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By Helfried Nafe

"For about a century thermodynamically absurd facts have been propagated in conjunction with the iron-carbon phase diagram. These facts concern fundamental relationships of chemical thermodynamics. Attention is turned here to the discussion of only one of the relevant aspects of the subject, i.e. the definition of the thermodynamic activity of the solute and its implications for the iron-carbon solution.IntroductionThe view on the iron-carbon solution is characterized by the assumption that the solute may appear in two different forms, i.e. graphite and cementite. Accordingly, two carbon solubilities are differentiated, on the one hand for graphite and, on the other hand, for cementite. As a consequence, two versions of the phase diagram exist simultaneously, the application of which depends on the prevailing conditions, (i) the so-called stable phase diagram with graphite as solute and (ii) the metastable one that is based on the cementite-in-iron solution. These diagrams are joined together in the double phase diagram that originates from Heyn [l ], with the first ideas mainly going back to Stansfield [2] and Charpy [3].Thermodynamically, the most inadequate implication of the Fe-C double phase diagram is that the carbon activity may take values larger than unity. With the standard state of the activity being that of the pure substance, i.e. the Raoultian one, such a value implies the nonsensical existence ofa state purer than pure. The explanation of this physical state, ifthere is any, vaguely refers to supersaturation and, in the wider sense, to the physico-chemical phenomenon of metastability. Other aspects of chemical thermodynamics are likewise involved. Therefore, the comprehensive investigation into the present subject requires more topics to be considered than only one separate issue. Not only should the criticism of the present view be in the focus but also the discussion of new ideas capable of reconciling the experimental facts, known about the F e-C system, with the fundaments of chemical thermodynamics. All this, however, cannot be provided here because of the limited space available. As a consequence, in what follows only a part of the whole problem is under scrutiny, i.e. the definition of the thermodynamic activity and its role for the interpretation ofrelevant experimental facts."

Jan 1, 2014

By R. W. Adams

A new process has been developed for leaching zinc sulphide concentrates at atmospheric pressure using air or oxygen plus nitrogen dioxide in dissolved or gaseous form as? an oxygen carrier. The process is flexible and can cope with variations in the degrees of retention and regeneration of dissolved nitrogen dioxide in the leaching phase. By controlled addition of concentrate a leach solution with low residual nitrate concentration can be produced. Following separation by filtration of unleached solids and elementa1 sulphur and conventional oxidation/precipitation of dissolved iron, the leach liquor can be treated with metallic zinc to remove the remaining nitrate and other meta111c impurities such as copper, cadmium and cobalt to provide a solution suitable for electrolytic recovery of zinc. Pilot scale testing of the process .has given zinc recoveries in the high nlnet1es, production of a hi.gh grade jarosite-free Pb/Ag residue (50% Pb.) and a saleable high grade of elemental sulphur. .A wide range of concentrates can be treated containing substantial levels of lead and copper as well as zinc. Indicative cost estimates suggest that the new process is competitive with alternative procedures such as pressure leaching.

