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By W. R. Opie

Fundamentals of blast furnace smelting of low grade copper and precious metal scrap and residues are reviewed with emphasis on emission control, by-products produced, slag cleaning for high recovery of metal values and the evolution of an off-gas system to eliminate hydrocarbons that result from decomposition of plastics in the blast furnace- charge. Problems with tin, antimony and nickel in the smelter-refining cycle are discussed.

Jan 1, 1985

By Wei-ling Wang, Ryosuke O. Suzuki, Xiang-ning Meng, Miao-yong Zhu

"A finite-element thermal-stress model of continuous casting mold is conducted to predict deformation of copper plates and its change with different cooling structure. The results show that deformation behavior of copper plates is mainly governed by cooling structure and thermal- mechanical conditions, deformation amount is related to structure geometry, and a small deformation mutation occurs in cooper-nickel boundary due to different properties. The maximum deformation of hot surface centricities of wide face locate at 100 mm below meniscus and that of narrow face locate at meniscus and terminal of water slots and significant curvature fluctuations on both sides of copper-nickel boundary. The maximum deformation of centricities is increased up to 0.05 mm with thickness increment 5 mm of copper plates, and maximum deformations are only depressed 0.01 mm and 0.02 mm with increments of 1 mm nickel layer thickness and 2 mm water slot depth respectively.IntroductionIn conventional continuous casting of steel, a large amount of sensible and latent heat of molten steel dissipate in primary cooling zone and make continuous casting mold under enormous heating load giving rise to thermal stress, deformation, high-temperature fatigue and creep not only depress mold life-span, but reduce casting stability [1] Many studies focused more on heat transfer, solidification and shrinkage of solidifying shell to provide inverse proposals for optimizing cooling system and even designing new taper of mold [2,3], but it is generally useless to those of having been manufactured or being put into production. Therefore, mold-related forward problems show necessity to be discussed deeply, and stress and deformation distributions based on special thermal conditions in mold should be analyzed in order to explore suitable cooling structure of mold directly. Samarasekera et al. [4] examined heat flow and distortion of two-dimensional longitudinal sections and investigated effect of cooling water velocity, copper plates thickness and carbon content on formation of rhomboidity and longitudinal comer cracks. O'Connor et al. [5] developed a three-dimensional mathematical model to compute thermo-mechanical state in thin-slab mold and calculated temperature and deformation of mold wall to assess roles of various process parameters on impacting mold life. Thomas et al. [6] predicted temperature, distortion and residual stress in mold and indicated increased distortion requires increased remachining, which reduces mold life and increased residual stress increases the probability of a catastrophic crack failure. Park et al. [7l determined heat-flux profiles in funnel-shaped and parallel thin-slab molds based on an inverse heat conduction model and thermocouple temperature measured in-plant and put them into three- dimensional finite-element thermal-stress model to predict temperature, distortion and residual stress of mold wall. Korie et al. [SJ focused on prediction of temperature, distortion and residual stress in mold and in particular to clarify that mold life is significantly affected by temperature and its rigidity, but little effect by mechanical including clamping force, bolt prestress, friction and ferrostatic pressure. Meng et al. [9l predicted temperature and thermal stress in a slab mold and analyzed effect by cooling system geometry and casting speed quantitatively. In present study, a three-dimensional finite-element thermo-mechanical model with type-switched element is transformed from previous heat-transfer finite-element model [9l, and mold deformation is simulated in order to shed light on thermo-mechanical behavior with special thermal conditions and different mold geometry at high casting speed."

