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By Arthur E. Morris

Fifty years ago when Professor Yazawa began his career, the field of process simulation and modeling was in its infancy. Since then, tremendous progress has been made in our ability to model metal production flowsheets from mine to refined metal. This progress has come about by parallel developments in basic understanding of process chemistry and in computational techniques, This paper will review the progress made in process understanding and modeling in lead, zinc, and copper metallurgy from its inception to the present, and the role of Professor Yazawa's work in furthering this progress. Specific examples will be given for the sintering of lead concentrates, slag fuming, zinc concentrate roasting, flash smelting of copper, and pyro-extraction of zinc. Factors limiting further progress will be described.

Jan 1, 2003

By Arthur E. Morris

Fifty years ago when Professor Yazawa began his career, the field of process simulation and modeling was in its infancy. Since then, tremendous progress has been made in our ability to model metal production flowsheets from mine to refined metal. This progress has come about by parallel developments in basic understanding of process chemistry and in computational techniques. This paper will review the progress made in process understanding and modeling in lead, zinc, and copper metallurgy from its inception to the present, and the role of Professor Yazawa's work in furthering this progress. Specific examples wi1\ be given for the sintering of lead concentrates, slag fuming, zinc concentrate roasting, flash smelting of copper, and pyro-extraction of zinc. Factors limiting further progress will be described.

Jan 1, 2003

By R. Hammen

Processes are needed to rapidly and cost-effectively produce highly pure lithium salts for the rechargeable battery sector. Lithium purification is a chemical engineering challenge, due to the low concentration of lithium compared to sodium, potassium, magnesium, calcium, and transition metal ions commonly occurring in lithium brine resources. We describe a Solid Phase Extraction (SPE) process that rejects sodium and potassium, while binding lithium and other higher valent ions. Lithium is then harvested by selective displacement from the SPE column. The rapid equilibration kinetics of SPE composites enables these ion separations to occur in a small SPE column and in one column stage. The chemical parameters of the process are described.

By Zhang Yongzhu

In hydrometallurgical processes of PGMs separation and refining, differences between 1-PGMs (Ru;Rh;Pd) and h-PGMs(Os;Ir;Pt) in thermodynamics and kinetics have been observed. The successful practice in the separation and refining of PGMs in China, is mainly based on the following two kinetically extraction sequences of: (1) for the extraction of PGMs complexes in different configurations with coordination mechanism (AuCI,) -> (MCl6)2-> (MCl4 )2-> (MCI6) 3- , and the substitution rate for h-PGMs complexes with higher effective nuclear charge Z' is much more slow than that of I-PGMs. and (2) for the extraction of PGMs in different configurations with oxonium (or ion -exchange) mechanism (AuCl4)-> (MCl4)2--> (MCl6)2-> (MCl6)3- and the extraction of h-PGMs complexes with low surface charge density is more fast than that of I-PGMs complexes. In view of atomic structure theory, the similarity of atomic radii and chemical properties and difficult separation of PGMs resulted from the Lanthanide Contruction between 5th period (1-PGMs) and 6th period (h-PGMs). The differences between h-PGMs and 1-PGMs are due to the loss shielding of 4f subshells on 5d electrons for h-PGMs with higher nuclear number, which makes h-PGMs have a higher Z' (effective nuclear charge) and strong attraction for outer space electrons. As a result, h-PGMs metals and complexes are thermodynamically more stable and kinetically more inert than the corresponding 1-PGMs. The differences between h-PGMs and 1 -PGMs in aspects of elements properties, complexes, hydration, substitution and redox reactions , are discussed.

Jan 1, 1993

By Dirk Bergmann

During the spray forming process, a continuous molten metal stream is atomized by impinging high speed inert gas jets. In the generated spray cone, the resulting metal droplets are rapidly cooled by the huge temperature difference to the surrounding gas phase and thereby partly solidified during flight. After a certain flight and residence time inside the spray cone, the droplets impinge onto the solid substrate and form the product (deposit) by compaction. Material properties of this preform strongly depend on several process parameters and especially on the thermal and kinetic state of the deposited droplets at the point of impingement. Smaller droplets may cool very fast due to their low mass and impinge onto the product in a completely solidified state as solid metal powder particles. Larger droplets with big mass contain a higher amount of thermal energy and impact during the state of phase change or still as completely liquid. It is obvious, that a certain amount of liquid content in the droplets is needed for forming a homogeneous deposit. Therefore, the thermal history of metal droplets during flight in the spray cone is of great importance for overall process modelling and control. Modelling the effects of the impinging droplet mass on the formation and heat balance of the deposit, the thermal conditions of the droplet stream need to be temporary and spatially averaged at different locations. Averaging may be achieved in different ways, giving alternative results. A first method is averaging over the droplets total enthalpy which consists of the thermal content and the remaining latent heat of fusion within the droplets. A second method may yield the average over the heat content and the solid fraction separately. Results of these two methods depend on the application and the kind of information which one wants to achieve and show some deviations, which will be discussed in terms of consolidation and energy conservation of the deposit.

