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By B. Mishra, W. A. Averill

"The application of various hydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, ego metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been investigated and suggested for dealing with some of these wastes and scrap material.The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EM] and decontamination and decommissioning [D&D].IntroductionThe high temperature carbothermic or metallothermic smelting reduction methods for metal production are associated with the generation of significant quantity of waste as slags, flue dusts, sludges, residues, effluent salts etc. Certain hydrometallurgical processes also generate lots of aqueous waste due to the inherent nature of the technique. Also, the gas-based reduction processes are not applicable to many stable metal compounds, such as alumina, titania, beryllia, lanthanide and actinide oxides, etc. due to thermodynamic considerations. All these methods cause substantial environmental hazard. There is a need to develop alternative processes which have low waste or ideally a ""zero-waste"" generation.Pyrochemical processes using molten salts provide a unique opportunity for the extraction and refining of many reactive and valuable metals either directly from the beneficiated ore (aluminum, beryllium, neodymium, plutonium, uranium, etc.) or from other process effluent that contain reactive metal compounds. The processes reduce metal compounds electrolytically (A12O 3 and BeCI2) on a carbon anode or by calciothermic reduction (Po, Nd). The by-product, in the latter case, is a calcium oxide saturated halide salt. The waste-treatment to recycle the halide has to be done as a separate step or stored as a contaminated waste. A successful separation technology can provide a new insight to the waste minimization strategy for the nuclear industry."

Jan 1, 1996

By Dean Ilievski

Mathematical modelling of the precipitation process requires that the kinetics of crystal growth, nucleation and agglomeration be known: This paper reviews the current state of knowledge on these precipitation sub-processes (ie. growth, nucleation and agglomeration) and describes a number of experimental techniques for estimating their kinetics. The experimental methods used to generate the precipitation data and the data analysis techniques used to extract the kinetics information from the data are discussed separately. There is no universal "best" technique for determining the kinetics. However, studies on multi-crystal systems are more reliable for modelling purposes than are single crystal studies. The selection of a technique will depend on which sub-processes are present. A problem with all kinetics studies is that there is generally a large uncertainty in the estimated kinetic parameters. This stems from the scatter in the experimental data being further propagated by the mathematical techniques used to extract the kinetic parameters.

Jan 1, 1996

By Ricardo Melamed

Metallic mercury has been extensively used for gold recovery. Although the solubility and mobility of metallic mercury is low, this metal can undergo many transformations, leading to mercury contamination in humans. The complexity of Hg chemistry in the environment reflects its different possible oxidation states and species, with different physical-chemical properties. The interaction of Hg in the terrestrial system, as well as in the aquatic environment, is important to understand the mercury cycle. This paper reports data on the adsorption of Hg onto an Oxisol soil. Results show that the interaction of Hg(II) at the soil-solution interface depends strongly on ligand concentration in solution, which can affect Hg mobility. The presence of the chloride anion in solution increases the mobility of Hg(II) through the soil, due to a relative lower affmity of mercury chloride at the oxide surface. In the absence of chloride, Hg(II) form strong complexes with the surface, and its adsorption behaviour is similar to the adsorption of other hydrolizable cations.

Jan 1, 1996

By R. Gampala

The consolidation of mom matrix composite monotapes occurs by the plastic (time independant) and creep deformation of monotape asperities. Past models of the process used seperate micromechanical analyses of the contact deformation by (rate independent) plasticity and power law creep (i.e steady state creep). These models are now used to simulate consolidation and to optimize/control consolidation process cycles so that the composite's microstructure is "steered" to, a user defined goal state. However, the models do not incorporate the sometimes dominant transient creep process and the instantaneous response of the plasticity mechanism causes finite discontinuities in the microstructure state vector field and therefore eliminates the possibility of using the powerful array of trajectory optimization schemes that all require continuous vector field for optimization and control. To overcome this problem, a inified creep/plasticity constitutive model that results in a continuous state vector field is used to rederive the contact deformation response during monotape consolidation. The contact blunting of a laterally constrained hemispherical asperity is first analyzed and its response represented by two coefficients; one relating the contact area to the blunting strain (C), the second, the mean contact pressure to the blunting rate (F).The C and F coefficients for this unified blunting problem are then obtained by finite element analysis, and detailed results presented for two composite matri-ces of topical interest (Ti-24A1-11Nb and Ti-6Al-4V).

