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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 Ryosuke Matsuoka

Keywords: Tantalum capacitor, Scrap, Recovery, Titanium, Chlorination A recycling process for tantalum from capacitor scraps using an oxidation process followed by mechanical separation and chemical treatment was investigated. This study demonstrates that sintered tantalum electrodes inside the capacitor scraps can be mechanically collected after the oxidation of the scraps in air, and high-purity tantalum oxide powder (Ta2O5) was efficiently recovered after chemical treatment. By reducing the Ta2O5 obtained through magnesiothermic reduction, tantalum powder with 99 mass-% purity was obtained. Using the chlorination for tantalum recovery was also investigated, and the tantalum or tantalum compounds were reacted with chloride wastes such as FeClx. It was found that tantalum was effectively separated and purified when tantalum powder is reacted with FeClx at 1100 K under an argon atmosphere. This recycling process utilizing chloride scrap has now been extended to other reactive metals such as titanium.

Jan 1, 2004

By Luiz A. Teixeira

This paper reports the results of kinetic studies involving the precipitation of arsenic from aqueous solutions as FeAs041 Fe(OH)3' using FeS04 as source of Fe ions, and Air or H202 as oxidizing agents. Both systems lead to an efficient removal of arsenic. The differences in oxidants performances are in the precipitation reaction rate -much faster using hydrogen peroxide. Mechanisms of reactions were suggested based on the following main steps:

Jan 1, 1996

By R. L. Nyirenda

One of the problems with ammoniacal-ammonium carbonate leaching of EAF carbon steelmaking flue dust is that zinc present in spinel phases is not leached. This paper presents results of test work in which prior to leaching, EAF dust was reduced with CO containing gas to decompose the spinels into zinc oxide and iron bearing phases, mainly metallic iron and wustite. From such reduction products, the amount of zinc leached increases but the iron co-leached becomes extensive. The effect of various leaching parameters such as liquor concentration and redox potential on zinc and iron dissolution has been investigated. Supplementary experiments utilizing pure zinc oxide and pure iron phases were also carried out. Results show that the co-dissolution of iron from severely reduced EAF dust cannot be prevented. This is because the wustite phase contains zinc which can only be leached when iron also dissolves. Further, the zinc bearing wustite phase is not totally soluble so that the residue cannot be made zinc free. In the absence of air, dissolution of metallic iron hardly occurred, though in leaching experiments of a long duration its transformation to a spinel structure was observed.

Jan 1, 1992

By James E. Hoffmann

Oxidative pressure leaching is gradually supplanting other techniques for the decopperizing of slimes. The reasons for this include: much more rapid reactions, more compact equipment, a reduced environmental burden, and perhaps most important, a much lower final copper concentration in the decopperized slimes. This paper will discuss the reactions occurring during decopperization, the acidity and temperatures encountered and the techniques employed for discharging non condensable gasses. A spreadsheet is provided which allows adjusting the operating conditions depending upon raw (undecopperized) slimes composition, solids concentration and lixiviant composition. A typical process equipment flowsheet is provided along with a process narrative.

Jan 1, 2000

By Takahiro Miki

In order to use metallurgical grade silicon (MG-Si) as a starting material for solar cell, phosphorus has to be removed from silicon because phosphorus is a n-type dopant. On the other hand, silicon, ferrosilicon, and silicomanganese are widely used as deoxidizers in steel refining processes. Since most of the phosphorus introduced during the deoxidation process is brought into final products, it is important -to lower the phosphorus content of these alloys. Hence, thermodynamics of phosphorus in such metals is important for the evaluation of dephosphorization processes. In the present study, thermodynamic properties of phosphorus in molten Si-P alloys at 1723- 1848K and those of Si-Fe-P and Si-Mn-P alloys at 1723K have been determined by equilibrating respective metals in a controlled phosphorus partial pressure. The results are expressed as follows.

