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By Fiseha Tesfaye, Pekka Taskinen, Daniel Lindberg

Due to increasing complexities of raw materials for base metals production the conventional pyrometallurgical processes are challenged. To make the appropriate modifications, thorough evaluations of the thermal stabilities of phases and phase assemblages which are commonly encountered in these processes are essential. In this work, phase relations and thermal stabilities of equilibrium phases in the Cu-Ni-S system have been reviewed. The calculated phase diagram of Cu-Ni system has been validated. At T < 630 K, in the Ni-rich corner, large scatter in data has been observed and discussed in detail. The other binary systems, Cu-S and Ni-S, have been also critically reviewed together with the ternary Cu-Ni-S system. The reviews were focused on compiling and discussing phase relations and thermal stabilities of the selected systems in the pyrometallurgical processes of Cu and Ni productions.

Jan 1, 2016

By Baozhong Zhao

The direct smelting of copper concentrates to copper metal in a single furnace offers environmental and energy advantages over conventional two-stage copper smelting processes. However, the direct copper making results in unacceptably high level impurities (As, Sb and Bi) in the anode copper. Experimental studies have shown that it is possible to remove these impurities from molten copper by injection of sulfur-hexafluoride. This paper discusses the experimental findings on the influence of various factors on the rate of removal of impurities, such as the impurity inter-effects, initial oxygen content in the metal and injection rate of SF6.

Jan 1, 1995

By W. K. Connor, O&apos

The Bureau of Mines has conducted beneficiation, carbothermic reduction, and leaching tests of Mn oxide ores as part of its evaluation of the Mn and Co resources of the West- Central Arkansas District. The major Mn oxides in the ore include cryptomelane, psilomelane, pyrolusite, and lithiophorite. Cobalt is contained within the Mn oxides. Nonbeneficiated ore was reduced at 800&apos; C with coal and leached in ammonium sulfate and ammonium carbonate leach liquors. Ore concentrates were calcined at 600" C prior to reduction under the same conditions as the raw ore. Head analyses reported up to 21 ptt Mn and 0.11 pct Co. Extractions of 70 to 90 pct Mn and 40 to 60 pct Co were achieved.

Jan 1, 1992

By D. M. Hausen

It has been demonstrated that microscopic techniques can be applied in a practical manner to the study of spodumene liberation in the processing of pegmatitic ores at the Kings Mountain spodumene plant, Kings Mountain, North Carolina. Spodumene and associated non-opaque gangue minerals are identified and quantified by microscopic point-counting of polished thin sections of heads, concentrates, middlings and tails fractions. Specially prepared polished thin sections? provide uniform thickness of particles for measurement of diagnostic optical properties and the alternate use of incident and transmitted light in distinguishing the various gangue and ore minerals. Spodumene is commonly associated and interlocked with quartz, albite, microcline and muscovite. Concentrate grade depends on the degree of spodumene liberation, which in turn depends on the crystal size and textural association of interlocked minerals. The liberation of spodumene can be measured as a function of screen size by means of microscopic point-count data. Microscopic data also provide useful metallurgical information about the nature of diluent minerals in spodumene concentrates, and the form of lithia losses in the tails. Lithium assays correlate closely with microscopic spodumene analyses in various flotation products from Foote Mineral&apos;s Kings Mountain plant, and confirm the applicability of quantitative optical microscopy to the study of liberation and recovery of spodumene from pegmatitic ores. A better understanding of recovery-grade relationships was developed as a result of quantitative microscopy studies.

Jan 1, 1981

By F. Patisson

During exothermic gas-solid reactions, heat generation makes temperature rise and modifies the rate of the various mass transfer processes, namely the chemical reaction itself, the pore diffusion and the external transfer. We have investigated this thermal effect during the oxidation of zinc sulfide porous pellets in a thermo balance furnace, between 550 and 900°C-and under O2-N2 atmosphere. The results have been&apos; analyzed by using, firstly, the law of additive reaction times derived from the isothermal Grainy Pellet Model, and, secondly, a new numerical model taking into account non-isothermal conditions. Both the models can satisfactorily simulate conversion versus time, but the numerical model also depicts the temperature evolution within the pellet. Finally it is shown that owing to the heat generation the zinc sulfide oxidation takes place under diffusion control (3/4 internal, 114 external) in all the cases studied. During the course of reaction, the. pellet undergoes strong temperature variations, with thermal gradients confined to a shell oxide layer.

