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By Jerold L. Johnson

Remediation of small-arms firing ranges is being investigated by the Naval Civil Engineering Laboratory and the U.S. Bureau of Mines. Scheduled closures of military installations, as well as the management of active ranges, require the development of methodologies for heavy metals removal to prevent their entering the surrounding environment. The impact berms contain high concentrations of metals, and the soil and vegetation surrounding the berms were found to have slightly elevated levels. The heavy metals characterized are in the form of whole bullets, a wide size distribution of free fragments, smeared lead on the surface of the soil grains, and very finely attached particles. Gravity beneficiation can remove liberated metal contamination effectively. Weak acetic acid leaching shows promise in lowering the final metal contamination to allow the ,soil to pass the Environmental Protection Agency's (EPA) Toxicity Characteristic Leaching Procedure (TCLP) criteria.

Jan 1, 1993

By G. Belardi

The purpose of the study was to check on the level of environmental contamination and to design a project for cleaning up the Abetina Mine area at Piancastagnaio (Grosseto, Italy). Contamination of this area had occurred during the mining and treatment of cinnabar (HgS) over a prolonged period. The aim of the project is to remove the sources of contamination or render them harmless. Mining of the Piancastagnaio deposit started in 1840, mercury metal being extracted from the ore by thermal treatment. Together with Spain, Italy was the first country to produce this metal and was the world leader in this field between 1936 and 1943. Though mercury production in the Monte Amiata region of Tuscany ceased in 1974 the ensuing environmental impact is very evident, taking the form of rusty old mining and processing works, plus waste tips which still contain considerable amount of mercury even after the ore had been subject to thermal extraction treatment. The research which has been conducted included mapping the area to identify the main sources of mercury and arsenic pollution, as well as the level of environmental contamination. Mercury and arsenic values in excess of 16,000 and 150 ppm respectively are encountered in the most highly-contaminated places. The cleanup project has been drawn up on the basis of the field and laboratory investigations. This provides for a combination of remediation measures on the land concerned, as well as in situ inertization of contaminating elements by means of mixtures of chemical compounds such as cyclosiloxanes. Due account has been taken of Italian and EU environmental regulations when establishing the measures for rendering the various polluting element innocuous. 'The efficacy of the inertization techniques has been checked by yield tests in acetic acid and carbon dioxide, reducing the Hg and As contents of the material in the untreated and treated states from maximum values of 7 mgll to minima close to zero.

Jan 1, 1996

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 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 Geoffrey S. Plumlee

The Summitville gold mine, located in southwestern Colorado, received tremendous publicity in the 1980's and 1990's for leaks of cyanide solutions from its heap leach facility. As is typical with cyanide spills, real time, geochemically rigorous assessments of the environmental effects were not performed. Past United States Geological Survey (USGS) research used simple mixing experiments to model the influx of alkaline cyanide heap leach solutions from Summitville into a nearby stream, whose waters were highly acidic due to severe acid-rock drainage (ARD) from the mine. These experiments indicated WAD cyanide rapidly degraded due to formation of Fe-Cu-CN solids and lesser HCN volatilization. The alkaline heap leach solutions also precipitated hydrous iron-and aluminum, oxides and hydroxysulfates (iron and aluminum 'supplied by the acid. rock drainage (ARD]), which then sorbed copper and other heavy metals from the ARD. These results indicate that mixing of cyanide heap leach solutions with ARD may be a cost-effective remedial method at mine sites where treatment of both is required. New experiments are currently in progress to further refine a potential remedial process.

