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By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (M-f'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By Mike Trovant, Stavros A. Argyropoulos

"A fixed grid numerical model for phase change problems is proposed. The model solves for heat transfer and fluid flow, via the coupled solution of the energy, continuity and momentum equations. In addition, the numerical scheme accounts for temperature varying thermophysical properties and determines the shrinkage profile resulting from phase and density change. Simulations are run to determine the effect of varying model parameters and wall cooling rates on the location and shape of the shrinkage void formation in cylindrical casts. Results are shown for both aluminum and magnesium.IntroductionThe mathematical modeling of phase change processes (be they solidification or melting problems) entails solving for many interrelated phenomena. A comprehensive numerical simulation of the casting of a metal, for example, would have to account for: (a) heat transfer in both the solid and liquid portions of the metal and in the mold, (b) the release of latent heat during phase change, (c) fluid flow behavior in the liquid portion of the metal, (d) temperature induced shrinkage caused by liquid contraction and solidification contraction, and (e) the development of thermal stresses with accompanying shrinkage in the solid portion of the cast and mold. A schematic of the relationships that exist between the coupled equations which govern solidification is shown in Figure 1."

Jan 1, 1994

By P. Myllykoski, J. Nylander

"A commercial program package called Crownoff for the simulation of temper rolling in four high mills has been verified against measured data. The agreement between measured and calculated transversal strain distributions of the strip was found to be good. Effects of the strip crown and work roll bending force on the strain distribution were simulated. The results showed that when a single ground camber of work rolls is used for all strip widths; the strip crown should be parabolic, excluding the edge drop. An increase or decrease of the strip crown by 30 % during a coil can be compensated by a 2 to 5 t change in the work roll bending force. The ability to control the strip crown by work roll bending was insensitive to strip width. IntroductionCold rolled steel strips are usually temper rolled after recrystallization annealing, which follows cold rolling. The purpose of temper rolling is to suppress the yield point, finish the strip surface and correct possible flatness errors. The presence of a yield point might otherwise cause problems during subsequent forming processes. The in homogenous yielding in non-temper rolled steels leads to the formation of Lüders bands in the strip surface.The rolling force is influenced by the rolling speed and changes in frictional conditions in the roll bite. Therefore it is very important to plan carefully the mill settings and control algorithms during rolling. The purpose of mill control algorithms is to ensure constant reduction and the best possible strip flatness during the entire coil.Correctly predicting the rolling force is important for determining the mill presettings. Torque, forward slip and power requirements are not usually critical, if the reductions are small. However, the large elastic deformations occurring in the roll bite make the physical description of the process difficult. Physical rolling models developed for cold rolling contain assumptions that lose their validity as the reductions decrease to the level of one per cent."

