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By John J. J. Chen, Barry J. Welch

"As in many industrial processes, the detailed mechanisms involved must first be understood before being able to redesign, or to carry out improvements or optimisation of the process and equipment performance. In a great majority of metallurgical processes, visual observation and actual measurement of process variables are either very difficult or near impossible. Often, the cost and effort involved are prohibitive. Consequently, physical modelling is often used to provide some understanding of the process and for the validation of computer numerical models. In this paper, we summarise some of the work carried out at The University of Auckland on the modelling of the Hall-Héroult electrolytic cell, the in-line melt treatment process, and the steel casting tundish. IntroductionIn any industrial process, it is essential to understand the underlying mechanisms before any optimization or process improvement can be carried out. In many metallurgical operations, the processes are conducted at elevated temperature and under rather hostile environments. Consequently, it is often difficult, and sometimes impossible, to observe the actual processes occurring, or conduct measurements which are pertinent. In some situations, it is possible to formulate mathematical equations purported to describe the process, and obtain the solutions numerically. However, in this latter case, the validity of the simplifying assumptions made are often uncertain. Physical modelling may provide the necessary information for the validation of such numerical models. Furthermore, through an application of the principle of similitude, it is possible to apply data obtained from physical modelling to actual metallurgical processes. This paper will summarise some the work carried out at The University of Auckland on the physical modelling of gas-induced flow in the Hall-Héroult electrolytic cell, an in-line melt treatment unit, and the flow in a steel casting tundish.Gas-Induced Flows in a Hall-Héroult CellIn an aluminium cell, the effects due to electro-magnetic forces have been addressed and various design modifications such as magnetic shielding and the positioning of risers have been carried out to control or lninimise the effects of magnetic fields'. Consequently, the effects of gas-induced flows are now becoming significant providing the impetus for the study of the gas behaviour in the bath. Furthermore, the shape and size, and the rate of evacuation of the anodically generated gases affect the cell voltage affecting the energy efficiency; at the same time, the back-reaction between the anode gas and the metal produced is the predominant cause of the loss of current efficiency. Figure 1 shows a cross-section of a conventional cell in which the gas evolution occurs directly under the anodes, and the gas induced flow is confined mainly to the region occupied by the bath"

Jan 1, 1994

By Stephen Chryssoulis, Stamen Dimov

Detection and quantification of precious metals (Au, Pd, Pt, and Rh) in spinels and silicate minerals is important for establishing the maximum attainable recovery by sulphide flotation. To achieve this goal subpart per billion (ppb) detection limits are required plus the ability to quantify results. Existing quantitative microbeam techniques (EPMA, PIXE, SIMS, TOFLIMS) have limits of detection in the O. l-200ppm range. Time-of-flight resonance ionization mass spectrometry (TOF-RIMS) is a microbeam analytical technique that allows for the identification and quantification of atomic species in very small quantities. It utilizes a tunable laser source for resonant excitation and ionization of a particular element of interest and has some unique features: elemental selectivity, linear response over a large dynamic range and very high sensitivity. The analysis consist of three steps: (i) the solid sample is vaporized by laser ablation to form a plume containing neutral atoms, (ii) the neutral atoms of a specific atomic element in the plume are resonantly excited and ionized by another tunable laser, and finally (iii) the ions created are mass analyzed in a time-of-flight mass spectrometer. A TOF-RIMS mass spectrometer was developed at AMTEL for trace element analysis of Au, Pd, and Rh in minerals. The spectrometer was calibrated using homogeneous CANMET and NIST reference samples covering three orders of magnitude in concentration. Attained minimum detection limits (MDL=2cr of the background) are in the low ppb range.