Jan 1, 1996

By Patricio Barrios

The Rio Tinto Metal (RTMetal) copper smelter, located 5 Km from Huelva, Spain, began operations in 1970. Since then a series of expansions and modifications have allowed a progressive increase in copper production. Environmental considerations having become increasingly important, environmental protection has come to represent an important aspect of the investments in production. As a result, modifications have been carried out in the two existing acid plants: -Modification of the RTM I gas cleaning section to closed circuit. -Substitution of cascade filters and acid lines. -Modification of the RTM I plant to double absorption. The Expansion and Environmental Improvement Project, completed end 1995, will allow 270,000 t Cu and 800,000 t H2SO4 to be produced yearly, at the same time achieving a decrease in specific and overall emissions. RTMetal's goal is to be an efficient smelter, with the avowed intention of respecting the environment and adopting the best available technologies.

Jan 1, 1996

By Timothy W. Ellis

This paper presents the basic theory of operation, physical chemistry and phase equilibria which allow the development of liquid-liquid extraction circuits based on metallic solvents. The incorporation of reduction and reduction/diffusion processes into the process 'scheme is discussed and a detailed description of ,several liquid-liquid extraction schemes are developed. A synopsis of experimental results obtained using this: method to separate rare earth and other metal based materials will be given.

Jan 1, 1996

By Regina Krachler, Herbert Ipser

"The principles of the derivation of statistical-thermodynamic models to interpret the compositional variation of thermodynamic properties in non-stoichiometric intermetallic compounds are discussed. Two types of models are distinguished: the Bragg-Williams type, where the total energy of the crystal is taken as the sum of the interaction energies of all nearest-neighbor pairs of atoms, and the Wagner-Schottky type, where the internal energy, the volume, and the vibrational entropy of the crystal are assumed to be linear functions of the numbers of atoms or vacancies on the different sublattices.A Wagner-Schottky type model is used for the description of two examples with different crystal structures:For B'-FeAl (with B2-structure) defect concentrations and their variation with composition are derived from the results of measurements of the aluminum vapor pressure; the resulting values are compared with results of other independent experimental methods.For Rh3~ (with an NiAs-derivative structure) the defect mechanism responsible for nonstoichiometry is worked out by application of a theoretical model to the results of tellurium vapor pressure measurements. In addition it is shown that the shape of the activity curve indicates a certain sequence of superstructures.In principle, there are no limitations to the application of statistical thermodynamics to experimental thermodynamic data as long as these are available with sufficient accuracy, and as long as it is ensured that the distribution of the point defects is truly random, i.e. that there are no aggregates of defects."

Jan 1, 1996

By Batric Pesic

A hydrometallurgical process for recovery of Zn and Mn from Bunker Hill Water Treatment Plant sludge was developed. The process is unique because it treats an unusual combination of metals, Zn and Mn. Another non-standard feature of the process is that leaching takes place with ~S04 in the presence of a reductant (SO2). Zn and Mn are recovered simultaneously by electrowinning, Zn on a cathode and Mn on an anode, as MnO2 The major purpose of the process is to detoxify the sludge by removing toxic heavy metals. The recovered metal values could be marketed to offset the overall costs of water and sludge processing. This work is presented in two separate parts, 1. Leaching and Solution Purification, and II. Electrowinning. This paper covers only the first part of the hydrometallurgical process: Leaching and Solution Purification. Initially, the paper briefly discusses the history of the pollution problem at the Bunker Hill Superfund Site, the origin of heavy metals in the mine waters, and the development and use of the water treatment plant. The leaching of sludge was examined as a function of the following parameters: constant vs. initial pH, initial vs. delayed addition of SO2, temperature, and pulp density. It was found that leaching with H2SO4 at pH 2.0 for 15 minutes (at 60°C), followed by S02 addition for another 15 minutes, could completely dissolve Zn and Mn. Solution purifIcation was done in three stages. In the first stage iron was removed by adjustment of pH (to pH 5.0) and oxidation offerrous to ferric iron (with H2O2). In the second stage, Cu and Cd were removed by Zn dust cementation. Finally, Co and Ni were precipitated with the organic reagents 1-2 nitroso-naphthol and nitroso, respectively. Electrowinning of Zn and Mn is discussed separately in Part II of this paper.

