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By Sanaz Mosadeghsedghi

The feasibility of the application of electrodialysis in separation of light and heavy rare earth elements (REE) in synthetic solutions was investigated. The experiments were carried out using single and binary solutions of a light (cerium) and heavy (ytterbium) REE. The effects of electrical voltage, electrical current, and the addition of complexing agent (EDTA) to increase the separation selectivity were investigated. Separation of Ce and Yb was achieved in binary solutions with and without the addition of EDTA. Higher degrees of separation were seen at higher voltages. Ce–Yb separation was more significant in the presence of EDTA. The separation factor of Ce–Yb and Ce–Yb-EDTA were 1.44 and 2.60, respectively.

By S. E. James

EAF dust has been listed as a "hazardous waste" due to the presence of lead and cadmium, and at times chromium. The 550,00 tpy production of . .EA]' dust, estimated for the United States alone, contains more than 10,000 tpy of lead and about 250 tpy of cadmium in addition to nearly 1'00,000 tpy zinc. Even though the listing of .EAF dust as a hazardous material stimulated extractive metallurgical work worldwide, process development efforts have focused only on the recycle of the potentially-valuable zinc units. However, the recycle of the lead and cadmium, while not lucrative, is the more critical effort. Horsehead Resource Development Company, Inc. (HRD), in conjunction with its sister company, Zinc Corporation of America (ZCA), has taken a unique approach to total recycle of the toxic heavy metals found in the EAF dust. Impure oxide, produced by either a Waelz kiln or FLAME REACTOR Process and containing the lead and cadmium, is calcined in a rotary kiln at Palmerton, Pennsylvania, to produce a refined zinc-rich intermediate for ZCA's electrothermic zinc plant at Monaca, Pennsylvania. During the calcining operation, lead and cadmium are concentrated in a fume product and shipped to ZCA's electrolytic plant at Bartlesville, Oklahoma. At Bartlesville, a new hydrometallurgical circuit has been constructed and the existing cadmium plant expanded. The combined facilities permit the total recovery of cadmium to refined metal and the lead to .a silver-rich intermediate, which is sold to lead smelters. In this paper the Waelzing, calcining and new leaching facilities will be described.

Jan 1, 1990

By S. J. Buckler

Many chemical and metallurgical processes use submerged gas injection to increase contact area between gas and liquid phases in order to promote faster overall reaction or refining rates. The total interfacial area produced by gas injection through lances, nozzles or tuyeres is both an important design parameter for new vessels and a measurement for estimating the maximum processing capacity of existing equipment. Estimating total interfacial area from submerged injection into industrial pyrometallurgical vessels from existing knowledge is a problem with two aspects. The first difficulty is the difference in behaviour of cold (aqueous) and hot (molten metal) systems, implying that existing models and correlations of gas-liquid behaviour developed in low temperature systems are not necessarily appropriate for estimation of high temperature behaviour. The second difficulty is the issue of scale-up of correlations from laboratory to industrial sized vessels. The work presented in this paper is part of an ongoing experimental investigation, at the GK Williams CRC for Extractive Metallurgy, to quantify the total gas-liquid interfacial area available in pyrometallurgical vessels using chemical measurement methods. The effects of three operating variables, injected gas flow rate, nozzle diameter and nozzle submergence, on total interfacial area are quantified in a IOOL aqueous system - the first stage of a three stage process in examining the implications for scale-up of high temperature, medium-scale results are discussed. The results of work at high, injected gas flow rates (up to 500/min) show that the submerged Froude number is not sufficient for use as the sole variable in a predictive model of total interfacial area. Further work is being undertaken to identify other dimensionless variables that will better represent the gas-liquid characteristics in submerged injection that influence the formation of total interfacial area. The second and third stages of the experimental investigation involve measuring the total interfacial area in a large-scale (1000L) aqueous sodium sulphite and small-medium scale molten metal baths.

