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By R. Padilla, M. C. Ruiz, R. Villa

"Bismuth is an impurity in copper minerals where it occurs mainly as the mineral bismuthinite (Bi2S3). In smelting of copper minerals, most of the bismuth reports to the white metal, as a result, a substantial amount of bismuth accompanies the copper to the electrorefined cathodes. Thus understanding the behavior of Bi2S3 at high temperatures is crucial to eliminate bismuth before electrorefining. In this paper, some experimental data on the decomposition/volatilization of bismuthinite in nitrogen- oxygen atmospheres is discussed. The results indicated that in nitrogen atmosphere, bismuth volatilization occurs through a fast decomposition of bismuthinite to metallic bismuth and sulfur with subsequent volatilization of bismuth in the range 850-1100 °C. Similarly, in the presence of oxygen, bismuthinite decomposes to bismuth too, followed by oxidation to the non-volatile bismuth trioxide at temperatures higher than 750 °C. Both, temperature and partial pressure of oxygen affect significantly the bismuth volatilization and the oxidation rates.IntroductionCopper sulfide minerals are the major source for the production of metallic copper by pyrometallurgical processes, which are the dominant processes in the production of copper by selectively oxidizing the sulfide sulfur to SO2 and the accompanying iron in the concentrates to iron oxide, which can be conveniently removed as a stable slag.Generally, copper concentrates contain some deleterious minor elements such as arsenic, antimony, bismuth and lead, which are present as sulfides. These elements depending on their concentration may originate problems in the copper smelting processes and they can ultimately lead to a final copper product with unacceptable high levels of impurities.During the treatment of these copper concentrates by smelting, the impurities generally distribute themselves in the condensed and gas phases and they are eliminated mainly through the gas phase [1-3]. Thus, smelter off gases contains substantial amounts of volatilized impurity elements. For example, in the case of bismuth, the estimated distribution of bismuth in flash furnace smelting [2] was 15 % in the matte, 5 % in the slag and 80 % in the gas phase, and recently, for Outokumpu flash smelting Davenport [3] reported the distribution of bismuth as 30-75% in matte, 5-30% in slag and 15 -65 % in the off gas."

Jan 1, 2011

By D. Georgiou

Direct sulphuric acid leaching of nickeliferous limonites is the process of choice to recover nickel and cobalt from equatorially located lateritic ores. These ores are rich-in-iron (-45 wt%) existing in the form of goethite enriched with nickel. The merit of this process is due to its high nickel selectivity because of simultaneous iron separation and acid regeneration. Under acid leaching conditions (-250 to 270°C) iron follows an acid dissolution-hydrolytic precipitation path yielding a very low concentration level depending on temperature and acidity of the final leach liquor. The primary precipitation product of iron is hematite which also forms as a scale on reactor internals along with co-existing aluminum. In this paper, an overview of the behaviour of iron solid products under process conditions is made. The evolution of goethite to hematite transformation, as well as the role of iron in reactor scale production, are studied using SEM/EDX characterization techniques.

Jan 1, 1995

By Devon A. Hannan

Thermodynamic modeling calculations were undertaken for the recovery of mercury from HgTe using a vacuum retort reactor. However, discrepancies were noted in the available thermodynamic data which introduced uncertainty in the model results. Consequently, a series of transpiration experiments were first undertaken on the thermal decomposition of HgTe into an inert carrier gas stream according to the following reaction: HgTe(s) Hg(g) + Te(s) From the measured weight loss of the HgTe samples, the Gibhs free energy change for the above volatilization reaction was determined as a function of temperature. The experimentally determined Gibbs free energy values were found to be approximately 30% larger (more posi-tive) than the values available in databases such as HSC Chemistry. By conducting a second-law analysis on the experimental data, the heat of formation of HgTe at 298.15 K and the en-tropyat 298.15 K were determined, which then formed the basis for a new database for the modeling calculations. The results of this study showed that HgTe was more stable at elevated temperatures than was generally indicated in the literature. The new database is given in a for-mat for direct insertion in HSC Chemistry. Using the new database, modeling calculations were conducted to examine the effects of the re-tort pressure and the molar ratio of purge gas to HgTe on the volatilization of mercury from HgTe. A diagram is presented that shows the minimum temperature for 100% volatilization of mercury from HgTe as a function of retort pressure for different molar ratios of purge gas (N2) to HgTe. For example, it was found that the minimum temperature for 100% volatilization could be decreased by 175 K, at a retort pressure of 0.05 bar, if the molar ratio ofN2 to HgTe is increased from 1.0: 1 to 100.0: I.