Jan 1, 1996

By Amir Rehmat

The Institute of Gas Technology has developed a fluidized-bed process for recovering direct reduced iron from blast furnace flue dust a material currently considered to be a waste from the iron and steel industry. In the process, a portion of the carbon in the flue dust is combusted to supply energy for the endothermic reaction between carbon and steam. The reaction produces reducing gases comprised of carbon monoxide and hydrogen both of which react with iron oxides to produce reduced iron. Up to 95 percent of the iron oxides contained in the waste stream can be reduced to elemental iron. The vitiated reducing gases emanating from the process can be used as fuel in the plant. The yield of iron depends upon the quantity of iron oxide present in the flue dust and generally ranges from 20 to 30 percent of the waste stream. The investment cost estimated for a single processing train dedicated to one steel plant can be recovered in less than one year.

Jan 1, 1996

By F. J. J. van Loo, J. K. Kivilahti, M. Paulasto

"Activation mechanism and interfacial reactions in brazing of ShN4 with different AgCuTi filler alloys has been investigated thermodynamically and experimentally. During brazing the AgCuTi filler alloy is divided into two liquids Ll and L2, where the (Cu,Ti)-rich liquid L2 gathers at the ShN4 interface and reacts with it. The concentration of Ti in L2 is high, but due to the strong attractive interaction between Cu and Ti, the activity of Ti in L2 is considerably low. In reaction between ShN4 and Cu-containing brazes a Ti-Cu-Si-N compound is typically formed at the interface. In absence of Cu, in joints brazed with AgTi based filler alloys, extremely Ti-rich solution reacts with ShN4 and as reaction products TiN and TisSh[N] are formed. IntroductionAdvanced ceramics like silicon nitride are increasingly used as structural components in demanding applications as well as in electronics industry. Complex, multicomponent structures for engineering applications generally require interconnections and therefore joinability of ceramics largely determines the possibilities of metal-ceramic structures to enable demanding functions. Brazing with active filler metals, most of which are based on the Ag-Cu-Ti system, has been commonly employed for joining of ShN4 to other ceramics and metals. The interfacial microstructures formed when ShN4 is brazed with Ag-Cu-Ti braze alloys have been discussed in several recent studies [1-7]. However, some inconsistencies exist in the reported results. The formation of layers of TiN and titanium silicides, possibly TisSh, next to the ShN4 has been reported in several studies [1-5], while in another investigation, a layer of an orthorhombic TiSi- Cu-N phase was found beyond the TiN layer [6]. In few investigations the thermodynamics of the ShN4-Ti system has been considered, but no detailed thermodynamic analysis of the chemical interactions between the braze and ShN4 has been provided. In order to resolve which chemical reactions are possible under various joining conditions and thereby to be able to control the brazing of ShN4 the reactions in brazing has to be studied using both microstructural and thermodynamic analysis."

Jan 1, 1996

By Fathi Habashi

Solid gas reactions of metallurgical importance can be classified into three groups: Physical processes, e.g., drying and sublimation Chemical processes which may be an addition or a thermal decomposition reaction Electrochemical processes which may be addition, oxidation-reduction, or displacement reactions. Examples are given and the role of the boundary layer is emphasized.

Jan 1, 1996

By P. Tapp, T. Evans, N. A. Molloy, J. Lucas

"Consideration of the protoype tuyere geometry for injection of inert gas through the bottom in a basic oxygen steel furnace and a requirement to specify an optimal flow for bottom wear and metal penetration led to experimental investigations[l,2] to apply the results of previous workers to this specific case, Flow velocity profile development within the tuyere was proposed as significant and the experimental scheme was designed to test this. It is proposed that the design criterion for the conditions of optimal flow of the prototype geometry be based on the non-dimensional mass velocity.INTRODUCTIONSharma[3] tested small diameter tuyeres in a laboratory hot model using molten iron to define a flow criterion for prevention of penetration of the bath liquid into the tuyere. Using argon, nitrogen and helium through a range of tuyeres (1 to 3 mm ill ) he proposed the jet Froude number C Fr' ) with the critical value being 2400 - 2500 or higher. Sonic or supersonic velocity was not a sufficient criterion. The tuyere design was a parallel tubular duct of moderate aspect ratio CAR) i.e. the ratio of length to diameter ranging from about 22 to 36 in the experimental furnace.Farmer et al[4] stated their their aim ""to develop a unifying explanation and procedure for the proper design of tuyeres"" but disagreed with Sharma's jet Froude number criterion. Recalculating Sharma's data they proposed instead a fully expanded Mach number of 1.75 with an initial expansion angle of ten degrees as the lower bounds of flow to meet the design requirement. They experimented with tuyeres in a water model using tubular, annular and convergent-divergent nozzles. The aspect ratio of the parallel duct tuyeres was from 533 to 762 using diameters of 1.4, 1.7 and 2.0 mm C the diameters being of tubes to be used full scale). Subsequently these results were applied to a prototype tuyere using a diameter of 1.7 mm with beneficial results in practice. This tuyere had an aspect ratio of 1067."

