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By B. Mishra, W. A. Averill

"The application of various hydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, ego metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been investigated and suggested for dealing with some of these wastes and scrap material.The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EM] and decontamination and decommissioning [D&D].IntroductionThe high temperature carbothermic or metallothermic smelting reduction methods for metal production are associated with the generation of significant quantity of waste as slags, flue dusts, sludges, residues, effluent salts etc. Certain hydrometallurgical processes also generate lots of aqueous waste due to the inherent nature of the technique. Also, the gas-based reduction processes are not applicable to many stable metal compounds, such as alumina, titania, beryllia, lanthanide and actinide oxides, etc. due to thermodynamic considerations. All these methods cause substantial environmental hazard. There is a need to develop alternative processes which have low waste or ideally a ""zero-waste"" generation.Pyrochemical processes using molten salts provide a unique opportunity for the extraction and refining of many reactive and valuable metals either directly from the beneficiated ore (aluminum, beryllium, neodymium, plutonium, uranium, etc.) or from other process effluent that contain reactive metal compounds. The processes reduce metal compounds electrolytically (A12O 3 and BeCI2) on a carbon anode or by calciothermic reduction (Po, Nd). The by-product, in the latter case, is a calcium oxide saturated halide salt. The waste-treatment to recycle the halide has to be done as a separate step or stored as a contaminated waste. A successful separation technology can provide a new insight to the waste minimization strategy for the nuclear industry."

Jan 1, 1996

By M. T. Thomas

Sufficient development of the X-Ray Photoelectron Spectroscopy (XPS), the Auger Electron Spectroscopy (AES), and the Secondary Ion Mass pectroscopy (SIMS) has made these instruments ideal for solving problems related to mineral processing -particularly gold ore processing. XPS can determine both the surface composition and chemistry of ores and tailings, and the various phases within either of them. AES can also determine surface composition with the further advantage of having greater spatial resolution so the surface chemistry associated with specific minerals in the ore can be identified. This identification helps to clarify why some minerals pass through a chemical process unaffected, while others can be successfully treated. SIMS has an elemental sensitivity from one to four orders of magnitude greater than XPS or AES which makes it useful for detecting the presence of some elements in very low concentration (parts per million).

Jan 1, 1981

By C. A. Young, J. D. Miller

Adsorption isotherms previously determined by in-situ Fourier transform infrared/internal reflection spectroscopy (FT-IR/IRS) for oleate adsorption at calcite and fluorite surfaces near pH 9 and at various temperatures are compared. Results indicate that, at both mineral surfaces, chemisorption occurs at equilibrium concentrations below approximately l x l0-5 M oleate while calcium dioleate surface precipitation occurs at higher equilibrium oleate concentrations. The extent of chemisorption at the calcite surface is 3 to 5 times less than that at the fluorite surface while the extent of calcium dioleate surface precipitation on calcite is nearly a magnitude larger than that on fluorite. However, for both minerals, surface precipitation decreases with increasing chemisorption. Contact angle measurements and flotation recoveries show the hydrophobicity of fluorite to be greater than that of calcite at each of the temperatures and oleate concentrations studied. Significant differences are noted only in the chemisorption region. Unlike calcite, the hydrophobicity of fluorite was sensitive to the presence of oxygen in the system. Multichannel Laser Raman Spectroscopy (MLRS) showed this behavior was caused by the double-bond reactivity of adjacent chemisorbed oleate molecules and subsequent formation of an epoxide/polyether complex at the fluorite surface. Such a reaction product could not be detected at the calcite surface. These differences in adsorption density, hydrophobicity, and polymerization behavior are discussed in terms of the intrinsic surface properties of the minerals.