Jan 1, 1998

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

By S. Fitzel

The Betts process for electrorefining of lead has been in operation since 1902 in the Trail Operations Metallurgical complex. The Betts process allows production of high purity lead in a single electrochemical step. Process improvements and plant expansions have taken place over the many decades of operation of this process which has proven to be robust, flexible, and capable of successfully treating a large range of anode bullion compositions. This paper reviews the history of the Betts lead electrorefining process, the innovations and quick industrial adoption of new discoveries that took place at the end of the nineteenth century. The process was first implemented in Trail Operations and integrated very well with metallurgical needs then and now.

By Petrus Christiaan Pistorius, Farzin Fatollahi-Fard

The production of titanium oxycarbide – a consumable anode material used in molten-salt processes for electrowinning titanium – from heavy mineral concentrate, such as a high-titania leucoxene and natural rutile is described. The oxycarbide is prepared by carbothermic reduction of the oxide at elevated temperature. Particle size distribution (of the titanium oxide raw material) and temperature have large effects on the kinetics of the reaction, which seem to follow a “shrinking-core” model. It is anticipated that low porosity (in the anode pellets) would be advantageous during electrolysis. Particle size distribution, extent of reaction during carbothermic reduction, and sintering temperature are expected to affect pellet porosity after sintering, and are being tested experimentally.

Jan 1, 2015

By Jack S. McPartland

The recent developments on the concentration and recovery of gold from leached gold thiosulfate solutions by solvent extraction, reduction-precipitation, and electrochemical deposition are reviewed in this paper. Alkyl phosphorus esters have been found to extract gold only in alkaline thiosulfate solutions, The recovery of gold increases with thiosulfate concentration in the aqueous phase and with alkyl phosphorus esters concentration in the organic phase with aliphatic hydrocarbon diluents. The addition of ammonia improves the extraction. The extraction of gold with amines in either aliphatic or aromatic diluent decreased in the following order: primary>secondary>tertiary amines. Increase in the extractant concentration at high pH increased the extraction of gold. At pH < 9, the primary amine, RR&apos;CHNH2 with 1&apos;9-23 carbon atoms is the main extractant with TBP as the synergistic reagent and at pH >9, the primary amine shows a synergistic effect on the extraction of gold&apos; with TBP. TheAu(I) ions in thiosulfate solution are reduced by sodium borohydride (SBH) to metallic gold, with particles in the sub micron range, At an SBH/ Au ratio of 6.25, pH = 6, and at room temperature, the I e ppm Au(I) in a solution of ] 0 gil thiosulfate was completely reduced to metallic gold in about 60 minutes.

Jan 1, 1999

By S. P. Marsh, D. Banerjee

"Casting processes involve phenomena that occur on widely disparate length-scales. Simulation of macroscopic effects, such as heat transfer and convection, are generally addressed by solving the appropriate equations in discretized form on a finite-element mesh. Microscopic phenomena are described by micromodels that may be empirical or analytical in form. Coupling of phenomena in these two regimes is a critical issue in predicting microstructure and defect formation resulting from macroscopic process conditions. A formalism has been developed for expressing micromodels in a consistent manner using stereological parameters to quantify the geometric characteristics of the developing microstructure. This approach provides a robust and physically consistent method for coupling local micromodels with the macroscopic fields. The macroscopic state variables at each node serve as global constraints on the micromodels that are applied to a local unit volume. An outline of an equiaxed solidification model based on this approach is presented, along with preliminary simulation results. Coupling of convection and enthalpy effects between the micro and macro regimes is also discussed. IntroductionThe primary goal of casting simulations is to improve the reliability of cast parts while minimizing cost and development time. Effective simulations can speed up the mold design process and reduce the likelihood of defective parts by refining a particular casting process on a computer, reducing the dependence on cost- and time-intensive prototype castings. The challenge in developing effective simulations stems from the need to address physical processes that occur over a wide range of length-scales, from microscopic (atomic) and mesoscopic (microstructural) scales to macroscopic distances comparable to the size of the casting itself. Overviews of the various thermophysical phenomena and computational factors that are important in solidification modeling are provided in the literature by Rappaz [1] and Tseng et al. [2].Macroscopically, the solidification process is largely governed by the rate of heat flow from the alloy through the mold wall. Another important effect that occurs on the scale of the casting size is convective flow of the melt, which is driven by density-variations in the melt. Macroscopic calculations employ finite-element or finite-difference methods to solve the sets of equations that govern these effects, and the spatial resolution is determined by the grid spacings used for the calculations. Typical spatial resolutions are on the order of 10-2 to 10-3"" meters. This represents a compromise between the resolution required to simulate the continuum transport processes accurately, and the computational time required to model the entire solidification and cooling process."

