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By T. K. Mukherjee

The importance of the processing of secondary resources such as solid industrial wastes and liquid effuents as well as byroducts for the recovery of the associated metal values hardly needs any elaboration. Such processing contributes in no small measure.towards the augmentation of the availability and the supply position of resources. As an added benefit, it leads to a reduction in environmental pollution caused by the undesirable waste materials. As some typical examples of secondary resources in the Indian scenario, mention' can be made of spent catalysts, metal/alloy scrap, ash, consumed batteries, flue dust, slag, sludge and slime, pickling solutions, spent acids; plating rinse solutions, spent etchants, waste water from synthetic fibre manufacture and from tanneries etc. These wastes constitute a source of a variety of non ferrous metals. In the processing of secondary resources like these, the techniques of hydrometallurgy such as solvent extraction play a pivotal role. This paper outlines the efforts made to use solvent extraction to recover (1) base metals such as copper, zinc, nickel and cobalt from a number of secondary resources like cake, and sludge(2) refractory metals like molybdenum and vanadium from sulphidic, byproducts and spent catalyst and (3:) nuclear metal like uranium from phosphoric acid. In the case of base metals, process flowsheet involving the use of acidic extractants such as DEHPA and PC88A have been optimised. The problem of iron removal from the leach liquor, "which influences the metal recovery process significantly, has drawn a special emphasis. hi the case of refractory metals, basic extractants .like Alamine 336 has been pressed into service to produce kilogramme. quantities of pure salts of molybdenum and vanadium, Finally, the paper gives a brief account of plant experience in recovering uranium from phosphoric acid, using 'a solvent system comosed of DEHPA and TOPO.

Jan 1, 1996

By Shu Yamaguchi

The behavior of halide impurities in pyrometallurgical processes such as Wealtz kiln and MF process has been discussed based on the thermochemical data and the reported data of PbO activity in PbCl2-PbO melts. The role of PbCl(g) has been estimated to be significant in the chloridization evaporation reaction. From reported data on the PbO activity in PbC12-PbO melts, activity of PbCl2 has been calculated by the numerical integration of Gibbs-Duhem equation, and the stability domains and the composition of the liquid phase as well as the vapor pressure of PbCl2 have been estimated as functions of log P2HCI/PH2O and temperature. From the discussion of the path during cooling process on the log P2 HCI . PH2O vs. temperature diagram, the authors proposed a possible dechioridization process that utilize water vapor as a dechloridizer for the direct precipitation of PbO from gas phase.

Jan 1, 2003

By K. D. Peaslee, V. L. Richards, C. H. Rawlins, S. N. Lekakh

"Steel-making processes generate carbon dioxide air emissions and a slag co-product. The aim of this project was to develop a functional sequestration system using steelmaking slag to permanently capture carbon dioxide emitted in steelmaking offgas. A possible parallel benefit of this process would be rapid chemical stabilization of the slag minerals with reducing swelling or leaching.This paper summarizes the original results of the project, including mineralogical and structural features of carbon sequestration with steel making slag, mathematical modeling of reaction phenomena using a modified shrinking core model, METSIM modeling of several possible industrial applications, a thermo-gravimetrical study of the reaction between slags and different gases, and design and testing for a lab scale apparatus consisted of two reactors.1. IntroductionThe U.S. produces 9-14 Mt of steelmaking slag annually, which represents approximately 10-15 wt. % of crude steel output.1,2 Primary uses for steelmaking slag include high quality mineral aggregate, Portland cement, unconfined fill, soil conditioning, and pH neutralization of abandoned mine drainage.3,4 The key factor prescribing slag use is the alkaline-earth metal (e.g. Ca and Mg) oxides content, which contribute to overall basicity and cementitious strength. However, as-produced steelmaking slag is chemically unstable. Calcium and magnesium oxides readily form hydroxides and carbonates through reaction with atmospheric gases. Both hydroxide and carbonate formation produce substantial mechanical swelling leading to heave failure in confined construction applications, thus many states dictate stockpile aging for 3-6 months prior to commercial use.5,6 Sequestration of carbon dioxide is a natural corollary to forced carbonation. The conversion of CaO/MgO to carbonates serves both to stabilize the slag, and permanently capture and store the CO2."