Jan 1, 1994

"EAF dust is categorized as a hazardous solid waste. EPA approves only two treatment methods: either sending the dust to zinc recycling facility, or stabilizing it first and then disposing it to a specially-lined landfill. Both treatment methods are costly to EAF steelmakers. In order to reduce the cost and even better to make profit from the dust, EAF steelmakers need to find a costeffective technology to separate zinc from EAF dust. This paper is dedicated to discussion of a novel recycling strategy: in-process separation of zinc from EAF dust. The concept of in-process separation of zinc from EAF dust is first defined, and then a simple Zn concentration model is developed. From this model, two approaches of in-process separation of zinc from EAF dust are derived: (1) prematurely capturing dust at very high temperature when zinc is still in vapor status, (2) prematurely collecting dust immediately after quickly cooling EAF off-gas from high temperature to low temperature. Next, thermodynamic analysis is conducted to understand zinc behavior in EAF off-gas. It is demonstrated in theory that zinc is in vapor status while it exits from electric arc furnaces. At last, recycling routes and economics of in-process separation of zinc from EAF dust are discussed.IntroductionElectric arc furnace (EAF) plays an increasingly important role in steel production. According to USGS, steel production from electric arc furnaces has long exceeded that from basic oxygen furnaces [JJ. In 2009, electric arc furnaces produced 64% of total steel in the United States.Along with the fast growth of EAF steel production, generation of EAF dust is also rapidly increasing. A survey by AIM Market Research showed that 10 - 20 kg EAF dust was generated for every ton of EAF steel produced [2] In 1999, the United States alone produced 770,000 metric tons of EAF dust [3] In Europe, annual generation rate of EAF dust is more than one million tons [4-5]. In Japan, about 450,000 tons of EAF dust is produced each year [6] Globally, total generation of EAF dust was estimated to be more than 5 million tons per year [5] EAF dust is categorized as a hazardous solid waste since it often contains heavy metals, such as lead, chromium and cadmium. US Environmental Protection Agency (EPA) approves only two methods for treating EAF dust: (1) recycling the dust by EAF-dust recyclers, and (2) specially landfilling the dust for disposal after it is chemically stabilized. These two methods of treating EAF dust are both very costly to EAF steelmakers. It was estimated that a fee of $150 to $200 per ton of EAF dust was paid for various treatment options, which added approximately $2 - 3 cost for every ton of liquid steel produced by electric arc furnaces [?J."

Jan 1, 2011

By D. J. Droppert

This paper describes the precipitation-production of crystalline scorodite (FeAs04.2H20) from arsenic-rich sulphate-based metallurgical solutions at ambient pressure (95°C). Arsenic is precipitated by means of a controlled precipitation technique in which the supersaturation of the solution is carefully controlled. By controlling the supersaturation in the presence of seed material. the formation of amorphous ferric arsenate is prevented. Scorodite is known to be the most stable As(V) compound and is therefore preferred as host mineral for arsenic immobilization. The effect of the following parameters on the preCipitation behaviour and kinetics of scorodite are discussed: Type of base seed concentration initial [As]. sulphate concentration. neutralization rate. seed recycling and method of Fe(ll!) addition to Fe-deficient arsenic solutions.

Jan 1, 1996

By S. J. Buckler

Many chemical and metallurgical processes use submerged gas injection to increase contact area between gas and liquid phases in order to promote faster overall reaction or refining rates. The total interfacial area produced by gas injection through lances, nozzles or tuyeres is both an important design parameter for new vessels and a measurement for estimating the maximum processing capacity of existing equipment. Estimating total interfacial area from submerged injection into industrial pyrometallurgical vessels from existing knowledge is a problem with two aspects. The first difficulty is the difference in behaviour of cold (aqueous) and hot (molten metal) systems, implying that existing models and correlations of gas-liquid behaviour developed in low temperature systems are not necessarily appropriate for estimation of high temperature behaviour. The second difficulty is the issue of scale-up of correlations from laboratory to industrial sized vessels. The work presented in this paper is part of an ongoing experimental investigation, at the GK Williams CRC for Extractive Metallurgy, to quantify the total gas-liquid interfacial area available in pyrometallurgical vessels using chemical measurement methods. The effects of three operating variables, injected gas flow rate, nozzle diameter and nozzle submergence, on total interfacial area are quantified in a IOOL aqueous system - the first stage of a three stage process in examining the implications for scale-up of high temperature, medium-scale results are discussed. The results of work at high, injected gas flow rates (up to 500/min) show that the submerged Froude number is not sufficient for use as the sole variable in a predictive model of total interfacial area. Further work is being undertaken to identify other dimensionless variables that will better represent the gas-liquid characteristics in submerged injection that influence the formation of total interfacial area. The second and third stages of the experimental investigation involve measuring the total interfacial area in a large-scale (1000L) aqueous sodium sulphite and small-medium scale molten metal baths.

