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By A. Mezei

A process has been developed to recover cobalt, gold and bismuth from the NICO deposit in Canada. The process consists of a bulk rougher flotation followed by an optional separation by flotation to produce a bismuth concentrate and a cobalt concentrate, grading on average 12.8 % Bi and 1.8% Co, respectively. Cobalt is leached by pressure oxidation at 97% efficiency, producing a pregnant solution suitable for further processing. Before optimization, about 38% of the bismuth is recovered in the selective concentrate, wherefrom it is recovered by ferric chloride leaching followed by cementation, at overall efficiencies exceeding 98%. The gold is recovered from the cobalt and bismuth leach residues by cyanidation, at 95% efficiency. Previous work described the results of the leaching of the concentrates, recovery of gold (Part I) and the recovery of bismuth (Part 11). This work describes the results of the cobalt recovery testwork and the resulting conceptual flowsheet. The sulfur dioxide-oxygen system was the most efficient for the oxidationlprecipitation of iron and arsenic from cobalt bearing pregnant leach solutions, producing purified solutions assaying <1 mg/L As and <8 mg/L Fe. The efficiency of cobalt solvent extraction (from the resulting purified PLS containing about 1 g/L Co) ranged from 9 1 to 98%; the co-extractions ranged from 88 to 100% for copper, from 28 to 33% for magnesium, from 6 to 7% for calcium and from 96 to 98% for zinc. Sulphide precipitation processes (using either sulfur dioxidelelemental sulfur or sodium sulfide) produced residual copper concentrations in the cobalt strip solution ranging from 0.1 to 2 mg/L Cu. About 90% of the calcium and magnesium were separated by scrubbing the organic with cobalt sulfate, producing residual concentrations of 12 mg/L Ca and from 180 to 330 mg/L Mg in typical feed solutions directed to cobalt carbonate precipitation tests. Cobalt carbonate precipitation efficiencies ranged from 75 to 78% when calcium and magnesium co- precipitations were restricted from 8 to 17% and 0.3 to 0.4%, respectively. The limits required by most stringent specifications on commercial grade cobalt carbonate products were met or exceeded.

Jan 1, 2002

By S. q. Honingh, G. Van Weert

Currently produced zinc-enriched blast furnace dust is stored on site at CORUS IJmuiden. To end this practise, a research program was started in 1996. Four technologies were studied: oxidative autoclave leaching in a chloride medium, fluid bed pyrohydrochloridisation (pyrohydrolysis) to yield lead-zinc-free (hematite) calcine, EAF (plasma) smelting/zinc fuming, and incorporation of the dust in 'iron foundry cupola charges. All aim to remove zinc and lead, recycle the iron residue internally, and produce a saleable zinc-lead product.

Jan 1, 2000

By A. René Silva

The separation of Fe(III) from simulated Ni(II) solutions using different ion exchange resins was studied. The resins tested included cation exchangers with sulfonic and carboxylic groups and chelating resins with iminodiacetic, aminophosphonic, and mixed sulfonic and phosphonic groups. The dosage of resins was varied from 0.1 to 0.5 g/mL to study the impact of resin type and dosage on iron separation from simulated nickel leach solution containing 25 g/L Ni(II) and 25 g/L Fe(III) at pH 1.5. Also, the effects of different metal ion concentrations, Fe (III):Ni(II) ratios in solution, pH, and adsorption times were investigated. Experimental results demonstrate that all the chelating resins selected favored the adsorption of Fe(III) over Ni(II) with high Fe(III) loading. Soft cation exchange resins also favored the adsorption of Fe(III) over Ni(II), but no significant Fe(III) loading was observed. In contrast, strong cation exchange resins did not show adsorption preferences. The most efficient separation was observed using resin with aminophosphonic groups at resin dosage of 0.2 g/mL, having a Fe(III) adsorption over 94% and Ni(II) adsorption below 5%.

