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By G. Diáz

The PLACID process applied to the recycling of spent lead-acid batteries is being developed by an European Consortium within the Brite-Euram II programme. The status of the project entitled "Lead Recovery from Lead Oxide Secondaries" is described in this paper. The main laboratory and batch experimental results and the preliminary feasibility study are summarised. The description of the demonstration pilot plant and continuous campaigns programme for 1995 are also included. An interesting global approach is proposed, integrating the Placid process in the existing spent battery recycling pyrometallurgical facilities. This yields important improvements in the overall process. Grids would be easily treated by the conventional pyrometallurgical route, obtaining lead alloys,, while battery pastes, slags and fumes would be fed to the Placid process, obtaining pure electrolytic lead (>99.99 %), ideal for battery paste manufacturing. The implementation of the Placid process into the existing battery recycling pyrometallurgical facilities is analyzed from technical, environmental and economical viewpoints. Greater overall lead recovery, lower operating costs, reduced waste production, environmentally safer residues and much better lead product quality are the key advantages. The authors draw the following final conclusion : Integration of the Placid process with conventional pyrometallurgical treatment is a feasible and very attractive alternative route for spent lead-acid battery recycling.

Jan 1, 1995

By J. Brent Hiskey

The global copper industry faces a technological challenge to develop processing schemes for more complex and impure ores and concentrates. Group 15 elements (As, Sb, and Bi) represent impurities that are troublesome both in terms of environmental impact and metallurgical processing. The so-call "dirty" copper concentrates are either unacceptable for smelting and refining or incur high penalties. The behavior of the Group 15 elements is of critical importance in maintaining product quality and process performance. During copper electrorefining, these impurities are released to the electrolyte by electrochemical dissolution of the anode. Depending mainly on temperature, concentration, and oxidation state these elements can spontaneously coprecipitate from the electrolyte. Some of these precipitates are referred to as floating slimes and their formation can have extremely detrimental effects on cathode purity. In this paper, the mechanism of floating slimes formation will be discussed and the fundamental thermochemistry will be reviewed and analyzed in relation to solubility properties.

Jan 1, 2012

By Keiji Okumura, Hong Lan, Masamichi Sano

"Magnesium has been well known as one of the excellent agent of desulfurization, deoxidation, etc. in iron- and steelmaking because of its high reactivity. Since its production is energy nitensive, the price is very high. Thus magnesium has not widely been used as an agent in metal refining ·processes. In the present work, reduction of magnesia by carbon and aluminum is examined. Because the reaction is very sensitive to temperature, non-isothermal technique is applied to investigate the reaction kinetics. The effects of heating rate .and reaction interface area on the reaction kinetics .are studied. .A kinetic model is proposed based on the experimental results.IntroductionFor the metal refining processes, the production of high purity metal has been one of the most important research subject. In order to produce the high purity metal, the amount of the refining agent and the consumed energy is increasing. Therefore, if the future earth environment is taken into consideration, the further efficient and energy saving processes are required. Generally, Cao slag has mainly been used for desulfurization of molten iron as a desulfurization agent. However, environmental problems, such as recycling of disposal slags, are still unsolved. On the other hand, the deoxidation of molten steel is mainly performed by addition of aluminum. Therefore, the alumina inclusions· remain in. molten steel and the great efforts have been made to the removal of the inclusions. The affinity of magnesium with sulfur and oxygen is strong, and magnesium is well known as a powerful desulfurization and deoxidation agent. However, magnesium has been seldom used for the steel' refining process. The following reasons are considered. Generally, magnesium is expensive. And at iron- and steelmaking temperatures, the refining efficiency becomes low due to its abruptly .evaporation."

Jan 1, 2000

By José Roberto de Oliveira

In a smelting reduction process the reduction reaction occurs predominantly in the liquid state. The main reduction agent is the carbon from the carbon saturated iron bath. The aim of the present work was to determine the velocity equation and the rate constant of the reduction rate of MnO content in a Mn0-SiO2-Fe0 slag by iron saturated carbon and the carbon dissolution rate in a Fe-Mn bath. The manganese content in the iron bath was in the range of 5 to 15 wt.%. It was observed that the rates of carbon dissolution in all Fe-Mn baths are faster than the rates of MnO reduction by the carbon saturated liquid iron.

