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By Mingming Zhang, Ramana G. Reddy

"Carbon dioxide (CO2) is one of the most common by-products produced during light metals production. It is considered to be the cause of greenhouse effects. Efficient reduction of CO2 can help minimize the rate of global warming and improving energy sufficiency. In this paper, a novel light metal production process was developed using ionic liquid electrolytes. This process has significant advantages compared to the traditional high temperature processes such as zero CO2 and CF4 emission, low energy consumption due to the low temperature operation and nonconsumable electrodes. Two types of anode materials (graphite, extruded carbon) were tested in electrolysis experiment. The results showed that both anode materials were stable (negligible weight loss). However, the extruded carbon was found to be superior to graphite in terms of current density and current efficiency. The calculated energy consumption for aluminum production was less than 10 kWh/kg at current densities up to 300 A/m2.IntroductionGlobal demand for ultra-light, ultra-strong, recyclable metals is growing as the world switches to low-emission vehicles, energy-saving devices and sustainable products. Aluminum demand is forecast to climb by 30 percent; magnesium demand by 200 percent, while for the emerging industrial light metal, titanium, the demand is expected to be at least double in the next decade. However smelting of light metals is the most energy intensive among all the steps of light metals production. For example, on an average it takes about 15.7 kWh of electricity to produce one kilogram of aluminum from alumina [1, 2, 3]. Advancements in energy efficiency have been steady, but slow, and most U.S. aluminum smelting production operates at 95% current efficiency. Besides high energy consumption, another major concern of the light metals smelting process is the emissions of greenhouse gases (GHG). Electrolysis green house gas emissions in the Hall-Héroult process can be split into three groups: 1) reduction reaction emissions, carbon dioxide (CO2) and carbon monoxide (CO); 2) process upset perfluorocarbons emissions; and 3) hydrogen fluoride (HF) formed from the moisture (H2O) present in the raw materials [2, 3]. Hydrogen fluoride gas can be captured and returned to the cells by the alumina dry scrubbing system used in modern facilities. A total of 5.31 kilograms of CO2 is generated from the reduction process for each kilogram of aluminum produced in the average U.S. primary facility. The perfluorocarbon emissions are related to the “anode effect.” If the concentration of alumina in the bath becomes too low, other reactions between the carbon anode and the bath occur and tetrafluoromethane (CF4) and hexafluoroethane (C2F6) are generated. These gases have high global warming potentials (GWP), which is a ratio developed to compare the ability of each greenhouse gas to trap heat in the atmosphere relative to carbon dioxide"

Jan 1, 2008

By Eoghan T. M Doyle

Oxide mixtures of nickel (NiO), cobalt (COO) and chromium (Cr203) were prepared with graphite in stoichiometric amounts and the powder mixtures were compacted to produce cylindrical pellets. The composition of chromium oxide in these mixtures were varied. Pressed pellets were reduced in a flowing stream of argon-4% hydrogen gas (500 ml/min). Both slow and rapid heating methods were adopted to raise the temperature of a pellet during reduction of oxides to form superalloy powder. The reduction temperature was varied between. 1523 and 1623K. The effect of heating rate and niobium oxide addition on the microstructure of the superalloy produced was studied by using ordinary light and scanning electron microscopes. New phases formed as a result of reduction were identified by X-ray powder diffraction technique. The mechanism of reduction of oxides together with the microstructure of NiCrCo alloy are discussed. The thermodynamics of formation of ternary alloy phase is elucidated on the basis of binary phase equilibria and Gibbs free energy of mixing data for the constituent alloy compositions.

