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By Kandipati Sreenivasarao

A promising method for removing heavy metal ions from dilute effluents is ion- or precipitate- flotation, in which a suitable collector is added to form hydrophobic metal-collector complexes or compounds that can be collected as foams. We have successfully removed Cu(II), Cd(II), and Pb(ll) from dilute solutions using sodium dodecylsulfate and ethanol as collector and frother respectively. However the process would not be economically viable unless the collector could be recycled, and the heavy metals recovered in a concentrated, preferably marketable, form from the foams. We investigated four different methods to decompose heavy metal-dodecylsulfate complexes, namely precipitation of hydroxides, precipitation of sulfides, chemical stripping, and electrolysis. We compare the performance of these methods. In each case the observed behavior is related to known thermodynamic data, and potential applications are discussed.

Jan 1, 1995

By Ray D. Peterson

The hydrothermal enrichment of chalcopyrite by CuSO, occurs in the absence of oxidizing or reducing reagants. Kinetics of the enrichment process were determined under autoclave conditions in the temperature range of 398°K (125°C) to 473°K (200°C). Covellite (CuS) formed first, followed by digenite (Cu,,,S), with rejection of iron to the solution. The kinetics have been explained by a model which includes diffusion during the first stage formation of covellite followed by surface reaction rate control when digenite be. The effects of particle size, temperature, pH, and cupric and ferrous ion concentrations on the leaching kinetics were examined. Additions of ferrous ion to solution markedly increased the rate of reaction.

Jan 1, 1994

By Jennifer Mager, G. P. Martins, Dean Mussatti

"The role of lead, at low concentrations in high pH cyanide-electrolytes, on the dissolution behavior of gold, has been a topic of scientific and industrial concern for well over a century. The recent paper by Kondos et al [1] at CANMET (1995) this continuing interest and apparent importance. Nevertheless, the mechanism(s) by which this (and other heavy metal) component influences the electrodics of this electrochemical system has still not been unequivocally demonstrated. Instead, several plausible hypotheses, by pioneering researchers in this field, have been advanced and reiterated OVer the ensuing years. While it is generally accepted, based on equilibrium elctrode-potential calculations, that reduction (or co-reduction when oxygen is present in the electrolyte) of lead on the gold surface may occur due to cementation (contact reduction), the cemented lead has never been characterized. The work presented has reexamined the role of lead in this system, by delineating the species distribution of these system components and by interpreting the results of potentiodynamic studies in conjunction with SEM analyses of a gold electrode.1. INTRODUCTIONThe leaching of gold ores in cyanide electrolytes has been practiced for well over a 100 years. Research conducted on this topic has been primarily focused on the effects of operating parameters such as concentrations of oxygen and cyanide, and the pH of the electrolyte; or the leaching behavior of carbonaceous and sulfitic gold-bearing materials.Mechanisms by which pure gold is leached in alkaline cyanide media, with oxygen serving as the oxidant, have been subjected to continual examination and re-examination in the published technical literature during this century. Recently, it has been speculated that without the presence in the electrolyte of trace heavy metals, such as lead or mercury, that gold would not be leachable. Researchers who have tackled this topic, have either considered heavy metals to be a natural occurrence in these systems and ignored the role they may serve in the leaching process, or they have deliberately focussed on controlling their concentrations in the system to undetectable limits. As a result, conflicting findings have been reported for what would appear - depending on the details provided in these reports - to be identical systems."

Jan 1, 1997

By D. de la Villa

From 1989 to 1992 Rio Tinto Minera has developed and implemented a productivity program in its Huelva Plant, including Smelter, Acid Plant and Electrorefinery. This Plan was designed in order to increase productivity, reduce emissions and produce a better quality of cathodes. This paper describes investments and operating improvements involved in this project, focusing on Smelter and Acid Plants, and comments the results obtained so far.

Jan 1, 1993

By Bora Derin

This work deals with the recovery of valuable metals from the ancient copper smelting slags located in Küre-Turkey. In this process, copper and cobalt were recovered in metallic form and/or as their compounds, whereas iron was recovered as magnetic oxide or pigment. Abrasive grit material was produced using reduced final slag. The process stages involved carbothermal reduction in a DC arc furnace, granulation, leaching, chemical precipitation, selective sulfidizing roasting and product preparations. In this paper, the process stages were described as theoretically and experimentally whereas slag and products were characterized in detail.

