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By Rainer Köster, Tobias Wagner, Markus Delay, Fritz Hartmann Frimmel, Wolfgang Ferstl, Wolfgang Höll

"The mobilization of contaminants from industrial residues like ashes from municipal solid waste incinerators in case of leaching is investigated world wide. In classical leach tests only soluble species are considered. In addition the geochemical behaviour of residues has to be completed by assessing the mobilization via colloidal particles. This transport is well known from natural aquatic systems. Quantification of aquatic colloids is associated with considerable difficulties, because they are often found in low concentrations and in a size distribution where small particles with diameters below 0.1 µm predominate. In the past years, the Laser-induced Breakdown Detection (LIBD) has been developed as a novel sensitive method for quantifying colloids. Column leaching experiments with directly coupled LIBD were used to quantify the release of heavy metals and colloids out of bottom ashes. Some typical colloid bound heavy metal concentrations in the leachate are in some cases exceeding the limits defined by German authorities. The LIBD with a flow-through cell allowed to assign absolute values to colloid size and concentration."

Jan 1, 2008

By Donald O. Voit

A BASIC language program has been written that simulates the performance of an integrated solvent extraction circuit consisting of an extractor, a reflux fed scrubber, and a stripper. The program is designed to simulate the performance of a circuit having an aqueous feed containing each of the lanthanides as well as yttrium. The Kremser equation is used to determine the separation occuring in each section of the circuit. The required input variables are the feed composition, the separation factors, the light key extraction factors and extractor feed zone distribution coefficient, the number of stages, and the reflux ratios. The program calculates the composition of the streams at each node in the circuit, the total loading, and the remaining distribution coefficients. User interaction with the program is essential. The program has no capability to determine if the calculated values are consistent with various real restraints. Knowledge of the physical, chemical, and equilibrium behavior is essential to successfully utilize the program. The number of iterations required to achieve steady-state provides insight to the circuit response times. With suitable supervision the program can be used as a simulator for operator training.

Jan 1, 1989

By N. Kanarin

A thermodynamic study is reported on the chlorination of Fe(1-x.)O, Fe2O3, Cr2O3, MgO, Mg2SiO4 with chlorine in the presence or the absence of reducing atmospheres. The reactivities of these compounds as well as that of Mg3Si2O5(OH)4 using Cl2+N2, Cl2+air, and Cl2+CO gas mixtures were studied by non isothermal thermogravimetric analysis between 20 and 1000 °C. The same solids were chlorinated in a horizontal experimental set, during two hours between 350 and 1000 °C, in reducing and oxidizing atmospheres: The chlorination products were examined by XRD and SEM, and possible reaction paths were examined. Results indicate that the carbochlorination of these solids was better than their chlorination; Furthermore, the carbochlorination was performed at lower temperatures than those of the chlorination. Finally, the reaction extent was higher in the case of carbo-chlorination of these compounds. Based on these results, a process was suggested for the selective recovery of chromium compounds from the chromite concentrate.

Jan 1, 1995

By E. Almendras de Siegel

Pyrometallurgical processes have the thermodynamic capability of treating complex and dirty ores and concentrates to produce high purity metals and inert slags. Modem pyrometallurgical processes are environmentally sound and competitive with other processes. However, there is still a need for sensors and other practical tools that permit a rapid evaluation of the performance of these processes. In order to contribute to satisfying this fundamental requirement, the authors developed the IDENT.LA software that permits the automatic mineralogical analyses of inorganic materials, including the final and intermediate products of pyrometallurgical processes. The technique allows determining the grain size distribution of mineralized inclusions, the surface relations between metallic phases, and conducting modal analyses of the essential phases that are present in the samples. Three basic automatic operations are performed: creating a representative image of the sample; identifying the metallic and non-metallic phases; and measuring the features of the resulting image. The results are used to evaluate the performance of pyrometallurgical and other processes. In this paper, the authors discuss the application of the technique to a sample of slag from a slag cleaning process that uses a carbonaceous reductant. In this case, process performance impacts not only on the efficient reduction of the slag magnetite and on copper recovery but also on the quality of the process off-gas. The mineralogical analysis of the slag is a valuable tool in assessing process performance and in recommending changes of operating conditions.

