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By A. V. Tarasov, S. D. Klushin

493 The most common method for minimizing the copper content of residual slag in the process of autogenous smelting of sulfide raw materials is treatment of molten slag in an electric furnace, with optional addition of solid reducing agents, such as coke, and/or sulfiding agents such as pyrite. A drawback of this technique is the fact that the final slag produced still contains 0.5% or more Cu. We have tested a method for treating molten slag obtained as a result of autogenous smelting by a gaseous mixture of sulfur dioxide and methane at a ratio of. SC:SO2 = 0.75 :1.0 in the presence of oxygen. Interaction reaction within the SO2-O2-CRi system proceeded at a high rate at 1373 to 1573 K to form reducing and sulfiding agents: H2S, S, COS, CO, CO2, H2, H2O. The gas mixture requirement was about 100 to 150 Nm3 per 1 tonne of slag. A decrease in the ferric iron concentration (Fe3+) from 10-15% down to 2-3% resulted in lower solubility of copper in slag, and agitation of the melt with gas stream accelerated. the separation of the sulfide phase and slag. Removal of copper from slag was performed in a pilot unit within the second V anyukov furnace zone where slag arrived with a copper content of 0.8-1.3%. The temperature of molten slag was maintained within 1523 to 1573 K. The copper content of the final slag was at a level of0.12 to 0.14%. The matte sent to converting was a mixture of bottom matte from the smelting zone and the slag treatment zone. It had a copper content of about 50 to 55%. Process gases from both furnace zones were combined and sent to the acid plant for sulfur recovery. This process was offered for commercial use at two copper smelters in Russia and CIS.

Jan 1, 2000

By R. D. Osmanson

A series of batch roasting tests was performed on minus 1/2 inch gold bearing refractory samples from the Gold Acres deposit, and 67 select particles were polished and the sulfide alterations were examined microscopically. The suite of specimens represents two hour batch roast treatments at 600°C, 700°C, 725°C, 750°c, 800°C, and 900°C. Auriferous pyrites were found to alter sequencially to pyrrhotite, magnetite and finally to hematite. It was found that the decrease in cyanidation extraction with high temperature roasting is likely due to the increas ing stability of magnetite and more crystalline hematite, and the decrease in porosity with these phases which occlude the gold. Gold has been noted to occur very early in the mineralizing sequence, with gold being found in quartz and in clay/carbonate rock matrix. No gold was found in the two pyrite phases, but numerous gold grains were found in pyrrhotite after pyrite and in subsequent iron oxides. Gold mineralization had apparently ended by the time base metals were introduced into the deposit.

Jan 1, 1987

By Thomas M. Harris

Cation exchange is not sufficiently selective to be used for the removal of heavy metal ions from a general industrial wastewater. However, if the metals can be converted to polyvalent anions through complexation, they may be removed both selectively and efficiently by anion exchange. This approach, referred to as chelation-assisted anion exchange (CAAE), has been examined using industrial wastewater samples contaminated with Ni2+ and Cr3+. For this particular application, the Ni2+ is complexed with 8-hydroxyquinoline-5-sulfonic acid, and the Cr3+ with sulfosalicylic acid. Removal efficiencies and adsorption isotherms for both the complexants and the complexes were determined in batch-mode tests.

Jan 1, 1994

By C. A. Pickles

At the present time, pyrometallurgical processes are employed for the recovery of lead from battery scrap. These processes have serious pollution problems, primarily due to the emfssion of sulphur dioxide and airborne lead in the form of dust and fume. In addition it is necessary to dispose of solid wastes and liquid effluents which contain lead and in some cases sodium sulfide-containing compounds. In this work an improved process was investigated for the recovery of lead from battery residue. This involved pelletization of the residue with sodium carbonate and moisture. Then, the pellets were melted without carbon and the .sodium sulphate salt was removed. Subsequently, the molten lead oxide was reduced with carbon. This process minimizes the sulphur dioxide emissions and leads to very low sulfide contents of the sodium sulfate salt

Jan 1, 1992

By G. H. Khoe

Although some hydrometallurgical process liquors contain significant amounts of ferrous and arsenate ions, no reliable thermochemical data for the aqueous complexes and the solubility of the ferrous arsenate precipitate are available. The complexation of iron(11) with arsenate has been investigated using the potentiomemc titration method. The results indicated that virtually no complexation of iron(@ with arsenate has been observed. This is in contrast to the significant complexing reported for iron(1n) with arsenate. The solubility product of the precipitate was calculated using the concentrations of appropriate arsenate species pertaining to the observed precipitation pH's. The fit of the observed precipitation points on the solubility curve of the computed stability diagram was used to assess the appropriateness of the equilibrium model.