Jan 1, 1999

By Robert D. Rogers

The demand for phosphate will continue into the future, because phosphate is currently irreplaceable as a plant nutrient and in many chemical applications. Phosphate is not recycled, so the supply must be replenished through a process of mining and purification. Numerous microbial isolates. obtained from the environment were screened find those which demonstrated the greatest promise of solubilizing PO4 from the ore of interest. Screening was accomplished in a step wise manner an agar plate bioassay, shake flask studies, and semi continuous growth conditions. It was found that with the proper conditions of nutrient supply and solution pH; the bacteria and. fungus used in the semicontinuous process were able to solubilize in excess of 80% of an Idaho rock phosphate ore (RP) within nine days. A significant amount of solubilization occurred within the first six days. There was a 'reasonable correlation between the occurrence of soluble Ca and PO.4 during the processing of the RP thus providing evidence that the RP was being disintegrated by the organisms. In all cases, HPLC analysis of the solutions in which PO4 had been. extracted from RP showed that organic acids, which have been implicated as the mechanism of solubilization, were present.

Jan 1, 1991

By Du Sichen, S. Seetharaman, A. Jakobsson

"In the Present paper, the principles of oxygen potential measurements have been discussed along with the design details for oxygen sensors that are used in copper industry. A description of some of commercial probes is presented along with their salient features. The application of these sensors in flash smelting, converter and casting sections of copper production are discussed along with their implications on process optimization.I. IntroductionThe high temperature galvanic cells have come into prominence on account of their numerous applications in both fundamental as well as applied measurements. Since the inception of the oxygen-ion conducting electrolytes like ZrOrCaO·by Kiukkola and Wagner [1], the oxygen concentration cells have been extensively used in laboratories as well as in industries. In metal-production technology, these cells have been used to monitor the oxygen potentials in metallic, slag as well as gas phases and also to control and styr metallurgical processes. The pioneer among the various industrial users of such cells is the copper industry. To-day, high temperature solid electrolyte cells involving oxygen ion conducting electrolytes have become an integral part of copper pyro-refining and continuous casting. In the present paper some of the applications according to the industrial processes are described including the developments that are going on in the European scene."

Jan 1, 1997

By R. J. Kuczynski

The U.S. Bureau of Mines Reno Research Center operated a batch pilot plant to demonstrate high-temperature cyanide leaching for recovering platinum group metals (PGM) from automobile catalysts. Approximately 1,600 kg of used pellet, monolith, and metal support catalyst containing 1,680 g (54 tr oz) of PGM were processed. Forty-five-kilogram batches of used catalyst were leached with sodium cyanide solution at 160° C for 1 h under basic conditions in a countercurrent processing sequence to dissolve the PGM. Extractions from the used pellet catalyst ranged from 94 to 95 pct for Pd, 95 to 97 pct for Pt, and 64 to 81 pct for Rh. Extractions from the used monolith catalyst ranged from 7B to BB pct for Pd, 75 to 90 pct for Pt, and 43 to 71 pct for Rh. Heating the pregnant leach solutions to 275' C for 4 h destroyed the PGM-cyanide complexes, resulting in over 99.7 pct of the PGM precipitating from solution. The PGM precipitate was predominantly a powder metallic concentrate, typically analyzing greater than 50 pct PGM. Heating destroyed cyanide to less than 0.2 mg/L. Both the pellet and monolith residues were evaluated for disposal using the EPA Toxicity Characteristic Leaching Procedure.