Jan 1, 1999

By Hidekazu Nakagawa

We investigated the anodic dissolution behavior of titanium in TMHA-Tf2N molten salt, which has a wide electrochemical window of about 5 V, in order to develop an electrodeposition method for titanium. By etching a titanium electrode in HF?HNO3?H3PO4 solution, the titanium electrode became electrochemically active, and a redox reaction was observed at around -0.15 V vs. I-/I3- in (TMHA-Tf2N)?HTf2N solution. We identified the redox reaction consists of the reduction of the proton and the oxidation of hydrogen. The diffusion coefficient of the proton in TMHA-Tf2N was calculated to be 6.9 10-8 cm2 s-1 at 50 °C from the cathodic peak current in the cyclic voltammogram. Anodic decomposition of the molten salt was not observed up to 6.0 V vs. I-/I3- on titanium electrode, while it was observed at around 2.0 V vs. I-/I3- on platinum and glassy carbon electrodes. Cathodic decomposition of the molten salt was observed at around -3.0 V on the titanium electrode, as well as on the platinum and glassy carbon electrode.

Jan 1, 2006

By K. Kashiwaya, N. Hiroyoshi, H. Furuya, N. Sumiya, M. Tsunekawa, M. Ito

"The number of hybrid vehicles is increasing and this is causeing an increase in waste nickelmetal hydride batteries. The cathode activating agent of batteries is made of nickel hydroxide and the anode activating agent is an alloy of nickel and rare earth elements. Conventional rotary kiln methods cannot recover the rare earth elements, and hydrometallurgical treatment of crushed product consumes large volumes of agent. The physical separation of the anode alloy from the cathode hydroxide would make it possible to reuse the alloy. The authors have reported separation of anode and cathode components in the large size fractions using a newly developed dry magnetic separation method. Wet magnetic separation has been applied to the powder fraction and about 90% anode purity was achieved. This paper reviews experimental results from previous publications and proposes an integrated treatment process for crushed nickel-metal hydride batteries.IntroductionEnvironmentally-conscious clean energy vehicles have attracted much attention in developed countries and particularly hybrid vehicles are increasingly mass-produced as low emission vehicles. Hybrid vehicles have both a gasoline engine and an electric motor to save on gasoline usage and a nickel-metal hydride battery is used to store electric energy. The battery contains Nihydroxide and Co as the cathode activating agent and an alloy of Ni and mischmetal (mM), a rare-earth element mixture consisting of La, Ce, and Nd, as the anode hydrogen adsorption component. In conventional recycling, the Ni and Fe are recovered with a rotary kiln-electric melting process and the Co and mM go to the slag component [1] and hydrometallurgical treatment of crushed product consumes large volumes of agent. Japan Oil, Gas and Metals National Corporation have proposed a low energy and low cost recycling treatment process combining the physical and chemical treatments and the authors are investigating the physical treatment process."

Jan 1, 2008

By E. García-Ramos, P. Flores-Sánchez, E. G. Palacios, B. Zeifert, A. Romero-Serrano, M. Hallen-López

Chromium containing slags from stainless steelmaking may eventually be leached by acidic environments, therefore they should be treated before being stockpiled or land filled. In this work, synthetic slags were prepared and the effect of CaO/SiO2, Cr2O3, MgO and Al2O3 contents on the stability of the mineralogical species formed was analyzed. The morphology and composition of the slags were analyzed by XRD and SEM-EDS, whilst their chemical stability was evaluated by leaching with an aqueous acetic acid solution. It was found that CaCr2O4 and CaCrO4 are present in slags prepared with neither MgO nor Al2O3. The Al2O3-based slags mainly produced Ca2Al2SiO7 and the Cr(VI)-containing oxide complex Ca4Al6CrO16, whilst MgO-based slags produced MgCr2O4 as main mineralogical species. Additionally, Eh-pH diagrams for the Ca-Cr-H2O and Mg-Cr-H2O systems at 25 °C were constructed. The lowest Cr concentration levels in the leaching liquors corresponded to MgO-based slags owing to the stable binding of Cr in spinel with MgO. It was also observed in the Al2O3-based slags that increasing the slag basicity from 1 to 2 the leachability of the slags are notably increased.