Jan 1, 1992

By H. Sieber

Multilayer samples of tantalum and aluminum with the composition of Al-25Ta were prepared by cold rolling of elemental foils. The microstructure and phases were characterized by XRD, SEM and TEMISAED and the reactive phase formation was examined by DSC and DTA measurements in multilayer foils rolled for different deformation levels. The rolling procedure yields a decrease of the Ta particle size in the Al matrix and also results in the formation of a multilayer structure with a thickness of the elemental foils down to 200 nm in average. No phase formation is observed during the cold rolling procedure. While XRD and DSC measurements show no phase formation up to the melting of aluminum for samples rolled up to 40 F&R (fold and rolling) passes, in samples rolled for 50 or more F&R passes a first phase formation reaction yield an interfacial layer of TaAl3. Contrary to former studies in the investigated cold rolled Al- 25Ta multilayers the reaction starts at temperatures as low as about 340°C. The first stages of the reaction are associated with two exothermic maxima, that increase in amplitude and shift to lower temperatures with increasing number of F&R passes. At higher temperature the TaA13 reaction layer thickens very sluggishly and yields a third exothermic maxima at about 600°C. Isothermal DSC scans show the reaction is not finished for samples containing elemental particles larger than 1 pm after annealing at 550°C for 5h. In all the investigated samples no Al- Ta phase other than Tad3 was observed to grow for heat treatments up to 800°C. Multilayer samples heated up to 1400°C show a morphology consisting of small AITa2 particles embedded in a single phase TaA13 matrix. The multilayer microstructure and reaction product morphology are characterized by SEM and TEM investigations in cross-section and plan view geometry.

Jan 1, 1998

By A. M. Alfantazi, M. Boissoneault, D. B. Dreisinger, J. Synnott

Acid mist generation is a major concern in zinc, copper and nickel electrowinning industries and there is a strong environmental drive to control its emission into the work environment. Foaming reagents are typically added to the electrolyte to alleviate this problem. In zinc electrowinning, Licorice and Saponin are examples of foaming reagents used for this purpose. In order for the foaming reagent to be effective, its foaming behavior must be determined. In this work, a test procedure was developed to study the foaming characteristics of various surfactants for use as foaming agents to control acid mist in aqueous metal electrowinning. This new test was termed as "mini-flotation test" and it was used to study the foaming behavior of a large number of reagents in an industrial zinc sulfate electrolyte under simulated zinc electrowinning conditions (gas sparging). In addition, the influence of important process parameters such as current density, electrolyte temperature, reagent addition level and sulfuric acid concentration on the foaming characteristics of the electrolyte for each surfactant were investigated. The results of this study have identified the most important factors that influence foam formation, growth and stability. This method could be used as a process control for reagent addition in the cellhouse by generating a calibration curve for the optimum electrolyte conditions.

Jan 1, 1997

By R. E. Aune

In the present work, a critical assessment of the thermodynamic information available for the ternary system Ni-W-0 has been carried out; This was complemented by experimental measurements of the standard Gibbs energy of formation of the ternary compound NiWO, by solid state galvanic studies involving Zr02-CaO solid electrolyte. The assessed thermodynamic data, together with the phase diagram information available in literature, were employed to generate the ternary phase diagram for the system Ni-W-0 in the temperature range 1073-1273 K. The calculation of the phase diagram was carried out by computer optimization according to the "CALPHAD" method. The computed phase diagram has been confirmed at isothermal sections by identification of the phases present in samples equilibrated at defined temperatures.

Jan 1, 1994

By Cody Burcher-Jones

The recovery of rare earth elements (REEs) through heap leach/in situ techniques from so-called ion adsorption clays (IACs) is attractive due to their inherent simplicity. However, the underlying mechanisms of these processes are poorly understood. In this study, the deportment of REEs in a typical IAC material has been investigated and was found to concentrate in the phyllo-layers of the clays, especially hallyosite, and was readily desorbed by various ion-exchange reagents indicating various potential routes to liberate them. Here we are reporting the use of seawater (0.5 M NaCl), spiked with various amounts of (NH4)2SO4, and found better extraction using a reagent mixture than NaCl on its own. Further, the leaching of REEs from a bed of clay material was investigated over time to understand the rate of transport through the stagnant material. Results indicate that REE release is likely to be controlled by diffusion through the clay material, while desorption in agitated systems is rapid. A degree of fractionation between different REEs can be observed during diffusion. Nonetheless, the successful operation of in situ leach operations for this type of material would depend primarily on how easily solution cocktails can be made to flow through the bed material.