Jan 1, 1990

By L. M. Abrantes, A. P. Paiva

"A brief review of some innovative methods for the direct recovery of metals from loaded organic phases is presented; emphasis is given to electroreductive stripping and cementation, which are described and illustrated by examples: of current research. The recovery of silver using a two-phase electrolysis - by direct application of an electrical potential to a mixture of a metal loaded organic phase· containing Cyanex 471X, obtained by solvent extraction, and a stabilized sodium thiosulfate solution - is more extensively discussed. The overall efficiencies are analyzed and compared with data obtained by conventional stripping procedures. Some preliminary results achieved for the recovery of the precious metal using galvanic stripping, applied directly to similar organic solutions and involving zinc and iron powders as reducing agents, are also evaluated.Introductory ReviewThe application of hydrometallurgical methods to the recovery of metal values from ores and concentrates has been receiving a growing interest, either from researchers or from the mining industry [1].For the concentration / purification of the relatively low concentrated metallic solutions resulting from the leaching of those raw materials, solvent extraction (SX) is a well established technique [2]; the loaded organic solvent is then conventionally contacted with a suitable aqueous solution, the metal in its final form being usually recovered from this solution by electrowinning.As an efficient and / or selective stripping is sometimes difficult to achieve, depending on the specific characteristics of the system under consideration, some alternative procedures have been analyzed in order to overcome this problem. One of the chosen routes, mainly developed by Hirai and Komasawa, is to promote the reduction of the desired metal species in the organic phase, in such a way that the stripping stage becomes feasible; for the selective stripping of vanadium from a solvent containing a mixture of vanadium and molybdenum, the authors successfully used reductive [3], electro-reductive [4,5] and photo-reductive [6] techniques. The two latter methodologies have also been applied to the recovery of europium from a solvent containing europium, samarium and gadolinium [7,8].However, further processing is necessary to recover the metal in its solid state; therefore, methods causing the direct reduction of the metal species in the organic phase to their fmal metallic form would be of interest, as an intermediate step would be avoided"

Jan 1, 1997

By B. C. Blakey

Unlike most hydrometallurgical slurries, those containing significant concentrations of goethite are typically highly viscous and shear-thinning, even at solid volume fractions below 5%. The viscosity may also depend upon time. These characteristics must be taken into consideration in slurry transport and heating. The technical literature is replete with apparent contradictions regarding the viscous behavior of these slurries, which may be due, in part, to variations in viscosity-measuring techniques. We present techniques that yield consistent results suitable for use in process design. A striking degree of time-dependent behavior is demonstrated for a laterite slurry. Reliable methods to design and analyze tubular transport and heating systems for time-independent slurries are summarized. Rules of thumb are then offered to account for the effects of time-dependency.

Jan 1, 2000

By Gopalakrishna M. Rao

"Several industrial and government laboratories are of the opinion that solar--cell technology will grow into a billion-dollar industry by the year 2000, especially if oil prices rise again. Of the variety of materials that have been investigated as the major component of photovoltaic systems, silicon appears to have an outstanding advantage. The cost factor is the primary importance in photovoltaic development, since the technology to make silicon cells of acceptable efficiency and life time has existed since the early stage of the space program. Electrometallurgy is one of the low--cost processes for the production of silicon, since it allows direct, single-stage production from some abundant, inexpensive source materials such as silica and fluorosilicates. Among several systems, two are given particular attention, using inorganic baths with Si0 2 or K2SiF6 as the source of silicon respectively. They appear capable of development to commercial production. Conceptual designs of a commercial--scale cell for silicon production at temperatures above its melting point, and of a pilot' plant for plating silicon from an all-fluoride bath are presented. Energy ProspectsThe major changes in the world energy since the first energy crisis in 1970 have impacted on our community. When oil was $40 a barrel in the mid-1970s, we became obsessed with the energy conservation and a search for alternate energies. Even though the crude oil fell below $15 a barrel during the last several years, our energy security fears continue to haunt us. This time it is not the scarcity, but the abundance of foreign oil and the decline in the domestic production.The prospects of energy depends on the demand and supply of energy. These, in turn, depend on future energy prices, which are linked to economic factors, political events, and unforeseen circumstances. Although no one can predict the future with certainty, three energy consumption patterns used by the Ford Foundation are as shown in Fig. 1."

Jan 1, 1988

By Joseph Goodwill

1. PURPOSE The objective of this paper is to summarize a study undertaken by the EPRI Center for Metals Production (CMP). The overall purpose of the study was to identify electrolytic opportunities that might merit consideration for joint development by industry and EPRI. 2. SCOPE The electrolytic technologies of interest to this study include: Electrorefining, Electrowinning, and Fused-salt electrolysis. Recovery from primary, secondary, and waste materials were included in this effort; however, we excluded from consideration: Plating and coating operations, such as electrogalvanizing; Mining and milling operations in which electric energy is predominantly used for comminution; Electrothermal processes in which submerged-arc, open electric-arc, and plasma-based smelting processes use electric energy largely to provide a melting or refining ("heating") capability; and Aluminum electrotechnologies since these were the subject of a separate study (CMP 86-2). We recognize that there may be some "gray areas" between these excluded areas and the electrolytic sectors of interest. For this reason, a secondary criterium was used, namely, if the major use of electric energy was to extract or refine the