Jan 1, 2013

By Barry Welch, Kai Grjotheim

"The capital intensive nature of the present process for aluminium smelting, the low productivity per unit reactor, and pressure to reduce the electdcal energy demand have motivated the search for an alternative process. Optional routes include carbo-thennal reduction of alumina (using an alloy phase immediate), chlorination followed by electrolysis of aluminium chloride, and electrolytic decomposition of alumina using inert electrodes. Materials performance and reactor design constraints have been a major limitation for alternatives. However parallel research has led to considerable advances in the process efficiencies and scale of both the Bayer process and the Hall-Heroult cells.Future development of alternatives is dependent on breakthroughs in Materials Science such as the development of stable conducting anodes and stable wettable cathode materials. However if successful it is probable that some spin-offs will be retrofitted to existing cells. Therefore the basic Hall-Heroult technology will continue as the dominant process for at least the next half century.IntroductionThe present Bayer/Hall-Heroult process for production of aluminium is just over 100 years old. Frequently, during the century of its technological development questions have been raised as to whether it is the ideal route for metal production. The questioning was particularly intense in the period between the mid-1950s and the mid-1060s when the limitations of the Hall-Heroult electrolytic stage were evident. Then the cells were only 30 to 35 % efficient with respect to the utilisation of the hydro-electricity (requiring 16 18 kWh/kg, thus making it strongly dependent on cheap electrical energy), while the size of cells being installed were 80 to 130 kA. Hence the process was capital intensive, the productivity per reactor volume low, and the process was labour intensive (requiring about 15 man hours per tonne of aluminium). In addition, the use of pitches for Soderberg anodes and the fluoride electrolyte were creating problems through emission. At that time material science had paid little attention to the manufacture and use of carbonaceous materials or the development of alternatives that were corrosion resistant to cryolite or liquid aluminium. Hence cell lives were short - typically 600 to 1000 days - thus adding to operating costs. Thus the grass over the fence, as foreseen in 1960s vintage crystal balls appeared much greener for alternative processes."

Jan 1, 1988

By George P. Demopoulos

n this study we have sought to highlight the critical linkage between individual reaction kinetic parameters (usually determined in small bench scale experiments) and large continuous reactor performance by focusing on the industrially significant zinc pressure leach process. To this end a comprehensive mathematical model previously developed for the description of this process was employed. In this paper we have examined in particular how small variations in key kinetic parameters impact on the autoclave&apos;s performance, i.e. attainment of autogenous steady-state temperature, zinc conversion and solution chemistry. The reaction parameters studied were: (i) stoichiometry of the marmatite leaching reaction; (ii) the activation energy of the same reaction, E,; (iii) the rate constant of the ferrous to ferric oxidation reaction, k,; and (iv) the apparent equilibrium constant for ferric precipitation, K,. This parameter sensitivity analysis was done under no oxygen mass transfer control limitations. Model predictions were found to be more sensitive to the kinetic parameters under certain conditions than others. The most dramatic finding was the one related to the small amount of sulfate produced during marmatite leaching. In connection to this it was found that the small percentage (< 5 %) of sulfate produced enhances the autothermal operational stability of the autoclave. The need for accurate kinetic parameter determination under conditions similar to those encountered in industrial zinc pressure leaching was demonstrated.