Jan 1, 2002

By Dany Racine, Daniel Marceau, Denis Laroche, Dmitry Lukovnikov

Carbon base materials play a critical role in the performance of Hall-Héroult cell. The determination of their thermo-physical properties is of primary importance for modeling and designing complete cell systems. However, overcoming the associated experimental hurdles is complex and often underestimated. Of them are the Poisson’s ratio measurements and the continuous oxidation/burning of the materials at temperatures above 200°C. The novel procedure developed in this research is based on the Gleeble® 3800 system. Its vacuum chamber allows test with a chosen atmosphere at temperature of more than 1000°C. Young’s modulus, Poisson’s ratio and the coefficient of thermal expansion values can all be adequately measured using a single test. Cylindrical carbon samples (: 50mm, L: 100mm) were tested in the modified system at temperatures ranging from room to 950°C without any trace of oxidation. The resulting values were also in good agreement with literature data for a specific graphite material.

Jan 1, 2015

By Peter C. Hayes

"The high temperature reduction of solids through the use of reactive gas atmospheres has application in a wide range of industrially important processes. Whilst significant advances have been made in understanding and describing these processes, some key aspects of the chemical reactions and reaction mechanisms operating in these systems, for example, the transformation from metal oxide to metal, remain poorly understood. A number of different product morphologies have been identified in these reaction systems and the reaction rates have been shown to be critically dependent on the product structure.Theoretical examination of the elementary process steps taking place in the region of the gas/metal/metal oxide interface, combined with electron microscope studies of the resultant product microstructures, have enabled the key process and material variables responsible for the development of the various product morphologies to be identified. By considering i) established criteria for the stability of moving interfaces in a thermodynamic potential gradient, ii) the relative rates of chemical reactions on the oxide and metal surfaces, and iii) key process phenomena and physico-chemical properties of the solid phases, the mechanisms and conditions for the formation of various product morphologies are identified. Interestingly the analysis points to direct analogies between these phase transformations and, the phenomena and microstructures observed in metal solidification, and the potential to develop generic models of these fluid/solid reaction systems."

Jan 1, 2013

By D. M. Hausen

It has been demonstrated that microscopic techniques can be applied in a practical manner to the study of spodumene liberation in the processing of pegmatitic ores at the Kings Mountain spodumene plant, Kings Mountain, North Carolina. Spodumene and associated non-opaque gangue minerals are identified and quantified by microscopic point-counting of polished thin sections of heads, concentrates, middlings and tails fractions. Specially prepared polished thin sections? provide uniform thickness of particles for measurement of diagnostic optical properties and the alternate use of incident and transmitted light in distinguishing the various gangue and ore minerals. Spodumene is commonly associated and interlocked with quartz, albite, microcline and muscovite. Concentrate grade depends on the degree of spodumene liberation, which in turn depends on the crystal size and textural association of interlocked minerals. The liberation of spodumene can be measured as a function of screen size by means of microscopic point-count data. Microscopic data also provide useful metallurgical information about the nature of diluent minerals in spodumene concentrates, and the form of lithia losses in the tails. Lithium assays correlate closely with microscopic spodumene analyses in various flotation products from Foote Mineral's Kings Mountain plant, and confirm the applicability of quantitative optical microscopy to the study of liberation and recovery of spodumene from pegmatitic ores. A better understanding of recovery-grade relationships was developed as a result of quantitative microscopy studies.

Jan 1, 1981

By T. E. Warner

In order to detect arsenic and antimony in zinc, various electrochemcial experiments were performed involving the electrochemical introduction of sodium atoms into molten zinc using a solid electrolyte. Under high rates, the formation of the intermetallic phase NaZn13 was assumed to form. Under more moderate injection rates of sodium, employing a symmetric "zinc/zinc cell", a qualitative relationship between the current generated during cyclic voltammeuy and the arsenic and antimony concentrations in molten zinc was observed.