Jan 1, 1990

By B. C. Jena

Activities of carbon, cobalt and nickel were evaluated in the ternary systems iron-carbon-cobalt and iron-carbon-nickel for the temperature range 1300-1600°C for cobalt and 1300-1700°C for nickel. The carbon activities were determined from the knowledge of activities (1) in the binary system iron-carbon, (2) in the dilute ternary systems and (3) from the knowledge of carbon saturation data. The activities were mathematically expressed with the Taylor series expansion of Wagner's interaction parameter formalism modified to suit concentrated solutions. The cobalt and nickel activities were determined from the knowledge of carbon activities by applying the Gibbs-Schuhmann integration and from cobalt and nickel activities in the binary systems iron-cobalt and iron-nickel. Partial molar enthalpies of mixing were determined based on the temperature behaviour of the activity coefficients.

Jan 1, 1992

By J. M. Skeaff

As much as 100% of the gold and 67% of the silver in a sulphur-bearing hydrometallurgical leach residue have been transferred to copper metal at copper smelting temperatures by dissolving the partially calcined residue in an iron-bearing slag maintained in equilibrium with the liquid copper metal and matte phases. The precious metals can then be recovered by conventional refining techniques. Copper can be recycled at least four times without any detrimental effects on gold and silver transfers and recoveries. Apparent copper recovery in the .process can be over 100% because of the copper content of the residue. Based on slag analys.es, the overal1 recovery of gold in the copper metal and matte phases varies from 94% to 100% under all conditions investigated. On the? same basis, silver recovery varies .from 9S% ?to 99% under optimum conditions, but is only 4S% to 73% under other, less attractive conditions. Unaccounted for silver losses of' about 30% make it difficult to determine the major factors affecting ?silver transfer and recovery. A method for implementing the technology on a commercial scale at a Canadian copper/zinc smelter has been proposed. A preliminary economic assessment and comparison of the proposed pyrometallurgical process with conventional cyanidation indicates that either process is economically attractive for recovering gold and silver from leach residues. Although the capital costs are higher, the pyrometallurgical process is simpler, has higher recoveries, lower operating costs and no .potential environmental problems related to cyanide disposal.

Jan 1, 1989

By Dong-Wei Li, Tao Zhang, Diao Jiang, Zhou Wang

The feasibility of simultaneous vanadium extraction and phosphorus removal from vanadium-containing hot metal was demonstrated with laboratory experimental investigation.The effect of CaO addition on the distribution behavior of vanadium, phosphorus between basic vanadium slag and semi-steel as well as the influence of basicity on the leaching behavior of vanadium, phosphorus was particularly studied. Results show that vanadium oxidation ratio slightly decreases with the increase of basicity, but phosphorus oxidation ratio rapidly increases with the increase of basicity. The leaching of roasted vanadium slag with various CaO contents indicated that the optimal slag basicity for extracting vanadium was 1.5. The maximum leaching efficiency of vanadium could reach 84.02% and the sequence of vanadium leaching efficiency by using different leaching reagents was: 160 g/L Na2CO3 > 100 g/L NaHCO3 > 400 g/L (NH4)2CO3 > 5% H2SO4.

