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By A. Raraz

The optimization of the plutonium electrorefining process has been studied on the basis of modeling and model materials. The plutonium electrorefining process has been reviewed and the basics of the electrorefining process with molten salts as electrolytes and under forced convection has been presented. The definition of the problem in plutonium electrorefining has been related to three factors and this research has addressed these three factors to provide an insight to this process. The hydrodynamic factor gives information on the behavior of the mechanically stirred system. The chemical stability and solidification factor shows the interactions among the components of the electrorefining cell. The electrochemical factor is oriented to study the efficiency of the electrorefining process on the basis of limiting current density, stirring rate and configuration cell. As a result of this study the optimization of plutonium electrorefining implies mainly a re-design of the cell.

Jan 1, 1995

By Marco Olper

Zinc bearing materials containing chlorides and fluorides of alkali metals, such as EAF dust, Waelz oxides, galvanizing ashes, zinc & brass foundry fumes and converter fumes are little attractive, both technically and economically for processing in ISF plant or in a conventional zinc sulphate electrolysis works. The Ezinexm Process allows for the recovery of high purity zinc in cathode form, from these materials, regenerating the leaching liquor. The process is based on a new electrochemical system which depolarizes the anode reaction with reduction of the cell voltage, compared with the traditional sulphate electrolysis method. The electrolyte, based on a chloroamrnino complex, allows for the recovery of other valued metals present in the zinc bearing materials such as lead, copper and silver, these being recovered as a metallic cement consequently improving the economics of the process.

Jan 1, 1994

By V. A. Luganov

During the treatment of raw materials containing arsenic and antimony, problems in the distribution of these elements in the process products occur. In a number of cases in processing of copper-bearing materials, it is possible (or necessary) to obtain speiss. The purpose of the present research is to study the theoretical aspects and analyze the technological possibilities of producing copper-bearing speiss and the subsequent electrometallurgical processing with copper extraction as well as arsenic and antimony utilization. Copper arsenide (Cu3As) and copper antimonide (Cu3Sb) are the main components of the speiss. A thermodynamic analysis of the electrochemical oxidation of Cu3As and Cu3Sb, carried out using Pourbaix diagrams, showed that in a pH range from 0 to 2, oxidation potential 0.45-0.55V, ions of copper and arsenic and antimony trioxide are in the equilibrium. The kinetic study has shown, that with an increase in the polarization potential, the dissolution process changes from chemical to diffbsion control. An increase in temperature stabilizes the electrolysis process due to dissolution of arsenic trioxide forming on the anode. Electrolysis of speiss using a cathode diaphragm with the solution pH = 1-2, current density 150-200 A/m2 and temperature 60-70°C makes it possible to obtain cathode copper with a current efficiency of 95-96% and to remove the arsenic from the process during the electrolyte cleaning process. The arsenic content in the cathode copper did not surpass 0.002%. As the result of the research, a technological flowsheet for copper-lead speiss processing was developed. At the present time this technology is undergoing pilot testing.

Jan 1, 1999

By J. P. Ibáñez

The uptake of copper from extremely dilute aqueous solutions by alginate in the form of protonated dry alginate beads was investigated. Barium was used to cross link the alginate forming the beads. The effect of various experimental parameters such as pH and metal ions concentration on the uptake of copper were studied. The uptake was strongly dependent on the Cu-bearing solution pH up to a value of 4.5. A removal of 100% o was achieved when the initial concentration of copper was as low as 8.0 mg/L. The maximum uptake, i, e., the loading capacity, was found to be 167 mg of copper per g of beads. The mechanism governing the removal of copper was found to be ion exchange between protons of the alginate beads and cupric ions of the solution. For this ion exchange process a molar ratio, d[H+]/d[Cu2+], of 2.0 was determined. EPMA-EDX analysis of the Cu-loaded beads showed a uniform distribution of the ions throughout the structure of the alginate, regardless the solution pH. This may suggest that this sorbent material is a porous ion exchanger having high permeability and capacity. The uptake of copper and of the heavy metals cadmium and zinc by this sorbent is compared.