Jan 1, 1996

By D. H. Rubisov

The neural networks modelling approach is one of the most elegant black-box type methods to model industrial processes. In this paper, this approach is applied to model the performance of the CEZ zinc electrowinning plant. The model that was built was found to exhibit an excellent predictive ability for voltage and current density. The model was also used to investigate the sensitivity of the process to various key variables such as temperature, current density, zinc and sulphuric acid concentration, etc. Optimal regimes for zinc production were identified from the power consumption standpoint.

Jan 1, 1996

By J. M. Floyd

"Top submerged lance furnace developments started in CSIRO in the early 1970s and was given the name Sirosmelt. In the early work the technology was developed for tin smelting and processing tin slags but once a small pilot plant was established other slag processing applications were soon recognised and evaluated for various copper, nickel, zinc and cobalt-containing slags. The process was tried for copper smelting and converting, which was proven in the small pilot plant in 1978. In the same year the first commercial application of the technology was established for the recovery of tin from slags at Associated Tin Smelters, Sydney. Work on lead smelting was initiated by the CSIRO team in the late 1970s and laboratory work led to pilot plant trials by Mount Isa Mines.In the second decade of the technology the focus of development became commercial acceptance of the technology through marketing, development and application by Ausmelt and Mount Isa Mines; the former commercialising and developing the technology for a wide range of applications, while the latter concentrated on its own commercial needs of copper and lead smelting. This decade saw a number of commercial plants built in Australia, with considerable interest becoming evident from other parts of the world. Towards the end of this decade Mount Isa also entered into the business of marketing of the technology through rights dating to the joint work with CSIRO in the late 1970s.So far, after five years, the third decade of the technology has been characterised by diversification of applications of the technology to areas outside the non-ferrous and precious metals production industry. The waste processing and recycle industry and the iron and steel industry have recognised that the top submerged lancing system is a new type of reactor with many significant features which provide new opportunities for processing a range of materials under good environmental controls in a cost effective manner.I hope this audience will excuse my boldness in talking about the third decade of the technology when we are only half way through! I am aiming in this paper to not only talk about the past, but to try illustrate the future directions which I envision."

Jan 1, 1996

By V. I. Lakshmanan

Wastes when produced can be reused or recycled prior to disposal. Industries that cause environmental concerns during manufacturing include primary materials and primary metals. Pollution prevention mechanisms to achieve waste reduction require new separation, reclamation, control and process simulation technologies. Substituting recyclables for virgin resources will reduce energy use, water pollution, air pollution, water use and mining wastes. Shrinking landfill space will spur new technologies for waste treatment and recycling. These situations hence offer opportunities for innovative flowsheets with appropriate separation technologies. Development of innovative flowsheets to treat recyclables offer unique opportunities for process/product development, obtain green products and hence market advantage. The paper will illustrate with selected innovative flowsheets to treat recyclables.

Jan 1, 1996

By M. Nilmani, H. Pham

"A mathematical model was developed for the dissolution of particles in gas-stirred liquid baths, linking the hydrodynamic flow field of the bath, the average particle trajectory and liquid-side mass transfer controlled dissolution kinetics. The model was validated by comparison with experimental data for the dissolution rates of urea particles in gas-stirred aqueous CaCl2 solutions measured during this study. The dissolution rates of urea. particles were measured using an image analysis system.The effects of operating conditions on the dissolution rates of urea particles were investigated. It was found that the key operating parameters influencing the utilisation efficiency of particles were the gas flowrate, particle diameter and lance submergence. An optimisation of the operating conditions for the model urea-aqueous CaCl2 system indicated that the utilisation efficiency increased with decreasing gas flowrate and decreasing particle size for a given lance submergence.IntroductionThe utilisation solid reagents in molten baths varies from one process to another, depending upon the rates and mechanisms of the reactions between the particles and melts, as well as the trajectory and residence time of the particles in the melts. Previous studies have not attempted to predict the utilisation efficiency of injected solids by coupling the motion of the particle with its dissolution rate. Instead, the particles have usually been assumed to remain suspended in the bath until completely dissolved, and the mass transfer coefficients were based on the average specific mechanical energy dissipation rates in the bath. Investigations of this nature relevant to the present study have been undertaken by Apelian et al. [1], Brucato et al. [2] and Langberg and Nilmani[3]. The objective of the present study was to develop a mathematical model, incorporating both the reaction kinetics between the particles and liquid and the particle motion simultaneously, to predict the dissolution rates and times of the particles. The mathematical model was validated by comparison with experimental dissolution rates of a cold model analogue system measured using an image analysis technique, and then applied to optimise the operating conditions in the model system."