By Timothy W. Ellis

"This paper presents the basic theory of operation, physical chemistry and phase equilibria which allow the development of liquid-liquid extraction circuits based on metallic solvents. The incorporation of reduction and reduction/diffusion processes into the process scheme is discussed and a detailed description of several liquid-liquid extraction schemes are developed. A synopsis of experimental results obtained using this method to separate rare earth and other metal based materials will be given.IntroductionConcerns over the effects of waste materials in the environment has been one of the significant social hallmarks of the late 20th century. Essentially every industrialized country has had to incorporate the cost of waste material into the equation of production. Legislative initiatives have led to the passing of very tough laws, by historical standards, which govern the environmental impact of materials processing.Liquid-Liquid extraction is a very common unit operation normally using aqueous and/or organic based solvents. Early work at the Ames Laboratory focused on the use of this technique for the reprocessing of spent fuel from liquid metal breeder reactors by the use of metallic solvents. Recently, we have revisited this area as a means to recycle/reprocess several emerging rare earth based materials, although this method has a much wider range of application. The reinvestigation of this technology is particularly timely as hydrometallurgical based processes are coming under increasing scrutiny in the U.S.A. by the Environmental Protection Agency (EPA). Although technology currently exists to remove contaminants from aqueous based waste streams, often the application of such methods is expensive. With proper design and judicious selection of reagents liquid metal extraction can achieve a high recovery along with a benign waste stream.This process has several possible advantages over other technologies. First is the elimination of aqueous solvents. Therefore, problems associated with disposal or reprocessing of the aqueous carrier are eliminated. Second, with proper system design, very high separation coefficients can be obtained thus limiting the number of stages required. Third, metals are extracted from metals with a metallic product, thereby eliminating the need to re-reduce metal for oxides or other compounds which are the common output for aqueous based extraction procedures."

Jan 1, 1996

By V. D. Tathavadkar

Natural chromite mineral is a solid solution of spinet end members namely: chromite (FeCr2O4), hercynite (FeA1204), magnetite (Fe3O4), magnesio-chromite (MgCr2O4), (MgA12O4), and magnesio-ferrite (MgFe2O4). A phase transformation in chromite minerals occurs in oxidising conditions during the soda-ash roasting reaction. This phase transformation plays an important role in improving the extraction efficiency of Cr3+ from mineral phase. The extraction efficiency of chromium (Cr3+) from chromite to a water¬soluble sodium chromate (Cr6+) salt depends upon the decomposition kinetics of the spinet phase. An investigation of the phase changes in chromite ores in the absence of sodium carbonate was carried out in air, argon, and in argon +5 % hydrogen gas mixture. The thermodynamics of phase transformation reaction in chromite solid solution phase is discussed using the solution model proposed by Sack and Ghiorso [1]. The microstructural changes and the changes in elemental compositions of different phases were examined by SEM and electron probe microanalysis (EPMA) respectively. The experimental results indicate that the solid solution spinet phase in chromite mineral undergoes spinodal decomposition under the influence of oxygen partial pressure and temperatures. The structure of phases formed and their morphologies suggest that the phase decomposition may be similar to those observed by Burkert et. a]. 121, although the scale of phase separation in chromite appears to be strongly dependent on oxygen partial pressure.

Jan 1, 2001

By Douglas K. Modrow

In the fall of 1993, construction was completed on a state of the art industrial waste water treatment plant at Asarco&apos;s East Helena Lead Smelter. Purpose of the plant was to remove arsenic and metals using hydroxide precipitation. Completing of the plant culminated a lengthy process of laboratory bench-scale test work, engineering, construction, and Environmental Protection Agency (EPA) oversight. Unfortunately, the effiuent requirements for the plant were made significantly more stringent as construction was rearing completion. As a result, optimization activities were initiated to determine and implement measures to substantially improve effiuent quality so the new discharge limits could be met. These activities consisted of acquiring a thorough understanding of process chemistry and plant operations, and developing simple, practical methods of automating unit operations associated with the treatment plant. Implementation of these modifications in the second half of 1996 will not only significantly improve the constancy and reliability of treatment plant operations, but also result in operating cost savings and reduced need for increased operator attention at capacity flows, plus allow the treatment plant to meet the new discharge limits.