Jan 1, 2008

By P. D. Ferro

The direct oxide reduction (DOR) of plutonium oxide generates significant amounts of contaminated waste. This waste primarily consists of calcium oxide-saturated calcium chloride salt. This investigation explores the possibility of recycling the salt, by the electroreduction of the calcium oxide. Fused salt electrolysis of a simulated salt mix (CaC12 + ~10 wt. pct. CaO) is being carried out to electrowin calcium, and the process is being optimized in terms of the calcium solubility, cell temperature, current density and cell design to maximize the current efficiency. This work identifies the major concerns in the development of a process to electrowin calcium from this simulated salt mix.

Jan 1, 1992

By Jochen Petersen

Design and operation of heap leach processes are still largely based on,operator experience and rule of thumb. Although considered a low-cost, low-tech route for mineral extraction, the underlying physical, chemical and biological processes are actually rather complex. Numerous heap leach models have been devised over time, but the majority of these tend to simplify the true process and are of limited use in practise. The modelling approach presented here combines the more conventional reaction-diffusion model with models accounting for equilibrium reactions in solution, bacterial growth kinetics, complex reactions schemes, gas flow, heat conservation, etc. One particular model application is discussed in the context of developing a novel high temperature heap leach processes using thermophile micro-organisms. The complexity of processes such as this can only be appreciated with the aid of a systematic model. For the designing engineer an accessible, personal computer based model should be an indispensable tool for the design and optimisation of efficient heap leach operations.

Jan 1, 2002

By Andrew Case

The Port Nickel facility in Braithwaite, Louisiana, is known for pioneering hydrometallurgical processes for the 'separation and recovery of nickel, cobalt and copper. Ten years ago, in 1985, a new CRI-MET process for the recovery of molybdenum, vanadium, nickel, cobalt and alumina from spent catalysts was developed and implemented. Spent- catalysts from the petroleum industry consietute the majority of feed. These are not only a valuable-source of metals, but due to EPA regulations are frequently classified as hazardous under RCRA. Molybdenum and vanadium are selectively leached in an oxidative hydrothermal step. Alumina is then extracted in a caustic digestive leach. The unique technology produces four primary commercial products l molybdenum trioxide, vanadium oxide, aluminum trihydrate and nickel-cobalt concentrate. This paper discusses the process, modifications. during ten years of operation, and the relationship of these modifications to the future of the catalyst recycling business.

Jan 1, 1995

Thermodynamics and kinetics? of the removal of Va elements (As,Sb,Bi) from copper were investigated 1n the fire relining by alkaline carbonate fluxes such as Li 2co3 , Na 2CO3 and K2CO3. The distribution coefficients of As, Sb and Bl between alkaline carbonate fluxes and mo) ten copper were ?obtained at 1200°C under the different oxygen potentials. As and Sb were easily removed from copper to fluxes as pentavalent oxide form. On the other hand, Bi was hardly removed except by a Ll2CO3 flux. The removal rates of Va elements from copper were also measured In the temperature range of 1150°C.- 1250°C. The removal rates of As and Sb were much higher than that of Bi. The removal rates of Va elements showed the same order of the distribution coefficients. The removal rate could be expressed by following equation. (1).

Jan 1, 1987

By O. Durand

The Cerro Verde Hydrometallurgical Plant, located at Arequipa in the southern part of Peru, started its operation in 1977 with a design capacity of 33,000 MT/year of copper cathodes. The plant has treated 61,055,000 MT of ore mainly oxides with a content of 1.01% total copper and 0.67% of soluble copper. The leaching plant has three pads that produce 4.0 gpl copper solution. The solvent extraction plant has four trains with three extraction stages, two stripping stages with a single mixer in all stages. The mixer-settlers are 316 stainless steel and the pumps are vertical turbines. The flowrates of 1,300 gal/mil of aqueous and 1,300 gal/min of organic at a 1/1 ratio. The electrowinning plant contains 208 commercial cells and 18 starting sheet cells. Each cell has 47 anodes and 46 cathodes. In addition to describing the hydrometallurgical plant, this paper also mentions efforts directed at reducing costs and improving operations. The initial results from leaching secondary sulfides, which started October 1985, are also discussed.

Jan 1, 1987

A novel, low-pressure adaptation of Praxair?s coherent jet technology utilizing CoJet lances was developed for application at Inco&apos;s Copper Cliff Smelter where oxygen is available in large tonnage quantities but only at relatively low supply pressures (< 193 kPa header pressure). The project objectives were to evaluate the effect of coherent jet technology on controlling oxygen lance accretion (?horn?) formation and to increase oxygen efficiency in the Inco Oxygen Top-Blowing Nitrogen Bottom Stirring (TBBS) MK Reactor used for converting nickel- contaminated chalcocite to semi-blister copper. This paper describes the development and subsequent implementation and testing of two CoJet lances in this application.