Jan 1, 1999

By Ravi S. Bellur-Ramaswamy, Daniel A. Tortorelli, Robert Haber, Nahil A. Sobh

We optimize continuous quench process parameters to produce functionally graded aluminum alloy extrudates. To perform this task, an optimization problem is defined and solved using a standard nonlinear programming algorithm. Ingredients of this algorithm include 1) the process parameters to be optimized, 2) a cost function: the weighted average of the precipitate number density distribution, 3) constraint functions to limit the temperature gradient (and hence distortion and residual stress) and exit temperature, and 4) their sensitivities with respect to the process parameters. The cost and constraint functions are dependent on the temperature and precipitate size which are obtained by balancing energy to determine the temperature distribution and by using a reaction-rate theory to determine the precipitate particle sizes and their distributions. Both the temperature and the precipitate models are solved via the discontinuous Galerkin finite element method. The energy balance incorporates nonlinear boundary conditions and material properties. The temperature field is then used in the reaction rate model which has as many as 105 degrees of- freedom per finite element node. After computing the temperature and precipitate size distributions we must compute their sensitivities. This seemingly intractable computational task is resolved thanks to the discontinuous Galerkin finite element formulation and the direct differentiation sensitivity method. A three-dimension example is provided to demonstrate the algorithm.

Jan 1, 2001

By M. W. Kennedy

Prediction of the thermal duties of copper coolers in freeze lined furnaces is challenging. Where copper coolers are immersed in liquid slag the heat transfer is often defined by a natural convection cell immediately adjacent to the wall, in the absence of other factors producing forced convection. Slag coolers are typically not fully immersed, slag temperature, liquidus and superheat can vary, and bath levels may change significantly with batch tapping, leading to substantial variations in radiation heat fluxes. Radiation heat transfer is discussed with reference to the non-obvious impact of slag liquidus on radiation losses in the exposed cooler sections. Reference is made to literature and the results of analytical and FEM models.

By Theo Lehner

"The Boliden Rönnskär Smelter operates in the European Context of tight EH&S limits, with ever increasing regulations and tribulations. The near future promises to bring new burdens in the form of C02 trading, miners and pre-treaters increased appetite for a larger share of contained values, and changing compositions and competition in raw materials. On the other hand, European Smelters such as Rönnskär, Harjavalta have demonstrated an astonishing power of survival. This presentation lists and comments on current challenges but opportunities for increased survival power are also presented. One example of the latter is the ongoing investment into increased treatment capacity for e-scrap.UPDATE ON RÖNNSKÄR OPERATIONSThe Rönnskär Smelter has achieved 80 years of age with no signs of retirement. The smelter is most active in spite of its age! And it has undergone some face lift operations to maintain its attractiveness.Raw material, processing facilities and a market for the products are some essential prerequisites for a viable operation. To justify long term survival, economic terms such as return on investments and positive cash flow need to be considered. Below, we illustrate how the Rönnskär Smelter complies with these terms. To update the reader on current operations, our current flow sheet is depicted in Figure 1. The figure summarizes our current input and output."

Jan 1, 2012

By Jeffrey R. Taylor

The distribution of low concentrations of Cr, Mn, Rh, Co, Ni, Ag and Fe between copper matte and bullion phases has been measured at 1200oC. These results. together with values for nine other elements, have been used to develop a simple model to describe the distributions in terms of known thermodynamic properties?. The Temkin model for ionic melts was assumed to apply to the sulphide species in the Cu-S matte? phase and it is shown that the choice of sulphide species is particularly important for successful representation of the experimental .results?. In general, the lowest sulphlde (minimum sulphur :. metal ratio)? formed by the. metal is most suitable, although Ni, Co, Rh and Pd appear to associate with more sulphur in the melt than suggested by the? composition of their lowest sulphide. A correlation between the composition of the metal sulphide species formed in the ternary system and the? position of the minimum in the free energy of mixing curve in the metal-sulphur binary -system is? proposed.