Jan 1, 1999

By S. Tandon

Equilibria studies of selenium distribution for sodium-borate slags were initiated at 1473k under reducing condition as a function of slag composition and alloy composition. The Se distribution coefficient (% Se in slag/% Se in metal) increased from 0.4 to 2.9 with increase in basicity (0.53 to 0.86) for Cu-0.446% Se alloy. However, the results are not very useful from industrial application viewpoint. Therefore, in order to improve the distribution of Se, CaO (10% to 50%) was added to the sodium-borate slag of basicity 0.864. On addition of 502 CaO, the distribution coefficient increased roughly by 100% for slag composition - 44.5% Borax, 22.2% Na2C03, 33.3% CaO and Cu-0.44677 Se alloy. Further, the value of this distribution coefficient has been found to increase by an additional 80% on addition of 20% CaF2 to the above slag for all Cu-Se alloy compositions. Also with increase in initial concentration of Se, the distribution coefficient has been noted to increase.

Jan 1, 1992

By R. D. Irwin, W. M. Mullins, E. A. Medina

"Various stability criteria are introduced and thermo-kinetic models for metallurgical processes are used as concrete examples for evaluation. Kinetic criteria for the process of dynamic recrystallization are proposed. These criteria are compared to the non-equilibrium thermodynamic approaches discussed in the literature. The application of macroscopic stability criteria to materials processing is then discussed.IntroductionThe mechanical behavior of metals at elevated temperature is very well predicted by any of several empirical constitutive relations. Typical is the power-law (or Swift's) form,Equationwhere r-is the stress, y is the strain and m, n , t0, y0 and Q are material constants. This form has been used with some success in the metals processing area [1]. In general, though, all of the empirical constitutive equations are static, failing to account for any dynamical properties of the system they seek to describe.The physics of warm deformation is qualitatively well understood. An example is power-law creep, where the dominant mechanism is assumed to be lattice diffusion limited climb of dislocations, which allows the strain-rate to be determined by the applied stress through"

Jan 1, 1997

By Courtney Young, Jerome Downey

"The various technologies developed for treating spent potlining (SPL) from primary aluminum smelters have been reviewed on several occasions. The technologies generally involve physical, chemical, and thermal processes, either individually or in combination, with the primary objective of total recycle, waste minimization, or complete disposal. In general, those technologies geared for recycling involve separations and are therefore subject to recovery inefficiencies that are attributed to several factors. However, the inefficiencies could be reduced or possibly eliminated if the pots were designed for recyclability. This concept is applied to SPLASH, a recently developed SPL management technology.IntroductionAluminum is produced by molten salt electrolysis via the Hall-Héroult process. The process is conducted in an electrolytic “pot,” which is comprised of a steel frame first lined with insulating refractory brick, and then conductive graphite blocks, which serves as the carbon cathode [1, 2]. These materials are collectively referred to as “potlining.” Anodes comprised of petroleum coke/pitch are suspended above the pot and extend down into the molten cryolite (Na3AlF6) electrolyte. The electrolyte temperature is maintained at approximately 980 °C by resistance heating as low voltage (4-5 volts) and high current (50,000-300,000 amps) are applied across the two electrodes.High purity alumina is added to the cryolite bath, where it dissolves and becomes amenable to aluminum reduction at the cathode:"

Jan 1, 2008

By D. de la Villa

From 1989 to 1992 Rio Tinto Minera has developed and implemented a productivity program in its Huelva Plant, including Smelter, Acid Plant and Electrorefinery. This Plan was designed in order to increase productivity, reduce emissions and produce a better quality of cathodes. This paper describes investments and operating improvements involved in this project, focusing on Smelter and Acid Plants, and comments the results obtained so far.