Jan 1, 2005

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to predict the distribution behaviors of Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag in copper pyrometallurgical process. In this model, as more as 21 elements (Cu, S, Fe, Ni, Co, Sn, As, Sb, Bi, Pb, Zn, Au, Ag, 0, N, C, H, Ca, Mg, Al, and Si) and 72 compounds (in fayalite-slag-making system) or 74 compounds (in ferrite-slag-making system) are considered. Accessory-element behavior is studied for two types of slag , fayalite and ferrite, and two levels of oxidation. The allowance is also made to account for physical entrainment in the melts.-Model simulations are carried out to study the effects of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxygen enriched air. The model can be used in copper flash process, Mitsubishi process and Noranda process. The predictions by the present computer model are compared with the known industrial data from Gui Xi Smelter in China, Home Smelter in Canada and Naoshima Smelter in Japan and excellent agreement between calculations and industrial data is obtained. In this paper, the effects of oxygen enrichment, matte grade, smelting temperature, and types of slag on accessory-element behavior among matte, slag and gaseous phase have been elucidated.I . IntroductionThe presence of trace quantities of minor elements such as As, Sb and Bi in copper significantly reduces its ductility, electrical conductivity, and lowers its thermal conductivity. Embrittlement of copper also occurs due to impurity-phase precipitates at the copper grain boundary interfaces. They deteriorate not only the electrical conductivity of copper but its workability in hot working."

Jan 1, 1998

By T. Xin

A vertical grain boundary intercepting a horizontal free surface forms a groove to reduce the combined surface energy of the system. We study grooving by surface diffusion with anisotropic surface energy. A recently developed delta-function model of facets is used to describe the surface energy with three or four fold symmetry. It is found that the groove grows following a similarity law. The self-similar groove profile is solved numerically by a shooting method. Even with strong anisotropy, the groove profile can be smooth if the exposed surface orientations do not include a facet orientation. The smooth self-similar groove shape is the same as an isotropic groove, but the size is reduced by a factor that depends on the degree of anisotropy. This induces a large error on the value of surface diffusivity if the isotropic model is used for an anisotropic system. In this talk. we will describe how to correct for this error.1 I Xin, T. and H. Wong, "Grain-Boundary Grooving by Surface Diffusion with Strong Surface Energy Anisotropy," Acta Materialia 51, 2305-2317 (2003). Keynotes: Grain growth, Surface Diffusion, Surface energy, Anisotropy

Jan 1, 2003

By Chen Zhang

Polycrystalline Ti-rich NiTi thin films have been deposited from a single NiTi target using a DC magnetron sputtering system. Free standing film was obtained by using a single crystal silicon substrate. Thickness ofthe thin films is controlled at around 12 pm. In this investigation, the effect of deposition temperature on the microstructure and transformation temperatures of the thin films is studied. Influence of post heat treatment temperatures on the properties of the thin films is also investigated. Transformation temperatures of the thin films are determined by differential scanning calorimetry (DSC). The surface microstructure of the thin films is studied using a scanning electron microscope (SEM), and the crystallinity is determined using x-ray diffractometry. It is found that the thin film deposited on a hot substrate is crystalline even when the substrate temperature is as low as 300°C, while the normal crystallization temperature for an amorphous thin film is around 500°C. The microstructure of the film deposited on a hot substrate shows a very fine grain size. The grain size increases with increasing substrate temperature during deposition. The effect of post deposition heat treatment on grain size is minimal.

Jan 1, 1999

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 E. Allaine

Carbochlorination kinetics of pure MoO3, Nb2O5, Ta2O5 and V2O5, by Cl2+CO+N2 gas mixtures was investigated between 380 and 1000 °C. Standard free energy of carhochlorination reactions and phase stability diagrams of these refractory metal compounds were calculated. The influence of total gas flow rate, temperature, reactants partial pressures on the reactivity of these oxides were investigated. The apparent activation energies were found to be about 83, 75, 110 and 100 kJ/mole below 650°C for MoO3, Nb2O5, Ta2O5 and V2O5, respectively. Above this temperature, the Arrhenius plots exhibit a rate anomaly attributed to thermal decomposition of COCl2 and/or structural changes of these refractory metal oxides. The apparent reaction order of carbochlorination of these oxides with respect to Cl2+CO was determined. For these refractory metal oxides, the reaction rate was maximum for a Cl2/CO ratio of about 1 in the chlorinating gas mixture. Results of carbochlorination of these oxides are compared and discussed.