Jan 1, 1991

By Ullrich Kammer

Metaleurop's secondary lead smelter at Oker produces 60.000 mtpy of lead and lead alloys. More than 8O2 % of the raw materials are spent lead acid batteries. The other 2O2 % consists of drosses, ashes, scrap lead, type metal, sludges, etc., and is processed in a short rotary furnace (SRF). Also, industrial batteries not fitting in the battery scrap treatment plant are processed in the SRF provided with gas/oxygen-burner. Till Sept. 199O2, a soda ash slag was used in the SRF-smelting similar to the rotary kiln-smelting at Oker. Facing the future problems of handling and dumping soda ash slag, Harz-Metall GmbH has improved SRF-smelting with a non¬hazardous slag, insoluble in water, easy to dump and cheap in fluxes. This slag is based on a CaO-SiO2 -Fe0-type. Aim of the slag smelting is to be within the temperature range of 2 1100° and 1200°C - the eutectic line of Olivine in the corresponding ternary system. Since Sept. 199O2 Harz-Metall GmbH has operated the SRF with an "Olivine-type slag" with good results. Although the material is a "leady" slag. HMG is optimistic of using it as a filling material for construction purposes.

Jan 1, 1993

By J. N. Hryn

This paper describes some of the work done in Phase 1 of a multi-year, five-phase program aimed at demonstrating the economic feasibility of producing commercial-scale quantities of commodity materials derived from salt cake residue-oxide. The amount of salt cake generated annually in the U. S. is estimated to be 510,000 tons, including 340,000 tons of residue-oxide. Used beverage can (UBC) processing accounts for the majority of residue-oxiae that could be made available for further processing into commercial products. To characterize the composition of residue-oxide. eight residue-oxide samples from various secondary processors were obtained and analyzed. Surprisingly, the composition of residue-oxide was found to be independent of source or alloy family being processed, with? the exception of slightly elevated silicon levels in 3XXand UBC residue-oxide samples. Major phases detected in the residue- oxide were? alumina, spinel, and aluminum hydroxides. Preliminary economic analyses indicated that the refractory market appears to be the best choice for high value-added products produced from residue-oxide with minimum processing. Bench-scale tests indicated that low silicon containing residue-oxide is ready to enter this market, but the elevated silicon content of UBC and 3XX residue-oxide preclude this possibility. A separation technology should 'be developed to remove silicon-containing . species from the alumina and spinel values Present in residue-oxide. This technology would then allow UBC and 3XX residue-oxides to be converted to significantly higher value-added products.

Jan 1, 1995

By E. Ilgar

"Deposition studies were conducted in acid copper electrolyte to determine the influence of chloride ions on cathode morphology. A statistically designed screening test was carried out in the absence and presence of 20 ppm CI- using a three factor, two level factorial design, in an electrolyte containing 36 gl'! Cu2+ and 150 gl-! H2S04, The independent variables evaluated were agitation; current density and temperature and their influence on surface roughness was determined. The copper deposited at current densities where activation was the primary control mechanism appeared similar in morphology whether stirring was used or not. The addition of 20 ppm CI- to the electrolyte gave rougher deposits under the same conditions. In the mixed control regions, considerably rougher, dendritic deposits were obtained when CI- was present. Agitation was effective in reducing the copper surface roughness both in the apparent activation and mixed control regions in the presence ofCI-. The results of this study showed that 20 ppm Cl- polarized the copper deposition at low overpotentials but caused depolarization at higher overpotentials.IntroductionChloride ion is inherently present in copper electrolyte, either as an additive or from other sources such as make up water. The behavior of the chloride ion is well documented in electrorefining operations, but its role in copper winning is less obvious. However in both cases there is evidence that cathode growth and solution chemistry are strongly influenced by its presence. The mechanism and electrochemical action of the Cl"" have been shown to be very complex, therefore a better understanding of its influence on electrocrystallization is essential for improved cathode deposit growth control. It was proposed that Cl"" polarizes the copper deposition reaction at low concentrations due to CuCI formation but depolarization occurs at higher concentrations due to the formation of a soluble CuCI2"" complex [1,2]. Franklin [3] reviewed the mechanism of additives in the electrodeposition process and proposed that the Cl"" complexed with copper, adsorbed on the cathode as an induced anion leading to an increase in the reduction rate. At cathodic overpotentials less than 100 mY, lppm NaCl had a polarizing effect, i.e. an increase in impedance of the charge transfer step. At higher Cl"" concentrations up to 100 ppm, depolarization occurred as evidenced by a decrease in impedance, which was attributed to soluble cuprous complexes [4]."