Jan 1, 1996

By Andreas Siegmund

During the decade of the nineties the conventional method of primary lead smelting (sinter machine/blast furnace) was successfully challenged by the introduction of novel direct and continuous smelting processes. In combination with a significant shift in market structure, as well as more stringent government regulations these modem technological innovations like the QSL, Kivcet, and Isa/Ausmelt processes became more than major competitors. They have proven to be economically and environmentally viable. The intensification of the metallurgical reaction by applying oxygen enriched or pure oxygen bath or flash smelting principles resulted in cost savings and a higher flexibility with respect to raw materials and additives usage. By synchronizing individual auxiliary plant sections with the smelting process a virtually waste-free production and low-emission mode of operation with nearly optimum energy exploitation is achieved. The primary lead industry will gradually substitute the sinter -blast furnace operation with novel high-energy efficient technologies in the new millennium.

Jan 1, 2003

By Chuanhong Li, Zuohua Lin, Zhancheng Guo

"Catalytic mechanism of CeO2 in combustion of coals was investigated in this paper. Catalytic combustion of four kinds of coals with different metamorphic grades by CeO2 was examined, suggesting that catalytic function of CeO2 increases with increase of metamorphic grade of the coals. One important reason for CeO2 promoting combustion of the coals is that pyrolysis of anthracite is advanced by CeO2, which not only raises the pyrolysis rate and pyrolysis conversion ratio, but increases contents of light components in pyrolysis gas; and both pore space and specific surface area of the pyrolysis char are enlarged by CeO2, which is another reason. In order to realize in situ catalysis for reducing catalyst consumption, it is crucial to increase catalyst particle number and enhance the bonding force between catalyst and coal. In addition, remarkable energy saving effect was observed when a nanometer calcium-based rare earth catalyst obtained by hydro-thermal synthesis was applied to catalytic combustion of coal injection into blast furnace.Introduction Coal combustion is acknowledged as one of the most important coal applications. Since addition of catalysts could reduce the ignition temperature of pulverized coal and accelerate the coal combustion, catalytic combustion is generally accepted as an effective measure to realize fast combustion of coal. Furthermore, different catalysts added may produce different effects on ignition temperature of coal. It is reported activity of catalysts with the same cation follows this order: OH->CO3 2->Cl->SO4 2-; while that of the catalysts which have the same anion follows: Cs+>Rb+>K+>Na+>Ba2+>Li+>Sr2+>Ca2+>Mg2+>Be2+ [1-4] .Due to the special physical and chemical structure, CeO2 plays an important role in the catalysis field. Many literatures point out that CeO2 not only has great catalytic effect on energy conversion, succeeded in catalyzing combustion of gaseous fuels such as CH4, CO, etc. but also can catalyze combustion of some liquid and solid fuels such as JP-10, black carbon, carbon deposit in the automobile exhausts and so on [5-9].Pyrolysis, the first step of combustion, directly influences ignition temperature and combustion rate of coals. So a great variety of catalysts were applied to catalyze pyrolysis of coals. And plenty of studies suggest that the alkali and alkaline-earth metal compounds inherent in the coals show apparent catalytic effect on coal pyrolysis. Meanwhile, addition of alkali and alkaline-earth metals into coal combustion process also indicates obvious catalysis effect, accelerating coal pyrolysis, improving pyrolysis conversion ratio, increasing contents of pyrolysis gases and changing composition of the pyrolysis gases [10-15].Although alkali and alkaline-earth metal compounds have good catalysis effect on coal combustion, their application in the catalysis field was limited because of their erosive attack to the combustion equipments. In contrast, CeO2, as a substitution of the traditional coal catalysts, presents widely potential application due to its good catalysis ability, non-corrosive and nontoxic. However, investigation on CeO2 catalyzing coal combustion is rarely reported. In this work, catalytic mechanism of CeO2 in coal combustion was studied, in an attempt to provide theoretical foundation for developing new catalysis technologies."