Mar 1, 2017

By Zhendong Tao, Wei Huang, Zhongxi Yang, Hang Guo, Haoran Geng, Jingxiang Yao

"CaSO3.0.5H2O typed Flue Gas Desulfurization (FGD) gypsum is a by-product formed in flue gas desulfuration by double-cycle fluid bed method, its composition is different remarkably from that of gypsum yield by normal desulfuration methods, and few studies using it as cement retarder have been carried out. In this paper, the experimental study using CaSO3•0.5H2O typed FGD gypsum as cement retarder was carried out. The experimental results indicate that, when FGD gypsum is added solely into cement, the retarding action is not satisfactory because of its slow dissolution rate; The composite retarder composed of FGD gypsum and natural gypsum can regulate efficiently setting time of cement over a wide range of addition and rate of both each other, and the mechanical property of cement can be improved significantly.Fire-power plants have discharged a lot of harmful gases such as SO2 etc., which has resulted in serious pollution on the environment. To reduce harmful gas containing sulfur in the flue gas, various flue gas desulfuration (FGD) techniques have been developed. At present, the FGD method used widely is to add desulfuration agents such as limestone powder or other calcareous-contained materials during the coal burning or in the flue gas so that the components containing sulfur react with them to form solid sulfate or sulfite and to be separated from the flue gas by collectors. CaSO3•0.5H2O and CaSO4•2H2O typed FGDgypsum can be obtained respectively by dry and wet FGD process[1,2]. As a by-product of fire-power plant, features of of FGD gypsum and its applications have been paid great attention. Pavel Tesa'rek et al [3] presented in full the characters and properties of FGD gypsum; Zofia Konik et al[4] prepared expansive additive used to cemnent industry by using FGD gypsum and aluminate clinker; A. K. Alva et al [5] investigated the effects of FGD gypsum and fly ash on soil properties and found the growth of seedlings of either rootstock improved significantly in soils amended with FGD gypsum and fly ash. FGD gypsum also can be used in gypsum binders, plasters and plasterboard manufacture [2.6]. C. S. Poon et al [7] investigated the effects of FGD sludge on the pozzolanic reaction of reject-fly-ash-blended cement pastes. Many studies using CaSO4•2H2O typed FGD gypsum as cement retarder has been reported[2,8-12]. Howevere, few studies using FGDG as retarder were reported so far. In present study, the chemical compositon, phase composition, structure and features of CaSO3•0.5H2O typed FGD gypsum have been analyzed, and its application characters used as cement retarder have been investigated experimentally."

Jan 1, 2008

By R. Padilla

The reaction of chalcopyrite with gaseous sulfur has been investigated in the range 350-450 °C in order to transform this mineral into a more acid soluble copper sulfide and insoluble iron sulfide. The results of thermodynamic analysis of this system as well as the X-ray diffraction analysis of the reaction products showed that in the temperature range 350 400°C the sulfidation reaction proceeded without formation of intermediate copper-iron sulfides according to: The effects of temperature and time on the conversion of chalcopyrite were studied. Conversion of chalcopyrite reached about 80% very rapidly with increase in temperature up to about 400°C. The recovery of copper from the sulfidized samples was determined by leaching in oxygenated 1.2M H2S04, 2M NaCI solution. Copper recoveries over 90 % were obtained from samples sulfidized for 30 min at temperatures lower than 400°C.

