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By Xiaobing Yang, Animesh Jha, Greg Doughty

"Successful use of inert anodes should reduce the CO2 footprint in aluminum production. The search for a “holy grail” inert anode for metal electro-winning from constituent oxides using molten salt bath as an electrolytic medium is continuing. In this article we demonstrate the engineering approaches for the fabrication of intermetallic anodes, based on a quaternary Al-Ti-Cu-M (M:Ni, Fe) system for primary aluminium production. In particular, we examine the microstructural and electrochemical properties of alloys, based on the quaternary compositions. We explain the aspects of phase stability under anodic potential, which leads to the loss of anodic materials in the temperature range of 850-1050oC. The results are analysed in the context of oxidation reaction and formation of oxide layers which readily dissolve in the cryolite melt and prevent passivation. The paper also describes the conditions under which the reduction of aluminium at the graphite cathode occurs which also strongly depends on the molten salt chemistry for the nucleation of molten aluminium at the cathode.1. IntroductionOxygen-evolving inert anodes are an alternative to the conventional consumable carbon anodes for the production of primary aluminium. In this paper the materials selection criteria chosen for the engineering of anode is based on the understanding of the thermodynamic stabilities of aluminide intermetallic phases, some of which are formed and remained stable in fluoride melts. For example, the formation Al3Ti dispersed in aluminium metal via molten-fluoride flux reaction is well known in the context of aluminium casting and grain refining [1-3]. It is for this reason in our research we concentrated on the engineering of stable intermetallic phase mixture in the Al-Ti-Cu ternary system, shown in Figure 1 [4]. In this figure two compositions in the Al3-0.5zTi1-0.5zCuz family are shown with the substitution of 7 atomic % and 11 atomic % copper. However initial investigations showed that these two compositions were unsuitable due to the formation of low-temperature liquid (~540oC) and intermetallic phase, Al2Cu along the Al-Cu binary edge during solidification. The Al2Cu phase segregated along the boundaries of Al3Ti and Al5Ti2Cu, and dissolved away when electrolysis was carried out using these anodes above 800oC. The presence of consequential porosity in the anode material increased the corrosion of the alloy through local heating due to high current density at 0.8 A cm-2. The early tests were carried out with cryolite melts, shown in Figure 2, having 3 weight percent of Al2O3 in the bath at 850oC."

Jan 1, 2010

By M. R. Dahm

The demand for low sulfur steel by steel manufacturers and their customers has been steadily increasing for 25 years. Historically sulfur has been controlled by various means and with various additives but lime-magnesium external desulfurization of hot metal has become established as the dominant method in North America today. Magnesium powder produced from primary magnesium ingot has been the major source or raw material. However, periodic increases in the price of this commodity have encouraged producers to look to secondary magnesium for an alternate source of magnesium. Secondary magnesium from post-consumer scrap can be cleaned, sized, and prepared to produce a high quality magnesium reagent for use in hot metal desulfurization at a lower cost than material processed from primary ingot.

Jan 1, 2000

By U. Lauwers

The influence of different waste materials in sinter blends on the quality and mineralogical composition of a sinter is described. As a result of partial preservation of the original textures of waste materials in the final product the degree of assimilation of the original material in the sinter product can be ascertained. Recycling of waste materials such as dolo char , arc-furnace slag, scrap fmes, mill scale and BOF-mud via the sintering process a saving on costs of raw materials such as flux and fuels, and a reduction on pollution can be achieved. A comparison of a typical sinter with a sinter produced through the utilization of waste materials showed a distinct correlation between certain types of waste material and some metallurgical properties. Dolochar in a sinter blend acts as part of the fuel and flux that are normally added to a sinter mix. Generally dolochar improves the quality of the sinter and decreases the consumption of coke. Other waste materials adversely influence the quality of the sinter. The glass and calcium ferrite content of a sinter when dolochar is used in the blend is similar to that of a sinter produced with only coke as a fuel in the sinter mix. The glass content is lower and the calcium ferrite content is higher, in a sinter produced from dolo char in the blend compared to a sinter produced with additions of other waste materials. Changes in the mineralogical composition are related directly to the metallurgical properties of the sinter product.