Jan 1, 1983

By B. J. Elliot

The Outokumpu Oy flash smelting furnace was designed for a capacity of 69,5 mtph of concentrate. The history of developments on the flash furnace, from the original operating capacity of 55 mtph to a proven capacity of 115 mtph of concentrate, is summarised. The new feature of operation at BCL Limited is ?the use of screened lump coal reduction in the settler region of the furnace. This paper considers the effects of settler bath reduction on the furnace smelting capacity, the condition of the furnace ?lining and bath, and ,the slag losses generated from the flash furnace and ultimately to discard. By using the settler bath reduction technique the capacity of the furnace for smelting new concentrate has been increased by 15% and hearth accretion has been eliminated by direct reduction with coal, which has also allowed the generation of a substantial protective lining on the furnace walls and roofs. As a result of improved slag losses from lump coal charging the metal recoveries on the flash furnace have increased from 70% to 87% for nickel, 68% to 82% for copper, and 28% to 45% for cobalt.

Jan 1, 1983

By B. Mishra

Several reactive metal purification processes using molten salts generate effluent from which significant quantities of metal can be recovered prior to discardinglrecycling the salt. A Salt-scrub [SS] process has been applied where the reactive metals are recovered as a metal-gallium alloy by calciothermic reduction of the metal compounds. The SS alloy compositions were produced by mixing, pressing and sintering the metal-powders. Measurement of metal recovery has been studied for cerium, silver, tin and lead. The process has been optimized for variables such as the metal quantity per kg of effluent salt, amount of excess calcium over stoichiometry, stirring rate and time and holding time at reduction temperature. Over ninety-seven percent metal recovery has been obtained under optimized conditions. The development of an alloy for efficient Salt Scrub processing reduces a major contaminated waste disposal problem as well as recovering the valuable reactive metal. Surrogate metals have been used in this work to study the behavior of plutonium.

Jan 1, 1994

By Raj P. Singh Gaur

Due to high concentration of NaOH in the digested slurry after scheelite digestion, it is diluted to about 4N before filtration to separate sodium tungstate solution from the sludge (residue). However, in practice there may be deviations in the normality of NaOH present in the slurry. There may also be variations in the temperature of the slurry and filtration time. Slight variations in these parameters could cause tungsten losses in the sludge via the back reaction: Ca(OH)2 + Na2WO4? CaWO4 + 2NaOH This paper pertains to the effect of normality, temperature and time on the tungsten losses in the sludge that is separated from ?diluted-scheelite-slurry-in-NaOH? via filtration. Results indicated that tungsten losses in the filtered residue (sludge) were quite significant when the slurry temperature was kept at 70°C or higher. The effect of high temperature was less significant at the slurry normality of 3.6 or higher. Combination of low slurry normality (<3.6) and high temperature (>60°C) resulted into large W-losses in the sludge.

Jan 1, 2006

By John H. Schloen

Copper refineries are constantly looking for methods to upgrade their plants to reduce refining costs and to improve the purity of their electrolytic cathodes at the same time that the purity of the anodes they refine is being lowered by the rehabilitation of reverberatory furnace smelters to one of the direct smelting processes. The comments given below are based on the answers to the questionnaire returned bf the 36 copper refineries that represent 66% of the western world s refining capacity. Eleven refineries employ some form of uniform weight anade casting, e.g., Outokumpu, Contilanode, Mitsubishi, Lurgi, or Hazelett. This type of anode casting presents the best possibility for improving cathode purity. The cathode press of Phelps Dadge can improve current efficiencies and cathode quality. The press is used on first-run cathodes, after 48-60 hours, on half-cells at a time without interruption of the cell current. One refinery interrupts current for sever.al hours to allow the anode slime to settle before the, cathode pressing. The cathode press is now used at eight refineries. Apart from periodic reverse current (PRC), it is not expected that current densities will be increased. Thirty refineries, using direct current, average 231 amps/M, with a low of 178 and a high of 350. Five refineries use PRC at an average of 338 amps/M, with a low of 290 and a high of 380. Current efficiencies are good at an average of 94%, with a low of 88% and a high of 99% for the 34 refineries that reported. It must be remembered that the cycle efficiency with PRC is about 93%., so that the effective current efficiency with PRC would be only .94 X .93 or 87% However, PRC should be considered seriously for refinery expansions because it can save about 25% on capital costs.