Jan 1, 1996

By A. Perillo

The process, realized in. the Kivcet furnace, can convert continuously lead concentrates, residues and secondary lead bearing materials into a lead bullion free of sulphur and a discardable slag. The lead recovery can be up to 99%. The long experience of about three years at Portovesme demonstrates the capability of the furnace to smelt a very. high range of lead raws without interruption of the operation. The operating costs are very competitive in comparison to the traditional technology. The work place and environment are clean and new tight regulations for the? hygiene control are met. The Kivcet furnace can be considered as consisting of three parts (reaction shaft, waste gas shaft and electro-furnace) connected with a common hearth. The technical basis of the furnace construction is the application of a number of design elements .which have mostly been used before in designs of industrial furnaces, such as open hearth furnace, refining furnace and other furnaces dealing with liquid meta1s. Refractory wear in the reaction shaft with typical pattern from watercooling soon has been stabilized and since maintained. No deformation of the furnace shell and no leakage of metal or s:l:ag through the bottom is? appeared after three years&apos; operations.

Jan 1, 1990

By P. Lussiez

Precipitates consisting of amorphous ferrihydrite and crystalline goethite have been prepared by aging hydrolyzed Fe (III) solutions at room temperature. The precipitates have been characterized by x-ray diffraction and differential thermal analysis. The amorphous ferrihydrite transforms to goethite with time. The ferrihydrite to goethite transformation is affected by the presence of small amounts of copper or nickel coprecipitated with the iron. .The addition of copper decreases the amount of goethite at a given aging time and increases the amount of coprecipitate which is initially dissolved in sulfuric acid, but it does not seem to affect the dissolution of the crystalline part&apos;. It is proposed that adsorption of copper hydroxo species on goethite nuclei delays the ferrihydrite to goethite transformation. The effect of nickel is less dramatic than that of copper. Apparently a portion of the added nickel is adsorbed on the goethite crystallite surface rather than incorporated into the goethite lattice.

Jan 1, 1981

By A. Christlo

Short circuit detection in 1984 involved nine inspectors for production rates of 43,000 tpa. Trials indicated the feasibility of applying cell voltage monitoring to short circuit detection and improving operational efficiency. A computerised cell voltage monitoring system was commissioned in February 1986, to read voltages from 648 cells. The system incorporates 16 evenly distributed work face units which communicate with a central computer system. Provision has been made in the computer program for the automatic adjustment of cell reference voltages. This allows for the effect of polarization and other process variables which might other wise interfere with short circuit detection. The work face units can continue to work independently for several days should this become necssary. Current efficiencies have been maintained and the number of inspectors reduced from nine to five.

Jan 1, 1987

By Saskia Duyvesteyn

Small ion-exchange resin particles provide faster mass transport than conventional-sized beads. Unfortunately, high pressures are needed to pump solutions through columns containing small resin particles. It is preferable to disperse fine resins in the solution being treated. Screens have been used to separate the resin from the solution, but screens do not retain fines created by attrition of the resin particles. We have developed a separation process based on flotation, which relies on the surface characteristics of the resin, instead of size. The resin is conditioned with a surfactant before dispersing it in the solution to be treated; this increases the hydrophobicity of the resin sufficiently for froth flotation, without introducing surfactant directly into the solution. The surfactant adsorbed on the resin surface does not appear to impair the kinetics of metal ion removal. A flowsheet for an effluent treatment process is proposed; other applications are clearly possible.

