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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 Raymond F. Dalton

Despite the ready availability of numerous zinc sources, the process of solvent extraction- electrowinning (SX-EW) has as yet found little favour in the zinc industry. It is suggested that this is largely due to the previous lack of availability of suitable selective reagents having the particular features required to enable them to fit in to a solvent extraction-electrowinning based process for zinc, particularly with regard to strength and selectivity for zinc over iron. This paper describes work on the development of new selective extractants for the recovery of zinc from both sulfate and chloride aqueous solutions and suggests how they might be integrated into new zinc processes.

Jan 1, 1994

By Gus Van Weert

This paper describes the results of autoclave testwork where ferric nitrate was hydrolysed in the presence of certain cations and anions and the resulting hematite analyzed for foreign constituents. For the cations Zn++, Ni++, Cu++, and AI+++, selectivity factors of over 107 were found. Magnesium gave 3.106. These factors are calculated as Me/Fe in solution over Me/Fe in the hematite; Me representing the metal in ion added. As-a result of the testwork at Delft University of Technology, BUDELCO (the Netherlands electrolytic zinc producer) ran a series of ferric nitrate hydrolysis tests in the presence of 10 additional trace elements. Impurity levels were prejudiced on Me2 EPHA extraction of iron from their zinc circuit, followed by HNO3 stripping. Good selectivity against base metals was confirmed, but trace elements forming anions (As. Sb) and sulphate were incorporated in the hematite. These BUDELCO results are also presented.

Jan 1, 1995

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By Z. M. Zheng

Cyclic voltammetry, potential step, and ac impedance techniques were applied to study the electrochemical reaction of arsenopyrite in chloride solutions. The relationship between anodic current density and time in potential step measurements indicates that the oxidation of arsenopyrite is irreversible. The results of the constant potential coulometry show that the stoichiometric factor of the total electron involved in the overall reaction is 14. It is proposed that the dissolution of arsenopyrite is retarded by coverage of sulfur produced in the reaction as an intermediate product. The measured results of ac impedance strongly support the proposition. The proposed reaction mechanism also explains satisfactorily the charging current density and Tafel slopes measured in potential step measurements.

Jan 1, 1995

By Klaus Gamweger

"This paper introduces an innovative solution to open and close the tap hole of different furnace types in the copper industry with a slide gate system. Two plates with defined drilled holes are slid against each other, which enables effective starting and stopping of the copper flow as well as throttling. Typically, the copper is poured via a tap hole into a launder system by rotating the furnace into an appropriate position. Control of the casting rate is also performed in this manner. Or, in case of stationary furnaces the tap hole is opened by oxygen lancing and closed manually with a clay- or copper-cone. These procedures show a lot of disadvantages including splashing, oxygen pick-up, and energy losses as well as a severe danger for the working staff. All these problems can be overcome with an appropriate slide gate system.IntroductionThe control of the casting rate of a copper anode furnace usually is performed by rotating the furnace into an appropriate position. This implies that the taping starts with the tap hole at a very high position. Copper splashing and an uncontrolled oxygen pick up are - with several more disadvantages - the consequences. RHI AG has developed an innovative solution for copper applications to open and close the tap hole with a slide gate system which allows also an accurate control of the flow rate. By using this system it is possible to start the casting procedure with the tap hole at the deepest position, directly above the launder. This paper presents this new slide gate system in detail and shows the advantages in production and safety issues."

Jan 1, 2012

By Terence Makanyire, Animesh Jha

The dissolution and chemical properties of vanadium, zirconium, and niobium in rutile lattice are analyzed by comparing the octahedral site preference energies, with respect to Ti4+ ion in the solvent phase. The oxides are often present in rutile lattice and interfere in achieving the quality of pigment grade TiO2 due to favourable Gibbs energy for dissolution in the solvent rutile matrix. Binary mixtures of V2O5 { TiO2; Nb2O5 { TiO2 and ZrO2 { TiO2 with compositions of 80, 85, 90, 95 and 97 wt% TiO2 were made, pelletized and sintered at 1100 °C for 24 hours. The solidsolution mixtures were then cooled and leached in 2M NaOH for 3 hours at 60 °C. Phase and lattice parameter characterizations, and microstructural and compositional analyses were then carried out using X-ray diraction and SEM/EDX, respectively. The leachates were analysed by Atomic Absorption Spectroscopy (AAS), using which the solute dissolution model for oxides were investigated.