Jan 1, 1999

By Christina V. White

An experimental study was undertaken to investigate the feasibility of utilizing vapor transport for the treatment of heavy metal contaminated smelter soils. The focus of this project was to develop process chemistries that would make incineration a viable process for the treatment these soils. The experimentation concentrated on the elimination of arsenic, cadmium, and lead, and was performed in a laboramry scale rotary kiln setup. Three soil samples from non¬ferrous smelter sites, which contained various concentrations of contaminants, were utilized in the experimentation. Three chemistries were investigated for the volatilization of the heavy metals: Chloridizing volatilization, ferric chloride vapor complex formation, and the use of oxygen potential control. The samples were analyzed for residual heavy metals so that the extractions could be determined. However, the ultimate test was the leachability of the residual arsenic, cadmium, and lead, as determined by the TCLP test. The results firmly establish that incineration is a feasible process for the treatment of metal contaminated soils. It was found that no one process chemistry is suitable for all different soil samples. A two-step process consisting of a reducing step followed by a hydro-chlorination step was required to make Soil Sample-B pass the TCLP tests for all three heavy metals. Soil Sample-A passed the TCLP tests for arsenic, cadmium, and lead using a hydro-chlorination process at a minimum temperature of 700°C. In addition to passing the TCLP mm for Soil Sample-A and Soil Sample-B, 70 to 80 percent removal of the impurities was accomplished. This demonstrates that the leachability of the impurities was decreased primarily due to the removal of a large fraction of the contaminants, Soil Sample-C possessed very high levels of cadmium and lead and only moderate extractions of the impurities were generated from this soil. The arsenic TCLP test was passed at 500'C using a process gas containing ferric chloride and at temperatures of 700°C and above using chlorination of hydro-chlorination.

Jan 1, 1996

By L. Y. Zhang

The current status of metal hydride alloys for NiMH batteries was systematically reviewed. Extensive application-oriented research and development has successfully made the NiMH battery an important part, with growing potential, among rechargeable batteries. The rare earth based metal hydrides (AB5) have been considered the best alloy material for use in the negative electrode in NiMH batteries. However, being in demand for high performance electronic markets, the still young NiMH industry is facing serious technical challenges in developing better products. Among all the efforts to respond to the challenges, advanced AF3, alloys are in great demand: the capacity enhancement race requires new or improved alloys possessing higher volumetric capacity; price competition mandates MH materials with low cost; high performance under severe service environments calls for alloys with high corrosion resistance when subjected to electrochemical cycling; and finally, high power service requires the negative electrode to deliver current at high rates.

Jan 1, 1997

By Victor Bredykhin

The report is devoted to the investigation and improvement of processes taking place at contact of large quantities of water insoluble liquid and particles of solid phase in a pulp. Theoretical analysis and simulation of acting conditions have allowed to determine that after attaching of oleophilic particles on the «water-reagent» separation surface the break of a formed complex is taking place according to the reagent volume and for oleophobic minerals along the «solid-reagent» separation surface. As a result particles are selectively treated if the magnitude of the reagent adhesion to the surface of solid phase in water is great. The results of dispersion are influenced significantly by availability of sharp edges on the surface of real particles. They keep tree phase perimeter of moistening. It is possible to fix reagent in the form of lens whose contact angle is significantly smaller in comparison to the thermodynamic angle. In adhesion dispersion the reduction of reagent volume, covering the equal area of particles surface is possible when the reagent is in a pulp in the form of thin films on the «water-gas» separation border. The process is tested in laboratory conditions as well as at pilot concentrating mills in flotation of sulfide ores, non-ferrous metals (copper-molybdenum ore), native sulfur and coal.