Jan 1, 1995

By Simon Lekakh, Von Richards, C. Hank Rawlins, Kent Peaslee

"Batch aqueous leaching and carbonation tests were conducted using industrial steelmaking slags to determine the effect of carbonic anhydrase enzyme as a catalyst. Calcium leaching is a strong function of particle surface area, and the extent can be expressed as a function of time and particle size. Carbonic anhydrase did not affect the calcium-leaching rate, however, it did catalyze calcium carbonate formation to achieve a neutralization time near the theoretical rate. Additionally, carbonic anhydrase modified the precipitate morphology due to accelerated particle nucleation. Time controlled tests in which the pH dropped to ~6 decreased the amount of carbonate produced, and this effect was exaggerated by carbonic anhydrase, while pH controlled tests (>8.5) exhibited the highest rate of carbonation. Because the leaching rate was ~50% faster than the carbonation rate, a further increase in the amount of carbonation may be realized by using carbonic anhydrase however pH must be >10.3.IntroductionSteelmaking slag contains high fractions of alkaline earth oxide based phases (i.e., CaO and MgO) that exothermically form carbonates. Thus, it is being considered as a means of permanent carbon dioxide sequestration. At current U.S. steel production rates, approximately 13-17 million tons/year of slag are generated from basic oxygen furnace (BOF), electric arc furnace (EAF), and ladle metallurgy furnace (LMF) processes [1]. BOF and EAF slag is used as high quality mineral aggregate or cement clinker, while LMF slag, produced at ~15% the rate of BOF and EAF slags, has limited use as blast furnace flux or acid mine neutralization with the majority going to landfill [2]. Based on slag’s chemical nature and immediate availability as a co-product from steel production, the steel industry initiated a project to investigate hydrous carbonate formation in steelmaking slag as a method of sequestering carbon dioxide emitted in steelmaking offgas [3]. The goal of this project is to determine the reactor parameters suitable for the design of an industrial system for treating steelmaking offgas with raw or minimally processed slag."

Jan 1, 2009

By Thomas R. Wildeman

Experimental methods for studying vapors over solid minerals are reviewed and an especially developed method using atomic absorption is described. The method is used to study vapor pressures over Te. Ag, Au, Ag2Te, and AuTe2 from 250°C through 10S0oe. Vapor pressures observed and, concurrently. sintering properties are significantly altered by the form of the solid. The vapor pressures of the tellurium compounds reveal complex processes occurring on the surfaces of the solids. The data given also point out a method of recovering precious metals from their telluride minerals w

Jan 1, 1987

By Kenneth P. Michalek, James E. Kelly, Jonathan A. Dantzig

"Many investigations have been reported regarding the simulation of continuous casting with emphasis on in-mold heat transfer. These analyses have been limited, however, because they require either estimation or measurement of the characteristic heat transfer between the ingot and the mold. In this paper, a self-consistent model 'is presented for calculating the heat transfer between a solidifying continuous casting and the mold, in the context of the continuous casting of steel. Using both thermal and stress analyses, the air gap formed during continuous casting is calculated and used to compute the heat transfer coefficients. Iteration between the thermal and stress analyses is used to determine a self-consistent solution. IntroductionThe continuous casting process for steel is illustrated schematically in Fig. 1. Molten steel is tapped into a tundish from which it flows at a controlled rate into the continuous casting mold. The initial shell of the casting forms in the mold by transfer of heat from the metal through the mold wall to the cooling water. The remainder of the casting is solidified by application of water sprays, and/or radiation cooling below the mold.Heat transfer in the mold portion of the process is important because it controls the formation of various defects which are deleterious to subsequent processing. Examples of defects formed in this region are surface irregularities, such as cold folding and oscillation marks, and more serious defects, such as longitudinal or transverse cracks. A more catastrophic problem which may occur is a breakout, in which the shell ruptures and molten steel is discharged in an uncontrolled way."