Jan 1, 1991

By B. Wasmund, K. Adham, K. O'Keefe, C. Lee

"Metal chlorides (e.g. iron and nickel) can be pyrohydrolysed at elevated temperatures to yield an HCl rich off-gas and a metal oxide product. Typically, the high energy requirement for pyrohydrolysis is provided by the combustion of a hydrocarbon fuel with air. Here, it is demonstrated that the use of oxygen-enriched combustion can result in lower fuel requirements and higher HCl concentrations. In addition, the oxygen enrichment can result in a smaller volume of off-gas and thus, smaller and less expensive process equipment. This new concept can be applied to both the spray roaster (SR) and the fluidized bed reactor (FBR). Similar to the aircombustion case, the oxygen-enriched process can use a direct contact venturi scrubber, to recover energy from the roaster off gas, but at a higher efficiency. The new process also uses an absorption tower for capturing HCl from the roaster off-gas, but generates a stronger HCl solution than is possible with pyrohydrolysis in air.BackgroundIn recent years, the metallurgical industry has become increasingly involved with developing methods for extracting metals, upgrading products or cleaning metallic products by using hydrochloric acid. These applications of chloride metallurgy often result in metal chloride solutions, which should be processed to regenerate HCl for reuse, and to recover the metal value as a product or by-product oxide [2, 3, 4].The pyrohydrolysis of metal chloride solutions has been done in two types of air roasters: spray and fluidized bed. The existing roasters burn a hydrocarbon fuel in air, to provide the required energy for evaporating the feed solution and to provide an elevated temperature for the chloride pyrohydrolysis to occur, according to the following reactions:"

Jan 1, 2011

By Alex Moyano

Due to very demanding environmental rules, and to the incrementing impurities contents in the processed concentrates, Codelco Norte smelter permanently faces new demands for planning the production program with the present fulfillment of the environmental regulation. Accordingly, the CN smelter along with IM2, developed an impurity distribution simulation model, M-DICE, which predicts the impurities behavior for each of the process units of the smelter under different process configurations and concentrates quality. The development of the M-DICE included the gathering of operational data for the process units of the CN smelter, including temperature, oxygen enriched air, matte grade, etc. Then based on a mass balance for each of the process units involved in the smelter a thermodynamic evaluation was done to derive the arsenic fractional distribution among the condensed (matte/white metal/copper/slag) and gas phases. Then, the validated M-DICE was able to predict the arsenic behavior in the Teniente converter processing complex concentrates with high arsenic content, among others. At present, M-DICE is in its last stage of development, and is expected to be a suitable environmental and process management?s tool for the Codelco-Chile?s smelters.

Jan 1, 2006

By Shun Fujieda, Shigeru Suzuki, Kozo Shinoda, Tetsuo Fujita

"Dowa's scorodite, synthesized by oxidation of Fe(II) ions in the presence of As(V) ions at atmospheric pressure, was characterized. The scorodite was well crystallized and had a very low solubility. To examine the conditions for stable storage of the scorodite for long periods, experiments with various synthesis and leaching conditions were done. The scorodite had a very low arsenic solubility in sea water. It was estimated in consecutive leaching tests that the arsenic concentration would eventually converge to zero. The prevention of arsenic leaching by adding goethite or ferrihydrite was limited in some cases. Very low toxicity was confirmed by toxicity tests. The investigation results suggest that disposal at a specifically designed well-controlled storage place is preferable for the scorodite whose toxicity had been made sufficiently low. Disposal to an isolated final disposal site with more stringent prevention for the outflow of toxic substances was thought another option.IntroductionArsenic is a considerable environmental concern. A system of technologies for the effective immobilization, storage and final disposal has been sought. Dowa Metals & Mining Co. Ltd. has developed a unique scorodite synthesis method (DMSP®) which works at ambient pressure [1]. The scorodite is precipitated by oxidizing Fe(II) ions in a high-concentration As(V) solution. The scorodite produced in this way does not readily release arsenic because of its high crystallinity. Final disposal is necessary because scorodite currently has no commercial value. A standard method for the final disposal of scorodite has not been established because its long-term stability under various conditions has not been fully examined."