Jan 1, 2003

By William E. Frazier

The presence of minute amounts of sulfur (10ppm) in nickel-base superalloys has been associated with reduced oxidation resistance and the premature spallation of protective coatings. Removal of sulfur by annealing these alloys in a hydrogen atmosphere has been successfully attempted by several researchers. This paper examines the fundamental thermodynamics and kinetics governing hydrogen desulfurization of elemental nickel. Limiting conditions for successful desulfurization are delineated. Assuming that the diffusion of sulfur is the rate limiting process of desulfurization, the effectiveness as well as time associated with hydrogen desulfurization is explored.

Jan 1, 1994

By Yoshio Waseda, Tetsuya Uda, Tom H. Okabe

"Halide salt has been tested as a reductant for producing titanium powder directly from TiCl4. From the results of thermodynamic investigation for several rare earth chloride systems, DyCl2 was found to be used for the reduction of TiCl4 instead of the conventional metallic reductant. When TiCl4 was fed into molten salts containing DyCl2 at 1073K, titanium powder of several ten micron meters in diameter was obtained. In contrast to the sponge titanium produced by the conventional Kroll process, the present new process using a halidothermic reduction in a reactive molten salt appears to be suitable for producing metal powder. From the thermodynamic point of view, the resultant DyCl3 can be reduced to DyCl2 by magnesium. By utilizing the multivalent halide redox couple, some possible ways of titanium powder production directly from TiCl4 by magnesiothermic reduction are shown to be feasible. This can also be applied to the development of a new continuous titanium reduction process.1 IntroductionTitanium and its alloys show attractive mechanical properties such as strength-to-weight, rigidity-to-weight ratios and excellent corrosion resistance. Nevertheless, the application of titanium alloys is limited compared to other structural materials (e.g. steels, aluminum alloys) because of its high cost of production. Currently, almost all of titanium is produced by metallothermic reduction of TiCl4 by magnesium (Kroll process)[1] in an airtight metallic reactor. This process is batch type and labor intensive. Therefore, many attempts to develop new process for producing titanium are investigated so far."

Jan 1, 2000

By Jim A. King

The total pressure oxidation of copper concentrates is a potentially viable option for treating copper concentrates that are either low grade or contain significant impurities. Both concentrate types are heavily penalized in smelter contracts. The total pressure oxidation process involves autoclaving the copper concentrate at temperatures of 200-220 C under oxygen pressure. The autoclave discharge can be separated into a solid (oxidation residue) and a liquid (oxidation solution) product. The oxidation solution can be treated for copper recovery by solvent extraction - electrowinning or by direct electrowinning. The direct electrowinning recovery of copper requires prior removal of selenium and tellurium by cementation on finely divided scrap copper. The oxidation residue is washed thoroughly to remove acid and dissolved copper prior to precious metals recovery by conventional cyanidation in the presence of lime. The results of a benchscale investigation involving a number of copper concentrates are reported. Copper recoveries in autoclave oxidation and gold recoveries by cyanidation of the oxidation residue exceeded 99%. The results of benchscale experiments to demonstrate copper recovery are described. Various flowsheet options are presented.

Jan 1, 1993

By Richard A. Leiby

The recycling of lead-acid batteries in the United States has become a challenge as to how to balance ever increasing environmental regulation and cost with efficient operations. East Penn's captive secondary lead smelter has developed into a recycling facility producing lead, polypropylene, sulfuric acid, ammonium bisulfite, and non-hazardous discard slag. The emphasis has been to design a facility to comply with environmental regulations, to eliminate wastes, and to produce products, while at the same time, continuing to supply the company's battery manufacturing raw material needs.

Jan 1, 1993

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, Pso, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of 02 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By J. G. Zafiratos

The leaching of a Greek low-grade manganese dioxide ore, not amenable to conventional mineral processing operations, was studied using a mixed culture of Thiobacillus sp. bacteria. The experiments were carried out in specially designed continuously aerated and stirred tank reactors arranged in two-tank series. The first tank of each series was loaded with an elemental sulfur culture suspension while the second was loaded with a manganese ore high density slurry. The bacterial culture had been previously adapted to grow on elemental sulfur and also in the presence of manganese ore and dissolved manganous ion. A two level full factorial design was constructed in order to study the effects of the ferric ion concentration in the leach solution, the "elemental sulfu weight to ore weight" ratio, the ore pulp density and the composition of the dispersed gas. The responses which were investigated included percentage manganese recovery, co-dissolution of iron and manganese dissolution rate. Parameters with constant values throughout the experiments were the leach solution pH, the nutrient medium composition, the dilution rate and the ore and sulfur grain sizes. It was found that the ferric ion concentration was the most significant factor and had a positive effect on the final percentage extraction of manganese from the ore and also on the rate of manganese solubilization from the ore. The effects of the other factors studied are discussed in detail.