Jan 1, 1999

By Bora Derin, Sertac Yazici, M. Seref Sonmez

"In this study, the recycling conditions of waste liquor obtained after the production of tungsten boride powder from calcium tungstate by self-propagating high temperature synthesis (SHS) and the following hydrochloric acid leaching were investigated in detail. Environmentally unfriendly and extremely acidic (pH~ -0.3) liquor consisting of calcium, magnesium, and boron ions was treated with 1 M sodium carbonate solution to precipitate magnesium carbonate and calcium carbonate phases. The obtained amorphous precipitates were heated up to the temperature of 400°C for re-crystallization. As a result, MgO, CaC03 and CaMg(C03)z phases were obtained, while sodium, boron, chlorine ions were remain in the solution. The present study is still in progress.IntroductionSelf-propagating high temperature synthesis (SHS) is one of the techniques used in the production of a variety of advanced ceramics, inter-metallic, organic and inorganic compounds, oxygen free single crystals, and polymers [ 1, 2]. The reaction becomes selfsustaining and propagates in the reactant mixture, after initiation in SHS process. SHS products may contain the mixture of several unwanted compounds and elements. Therefore following acidic leaching process may be needed to purify the target product. In the previous study, calcium tungstate (Ca W04), magnesium (Mg) and boric acid (B20 3) mixture were reacted to produce tungsten boride powder by SHS process according to the Reaction 1. Then, magnesium and calcium containing byproducts (i.e. MgO, Mg3B206 and Ca3B206) found in the SHS product were leached out by using concentrated hydrochloric acid (HCl) solution to obtain pure tungsten boride powder [3].Ca W04 + 0.5B203 + 4.5Mg = WB + 4.5Mg0 + Cao (1)After the leaching, filtrate solution consisting of different amounts of magnesium, calcium, and boron requires additional treatment for the environmentally acceptable disposal.Several works were carried out about magnesium precipitation conditions and kinetics from brines. Rabadzhieva et al. investigated the precipitation of Mg(OH)z from brines by using NaOH as well as caustic soda [ 4]. Turek ve Gnot investigated the precipitation efficiency of Mg(OH)z for the temperature range between 10-40°C, while the reaction was kinetically experimented by Alamdiri et al [5, 6]. Homogeneous precipitation of nesquehonite (MgC03.3H20) by the reaction of MgCli with (NH4)2C03 in supersaturated solutions and factors that influence the precipitation of MgC03.3H20, such as reaction temperature, initial concentration, stirring speed, titration speed, equilibration time, have been studied by Wang et al [7]. The precipitation of Mg(OH)z by calcium hydroxide from aqueous solutions was studied by Baird et al. [8]. Stratful et al. focused on conditions influencing the precipitation of magnesium ammonium phosphate from wastewaters [9]. 1031"

Jan 1, 2011

By C. M. Iheagwara

This paper has addressed the issues that constitute major obstacles to the cost- effective and efficient operation of metallurgical vessels from the refractory standpoint. Refractories generally withstand severe conditions of high temperature reactions as well as physical loading/impingement and hence degenerate and need replacement. Scarcity of some refractory materials especially high alumina and magnesite ores in some places, the prohibitive cost and the frequency of replacement of damaged refractories threaten the continued support for metallurgical operations. Some of the causes, prevention and cure for refractory wear have been discussed and rational strategies (short and long term) have been recommended which if implemented should go a long way towards arresting the perennial problems they portend.

Jan 1, 1991

By M. Bhattacharya, A. Dutta, P. Barat

"Pinning of dislocations at nanosized obstacles like precipitates, voids and bubbles, is a crucial mechanism in the context of phenomena like hardening and creep. The interaction between such an obstacle and a dislocation is often explored at fundamental level by means of analytical tools, atomistic simulations and finite element methods. Nevertheless, such studies fail to predict the effect on the overall plasticity on account of insufficient information about the underlying statistics of this process comprising a large number of dislocations and obstacles in a system. Here we propose a new statistical approach, where the statistics of pinning at idealized spherical obstacles is explored by taking into account the generalized size distribution of the obstacle along with the dislocation density within a three-dimensional framework. The application of this approach has been demonstrated for dislocation pinning at nanovoids in neutron irradiated type 316-stainless steel.IntroductionPresence of nanoscale obstacles like precipitates, voids and bubbles play a crucial role in determining the deformation behavior of a crystalline solid on account of the interactions between the line defects and such localized obstacles. In the context of the glide motion of dislocations, the obstacles can offer resistance to a moving dislocation, thereby causing a hardening effect [l-3]. In some other cases, inclusions like voids and bubbles can affect the rate of dislocation climb through diffusive [4] and non-diffusive [5] mechanisms. Over the last few decades, numerous studies have been performed to gain an insight of the dislocation-obstacle interactions at a fundamental level. These include the interactions responsible for the hardening effect, in addition to those pertaining to the non-conservative motion of dislocations.Although the elementary mechanisms of the various dislocation-obstacle interactions have been vastly explored and understood by means of analytical theory and numerical simulations, it remains difficult to quantitatively understand their effects on the macroscopic deformation behavior. This is due to the fact that their influence on the gross plastic deformation of a bulk sample would be the collective outcome of a large ensemble of such interactions. As a result, it becomes infeasible to predict the bulk deformation behavior of a material until the statistics of pinning of the dislocations at the localized obstacles is available. In the context of precipitate hardening, some well known attempts to extract the pinning-statistics were made by Friedel-Fleischer [6] and Mott [7] by analytical means, which were later tested through simplified 2-dimensional in-silica modeling [8]."