Jan 1, 2009

By Dale W. Collins

The disposal of arsenic from copper operations possess various health, environmental and processing problems. There are basically two areas of concern. The first being the disposal or treatment of smelter flue dusts and the second the removal of arsenic from refinery electrolytes. A number of treatment options have been proposed including the addition of soluble arsenic wastes to copper heap and dump leaching solutions. This approach will allow arsenic to be reintroduced to the ore via Solvent Extraction (SX) raffinate associated with hydrometallurgical operations. Knowledge of the attenuation behavior and mechanism during leaching is important in determining the long term stability of arsenic and the success of this approach. Parameters, such as uptake capacity, pH, particle size and solution chemistry have been investigated. Arsenic attenuation has been examined using column leaching with experiments employing both continuous flow and pulsed additions of As(V). In the initial stages of leaching, the attenuation of arsenic appears to depend on the pH and iron concentration in the effluent. Arsenic stability in the copper oxide ore has been examined with rinses of progressively lower pH.

Jan 1, 1994

By Graham Cooke, Abhishek Lahiri, Animesh Jha, E. Jeya Kumari

"CO2 reduction by alternative energy devices such as wind-power, electric vehicles utilize rare-earth elements (REE) in several forms; such as in piezo-electric devices, batteries and magnetic materials. In 2010, the 95% of Rare Earth supply is controlled by China, compared to USA being dominant supplier in the 1980s. The dependence upon a single source of lanthanides has prompted the utilization of lower grades of titaniferous mineral concentrates, which often have rich seams of REE. We propose a new methodology, which utilizes the low-grade minerals for the extraction of synthetic rutile and also significant quantities of REE. We demonstrate the alkali roasting of lower grades of mineral concentrates and subsequent leaching in an aqueous medium for preferential flocculation of REE during the extraction of synthetic rutile. Changes in mineral structure during alkali roasting and leaching determine flocculation of REE and permit their separation at the front end of unit process.The physical chemistry and crystal structure of minerals in equilibrium with alkali and aqueous medium play an important role, which we explain by demonstrating the changes in the crystal structure. The quantification of separation of RE oxide via chemical analysis suggests that it may be possible to separate rare-earth oxides between 50 and 80% of the initial concentration in the non-magnetic fractions of ilmenite, for example. The microstructural and X-ray diffraction analysis points out that the presence of alumina and roasting with potassium based alkali enhances the separation and flocculation of rare-earth elements at the front end of the process after roasting. The process allows the recovery of CO2 generated by recycling into the process for the regeneration of alkali."

Jan 1, 2011

By Dajian Wang

To obtain the thermodynamic properties of a multicomponent liquid alloy system over the whole range of concentration at an arbitrary temperature, the free volume cell theory has been applied to derive the formula of activity coefficients of liquid solutions based on the infinitely dilute solutions at some temperature. The linear logarithmic relationship between activity coefficients of binary dilute solutions and reciprocal of absolute temperature have been verified, and are in good agreement with the experimental values from the literature. The Monte-Carlo algorithm was used to calculate the nonlinear end value equations of binary systems, then the free volume parameters obtained were correlated with the activity coefficients of liquid binary, ternary, and quaternary systems at an arbitrary temperature. Three dimensional a-X-T diagrams of some binary systems representing the temperature and concentration dependence of activities were plotted. The calculated results regarding non-ferrous alloy systems have been statistically examined with the experimental values from the literature. Hence, this simple approach could be useful for analyzing thermodynamic properties of liquid alloy systems.