Jan 1, 2002

By Chonghe Li, Xionggang Lu, Wei Xiao, Xingli Zou, Weizhong Ding

The reduction degree and rate of the initial ilmenite concentrate and pre-oxidation samples by hydrogen were investigated by using thermogravimetric analysis system. H2-TPR was used to detected reduction properties of the pre-oxidation products which were oxidized at different temperatures. The phase transformations and micromorphology changes during pre-oxidation and hydrogen reduction were identified by XRD and SEM. The FeTiO3 was decomposed into TiO2 and Fe2O3 at the temperature below 900 oC. With the temperature rising, Fe2TiO5 was the only stable phase in high temperatures. The reduction of pre-oxidation ilmenite concentrate was faster than the natural sample, which was attributed to the micropores generated on the surface of ilmenite concentrate during oxidation. The main phases of the reduction product were metallic iron, ferrous pseuodbrookite.

Jan 1, 2014

By J. W. Lyman

Nickel-metal hydride (Ni-MH) battery electrodes have been developed as a substitute for cadmium-containing negative electrodes. Use of Ni-MH electrodes offers enhanced electrochemical properties in many instances as well as reduced environmental toxicity. Rechargeable batteries using Ni-MH electrodes are also strong candidates for electric vehicles. During the production and secondary reclamation of these battery types, recycling procedures will be needed to prevent environmental impact caused by these wastes as well as to recover the value inherent in the scrap. The U.S. Bureau of Mines (USBM) is investigating hydrometallurgical technology that separates and recovers purified metallic components from Ni-MH battery scrap of two types, AB, and AB,. An investigation of acid dissolution and metal recovery techniques has determined several processing alternatives that may be used to promote the successful recycling of much of the battery fabrication scrap and eventual secondary scrap. Although recovery techniques have been identified in principal, their applicability to mixed battery waste stream and economic attractiveness remain to be demonstrated.

Jan 1, 1995

By Kirsi M. Riihilahti

The oxidation characteristics of solid copper matte particles under simulated Kennecott-Outokumpu Flash Converting conditions are presented. The effects of feed matte grade, matte particle size, oxygen-to-matte mass ratio, oxygen content of the process gas and temperature on the particle oxidation rate, quality of conversion, particle size change and particle morphology were determined. The converting quality was highest (~68) with the 58% copper matte at 1100°C. At similar conditions, the 72% copper matte was more likely to produce copper oxides and leave unoxidized particles rather than directly produce sulfur dioxide at 1100°C, resulting in an average converting quality of 55. The quality of conversion was poorest for the 72% matte at 920°C (~45); the sulfur removal was extremely low even with a relatively high degree of oxidation. Fragmentation of the particles was significant in all cases with the 72% matte. A higher O2/matte .ratio and higher temperature, in general, resulted in increased fragmentation while oxygen enrichment had no significant effect. With the 58% matte, particle size was found to increase for the finest fractions rather than to decrease due to particle expansion.

Jan 1, 1998

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 Jagdish C. Agarwal

Although copper ranks very low in the order of abundance of elements in the crust of the earth, it has been one of the first metals utilized by mar, at his emergence from the Stone Age, about 10,000 years ago. Use of copper for weapons, tools, utensils and ornaments dates back to the twilight of history, 6,000-5,000 B.C. Native copper outcrops and the malleability of the metal explain its very early use by the cave-dwellers. The working, melting and extraction of copper from its minerals are among the oldest metallurgical achievements of the human race. The oldest complete smelting installations for the extraction of copper from its minerals, dated about the fourth millenium B.C., were recently discovered in the Timna Valley, Wadi Arabah, Israel. (1) The history of the developments of the extractive metallurgy of copper has been adequately reviewed recently. (2,3) The center of copper production migrated from the Eastern Mediterranean to Northern Europe (Mansfeld, Germany, Swansea, Wales) towards the end of the Middle Ages (1500 A.D.). The production of the metal was boosted tremendously in North America since the end of the nineteenth century (Fig. 1).