Jan 1, 1997

By Merete Tangstad, Ragnar Tronstad

Ferromanganese production in electrical furnaces is quite an old process. However, as the furnaces are getting bigger, the requirements of cost, yield, product quality, emissions and security are raised. With the increased expectations, the fundamental knowledge must follow. Within the last 25 years there has been a great effort both in the industry as well as the academic environment to push the limits of this process. This article will show some examples of improvements within fundamental data, reaction mechanisms and emissions over this time period.

Jan 1, 2014

By Sergio Sanchez-Segado, Yuan Zhang, Animesh Jha, Ahmad Fahmi Ruzaidi

Niobium and tantalum are considered critical materials because the increasing demand in the energy sector which is reliant on limited abundance of these two metals in minerals. Traditionally, niobium and tantalum mineralsare digested using hydrofluoric acid at moderate temperatures, producing oxy-fluorides which are separated by solvent extraction, involving the use ofhazardous chemicals. The increasing environmental pressures are forcing the industry to search for alternative low carbon processing methods. In this paper alkali roasting based separation and beneficiation, which is not well understood in the literature, is proposed, for which the kinetics and thermodynamic equilibria for the formation of sodium tantalate and niobate with sodium hydroxide are analyzedat the temperature range of 400ºC to 700ºC. The apparent activation energy of formation,changes from 31.0±0.8 to 22.3±1.2 kJ mol-1 and from 23.8±1.2 to110.2±12.8 kJ mol-1, for tantalate and niobate, respectively. The reaction mechanism is examined on the basis of the analysis of reaction products using X-ray powder diffraction (XRPD) and X-ray fluorescence (XRF).

Jan 1, 2015

By Mitsuhiro Ito

"To allow various wastes containing high levels of chlorine to be used as alternative raw materials for Portland cement, two practical methods of chlorine removal were developed. In the first method, chlorine is extracted from the wastes during the cement manufacturing process. In the second, ash-dust waste with high chlorine content is first washed and then dehydrated to cake before being introduced to the cement manufacturing process. This cake can be used as an alternative for some cement raw materials. By combining the two methods, various wastes previously considered unsuitable for recycling due to their chlorine content can often now be used in cement manufacturing plants. As such, these methods represent a major contribution to environmental protection as well as a solution to problems relating to the diffusion of heavy metals and dioxins from cement plants.1. IntroductionWaste generation levels have risen rapidly in recent years. in both the consumer and industrial sectors and today, the need for effective, efficient waste management is one of the most pressing and serious problem of today's society.The Japanese cement industry has reacted to the increase in waste generation by using certain materials as alternative raw inputs or fuels for cement production, in an effort to contribute to society and conserve energy resources.These wastes often contain non-negligible levels of chlorine and heavy metals, however, both of which are unsuitable for cement production. Depending on the element content, Heavy metals have a particularly negative effect -on cement quality; in addition, they can be released into the environment. Chlorine, on the other hand, is contained in large amounts in incinerated ash from household wastes as well as in certain plastics. Both substances are considered impediments in cement-production, not only because they reduce the quality of the cement produced but also because they impair operating safety on cement production lines.To address this problem, two practical technologies have been established for separation and recovery of chlorine components during cement pre-processing and production. This paper introduces the application of these technologies with a special focus on incinerated ash from urban wastes, a representative form of waste material having notably high concentrations of chlorine, heavy metals, and dioxins. We also outline the technologies enabling this material to be used as an alternative input to cement production."