By Patrick Clark

As part of the Mine Waste Technology Program (MWTP), a large-scale column test using bacteria and a sulfide ore was conducted at McClelland Laboratories, Inc., in Sparks, Nevada. Four technology providers participated in this demonstration. A mining company in Nevada provided the sulfide ore, process effluent and make-up water. A process effluent column, a chemical oxidation column, and the four biological treatment columns were set side by side on a test pad outside the laboratory building. The process effluent and chemical oxidation columns were used for experimental control. The goal of this project was to evaluate the viability and feasibility of using these biodegradation technologies to reduce the cyanide to the regulatory level of 0.2 parts per million (ppm) within an acceptable timeframe and with low operational costs. The column testing began on December 3, 1998 and operated until May 17, 1999. One technology provider reached the regulatory level within the 158 days. The remaining three biotechnology columns were approaching the regulatory limit at completion of the demonstration. The MWTP is funded by the U.S. Environmental Protection Agency (EPA) and is jointly administered through an interagency agreement with the U.S. Department of Energy (DOE).

Jan 1, 1998

By Dale A. Zuck

Recovery of aluminum metal from drosses? is a major factor in the recyclability success story enjoyed by the United States aluminum industry. Today's modern dross processor uses the latest technology to maximize metal recovery at the lowest cost while complying with all environmental laws and regulations. Most dross processors, however, pay little attention to the resulting saltcake, the end residual of dross recyCling, and rely on landfills for .disposition of this material.. The alternative is to recycle the saltcake, but the success of this technology is dependent on the development of reliable outlets for each of the saltcake constituents. This paper discusses the evolution of an aluminum dross oxide processing technology that ,produces an economically attractive source of alumina for the production of portland cement.

Jan 1, 1995

By Toru H. Okabe

As part of a systematic study on the thermodynamic properties of complex nitrides, phase equilibria of the system Li-M-N (M Mg, AI, Ga) at 900 K were investigated. An attempt to determine the thermodynamic properties of complex nitrides was made by using the galvanic cell method, which utilizes LiMgN as an electrolyte under nitrogen atmosphere. The electromotive force (Emf) of ilie cell at temperatures between 800 and 1100 K was measured. Whilc the Emf of the cell at 900 K was measured to be 0.137 V, data discrepancies of ±0.03V were found. It was difficult to determine temperature dependence of ilie Emf. The Gibbs energy change for the reaction, 113 LbN (s) + 1/3 Mg3N2 (s) = LiMgN (s), at 900 K was determined to be tJ.Gor (LiMgN) -13.2 (±2.9) kJ/mol. Using thermodynamic information on ilie binary nitride from literature, the standard Gibbs energy of LiMgN was derived to be AGO f (LiMgN)= - 121 kJ at 900 K. The thermodynamic stability range of nitride was discussed by constructing isothermal chemical potential diagrams that provide a better understanding of ilie stability region of the LiMgN phase. The diagram was found to be in good agreement with the isoiliermal phase diagram determined by ilie alloy equilibration meiliod. Although the obtained data includes large uncertainties, the results provide a better understanding of the iliermodynamic stability of nitrides. The potential application of this complex nitride to nitrogen chemical sensors or a medium for controlling nitrogen potential is also shown.