Jan 1, 1998

By N. A. Barcza

DC plasma-arc technology using a hollow graphite electrode (cathode) has been successfully implemented in the primary metallurgical industry in South Africa up to the 30 MW scale. Mintek has applied its expertise base, established over the past fifteen years, to testing the treatment of metallurgical wastes such as carbon- and stainless-steel plant dusts, lead- and zinc-containing slags, and residues from the base-metal industry. Favourable results have been achieved, and disposable products were produced. The evaluation of numerous wastes indicates that recovery of zinc as metal gives the best economic return from these sources. Direct recovery via a splash condenser or electrolytic zinc extraction from fume are the two preferred alternatives under review. In both instances dehalogenation is an important issue, but can be achieved by suitable treatment processes. The Enviroplas technology provides a flexible, commercially viable approach to the treatment of a wide variety of wastes. Mintek, together with its associate Pyromet CC, are installing a plasma- arc pilot-plant facility with both an ISP lead-splash condenser of about 5 t/d condensed zinc capacity and a combustion chamber to burn zinc vapour to zinc oxide. This will demonstrate the suitability of the Enviroplas technology for treating specific metallurgical wastes, so that customized industrial plants can be engineered based on large-scale testwork.

Jan 1, 1994

By Kun Wang, Xinhui Li, Huaqing Xie, Qingbo Yu, Qin Qin

"Three typical model compounds of bio-oil (ethanol, acetone and phenol) were studied in the steam reforming process for hydrogen production. In the thermodynamic analysis, the three componds showed the similar trends. The hydrogen yields increased with the increase of steam/carbon (S/C) ratios, and the temperatures of the maximum hydrogen yields moved afterward to low temperature zone. However, the hydrogen contents were just about 70%. For improving hydrogen yield, a new system for steam reforming of bio-oil with site CO2 capture was put forward. This system required the catalst with the larger granularity having greater mechanical strength and higher abrasion resistance. So, six Ni-base catalysts loaded on Al2O3 particles prepared were used and among them, Mg-Ni/Co catalyst showed the best catalytic performance. For the simulated bio-oil (the mixture of the compounds), the hydrogen yield can attain 63% with Mg-Ni/Co catalyst with the good stability and regeneration ability.IntroductionCurrently the interest in the use of hydrogen as a clean energy carrier is increasing, and the main way for producing hydrogen is steam reforming of fossil fuels, containing steam reforming of nature gas, naphtha and coal. But this way caused substantial amounts of CO2 emitted, and these sources of hydrogen which are non-renewable energy will eventually be used up [1, 2]. As a kind of renewable energy, biomass is recognized as an attractive alternative to fossil fuels, because of its neutral CO2 emissions [3]. There are mainly two thermochemical processes using biomass to produce hydrogen, gasification and flash pyrolysis followed by steam reforming (SR) of the biooil produced in the flash pryolysis process [4]. The latter was known as one of the most promising and economically viable methods for hydrogen production [5]. In the last decades, the biomass flash pyrolysis technology was adequately developed and fairly mature [6]. But the steam reforming of bio-oil is still at the research stage and yet has been leading to more and more concerns by the researchers. In their research, the catalysts were widely studied and yet mainly were powdery[7-10], and the reactors manily were fixed bed reactors[11-13], readly causing the carbon deposition and the catalyst deactivation, against the continuous running. In this paper, a new systerm was put forward and could realize continuous production of hydrogen, yet needed catalysts with the larger granularity having greater mechanical strength and higher abrasion resistance, as well as powdery CO2 sorbents which mainly calcium oxide based ones.In this paper, the thermodynamic analysis of the steam reforming processes of three typical bio-oil model compounds (ethanol, acetone, phenol) was performed, and the effect of S/C ratio and temperature on the hydrogen yield and the compositions of gaseous products were investigated. Then, a new systerm for steam reforming of bio-oil with site CO2 capture was put forward, and the catalysts with a certain granularity were prepared and studied."

Jan 1, 2014

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 M. Cross, K. Pericleous, A. Mouchmov

"Copper - nickel - sulphide alloys are typically cooled and solidified in 4, 8 and 16 tonne ingots. These ingots exhibit a variation of grain size distribution and macro segregation of the prime alloy components throughout. The former is assumed to be primarily due to the dominant relation between grain growth rate and the cooling profile, whilst the latter is heavily influenced by buoyancy driven residual convection. The objective of this research program is to examine the extent to which it is possible to develop a 'broad brush' computational model of this ingot cooling process, that can predict some 'integral' measure of the grain size (e.g. average diameter) and the macro-segregation as a function of operating conditions.A computational modeling software framework, PHYSICA+ is used to simulate the complex process of ingot casting, which involves coupling between different physical phenomena. The entire model involves:(i) a 'broad brush' grain growth model that could be used in the prediction of micro/macro-structure of alloy ingot cooling processes,(ii) a heat transfer and solidification model which takes into account a second phase transformation of P NhS2 to heazlewoodite, and (iii) NS fluid flow simulation which provides a good basis for further micro/macro segregation modeling.At this stage some results of the 3D convection driven thermal cooling and solidification profiles will be shown, together with the 'integral' model for the grain size prediction."