Jan 1, 1999

By Jingwei Lou, Bing Li, Suzhen Li, Miao Shen, Jianguo Yu

"As a main impurity in primary lithium metal, magnesium is difficult to remove because of the very close relative volatility of the two metals. Electrochemical refining provides a possibility to completely remove Mg in the LiCl-KCl melt prior to Li reduction. MgCl2 reduction processes in LiCl-KCl- MgCl2 melt were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry and chronopotentiometry. Then potentiostatic electrolysis was carried out and Mg (II) ion was reduced onto a liquid lead cathode from the LiCl-KCl-MgCl2 melt at the Mg deposition potential. The results show that Mg ( II ) is reduced in one step with two-electron transfer. The reduction potential of Mg ( II ) was well defined. The reduction of Mg( II) results in Li ( I ) underpotential deposition at 0.2V more negative potential than that of Mg( II) reduction. Therefore, in order to prevent Li ( I ) from codeposition with Mg, accurately controlling Mg ( II) reduction potential during the potentiostatic electrolysis was necessary. Ninety three to 99 % removal rate of MgCl2 was achieved after 8-12 h electrolysis when liquid lead was used as cathode.IntroductionMetallic Li has been widely used in batteries, light weight alloys and in fusion reactors because of its excellent properties. Currently, the only way in industry to produce metallic Li is by electrowinning from molten LiCl-KCl at about 450 °C [l-5]. LiCl-KCl is the only electrolyte used, because they presents a lower eutectic temperature and KCl shows a slightly higher theoretical decomposition voltage than LiCl, as shown in Table l .The produced metallic Li generally contains 1-2 wt% impurities including Na, K, Al, Ca, Mg, Si, etc. [6l, which are derived from the corresponding metal chloride compounds or metal oxide compounds existing in the LiCl and/or KCl raw materials. These impurities have to be removed by subsequent vacuum distillation at high temperatures to meet the requirements for metal Li purity in the final products. Separation of Mg from Li by vacuum distillation is difficult because their relative volatilities are very close, as shown in Table 2."

Jan 1, 2011

By Caisa Samuelsson

Experimental studies in laboratory-scale equipment have been carried out to study the vaporisation from dust generated during the copper converting process. In the present work the vaporisation of Zn, Pb, As, Sb, and Bi from a dust collected in the electrostatic precipitator after the copper converter were studied. The results show that Pb, Bi and As were vaporised to a high degree from the dust at a temperature above 900°C in a gas containing N2, SO2 and a small amount of H2. The vaporisation was high for these elements also in a gas containing N2, SO2 and 02 at temperatures above 1120°C. In an earlier study, thermodynamic calculations showed that it is possible to selectively condense metals at high temperature' in a gas atmosphere generated during a copper converting process. The present study was carried out to verify the thermodynamic model. The results indicate that it should be possible for a selective condensation of Zn at high temperature. The temperature required for a selective condensation of Zn is dependent upon the gas atmosphere, e.g., the oxygen potential.

Jan 1, 1998

By D. E. Karvelas

Argonne National Laboratory is conducting research to develop a cost-effective and environmentally acceptable process for the separation of high-value plastics from discarded household appliances. The process under development has separated individual high purity (greater than 99.5%) acrylonitrile-butadiene-styrene (ABS) and high-impact polystyrene (HIPS) from corruningled plastics generated by appliance-shredding and metal-recovery operations. The process consists of size-reduction steps for the commingled plastics, followed by a series of gravity- separation techniques to separate plastic materials of different densities. Individual plastics of similar densities, such as ABS and HIPS, are further separated by using a chemical solution. By controlling the surface tension, the density, and the temperature of the chemical solution, we are able to selectively float/separate plastics that have different surface energies. This separation technique has proven to be highly effective in recovering high-purity plastics materials from discarded household appliances. A conceptual design of a continuous process to recover high-value plastics from discarded appliances is also discussed. In addition to plastics separation research, Argonne National Laboratory is conducting research to develop cost-effective techniques for improving the mechanical properties of plastics recovered from appliances.

Jan 1, 1996

By Feng Liu

A thermal upgrading process by which nickel value can be concentrated in a ferronickel alloy is a possible alternative to treat Sudbury pyrrhotite (Po) tailings with nickel content of 0.5–1.5 wt%. The basis of this process is precipitation of Ni from Po at high temperature once Fe/S ratio in the iron-deficient Po is shifted towards stoichiometric or near stoichiometric FeS (troilite) either by the addition of iron and/or the removal of sulfur. For the iron addition route, the reaction between elemental iron and nickeliferous pyrrhotite to produce ferronickel alloy and Ni-depleted iron sulfide phase plays a critical rule. In this paper, the formation mechanism of ferronickel alloy was investigated using the diffusion couple technique to better understand the nickel diffusion behavior in the iron and sulfide phases.

By J. R. Sarazin

Density driven convection during solidification has been recognized for some time to result in macrosegregation particularly when lower density alloying elements are rejected into the interdendritic liquid. The resulting segregates are commonly referred to as channels, freckles or A-segregates. Buoyancy driven convection leading to channel formation has been examined in three model systems possessing somewhat different materials parameters. They are the Pb-Sn eutectic system, the transparent aqueous-salt NH C1-H 0 4 2 eutectic system and the transparent organic succinonitrile-ethanol monotectic system. Convection in these systems is controlled by a balance of buoyant and viscous forces, which are strong functions of composition and temperature. Composition, temperature and flow velocity were measured and elimination of channels through heavier ternary additions is discussed.