Jan 1, 2008

By Bradford C. Wesstrom, Omar Araujo

"Impurities from an electrolytic refinery are typically extracted from the electrolyte utilizing conventional electrowinning cells. These cells are arranged in series with cascading solution flow and are commonly referred to as liberator cells. The Freeport McMoRan Copper & Gold El Paso Refinery has optimized the removal of arsenic in cascading liberator cells by utilizing two separate feed solutions. The primary feed solution is recycled liberator electrolyte and the secondary feed solution is ""neat"" tank house electrolyte. The secondary feed solution is added based on the voltage response across the individual cells utilizing independent variable frequency drive (VFD) pumps. When the voltage across a cell changes, a signal is sent to the VFD pump to maintain a cell voltage of 1.98 volts. By maintaining this voltage the copper content in each cell exits at 2-4 grams per liter. This safely optimizes the arsenic removal as copper arsenides on the liberator cathodes.IntroductionDuring the electrolytic refining of copper, impurities from the copper anode report both to the bottom of the electrolytic refining cell as slimes and to the electrolyte. The impurities which enter the electrolyte are arsenic, antimony, bismuth and nickel. The impurities that report to the electrolyte during the electrolysis process gradually increase. As these impurities increase, they are incorporated into the refined copper cathode. There are many processes that have been used to remove these impurities from refinery electrolytes. Some of them are listed as follows: solvent extraction, ion exchange, hydrogen sulfide reduction, bioreactor, adsorption onto a low - solubility metal-oxide hydrate, adsorption onto activated carbon and EMEW cells. The conventional process used by the copper refining industry for controlling the level of impurities in electrolyte involves multistage electrolytic cascading liberator cells. In these cascading liberator cells copper, arsenic, antimony and bismuth are removed as various mixed deposits from the electrolyte. Removal of these impurities is achieved through an increase in voltage resulting from the depletion of copper in the electrolyte through electrowinning. With this higher voltage, the Group Vb elements, arsenic, antimony and bismuth are deposited on the copper cathode and report as slimes to the bottom of the cells. Nickel is removed in a subsequent process."

Jan 1, 2012

By Shadia J. Ikhmayies

"Nanocrystalline fluorine-doped tin oxide, SnO2:F, thin films were prepared by the spray pyrolysis (SP) technique on glass substrates. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray dispersive spectroscopy EDAX and transmittance measurements. X-ray diffraction patterns revealed the nanocrystalline nature of the films where the grain size was estimated based on the Sherrer formula. SEM micrographs showed that the films are uniform and totally covered with the material and they confirmed the nanocrystalline nature of the films. The absorbance was deduced from the transmittance measurements, and its first derivative was used to estimate the optical bandgap energy. Bandgaps larger than the bandgap of the bulk SnO2iF were obtained, indicating the presence of quantum dots. The hyperbolic band model was used to estimate the radii of the nanocrystallites. A comparison between the results of the different methods was performed.IntroductionTin oxide, SnO2, thin films are n-type semiconducting, transparent materials, which have numerous important applications in optical-electronic device technology. The optical transparency of SnO2, together with its chemical and mechanical stability, makes SnO2 films suitable for many other applications, such as transparent conductive coatings, gas sensors and heteroj unction solar cells [1]. In particular, SnO2 thin films have drawn much interest because of their potential application and integration with microsensor devices. Considerable attention has recently been focused on the development of solid state gas sensors based on thin films with a crystallite size smaller than the Debye length of the material, which show increased gas sensitivity and short response times [2]. In many of these applications, a doped SnO2 film is used as an active layer. Among the various dopants, fluorine is often preferred, because fluorine doping results in films with high transparency and good conductivity [1]."

Jan 1, 2012

By Cyro Takano

An alternative use for recycling of waste from bag house of iron ore sinter plant was tested by producing and evaluating" at laboratory scale, the self reducing cold bonded pellets. This waste was characterized and the self-reducing pellets were produced using anthracite coal fines as reductant and Portland cement or hydrated lime/Blast Furnace slag as binder. It was used the molar ratio of Fe2O3/C (fix) equal to 3. Evolution of cold strength with curing time, for different contents of binder, was evaluated. Cold strength of 200N/pellet was obtained, for sinter dust, after 10 days of curing. Suitable hot strength was also presented and no decrepitation and swelling were observed. Good fractional reduction was obtained at 950°C and 1137°C. These results show that this material may be used by the Self-Reducing Processes for hot metal production, as an alternative route for this dust destination.

Jan 1, 1996

By K. S. Kumar

FLS miljø, Inc. markets, designs and supplies particulate collection devices for dusts, fumes, and mists; In this paper, the application of both wet and dry electrostatic precipitators (ESPs) in smelting, and roasting plants is discussed.

Jan 1, 1998

By Susana Caballero, Lourdes Yurramendi

Air Pollution Control (APC) ashes from Municipal Solid Waste Incineration (MSWI) plants need to be treated prior to landfilling due mainly to their heavy metals content. This research evaluates the capacity of the APC residues to sequester carbon dioxide, while the ash becomes stabilized for storage. It has the benefit of using two wastes, with no addition of any raw material. APC samples from different MSWI plants were treated by gas/solid accelerated carbonation at different temperatures and carbon dioxide concentrations to evaluate the residue behaviour to the process. The extent of carbonation was evaluated by means of weight gain upon carbonation and by the measurement of the final carbonate content. The APC residues were analyzed before and after the treatment in order to know their composition and their leaching behaviour according to the criteria for the acceptance of wastes at landfills established by the European Council Decision 2003/33/EC.