Jan 1, 1998

By Shengqi Chen

The reduction smelting of nickel laterites produces slag, consisting principally of the chemical components MgO, "FeO", SiO2, and A12O3, and ferro-nickel alloy. Despite the fact that the phase equilibria for the ternary MgO-"FeO"-SiO2 up to 1500°C is well established limited experimental data are available in the MgO-"FeO"-SiO2-Al2O3 system, which is relevant to commercial operation of the process. A methodology has been developed for the experimental investigation of the liquidus temperatures for the multi-component system MgO-"FeO"-SiO2-Al2O3-Cr2O3 in equilibrium with metallic iron. Experiments have been carried out using high temperature equilibration, quenching, followed by electron probe X-ray microanalysis (EPMA). Liquidus temperatures have been determined in the silica primary phase field in the composition ranges directly relevant to the Cerro Matoso S.A. ferro-nickel smelting slag. Liquidus isotherms have been determined for temperatures between 1450 to 1600°C. The study enables the liquidus to be described for a range of MgO/FeO ratios. It was found that liquidus temperatures in the silica primary phase field decrease significantly with the addition of AI2O3. Keywords: Liquidus temperature, ferro-nickel, pyrometallurgy, smelting

Jan 1, 2004

By Pertti Koukkari, Nagendra Tripathi, Karri Penttilä, Justin Salmine

ChemSheet is a thermodynamic multi‐phase multi‐component simulation software, which is used as an Add‐in in Microsoft Excel. In ChemSheet, the unique Constrained Gibbs free energy method can be used to include dynamic constraints and reaction rates of kinetically slow reactions, yet retaining full consistency of the multiphase thermodynamic model. With appropriate data, ChemSheet models can be used to simulate reactors and processes in all fields of thermochemistry. The presentation will cover off‐line modeling of Cu‐flash smelters and advanced thermochemical simulation coupled with on‐line process control of Cu‐Ni smelting. The presentation will describe an off‐line model of Cu‐smelter based on critically assessed properties of the Al-Ca-Cu-Fe-O-S-Si –system (slag, matte and liquid metal) by using the quasichemical model. A four‐stage reactor model (shaft, settler, uptake and bath) is used for optimizing process parameters and feed particle distribution. As a second example, an advanced thermochemical model of a Ni-Cu sulphide smelting plant will be given. The on‐line model covers the operation of treating Ni-Cu-S concentrate via roasters, electric furnace and converters, producing a high grade Bessemer matte product for further refining. The model integrates the thermochemistry of the roasters and electric furnace, and predicts important process parameters such as degree of sulphur elimination in the fluid‐bed roasters, matte grade, iron metallization, slag losses and the iron to silica ratio in the electric furnace slag. Both models can be used to assist process engineers and operators in calculating the addition rates of coke, flux and air for different feed scenarios.

Jan 1, 2014

By Lan Li, Izaak Williamson

"The efficient separation and storage of CO2 from power plant flue gases can reduce the amount of CO2 released into the atmosphere and mitigate global warming. Potential candidates for industrial applications are solid sorbent materials. Crucial factors to control the efficiency of porous sorbent materials include the framework and pore structure, and the chemical and physical reactivity of CO2 within the pores. Computational modeling approaches, based on density functional theory (DFT) and van der Waals-DFT, have been applied to nanoporous solid – manganese dioxide a-MnO2. We found that the types and charges of cations as dopants in the a-MnO2 and the concentration of CO2 influence the structural features of a-MnO2, which control its CO2 selectivity performance within the flue gases.IntroductionCarbon capture and storage is a technique to separate large quantities of CO2 from power plant flue gases before being released into the atmosphere. Porous solids are a potential candidate as sorbents to “trap” CO2 through chemical or physical adsorption on their porous surfaces[1]. Such separation efficiency is determined by the size and shape of its pores and by the interaction between the porous surface and the gas adsorbates. The incorporation of cations into the pore can act as a means of structural support and alter the pore diameter to be comparable to the kinetic diameter of the gas adsorbate, such as CO2.A porous solid of particular interest for CCS is manganese dioxide a-MnO2, an octahedral molecular sieve (OMS) composed of edge-sharing MnO6 octahedra that are linked into a nanoporous framework[2]. The framework consists of (1×1) and (2×2) tunnels, referred to as OMS-2. Due to the larger tunnel size, cations and gas adsorbates prefer to reside along the (2×2) tunnel axis of the OMS-2. As seen in Figure 1, a potassium cation K+ is located in the (2×2) tunnel, known as cryptomelane-type MnO2. Its pore diameter of ~ 4.6 Å gives it a good CO2 selectivity performance, because the diameter is comparable to the kinetic diameter of 3.3 Å for CO2[3]. Alternatively, replacing potassium K+ with other cations, e.g. barium Ba2+, sodium Na+ or lithium Li+, in the OMS-2 tunnel is of great research interest, due to the effects of their concentrations, types and charges on the CO2 selectivity efficiency and sorption hysteresis phenomenon[2,4]."