Jan 1, 1997

By Mike Trovant, Stavros A. Argyropoulos

"A fixed grid numerical model for phase change problems is proposed. The model solves for heat transfer and fluid flow, via the coupled solution of the energy, continuity and momentum equations. In addition, the numerical scheme accounts for temperature varying thermophysical properties and determines the shrinkage profile resulting from phase and density change. Simulations are run to determine the effect of varying model parameters and wall cooling rates on the location and shape of the shrinkage void formation in cylindrical casts. Results are shown for both aluminum and magnesium.IntroductionThe mathematical modeling of phase change processes (be they solidification or melting problems) entails solving for many interrelated phenomena. A comprehensive numerical simulation of the casting of a metal, for example, would have to account for: (a) heat transfer in both the solid and liquid portions of the metal and in the mold, (b) the release of latent heat during phase change, (c) fluid flow behavior in the liquid portion of the metal, (d) temperature induced shrinkage caused by liquid contraction and solidification contraction, and (e) the development of thermal stresses with accompanying shrinkage in the solid portion of the cast and mold. A schematic of the relationships that exist between the coupled equations which govern solidification is shown in Figure 1."

Jan 1, 1994

By G. A. Irona

Solids injection into non-ferrous converters and furnaces is becoming increasingly important for concentrate injection, removal of impurities, and recycling of dusts and other waste materials. The fundamental design aspects of these technologies will be reviewed, including gas and particle trajectories, lance clogging, heat transfer, and mass transfer including reaction rates and mixing. The use of soda ash for removal of impurities such as antimony and selenium will be used as an example of versatility of powder injection processes.

Jan 1, 1993

By A. H. Castillejos E., F. A. Acosta G.

Filtration is widely used as a terminal refining step for metals, particularly for the casting of aluminum alloys, but still more knowledge is required to understand how several factors affect the efficiency of removal of inclusions. In this study, both, initial and long term filtration efficiencies of a ceramic foam filter have been obtained from the computed trajectories of solid particles suspended in molten aluminum. The complex structure of the foam filters is represented by a unit cell which is formed by a pair of pores with average dimensions. The fluid flow field was determined from the numerical solution of the Navier-Stokes equation, and periodic fully developed flow was assumed at the inlet of the calculation domain, as a boundary condition. This flow field corresponds to laminar flow as that found in ceramic filters operating under normal conditions. Computed initial filtration efficiencies showed that filtration efficiency decreases sharply with fluid velocity for particles larger than 30 µm, but smaller particles are better trapped at higher fluid velocities. Finally, it was found that long term filtration efficiency for particles of 8 µm decreased with time, in spite that perfect particle-wall attachment was assumed. Filter aging was considered in this study, and it was found that the distorted flow field, around the already trapped small inclusions prevented further collection.