Jan 1, 2003

By Stephen M. Testa

Several methodologies are available for the remediation of contaminated soils including bioremediation, vapor extraction, chemical fixation, incineration and direct disposal. A proven innovative and cost effective alternative for the fixation of contaminated soils is via cold-mix Environmentally Processed Asphaltm (EPA"'). EPAm methodology utilizes contaminated soil as an ingredient in an industrial process to produce a commercially viable product. Petroleum hydrocarbon and metal affected soil is incorporated with a water-based asphalt emulsion and varying amounts of aggregate to produce a range of cold-mix asphaltic products that fulfills the requirements of a variety of end uses. This viable and creative use which is within the intent and spirit of current regulations in producing, in lieu of a landfill waste, an end product for use as a berm, road base, liner, or other site specific application. Consideration of certain engineering and environmental factors including durability, stability, chemical resistance and ageing, biological resistance, permeability, leachability and geochemical aspects suggests that cold-mix asphalt incorporation of affected soil will perform more than adequately under normal conditions for a long period of time.

Jan 1, 1994

By I. D. Reznik

Results of thermodynamic computations have been presented for reactions occurring in the process of segregation roasting of oxide nickel ores to describe more accurately the mechanism of the process. Under conditions of laboratory-scale roasting in combination with close-circuit flotation flow-sheets and magnetic separation, a recovery of 80-82% of nickel into 8 to 10% Ni concentrate and a recovery of up to 66% of cobalt was achieved. Process conditions have been selected for processing of both high-iron and high-magnesium ores. The feasibility of conversion of 94-98% of nickel and cobalt into solution by oxidizing pressure leaching with sulfuric acid has been demonstrated. It has been substantiated that it is reasonable to introduce double-stage segregation roasting.

Jan 1, 2003

By Carlos G. Levi

"The principles involved in the rapid solidification of supercooled metal droplets and existing numerical models are reviewed. The limitations of these models for studying alloy solidification are discussed in terms of the effects of alloying elements on the relevant heat transfer, thermodynamic and kinetic parameters. Analysis of the enthalpy-temperature diagram reveals how the extent of rapid solidification is hindered by the addition of solute. A solidification model incorporating thermodynamic and kinetic relationships into a Newtonian heat transfer formulation is used to analyze the thermal history and concurrent solute redistribution during recalescence. IntroductionIt is well acknowledged that microstructural evolution during solidification is intimately associated with the thermal history of the liquid-solid interface. Structural parameters like chemical homogeneity, morphology and size scale of the phases can be related to the interfacial temperature and velocity. These in turn change by the interaction of the interface with the thermal and solutal fields in its neighboring environment.The thermal history of powder solidification can be conveniently described on the enthalpy-temperature diagram for a pure metal shown in Figure 1 and discussed in detail elsewhere [1). A system can conceivably follow any path of decreasing enthalpy in the supercooled region of Figure 1 (~ < 1), starting at the nucleation temperature (oN < 0) on the liquid line, and ending at some point on the solid line. A vertical path represents an isothermal transformation, of which a limiting case is solidification without significant barriers to nucleation and growth, with the interface at the equilibrium temperature TM (path one in Figure 1). A horizontal path represents isenthalpic (or adiabatic) solidification whereby the system could form an amount of solid proportional to the initial supercooling of the liquid without further heat loss to the environment. A liquid that can completely transform to solid under adiabatic conditions is said to be ""hypercooled""."

Jan 1, 1986

By Raj P. Singh

Applications of cementation in the recovery of metal ions from process solutions have been known for a long time. Cementation reactions involve electrochemical precipitation of a noble metal from solutions of its salts on a more electropositive metal which, in tum, progressively dissolves. For example, addition of zinc metal powder in a solution containing zinc and cobalt ions would allow for the precipitation (separation) of cobalt according to the following chemical reaction. This paper pertains to the recovery of cobalt from cobalt process solutions via a cementation reaction on aluminum shavings (metal scraps from cans etc). Specifically, we report on the characterization of cobalt process solutions, a by-product obtained from cobalt chemicals, and the kinetics of cobalt, nickel and manganese cementation from process solutions on aluminum shavings.

Jan 1, 2000

By Joon H. Jang

At a selected pH, hydrothermal oxidation of chalcopyrite was carried out under controlled F+,, at elevated pressures and temperatures (172-200°C) by balancing the rate of oxygen injection against the rate of consumption. Chalcopyrite was converted to covellite (CuS) and digenite (CU1.8S) with rejection of iron and sulfur to the solution. Covellite forms in the first stage, followed by nucleation and growth of digenite in the second stage. The effects of rapid and slow injection of stoichiometric quantities of oxygen are compared. Both the covellite and digenite form a porous layer occupying the same volume as the original chalcopyrite grain. An electrochemical kinetic model is presented to correlate the observed results.