Jan 1, 1993

By Etsuro Shibata

The saturated solubility of chromium oxide and the valence of chromium in the slag are important matters when considering how to effectively utilize chromium-containing slags. The experimental data of various types of slags cited in the literature were arranged according to the optical basicity in order to evaluate the effects of the oxygen potential and the slag composition. The saturated solubility of chromium oxide and the Cr2+/ Cr3+ ratio tend to decrease with the increase of the optical basicity of the slag at an oxygen potential below 10.5 atm. However, at an oxygen potential of 0.21 atm, the saturated solubility and the Cr6+/Cr3+ ratio tend to increase with an increase of the optical basicity. A practical approach was suggested to reduce chromium in the stainless steel slag and simultaneously recover it as a ferroalloy by the direct smelting reduction of chromium oxide in the molten slag using some reductant in a small furnace.

Jan 1, 2003

By J. E. Allen

The trend in refractory technology for the copper and nickel industries has been to higher quality raw materials and improved processing technology. These changes have been dictated by the changes in pyrometallurgical processes in these industries. For example the introduction of flash smelting, reaction type smelting and auxiliary slag cleaning furnaces havedemanded better refractories materials. Extensive field applications and improved laboratory testing procedures have helped make this transition possible. Changes in refractory technology, primarily in basic refractories, are followed from the late fifties to the present and into the future.

Jan 1, 1994

By T. M. Dreher

The difficulties associated with the operation of a classical rhodium refining process have prompted many attempts to develop a viable solvent extraction flowsheet for rhodium. Recent investigations at McGill University have involved the activation of rhodium prior to its solvent extraction. The role of activation is to convert the aquochloro complexes of rhodium to a form extractable by conventional solvent extraction reagents. In the novel separation scheme identified, chloro complexes of rhodium are converted to bromo complexes, which undergo aquation to a lesser extent, making them more easily extracted. Rhodium is then extracted using Kelex 100, and stripping is achieved by use of a concentrated chloride based solution. Separation of rhodium from iridium is achieved by either prior reduction of Ir(IV) to Ir(III), as the latter is not extracted, or via co-extraction and differential stripping. A conceptual flowsheet for the refining of rhodium using this method is proposed.

Jan 1, 1998

By Tao Zeng, Jianchao Li, Chang Jie, Jieyu Zhang, Jifang Xu, Kuochih Chou

"The densities of the selected quaternary Ca0-5%Mg0-Alz03-Si02 slag with low silica were measured by the Archimedean method in a wide temperature range from l 723K to 1823K. Slag compositions were chosen based on five different levels of Si02 content between 0.00 pct and 11.40 pct. The MgO content was equaled to 5.00 pct. The mass ratio of CaO/Alz03 was varied from 0.67 to 2.14. The effects of temperature, Ca0/Alz03 ratio and optical basicity were studied. It is shown that density decrease approximately linearly with an increase in temperature. With the same Si02 content, the density decreases with increasing of CaO/Alz03 ratio and optical basicity. Based on the experimental data as the boundary of the homogenous phase region predicated by F ACTSAGE software, the mass triangle model is used to calculate the density of selected limited homogenous phase region. The results showed that the mass triangle model is working well.IntroductionIt is of great importance to measure density of slag melt not only to the theory research for melt, which that is directly amenable to the structure correlations of molten slags, but also to the industrial application. Many metallurgy phenomena such as inclusion formation in molten melt and its removing, slag foaming, slag-metal reaction are closely related to the density of slag. Density is also required to estimate other fundamental properties, like surface tension, viscosity, and thermal conductivity from thermal diffusivity so that a relatively complete picture in regard to the behavior of high-temperature molten oxides could be made."