Jan 1, 2012

By C. -S. Jiang

In most copper refineries, addition agents are added at predetermined rates with no further monitoring of their activity or concentration in the electrolyte. Increasingly stringent cathode quality requirements, and a desire for better process control in tankhouse operations, have recently directed a number of refineries to search for a better addition agent control strategy. Extensive development work has been carried out at the Noranda Technology Centre for the monitor in of glue and thiourea in copper refinery electrolyte using cyclic voltammetry (cv~. Data from both synthetrc and commercial electrolytes are presented, showing the ability of CV to produce reliable and easily identifiable fingerprints of addition agent concentrations in copper refinery electrolyte.

Jan 1, 1991

By Vaughan R. Voller

"Over the last ten years an increasing number of heat and mass transfer models of solidification processes have been presented in the literature. A key component in these models is the coupling between thermal and solute fields. This is achieved by developing relationships based on the behavior at the microscopic scale in the casting (typically a secondary dendrite arm space). An important class of models in this respect are models that describe the local scale redistribution of solute alloy components-collectively referred to as microsegregation models. This paper explores this class of models.IntroductionModeling takes a key role in processing materials for properties. This is particularly time in solidification processes where current computer techniques allow for a detailed treatment of the critical macroscopic phenomena. Typically these macro scale models consist ·of three main coupled components.1. A model of flow in the melt and solid + liquid mushy region.2. A model of heat transfer.3. A model of solute transport.The focus of this paper is the solute transport component, in particular the manner in which process scale transport is coupled to transport ·at the local scale of the solid-liquid interface. This step requires a modeling of the redistribution of solutes at the scale of the secondary arm spaces in the dendritic mushy region-a process referred to as microsegregation. Basic microsegregation models use the limit assumptions of no mass diffusion in the solid (Gulliver-Scheil [l]) or complete diffusion in the solid (equilibrium lever rule) in a fixed and space. Recently, however, more sophisticated microsegregation models that account for finite mass diffusion and coarsening of the arm space have been developed [2-19]. In this paper governing equations for a general microsegregation model for a multi-component alloy in a coarsening and spacing _are introduced. From these general equations various models for a binary system are developed and tested"

Jan 1, 2000

By C. M. Egert, S. Rajic

"We have developed a monolithic micro-spectrometer suitable for a variety of sensing applications including industrial process monitoring. The device consists of a solid structure with a volume less than 6 cubic centimeters. All optical components of the spectrometer including two aspheric mirrors, a diffraction grating, and entrance and exit surfaces are fabricated onto the surface of the structure. All light paths are internally contained within the structure. The result is a small, rugged spectroscopic sensor ideally suited for use as a process monitor. Due to its monolithic nature the device requires no post-fabrication alignment; nor can it be knocked out of alignment during use. Although many materials and thus wavelength regions were possible, the prototype device discussed here was produced in PMMA by precision diamond turning. However, lower cost manufacturing approaches involving injection molding are under development to produce an affordable sensor.Due to its rugged monolithic design, small footprint, and low cost the monolithic micro-spectrometer is ideally suited for distributed monitoring applications often required for industrial processes. It is expected that modified versions of this sensor designs will be required for specific applications so as to maximize the performance and resolution over the operating range. For example, the prototype device described here operates over a wavelength range of 500 nm to 1000 nm. The performance of this device as a real-time surface monitoring sensor will be discussed in detail. Our approach of using wavelength dependant scattering resulted in the reduction to practice of a miniature, monolithic, rugged, low-cost, micro-instrument in a sensor sized package. The process sensor applications community has been faced by the cost versus performance issue. Simple go/no-go sensors are typically inexpensive but they provide very limited and sometimes dubious data. Scaled down traditional instruments offer very good measurand information but are typically cost prohibitive, fragile, and still relatively large. This work will bridge the gap between these two extreme sensing alternatives."