Jan 1, 2014

By Zhijing Zhang

Long-term thermal stability of ionic liquids is essential for reliable performance of ionic liquids in any engineering applications. TGA studies were carried out on a series of ionic liquids with different cations and anions such as 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), 1-hexyl-3-methylimidazolium chloride ([C6mim]Cl), 1-hexyl-3¬methylimidazolium tetrafluoborate ([C6mim]BF4), 1-hexyl-3-methylimidazolium hexafluorophosphate ([C6mim]PF6), 1-octyl-3-methylimidazolium hexafluorophosphate ([Csmim]PF6), and 1-butyl-3-methylimidazolium bis(trifluromethanesulflonyl)imide ([C4mim][Tf2N]). The short-term thermal stability of ionic liquids was evaluated by measuring the onset temperature of decomposition of ionic liquids, and the long-term thermal stability of ionic liquids was also evaluated by weight loss of ionic liquids over a long period of time at various temperatures. The experimental results showed that the long-term thermal stability of ionic liquids decreased with increasing temperature and was significantly lower than the onset temperature of decomposition of ionic liquids.

Jan 1, 2002

By M. S. Lee

A cold model study on the effects of various operating conditions on the dispersed-phase holdup in a liquid-liquid emulsion generated by bottom gas injection has been performed using water and kerosene. Dimensional analysis was used to correlate the holdup with the operating conditions and the sampling locations. The holdup increased with gas velocity, and decreased with axial and radial distances. The radial distribution of holdup follows a Gaussian function. The holdup increased with increasing ratio of the heavy phase to light phase volumes and decreased with the total height of the heavy phase. The combined effects of various operating conditions can be represented by the Froude number. The variation of the holdup within the plume was correlated by a single equation involving a set of dimensionless numbers.

Jan 1, 1995

By R. P. King

The linear intercept distributions provide unambiguous and accurate characterizations of the texture of mineralogical materials. The relation between the measured linear intercept distributions and the spatial correlation function is shown to be given by: in the Laplace Transform domain. The linear intercept distributions of the two phases in a low- grade chromite-serpentinite ore were measured. and the spatial correlation functions for both phases were evaluated using the above relation. The correlation functions are the primary relations for integral geometric models of mineralogical texture and this work demonstrates the relation between the 10 stereological model and the 3D integral geometry model for mineral liberation.

Jan 1, 1991

By Edgar Peek

Lixiviant regeneration is by definition a precondition for any hydrometallurgical process. In chloride hydrometallurgy either HCl or Cl2 has to be regenerated in order to establish an economically viable metallurgical process. One such regeneration process is widely used with steel pickling where HC1 is regenerated through the thermal decomposition of ferrous chloride in either spray roasters or fluid bed pyrohydrolyzers. This standard HC1 regeneration process deserves to be considered as a potential separation process, since thermodynamic calculations show that a fluid bed pyrohydrolyzer can function as a ferrous-nonferrous separator. Several nonferrous,metals such as zinc, lead and cadmium can be volatilized as a chloride under ferrous chloride pyrohydrolysis conditions. If such a nonferrous metal volatilization could be achieved in the case of slurry feeding of "contaminated" iron oxides, then this would increase the Fe/H2O ratio of the (process) feed and thus save on fuel per ton of iron, while yielding a marketable iron oxide product. Previous test work on synthetic materials revealed that the near-complete separation of zinc, lead and cadmium from iron oxide was possible in a pyrohydrolytic atmosphere, even if zinc was present as zinc ferrite (more than 99.5%). This investigation, which was carried out in a tube furnace at 1100 K has now been extended to treat synthetic zinc minerals and also franklinite ore. For the latter, it was found that 85% zinc volatilization could be achieved in 4 hours at 1300 K. It is postulated that complete zinc volatilization could not be attained due to the formation and/or presence of gahnite and hardystonite, which might be stable in HCl/H2O atmospheres at 1100 K. The effect of adding small amounts of calcium chloride to react with gahnite and hardystonite to give zinc chloride and both calcium aluminates and silicates is being discussed. Test work on slurry feeding of this complex ore in a recently constructed 4-inch diameter fluid bed pilot unit has been planned for the near future.