Jan 1, 2008

By Guozhu Ye

"One of the most essential problems associated with the treatment of EAF dust is its high content of halogens. For most thermal processes for zinc recovery, such as the plasma processes with a zinc condenser, the halides in the gas stream will form a dross phase that results in a low zinc yield. For those with zinc oxide as main product, such as Waelz oxides, the high halogen content in the product implies a great degradation of the product quality and the product can only be sold at a low price. Further processing of zinc oxide with high halogen content either by pyrometallurgical or hydrometallurgical processes will also result in process problems.This paper will review the pre- and post-treatment alternatives for halogen removal based on the comprehensive characterization work that has been carried out at MEFOS and the preliminary experimental results.The experimental results show that chlorine and fluorine content could be reduced to 450 ppm and 50 ppm respectively by selective sulfation, and to about 200 ppm by soda leaching. Selective sulfation of zinc oxide in the EAF dust will also be discussed."

Jan 1, 2000

By Cz. Mazanek

Specific biostimulating and anticancerous properties have been observed in peat, Ash Vacanta, and in an amorpous silica that is obtained as a by-product of alumina production from Turow clay in Poland. The anmphous silica was characterized and found to have a large specific surface area. This property may account for the beneficial characteristics of the material.

Jan 1, 1989

By Yuan Lu, Yiming Rong, Richard D. Sisson Jr

With the development of quench technology, there is a trend of using gas quench to replace liquid quench for less distortion and residual stress. The fundamental difference between the liquid and gas quench is the heat transfer coefficient, not only the values but also the shape of the curve as a function of temperature. The equivalent heat transfer coefficient for the liquid and gas quench is analyzed by simulations and experiments. Even it may result in the same hardness in the liquid and gas quench, the steel microstructure may be different because of the different cooling processes, and therefore other steel properties, such as toughness, may be different. The cooling process, microstructures and properties such as hardness and toughness should be examined when designing the liquid or gas quench processes.

Jan 1, 2015

By Frank Field, Elsa Olivetti, Randolph Kirchain, Elisa Alonso, Gabrielle Gaustad

"The primary technological challenge to increased use of secondary raw materials is the presence of undesirable elemental species in scrap streams. Recent literature indicates that this may become exacerbated by accumulation of impurities over time. Devising strategies to mitigate this problem depends upon understanding the mechanisms of accumulation. This paper takes a first step at characterizing the extent of this issue by presenting a simple analytical model of recycling rate for materials experiencing exponential growth. Low potential recycling rates limit accumulation due to dilution. Empirical analysis of several major materials indicates that, even for current recovery rates, theoretical recycling rates can reach above 60%, making accumulation issues a possibility.IntroductionIt is well known that recycling of secondary materials can provide significant environmental and economic benefits. Energy savings, in particular, can be quite large when substituting secondary materials for primary. Nevertheless, over the past decade, the recycling rates within the U.S. of many materials appear to not be increasing as rapidly as one would predict or even at all (Figure 1). While many barriers exist to increasing materials recycling, one that is cited consistently by the literature and producers[1-3] is compositional limitations; that is the mismatch between the characteristics of secondary materials and those desired for the finished goods into which they would be transformed..One particular aspect of compositional limitations that is receiving increasing attention is the potential for progressive deterioration of the quality of secondary raw materials streams. For some materials, for example paper or polymers, this phenomenon is inherent and relatively rapid[4, 5]. As such, it is well documented and plays a significant role in recycling decision-making even for prompt or in-house material recycling. Conceptually, this issue can manifest in other secondary materials as well, albeit through a different mechanism.As materials are mixed, used, and reprocessed during recycling, they come into contact with and often pick up other elements. The presence of these, so-called, tramp elements alters the original known composition, possibly requiring additional measurement and processing and may even preclude economic, productive reuse; ultimately, this unintentional pick up is unwanted. A growing number of studies and literature would suggest that accumulation of unwanted elements is an emerging problem, in most recycled material streams. Table I provides a brief literature review of various recycled material streams and the accumulated elements noted as problematic by various authors"

Jan 1, 2008

By Rush Kramer

A bulk compositional chemical analysis often provides incomplete information to help the mineral processor when faced with the problem of removing troublesome contaminants in low concentrations. Michigan Tech has developed a unique approach for addressing this problem. A combination of Scanning Electron Microscopy (SEM). Energy Dispersive Spectroscopy (EDS). and image analysis was successfully used to characterize the species responsible for phosphorus contamination of less than .05 weight percent in iron ore. An automated routine acquired the chemical signature of each particle on a backscattered electron image. The few particles containing phosphorus were identified from the hundreds of particles examined. and the phosphate phases present were easily characterized.