Jan 1, 1999

By Zhiqiang Han, Anil K. Sachdev, Baicheng Liu, Guomin Han, Alan A. Luo

The growth of precipitate phase ,B-Mg11Al12 in Mg-Al alloy is closely related to interface anisotropy and elastic interaction. The aim of this work is to investigate the effects of the interface anisotropy and elastic interaction on the morphology evolution and growth kinetics of the precipitate. In the work, the precipitation of ,B was studied using phase field modeling. In the model, the chemical free energy of the precipitate and the matrix were obtained via thermodynamic calculation. It is demonstrated that the interface anisotropy results in lath-shaped precipitate and the elastic interaction affects the shape of the end of the precipitate. The interface anisotropy causes uneven growth in different directions and the elastic interaction influences its preferential growth orientation. By combining the interface anisotropy and elastic interaction in the phase field modeling, the results showed that the precipitate phase has a lath-shape with lozenge ends, which is in agreement with experimental observations.

Jan 1, 2013

By J. L. Sanchez

Using a special double-zone transpiration reactor, the vapor transport chemistry of vanadium pentoxide in the presence of water vapor has been investigated. Three possible volatile hydroxides above V,O,(s) are reported in the literature: VO,(OH),, V,O,(OH),, and VO(OH),. In the present study, it was established that VO(OH), is the principal gaseous hydroxide species formed. The predominant reaction was found to be: { } The vapor pressure of VO(OH), was measured as a function of temperature, water pressure, oxygen pressure and flowrate. The results have been used to determine the Gibbs free energy of the above reaction as a function of temperature: { } The results of the present work were combined with thermodynamic data reported in the literature to obtain expressions for the AGO for the reaction above V,0,(1) and the AGO of formation (units in cal/g-mole).

Jan 1, 1993

By Toru H. Okabe

As part of a systematic study on the thermodynamic properties of complex nitrides, phase equilibria of the system Li-M-N (M Mg, AI, Ga) at 900 K were investigated. An attempt to determine the thermodynamic properties of complex nitrides was made by using the galvanic cell method, which utilizes LiMgN as an electrolyte under nitrogen atmosphere. The electromotive force (Emf) of ilie cell at temperatures between 800 and 1100 K was measured. Whilc the Emf of the cell at 900 K was measured to be 0.137 V, data discrepancies of ±0.03V were found. It was difficult to determine temperature dependence of ilie Emf. The Gibbs energy change for the reaction, 113 LbN (s) + 1/3 Mg3N2 (s) = LiMgN (s), at 900 K was determined to be tJ.Gor (LiMgN) -13.2 (±2.9) kJ/mol. Using thermodynamic information on ilie binary nitride from literature, the standard Gibbs energy of LiMgN was derived to be AGO f (LiMgN)= - 121 kJ at 900 K. The thermodynamic stability range of nitride was discussed by constructing isothermal chemical potential diagrams that provide a better understanding of ilie stability region of the LiMgN phase. The diagram was found to be in good agreement with the isoiliermal phase diagram determined by ilie alloy equilibration meiliod. Although the obtained data includes large uncertainties, the results provide a better understanding of the iliermodynamic stability of nitrides. The potential application of this complex nitride to nitrogen chemical sensors or a medium for controlling nitrogen potential is also shown.

Jan 1, 2003

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carned out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XQ >10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By J. Boitano

This paper discusses the study, design and implementation of the new gas handling system for the Caletones Smelter of Cbdelco..Chile. A discussion on design conditions for a Mure Sulphuric Acid Plant using Teniente Converter.gases.is also included. The old system which started to be modified in 1985 and relied on natural draft and used balloon flues, resulted in a limited .gas handling capacity for operation under Mure process conditions. This system also caused excessive fugitive gases in the smelter working areas. The new system permits handling of process gases from the higher capacity Teniente converters installed in 1987-1989 Improving the gas handling of the reverberatory furnaces and Peirce-Smith converters as well as the environmental conditions of the smelter. This system utilises improved converter gas hoods, evaporative cooling and electrostatic precipitators gas cleaning, and is based on natural draft.

Jan 1, 1992

By Daniel Kittelty

A fully instrumented laboratory electrowinning cell has been used to produce nickel cathodes from synthetic solutions containing various impurities in order to evaluate the effects of both metallic ions and organic reagents (from prior solvent extraction and other processes) on the quality of the electrodeposited nickel. The conditions used were typical of those employed in industrial electrowinning operations. The impurities were found to alter the crystal size and shape, induce the development of hydrogen pits on the deposit surface, incorporate as metal hydroxide crystals in the deposit, and alter the internal stress and current efficiency. These effects have been interpreted in terms of previously established relationships between the solution composition and the physical properties of the cathodes. The incorporation of the common metal impurity ions into the deposit have been interpreted in terms of a mass transport controlled reduction or precipitation reactions. In particular, a low concentration of aluminium ions resulted in an initial highly deleterious effect, which was replaced by a positive influence at higher concentrations. A model which involves the buffering effect of the aluminium on the pH at the cathode surface has been proposed.