Jan 1, 1999

By Harsh Deep Chopra, Jason N. Armstrong, Susan Z. Hua

"Existence of anisotropic Curie temperature materials [E. R. Callen, Phys. Rev. 124, 1373 (1961); J. Appl. Phys. 32 S221 (1961)] is a longstanding prediction - materials that become paramagnetic at a lower temperature along certain crystal directions while remaining magnetically ordered in other directions up to a higher temperature. Validating Callen's theory, we show that all directions within the basal plane of monoclinic F e1Ss (pyrrhotite) single crystal remain ordered up to 603 K while the c-axis becomes paramagnetic at 225 K. Results prompt a re-evaluation of existing magnetic materials with a focus on magnetic characteristics along different crystal orientations above instead of below the ordering temperatures. Theoretical guidelines for identifying new materials with large anisotropy of Curie temperature are also given, and analysis protocol to characterize them in a self-consistent manner is discussed. Materials with such a large directional dependence of Curie temperature open the possibility for uniquely new devices and phenomena, including energy storage and spintronics devices.IntroductionThis paper is an overview of our recently published work on anisotropic Curie temperature materials [l]. As a background, ferromagnetic and ferrimagnetic materials are characterized by a critical temperature below which magnetic interactions prevail over thermal agitation, leading to the appearance of a spontaneous magnetization. Above this critical point, called the Curie temperature, thermal energy eventually overcomes magnetic interactions and the material becomes paramagnetic.It is less well known that the Curie temperature varies with the orientation of the crystal. In ordinary ferromagnets this orientation dependence of Curie temperature is negligible because of the vanishingly small ratio of anisotropy to exchange energy, i.e., the spherical or isotropic exchange term dominates. Thus Curie temperature in ordinary ferromagnets appears to be an isotropic property, and assigning it a single characteristic ordering temperature suffices. However, a 'small' difference is not equivalent to being the 'same', and under appropriate set of conditions the anisotropy of Curie temperature is predicted to become appreciable, as discussed in the following.In formulating the theory of 'anisotropic magnetization' [2, 3] E. R. Callen and H. B. Callen first discussed the ""interesting possibility"" of anisotropic Curie temperature [2] or ACT; Callen and Callen noted that it was W. J. Carr, Jr. who initially raised this question, and they discussed it in detail at the Conference on Magnetism and Magnetic Materials (NY, November 1960), see footnote on page 320 of Ref. [2]. Soon thereafter, E. R. Callen developed the theory underlying the anisotropy of Curie temperature and conditions conducive to its observation [4, 5]."

Jan 1, 2013

By Ningchuan Feng

A biosorbent, the chemically modified orange peel, was prepared from hydrolysis of the grafted copolymer, which was synthesized by interacting methyl acrylate with cross-linking orange peel, and FT-IR spectroscopy was used for determining the structure of the biosorbent. Adsorption characteristics and effects of various factors of the biosorbent on Cu (II) were investigated including pH, adsorption time and initial concentration of Cu (II). Experiment results show that when pH was 6.0 and the initial concentration of Cu (II) was 50mg·L-1, the removal rate was 91.7% after 3 h adsorption. After four cycles being reused, 85.3% removal rate could be obtained by the biosorbent.

Jan 1, 2008

By Eugene Jak

Copper sulphide processing technologies face increasing pressures associated with decreasing concentrate grade leading to increasing thermal inefficiency and lower productivity. Impurity concentrations are on average increasing, creating potential environmental risk and additional treatment costs. In copper flash smelters dust, partially oxidised materials and fume formed from the condensation of volatile impurities, are routinely recycled to the feed. In the converting stage the heat balance is maintained by charging anode reverts and other inert materials. In both cases, the thermal energy available from sulphide oxidation is not fully utilised or optimised. The productivities of both smelter and converter stages can be potentially increased through the addition of a high copper, low iron, low impurity precipitated copper product. Calculations are carried out for fayalite smelter and calcium ferrite converter slags using an optimised FactSage thermodynamic database. The potential for significant increases in smelter and converter productivities using existing technologies are predicted.

By Andrzej Warczok

Intensive smelting of copper concentrate in Teniente Converter (CT) leads to the production of high grade matte and highly oxidized slag. Smelting slag is processed in Teniente vascular slag cleaning furnace. The slag composition and forms of copper affect the slag cleaning process and final copper content. Converting of high grade matte in Pierce-Smith converter faces some difficulties in proper slagging of iron oxides. Overblowing in copper making stage allows for slag liquidation but leads to high content of copper oxide in converter slag. Converter slag recycling into CT results in the increase of the participation of oxidic copper. Separate treatment of converter slag and its impact on the forms of copper in CT slag has been analyzed. Thermodynamic properties of a system and kinetic limitations pointed out the negative effect of converter slag recycling on the forms of copper and copper recovery in slag cleaning stage. Experimental results of slag cleaning tests in a crucible scale as well as microscopic examination of laboratory and industrial slag samples supported the above analysis and permitted to formulate recommendations of separate processing of converter slag. Keywords: copper, losses, slag, recycling

Jan 1, 2001

By A. E. M. Warner

Inco Limited has long and extensive experience in converting nickel-copper primary smelting mattes over a broad range of nickel/copper weight ratios and combined nickel-copper-cobalt contents. At the Copper Cliff Smelter, the composition of the converter product matte has to meet the requirements of the matte separation process; at the Thompson Smelter, converter matte of a different composition is cast into anodes for nickel electrorefining; and in Soroako, Indonesia, a very low copper product matte is granulated for the Japanese market. Recently, Inco has conducted pilot plant testing of three possible nickel-copper matte continuous converting routes, namely flash converting, oxygen top blowing-nitrogen bottom stirring, and tuyere blowing. This test work has generated substantial new information on nickel-copper matte converting chemistry. This overview paper reviews the metallurgy of nickel-copper matte converting, in particular the behaviour of cobalt and the operating conditions required to meet the iron and sulfur specifications of the product matte. The relevant thermodynamic information is used to discuss the industrial data.

