of copper and cobalt from nickel sulphate solution, the effects of constitutions and compositions of mixed extractant D2EHPA and PC88-A or Cyanex 272, has been studied. In one step extraction cycle, the following results are obtained:[Ni]/[Co]>4000 and [Ni]/[Cu]>40000 in nickel sulphate solution, [Co]/[Ni]>1000 and [Co]/[Cu]>30000 in cobalt chlorinate solution, [Cu]/[Ni]>10000 and [Cu]/[Co]>200 in copper sulphate solution. It was elucidated that the above-mentioned synergistic mixtures can effectively separate cobalt and copper from nickel sulphate acid solution and achieve a greater synergistic effect.

Jan 1, 2005

By Emmanuel N. Zevgolis

In the present work, a reduction roasting experimental study of Greek nickeliferous laterite samples with a gaseous reducing mixture ? CO:N2- is presented. The effect of parameters such as temperature, ore grain size, and composition of the reducing mixture were examined. It is deduced that the reducibility of intermediate type laterite sample, where iron appears mainly in the form of goethite (a-FeOOH), is considerably higher than that of limonitic type laterite samples, where hematite (a-Fe2O3) is the predominant iron mineral phase. The degree of reduction of the limonitic type laterite samples does not exceed 50%, while it reaches 95% in the case of the intermediate-type laterite sample under the same experimental conditions. Increasing the temperature in the range 750-900°C does not considerably favor the reduction of the limonitic type laterites, whereas decrease of ore grain size of the limonitic-type ore samples and more intense reducing conditions increase the reduction. The considerably higher specific surface area values of the intermediate laterite samples, diminishes the effect of the ore grain size and this can be regarded as the critical parameter leading to the higher reducibility of this ore.

Jan 1, 2009

By María Eugenia Castro, Silvia Galasso, Jorge Duca, Claudia Osuna, Ernesto Esparza

"We present a procedure for treatment of non-active solutions equivalent to the solutions obtained from dissolution of ionic exchange resins used in purification of a nuclear reactor primary cooling system containing Co, Ni, Cs and its isotropic varieties as main radioactivity source. Finally it is immobilized into a ferritic matrix by calcination which avoids its future leaching into environment.In order to achieve the objective of this treatment, a bivalent and a trivalent iron salt is added to the solution. Then, either a base or an acid is added, depending on the initial pH of the treated solution, with a Cs precipitating additive in order to reduce Co and Cs by precipitation, flocculation and adsorption. Controlling the amount of precipitating reactives it is possible to modify the activity/volume rate becoming a medium into a low radioactivity waste.The leaching test result applied over the ferritic sample is lower than the minimum limit established by law. Therefore, it can be kept safely in a interim storage."

Jan 1, 2008

By A. E. M. Warner

Inco Limited has long and extensive experience in converting nickel-copper primary smelting mattes over a broad range of nickel/copper weight ratios and combined nickel-copper-cobalt contents. At the Copper Cliff Smelter, the composition of the converter product matte has to meet the requirements of the matte separation process; at the Thompson Smelter, converter matte of a different composition is cast into anodes for nickel electrorefining; and in Soroako, Indonesia, a very low copper product matte is granulated for the Japanese market. Recently, Inco has conducted pilot plant testing of three possible nickel-copper matte continuous converting routes, namely flash converting, oxygen top blowing-nitrogen bottom stirring, and tuyere blowing. This test work has generated substantial new information on nickel-copper matte converting chemistry. This overview paper reviews the metallurgy of nickel-copper matte converting, in particular the behaviour of cobalt and the operating conditions required to meet the iron and sulfur specifications of the product matte. The relevant thermodynamic information is used to discuss the industrial data.