Jan 1, 2006

By Adam Powell, Soobhankar Pati

"Solid Oxide Membrane (SOM) Electrolysis is a new energy-efficient zero-emissions process for producing high-purity magnesium and high-purity oxygen directly from industrial-grade MgO. SOM Recycling combines SOM electrolysis with electrorefining, continuously and efficiently producing high-purity magnesium from low-purity partially oxidized scrap. In both processes, electrolysis and/or electrorefining take place in the crucible, where raw material is continuously fed into the molten salt electrolyte, producing magnesium vapor at the cathode and oxygen at the inert anode inside the SOM. This paper describes a three-dimensional multi-physics finite-element model of ionic current, fluid flow driven by argon bubbling and thermal buoyancy, and heat and mass transport in the crucible. The model predicts the effects of stirring on the anode boundary layer and its time scale of formation, and the effect of natural convection at the outer wall. MOxST has developed this model as a tool for scale-up design of these closely-related processes.IntroductionSolid Oxide Membrane (SOM) Electrolysis is a variation on the Hall-Héroult process for molten salt electrolysis of oxides which promises to solve many of the problems of its predecessors. Magnesium in particular is both soluble in molten salts and highly reactive, such that it migrates to the anode and reacts with the oxygen or C02 anode product, reducing current efficiency to as low as 10-20%. But a zirconia solid electrolyte between the molten salt and anode blocks this reaction, boosting current efficiency to at least 90%. Separating the anode from the molten salt also opens up anode material selection to liquid metals and SOFC cathode materials such as Lai.xSrxMn03 (LSM) and YCr03. And zirconia's selectivity makes the oxygen by-product very pure."

Jan 1, 2012

By Toshia Suzuki, Keiji Kakudate, Yoshihiro Adachi

"A macro model for the steel usage pattern in Japan is proposed. The steels are classified into four types; converter steel for machinery and for construction and electric furnace (EF) steel for machinery and for construction. The steels are assumed to be discharged from the society in accordance with lifetime distributions of each usage. The amount of EF steel and the accumulation in society are calculated using a population balance model. The comparison with the calculated results and statistics ensures the validity of the model. Since the amount of EF steel for construction will increase and be oversupplied, EF steel will have to be used for machinery. The required and available amounts to supply EF steel for machinery are considered from the point of allowable· copper concentration for machinery use. Copper contaminates steel used for machinery during recycling process and contamination ratio is evaluated with the model. Copper concentration in EF steel is predicted for various scenarios.IntroductionThe amount of CO2 emission from Japanese steel industry is 48.0 million C-ton in 1990 and it occupies 15.1% of the total amount in Japan. In order to reduce the C02 emission and to save the natural resources, it is strongly required to promote the recycling of steel. However, the impurity contaminates steel in recycling process and lowers its quality. The copper concentration in EF steel is analyzed by Toi et al. using a macro model with the assumption that steel is discharged in proportion to the accumulation amount [1]. However the discharged amount of products is dependent on their age for service and usage pattern and not on the accumulation amount. In addition, the degree of copper contamination is different depending on the usage of steel. Therefore a precise model that contains the age for service within the society as a parameter and distinguishes the usage· of steel is necessary in order to clarify the problems in the recycling of steel."

Jan 1, 2000

By J. W. Dini

Introduction The mission of the Materials Fabrication Division (MFD) is to provide fabrication services and technology in support of all programs at Lawrence Livermore National Laboratory (LLNL). MFD involvement is called for when fabrication activity requires levels of expertise, technology, equipment, process development, hazardous processes, security, or scheduling that is typically not commercially available. Customers are encouraged to utilize private industry for fabrication activity requiring routine processing or for production applications. MFD is .a large diversified service organization including approximately 400 full time employees. The group provides a wide variety of processes including all common machining and fabrications operations, laser and water jet cutting, electrical discharge machining, lapping, electron beam and laser welding, vacuum brazing, heat treating, forming, electroplating and metal finishing, optical polishing and grinding, vacuum coating, vacuum engineering and a variety of plastics operations. These operations occupy more than 1,250,000 square feet of floor space. For more detail on the many fabrication related services available from MFD, see Reference 1.

Jan 1, 1992

By KNona Liddell

Many metal recovery processes Involve heterogeneous reactions In porous media accompanied by fluid flow and mass transfer. Modeling such systems Is difficult because of the number of rate processes Involved and is complicated even further by effects due to the structure of the porous medium. Data on even bulk properties of the medium are often severely limited or unavailable. For many such systems, a cell model may provide, an attractive alternative to models based on transport ,mechanisms in a differential volume. A cell model requires less input data and is computationally efficient. Identical residence time distributions can be obtained with models of both types, and both allow conversion and concentration profiles and histories to be calculated. The formulation and properties of cell models for metals recovery are described in detail.