Jan 1, 2000

By David J. Kinneberg, Barbara E. Mangion, Arnold M. Savolainen

Analytical laboratories require a qualitative or semi-qualitative method of determining major and minor constituents in "unknown" samples to select optimal analytical techniques. This is exceedingly important in precious metal assay laboratories where the precision and accuracy requirements are exacting (routinely within 0.02%, absolute basis). This paper describes the use of an x-ray fluorescence spectrometer with a specially designed software package to select optimal analytical procedures and specify relevant analytical parameters. A wavelength dispersive XRF spectrometer is capable of quick and accurate analyses of properly prepared samples without extensive standardization. When coupled with a specially designed software package, this preliminary assay system is applicable to a wide variety of sample types including gold and silver bullion, karat gold and karat PGM alloys, high silver and high copper metallic samples as well as particulate samples of ores and sweeps. The system relieves the assayer of tedious calculations for silver inquartation and proofing, minimizes human error and standardizes selections over time. Most importantly, the system allows for independent verification of final assay results.

Jan 1, 1999

Physical and chemical methods were investigated to tower thorium levels in Eneabba Ilmenite from the natural levels of 180-500 ppm to give Becher Process synthetic rutile with less than 100 ppm thorium. Chemlcal treatments, but not physical separations were successful. A pilot plant trial of a sodium hydroxide leach (25M NaOH at 75°C and 40 wt% solids for Ih) followed by a sulphuric acid leach (3M H2S04 at 90°C and 60 wt% solids for 211) confirmed that thorium could be removed to below 100 ppm. However, the activity of the ilmenite was not lowered to the same extent

Jan 1, 1996

By T. T. Chen

Canadian Electrolytic Zinc has developed the "cement-stabilization of jarosite residue" Garofix) process to stabilize zinc plant jarosite residues for disposal. The cement-jarosite mixtures cure quickly, have good mechanical strength and low hydraulic permeability; they possess good neutralizing capability and chemical stability. In the jarofix process, Portland cement partly decomposes jarosite to form (SO4MOH)12.nH2O, ferric hydroxide and an alkali sulphate. Approximately 40% of the jarosite reacts in mixtures containing 30% cement. The jarofix product also contains various Ca-Al-Fesilicate-sulphate-hydrate phases and gypsum, which bond the individual particles together imparting mechanical strength and reducing the permeability. Most of the reactions take place in the first few hours of curing. Ammonium jarosite is slightly more reactive than sodium jarosite but releases NH3 gas; water-soluble Zn in the jarosite residue is stabilized in the cement reaction products.

Jan 1, 1996

By A. González

Arsenic is one of the main contaminants present in Chilean copper concentrates and its abatement represents a challenge for the process metallurgy, particularly under the strong environmental requirements in the global community. The possibility to form ferric arsenate directly from a gas phase by means of a heterogeneous reaction between an arsenic gas bearing and iron oxide was studied at laboratory scale. A thermodynamical analysis for the system Fe-As-O-S has been initially made, in order to obtain the stability conditions for the ferric arsenate or other FeAsyO2 type compounds. Experiments were made using an hematite sample suspended in a thermogravimetric device. AS4O6 gas generated from solid AS2O3 that was passed through the iron oxide sample and its instantaneous weight change was recorded directly. A kinetic study for the AS4O6 volatilization was made to control the gas composition. A chemical control between 300 and 600°C with an apparent activation energy of around 14 Kcal/mol As2O3 was determined. The samples after the reactions were chemically and XRD analysed. Arsenates detected corresponds to complex compounds. Results shows a dependence on temperature and oxygen content in the gas phase. The kinetics for iron arsenates formation is slow, reaching an arsenic capture of 6% after 80 minutes of reaction when an oxygen content of 50% is fed continuously at 800°C and 3,56% As in the gas. Experiences made at the same temperature but under higher oxygen content in a closed reactor, allowed arsenic capture close to 60%. For higher temperatures the capture is considerably lower.