Jan 1, 1994

The standard procedure of fire refining consists of sulphur removal via air injected through tuyeres, arsenic slagging via soda-lime flux and oxygen reduction by air or oxygen deficient air or a steam fuel mixtures. The use of porous plugs to stir with an inert gas has been mainly considered as a surface renewing agent that increases the product quality and shorten the refining cycle. In the present study the effect of the bottom stirring by nitrogen gas injection through porous plugs for the treatment of the crude copper in the range of 400-150 ppm sulphur, 3,000-2,000 ppm arsenic and 14,000-7,000 ppm oxygen content was investigated. The combined effect stirring-reducing, by the use of air or a steam fuel mixtures through tuyeres for oxygen removal, follows a kinetics of first order where the constant, K, can be represented by the following polynomial expression: K = A * R2 + B * R + C Where A, Band C are constants that depend on the nitrogen flow rate and R is the air-fuel ratio or the steam-fuel used in the reducing step. Depending on the optimization of the flow of nitrogen and the air-fuel or steam-fuel mixture and only if just the oxidation, complexing and reducing steps are considered, the process cycle might be shortened by 45%.

Jan 1, 2003

By Peter V. Barr

Despite the advent of modem firing control systems reheating furnace operations frequently allow significant thermal excursions in the discharged slabs or billets after furnace delays. Although HSM furnaces are not immune to this and other related problems, mini-mill operations are most vulnerable due to their more frequent delays and (often) less sophisticated control systems. In order to reduce these problems control systems will commonly include a thermal model, operating either on-line (interacting directly with the controller logic) or in an advisory, off-line mode. Using a new &apos;fast&apos; thermal model, the paper examines the thermal response of a typical mini-mill furnace during both delays and the subsequent recovery period. A variety of firing strategies are explored and compared on the basis of maintaining thermal excursions within allowable limits for rolling. Other factors, such as the potential for overheating of billets within the furnace during delays and the overall thermal state of the furnace, are also considered in some detail. Although common practice, the use of conventional thermocouple zone temperatures for furnace control during and after delays is shown to be a dubious proposition. Keywords: Reheat Furnace, Modeling, Process Control

Jan 1, 2003

By V. Gornitz

The Orphan mine uranium deposit, Grand Canyon, Arizona, is a cylindrical collapse-breccia pipe, 70 to 150 m in diameter and 500 m deep. Pipe fill was derived from the Supai Group, Hermit Shale, and the Coconino Sandstone. Uraninite, with Cu, Fe, Pb, Zn and Ni-Co sulfides is concentrated along the pipe boundary ring fracture (annular ring) and within the central porous sandstone matrix. There is some suggestion of vertical and lateral zonation of U with respect to Cu. Reduction of ferric oxide cement from red beds and recrystallization of carbonate, with formation of kaolinite preceded major ore deposition. Early Ni sulfides, arsenides and disseminated pyrite were followed by massive pyrite, and botryoidal uraninite, which in turn was suc-ceeded by Cu, Zn and Pb sulfides. A second, later generation of uraninite was closely intergrown with hematite and base metal sulfides. Oxidation of primary minerals may have been associated with Tertiary regional uplift. The paragenetic sequence closely resembles that of other Grand Canyon breccia pipes, except for the extensive development of the distinctive uraninite-hematite association. Mineral assemblages at the Orphan suggest possible mixing of the metal-bearing solution(s) with a more oxidized fluid, containing soluble uranyl complexes. Homogenization temperatures of fluid inclusions in calcite (GO-lIO?C) at the Orphan fall within the lower end of the range observed at other breccia pipes.