Jan 1, 1987

By Kazuyuki Kakegawa

The sintering characteristics and the change in the compositional distribution in the PbTiO3 PbZrO3-Pb(Mgl/3Nb2/3)O3 system during the sintering process by spark plasma sintering (SPS) method were examined. They were compared with those by a normal sintering method. The densification by the normal sintering was slow even at high temperatures, When SPS method was employed, much lower temperature and shorter period resulted in sintered bodies having almost the theoretical density. As expected in normal sintering, the compositional distribution decreased as the sintered density increased. On the contrary, the change in the compositional distribution by SPS was much smaller than that in the normal sintering. This sintering characteristic of SPS suggested a possibility of fabrication of sintered material having a desired compositional distribution.-

Jan 1, 2003

By Antoine Allanore, Guillaume Lambotte, Bradley R. Nakanishi

Current industrial methods used for rare earth element (REE) extraction involve: 1) ore enrichment, 2) separation of rare earth oxides (REOs), 3) chlorination or hydrofluorination, and 4) individual electrowinning of REEs from a molten halide electrolyte. The complexity of REE extraction is inherited from their electronic configuration. Recently, molten oxide electrolysis (MOE) has been used to produce reactive metals directly from their oxides, e.g. titanium. As a single-step alternative to processes 3) and 4), or laboratory has investigated rare earth extraction by MOE. A key challenge is to find a molten electrolyte more stable than REOs. One possibility is to use binaries of REOs directly as a solvent. We have, therefore, developed two experimental approaches for studying molten REOs at temperatures exceeding 2200oC. The present work reports the most recent experimental results obtained with La2O3-Y2O3. Those promising results demonstrate potential for operating with molten REOs and refine the underlying materials challenge for electrodes to enable metal recovery.

Jan 1, 2015

By Tadashi Aiura, Yasuhiro Miura

"A small amount(0.2mass%) of Scandium(Sc) was added to the 7.NOl and 5083 Al alloys as a refiner and stabilizer of microstructure, and the resulting microstructures were discussed in comparison with the effects of the conventional additives. The followings are summarized: 1) in the as-solidified structure, a ·decreased tendency of constitutional supercooling and increased solubility of Mg were recognized for the Sc-added 5083 alloy. Sc is a -better microstructure refiner for the 7N01 alloy than Zr, in a sense that it does not suppress the favorable effect of· coexisting Ti. 2) Sc effectively suppresses recrystallization both in the 5083 and 7N01 alloys. 3) The rod like primary Al3Sc crystals formed during solidification, as well as the fine dispersion of Al3Sc precipitates formed by subsequent heat treatment, can act as a strong recrystallization suppresser. IntroductionThe 7N01 and 5083 alloys are the most popular industrial Al alloys and they are widely' used for various structures because of their superior properties. Fine macro and micro structures of the materials are required for obtaining acceptable sec resistance,consistent appearance of anodized surface and good weldability, as well as good mechanical properties. In order to produce fine grain structures, transition metals, such as Cr, Zr, and Mn, have been conventionally added.It has been reported that Sc is an efficient refiner [l, 2] and can be an alternative for the conventional and also suppresses recrystallization in Al alloys [3,4]. Scandium is the lightest transition element and forms an equilibrium intermetallic phase. The equilibrium phase, Ll2-Al3Sc, is coherent with the matrix, and of _spherical shape. A fine dispersion of the spherical precipitates is obtained by quenching and aging after solutionizing annealing. The authors have already reported a part of the experimental results on the effect of Sc on the as homogenized microstructure of the 5083 alloy [5]. In the present study, the effects of Sc on the macro and micro structures of the industrial high strength Al alloys(7N01 and 5083) for extrusion are investigated, and the superior role of Sc as a grain refiner is shown"

Jan 1, 2000

By Roy J. M. van Lier

In industrial aqueous solutions, germanium generally occurs in trace amounts amid high concentrations of other metals, such as zinc, copper and iron. Separation of germanium from these metals as well as its isolation from gallium and indium pose a real challenge to the hydrometallurgist. After a brief discussion of the aqueous chemistry of germanium, this paper reviews the flowsheet of the Apex Mine in Utah. The Apex property was the only mine in the world to be operated primarily for production of gallium and germanium, but apparently closed due to great operating difficulties. Several process variants proposed for the treatment of the Apex ore, including bioleaching methods, are addressed. Following a more general description of the behavior of germanium in hydrometallurgical zinc processing streams, available technology for its recovery from aqueous solutions is summarized. Precipitation, solvent extraction, ion exchange, electrowinning, ion flotation and liquid-membrane separation are all outlined in terms of the aqueous chemistry of germanium. Finally, the production of high purity germanium dioxide and metal is briefly discussed