Jan 1, 2003

By J. L. Johnson

The U.S. Department of the Interior, Bureau of Mines, investigated recovery of concentrates containing tin, tantalum, and niobium from the Kougarok deposit on the Seward Peninsula, AK. To date, 25 million lb of tin has been delineated in occurrences containing 0.36 to 1.32 pct Sn, and the resource potential is estimated to be as high as 25 million short tons at average grades of 0.75 pct Sn, 0.025 pct Ta, and 0,025 pct Nb. Deslimed ore was concentrated to 54 pct Sn, 0.3 pct Ta, and 0.3 pct Nb, with recoveries of 74 pct Sn and 44 pct Ta/Nb using a Humphrey's* spiral followed by a Deister shaking table. Tin values in the slimes were upgraded to a 5-pct-Sn concentrate using a Bartles-Mozley separator followed by flotation. The 5- pct-Sn was further upgraded by fuming to give a concentrate containing approximately 60 pct Sn. The recovery of the two products combined was 80 pct Sn and 46 pct Ta/Nb, A flowsheet with mill-design parameters resulted from the metallurgical testing. An economic analysis was made based on the proposed process.

Jan 1, 1990

By Yasuo Ojima

A new copper continuous converting process was investigated to evaluate the possibility of its application in the commercial operation. The tests were performed both in the laboratory and in pilot plant scale. Bath smelting process with the use of the top submerged lance technology was applied in these tests. Furnace shape was modified to a lengthwise eylindrical one with a settling area. The furnace monitor was put in the settling area to check the furnace from inside, FeOx-Si02, FeOx-CaO and FeOx-CaO-Si02 based slag systems were used to check their efficiency, The optimum slag chemistry to have good metallurgical results was discussed and FeOx-CaO system with some Si02 content turned out to be preferable although it has not been practically used, In this pilot plant test feeding rate of I tIH of solid grain matte was charged consecutively for two weeks and continuous converting could be done successively. This process is expected to overcome the problems of existing processes and be easily applied in existing plants.

Jan 1, 2003

By J. David Chapman

There are a variety of choices of materials for mineral extraction processing. Traditionally, end users have used metallic piping for fluid handling and little is known about the advantages (or limitations) of non-metallic piping systems. This presentation will review custom FRP pipe systems and their use in severe corrosive and erosive process streams. These systems can be designed to various pressure and temperature ratings and different components (such as resin and glass type) can be varied to suit the process conditions

By Mark Jolly

"Instead of using the traditional batch casting process, the CRIMSON [1] (Constrained Rapid Induction Melting Single Shot Up-Casting) method employs a high-powered furnace to melt just enough metal to fill a single mould in a closed crucible. The crucible is transferred to a station for computer-controlled counter gravity filling of the mould for optimum filling and solidification. The CRIMSON method therefore holds the liquid aluminium for a minimum of time drastically reducing the energy losses attributed to holding the metal at temperature. With the rapid melting times achieved, of the order of minutes, there isn’t a long time at temperature for hydrogen to be absorbed or for thick layers of oxide to form. The metal is never allowed to fall under gravity and therefore any oxide formed is not entrained within the liquid. Thus higher quality castings are produced leading to a reduction in scrap rate and reduced overall energy losses.IntroductionEngineers at the University of Birmingham, England, with local company, NTec, have invented a new casting process that will reduce the energy costs of light-metal foundries. The technology, entitled CRIMSON, means that foundries need only heat the quantity of metal required to fill a single mould rather than large batches that use unnecessary energy and create waste. The complete concept of CRIMSON requires a change of philosophy in the approach to casting and requires the user to think holistically in order to reap the full benefits from the process. This paper will discuss the various aspects of energy wastage within the foundry sector and discusses the processes whereby the energy can be reduced. Primarily the author focuses on the aluminium sector but CRIMSON can be applied to many of the non-ferrous “light” alloys. Ferrous materials and non-ferrous “heavy” alloys can also benefit from some of the ideas but not necessarily directly from the application of CRIMSON."