Jan 1, 2001

By Antoine Allanore, Luis A. Ortiz, Donald R. Sadoway

"The steelmaking industry has drastically reduced its energy consumption in the last fifty years, and today’s technologies are considered to operate at their optimal efficiency with respect to energy needs. To cope with new constraints related to greenhouse gas (GHG) emissions, a change of paradigm is necessary. One of the promising technologies that could be deployed to help reach CO2 mitigation targets relies on the intensive use of electricity: molten oxide electrolysis (MOE). This paper presents the key process parameters that need to be tuned to address the practical needs for both high productivity in a steelmaking reactor and for an energy efficient process. Herein we show that contrary to common perception, the electrolysis process for ironmaking requires less energy than today’s chemical reduction route. Furthermore, we prove that most of the energy that must be provided to operate the electrolytic iron production cell is thermal energy which is readily generated by joule heating during electrolysis due to large currents being passed through the electrolyte. The energy consumption of the electrolysis cell is therefore shown to be highly dependent on the cell configuration and the chemistry of the electrolyte. As a consequence, the CO2-impact of the technology strongly depends on both the power production mode and the technological choices for design of the process, including cell configuration. Surprisingly enough, even when the electricity generation is not carbon-free, MOE still appears to be viable from the perspective of reducing GHG emissions providing sound reactor design considerations are made.IntroductionIn the context of greenhouse gas (GHG) emissions mitigation, the steelmaking industry is considering several techniques that could sustain the efforts and progress achieved by this sector in the last decades [1]. A recent report [2] on potential routes for low-CO2 steelmaking highlighted for all techniques both the strong dependency of CO2 emissions on electric power production mode and the need for a decrease in energy consumption per tonne of steel. Incited to innovate with respect to this last criterion, the steel industry considers electrolysis to be a promising technological solution, and in particular the molten oxide electrolysis (MOE) process. This process conducts electrolysis in a mixture of oxides that dissolve the iron oxide feed, which by the action of electric current is decomposed into liquid iron and oxygen gas. The opportunity for reduction in energy consumption during steelmaking by MOE is commonly attributed to the “direct” pathway from iron oxide to liquid metal offered by the use of a molten oxide melt and operation at a temperature above the melting point of iron, ideally 1600°C, to provide enough superheat for tapping the molten iron product:"

Jan 1, 2011

By Yosry Attia

Recent emphasis on environmental effects and costs of conventional mining processing, plus success in accelerating bacterial action, suggest that biotechnology be explored for gold ore processing. In our paper, the past experience with organisms in processing gold is reviewed. The use of microorganisms for liberation of gold from sulfide ores as a substitute for fine grinding is discussed. The possibility of accumulation of gold from solutions, such as cyanide solutions, is explored as a potential replacement for such processes, such as carbon-in-pulp or ion exchange. The improvement in engineering technology and kinetics needed to scale-up from laboratory experiments to production scale are outlined.

Jan 1, 1985

By Heikki K. Jalkanen

Thermodynamic properties of copper-iron mattes and slag-matte distribution of copper and some minor matte constituents (Ni, Co, Mo, As, Sb and Bi) are discussed on? the basis of equilibrium measurements: a change from. oxidic to sulfidic solubility as the predominant form of dissolution of copper takes place as matte grade decreases. Distribution coefficients of minor matte constituents are complex functions of sulfur and/or oxygen potentials?. The distribution behaviour of different? metals can be qualitatively derived from their affinities to copper and stabilities. of their sulfides and oxides. The equilibrium results are compared with commercially observed values. from Outokumpu.Oy flash smelting furnace.

Jan 1, 1983

By Rajashekhar Marthi

Lithium is a key component for future electric vehicle batteries and energy storage. The future availability of lithium to meet the growing demands remains in question. Around 60% of lithium resources exist in the form of continental brines. Traditional methods to recover lithium from brines use solar concentration with precipitation and have found limitations in lithium extraction due to interference of Mg in high Mg/Li brines. Thus, there is a need for highly selective adsorbents. Recently, spinel structured delithiated lithium manganese oxides have demonstrated promising results. However, due to the small particle sizes, it is economically difficult to recover the adsorbents and thereby limits industrial applications. In our work, LiMn2O4 ion sieve was synthesized and immobilized on diatomaceous earth. Fundamental adsorption studies were carried out in lithium buffer solutions to understand the nature of adsorption and kinetics. The adsorbents were also tested for recycle stability, as well as recovery of lithium from Great Salt Lake water samples.

By Ryosuke O. Suzuki

A new cell concept for calciothermic reduction is proposed in which the titanium dioxide instead of TiCl4 is used as the raw material for reduction, Metallic calcium is needed as the reductant of a thermochemicaily stable oxide, such as TiO2. CaCl2, is selected as the solvent of Ca and simultaneously as the solvent of CaO. The reduction system consists of a single cell where both the reduction reaction and the electrolytic reaction for recovery of reducing agent coexist in the same molten CaCl2 bath. A few mol%Ca dissolves in the melt and gives the media a strong reducing power. Sufficiently deoxidized metallic titanium deposits and forms a slightly sintered granular sponge. Both mechanisms of the halide flux deoxidation and the electrochemical deoxidation work efficiently for these fine precipitates, The reducing agent is in situ recovered by electrolysis of CaO because the molten CaCl2 he a relatively large solubility for CaO Some cell designs and modifications are proposed for industrial applications.