Jan 1, 1991

By Yuchun Wang

In principle, supported liquid membranes could be an exceedingly elegant separation process. However they tend to fail by displacement and emulsification of the organic solution in the pores, which allows mixing of the feed and strip solutions. We have stabilized supported liquid membranes comprising moctylamine in nylon and PVDF supports by covering the pores with semi-permeable polyamide films, using an in-situ polymerization technique. Scanning electron microscopy demonstrates that the polyamide films are sensitive to production conditions and the nature of the support. The transport properties of stabilized supported liquid membranes for Cr(VI) are compared with those of unstabilized membranes.

Jan 1, 1998

By G. Van Weert

The pellet reactor was developed approximately 20 years ago in the Netherlands for softening drinking water. Since then, some 35 plants have been built, ranging in capacity up to 8500 m3/h. Applications now also include removal of phosphates and fluorides and the production of metal carbonates and sulphides from waste streams. The pellet reactor consists of a fluidized bed, wherein the process solution is thoroughly mixed with the precipitation reagent at special inlet nozzles to give over-saturation of the compound to be precipitated. In water softening applications, the compound is CaCO,. In the case of nickel or other metal waste streams, Na2CO3 solution is added in sufficient amounts to precipitate metal (hydroxy) carbonate on the fluid bed particles. These grow typically to dense spheroids, which are removed when they reach 0.8 to 1.0 mm diameter. These spheroids are easily dewatered, free flowing and low dusting. The latter property is becoming an attractive advantage in connection with new plant hygiene regulations. The operation of a 60 cm diameter pellet reactor on nickel containing plating waste is described and the properties of the produced nickel carbonate spheroids are discussed.

Jan 1, 1993

By P. Henry

A novel electrochemical cell has been developed for the recovery of MnO2 from residue of pyrolusite ore leading loaded with Fe, Al Ni, Co and Si impurities, This new process can be considered as an alternative to the traditional methods : S02, H2O2 or bioleaching. It has been observed to proceed fairly rapidly and could prove to be a more economically viable process, as well as being more environmentally acceptable. Electrochemical characterization and kinetic studies have shown that MnO2 is effectively leached by electrogenerated ferrous ions at high current density from a pulp containing less than 5 g8 Fe. The chemical reactions are : Cathode (inox) : 2F23+ + 2e ? 2 Fe2+ Bulk: MnO2 + 2 fe2+ 4H+ ? Mn2+ + 2 Fe3+ + 2 H2O Anode (Pb-Ag) : H2O ? ½ O2 + 2H+ + 2e Global: MnO2 +2H+ Fe2+ = Mn2+ + H2O + 1/2 O2 The catholyte (MnO2 pulp) circulates upward in the expanded mesh cathode separated from the sulfuric acid solution anolyte by a separator which shows high mechanical resistance, low porosity, low potential drop, and reasonable cost. Laboratory and mini-pilot tests have led to the construction of an OT crating pilot plant (100 kg/hr) able to leach more than 95% of Mn, Ni, Co at 1000-1200 A/m2, 50°C with high faradic yield (> 95 %) and low power consumption (3.2 kWh/kg kWh/kg &4D). New applications like the treatment of spent Zn-Mn batteries, polluted soils, spent catalysts and oxide ore (cobalt, nickel) with electrogenerated redox species are now investigated at a laboratory and mini-pilot scale.

Jan 1, 2000

By Edward Rosenberg

The synthesis and characterization of silica polyamine composites modified with a variety of sulfur containing ligands is described. The two most successful ligands in terms of sulfur in-corporation and mercury capture are ethylene sulfide and carbon disulfide. The ethylene sulfide forms either an amino mercaptane or a polysulfide upon reaction with amino groups on the composite. The carbon disulfide undoubtedly forms a dithiocarbamate functional group upon reaction of the amino group under basic conditions. Both materials posses excellent capture kinetics and capacities for mercury, Once captured, the mercury is extremely difficult to remove from the composite materials, even with concentrated acids, and they easily pass the TCLP test. The materials are compared with related thioether modified silica polyamine composites and appropriate potential applications are discussed.