Jan 1, 2010

By Yiling Zhang, Paul A. Salvador, Gregory S. Rohrer

"Photocatalysis utilizes solar energy to produce hydrogen by splitting H2O. When a thin film of photocatalyst TiO2 is supported on a ferroelectric BiFeO3 substrate (band gap ~2.5 eV), the TiO2/BiFeO3 heterostructure is capable of photochemically reducing Ag+ to Ag0 in aqueous solutions under blue light with enhanced efficiency. The observation of spatially selective silver patterns on surface of the heterostructure after reaction suggests that photogenerated electrons and holes in ferroelectric BiFeO3 are driven in opposite directions to reduce their chance of recombination. Comparisons of the amounts of reduced silver on TiO2 film grains with distinct phases/orientations show that the reactivity is mildly preferential on anatase TiO2 phase and does not strongly depend on crystallographic orientation of BiFeO3.IntroductionTitania (TiO2) is capable of photocatalytically converting H2O to hydrogen and oxygen under the irradiation of ultraviolet light. [1, 2] One of the limiting factors for titania to be used as an effective photocatalyst is its band gap. Because the absorption edges of rutile and anatase titania are at 3.0 eV and 3.2 eV, respectively, they can only absorb light in the UV portion of the spectrum, which is about 3% of the available solar energy. [3-5] This limitation has motivated attempts to modify the absorption edge of titania so that it can absorb visible light.One strategy is to substitute a portion of the titanium and/or the oxygen with other atoms. There are numerous reports on visible light absorption of titania by doping and co-doping of Cr, V, Mo, Sb, Fe, N, S, C, and F. [6-34] Another strategy is to add an adsorbed molecular species that absorb visible light and donate an electron or hole to the titania, such as organic dyes [33, 35, 36] and Ce3+/Ce4+. [37, 38]The strategy in the present work takes the approach of depositing a pure titania thin film on a visible light absorbing substrate BiFeO3 to induce visible light activity of the heterostructure. BiFeO3 is a semiconductor with a band gap of about 2.5 eV [39-41] and is photocatalytically active in visible light. [42, 43] It is also ferroelectric with spontaneous polarization along pseudo-cubic <111> directions of 6.1 µC cm-2. [44] The spontaneous polarization gives rise to internal electric fields that drive photogenerated charge carriers, namely electrons and holes, in opposite directions to reduce their chance of recombination. [45-47] Additionally, the separation of electrons and holes leads to the spatial separation of reduction and oxidation half reactions so that the back reaction of intermediates is also suppressed. Such charge carrier separation has been reported in TiO2/BaTiO3 heterostructures with UV light illumination. [48-51] The TiO2/BiFeO3 heterostructures in this work combine both advantages of the relatively narrow band gap and the internal fields in BiFeO3 to enhance the overall photocatalytic activity."

Jan 1, 2014

By J. Antrekowitsch

Keywords: residues, fluorides, chlorides, zinc, steel mill dust The recyclability of various nonferrous metal wastes often suffers from a relatively high fluorine and chlorine content. Both are inserted in most cases by the use of plastic contaminated scrap and a wide variety of different coatings. These halogens lead to poor product qualities and off gas contamination. Especially the history of zinc recovery from steel mill dusts shows, that the today common hydrometallurgical options are on their limit and therefore are not sufficient in most cases. This thermochemical study should give more information about different pyrometallurgical options, that offer both a chlorine and fluorine reduction and efficient zinc recovery, preferably in one process step. Selective evaporation in different atmospheres and conversion with the use of hydrogen are the main parts in this study. The results combined with the relatively small information available from literature should provide a basis for further investigations in this field.