Jan 1, 2003

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. J. Dippenaar, W. H. Van Niekerk

"An injectable lime-based desulphurization reagent for the treatment of liquid iron was developed. Firstly, selected lime based slags containing small quantities of CaF2 to increase fluidity, and Na20 to increase the basicity, have been evaluated on laboratory scale from a thermodynamic point of view. Subsequently, pilot plant and full scale industrial injection trials were conducted. It was found that lime-based slags, containing Na20 and CaF2, are able to desulphurize liquid iron efficiently. By the injection of a lime based reagent consisting of 60% lime, 25% soda ash and 15% fluorspar at a rate of 7 kg reagent/ton hot metal, the sulphur level in the metal (115kg) was reduced from 0,07% to 0,01 % within 5 minutes. The lime-based reagent developed in this study was successfully injected, both from a metallurgical and from a pneumatic point of view, on an industrial scale. The mathematical model utilised in this study, can be used successfully to predict the course and extent of desulphurization by lime-based slags. IntroductionMainly due to environmental difficulties encountered with pure soda ash, dry slag formation with CaC2 and high cost when Mg are used as desulphurizers, much incentive exists for the development of an inexpensive, environmentally friendlier desulphurization reagent. As a first step in the development of such a reagent, selected lime based slags containing small quantities of CaF2 to increase fluidity, and Na2O to increase the basicity, have been evaluated on laboratory scale from a thermodynamic point of view. This was followed by pilot plant injection experiments in which the kinetics of the relevant desulphurization reactions were evaluated. Finally, full scale industrial trials were conducted. All three phases of the investigation will be discussed with the major emphasis being placed on the kinetic study."

Jan 1, 1996

By Toru H. Okabe

As part of a systematic study on the thermodynamic properties of complex nitrides, phase equilibria of the system Li-M-N (M Mg, AI, Ga) at 900 K were investigated. An attempt to determine the thermodynamic properties of complex nitrides was made by using the galvanic cell method, which utilizes LiMgN as an electrolyte under nitrogen atmosphere. The electromotive force (Emf) of the cell at temperatures between 800 and 1100 K was measured. While the Emf of the cell at 900 K was measured to be 0.137 V, data discrepancies of ±0.03 V were found. It was difficult to determine temperature dependence of the Emf. The Gibbs energy change for the reaction, 113 Li3N (s) + 1/3 Mg3N2 (s) = LiMgN (s), at 900 K was determined to be !'J.Go, (LiMgN) = -13.2 (±2.9) kJ/mol. Using thermodynamic information on the binary nitride from literature, the standard Gibbs energy of LiMgN was derived to be !'J.Go f (LiMgN)= - 121 kJ at 900 K. The thermodynamic stability range of nitride was discussed by constructing isothermal chemical potential diagrams that provide a better understanding of the stability region of the LiMgN phase. The diagram was found to be in good agreement with the isothermal phase diagram determined by the alloy equilibration method. Although the obtained data includes large uncertainties, the results provide a better understanding of the thermodynamic stability of nitrides. The potential application of this complex nitride to nitrogen chemical sensors or a medium for controlling nitrogen potential is also shown.

Jan 1, 2003

By James L. Whitlock

Biological treatment of mining and industrial effluents reached full scale commercialization around 1980. These proven, low cost, technologies have been limited in application due to a number of factors, including extended periods of time and cost required for pilot testing as compared to chemical treatment technologies, lack of biological expertise in metallurgical personnel, longer treatment periods in some cases, and performance failures based on improper application. Renewed interest in biological treatment technologies is being driven by permits with lower effluent concentration criteria, permits with bioassay evaluation, the need to remove thiocyanate, nitrates, sulfates and? other parameters. Chemical treatment processes, in general, have not been able to meet these present requirements, or require elaborate? combinations of processes, in terms of effluent quality and treatment economics. This paper addresses biologieal treatment of mining and industrial waste waters and selected recent advances in these technologies. The future looks very bright for application of these low capital and operating cost technologies,

Jan 1, 1998

By Jennifer Murphy, Brad S. Schake, Karol Holmes, John R. FitzPatrick, Mike H. West