Jan 1, 1997

By A. Pagliero

The coulombimetric reduction method has been used as an evaluation technique for Pb-Ca-Sn anode corrosion in the LIX-SX-EW process. The proposed methodology involves three consecutive steps, i.e., cleaning, oxidation and reduction. They are carried out in the same experimental unit, in solutions containing 180 g/L H2S04 with and without the addition of cobalt. The authors have worked in a wide range of oxidation current densities, from 150 to 500 A/m2 for in a period from 0.5 to 120 hours. It can be concluded from the results that there would be a linear relationship between the applied electrical charge I*T (Coulomb) and the anode corrosion expressed as transformed Pb mass (mg), for solutions with or without the addition of cobalt. The exception is that for the last one the corrosion rate is 5 times faster, which was observed for every layer. From the evaluation of different corrosion layers, one can point out that its composition is mainly in the form of sulphate. In the presence of cobalt, about 67% of Pb would be as sulphate (PbSO4), about 27% as a basic oxide (PbO) and only 6% as oxide PbO2 on the surface. From this result, it appears that great transformations occurred in the metal/sulphate interface. Without the addition of cobalt, the proportion of oxide Pb02 on the surface increased up to 11.5%. According to the previous statement and considering that Pb was found mainly as sulphate, the authors recommend its determination be used as quality selection criterion. Its evaluation should be performed in the acid solutions with 200 ppm cobalt addition at an oxidation current density of 300 A/m2 for a period of 24 hours.

Jan 1, 1999

Over the years, numerous hydrometallurgical processes have been proposed as an alternative or complement to smelters for the treatment of copper concentrates. Most of these initiatives met with limited success. Bioleaching is applied commercially for secondary copper minerals heaps and dumps, and bacterial leaching processes are being developed for copper concentrates, although industrial application is still years away. More recently developed processes usually include pressure leaching and/or ultrafine grinding. This paper proposes a new leach process to treat copper sulphide ores or concentrates: the process operates under atmospheric pressure and uses limited concentrations of ferric sulphate as oxidant; the key to the process is the regeneration of the ferric ion, which can be effected in-situ (direct process) or ex-situ (indirect process) using SO2/O2. Examples are presented for the treatment of copper concentrates by agitation leach and of copper ores by heap leaching. Application of the process to copper gold ores and chalcopyrite concentrates is also discussed.

Jan 1, 1999

By Cailing Zhen, Jian Pan, Deqing Zhu, Xianlin Zhou, Yanhong Luo, Guixiang Huang

The grate-kiln process has been widely applied for oxide pellet production with the quick development of steel industry in China, but ring formation takes place which adversely affects the productivity and properties of fired pellets. Rotary kiln at high temperature seems a black box, and ring formation is difficult to measure directly by current technology. It’s of great importance to monitor ring formation during firing of pellets. Therefore, a method for estimating the thickness of ring formation in rotary kilns was studied, based on working out theoretically the relationship between ring thickness and the outside surface of the kiln, according to steady-state heat transfer across a cylinder, which provides a soft-sensing technique for ring formation at high temperature, and achieves stable pellet production .

Jan 1, 2015

By Yiming Rong, Gang Wang

"Water quenching is one of common heat treatment processes but with complex physical phenomenon, in which vaporizing, bubbling and convection are involved. The general simulation of liquid quenching processes is conducted by using temperature dependent value of heat transfer coefficient (HTC) obtained from experimental measurement under a strong assumption. A preliminary multiphase flow model developed by using Ansys-CFX for water quenching has been presented in this paper, which shows a distributed HTC with a time dependent feature. The conjugate heat transfer is used to describe thermal conduction in the simplified workpiece, and generation, growth and flow of bubbles are modeled by using Eulerian-Eulerian method for the gas-liquid multiphase flow. The simulation result shows the intense variation of heat exchange through the interface between workpiece and liquid, and the unsteady distribution around the solid surface.IntroductionQuenching is a rapid cooling process which makes the desired solid phase transformations happen for the certain material properties. For aluminum alloy, rapid quenching will prevent all phase transformation and generate a supersaturated single phase."