Jan 1, 2005

By D. Gu, R. G. Anthony, C. V. Philip, M. E. Huckman

"In this paper, we review the equations needed to construct an ion exchange column model. These models contain three major components: 1) a differential material balance around the column, 2) a differential material balance around an ion exchange particle, and 3) a constitutive equation for diffusive flux. We then examine the ability of a fairly simple mathematical model to predict ion exchange column experimental data. This model contains the traditional absorption theory equations and is used to predict the behavior of a column filled with a hydrous crystalline silico-titanate and which is removing trace amounts of Cs+ from a high pH, complex electrolyte solution. Finally, we propose replacing Fick's law with the Nemst-Planck equation as the constitutive equation for diffusive flux. We use a NemstPlanck type model to predict batch experimental data, then evaluate it by comparing it's ability to predict experimental data to that of a more traditional Fick's law type model. The data from this comparison suggests that the Nemst-Planck type model yields better results.IntroductionMillions of gallons of strongly basic, radioactive waste are currently stored in underground storage tanks at Hanford and Savannah River and several locations within the United States. Due to the limited life expectancy of the tanks, there is a pressing need to remediate these wastes. This need has prompted the recent development of new ion-exchange materials for removing radioactive elements from aqueous solutions. A novel material called TAM-5 has been developed jointly by Texas A&M University and Sandia National Laboratories. TAM- 5, a crystalline silico-titanate, is highly selective for Cs + in the complex electrolytic solutions typical of these wastes. It is stable in very basic solutions and in radioactive environments [1, 2 ,3]. In laboratory testing to determine the selectivity of various materials, TAM-5 was superior to other candidate ion exchangers [4, 5]. The selectivities were determined by measuring a distribution coefficient, Kd, which is defined as the concentration, gig or mmols/g of Cs in the solid phase divided by the concentration, mg/L or mmols/mL, of Cs in the liquid phase. The units of Kd are ml/g or L/kg. Table 1 shows Kd values for TAM-5 compared to 9 other candidate materials in a typical waste solution [6]."

Jan 1, 1996

By Donald Voit

"The reaction between zirconia/zircon, coke, and chlorine involves a slow reaction between the coke and the zirconia/zircon and a fast reaction with chlorine. Because of the fast chlorine reaction, the reaction rate for zirconia/zircon is nearly independent of chlorine concentration for most conditions. The reaction between zirconia/zircon and coke is particle size controlled and related to the degree of physical contact between the zirconia/zircon and the coke. Since particle-particle contact is critical, compaction of finely ground coke and zirconia/zircon produces the highest reaction rates. Uncompacted, coarse coke and zirconia/zircon has the slowest reaction behavior with static bed tests.SummaryZirconia reacts with chlorine in the presence of carbon to form zirconium tetrachloride, carbon monoxide, and carbon dioxide. A similar reaction occurs with zirconium silicate with the additional formation of silicon tetrachloride. The reaction rate depends primarily on temperature and the intimacy of contact between the zirconia and the coke. The reaction is multi-stepped with a slow reaction between coke and zirconia to form an intermediate that reacts rapidly with chlorine, causing the order of the reaction for chlorine to be near zero. Chlorination rates in the range of 1 µmole/hr/cm2 are seen for fluid bed reactors. Plug flow, and static bed reactors have reaction rates of the order of 1 mmole/hr/cm2, where the area is based on the zircon surface area in plug flow and fluid bed reactors and the boat cross sectional area in a static bed. Chlorination rates measured in zirconia/coke briquettes are higher with rates as high as 400 mmole/hr/cm2 reported. High chlorine diffusion resistance, not accounted for in the analysis of experimental results, has led to a lot of confusion in the literature interpretation of chlorination data.In general coke and zirconia/zircon particle size, coke and zirconia/zircon intimacy, coke to zirconia/zircon ratio, chlorine concentration, and temperature are important variables for chlorination. Decreasing the coke and zirconia/zircon particle size generally increase the reaction rate. The coke to zirconia/zircon ratio affects the reaction in a more complex way. Increasing the chlorine concentration generally increases the reaction rate, but the effect appears to be more related to the concentration dependency of diffusion than to its role in the kinetics. The reaction rate increases with temperature but the exact behavior is complicated by temperature effects on diffusion."

Jan 1, 2011