Jan 1, 1987

By Marco Olper

Zinc bearing materials containing chlorides and fluorides of alkali metals, such as EAF dust, Waelz oxides, galvanizing ashes, zinc & brass foundry fumes and converter fumes are little attractive, both technically and economically for processing in ISF plant or in a conventional zinc sulphate electrolysis works. The Ezinexm Process allows for the recovery of high purity zinc in cathode form, from these materials, regenerating the leaching liquor. The process is based on a new electrochemical system which depolarizes the anode reaction with reduction of the cell voltage, compared with the traditional sulphate electrolysis method. The electrolyte, based on a chloroamrnino complex, allows for the recovery of other valued metals present in the zinc bearing materials such as lead, copper and silver, these being recovered as a metallic cement consequently improving the economics of the process.

Jan 1, 1994

By Masatoshi Ogasawara

Saganoseki smelter & refinery operated two flash smelting furnaces, producing a combined 330,000 metric tons per year (hereinafter mtpy) of copper. In 1996, however, it successfully shifted to a single furnace operation while maintaining production at the same level. Since then, the production capacity has been further increased to the present 470,000 mtpy by technological improvements. Also, in order to reduce the converter load which represents a bottleneck in efforts to increase production, the matte grade was gradually increased and currently runs at 65 to 66% attaining the low copper content in the slag (hereinafter slag loss) of 0.7 to 0.8%. This paper introduces some improvements, recent operation results and thermodynamic analyses.

Jan 1, 2003

By Alexandre Bonan

This paper reports the results of a kinetic study on the oxidation of free cyanide and Cu-cyanide complex ions with HO,. The variables and respective ranges studied were the following: [CN] total =10 - 500 mg/l; pH=10-11; (H2O2/CN) mole ratio = 1- 3; (Cu/CN) mole ratio = 0.10 - 0.25. The results were interpreted by a semi-empirical model that incorporates the useful oxidation reactions and the parallel alkaline decomposition of H2O2

Jan 1, 1994

By H. A. F. de Souza, Dana S. Mills, P. E. Burgener

"ICP-MS has moved from a laboratory curiosity to a functional analytical tool. This paper discusses how ICP-MS has been used to solve difficult analytical problems encountered when analyzing various mine materials. Comparisons between analytical techniques applied to the analysis of gold and the platinum group metals illustrate the advantages and problems of ICPMS when. applied to trace levels of some metals iri the presence of ore grade metals. Interferences and matrix effects are compared to ICP, AA and Neutron Activation. The necessity to select chemical extractions which are compatible with ICP-MS are also discussed.The ICP-MS techniques explained in the examples on Au and precious group elements (PGE) have validity in analytical problems encountered in testing of trace metals in the presence of major elements found in mine materials. Exploration and environmental testing are other areas that require the same analytical approach to quantify trace levels in the presence of major interfering elements normally associated with mining environments."

Jan 1, 1999

By Xuemei Zheng, Aiyuan Ma, Chao Liu, Guojiang Li, Chenyu Sun, Jinhui Peng, Libo Zhang, Yongguang Luo

In this paper, the removal of fluorides and chlorides from blast furnace dusts by water vapor enhanced microwave roasting was investigated, combined with the advantages of microwave selective heating and based on a thermodynamic analysis of zinc and lead halides. According to proposed reactions in the process, detailed experiments were systematically conducted to study the effect of roasting temperature, holding time, air flow, water vapor flow rates, and stirring speed on the efficiency of the removal of F and Cl. The results show that 97.26% of F and 64.23% of Cl could be separated when the condition of the roasting temperature of 650°C, stirring speed of 80 rpm, holding time at 60 min, air flow of 350 L/h and water vapor flow rate of 8 mL/min was optimized.

Jan 1, 2016

By Bora Derin

This work deals with the recovery of valuable metals from the ancient copper smelting slags located in Küre-Turkey. In this process, copper and cobalt were recovered in metallic form and/or as their compounds, whereas iron was recovered as magnetic oxide or pigment. Abrasive grit material was produced using reduced final slag. The process stages involved carbothermal reduction in a DC arc furnace, granulation, leaching, chemical precipitation, selective sulfidizing roasting and product preparations. In this paper, the process stages were described as theoretically and experimentally whereas slag and products were characterized in detail.

Jan 1, 2003