Jan 1, 2003

By José Carlos Abreu

This work presents a kinetics study covering the effects of temperature over the reduction rates of a carbon composite briquette, aiming its use as burden in some of the new alternate ironmaking technologies, such as the Tecnored process. It is reported that increases in the temperature increases the reaction rate. Additionally, the morphology of the iron phase generated during the reduction of these briquettes is presented. It was possible to verify that three types of iron morphology occurred during the process: an external, dense and continuous iron layer, the presence of iron globules at the center of the briquettes and whiskers at the briquette's core. The measurement of the carbon content on the globules and the external iron layer is also presented

Jan 1, 2003

By Chuanfu Zhang, Liwei Liang, Yanxin Wu, Jinliang Wang

"According to the reaction shaft operation characteristics during the flash smelting process, 15 groups of slag samples containing high Fe3O4 were prepared by some chemical reagents, and then the slag viscosities were measured using a RTW-10 type synthetic test instrument for melt physical property by the rotating cylinder method. The effects of Fe/SiO2 ratio (mFe/mSiO2), Fe3O4 content (wFe3O4), Cu2o), MgO content (WMgO) and Cao content (wCaO) on the slag viscosity were also studied. Results show that slag viscosity is decreased with the increase of temperature, mFe/mSiO2, wCu2o, wMgO and wCao, and with the decrease of wFe3O4, under the range of slag contents: mFe/mSiO2 1.36~1.78, wFe3O4 17.83%~21.18%, wCu2o 3.51%~8.34%m wNgI 2.21%~6.57%m w/caI 6.22%~9.387% and temperature range if 1250 o/c~1450 oC. Only wFe3O4m and w/caO have great influence on the slag viscosity when temperatures as high as 1400 oC. Only wFe3O4 and wCaO have great influence on the slag viscosity when temperatures as high as 1400 oC or so. To form a freeze slag with higher viscosity inside the reaction shaft, wFe3O4 should be more than 20% and wCaO should be less then 6%.IntroductionSince its appearance in 1949, Outokumpu flash smelting technology has making continuous innovation and has become the most competitive intensified smelting technology [1], widely considered to be the standard clean smelting process [2]. At present, flash smelting technology is adopted to newly build or reconstruct most of the world's copper or nickel smelting enterprise [3]. Reaction shaft is the most important part of the flash smelting furnace. During the flash smelting process, reaction shaft must be able to withstand the following harsh conditions at the same time: 1) high temperature varying from 1400 °C to 1500 °C. 2) strong oxidative atmosphere containing 50% - 80% oxygen. 3) solid particles and melt with speed up to l00 m/s. 4) high acidic or basic slag with strong chemical corrosiveness. 5) smelting gas containing 50% - 80% SO2. 6) matte with strong dissolution."

Jan 1, 2012

By Marion Dattilo

The search for an improved anode for the electrowinning of lead from fluosi1icic acid medium has led the U.S. Bureau of Mines to investigate composites. Polymer bonded metal oxide powders which may contain catalyst additions were prepared by pressing. These composites display an improved activity toward the oxygen evolution reaction over electrodeposited lead dioxide on titanium, carbon, and nickel substrates. These composite electrodes contain 5 to 10 wt. " binding polymer, with the balance being metal oxides. Lowered anodic potentials achieved using the compnsite anodes resulted in lower levels of lead dioxide deposition during electrowinning.

Jan 1, 1995

By R. Burkhard

Recovery of metals from complex mixed wastes is a challenging task of modem material and waste management strategies. Thermal methods are an important tool in this respect. Plasma turned out to be particularly useful for treatment of complex or toxic wastes and residuals. In order to study plasma processes at reasonable costs, a pilot plasma plant has been used and wastes like ~pent Raney-Nickel catalysts, copper and ah.:lminum drosses, and. other metal containing wastes were investigated. The paper summarizes the most significant findings

Jan 1, 1995

By Tatsuo Itou

Both sales volume of Aluminum Can and its recycling rate are remarkably increasing here in Japan. In 1993, recycled can volume was 11.78 billion cans ( 116,258 metric tons ) and its recycling rate 57.8 percent. We, MITSUBISHI MATERIALS CORPORATION. the leading manufacturer of aluminum can in Japan and our affiliated companies are very deeply involved in recycling used beverage cans ( U.B.C ) and recycling them back to can stock. In this paper. I would like to present the following; 1. Recent trend of beverage can consumption in Japan. 2. Trend of aluminum can and its recycling rate in Japan. 3. Future of aluminum can business in Japan.