Jan 1, 2000

By W. K. Tolley

The Bureau of Mines is investigating hydrometallurgical processing techniques to recycle metals from semiconductors and other advanced materials. Cadmium and tellurium were recovered from CdTe scrap produced in the manufacture of infrared optic devices. Sulfation, ferric chloride leaching, and oxygen-pressure leaching have been tested. Cadmium dissolution was achieved using oxygen-pressure leaching in dilute sulfuric acid. However, no satisfactory scheme for dissolution of the higher valued tellurium has been devised. Leaching the ground CdTe for 75 min at 110°C in 1.1M H2S0, under 120 psig 0, yielded 99.5% Cd extraction. Tellurium remained in the leach residue as TeO, and elemental tellurium; residual cadmium was less than 0.5%. The cadmium in the leach liquor was purified of coextracted metals such as gallium and iron by adjusting the pH. The cadmium was recovered as cadmium sulfate crystals by evaporating the solution. Recovery of by product metals, notably gallium, is possible.

Jan 1, 1991

By I. Gaballah

The chalcopyrite ore's anodic and cathodic electrodissolution are studied using a Porous Pulsed Percolated Electrode (3PE) reactor. Stationary solid electrode experiments are also performed to explore the mechanism of electrochemical dissolution of chalcopyrite. Experiments with a low - grade natural ore have been carried out at 25 "C in solutions containing 1 M NaCl and 1 M HCl. Galvanostatic and potentiostatic conditions are employed. The influences of current and potential on selectivity of the chalcopyrite ore dissolution are assessed. Anodic oxidation of this ore leads to a preferential dissolution of iron bearing minerals, whereas cathodic reduction is more selective with respect to chalcopyrite. However, in both cases the electrochemical dissolution is incomplete and the current efficiency is low. Design of the actual reactor has to be modified to increase the bed conductivity and to allow continuous experimentations.

Jan 1, 1994

By M. Olper, M. Maccagni

"The crude zinc oxides (CZO) produced in any thennal process dealing with EAF dust also contain lead, cadmium, and a considerable amount of halides (chlorides and fluorides). The high halide contents make these crude zinc oxides less and less attractive, both technically and economically, and a further refining procedure is nece'ssary to meet the zinc and zinc oxide market requirements.Hydrometallurgical techniques commercially used to dehalogenate the crude zinc oxides are not effective enough to upgrade the crude zinc oxides to the required specification for their direct use in the traditional sulphuric electrolysis by primary zinc producers.The EZINEX® PROCESS has solved the problem of the halides contained in the crude zinc oxides. This process is the only proven technology electrowinning zinc from a chloridebased electrolyte in a conventional cell house. This paper discusses the process economics taking the data from feasibility studies of different size commercial plants."

Jan 1, 2000

By Batric Pesic

A hydrometallurgical process for recovery of Zn and Mn from Bunker Hill Water Treatment Plant sludge was developed. The process is unique because it treats an unusual combination of metals, Zn and Mn. Another non-standard feature of the process is that leaching takes place with ~S04 in the presence of a reductant (SO2). Zn and Mn are recovered simultaneously by electrowinning, Zn on a cathode and Mn on an anode, as MnO2 The major purpose of the process is to detoxify the sludge by removing toxic heavy metals. The recovered metal values could be marketed to offset the overall costs of water and sludge processing. This work is presented in two separate parts, 1. Leaching and Solution Purification, and II. Electrowinning. This paper covers only the first part of the hydrometallurgical process: Leaching and Solution Purification. Initially, the paper briefly discusses the history of the pollution problem at the Bunker Hill Superfund Site, the origin of heavy metals in the mine waters, and the development and use of the water treatment plant. The leaching of sludge was examined as a function of the following parameters: constant vs. initial pH, initial vs. delayed addition of SO2, temperature, and pulp density. It was found that leaching with H2SO4 at pH 2.0 for 15 minutes (at 60°C), followed by S02 addition for another 15 minutes, could completely dissolve Zn and Mn. Solution purifIcation was done in three stages. In the first stage iron was removed by adjustment of pH (to pH 5.0) and oxidation offerrous to ferric iron (with H2O2). In the second stage, Cu and Cd were removed by Zn dust cementation. Finally, Co and Ni were precipitated with the organic reagents 1-2 nitroso-naphthol and nitroso, respectively. Electrowinning of Zn and Mn is discussed separately in Part II of this paper.