Jan 1, 1976

By Rolf R. von Oppenfeld

Onsite hazardous waste processors often find obtaining a Treatment Storage and Disposal (TSD) permit one of their first major challenges. Some processors may spend the time and money required by the permitting process, only to find out later that a permit was not necessary. This paper will present and analyze four strategies that processors may use to avoid obtaining a TSD permit. Some facilities will be able to remove their waste streams from RCRA's oversight by ensuring the material is not "hazardous" waste. Parties that treat waste while it is in process may be able to avoid generating "waste" altogether. Certain treatment facilities have been specifically exempted by EPA. Finally, treatment of waste while it is in generator storage tanks may be allowed without a RCRA TSD permit. Hazardous waste point of generation, an important determination relating to these strategies, will also be discussed. Generators and processors will find this paper useful when evaluating their permit exemption potential

Jan 1, 1996

By Filippos Patsiogiannis

Laboratory size (5 kg) aluminum killed low carbon steel melts were desulfurized with synthetic fluxes in zirconia crucibles. The sulfur, oxygen, aluminum, silicon, and manganese contents in the melt were determined as a function of refining time and temperature. With a good argon shield and synthetic flux cover, melt reoxidation was not observed. Sulfur removal followed first order reaction kinetics. The effectiveness of calcia saturated calcium-aluminate (12CaO.7Al2O3) based fluxes in desulfurizing the steel melts was evaluated. The effects of initial sulfur level of the melt, weight of the flux (slag), and additions of tellurium, fluorspar, and barium oxide to the melt on the kinetics of desulfurization were also studied.

Jan 1, 1993

By I. M. Ritchie

Cyanide owes its great success as a lixivant for gold to the great strength of the Au-CN bond. A replacement for cyanide must similarly be a strong complexant for gold (I) or gold (III). The various alternatives are briefly considered and it is concluded that only thiosulfate has a reasonable chance of replacing cyanide as a relatively non-toxic lixivant at the present time. However, there are considerable technical problems to be overcome before thiosulfate can be considered to be a realistic alternative to cyanide. Firstly, the leaching of gold using aerated ammoniacal thiosulfate with copper as a catalyst is a complex process which needs to be understood and controlled carefully in order to achieve maximum recoveries with minimum reagent losses. Secondly, there needs to be an option similar to the CIP process for recovering and concentrating the dissolved gold thiosulfate complex from pulps produced in the processing of low grade gold ores. The prospects for overcoming these technical' challenges are evaluated and discussed.

Jan 1, 1998

By Fathi Habashi

The recovery of uranium from wet process phosphoric acid was applied on industrial scale in the 1940's by using octylpyrophosphoric acid as an extractant. Later, more efficient reagents were used, e.g., di(2-ethylhexyl) phosphoric acid and actylphenyl phosphoric acid. In the 1970's the rare earths in Kola phosphate were recovered in Finland and recently (1997) in Norway using HNO, as a leaching agent and di(2-ethylhexyl) phosphoric acid as solvent. It was demonstrated later on laboratory scale that both uranium and rare earths could be extracted from the rock by tributyl phosphate but at different pH values provided that the rock is leached with nitric or hydrochloric acids instead of the commonly used sulfuric. This new concept opens the way to the possibility of treating phosphate rock by in-situ, dump, or vat leaching for the recovery of phosphate values as well as uranium and the rare earths. Another solvent extraction process is used industrially for the purification of phosphoric acid using butyl and amyl alcohols.

Jan 1, 1998

By Basant L. Tiwari

An electrolytic process, based on a three-layer concentration cell, to extract magnesium from commercial aluminum alloy scrap has been examined. The process was repeatedly tested at 1025 K with two cells of d1fferent sizes, 0.6 kg and 5 kg feed aluminum, to have a better understanding of the opera ting parameters and evaluate the scale-up potential. In both cells, the magnesium content of the scrap was selectively reduced ?from 1. 1 to less than 0.1 wt.% at anodic current dens-Hy as high as 1. 1 A/cm2 with current efficiency exceeding 85%. Magnesium was recovered in the form of salt coated globules. Comparison of performances for the two cells suggests that the process can be scaled up. With further development, this process could become a viable alternative for demagging secondary aluminum.