Jan 1, 1996

By Norbert L. Piret

From the copper smelter operation a various outputs are to exert negative impacts on the environment. Particularly, emissions like SO2 and dusts, solid wastes like contaminated gypsum and arsenic sludge, effluents and heated cooling water are generated. Most countries have sitipulated an environmental legislation to provide the framework for an efficient environmental management. As part of the planning activities for x major greenfield copper smelter, the Following elaborations are required and were drawn up. -The Environmental Impact Assessment which is the first step of environmental management and mandatory for every new project. - The Environmental Monitoring Plan, which describes the monitoring procedures for the main impacts identified and assessed. -The Environmental Management Plan, which deals with the minimization of environmental impacts, and the methods of its implementation.

Jan 1, 1996

The reported values of the standard reduction potentials of the Au(NH3)2+/Au(0) and Au(S2O3)23-/Au(0) couples are reviewed to emphasise the experimental difficulties associated with the measurement of reliable values for these quantities. The standard reduction potential for Ag(I)/Ag(0) in ammonia and thiosulphate solutions measured at ionic strength 0.1 and 25oCis used to predict the following relevant stability constants () for gold complexes based on the linear free energy correlations: Au(NH3)2+2 = 1013, Au(S2O3)23-2 = 1024 and Au(NH3)43+4 = 1033. The equilibrium constant ( 10-11) for the reaction Au(S2O3)23- + 2NH3 = Au(NH3)2+ + 2S2O32- based on these stability constants is in reasonable agreement with the measured value (10-9) based on potentiometric and spectroscopic data when excess ammonia was added to a solution of Na3Au(S2O3)2. This also indicates that the stability constant of Au(NH3)2+ is 9 to11 orders of magnitude less than that of Au(S2O3)23-. Relevant species distribution and Eh-pH diagrams based on the revised data are presented.

Jan 1, 2003

By Armin D. Ebner

A hetero-f1occulation model is developed to calculate the net force exerted on a paramagnetic nanoparticle that is moving in the proximity of a magnetite particle that is fixed or supported within an open flow and magnetically energized packed bed. Important variables investigated include the size and surface charge of the particles, the magnetic field, the ,flow velocity, the electrolyte concentration and the magnetic susceptibility of ,the nanoparticle. The ?influence: of other naturally occurring forces, such as hydrodynamic and DLVO(Le., van der Waals and electrostatic) forces on the magnetic attractive forces between the magnetite particle and the nanoparticle are also examined. This model reveals the feasibility of using magnetite particles instead, of stainless steel as the energizable element for high gradient magnetic separation.

Jan 1, 1999

By N. J. Tannyan

Laboratory bath smelting tests were conducted to determine the feasibility of smelting nickel- copper concentrate directly to a low iron matte in one step. Concentrate, air/oxygen and a silica flux were fed to a matte-slag bath kept in MgO crucibles at I 300°C. Various oxygen enrichments and smelting rates were used to maintain 0.5 to 2 wt% iron in the product matte. The slag losses are comparable to those obtained under similar industrial conditions. Due to the highly oxidizing conditions required to produce mattes with low iron contents, it is not recommended to target iron contents below about 2% in the matte. The specific bath smelting rates were equal to or higher than those in various industrial bath smelting processes.

Jan 1, 2003

By Pekka Taskinen, Hannu Johto

"Copper sulfide concentrates often contain impurities such as lead and iron. The phase stabilities of the sulfide impurity systems in metallurgical process conditions are in many cases unsatisfactorily known. Thermodynamic information of a system gives better understanding of its behavior of metal making processes, but also has effects on the economic and environmental factors of the production process. In this study, isothermal equilibrium and quenching experiments of the stable phases of the system Cu2S-FeS-PbS at 700 and 900 °C were carried out and based on the experimental results, Gibbs triangle of equilibrium phases of the system was outlined.IntroductionThe knowledge of stabilities of phases and the thermodynamic properties of many sulfide systems in the temperature range of 500-1200 °C are quite limited. Especially, the knowledge of liquidus surfaces of multicomponent sulfide systems is essential for making many metallurgical processes more environmental friendly and allowing the utilization of complex concentrates. In this work, the aim was to investigate the phase stabilities of the quasiternary system CU2SFeS- PbS using evacuated silica ampoules. Of greatest interest were the properties of the liquidus surface in the system, in order to be able to predict better the formation of a liquid phase in metallurgical processes."