Jan 1, 1993

By Lev Levin, Sergei Lesokhin

"The formation of titanium carbide during hot filament assisted carburizing of NiTi alloy was investigated. Phase content and morphology of the diffusion zone were examined by X-ray diffraction, X-ray microanalysis, SEM, and Auger electron spectroscopy. The growth of stable and adherent TiC film was observed. A non-planarity of interphase boundary was noticed. The applicability of the chemical diffusion approach to the analysis of the experimentally observed interface instability is discussed. A criterion, taking into account the influence of growth stresses on the stability of the flat interface, is developed by means of linear perturbation analysis.Introduction.Equiatomic intermetallic NiTi belongs to a class of materials exhibiting the shape-memory effect. The unusual property of this compound promotes its application in many fields, from aerospace technologies to medicine. The relatively high ductility ofNiTi also permits its use as a matrix material in metal-ceramic composites. The objective of this work was to investigate the possible incorporation of a ceramic material (titanium carbide) into NiTi by gas carburizing.Free energy calculations indicate the potential to obtain TiC by carburizing Ni-Ti binary phases. The main obstacle to such a process is the high affinity of titanium to oxygen. At moderate temperatures the formation of TiC is preferable to titanium oxidation only if the partial pressure of oxygen is extremely low [1]. This problem was overcome in this work by the use of hot filament assisted gas carburizing. Due to chemical reactions occurring near the hot filament, the gas mixture, initially consisting of methane and molecular hydrogen, was enriched by atomic hydrogen [2], drastically decreasing the content of free oxygen in the carburizing atmosphere.The second part of this article concerns the theoretical analysis of reasons that lead to the development of the experimentally observed morphology of the diffusion zone. In particular, the influence of the growth stresses on the morphology of an interphase boundary is investigated."

Jan 1, 1996

By Jae-Ho. Lee

Mercury is a toxic contaminant encountered in the extraction of gold from mercury-containing ores. It is found in the leach solution of CIP circuits and in the cathodes of the electrolyte cells used to electrodeposit the gold. The research conducted has examined the potential for selective removal of mercury from synthetic Au-Hg-CN electrolytes containing only gold, only mercury, and both gold and mercury. Cyclic voltammograms were obtained for mercury- coated copper electrodes with these cyanide electrolytes. Exchange current densities were determined from the voltammograms in the low overpotential region. Laboratory scale batch- electrolysis at constant current was also conducted for the electrolytes containing only mercury and both mercury and gold, at 20 and 50°C and from which the kinetic behavior associated with the process was analyzed. The surface of cathode before and after electrolysis was also characterized and a copper mercury intermetallic (CyHg,) was identified. Gold codeposited with mercury during the later stages of electrolysis. The results of this work corroborate that the mercury-amalgam copper electrode offers a viable electrochemical technique for the selective removal of mercury, however a high-surface-area cathode-cell would have to be utilized to provide for the desired selectivity.

Jan 1, 1994

By M. P. Bohrer

A closed-loop hydrometallurgical process has been developed for treatment of smelter flue dust generated by copper recycling. The process is a semi-continuous operation in which zinc, iron, and copper are first extracted from the dust with a sulfuric acid solution. The lead and precious metals, initially present in the dust, remain as solids and can be recycled to the copper smelting furnace. Cementation with iron and zinc metal purifies the zinc and iron-rich liquid stream prior to spray drying. The spray-dried product, consisting of a mixture of zinc sulfate monohydrate and iron sulfate monohydrate, is a desirable micronutrient additive for use in animal feeds. Treatment of the smelter flue dust in this manner will generate a positive return on investment, as well as mitigate a potential environmental liability.

Jan 1, 1992

By W. G. Davenport

A survey of world copper refining tankhouse .practices has been carried out. This paper compiles the results and examines changes in operating practices .since the similar 1987, 1991 and 1995 surveys. Continuing trends are the installation of ISA Process and Kidd Process stainless steel cathode technology, polymer concrete cells, anode preparation machines and automatic cranes. Instrumentation and automatic control are increasing, particularly for addition agent optimization; solvent extraction .and ion exchange techniques are being increasingly applied for electrolyte purification. The overall consequences of these changes have been &apos;improved cathode purities and enhanced tankhouse productivities.