Jan 1, 2014

By D. Bruce Wilson

The reaction of oxygen and solid aluminum produces the well-known surface coating of aluminum oxide, Al2O3. Thermodynamic properties and kinetic mechanisms of this reaction are extensively documented. Less well-defined are the corresponding liquid phase reaction and reactions which would be characterized. as &apos;burning&apos; of aluminum. This paper reviews the solid aluminum-oxygen reaction as a foundation for discussing the flammability of aluminum in oxygen-enriched atmospheres. Appropriate thermodYDan3ic analysis and kinetic reaction mechanisms are developed. Available models of aluminum burning are reviewed and evaluated, The appropriate information for design of engineering applications of aluminum in oxygen atmospheres? is summarized.

Jan 1, 1996

By M. C. Esposito

Seven pyrite samples purified from coal sources and one ore source pyrite (for comparative purposes) have been characterized by chemical and mineralogical analyses, inherent floatability, apparent specific gravity, surface area, semiconductor type, optical anisotropy, dissolution and oxidation rate. The data clearly demonstrate that pyrites from various coal sources differ not only from ore pyrite but from each other as well.

Jan 1, 1987

By R. L. Nyirenda

One of the problems with ammoniacal-ammonium carbonate leaching of EAF carbon steelmaking flue dust is that zinc present in spinel phases is not leached. This paper presents results of test work in which prior to leaching, EAF dust was reduced with CO containing gas to decompose the spinels into zinc oxide and iron bearing phases, mainly metallic iron and wustite. From such reduction products, the amount of zinc leached increases but the iron co-leached becomes extensive. The effect of various leaching parameters such as liquor concentration and redox potential on zinc and iron dissolution has been investigated. Supplementary experiments utilizing pure zinc oxide and pure iron phases were also carried out. Results show that the co-dissolution of iron from severely reduced EAF dust cannot be prevented. This is because the wustite phase contains zinc which can only be leached when iron also dissolves. Further, the zinc bearing wustite phase is not totally soluble so that the residue cannot be made zinc free. In the absence of air, dissolution of metallic iron hardly occurred, though in leaching experiments of a long duration its transformation to a spinel structure was observed.

Jan 1, 1992

By Riyad N. Ahmad-Bitar, Shadia J. Ikhmayies

"CdS/CdTe solar cells were built by depositing a 200 nm layer of Sn02:F on glass substrates by the spray pyrolysis (SP) technique, a 500 nm CdS:In layer by the same technique and a 1-1.5 µm CdTe layer by vacuum evaporation. The cells were CdCh heat-treated in nitrogen atmosphere for 30 minutes at 350 -.C. The photoluminescence (PL) spectra were measured at the CdS/CdTe interface for two cells with different values of the CdTe layer's thickness at temperature T = 60 K. A deconvolution peak fit was performed from which it is found that the peaks are characteristic of the solid solution CdSxTei-x· The parabolic relation that relates the bandgap energy with the composition was used to estimate x, where xis [S]/([Te]+[S]) and [Te], [S] are the concentrations of Te and S atoms respectively. The results show that the interface is smooth and the change of the bandgap occurs gradually.IntroductionCdS/CdTe heterojunctions represent a combination of materials promising various applications, and for solar energy conversion in the first place [1]. In photovoltaic cells the CdS material acts as a wide bandgap window. Direct bandgap CdTe with high optical absorption coefficient is used as an absorber [1]. Solar cells with efficiencies of 10 to 16% have been obtained with CdTe grown by close space sublimation, electrodeposition, vacuum evaporation and rf sputtering methods [2]. In this work the CdTe layer was prepared by vacuum evaporation because it results with films of minimum impurities, while the Sn02:F and CdS:In layers were deposited by the spray pyrolysis technique because it is a low cost method which enables intentional doping and large area thin films."