Jan 1, 2014

By Timothy W. Skszek, Adrian S. Sabau, Hebi Yin, Xiaoping Niu

The microstructure evolution during solution treatment plays an important role in mechanical properties of heat-treated aluminum alloys. In this paper, models were reviewed that can predict the microstructure evolution during the solutionizing process of the aging heat treatment of aluminum alloys. The dissolution ofMg2Si particles has been modeled as a diffusion process of Mg in the a-Al matrix. The evolution of volumetric fraction of fragmented silicon as a function of time and temperature was also considered. The growth and coarsening of silicon particles during the heat treatment was considered. It was found that constitutive equations and required property data for most of the phenomena that need to be considered are available. Several model parameters that need to be obtained from material characterization were identified. Pending the availability of these model parameters, this comprehensive model can be used to describe the microstructure evolution of aluminum alloys in order to optimize the solutionizing heat treatment for energy savings.

Jan 1, 2013

By Thomas Schemmel, Bertram Kesseiheim, Helge Jansen, Uwe Kreme

"During the last decades the refractory life time of the different aggregates of the secondary aluminium production was improved significantly. However, each repair and installation of refractory material affects the operating schedule and can cause costs in the million range. The downtime of just one melting furnace generate costs of 100.000 to 400.000 $ per day. Besides cooling down of the furnace and its repair, the heating-up procedure accounts for the longest time of the shutdown. Usually, heating-up of low cement or ultra low cement castables takes 120 to 150 hours. In order to reduce such expensive downtimes Refratechnik developed a unique and novel product series: Nanobond. These materials can be heated-up in only a third of the usual time. This paper talks about the theoretical aspects, as well as the mechanical and physical properties and especially practical experience of using Nanobond.Theoretical Aspects and Laboratory ResultsCement containing castables such as RCC, MCC, LCC or ULCC are considered standard in many refractory applications. Over the years a wide range of possible raw materials and practical installation methods were developed. However, all of these cement bonded refractory mixes possess one main important drawback. Such materials are characterized by the hydration of the cement bonding. As a result the physical bonded and the hydraulic water has to be removed in a relatively complicated drying procedure. The hydraulic water specifically demands a very careful and cautious heating up procedure. Most of the dreaded steam explosions can occur at a furnace temperature of approx. 250 oC. [1] To avoid such destructions, the heating-up of a new lined or repaired furnace can be very complex and slow. Depending on the furnace or the casted part a drying time of several days with long curing times are common."

Jan 1, 2012

By Yongfeng Jia

Lime neutralization and co-precipitation of As(V) with iron(III) is the most widely used and most economical method for the removal of arsenic from mineral processing solutions and effluents. However, the arsenate fixation mechanism in the coprecipitated solids is not fully understood. It was suggested by various researchers to be a ferrihydrite precipitation process during which arsenate is removed by adsorption on ferrihydrite. In this study, XRD, EXAFS and microprobe were employed for the speciation of arsenic and the effect of various factors on arsenic solubility was also investigated. The results indicate that coprecipitation is a more complicated process than simple adsorption resulting in lower arsenic solubilities. Poorly crystalline ferric arsenate was observed for the first time to be present in the coprecipitated solids. In case of lime as base, there exists some type of Ca-Fe-arsenate association. A general term ?coprecipitate? is suggested to describe the precipitated arsenic-bearing solids instead of those widely used specific terms ?arsenical ferrihydrite? or ?arsenic-bearing ferrihydrite?.