Jan 1, 2001

By René Winand

Due to chemical and electrochemical behavior of the most common additives in copper electrorefining i.e. gelatine, thiourea and chloride ions, it is essential to simulate as far as possible true industrial practice while performing laboratory experiments. The three additives must be studied simultaneously, and added continuously to the electrorefining cell. Ratio electrolyte volume to cathode area; ratio bleed flow to cathode area; hydrodynamic conditions; residence time of electrolyte in the cell; current density; electrolyte and soluble anode must be as near as possible to industrial ones. Experiments performed in the author's laboratory show that under these conditions, reproducible results can be obtained at normal industrial current density and at high current density as well. Problems are however still encountered when developing a sensor for additives monitoring, due to electrolyte redox potential and to substrate influenced thin layer deposition.

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 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 O. Barbosa F.

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

Jan 1, 1989

By David S. Holmes

An overview of existing biological technologies for the recovery of copper and uranium is presented. Engineering and biological challenges and opportunities in these areas. are discussed. New opportunities for the biooxidation of refractory gold ore are described. Techniques for the development of new strains of microorganisms. for commercial metal recovery applications are discussed with special reference to the genetic manipulation for bacterial strain improvement.

Jan 1, 1991

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 C. A. Silva

Ladle change-over, during continuous casting of steel, initiates transient flow in the tundish which influences the inclusion content and degree of mixing between two consecutive batches of steel. The mixing behavior in the tundish during this period is determined by the casting rate and the ratios of: inflow to outflow during the refilling period; and, the low liquid level relative to the nominal level in the tundish during the transiency. A 3:10 scale water-model of a typical one strand slab caster was operated in conjunction with a tracer technique to characterize the velocity fields for several combinations of these parameters. Steady operation, a limiting case of the transiency, provided a basis for comparison. High-order moments -- skewness and kurtosis -- of the residence time density function have been utilized as signature elements associated with a particular residence-time distribution for the system. A simple mathematical model incorporating the above parameters as well as a characteristic Peclet Number was successful in simulating the features of the transient period.

Jan 1, 1993

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 J. Brent Hiskey

Recently basic concepts of semiconductor electrochemistry and solid-state electronic structure theory have been applied to the dissolution of mineral electrodes. In this paper, fundamental aspects of semiconductor electro- chemistry and interfacial charge-transfer processes are reviewed. Information regarding the electronic and semiconductor properties of chalcopyrite is summarized. The electrochemical response of chalcopyrite in acidic solution is analyzed in terms of initial dissolution processes. The initial charge- transfer reaction involves the consumption of holes. It has been shorn that Fermi level pinning is consistent with observed electrochemical and dissolution behavior. Semiconductor electrochemistry has proved helpful in explaining the formation of intermediate surface films produced during the initial stages of chalcopyrite dissolution

Jan 1, 1993

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

By Thomas P. Battle

Ilmenite (iron titanate) is the source of over 90% of all the titanium produced in the world today. At some point during production of titanium dioxide or titanium metal the iron impurity must be removed. Too often it becomes a waste instead of a product. DuPont and MINPRO have developed a solid-state process which separates the iron and titanium components of ilmenite into different high-purity powders, which can be separated using conventional mineral processing techniques. The main reactor in this process is a unique high-temperature ball mill, where the iron segregates from the ilmenite lattice with the assistance of catalytic quantities of He\. The results of lab, pilot plant, theoretical, and scale-up studies are presented and discussed.

Jan 1, 1996