Jan 1, 2003

By R. C. Hubli

A panial equilibrium model? to simulate the dissolution of millerite (NiS) in aqueous solutions containing copper(II) chloride as the oxidizing species has been developed. The predominant copper(I) and copper(II) species are CuQ3 and CUO2 respectively. The model computes the initial concentrations of the species present in the aqueous phase under the specified input conditions, prior to the simulation of dissolution. During the dissolution of millerite, nickel enters the leach liquor as NiH and it has been found that the H+ decreases as a function of NiS dissolution. The simulation has been accomplished under conditions prevailing during actual dissolution, with only one mineral undergoing dissolution. The model can be applied for the simulation of co-dissolution of two or more sulfides. Under the given conditions, the precipitation of Cu1(OH»)O is negligible but loss of Cu(1l) could be significant if the initial H+ is lower than 0.03 M. The results of the simulation compare favorably with experimental observations.

Jan 1, 1996

By Onuralp Yücel, Mehmet Bugdayc, Murat Alkan

"In this study, iron based alloys (Fe-Mo, Fe-Cr-Ni, etc.) were produced by using aluminothermic methods starting from Mill Scales obtained continuous casting processes. Mill scales are an oxidised layer of steel alloys containing iron oxide, which includes + 2, + 3 values, on the surface of slabs and billets occurring during annealing in heating furnace at integrated iron and steel milling plant, and continuous casting unit. In the metallothermic experiments, different ratios of starting mixtures and addition of the oxide powders (Alz03, Si02, CaO, MgO) were examined, and their effects on the metal recovery and alloy compositions were carried out. The samples were characterized by using chemical analysis (AAS), XRD, XRF and SEM/EDS techniques.IntroductionSelf Propagating High Temperature Synthesis process (SHS) has many favour compared to the furnace applications, such as low energy requirement, low cost, very short processing time and simple operation, [l, 2]. In a SHS process, the ignition starts the combustion and propagates throughout the reactant mixture yielding the desired product. However, the disadvantages of the process such as inhomogeneous or unreacted products due to undesirable reaction rates needs to be overcome by changing some parameters such as ignition temperature, particle size, additive, atmosphere etc. [3, 4]. Mill scale is a layer of iron oxide which forms on ferrous materials cooling after being processed in hot rolling or continuous casting plants. Mill scale contains iron (II) and iron (III) oxides, which result in a 70% total iron content in oxide form. Not being able to reuse this material will prevent the raw material entering the production plant from being fully utilized [5]. This study aimed to produce Fe-based alloys via SHS (Self Propagating High Temperature Synthesis) metallurgy which is attractive process technique regarding fast and low-cost production ability of cast alloys by using high metallic iron content by reducing continuous casting mill scale."

Jan 1, 2013

By Benoit DeBecker

Laboratory-scale experiments have shown that chromium metal could be recovered from chromate wastes by modifying slightly the chromium electrowinning flow-sheet. After reduction by sulhr dioxide and precipitation of chromic hydroxide, the solid residue is dissolved in the chrome alum solution and the metallic impurities are removed by cementation on manganese. The presence of dissolved manganese in the electrolyte does not affect the cathodic deposition of chromium and it eliminates the anodic production of Cr(V1).

Jan 1, 1994

By T. Mutoh

Tellurium in raw slime has recently been recovered as copper telluride in Onahama Smelter & Refinery. The slime is decopperized with sulfuric acid solution in conventional leaching tanks. The pregnant leach solution containing 45 g/l of copper and 1 g/l of tellurium is introduced to a copper telluride recovering reactor. The tail solution from the reactor containing less than 20 mg/l of tellurium is recycled directly to circulation tanks of copper electrolysis. The impurities of the product copper telluride is kept below 1% without any purification.

Jan 1, 1990