Jan 1, 1995

By Liming Wang

One of the steps in the extractive metallurgy of lead is a refining process called drossing. Hot dross is mixture of impurity compounds that form on the surface during the cooling of lead blast furnace bullion, and in Missouri, the main impurities are copper and sulfur. The slow cooling of bullion throws out of solution all other minor impurity elements (or their compounds) which are much less soluble at lower temperatures (mainly nickel, arsenic, iron, and zinc). The transfer of bullion from the blast furnace to the refinery and the subsequent hot drossing step cause fugitive emission of lead-containing fume and dust, which creates a plant hygiene problem. One cause of the emissions is the high vapor pressure of lead and its compounds during transmission of = 1000 °C bullion to the drossing kettle. Another cause is the lifting of dross dust during manual skimming of dross. The environmental problems associated with the traditional hot drossing process provided an incentive to investigate a new drossing process that avoids contact between plant air and hot bullion or dross. A key aspect of the process development was a detailed mineralogical examination of dross from two different bullions. The bullion samples were cooled at different rates, and the dross filtered out and examined. The morphology, phase identification, and composition of the dross was examined by optical and SEM microscopy. The principal dross phases were copper and cuprous sulfide, galena, a complex sulfide containing copper, nickel and lead, and speiss (containing nickel, cobalt, iron, copper, lead, and arsenic compounds). The copper was acicular, with nickel and arsenic in solid solution. The cuprous sulfide was largely digenite in a granular or dendritic form. A substantial part of the dross was solidified matte with a eutectic microstructure, consisting mainly of CU2S and PbS. Small particles (some of which had a eutectic microstructure) never floated to the surface of the lead during the slowest cooling rate, thus indicating that flotation of tiny matte droplets and dross crystals is exceedingly slow. The success in separating dross and lead by centrifugal filtration suggests its application in industry as a replacement for traditional hot drossing.

Jan 1, 1995

By B. J. Elliot

The Outokumpu Oy flash smelting furnace was designed for a capacity of 69,5 mtph of concentrate. The history of developments on the flash furnace, from the original operating capacity of 55 mtph to a proven capacity of 115 mtph of concentrate, is summarised. The new feature of operation at BCL Limited is ?the use of screened lump coal reduction in the settler region of the furnace. This paper considers the effects of settler bath reduction on the furnace smelting capacity, the condition of the furnace ?lining and bath, and ,the slag losses generated from the flash furnace and ultimately to discard. By using the settler bath reduction technique the capacity of the furnace for smelting new concentrate has been increased by 15% and hearth accretion has been eliminated by direct reduction with coal, which has also allowed the generation of a substantial protective lining on the furnace walls and roofs. As a result of improved slag losses from lump coal charging the metal recoveries on the flash furnace have increased from 70% to 87% for nickel, 68% to 82% for copper, and 28% to 45% for cobalt.

Jan 1, 1983

By Veena Sahajwalla

The cupola furnace is a coke-fueled shaft furnace used as a primary melting unit in iron foundries. Control of chemical composition of the iron tapped from the cupola is a key factor in productivity and quality control. In an effort to develop a control model for the cupola, a fundamental approach based on physical and chemical principles has been taken to describe the melting process. The behavior of oxidation of the solid charge in the stack of the cupola has been studied. Sulfidation of the charge materials by sulfur-bearing components released to the furnace gases from the coke has been described. Carburization of metal droplets of iron and of steel in separate molten streams has been characterized. Finally, reactions with alloying elements in the hearth (well) of the furnace have been defined. These reactions have been described in a computer-implemented model developed to predict the composition of the iron tapped from the cupola. The model has utilized the thermodynamics and kinetics of the oxidation, sulfidation, and carburization reactions, including temperature and physical aspects, in the various zones of the melting unit. The model predictions have been compared favorably with operating results.

Jan 1, 1992

By Arthur E. Morris

Fifty years ago when Professor Yazawa began his career, the field of process simulation and modeling was in its infancy. Since then, tremendous progress has been made in our ability to model metal production flowsheets from mine to refined metal. This progress has come about by parallel developments in basic understanding of process chemistry and in computational techniques. This paper will review the progress made in process understanding and modeling in lead, zinc, and copper metallurgy from its inception to the present, and the role of Professor Yazawa's work in furthering this progress. Specific examples wi1\ be given for the sintering of lead concentrates, slag fuming, zinc concentrate roasting, flash smelting of copper, and pyro-extraction of zinc. Factors limiting further progress will be described.