Jan 1, 1995

By Kimio Itagaki

"As a contribution to understand the smelting of copper or nickel matte by blowing oxygen or oxygen-enriched air, the phase equilibrium and the distribution of minor elements between the iron-silicate based slag and the Cu2S-FeS or Ni3S2-FeS matte at 1573K were investigated in a magnesia crucible under controlled partial pressures of SO2 at 0.1, 0.5 and 1.atm. At a given matte grade, the solubility of copper in the slag was found to be independent of p5O2 while that of nickel was dependent on pSO2 and these behaviors were analysed thermodynainically based on a concept of oxidic and sulfidic dissolution of the components in the slag. When the matte grade was specified, the distribution ratios of X, defined as (wt pct X in slag)/(wt pct X in matte}, for As, Sb and Bi increased with increasing p5O2 while that for Ag was constant against p5O2.IntroductionA combination of intensive reactors with the use of oxygen or oxygen-.enriched air as the blowing gas has provided a number of improved copper and nickel smelting processes such as INCO-Flash, Outokumpu-Flash, Mitsubishi-Continuous and IBRC (top blown rotary converter) processes. Phase equilibrium and thermodynamic studies for the slag and the copper matte or the nickel matte under high partial pressure of SO2 are of practical importance for evaluating the behaviours of the related components in the oxygen-smelting.A series of experimental studies have been already conducted in a limited range of conditions for Pso2 around 0.1 atm, which corresponds to the smelting with air-Stowing [1-5]. However, there remain very few data on the phase equilibrium in the matteslag systems under higher partial pressures of SO2. Tavera and Davenport studied the phase equilibrium between the copper matte and fayalite slag phases under the partial pressure of SO2 controlled at 0.1 - 1 atrn but without controlling the partial pressures of sulfur and oxygen [6]. A potential diagram for the Cu-Fe-S-O-SiO2 system at 1523 - 1573K suggests that the partial pressure of S2 equilibrated with the matte and the fayalite slag with saturated SiO2 under the high SO2 pressure is considerably high at 10-4 - 10-2 atrn [7]. This condition must require controlling of p52 as well as Pso2, in the equilibrium experiments, otherwise, the equilibrium condition may be hardly attained due to the continuous flushing of sulfur from the system."

Jan 1, 2000

By C. J. Boreiko

Traditional patterns of lead and zinc utilization are being evaluated in accordance with new paradigms that seek to ensure the long-term compatibility of global industrial activity with precepts of sustainable development and sustainable consumption. As a consequence, both industry sectors are experiencing intense scrutiny from the international community, and numerous regulatory options are being considered that may impact upon international industry practice. This paper reviews the growing expectations being placed upon industry, and highlights some of the common regulatory concerns being expressed regarding both metals despite their differing toxicological profiles.