Jan 1, 2012

By O. Barbosa F.

The thermochemistry of the systems SCN-H2O, Au-SCN-H2O and Ag-SCN-H2O is discussed. Potential-pH diagrams at 25°C are drawn for each system considering several sets of concentrations of the species involved. The information provided by the potential-pH diagrams is.complemented by distribution curves for each series of gold and silver complexes with thiocyanate. The analysis includes comparisons between the thiocyanate systems and the analogous cyanide systems, pointing out analogies and differences between the leaching of gold and silver with thiocyanate and with cyanide. The possibility of using soluble oxidizing agents such as ferric ions, hydrogen peroxide and Caro's acid is evaluated. The thermodynamic data used in the calculations and the chemical reactions represented in the Pourbaix diagrams are all reported in three Appendices. The overall results indicate the thermodynamic conditions for gold and silver leaching by thiocyanate.

Jan 1, 1989

By Melinda Channel, Alan W. Weimer, Jonathan R. Scheffe

"There is a need to develop cost effective renewable energy processes for the production of clean fuels that can simultaneously mitigate the U.S. energy/global environmental security issue. If H2 can be obtained cost effectively via the splitting of water using concentrated sunlight, then it’s possible to operate a fuel cell using renewable H2 or to synthesize other fuels based on renewable H2 for generating electricity or for running internal combustion engines. For example, H2 can be reacted with sequestered carbon dioxide (CO2) to produce syngas (H2/CO) via reverse water gas shift (RWGS), i.e. H2 + CO2 ? CO + H2O. The syngas can be catalytically methanated to form synthetic natural gas (SNG) or it can be catalytically reformed to produce liquid fuels such as “green” gasoline via the MTG process (syngas? methanol ? gasoline). The desert SW United States is home to world class sunlight. Fundamental ferrite thermodynamics will be reviewed, an example of the beneficial effect of ferrite surface area on reaction kinetics will shown, and process economics will be investigated for a 100,000 kg/day facility to produce H2.Introduction and Background ThermodynamicsSpinel ferrites of the form MxFe3-xO4, where M generally represents Ni, Zn, Co, Mn, or other transition metals, have been shown to be capable of splitting water according to the two step cycle shown below:MxFe3-xO4 + solar thermal energy ? xMO + (3-x)FeO + 0.5 O2 (1)xMO + (3-x)FeO + H2O ? MxFe3-xO4 + 2H2 (2)This is an inherently clean and sustainable process, as the only net inputs are solar energy and water, and the net outputs are hydrogen and oxygen. Ferrite water splitting cycles are advantages compared to other high temperature water splitting cycles, such as the ZnO/Zn and Mn2O3/MnO cycles, because thermal reduction has been demonstrated at significantly lower temperatures[1, 2]. As a result, overall efficiency may be increased due to the fact that radiation losses increase as the fourth power of temperature, and material considerations for reactor design should be more flexible. Additionally, cycle repeatability has been demonstrated with relative ease as compared to other thermochemical cycles [3-6]. However, the amount of hydrogen per mole that is generated is significantly less than for other high temperature thermochemical cycles due to the fact that only Fe3+ is capable of being reduced at the temperatures of interest[6]. In addition, water oxidation kinetics appear to be very slow, likely due to diffusion or surface area limitations created by near surface oxidation [6, 7]."

Jan 1, 2010

By Peter Ryan

A patented process for agglomeration of Smelter ESP dusts is described. Addition of suitable binders followed by compaction, transforms fine, difficult to handle material into a dry, flowable agglomerate suitable for plant reentry. Details for the agglomeration process metallurgy and laboratory pilot plant testing are discussed. An example of full scale plant operations is described.