Jan 1, 2003

By Alvear G. R. F. Flores

It is now 35 years since the organization of the first sulfide smelting conference in 1983. Since then, the smelting base metals industry has experienced several changes driven by the necessity to improve economic, operational and environmental performances and resource efficiency and meet the increasing market demand for metals. In this continuously challenging environment, it is relevant to recognize which are the main challenges that the industry will face in the coming years and critically address our preparedness to respond to them. This analysis have to consider not only the effort required from the fundamental research and technology aspects but also how these pillars interact with the drivers behind the base metals industry. This paper discusses some relevant aspects required to continue developing the base metal industry focusing on copper. Aspects such as the need to supporting the generation of fundamental metallurgical knowledge, acquisition and proper use of data with advanced analytics methods, technological innovation to develop sustainable process flowsheet are discussed with emphasis on efforts conducted by Aurubis.

By Arthur W. Cooper

This paper contains a review of the development of blast furnace? slag handling and processing technology in the Ironmaking industry over the past 30 years, with an emphasis on economic and environmental factors. The requirements and practice of air-cooling slag for use as aggregate and of pelletizing and granulating slag for use in cement manufacture are described. The operation of slag pits, slag pots or ladles, the slag pelletizer and early granulation systems are compared with the new continuous .granulation, dewatering and handling systems developed in the past decade.

Jan 1, 1992

By Kirsi M. Riihilahti

The oxidation characteristics of solid copper matte particles under simulated Kennecott-Outokumpu Flash Converting conditions are presented. This project is concerned with the determination of the effects of operating variables on the reaction of the particles. Experiments were carried out in a large laboratory-scale flash furnace with 72 wt-% Cu matte by varying initial particle size, temperature, oxygen partial pressure, oxygen-to-matte mass ratio and residence time. Chemical analysis was used to study the oxidation extent and copper volatilization. Particle fragmentation was examined. Fractional conversion and sulfur removal slightly decreased with initial particle size, while a higher oxygen-to-matte mass ratio mainly resulted in higher fractional conversion and more efficient sulfur removal. The fractional conversion values represented the overall extent of oxidation more closely than degree of sulfur removal.

Jan 1, 1997

By Ravi S. Bellur-Ramaswamy, Daniel A. Tortorelli, Robert Haber, Nahil A. Sobh

We optimize continuous quench process parameters to produce functionally graded aluminum alloy extrudates. To perform this task, an optimization problem is defined and solved using a standard nonlinear programming algorithm. Ingredients of this algorithm include 1) the process parameters to be optimized, 2) a cost function: the weighted average of the precipitate number density distribution, 3) constraint functions to limit the temperature gradient (and hence distortion and residual stress) and exit temperature, and 4) their sensitivities with respect to the process parameters. The cost and constraint functions are dependent on the temperature and precipitate size which are obtained by balancing energy to determine the temperature distribution and by using a reaction-rate theory to determine the precipitate particle sizes and their distributions. Both the temperature and the precipitate models are solved via the discontinuous Galerkin finite element method. The energy balance incorporates nonlinear boundary conditions and material properties. The temperature field is then used in the reaction rate model which has as many as 105 degrees of- freedom per finite element node. After computing the temperature and precipitate size distributions we must compute their sensitivities. This seemingly intractable computational task is resolved thanks to the discontinuous Galerkin finite element formulation and the direct differentiation sensitivity method. A three-dimension example is provided to demonstrate the algorithm.

Jan 1, 2001

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 P. Heald-Wetlaufer

Doubly polished sections (i.e., sections polished on both sides) allow insights into complex paragenetic relationships, the interpretation of which is essential to understanding ore-forming processes. Alternate viewing of these optically superior sections in transmitted and. reflected light facilitates the recognition and definition of growth zones in ore and gangue minerals and the interpretation of postdepositional changes, such as hydrothermal leaching and replacement. Many such observations would escape detection by conventional petrographic methods. Our procedure for preparing doubly polished sections has evolved during the past 20 years and incorporates many standard procedures. Studies from such diverse districts as Creede, Colorado, Hokuroku, Japan, and the Upper Mississippi Valley zinc-lead district, southwestern Wisconsin, demonstrate the value of observations from doubly polished sections in constructing genetic models. The advent of doubly polished sections represents a major advance in the study of ore deposits and they should be a standard tool in every ore petrology laboratory.