Jan 1, 1996

By Gregory A. Knapp

Treatment of industrial wastewaters generally advances with specific chemical concentration and mass-flow targets, established by National Pollutant Discharge Elimination System (NPDES) permits. Treated discharges must also address toxicity to test and receiving water organisms. Various parameters might need consideration during treatment design and planning, such as the known toxicants, hardness, alkalinity, solids, nutrients, metals in both the dissolved and particulate state, and even flow. Since toxicity is used as a "catch all" regulatory monitoring tool, design of treatment systems should focus on the various factors contributing to toxicity.

Jan 1, 1996

By Peter Bates

"HIsmelt has faced and overcome many challenges in the understanding and development of injection technologies that satisfy process and engineering requirements for further scale up to a commercial plant.An overview of the design basis of bottom and top injection systems with plant results are described in this paper.IntroductionAn appropriate way to introduce this paper is to initially reflect on the genesis of the HIsmelt Process.It is appropriate that Professor Womer is the one we are honouring as it can be claimed that by the involvement of CRA in the WORCRA process that the concepts for irijection systems in iron and steel pyrometallurgical processes achieved significant attention by the company. The development of water cooled injection lances and their application injecting solids and gases with success was certainly a pre-cursor to the development of other injection systems commonly used today in arc furnaces and for top injection at HIsmelt.HistOrically it was the work of Savard and Lee in Canada with shrouded tuyeres and the subsequent commercialisation of this technology at the Maxhiitte Steelworks spawning the suite of bottom oxygen blown process as known as QBOP; OBM and the subsequent combined blowing process such as KOBM that first commercially succeeded in injecting solids under a molten metal bath. The next progressive step from the injection of calcined lime in the technology development was the injection of coal for coal gasification as developed by Klöckner technologies being called KG, KSG and KMS and also the injection of coal for increased scrap melting.A paradigm shift in thought process to leap from steelmaking and coal gasification to direct smelting by injecting coal and iron ore into a molten metal bath in the correct stoichiometric ratio to maintain the bath at a constant temperature and carbon level was the true genesis .of HIsmelt.A good overview of the state of the art of tuyere type injection technology is given in Ref. 1."

Jan 1, 1996

By Milton Blander

A review of concepts and theories for predicting thermodynamic solution properties of multi- component high temperature liquid solutions is reviewed. During the last 50 years the ability to predict :such properties for molten salts, silicates and metals based on the generally known properties of the lower order (often binary) systems has been developed and shown to provide predictions which are quite useful in science and technology. There are many gaps in our understanding of these high temperature solutions, especially for metals, and considerably more work is needed.

Jan 1, 1996

By Ljiljana Solujic

The need for the removal of mercury from the precious metals extraction circuits may be influenced by process, environmental, as well as by occupational hazard reasons. In these circuits mercury is mainly present as cyanide complexes. The effectiveness of any stabilization method will be influenced by the high thermodynamic stability mercury-cyano species exhibit in an aqueous solution. In this study, we have investigated the utility of the trisodium salt of trimmercapto-s-triazine (TMT) for precipitation of mercury from the corresponding cyano-complexes. The influence of pH molar ratio of TMT to Hg, coagulant and flocculant additions, excess of free cyanide, as well as the presence of other metal-cyano species on the effectiveness of mercury precipitation were investigated in detail. Also, a "teal world" precious metals mill effluent initially containing ~7 ug/mL (ppm) of Hg was treated and A was found that greater than 99.8% of the mercury was removed from the solution as am insoluble Hg/TMT complex.

Jan 1, 1996