Jan 1, 1995

By Kazuhiro Nisizono, Takashi Kuroki, Nobuyuki Mori, Keisaku Ogi

"The improvement of critical current density and mechanical property is essential to the practical application of the superconductive oxides. A solidification technique is developed in this study for the growth of columnar or single Y123 crystal with finely dispersed Y211 and Ag particles through a monotecto-peritectic reaction of Li.(Ba-Cu-Ag-0 rich liquid)+ Y211-+ Y123+Lz(Ag rich liquid). The large solidification rate and temperature gradient can refine the Ag and Y211 particles. But Ag-free region is widely formed along the crystal growth direction in the central part of the Y123 cell. Since this phenomenon occurs because of the cellular growth, it is necessary to narrow Y123 cell width or to grow Y123 crystal with flat freezing interface. By controlling crystal growth direction using a seed crystal, Y123 columnar or single crystal with uniformly dispersed fine Ag particles are obtained. The· behavior of Ag and Y211 particles during the solidification of Y123 crystal is simulated by the peritectic growth model of faceted Y123 crystals.IntroductionY-Ba-Cu-0 superconducting oxide (YBCO) with high critical temperature also has excellent superconducting characteristic under the high magnetic field. The critical current density (Jc) has been enhanced by ·using unidirectional-solidification technique, which can overcome the weak-link problem at grain boundaries and control the crystal orientation and the distribution of Y211 particles which give effective magnetic flux pinning centers in the Yl23 matrix [1-4].In addition to improving superconducting properties, it is necessary to improve mechanical property for the practical application. The silver addition to the melt-textured YBCO superconducting oxide has been reported as the effective method to improve mechanical properties without degrading superconducting properties. Since the material properties are considered to be largely affected by silver particle size, form, dispersion state etc. in the Y123 phase, it is important to control Ag distribution in YBCO/Ag composites. Besides, it is also reported that the silver addition improve the corrosion resistance to the water and CO2 [5,6]. Nishizono et al. [7-9] have reported that the silver distribution in the YBCO/Ag composites is largely affected by the solidification condition, but yet some unclear points are also remained. YBCO has been also fabricated by the zone melting method [10-12], and Furuya et al. [5] and Hirano et al. [13] have reported the fabrication of silver added YBCO composites, but the distribution and behavior of Ag are not investigated in detail"

Jan 1, 2000

By B. Madelin

Over the last ten years, Minemet Recherche and Metaleurop have used an approach in order to investigate and improve the operation of its Smelting furnace and its lead blast furnaces. This approach gives importance- to three complementary means of investigation : - Probing campains in the industrial furnace (temperature and gas analysis profiles), - Chemical and physical modeling (coke combustion, sinter reduction modes, flows patterns, ?.) , - Staged mass and heat balances or kinetic model. This allows to define the limits of operation of each blast furnace and to predict the influence of operating parameters on the furnace performances. For the zinc Imperial smelting furnace, the probing results show the existence- of both an Isothermal reserve zone at 1015ºc and a chemical equilibrium between ZnO and gas which makes possible the use of a practical model for heat and material balances. In particular, very good prediction on the influences of operating parameters can be made. On the contrary, for lead blast furnaces, the probing results show that the thermal and chemical equilibria are not reached. Consequently, classical models for staged heat and mass balances are not sufficient. The use of the other means allows then to characterize the specific influences of operating parameters on the thermal instabilities of these furnaces and their allowed limits.

Jan 1, 1990

By C. M. Wai

Metal species in solid and liquid materials can be extracted by supercritical carbon dioxide containing a suitable ligand. This in situ chelation-supercritical fluid extraction technique offers, several advantages over conventional solvent extraction including minimization of organic liquid waste generation and exposure of personnel to organic vapors. One unique feature of this technique is that metal species can be removed from solid materials directly using supercritical carbon dioxide as a solvent. Several ligand systems including dithiocarbamates, ß-diketones, organophosphorus reagents, and macrocyclic compounds have been tested for metal extraction in supercritical carbon dioxide. This novel extraction technique may have important applications for metal recovery and mineral processing.

Jan 1, 1996