Jan 1, 2000

By Philippe Henry

"Hydrometal provides an adequate technology to reintroduce otherwise lost metal units into the industrial cycle, thereby saving resources and energy, while keeping the environment cleaner. Two case studies at an integrated hydrometallurgical recycling facility (Hydrométal) in Belgium are discussed: (I) Residual low quality acid and caustic are used in the processing of zinc industry cements to produce copper, nickel, cobalt and zinc concentrates by several consecutive selective leach - precipitation processes.(II) Copper anode slimes are treated and their precious metal contents are recovered. Depending on the composition of the slimes, separate or combined concentrates of copper, bismuth, tellurium/selenium and silver/precious metals can be produced."

Jan 1, 2008

By John O. Marsden

The past fifteen years have seen a number of important developments in copper hydrometallurgy, including the commercial application of biological heap leaching of secondary (chalcocite-dominant) copper ores, the commercial demonstration of chalcopyrite concentrate leaching technology using pressure leaching and biological processes, and the application of novel configurations of solution extraction circuits. Significant emphasis is now being placed on the development of effective stockpile leaching practices for primary ores (chalcopyrite and bornite-dominant mineralization). Some of these developments have been highly successful, and will pave the way for further development and commercialization. Others have been less successful. These developments are reviewed in the context of the metal price cycle and trends for the future are identified.

Jan 1, 2006

By Gerson de Araújo Filho

This paper shows the use of tires as fuel to be employed into blast furnaces. The tires can substitute coal or even charcoal in the blast furnaces tuyeres. The injection into tuyeres, besides the contribution for energy generation, can also produce gas for iron oxide reduction. The tires, as powder to be injected into blast furnaces, contributes for an environmental use of this waste, which helps to obtain a high value product as well. So, the advantage of using such material is that it is waste and has lower cost for preparation. The obtained results showed that the tires have good combustibility. This one was obtained in a model that simulates the same conditions occurring in the blast furnaces tuyeres; these used raw materiais include tires and mixtures of tires with coal or even with charcoal.

Jan 1, 2006

By Li Qihou

Mono-disperse ZnS and CdS nano-particles were prepared by the homogenous precipitation method and the effects of SO42-,NO3- and Cl-ions on crystalline of particles were investigated experimentally. The results showed that these anions had no influence on the crystalline of ZnS, but different crystalline CdS ultrafine particles were produced in different anion systems, where the blend-type CdS was obtained from natrate or sulphate solution, and wurtzite-type CdS from chloride solution. It was ascribed to the coordination of Cl- and Cd2+ that altered the supersaturation of precipitate ions in the solution, the existing growth units and their connecting patterns, thereby producing wurtzite-type CdS with a more stable structure.

Jan 1, 2006

By Bryn Harris

Much has been written over the past twenty years on the removal and chemical stabilization of arsenic from metallurgical process solutions. This paper reviews again the latest developments in this field, and concludes as before that the high-iron arsenical ferrihydrites, together with the high temperature arsenic minerals, scorodite and Type II, remain as the best and most viable vehicles for industrial control and disposal. However, a cautionary note is introduced, in that chemical environments cannot be considered in isolation, and that cogniscence has to be taken of microbiological activity in determining the disposal method. Data are also presented on a survey of industrial practice, which shows that arsenical ferrihydrite is by far the most widely-practiced and accepted method used worldwide. Finally, the disaster in Bangladesh is briefly discussed with reference to lessons that the metallurgical community might learn from this.

Jan 1, 2003

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

By R. Cheng

The kinetics of the solvent extraction of ythium from HCl solution with mono-2-ethyl hexyl phosphonic acid mono-2-ethyl hexyl ester (HEHEHP) have been studied using a rotating diffusion cell (RDC). The effects of rotation speed, pH, ymium and extractant concentrations and temperature on the rate of extraction were examined. The rate of extraction of ythium appears to be controlled by an interfacial reaction of metal ion and extractant. The concentration of the latter is determined mainly by diffusion through the membrane. The contributions of the rates of diffusion in the diffusion layer, diffusion in the membrane and chemical reaction at the interface to the overall rate have been calculated on the basis of a kinetic model.

Jan 1, 1992