Jan 1, 1996

By Kandipati Sreenivasarao

Ion flotation is a promising separation process for continuously removing toxic metal ions from dilute process effluents. After treating the effluent with appropriate surfactant(s), the metal- bearing species adsorb onto the surface of rising gas bubbles and can be collected as foams. Suitable collectors have been identified for most of the elements of the periodic table. However, a better understanding of the thermodynamic, kinetic and engineering principles that determine the performance of ion flotation systems would facilitate commercial utilization of this technology. A model system of sodium dodecylsulfate-ethanol has been studied for the removal of Cu (11) from dilute solutions, using laboratory-scale flotation columns. This paper reports the effects of the air flow rate, solution height, foam drainage zone height and col1ector:metal ion ratio on the flotation kinetics, ultimate recovery of metal, flotation product grade, foam losses and effluent quality. Preliminary results for Pb (11) removal are also reported.

Jan 1, 1993

By Dean G. Heitt

"The Rain and SMZ mines from 1987 to 1994 produced a total of22.0 t of gold from a pre-mine reserve of 14.24 Mt of ore grading 2.13 g/t Au.Gold at Rain is hosted within the basal portion of the Mississippian Webb Formation. ·Mineralization is closely tied to the Rain Fault which is interpreted to be the main feeder for the deposit. Multiple collapse and hydrothermal breccia events provided permeability for the mineralizing fluids in the otherwise unreactive siltstones. Major alteration events include: decalcification and dolomitization of the Devils Gate Limestone; and silicification, baritization, argillization and oxidation of the Webb Fm. Six ore types based on XRD and visual rock chip Jogging have been identified: siliceous ore containing >40% quartz and <30% barite; siliceous-baritic ore containing mostly silica but >30% barite; baritic ore containing >40% barite; argillaceous ore containing >40% total clays (including alunite); calcareous ore containing mostly calcite and dolomite; and carbonaceous ore which has significant pyrite and organic carbon. Metallurgical testing of the oxide leach grade ores found that recoveries, on -1.3 cm crushed material, were greater than 70%. Results also found that Rain ore has strong grind dependency due to silica encapsulation.The Rain leach pad was commissioned in 1988, and to date 9.3·Mt at an average grade of0.65 g/t Au have been placed. Life to date recovery, through December 1995, is approximately 51 %, for a total of3.87 t of gold produced. Two major factors have contributed to the low leach recoveries at Rain when compared with the metallurgical testing: 1) More argillaceous ore than expected was placed on the pad especially late in the mine life and 2) approximately 50% of the tons placed were run-of-mine with no agglomeration."

Jan 1, 1997

By J. Boltano

This paper discusses the study, design and implementation of the new gas handling system for the Caletones Smelter of Codelco-Chile. A discussion on design conditions for a future Sulphuric Acid Plant using Teniente Converter gases is also included. The old system which started to be modified in 1985 and relied on natural draft and used balloon flues, resulted in a limited gas handling capacity for operation under future process conditions. This system also caused excessive fugitive gases in the smelter working areas. The new system permits handling of process gases from the higher capacity Teniente Converters Installed in 1987-1989 improving the gas handling of the reverberatory furnaces and Peirce-Smith converters as well as the environmental conditions of the smelter. This system utilises improved converter gas hoods, evaporative cooling and electrostatic precipitators gas cleaning, and is based on natural draft.

Jan 1, 1992

By J. T. Stanley

The identification of crystal phases and crystal chemistry can be critical to understanding the mechanisms of waste material interaction with native soils. Understanding these mechanisms can suggest correct methods for remediation and treatment. A program is outlined and examples are given of the development of effective techniques for rapid phase identification of environmental samples using electron microscopy. The program concentrates on the development of integrated object oriented software to aid rapid searching of online databases and rapid simulation of potential crystal diffraction patterns. Examples come from dried sludge taken from a former hard-chrome plating facility.

Jan 1, 1993

By K. Soldenhoff

The Bulong deposit, situated near Kalgoorlie in Western Australia and owned by Resolute Limited, is a lateritic deposit containing on average 1.1% nickel and 0.09% cobalt. A process has been developed and tested at the mini-plant scale for direct solvent extraction and separation of Co and Ni from solutions derived by acid pressure leaching of Bulong ore. In this paper, two solvent extraction processes are described. The first process uses Cyanex 272 to extract cobalt and reject nickel to the raffinate. The second process uses Versatic 10 to extract and purify nickel. The loaded strip nickel solution is suitable for electrowinning. Results of both batch laboratory tests and continuous mini-plant trials are presented. The selectivity of the solvents with respect to the major impurities such as Mn, Mg, Ca, and Zn is also discussed.

Jan 1, 1998