Jan 1, 2003

By J. -P. Nepper

It has been possible to largely contain converter aisle emissions of SO2 and fumes in the case of batch-wise operated Peirce Smith converters during normal blowing periods with the help of suitably designed primary hoods. Controlling the escape of off-gas during the periods of turning the converter in or out of the stack has been problematic in the past. Effective automated contro1 systems have been deve1oped for the purpose and successfully applied in smelter operations in Spain, Taiwan and Germany. This has led not only to an effective reduction of emissions in the converter environment but also to an improvement in the converter operation.

Jan 1, 1992

By R. N. O'Brien, E. Peters

"It has been discovered that copper concentrates can be leached in strong (40-60%) sulfuric acid with nitric acid, or with oxygen if nitric acid is present as a catalyst. Chalcopyrite is rapidly decomposed at temperatures well below the boiling temperature of the lixiviant (-150 C.) and the resulting copper and ferric salts are precipitated as CuS04.H20 and FeH(S04)z.4H20. Other metal sulfides such as zinc, lead, nickel, etc. are also converted to sulfates that are nearly insoluble. Sulfur is partially converted to elemental and partially to sulfuric acid. Reduction products of nitric acid can be recovered from the distillate with good recovery. Conversion of as-received copper concentrates is largely complete in about 1 hour. Introduction9 molar sulfuric acid is an unusual hydrometallurgical lixiviant: it has a boiling point of about 150 C. and a low solubility for base metal sulfates. Below about 6 molar acid, the boiling point falls below 120 C. and yields much higher sulfate salt solubility, while above 12 or 13 molar acid and at higher temperature sulfuric acid becomes an oxidizing agent, yielding gaseous S02' Thus, sulfuric acid within this range of concentration is capable of acting well above the temperature of boiling water without requiring autoclave conditions, and if typical oxidative leaching conditions are applied to suspended mineral sulfide concentrates, it is possible to obtain a conversion of these sulfides into 'crystalline sulfates. Thereafter, the sulfates can be separated by filtration or by solid - bowl centrifuge and the solution can be recirculated to the reactor vessel. Meanwhile, the solid sulfates can be treated in a typical hydrometallurgical circuit, i.e., dissolved in a return stream that is essentially water, separated from each other by, for example, solvent extraction, and recovered as metals by electrowinning."

Jan 1, 1997

By A. V. Tarasov

A flow-sheet for waste-less processing of spent lead batteries comprises mechanized separation of batteries, smelting of the metallic fraction in a kettle, electrothermal smelting of oxysulfate fraction, refining of crude lead and processing of reverts to produce commercial products. Smelting of lead-containing fraction is performed in an electrothermal furnace using a processing technology developed in the Gintsvetmet Institute and differing from conventional processes by the fact that it does not require any fluxing agent (soda); no matte is formed in the process and the amount of slag produced is minimal, because its formation depends only on the ash content of coke and the quality of battery scrap separation. The process has been patented. It has been introduced on a commercial scale in 1.8 MVA furnaces at the plant of A0 "RyazTsvetmet" (Ryazan, Russia). The process has the following main advantages as compared with conventional shaft-furnace smelting and smelting in a short-drum furnace: the process does not require technical-grade oxygen, the amount of process gas generated is minimized ensuring a decrease in lead-containing dust and sulfur dioxide emissions by 3 to 5 times per unit of lead recovered; a decrease in dust entrainment resulting in lower amounts of recycled dust; lower slag yield (a decrease from 20-25% to 3-5%); lower coke requirement (a decrease from 10-14% to 3-4%). Refining of crude lead is performed using conventional technology but there are several unique features for which know-how is available. Processing of by-products of electrothermal smelting and secondary lead refining (slag, drosses, skimmings) and ebonite fraction (crushed battery casings) is performed in a slag-fuming furnace.

Jan 1, 2002

By Toshihiro Kuzuya

A hydro metallurgical process has been developed for the recovery of metal values such as Co, Ni and rare earths from the electrode materials of spent nickel metal-hydride(Ni-MH) secondary battery. MmNis_xCo. (Mm : Misch metal) intermetallic compound could be separated from the electrode materials mixture by sedimentation. A typical chemical composition of MmN5-xCox was approximately, in mass%, 56.0%Ni, 13.4%Ce, 10.6%La and 7.9%Co. The time dependency of leaching intermetallic compound with sulfuric acid solution was examined with processing factors such as sulfuric acid concentration, temperature and agitation intensity, The leaching of rare earth metals proceeded very rapidly, reaching completion in less than 1.8ks. On the other hand, the slow leaching of nickel was observed. The percent of nickel leached at 328K could only reach about 70%.