"The separation and purification of uranium from either nitric acid or hydrochloric acid media can be accomplished by using either solvent extraction or ion-exchange. Over the past two years at Los Alamos, emerging programs are focused on recapturing the expertise required to do limited, small-quantity processing of enriched uranium. During this period of time, we have been investigating ion-exchange as a method for extraction/purification of uranium from acidic media. In addition, waste stream polishing is associated with this effort in order to achieve more complete removal of the uranium prior to recycle of the acid. Extraction chromatography has been demonstrated to further polish the uranium from both nitric and hydrochloric acid media thus allowing for a more complete recovery of the actinide material and creation of less waste during the processing steps.We will discuss contact experiments for evaluation of eleven different resins for uranium removal from nitric acid, the evaluation (again by contact experiments) of uranium elution from the ion-exchange media by various chemicals, and small-scale experiments for the removal of 235U from nitric acid. Larger-scale (1 DO-gram) flow experiments, using depleted uranium, were done after the small-scale evaluation of the selected resin. A discussion is also included concerning the shortcomings of the contact experiments and how the flow experiments were modified in order to overcome these problems. We will also discuss the application of ion-exchange for some specific process needs at Los Alamos.Contact experiments were used to evaluate some commercially available solvent-impregnated resins in addition to evaluation of several resins of this type synthesized in our laboratory. These experiments involved both nitric and hydrochloric acid media. The data from these experiments will be used to determine the column size and amount of resin required to polish the waste stream produced by the ion-exchange process described above. Small-scale flow experiments will be described and data given on the mass balances achieved using this two step process.Future work for evaluation of new ion-exchange and solvent-impregnated resins as well as the search for new eluants will be discussed. Other future experiments for both processes, including large-scale experiments, will be discussed in detail."

Jan 1, 1996

By C. Liliane Carvalho

In the current study, bio-oxidation tests were carried out in shaking flasks with a flotation concentrate containing the sulphides pyrite, arsenopyrite and gudmidite. The tests were performed with mesophilic microorganisms (At. ferrooxidans) at 30 °C and also with the moderate thermophile S. thermosulfidooxidans, at 50 °C. The effects of (i) previous adaptation of the microorganisms to the concentrate, (ii) ferrous iron concentration and (iii) pulp density (2%, 4% and 6% (w/v)) on the dissolution of the sulphide were studied through arsenic extractions. S. thermosulfidooxidans was more sensitive to the pulp density in comparison to At. ferrooxidans as a reduction in sulphide oxidation was observed with the increase in the solid content to 6%. Therefore, the mesophilic strain was selected for further work, which comprised a rolling bottle experiment at 10% solids. After 40 days of bio-oxidation, the solid material was subjected to cyanidation, which revealed 85% gold extraction as compared to 21% from the original concentrate. The antimony sulphide grains in the bio-oxidized product showed similarity to what was observed in the original sample, suggesting such particles were not susceptible to the bio-oxidation process.

By Yong Zhao, Yan-hui Sun

Behaviors and evolutions of MgO·Al2O3 in non-oriented silicon steel during calcium treatment were investigated by thermodynamic calculations and high-temperature experiments. MgO·Al2O3 inclusions were the main type of inclusions before calcium treatment, which is also confirmed by the stability diagram of MgO/MgO·Al2O3/Al2O3 from thermodynamic calculations. After calcium treatment, the majority of original MgO·Al2O3 inclusions were mainly modified to CaO-MgO-Al2O3 system inclusions, this would be beneficial to improve castability and product quality of silicon steel. But there was no modification happening to some MgO·Al2O3 spinels which were directly surrounded by CaS inclusions. The content of Al2O3 occasionally existed a sudden increase besides a common decrease in the product layer of CaO·MgO·Al2O3. Then the evolution mechanisms of MgO·Al2O3 inclusions were proposed in present work. Thus, Al/Mg atom ratio had a significant influence on the modification of MgO·Al2O3 spinel.