Jan 1, 2012

By J. M. Casas

This work presents the development of an ionic equilibrium model and its use to simulate the distribution and concentration of chemical species (speciation) in sulfuric acid - cupric sulfate solutions in the 0-2 pH range, 0.1-10 gpl copper concentration range and 15-45°C temperature range. The model consists of a set of equations which represent the equilibrium relationships for the ionic reactions and the mass balances for the components present in the system. The effect of ionic strength was taken into account by correcting the equilibrium constant in concentrated solutions. Several species can be formed at different pH and temperature values, the principal being: HSO-4, SO42-, CuSO4(aq), Cu2+, and H+ in order of increasing solution acidity. Simulations show that concentrations are highly dependent on pH. The sulfuric acid speciates mainly as bisulfate ion (HS0-4) and hydrogen ion (H+) at pH values lower than 1. The model presented in this work can be applied to predict and analyze the solution composition in electrolytic copper processes such as electrowinning, electrorefining and electrodialysis, as well as the purification of various industrial solutions.

Jan 1, 1999

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 Dieter Offenthaler

Catalysts used in petroleum industry often contain valuable amounts of PGMs. The typical recycling route for those materials is the pyrometallurgical one, but this treatment way offers limited flexibility with respect to small charge weights. A new process, combining a pyrometallurgical pre-treatment step of the ceramic carriers with a hydrometallurgical leaching procedure overcomes this disadvantage. It not only allows the economical treatment of even very small charge weights, but also gives the possibility to maximize the PGM yield by individually adapting the process to the different charge materials. Due to an ingenious process design, where all leaching agents and effluents are recycled in a closed loop and therefore no waste waters leave the process, process operation becomes very economical. However, the temperature-time-regime in the pyrometallurgical pre-treatment step is of major importance for the success of the whole process. Therefore various investigations have been done to identify how the different process variables in the pyrometallurgical pre-treatment influence the subsequent leaching procedure. It turned out, that the adjustment of the correct phase-modification in the ceramic carrier materials during the pyrometallurgical treatment is the key factor of this process step. Although it is a troublesome issue to exactly adjust the correct phase modifications, it is the prerequisite to take advantage of the benefits of this new process concept.

Jan 1, 2006

By B. Q. Li, S. P. Song

"Numerical models are developed to represent complex electromagnetic, free surface deformation and fluid flow phenomena in floating zone refining processes with radio frequency inductive heating. The computational methodology is based on the coupled finite/boundary element method for the electromagnetic field distribution and the Galerkin finite element method for magnetically driven fluid flow and free surface profiles of the molten zone. With the models, the complex transport and free surface phenomena in a floating zone system can be studied as a function of various operating conditions including applied current, frequency, inductor position and shape, surface tension, floating zone diameter and height. Results show that the equilibrium shape is sensitive to the height of the molten zone and that the free surface shapes can have a significant effect on the melt flow in the molten zone. Our extensive simulations also suggest that to ensure accurate results, the same mesh should be used, whenever possible, for both the electromagnetic forces and fluid flow calculations.1. IntroductionThe floating zone processes have been widely used in the materials industry to grow ultra-pure rare earth metal or semiconductor single crystals for sensor or electronic applications that have a tough demand on purity. Developed based on the principle of magnetic melting/levitation, the processes possess a main advantage that the molten zone is supported in air by the electromagnetic forces generated by the coil (see Figure 1), and therefore is free from contamination from a container. Consequently, the final products made from the floating zone processes have higher inherent purity than those by other techniques [1-4].Complex physical phenomena occur in the floating zone processing of materials. These include free surface deformation, magnetically-driven melt flow, which may be turbulent or mildly turbulent [5] depending on the applied conditions, and solidification. Thermal stresses also develop in the single crystals, which are affected by the flow and temperature field and which can have direct implications to qualities of single crystals [6]. An understanding of the fundamentals governing these physical phenomena can be of critical value in elucidating the physics that controls the properties of the metal or semiconductor crystals being produced, thereby providing a rational basis for process improvement and quality control."

Jan 1, 1997