Jan 1, 2003

By Atsushi Shibayama

The aim of this research was to develop a copper recovery process from mine tailings (0.34%Cu) using flotation followed by high-pressure oxidative leaching (HPOL) and solvent extraction. The results of HPOL using the concentrate of mine tailings obtained by flotation under the optimal conditions of the previous study shown that an efficient copper dissolution of 94.4% was achieved in an H2O media, while the copper concentration of PLS reached to be 2.9 g/L. The solvent extraction of PLS obtained from the optimal HPOL showed that 91.3% copper was recovered in stripped solution under the determined optimum conditions, in which the copper concentration achieved to be 44.8 g/L. Finally, a proposed copper recovery process from the concentrate of mine tailings was developed by combination of HPOL and solvent extraction, while a total copper recovery of 86% was achieved.

By George Nekoksa

The biofilm activity monitoring probes measure applied current during intermittent short-term polarization of the probe electrodes and current or potential between the electrodes after removal of the polarization. The probe polarization mimics conditions at crevices, welds and inclusions where the biofilm activity and microbially influenced corrosion usually concentrate. Monitoring of AC resistance between the probe electrodes can provide infornation about the thickness of deposits.

Jan 1, 1994

By Ray Y. Lin, Sunil G. Warrier

"Low cost processing of metal matrix composites is an essential requirement for this class of materials to be acceptable in commercial application. In an effort to reduce the cost of processing of metal matrix composites, an infrared pressureless liquid infiltration technique has been developed. The salient features of infrared infiltration are that it is rapid, simple and a low cost process. The rapid processing capability causes very little oxide formation on the alloy resulting in both improved wetting and flow characteristics and reduced oxygen contamination in the composite. Thus, vacuum is normally not required. Using infrared inflltration, aluminum and titanium matrix composites have been prepared under an ambient argon atmosphere. Reinforcements in these composites include carbon fibers, silicon carbide Nicalon fibers and Textron's SCS fibers. Microstructural and mechanical test results indicate that completely consolidated composites with good fiber distribution, limited interfacial reaction and high mechanical properties can be manufactured by this process. IntroductionAluminum and titanium matrix composites reinforced with ceramic reinforcements are strong candidates for numerous applications in the aerospace and automotive industries. Aluminum matrix composites are commonly fabricated by either solid state vacuum hot pressing, liquid state pressure infiltration or squeeze casting [1]. Although liquid state pressure infiltration and squeeze casting has significant advantages over solid state processes, the requirement for pressure makes these composites uneconomical for large scale industrial application. Titanium matrix composites are primarily fabricated by solid state diffusion bonding [2]. Pressureless liquid infiltration can significantly reduce the cost of fabrication in both the composite systems. However, during pressureless infiltration processes, several complications concerning the wetting characteristics and chemical compatibility arise."

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 V. B. Chernyavsky, Ladokhin S. V.

Equipment and continuous casting technology for the production of small diameter copper rods and tubes are described. Industrial copper wastes, such as scrap and shavings, were used as the charge. An electron-beam installation for rod and tube production includes a crucible with an electromagnetic stirring system and a pouring hole in its bottom, a bottomless mold, .and a special cooling system, which includes an oil and water cooling devices. For the first time in the electron-beam technology, rods of 8 mm and 14 mm diameter mm tubes of 14 mm external diameter and 7 mm internal diameter were produced through continuous casting by pulling them out of the vacuum chamder into the atmosphere with depressurizing the vacuum chamber. The production capacity of a single strand continuous casting machine was 200 mm/tnin for rod casting and 150 mm/min for tube casting.

Jan 1, 2000

By Peter Hayes, Evgueni Jak, Ata Fallah Mehrjardi

Modern analytical tools, such as electron probe X-ray microanalysis (EPMA), are used in experimental characterization of phase equilibria and microstructures of complex slags. Integrated thermodynamic computer packages, such as FactSage, are used to provide more accurate descriptions of complex slag systems. These advanced methodologies have been applied to characterize dynamic steady state freeze linings in slag systems using submerged cold finger probes at controlled laboratory conditions, establishing the effects of bath chemistry, temperature, heat extraction rate and bulk fluid flow. It has been found that stationary freeze lining deposit interface temperatures at steady state conditions can be lower than the bulk slag liquidus temperature, and that stable operation below the liquidus is possible. A conceptual framework has been developed to explain the phenomenon and the range of interface temperatures that can be obtained in dynamic steady state conditions. These findings have important implications for the design of freeze linings and possible improvements to high-temperature metallurgical operations.

Jan 1, 2014