Jan 1, 1999

By J. L. Holman

The Bureau of Mines is investigating recovery of Ni, Co, Cr, and other metals from mixed contaminated supera110y scrap. The scrap is melt-refined and cast into anodes for electrodeposition of recyclable Ni-Co alloy. Melt oxidation using roasted superalloy grinding sludge as oxygen source can divert the Cr to the slag but with excessive Ni-Co loss. Melt oxidation-carburization or direct melt carburization retains -95 pct of the Ni-Co in the anode alloy. With direct carburization, -90 pct or more of the Cr and other refractory metals report to the anode alloy, largely as carbide phases insoluble in electrolysis. Electrorefining data relate parameters such as controlled cathode potential, Fe and Cr impurities, pH, and compartmented cell use, to current efficiency and Ni-Co deposit quality. Recovery of -90 pct of the Ni-Co in the scrap can be achieved. Preliminary experiments to recover Cr, W, and other metals from the anode sludge and other byproducts are discussed. 347

Jan 1, 1987

By Brandon R. Ball

An investigation of the effects of ozone and ozone-induced hydroxyl radical on reducing whole effluent toxicity is described and discussed relative to the application of ozone for industrial water treatment. Results from operation of an ozone system treating industrial effluent from a lead and zinc mine in Colorado are presented. The mine discharges 1,000 gpm of wastewater into a tributary of the Arkansas River and has historically exceeded Whole Effluent Toxicity (WET) limits and on occasion has exceeded numeric limits for copper, ammonia, and cyanide. Based on results of a Toxicity Identification Evaluation (TIE) conducted on the effluent and individual process waste streams, the source of effluent toxicity is believed to be primarily associated with organic reagents used in the milling process. Based on test results, an applied ozone to COD ratio of 3: 1 by weight and a contact time of 30 minutes was found to be effective for reducing whole effluent toxicity at pH 11 but not at pH 7, indicating oxidation by hydroxyl radical to be the dominant mechanism responsible for toxic-ity reduction. At an applied ozone to COD ratio of 3:1 and a pH of 11, toxicity was improved from 0 percent survival to 100 percent survival for Ceriodaphnia dubia and fathead minnow (Pimephales promelas) based

Jan 1, 1996

By Antti Roine

HSC Chemistry is a widely-used therniochemical tool in the chemical and metallurgical industries and in universities. The main reasons for it&apos;s popularity is the easy user interface and the large integrated thermochemical database. This paper summarizes the main properties of the new HSC Chemistry version 3.0, and gives a short review of the new features: Some metallurgical applications with the new features are also presented. HSC Chemistry 3:0 contains seven calculation modules and a thermochemical database with more than 11 ,000 chemical compounds. The new spreadsheet type table editor gives more control to the user, the new graphics routines have fewer limitations and more formatting properties. The capability and speed of calculation routines have also been improved.

Jan 1, 1998

By H. K. Lin

Pyrite oxidation in chloride solutions was investigated with cyclic voltammetry, ac impedance and potential step techniques. The pyrite oxidation in quiescent electrolytes is irreversible and controlled by diffusion. Depression of the semi-circle in the complex plane plot has been explained mathematically based on the concept of the equivalent circuit. When the semi-circle is depressed, the mathematical formula indicates that the reaction resistance should be obtained from the intersection of the semi-circle with Z-axis instead of the semi- circle diameter. The peak charging current densities at 1.10 and 0.90 V vs. SHE obtained from the equivalent circuit coupled with the ac impedance measurements match the peak current densities obtained with the potential step measurements.

Jan 1, 1997

By Hui Zhang

The leaching behavior of palladium powder in aqueous solutions containing NaCI or N&apos;H4Cl was investigated. Cupric ion was used as an oxidant for the dissolution reaction. The effect of a number of leaching parameters such as temperature, concentration, stirring speed and surface area on the leaching rate was studied. The leaching system containing chloride and cupric ion was found to be very effective for the dissolution of metallic palladium. Based on the experimental results the overall leaching rate was believed to be controlled by a chemical reaction step. The dissolution rate of palladium was found to be first order with respect to the concentration of cupric ion and second order with respect to the concentration of chloride.

Jan 1, 1996

By N. Voennann

Stillwater Mining Company operates an electric furnace at its smelter in Columbus, Montana to treat a Ni-Cu-platinum group metal concentrate along with secondary PGM bearing materials. Hatch Associates has designed several improvements to this furnace, which was originally built by others. Implementation of these relatively low cost improvements has resulted in substantial increases in furnace availability and capacity, along with reduced unit costs. ? The improvements included: ? Installation of water-cooled copper cooling elements to stabilize refractory wear and increase furnace life.- ? Improved furnace &apos;bindings, to enhance the furnace&apos;s structural integrity by improving the contact between the refractory and cooling elements, and by promoting tight brick joints resistant to matte or slag leaks. ? Adjustment of the electrode regulator to allow higher furnace power levels. ? Installation of an automated air-slide (aeration conveyor) feed system to evenly distribute the furnace feed in an insulating layer on the bath surface. This "black-top" practice reduces unit energy costs and makes available additional smelting capacity.- ? Electrode seals to reduce ingress of air that absorbs heat before exiting the furnace in the off-gas stream. The saved energy can be used to smelt additional concentrate. This paper describes the above furnace modifications, and the benefits derived from their implementation.

Jan 1, 1998