Jan 1, 1991

By Y. Moriya, Y. Sadayoshi, Y. Nonogaki, Y. Takeda

"Preparation and growth processes of CaF2 on Si(111) and of . InxGa1-x,As islands on CaF2 by molecular beam epitaxy (MBE) are described. It was found that first of all the Si(111) surface treatment process to obtain the 7x7 reconstructed structure was necessary to ensure the cleanness of the surface and to grow a flat and high quality CaF2 on it. Growth of InxGa11-x,As islands on CaF2 was tried by droplet heteroepitaxy using the same MBE reactor. In,GaxGa1-xAs islands were successfully grown epitaxially, and the size and density of the islands dependent on the In composition were investigated.IntroductionThough semiconductor/semiconductor heterostructures are widely used for many device applications, small band off-sets of the conduction bands and the valence bands restrict the utilization of the intra-subband transitions to far-infrared regions. With InAs as the quantum well and fluorides as the barrier layers, we can design three-electronic-level systems in the infrared region, which is the low loss transmission window of the silica optical fibers. To realize those structures, we have grown InxGa1-xAs islands on CaF2 thin films that were epitaxially formed on Si(111) substrates by molecular beam epitaxy. By the droplet heteroepitaxy that we invented, the InxGa1-xAs islands with height of -10 nm have been obtained successfully. Optimum processing to obtain atomically smooth surfaces of Si and CaF2 and high quality InxGa1-xAs islands is reported.ExperimentsMBEMachineCaF2 was grown on Si(111) and InxGa1-xAs islands were grown on CaF2 successively by MBE. The MBE machine consisted of a growth (or reactor) chamber and a loading chamber. The reactor chamber was equipped with Ga, In, As and Er metal source cells and CaF2 and BaF2 source cells. Cell materials were P-BN for Ga, In and As metals, and were graphite for CaF 2, BaF 2 and Er to avoid reaction with BN cells. The electron gun and screen were attached to the reactor to observe the RHEED pattern during the substrate surface treatment and the growth of CaF2 and InxGa1-xAs islands. The substrate manipulator was designed to heat up the Si substrate up to 1,200°C for the surface cleaning. The QMS was also equipped to analyze the residual gas species in the reactor chamber. The base pressure of the reactor chamber was 2-5x10-11 Torr, being pumped by ion pump and the liquid nitrogen shroud"

Jan 1, 2000

By Virgil Optasanu, Yvon Lacroute, Eric Lesniewska, Tony Montessin, Pauline Vitry, Eric Bourillot, Cédric Plassard

A general challenge in metallic components is the need for materials research to improve the service lifetime of the structural tanks or tubes subjected to harsh environments or the storage medium for the products. One major problem is the formation of lightest chemical elements bubbles or different chemical association, which can have a significant impact on the mechanical properties and structural stability of materials. The high migration mobility of these light chemical elements in solids presents a challenge for experimental characterization. Here, we present work relating to an original non-destructive, with high spatial resolution, tomographic technique based on Scanning Microwave Microscopy (SMM), which is used to visualize in-depth chemical composition of solid solution of a light chemical element in a metal. The experiments showed the capacity of SMM to detect volume. Measurements realized at different frequencies give access to a tomographic study of the sample.

Jan 1, 2015

By S. Redik, C. Wenzl, D. Gregurek, A. Spanring

Zinc is a component of many input materials used in various pyrometallurgical processes, for example primary lead and zinc production from Pb/Zn ores and recycling processes dealing with zinc-containing residues (e.g., copper recycling, WAELZ process). Hence, zinc and its compounds are present in the respective metallurgical vessels and interact with the refractory lining. In the present work the zinc attack on the refractories out of various primary and secondary furnaces is briefly introduced and discussed. At the prevailing processing temperatures in the metallurgical vessels, zinc oxide is highly corrosive for the brick components. The knowledge of the wear behavior is based not only on a detailed chemical and mineralogical characterization carried out on provided post mortem samples, but also on FactSage calculations. This together with results obtained by practical testing in the RHI pilot plant represents an important prerequisite for product development and brick selection for the individual customer application.

Jan 1, 2016