Jan 1, 1982

By D. Lui, B. G. Thomas, B. Ho

"Results from mathematical models and plant experiments are combined to quantify the effect of transverse depressions and oscillation marks on heat transfer in the continuous casting mold. A heat transfer model has been developed to calculate transient heat conduction within the solidifying steel, coupled with the steady-state heat conduction with the continuous casting mold wall. The model features a detailed treatment of the interfacial gap between the shell and mold, including mass and momentum balances on the solid and liquid powder layers. The model predicts the solidified shell thickness down the mold, temperature in the mold and shell, thickness of the resolidified and liquid powder layers, heat flux distribution down the mold, mold water temperature rise, ideal taper of the mold walls, and other related phenomena. The important effect of non-uniform distribution of superheat is incorporated using the results from previous 3-D turbulent fluid flow calculations within the liquid cavity. Results from plant experiments confirm that transverse surface depressions and oscillation marks form at the meniscus and move down the mold. Measurements of mold thermocouple temperatures and breakout shell thickness were used to calibrate the models. The results indicate that the surface depressions and oscillation marks are filled with mold flux, but still have a significant effect on decreasing heat transfer. The predicted mold temperature fluctuations are consistent with measurements. If the depressions become filled with air, their effect is greatly increased. These results should be useful in the difficult task of interpreting transient mold thermocouple signals for on-line quality monitoring.IntroductionMany different types of intermittent surface defects on steel slabs arise during initial solidification in the mold of the. continuous casting machine. These defects include deep oscillation marks, surface depressions, and cracks. They may lead to quality problems, such as slivers, in the final rolled product. In severe cases, breakouts may occur, where liquid steel bursts through a thin section of the shell and drains over the casting machine below the mold."

Jan 1, 1997

By Arthur E. Morris

Fifty years ago when Professor Yazawa began his career, the field of process simulation and modeling was in its infancy. Since then, tremendous progress has been made in our ability to model metal production flowsheets from mine to refined metal. This progress has come about by parallel developments in basic understanding of process chemistry and in computational techniques, This paper will review the progress made in process understanding and modeling in lead, zinc, and copper metallurgy from its inception to the present, and the role of Professor Yazawa's work in furthering this progress. Specific examples will be given for the sintering of lead concentrates, slag fuming, zinc concentrate roasting, flash smelting of copper, and pyro-extraction of zinc. Factors limiting further progress will be described.

Jan 1, 2003

By B. C. Blakey

Unlike most hydrometallurgical slurries, those containing significant concentrations of goethite are typically highly viscous and shear-thinning, even at solid volume fractions below 5%. The viscosity may also depend upon time. These characteristics must be taken into consideration in slurry transport and heating. The technical literature is replete with apparent contradictions regarding the viscous behavior of these slurries, which may be due, in part, to variations in viscosity-measuring techniques. We present techniques that yield consistent results suitable for use in process design. A striking degree of time-dependent behavior is demonstrated for a laterite slurry. Reliable methods to design and analyze tubular transport and heating systems for time-independent slurries are summarized. Rules of thumb are then offered to account for the effects of time-dependency.

Jan 1, 2000

By Mahesh C. Meyer Jha

AMAX has developed a chloride refining process to produce pure nickel and cobalt metals from mixed sulfide .precipitates, Metal chloride solutions, generated in a hydrochloric acid leaching step and purified in a solvent extraction circuit, are converted to metal oxides .and HCI gas by pyrohydrolysis. A pilot plant consisting of a 30-inch diameter fluidized bed reactor and other ancillary units was designed, constructed, and operated for over one year. Process design was aimed at minimizing energy consumption, maximizing conversion efficiency, and achieving simplicity of operation and control. The operation provided valuable information on process scale up parameters, process control strategies, and materials of construction., Several process variables such as bed temperature, solution composition, solution feeding system, bed particle size distribution, and fines recycle system were investigated to determine their effects on process efficiency and the physical and chemical characteristics of the product.

Jan 1, 1985