Jan 1, 2011

By Rejane Tubino Geyer

The volume of electric arc furnace (EAF) plus oxygen (BOF) slag produced yearly in the world is about 84 million ton. Because of this, the study of recycling processes as a way to solve the storage problem of these slags rise in importance. There are, however, some inconvenients on using this byproduct: lime, which takes part of the process of steel production, remains as a non-reactive raw product in the slag. Since lime reacts in presence of humidity, forming expansive compounds, slag use is strongly limited. There are some utilizations for the electric arc furnace and oxygen slag in the Civil Construction Industry, mainly as base, subbase and asphalt covering in highways. However, independently of the type of recycling, a period of "cure" of about six months is necessary. Because of this slow cure process this byproduct may turn non-competitive in some regions if compared, for example, with the natural aggregate. The objective of this work is to present the flowsheet of the slags production as a residue both at the electric and oxygen steel plants and, through a bibliographic review, to analize the possibilities and limiting factors for the use of steelmaking slags in the Civil Construction Industry.

Jan 1, 1996

By A. J. Paul, K. O. Yu

"Today, foundries are moving towards the use of models and design tools to gain a competitive advantage in producing castings of high desired quality. This leads to a growing alliance between foundries, software developers and researchers seeking to model, visualize and understand the phenomena taking place during the casting process. In addition, there is a need to develop affordable techniques to produce parts in small lot sizes. This leads to the development of a Flexible Manufacturing System consisting of: (1) up-front computer-aided engineering; (2) computer integrated proto typing with solid freeform fabrication; and (3) fabrication of the actual mold and related equipment to cast the part.This paper discusses some of the developments that are taking place today in the areas of modeling the physical phenomena during the casting process as well as towards developing a Flexible Manufacturing System for producing cast parts. Areas that require most work involve prediction of defects and mechanical properties using simplified analyses. In addition, electronic data sharing for collaborative engineering between geographically dispersed team members is also discussed. Case studies are presented showing successes as well as failures.IntroductionCasting, one of the oldest forms of metalworking, has recently seen a flurry of developments in the area of solidification modeling. These developments have come about after the realization that, in order to stay competitive, foundries need to reduce their scrap rate and production costs, and increase casting quality. Even though this is not new knowledge for foundry engineers, the tools to help them achieve this goal are just being developed and put in place for use by foundries. Several state-of-the-art software packages are currently available to analyze the solidification behavior in complex shaped castings. These packages make use of several different approaches for solving the various problems associated with casting processes. The overall architecture of a comprehensive solidification modeling system is shown in Figure 1."

Jan 1, 1994

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 T. Kimura, H. Ohba

"Much effort has been made to reduce the energy requirement in zinc electrowinning. In order to keep energy consumption low, either to make cell voltage low or current .efficiency high is necessary. Decrease of cell voltage practically depends on how to reduce ohmic resistance in the electrolyte and the anode crust. To realize these, new concept was proposed and the pilot plant has been operated. The space between a cathode and an anode is halved by utilizing the frame insulator. With these frames the anodes and cathodes compose of a unit of electrodes, and this unit is handled by newly designed electrode handling machine (E.H.M.). The process includes lifting up electrodes, expanding the space between a cathode and an anode, cleaning them, stripping the deposited zinc and returning the unit to the cell. As a result, cell voltage is kept as low as calculated and predictable energy reduction has been achieved. IntroductionIn the recent trend of a rapid appreciation of the Japanese yen, Akita Zinc Refinery of Mitsubishi Metal Corporation has been confronted by problems of relatively high operating costs. In order to compete with other overseas zinc refineries, it is necessary to reduce the cost of zinc production, especially the cost of electric power which now accounts for .up to 35 % of the entire cost of production. Three fourth of the electric power used at Akita Zinc Refinery is for the electrolysis. Therefore it is extremely important to reduce the cost of electrolysis.There are two possible measures for solving the problem; one is to use more nighttime electricity taking the advantage of its inexpensive power price, and the other is to reduce electric power consumption.As a part of a rationalization plan carried out in 1986, Akita Zinc Refinery increased the number of operating cells. As a result, when nighttime electricity is used, the silicone rectifier has been able to operate at full capacity. Moreover, by new schemes of ""increase of area for electrodeposition by ralslng the liquid level of electrolyte"" and ""increase of the number of electrodes in each cell"", current density could be lowered and as a result, the electric power consumption has been improved. In order to raise nighttime ratio even higher, installation of an additional rectifier and cells would be required."

Jan 1, 1988