Jan 1, 2003

By N. A. Warner

Fundamental studies on the reaction of limestone or dolomite at high temperature with S02 are extended to the realm of large scale primary copper smelting. Whereas flue gas desulfurisation in the electric power utility industry is concerned with S02 concentrations normally less than 0.5 percent, high temperature smelting gases can have S02 levels approaching 100 percent. The reaction involved is very exothermic so proposals are made in this paper for returning the heat generated in sulfur fixation directly back to the copper smelting process. This integration leads to metal production with lower energy requirements than current technology. The anhydrite reaction product can either be disposed of locally with minimum adverse environmental impact or upgraded to a value-added product. It is assumed, of course, that no viable market exists to support sulfuric acid production.

Jan 1, 1996

By Brian Balmforth

Solvent extraction has been applied successfully to the recovery of a range of metals from a variety of process streams. Particular benefits are derived from the use of new highly selective extractants. These will be exemplified by case studies including the recovery of zinc from sulfate and chloride media using ZENECA&apos;s new extractants which show a very high selectivity over iron and the recovery of antimony and bismuth from copper refinery electrolytes using ZENECA&apos;s strong and selective extractant DS5834. The conclusions are drawn that solvent extraction is a cost effective technology for metal recovery and recycling, even when used to treat relatively small volume/low concentration process streams, and that it can provide the essential enabling components of a larger system for waste minimisation programmes.

Jan 1, 1996

By A. González

Arsenic is one of the main contaminants present in Chilean copper concentrates and its abatement represents a challenge for the process metallurgy, particularly under the strong environmental requirements in the global community. The possibility to form ferric arsenate directly from a gas phase by means of a heterogeneous reaction between an arsenic gas bearing and iron oxide was studied at laboratory scale. A thermodynamical analysis for the system Fe-As-O-S has been initially made, in order to obtain the stability conditions for the ferric arsenate or other FexAs2O2 type compounds. Experiments were made using an hematite sample suspended in a thermogravimetric device. AS4O6 gas generated from solid AS203 that was passed through the iron oxide sample and its instantaneous weight change was recorded directly. A kinetic study for the AS4O6 volatilization was made to control the gas composition. A chemical control between 300 and 600°C with an apparent activation energy of around 14 Kcal/mol As2O3 was determined. The samples after the reactions were chemically and XRD analysed. Arsenates detected corresponds to complex compounds. Results shows a dependence on temperature and oxygen content in the gas phase. The kinetics for iron arsenates formation is slow, reaching an arsenic capture of 6% after 80 minutes of reaction when an oxygen content of 50% is fed continuously at 800°C and 3,56% As in the gas. Experiences made at the same temperature but under higher oxygen content in a closed reactor, allowed arsenic capture close to 60%. For higher temperatures the capture is considerably lower.

Jan 1, 2003

By Kenneth L. Nash

The control of solubility of waste actinide ions, by conversion to highly insoluble mineral phases has been demonstrated in the laboratory. Actinide metal ions are removed from neutral pH solutions by a combined ion exchange-decomposition-mineralization process based on the application of the naturally-occurring hydrolytically unstable.polyphosphate organic compound phytic acid.

Jan 1, 1999

By Peter R. Sanford

Cyanides are present as a dilute constituent of streams from a variety of metallurgical and mineral-processing operations. In addition, a cyanide concentration in excess of approximately 100ppb is toxic to aquatic life, and consequently these operations require a waste-treatment process to reduce the already dilute cyanide species by several orders of magnitude. Furthermore, the waste streams may have flowrates in excess of a million gallons per day. The paper reports on research conducted with a laboratory?scale electrochemical porous (graphite felt) electrode (anode) flow-reactor, which was conducted in conjunction with a computer-aided simulation of a mathematical model describing the intrinsic rate-phenomena associate with the electrode processes. The laboratory-scale cell, of rectilinear geometry, was found to be capable of reducing a feed-stream anolyte (KCN-KOH and supporting electrolyte of a single salt ? K2SO4) with a cyanide concentration of 10ppm, to less than 100ppb, at current efficiencies in the neighborhood of 50%. The computer simulation of the cell performance based on the mathematical model (and constraints imposed for tractability) was found to provide only for qualitative agreement.

Jan 1, 1998