Jan 1, 1986

By James O'Brien, Lyman Frost, Grant Hawkes, S. Elangovan, Manohar Sohal, J. S. Herring, Joseph Hartvigsen, Carl Stoots

"Pressing environmental and energy security concerns have brought much needed attention to economic production of hydrogen as the secondary energy carrier for non-electrical markets as well as to meet increasing demand for crude upgrading and desulfurization. While steam reforming of natural gas is currently the dominant method of hydrogen production, it is depleting a valuable fossil fuel while emitting green house gases. Thus, in the long run, efficient, environmentally friendly, and economic means of hydrogen production using nuclear and renewable energy needs to be developed. High temperature electrolysis using solid oxide electrolyte cells is an exceptionally efficient means of generation of high purity hydrogen. It is also capable of directly converting steam and CO2 into synthesis gas. This co-electrolysis process enables conversion of CO2 recovered from concentrated industrial sources into a feedstock for synthetic fuels production. Use of CO2 provides a means of storing hydrogen in a concentrated and convenient form – a hydrocarbon. This is also an effective storage medium for intermittent renewable energy sources such as wind and solar.Ceramatec, Inc and the Idaho National Laboratory are applying solid oxide fuel cell technology to the production of synthesis gas by high temperature co-electrolysis of steam and carbon dioxide. This technology utilizes solid oxide fuel cell stacks to electrochemically remove oxygen from steam and CO2, leaving a clean stream of hydrogen and carbon monoxide suitable for fuel synthesis. By varying the relative concentrations of carbon dioxide and steam, the hydrogen to carbon monoxide product ratio can be controlled as required by the desired type of synthetic fuel being produced from the syngas. The resultant synthesis gas has been used as the feedstock to produce synthetic methane and Fischer Tropsch liquid fuels.Alkaline and proton exchange membrane electrolysis cells typically operate below 100°C, while solid oxide electrolysis cells operates in the 750-850°C range. This higher temperature improves the efficiency significantly. Practically, it translates into a lower cell operating voltage, 1.1-1.4V for high temperature electrolysis vs. ~1.8V for water electrolysis. Hydrogen production is stoichiometric with current in all types of electrolyzers.Carbon dioxide is a valuable resource as a feedstock for energy storage as a hydrocarbon. There is a vast amount of renewable energy that cannot be effectively utilized as grid electricity, but which could be used to convert CO2 to hydrocarbons, offering a solution to the even more difficult (than supplying grid power) challenge of production of sustainable, domestic transportation fuels. Conventional electrolysis and chemical processes could be deployed to accomplish this conversion. However, high temperature co-electrolysis of CO2 and steam to produce synthesis gas using solid oxide fuel cell technology has the potential of improving the efficiency by nearly 50%. A domestic synfuel industry will enable a much larger reliance on intermittent renewable energy than can be accommodated by conventional electric demand profiles while increasing our energy security."

Jan 1, 2010

By N. Kanari

One of the criteria to define the market value of chromite concentrate is its chromium to iron ratio. Changing this ratio for a definite chromite mineral is impossible by physical processing. This study investigated the possibility of increasing this ratio through the carbochlorination and the oxychlorination of chromite concentrates. Experiments are carried out up to 1000 °C. The characteristics of samples and reaction products are determined by SEM, XRD and chemical analysis. The carbochlorination of a chromite concentrate at about 600 °C leads to the . selective partial elimination of iron allowing a higher Cr/Fe ratio of the treated concentrate. Selective extraction of iron could also be achieved at about 950 °C by oxychlorination. In this case, a part of chromium contained in the concentrate is recovered as chromium oxychloride. The obtained residue had high content of Cr, Mg and A1 oxides. Such material has probably better chemical and thermal properties that may. be useful for foundary and refractory applications. Two flow-sheets for the beneficiation of the chromite concentrates using carho- and oxychlorination are suggested.

Jan 1, 1997

By A. Dadgar

The adsorption kinetics of AuBr4 on Dowex ® -21K ion-exchange resin were studied and found to be independent of the initial gold, bromine, and base metals concentrations. A commercially-available undivided hypochlorite generating cell was used to generate bromine from simulated mixed halide (Br-/CI-) solutions. Electrolyses were performed with solutions containing very low Br&apos; ion concentrations. The current efficiencies were 80-90%, and Br- ion utilization was maximized. A detailed economic assessment was made considering the capital and the operating costs for a 1000 mtpd gold ore processing plant. The toxicity and discharge levels of bromide, bromine, and cyanide were compared from a detailed analysis of the published literature data. Comparing bromine vapor with hydrogen cyanide gas for a given length of exposure, the lethal concentration of bromine is about 3 times less than hydrogen cyanide. The toxicity of sodium bromide is similar to that of sodium chloride. Acute poisoning to bromides and chlorides is rare because of their low toxicities. The allowed discharge levels of Br-, Br2, and CN- in fresh water are 250, 0.1, and 0.005 mg dm-3, respectively.

Jan 1, 1992