Jan 1, 2003

By Gaballah I.

Elimination of arsenic, mercury and zinc from synthetic solutions containing H;\A.sD4. HgCI2 and ZnCI2 using modified barks was investigated. The pH range was varied from ?1 to 10. The initial concentrations of individual element were 10,100 and 1000 ppm. More than 99 % of mercury and 65 % of zinc cations were removed by the modified bark .. In this case, the modified bark reacts as a cation exchanger leading to the release of ' two protons for every HgII or ZnII fixed by this material. About 30 % of arsenic was eliminated from the solution. This 'low efficiency could be attributed to? the presence of arsenic ,as. anion. Decontamination of a treated industrial effluent containing 4 ppm of ion? metals was performed on a pilot plant scale by the modified bll(k. More than 70'% of these ion metals were eliminated.

Jan 1, 1995

By J. B. Wiskel, H. Henein

"A study was conducted to establish the effective heat transfer coefficient for a single molten droplet moving in a gaseous medium. Towards this objective, a series of quench experiments were performed on molten droplets of AA6061 aluminum generated with the Impulse Atomization technique (IAP). IAP is a single fluid atomization process capable of producing powders with a predictable mean particle size and a relatively tight standard deviation under controlled atmospheric conditions. Microstructure analysis of the atomized powder was used to establish the extent of pre-quench solidification. A mathematical model was then employed to correlate the Ranz-Marshall and Whitaker equations with the observed particle cooling behaviour. These equations were found to provide a reasonable estimation of the heat transfer conditions only when the variation in gas thermophysical properties across the boundary layer was accounted for in the model. This model formulation of droplet heat transfer has important implications with regards to active sprays and atomization processing operations IntroductionAn understanding of droplet cooling is important in atomization powder production. It is well understood that dendrite arm spacing is inversely proportional to cooling rate during solidificationl1l. Through modification of the heat transfer conditions during metal atomization, the microstructure of a powder maybe tailored to the end user. However, owing to the complexity of gas flow it is difficult to determine a heat transfer coefficient for a moving droplet. This difficulty is further compounded when complex jets and/or streams and their interactions are considered. To provide a base for these more complicated types of analyzes, two approaches have been employed to calculate the effective heat transfer conditions for a single droplet. In one approach, Megardis [ZJ developed a numerical model to investigate the heat transfer process of a free falling droplet undergoing laminar convective cooling. The effective heat transfer coefficient as a function of angular position was determined by numerically solving the fluid and energy equations for the system."

Jan 1, 1999

By T. Shi, Q. Yuan, S. P. Vanka, B. G. Thomas

"The quality of continuous cast steel is greatly affected by fluid flow in the mold region, especially involving transient phenomena. Mathematical models are being applied to investigate many different aspects of these phenomena, but their accuracy must be validated before they can be applied with confidence. As part of a long-term effort to develop and apply comprehensive models of the continuous casting process, this work evaluates the relative accuracy of models of three different fluid flow phenomena in continuous casting through comparison with measurements.Firstly, transient flow simulations of velocities in the mold region are compared with digital particle image velocimetry (PIV) measurements in a single phase water model. Large-eddy simulations (LES) are found to reasonably match the flow measurements, including transient flow variations, except at long time scales, which could not be modeled owing to the excessive computation costs. The standard K-e model produced very good agreement with time-averaged velocities for relatively little computation time, although it is inaccurate at predicting the transient variations. Secondly, particle trajectory calculations are compared with water model measurements to study the distribution and flotation removal of inclusion particles. The LES model was able to match the measurements both qualitatively and quantitatively. Thirdly, steady, multi phase flow computations are compared with flow patterns observed in both a water model and an operating steel caster with argon gas injection. For the same conditions, the water model and steel caster produced very different flow behavior. The computational model was able to match the measured flow patterns in both cases.This work suggests that computational flow modeling has the potential to match real processes as well or better than water models, especially when complex related phenomena such as particle motion and multiphase flow are involved. Much work is still needed to further improve the models and to apply them in parametric studies."

Jan 1, 2001