Jan 1, 1999

By J. R. Donald

For processing copper, continuous converting has been successfully employed in a variety of locations, but for nickel, there has yet to be a successful commercial implementation of continuous converting technology. At Inco?s Copper Cliff smelter, there are specific requirements for the production of Bessemer matte relating to downstream processing that makes continuous converting for nickel mattes even more challenging. The nickel carbonyl refineries require very low iron levels in the matte, and the sulphur deficiency must be carefully controlled such that the appropriate quantity of PGM-rich metallics are produced from matte separation. The present paper outlines continuous converter technologies that have been implemented in copper, and evaluates their potential for nickel converting. The challenges of producing a Bessemer matte to the required specifications are discussed. The economic and environmental driving forces, and the challenges of justifying a novel technology in place of productive existing equipment, are discussed.

Jan 1, 2005

By K. Yamaguchi, Y. Takeda

"Partial pressure - temperature - composition correlation diagrams of the Ga-As, In-As, Ga-P and In-P systems were contracted based on the obtained experimental data of the phase diagram and thermodynamic properties for the III-V systems. The total vapor pressures of arsenic or phosphorus at melting point of GaAs, InAs, GaP and InP were determined as 101, 10.1, 1510 and 253 kPa, respectively, at the corresponding melting points of 1509, 1211, 1739 and. 1336K , These diagrams are applied to the analysis of the horizontal Bridgman method and the liquid phase epitaxial growth technique. On the other hand, the analysis of the equilibrium state of the. chloride-CVD process was carried out using the data of the Gibbs energy of the compounds obtained by· authors.IntroductionThe group III-V compound semiconductors ate important materials used in optoelectronic liquid high speed electronic device. The crystal growth of the III-V compounds can involve processes that require contact between the solid, liquid and vapour phases at near equilibrium condition. Examples of processes that involve contact between the solid, liquid and vapour phases include bulk crystal growth such as the horizontal Bridgman and the liquid encapsulated Czochralski method and liquid epitaxy, and between the solid and vapor include chemical vapour deposition and molecular beam epitaxy. Therefore, the knowledge of the phase diagram and thermodynamic properties for the III-V binary alloys is essential for the analyses of crystal growth techniques of III-V compounds.For these reasons, a series of different · types calorimetric measurements had been carried out: (1) The heat contents of alloys for the Ga-As, In-As, Ga-P and In-P systems by a drop calorimeter [1;2,3]; (2) the heats of formation of the GaAs, InAs, GaP and InP compounds by a twin solution calorimeter [4]; and (3) the standard entropy of these compounds by an adiabatic calorimeter [5]. Based on the third law method, the Gibbs energies of these compounds were derived from the heat capacity, standard heat of formation and standard entropy data obtained by authors. Integral molar thermodynamic quantities of the liquid III-V .alloys were also determined from combining the heat contents of alloys with standard heat of formation and standard entropy data of the compounds· by applying the thermodynamic analysis method developed by Oelsen [6]. In the present study, the thermodynamic calculations for the crystal growth processes of the III-V compound were carried out using newly experimental data of the phase diagram and thermodynamic .properties measured by authors"

Jan 1, 2000

By A. Kar

A mathematical model is presented for pure titaqium deposition from titanium tetrabromide on a stainless-steel (SS 304) substrate. Five three-dimensional, transient, and nonlinear partial differential equations are used to account for the diffusion of various species inside the deposition chamber and the thermal decomposition of titanium tetrabromide, titanium dibromide, and titanium monobromide at the surface of the substrate in order to determine the thickness of the titanium film deposited on the substrate. The effects of various process parameters on the deposition and shape of titanium films are examined, and under certain conditions, the deposited titanium films are found to have volcanic profiles.

Jan 1, 1992

By M. D. Crites

As part of a multi-year program for assessing the viability of chrome-free refractories in copper smelting, converting and refining furnaces, dynamic corrosion tests have been conducted on a series of refractories from the magnesia-alumina system, using a ferrous silicate slag. The corrosion rates of the test refractories are compared with those of a reference mag-chrome brick, and recommendations are made for more in-depth evaluations of the more corrosion-resistant materials.

Jan 1, 1999