Jan 1, 1985

By Kathryn C. Sole

A novel solvent-extraction process for the refining of gold was recently commercialised, with the commissioning in May 1997 of a 24 t a-' refinery at Harmony Gold Mine in Virginia, South Africa. The MinataurTM Process (Mintek Alternative Technology for Au Refining) uses solvent-extraction technology to produce gold of 99.99% purity from the cathode sludge arising from a conventional carbon-in-pulp / electrowinning circuit. Implementation of this process introduces significant cost benefits compared with the conventional dore smelting / toll-refining route previously followed. This paper outlines the process, presents selected operating results obtained during the first few months of operation, and provides some details of the associated techno-economic advantages.

Jan 1, 1998

By A. A. el-Geassy

High-grade iron ore fines rejected from the DRl plants (>96%Fe20) were isothermally reduced in 30-60%COIH2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either H2/CO or H2/CO/S mixtures at 823-1073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduction mechanism, The influence of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization reaction under the different experimental conditions.

Jan 1, 2003

By R. E. Sundell, S. M. Correa

"A mathematical model is developed for the fluid flow in tungsten-inert gas weld pools. The fluid is taken to be incompressible, viscous, electrically conducting, and confined within a pool of specified shape. The flow is driven by surface-tension gradient (thermocapillary), electromagnetic, and buoyancy forces generally in this order of importance. Analysis indicates that the electromagnetic field may be calculated a priori and so decoupled from the nonlinear fluid mechanics and heat-transfer problem. The resulting set of equations is solved numerically by a line relaxation process. Computational errors caused by truncation in finite-difference schemes and by inadequate grid distributions are considered. The model is used to study several cases of differing heat and current input to the pool with and without surfactant-induced thermocapillary forces. The principal conclusions are that the thermocapillary flow, when present, is dominant with surface velocities on the order of 1 m/s. The heat transfer, as deduced from isotherms within the pool, is crucially dependent on the flow. Also, flow velocities and weld-pool surface temperatures were measuredand agree well with the model.2. IntroductionThe requirements of improved control and of automation in the TIG (tungsten-inert gas) welding process have led to the development of mathematical models for the heat transfer to the workpiece. It is now widely recognized that the fluid flow in weld pools sufficiently distorts the conduction heat transfer pattern to warrant inclusion in a process model. The experiments of Woods and Milner (1), among others, demonstrated that TIG weld pools could be driven by the electromagnetic J x B body forces present, J being the current distribution and B the induced magnetic field. Atthey (2) calculated that in typical pools the buoyancy force was about an order of magnitude less important - despite the large temperature gradients present - and neglected it in a computational study of the magnetohydrodynamic (MHD) flow. This work also reviewed many earlier studies of MHD flow caused by a source of current at a fluid surface, including analytical studies by Shercliffe (3), Sozou (4), and Sozou and Pickering (5), and a numerical study by Andrews and Craine (6). These works establish the importance of the electromagnetic force in the weld-pool flow."

Jan 1, 1986

By Xun An

Slag from an electric slag cleaning furnace was injected with methane and air mixtures to facilitate the recovery of copper and cobalt. The effects of methane-to-air ratio, gas flow rate and temperature on the reduction and metal separation were investigated. The results showed that over 90 percent copper and up to 60 percent cobalt could be recovered from the slag with a gas utilisation of around 70 percent, as calculated by thermodynamic simulation. Methane-to- air ratio was a major factor affecting the rate of reduction under the present experimental conditions. Further, injection of gaseous reductants greatly enhanced the coalescence and settling of entrained metal droplets. A reduction mechanism is proposed and the factors influencing the coalescence of copper droplets are discussed.

Jan 1, 1998