Jan 1, 2005

By Hongfa Hu, Stavros A. Argyropoulos, Stephan Ferenczy

"Physical as well as mathematical modeling was carried out to investigate the exothermic mass transfer in liquid metal systems. In these systems, the exothermicity induces unique heat, mass and momentum transfer phenomena. Moreover, these phenomena are deeply coupled and they are further complicated by the presence of a moving boundary.In the physical model used, ice cylinders were immersed into sulfuric acid solutions, because the intermixing of ice with sulfuric acid is very exothermic. In this low temperature system, velocity and temperature measurements in the sulfuric acid were made as well as measurements of the ice melting in the sulfuric acid.The mathematical model developed solved simultaneously the heat, mass and momentum equations numerically, utilizing the control-volume finite difference approach. The enthalpy method was adopted to track the moving boundary. Predictions made by the mathematical model were in close agreement with the results obtained by the physical model.The results from the mathematical model were further validated with experiments involving high temperature liquid metals. Specifically, data were obtained in an experimental setup involving (a) dipping silicon cylinders into high carbon liquid iron and (b) dipping nickel cylinders into liquid aluminum. Results from these experimental studies supported the predictions of the mathematical model."

Jan 1, 1999

By Willem P. C. Duyvesteyn

A novel hydrometallurgical process for Escondida copper concentrates has been developed by The Minerals Laboratory of BHP. The Escondida Process consists of concentrate leaching, solution purification, electrowinning and residue flotation. Part of the copper will be sold as high grade concentrate and part as high purity SX-EW copper. Contrary to previous efforts for the development of a hydrometallurgical process for copper concentrates, this patented process does not advocate the total dissolution of copper. It only aims for the copper that is readily soluble in a mildly oxidizing environment with an ammoniacal or acidic lixiviant. Both lixiviants were studied, but ammonia was preferred because of fast kinetics at ambient temperatures and pressures. By controlling the oxidation potential, the formation of sulfate ions and, consequently, of an ammonium sulfate byproduct, is precluded. These mild leaching conditions also prevent the dissolution of unwanted impurities and result in the production of ultra-high purity electrowon copper. Solution purification is carried out by solvent extraction with LIX-54. The very high loading capacity of this organic results in a compact SX circuit, consisting of two loading, one scrubbing, and one stripping stage. As the organic is selective for simple copper ions, the copper amine complex is broken down and free ammonia is regenerated and recycled for leaching. High purity copper cathodes are produced in a conventional sulfuric acid based electrowinning system. One scrubbing step is needed to separate the ammoniacal circuit from the acid circuit. Limiting copper dissolution to less than 50% also provides an opportunity to produce high grade concentrates by residue flotation. Copper recoveries in excess of 98% with precious metal values reporting to the final concentrate can readily be obtained. Complete breakdown of the copper mineral- pyrite middlings results in a final concentrate grade that can be even higher than the original feed material. The Escondida Process also provides an opportunity to accept lower grade copper concentrates producing improved copper recoveries in the mill and yet high quality concentrates for marketing. The Paul E. Queoeau International

Jan 1, 1993

By Batric Pesic

The interactions of mineral-pyrite with T. ferrooxidans were studied by using a cyclic voltametry technique. The interactions with bacteria were carefully examined during the entire growth stage of bacteria (fermentation). Several very important discoveries were made. For example, the pyrite surface invariably drastically changed its properties at the second day of fermentation. Beyond two days of fermentation, the cyclic voltamograms were insensitive to convective diffusion produced by stirring. The SEM study revealed that bacteria populated the pyrite surface at an extremely high density levels. The high density of bacteria, and the solid reaction products formed on the pyrite surface created conditions for pore diffusion which explained why the CVs became insensitive to convective diffusion in solution (stirring).

Jan 1, 1990

By Seshadri Seetharuman

The present paper summarises a series of measurements of the interaction parameter of oxygen in liquid copper with respect to a third element, e(M)o, where M is Mn, Zn, As, Se or Te which are common impurities in the liquid metal. The technique employed was the solid electrolyte galvanic cell method. The cell used may be represented as Pt, W or cermet / Cu-O-M // ZrO2 - CaO // AO, A /PT where AO/A represents a suitable oxide/metal reference. The measurements indicate that Mn and Zn interact very strongly with oxygen in liquid copper while, in the case of arsenic the interaction parameter is nearly zero. The behaviour of the elements Se and Te is unique with respect to oxygen interactions in copper bath. At oxygen levels, xo= 10-4 ? 10-5, the apparent interaction parameters are negative, comparable to that for sulphur. On the other hand, at lower oxygen levels, the results indicate that the interaction parameter values are positive. The results are discussed in the light of some of the theoretical models for solute interactions in liquid metals.