Jan 1, 1995

By H. Matsuda, T. Iwashita, H. Awata, H. Liwei, D. Hirabayashi, Y. Saito, S. Ozawa, Y. Goto

"The present study is concerned with investigating the effect of chemical treatment on enhancing the HCl absorption capacities of coal burnt ash and slag. It was found that the HCl absorption capacity of coal burnt ash discharged from fluidized bed combustor was improved by hydration with water and 5% polyethylene glycol solution. This phenomenon was based on an increase of the specific surface area of treated coal burnt ash. The HCl absorption capacity of hydrated ash with polyethylene glycol solution was almost equivalent to that of standard CaO and Ca(OH)2. In particular, the specific surface area of hydrated ash with polyethylene glycol solution was found to be 19 m2/g, which was more than over eight times larger than that of raw sample. Hydrated slag treated with lON sodium hydroxide solution also showed high HCl absorption capacity, with highly improved surface area. It was found that the absorption capacity of slag for HCl depended on the treatment time, showing the maximum absorption capacity for 12 hours of hydration treatment.IntroductionA large amount of coal burnt ash, slag and dust are discharged from such industrial processes as coal combustion and metal refinery etc., and it becomes an serious problem to recover and diminish these solid wastes because of the shortage of dump sites and subsequent metal elution to the environment. Figure 1 shows the present situation of reutilization of coal burnt ash and slag in Japan [1,2]. It is shown in this figure that these solid wastes are recycled as materials in the fields of earthwork, agriculture and forestry etc. A part of these solid wastes, however, is still dumped to landfill. To decrease this dumped amount, the development of environmentally friendly reutilization technique for these solid wastes is of great importance."

Jan 1, 2000

By Yanhui Liu, Xuewei Lv, Chenguang Bai

A thermodynamic model for determining the surface tension of molten slag by considering the surface tension and molar volume of the pure oxide component, and their ionic radii was extended to the slag bearing high TiO2 (varying from 80 to 67%) at 1973 K. The iso-surface tension curves for the FeO-TiO2-Ti2O3 ternary system at 1973 K are almost parallel to the FeOTi2O3 line. TiO2 plays a role of surface-active solute, and its surface-active effect is attenuating with increasing the TiO2 content. The iso-surface tension curve shifts away from the TiO2 corner, indicating that the surface tension of the ternary slag decreases along with the addition of SiO2. The reasons include the addition of SiO2 with lower surface tension and the decrease of the total ion moment at the surface. Both CaO and MgO can bring about that the iso-surface tension curve shifts towards the TiO2 corner, indicating that the surface tension of the ternary slag increases along with the addition of CaO or MgO. CaO has a more pronounced effect on increasing the surface tension of the ternary slag than MgO at an equimolar amount addition. The increase of the surface tension results from both the compositional change and the variation of the slag structure.

Jan 1, 2015

By Valdeci Paula Alvarenga, Sergio Luiz Costa, Itavahn Alves da Silva, Filipe Bueno Carvalho, Varadarajan Seshadri, Carlos Antonio da Silva

Use of fluorspar in steel refining operations is one of the environmental concerns and as such reduced consumption of this material or substitution of the same is one of the objectives. Industrial runs were carried out at Aperam Steel making convertor unit (Timóteo, MG, Brazil) using recycled/briquetted slag for partial or complete substitution of fluorspar. Samples were collected from the metal bath and slag after oxygen blowing to assess dephosphorization with several combinations of recycled/briquetted slag and fluorspar. The results showed that partial substitution of fluorspar by BOF slag briquettes did not affect the efficiency of dephosphorization. In general average Phosphorus content was reduced to 0.010% in the case of partial substitution compared to 0.016% in the regular refining procedure with no substitution. This replacement also resulted in 40% reduction of the fluorspar consumption in the converter

Jan 1, 2015

By Duclerc Fernandes Parra, Luis Filipe Carvalho Pedroso de Lima, Washington Luiz Oliani, Danilo Marin Fermino, Ademar Benevolo Lugao

The modified polypropylene was obtained from isotactic polypropylene (iPP) in spheres by irradiation with gamma rays in the presence of acetylene. A new morphology with distinct rheology is obtained by this process in which occurs: degradation, branching and/or crosslinking. The objective of this study was to investigate the effects of thermal aging on the crystallinity and morphology of the modified polypropylene, High Melt Strength Polypropylene (HMS-PP). The thermal stability was evaluated after aging of samples using a stove at temperature of 90 °C, in presence of air at different periods of time. Aging effects were characterized by: Thermogravimetry analysis (TG), Differential scanning calorimetry (DSC), Infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM). In thermooxidative conditions, the formation of oxidation products essentially involves a hydrogen abstraction by the peroxyl radical, leading to hydroperoxides as primary products and chemical degradation in the immediate crack tips. The effect of thermal degradation (chain scission and oxygen diffusion) on iPP was a more intense crack formation. Surface cracks increased with the aging time. In comparison of iPP, the modified PP samples had a morphological barrier inhibiting the penetration of oxygen into the sample and in consequence limit the propagation of degradation

Jan 1, 2015