Jan 1, 2013

By W. K. Connor, O&apos

The U.S. Bureau of Mines, in cooperation with the Idaho National Engineering Laboratory (INEL), conducted over 30 hours of melting tests to vitrify simulated low-level radioactive wastes from the INEL Radioactive Waste Management Complex (RWMC). Five separate waste compositions were investigated, each consisting of noncontarninated soil from the RWMC and surrogate materials used to simulate the actual buried wastes. The RWMC soil and five waste compositions were melted in a 50-lb, single-phase electric arc furnace with a water-cooled shell. These tests were conducted to determine melting parameters in preparation for a large-scale melting campaign to be conducted in the Bureau's 1-metric ton (mt), water-cooled-wall, 3-phase electric arc fumace. Bulk chemical composition was determined for each of the feed materials and for the slag, metal, fume solids, and offgas furnace products, and distributions were calculated for the key elements. The material balance for the furnace operation indicates that from 63 to 84 pct of the feed reported to the slag. Cerium, used as the surrogate for the radionuclides in the wastes, demonstrated an extremely strong affinity for the slag product. Although slag temperatures as low as 1250° C were recorded when melting the RWMC soil, temperatures in excess of 1600° C were necessary to achieve the fluidity required for a successful slag tap.

Jan 1, 1994

By Mike Dry

While McCabe-Thiele plots are useful for designing single-component solvent extraction systems, not least because of their simplicity, they are less useful for multi-component solvent extraction. This paper presents a relatively simple method, compared to other approaches, for modelling solvent extraction as chemical equilibrium reactions between the various aqueous and organic species. The essence of this approach is how values for the equilibrium constants can be extracted from standard laboratory data. Synergistic solvent extraction of nickel is used to illustrate the method.

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of 873°K is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composition formed under roasting of concentrates with particle sizes less than 0.02 um (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CuFeSz2 each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forchamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By B. Q. Li, Y. Shu, K Lynn

"This paper discusses the effects of magnetic field and internal radiation on the melt flow and solidification morphology during solidification processing of oxide crystals for optoelectronic and remote sensing applications. The numerical solution of the integral differential equation characterizing the internal radiation and the magnetohydrodynamic equations describing the magnetic and transport phenomena is obtained by applying the combined discontinuous and continuous finite element method. The results show that both internal radiation and an externally applied magnetic field can have important effects on the melt flow and solidification behavior during the melt processing of oxide materials.IntroductionOptical single crystals are widely used in optical and electronic devices. These crystals are often grown from high temperature oxide melts under strictly controlled conditions. As in the well-known single crystal growth processes for semiconductor wafers, thermal gradient in the melt is a major contributing fuctor to the oxide melt pool. Unlike the semiconductor single crystal growth processes, however, the oxide melt is semitransparent and internal thermal radiation plays an important role in redistributing the thermal energy in the melt pool. Our recent experience with pilot-scale plant measurements also shows that the oxide melt is electrically conducting, although its electrical conductivity is considered much lower than the liquid metal or semiconductor melt.The fact that the oxide melt is absorbing and emitting in the thermal radiation frequency range makes it difficult to study the thermal energy transport in the melt pool. This is because thermal radiation is governed by a hyperbolic differential equation, which is different from those describing the transport processes in liquids. Also, our understanding of how thermal radiation interacts with other transport mechanisms such as convection and conduction is rather limited at point in time, in particular in high temperature oxide melts for optical single crystal processing."

Jan 1, 2004

By Chunhua Liao, Chao Peng, Guangsheng Huo

To get the separation of tungsten and molybdenum, we adjusted the pH of the solution to 7, at which tungstate (WO4 2-) will be polymerized into HW6O21 5-, while molybdate will still exist in the form of MoO4 2-. Two strongly basic anion exchange resins (D201, D213) were experimented for the separation of tungsten and molybdenum. The results of condition experiments indicate that D213 resin performs better in the treatment of lower concentration solution A (WO3 10g/L, Mo 4.12g/L) with a separation factor as high as 10.64. While D201 resin is more suitable for the high concentration solution B (WO3 70g/L, Mo 28.97g/L) with a separation factor of 6.9. The results of column testing performed on D213 resin show that the solution after loading process with a mass ratio of Mo/WO3 = 50 and the desorption solution with a mass ratio of WO3/Mo = 27 can be obtained

Jan 1, 2014