Jan 1, 1993

By Abbas H. Mirza

Arsenic and selenium are found in low quantities together with other metals in several nonferrous metallurgical process streams such as scrubber blowdown solution, acid plant wastewater, gas cleaning plant water, etc. Normally, the other metals in these streams are present as cations and can be precipitated by conventional lime treatment and sulfide polishing. However, arsenic and selenium are invariably present as anions, AsO33-and AsO43 in the case of arsenic and SeO32 and SeO42 for selenium. Conventional lime treatment removes most of the arsenic, but it does not remove selenium. The present paper reviews the processes and technologies developed to date on the removal of arsenic and selenium from metallurgical process streams.

Jan 1, 1996

By Kotaro Ogura

"The electrolysis process in which CO2 is selectively reduced to C2H4 at a three-phase(gas/solution/metal) interface on a copper-mesh electrode has been developed in a concentrated solution of potassium halide. At open-circuit potential, CO2 is captured on the electrode by being inserted into the double-layer consisting of halide anions specifically adsorbed and potassium cations which are located in the Helmholtz inner and outer layers, respectively. CO2 thus activated is subjected to the electrochemical reduction. In the early stage of reduction, CO2 is converted to formate radicals that are adsorbed on the electrode by taking the place of halide anions. The reductive coupling of these radicals results in the formation of intermediates such as -CH2C(O)- and CH2=CH-, and C2H4 is finally produced. The catalytic activity of the electrode process involving the insertion of CO2 into the double layer is not deteriorated at all during the electrolysis, and the continuous reduction of CO2 to C2H4 is possible with the addition of inorganic acid under the assistance of natural energy.Carbon dioxide is a serious pollutant released from fossil fuel power station, internal combustion and many industrial operations. The easy release of CO2 to the air has caused the global warming, and the technique which intends to curtail CO2 by pushing it back into the ground has been suggested. However, this problem should be greatly mitigated if CO2 can be converted to innocuous substances. Especially, the reuse of CO2 as fuels and chemicals is extremely effective not only for the mitigation of the global warming but also against the depletion of the fossil fuel reserves. Several processes for converting CO2 to valuable compounds have been proposed including hydrogenation over heterogeneous catalyst at high temperature and electrochemical and photochemical reduction. In the conversion and cutback processes of CO2, however, it is of importance that the process is feasible under mild conditions, because the secondary generation of CO2 is feared if high energy is required and supplied with a fossil fuel. In this meaning, the electrochemical reduction of CO2 taking place at room temperature, which is similar to photosynthesis, is promising. From the practical point of view, it is further necessary that the conversion rate is high enough and the product is satisfactorily valuable."

Jan 1, 2008

By A. W. Bryson, K. C. Lenthall

"With the growth in the use of cobalt in industry, interest in its extraction and recovery has increased. With this increased interest comes the need for a fundamental knowledge of the processes involved in the recovery of cobalt metal. This paper examines the effects of cobalt concentration, catholyte pH, operating temperature and current density on cobalt electrowinning with respect to the current efficiency, cell potential and nature of the cobalt deposit. It is found that the cobalt concentration and catholyte pH affect the current efficiency, while current density and temperature affect the cell potential and thus the specific power consumption. Pitting on the deposit is affected by the catholyte pH and the operating temperature. Furthermore, the effect of feed flow-rate on catholyte pH, and thus current efficiency, is investigated. A model to predict the cell performance, which includes the flux of hydrogen ions through the diaphragm, is proposed.IntroductionCobalt metal is a silvery transitional metal found between nickel and iron on the periodic table. Due to its resistance to corrosion and other properties under high temperatures and its good work-hardening characteristics, it is favoured in alloys used in high temperature applications. These include aerospace, aircraft and high speed tools. Other applications include its use as a colourant in glass and ceramics, a drying agent in paints, a nutrient for livestock, a catalyst in the petroleum industry and, in the medical field, in prosthetics and radiology.The main deposits of cobalt are found in Central Africa, specifically Zaire and Zambia, although deposits also occur in Morocco, Canada and Australia. The cobalt is generally associated with other transitional metals including nickel, iron and copper. It is generally extracted by hydrometallurgical means and recovered from solution by electrowinning or hydrogen reduction. Little data [1-2] exists in literature on the electrowinning of cobalt from aqueous solutions. This paper investigates the effects of various operating conditions on the current efficiency, cell potential and deposit nature under continuous operation."