Jan 1, 2016

By Shoji Taniguchi, Lifeng Zhang, Kaike Cai

"In the present paper, based on the two-phase (Eulerian-Eulerian) model, the 3D fluid flows in gas-stirred systems, i.e., air-stirred water vessel and argon-stirred liquid steel ladle, are simulated. In the Eulerian-Eulerian two-phase model, gas and liquid are considered to be two different continuous fields. The phases are assumed to share space in proportion to their volume fractions. The exchange between the phases is represented by source terms in conversation equations. Turbulence simulated by the k- e model is assumed to be the property of the liquid phase. The following effects of mathematical treatments and operational factors on the fluid flow are discussed, such as interphase drag force, turbulent model, the size of bubble, and gas injection mode.Some interesting results are derived. Except the interphase drag force, the interphase lift force should be taken into accounted in order to exactly simulate the fluid flow in gas-stirred systems. Suitable turbulent model and drag coefficient have effect on the mathematical simulation. Injecting small bubbles can realize a well mixing flow condition. The distance between the two gas-injection nozzles has effect on the fluid flow."

Jan 1, 2000

By Animesh Jha, Catherine Davey

"Carbothermic reduction and nitridation reactions using synthetic kaolinite mineral were investigated for the formation of silicon based nitrogen ceramics. The temperature dependence of the reaction rate and its effect on phases formed are reported. The effect of the reactivity of carbon on the kinetics of formation of AIN and ShN4 is discussed. Using the standard Gibbs free energy values for the formation of nitrides and oxides of aluminium and silicon, a log po2 verses I/T diagram is constructed. The experimental data results are discussed and compared with the predicted phase equilibria. We also report the influence of sub-oxide gaseous species on the microstructure of the ceramic phases produced.IntroductionSynthetic kaolinite is a clay containing alumina, silica and water of crystallisation, and has a chemical formula 3(Al2O 3.2SiO2.2H2O). This mineral is relatively inexpensive and, is therefore an ideal candidate for use in the production of ceramic powder mixtures for example silicon nitride and aluminium nitride for composite material formation, When the mineral is heated, the water of crystallisation from the crystal lattice is lost via the 3(Al2O 3.2SiO2.2H2O) = 3(Al2O3.2SiO2) + 6H2O reaction. It has been shown [1·2j that on further heating to 1673K, the anhydrous kaolinite decomposes to a mixture of mulllte and silica, 3(Al2O3.2SiO2) = 3Al2O 3.2SiO2 + 4SiO2 which is consistent with the alumina-silica phase diagram, shown in figure 1.The binary alumina-silica phase diagram has a well-defined sub-eutectic immiscibility dome and this characteristic dernixing behaviour is reflected in the thermal decomposition of anhydrous kaolinite consequently the microstructural features resemble the spinodal decomposition process. It is well established that the spinodal decomposition process raises the nucleation frequency due to their low free energy barrier, (?G). The small magnitude of this barrier consequently promotes the evolution of a very fine microstructure. The process of spinodal decomposition is therefore expected to be influential during the reduction-nitridation of kaolinite minerals."

Jan 1, 1996

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 Batric Pesic

Dissolution of gold with elemental bromine was studied by using a rotating disc technique. The main parameters studied were: bromine concentration, stirring speed, pH, and temperature. Additionally, effect of copper, iron, and manganese was also examined. A special attention was paid to elucidate the role of cations, primarily Na+, during gold dissolution. It was found that gold dissolution with bromine was characterized with two pH regions. Below pH=7, gold dissolution was independent of pH, and above this value, gold dissolution decreased with pH increase. Gold dissolution rates were proportional with concentration of bromine. Two regions, diffusional and kinetic, were observed with respect to stirring speed. with respect to the role of Na+, and cations in general, they play absolutely no role during gold dissolution with bromine, unless they are in their lower oxidation state and become oxidized by bromine. In that case they have a negative effect because of bromine consumption.

Jan 1, 1991