Jan 1, 1997

By V. I. Lakshmanan

The demand for elements such as nickel, cobalt, titanium and gold in various applications has increased significantly. Innovation to recover these elements now plays a major role in metallurgical processes as established technologies have challenges in treating the types of ores that are available while meeting the increasingly stricter environmental regulations. Alternative chloride based processes have been developed that can be used to recover the value elements from the available feed stocks with potentially lower environmental impact. Chloride-based hydrometallurgical processes have several advantages, including higher leachability of complex ores/tailings and relative stability of chloro-complexes of the metals. Process Research ORTECH Inc. (PRO) has developed mixed-chloride process flowsheets, where innovative solvent extraction process steps are used for the separation of nickel, cobalt, titanium and gold from their respective chloride solutions. This paper will discuss the potential aqueous chloro-chemistry of these metals and separation reaction mechanisms involved in the solvent extraction process.

Direct electrowinning is an electrochemical process which has been developed for the extractive recovery of copper from dilute, acidic leach solutions. In passing through a thin particulate coke cathode. copper is reduced and electrodeposited in a thin layer forming a solid copper-coke sheet. The product is melted in a furnace to separate the coke, then the molten copper is fire refined to produce a salable product. A description is given of a prototype unit which is designed to treat 20 gpm leach liquor and recover over 100 pounds of copper per day. Economic analyses show that in a commercial facility producing about 25.000 TPY copper.*the direct electrowinning process has lower overall cost than either conventional iron-cementation or the newer liquid ion exchange-electrowinning when the leach liquors contain less than 2 grams per liter of copper.

Jan 1, 1976

By M. Fafard, R. Ahmed, O. Dion-Martin

"The optimization of aluminum sheet and tube forming needs the use of large strain finite elements software. The precision of the predicted results from those simulations depends mainly on the quality of constitutive law of the material used. In order to improve quality of these simulations, Barlat has suggested a new yield function named YLD2000-2d. This criterion describes the anisotropic behavior of the rolled aluminum plates. This work consists of characterizing the AA5754 alloy and estimating the material parameters needed for the YLD2000-2d criterion in LS-DYNA. In order to get these parameters, various mechanical testing were performed such as bulge and tensile tests. Moreover, the bulge test was also used to obtain an estimation of work hardening curve in large strain condition, up to 50%. The objective of this paper is to share the experimental results of the characterization of AA5754 aluminum alloy.IntroductionResearchers from National Research Council Canada's Aluminium Technology Center (NRCATC) and Aluminium Research Centre - REGAL, are working on aluminium tube hydroforming processes of AA-5754-0 alloy, used in automotive industries. Hydroforming process presents several difficulties such as wall thinning and section changes. In order to control them, some parameters can be set during the process like pressure rate and end feed level [1]. Given the complexity of the parts and the variability of the control parameters, the use of finite element method (FEA), like LS-DYNA, based on large strain theory is thus necessary. The accuracy of predicted results depends mainly on the quality of the constitutive law used to model the behavior of material. FEA results seem to be valid with the von Mises yield criterion used in some cases. But, given the anisotropic properties of the AA-5754 alloy, a more appropriate criterion could be used. The *MAT_ BARLAT YLD2000 shell material criterion, developed by Barlat [2], who's taking into account the anisotropic behaviour, was chosen due to its large flexibility and its good adaptation to particular elastoplastic behavior of aluminum. However, the use of this criterion needs to determine some material parameters by experimental way."

Jan 1, 2013