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By T. K. Mukcherjee

The importance of the processing of secondary resources such as solid industrial wastes and liquid effluents as well as byroducts for the recovery of the associated metal values hardly needs any elaboration. Such processing contributes in no small measure.towards the augmentation of the availability and the supply position of resources. As an added benefit, it leads to a reduction in environmental pollution caused by the undesirable waste materials. As some typical examples of secondary resources in the Indian scenario, mention' can be made of spent catalysts, metal/alloy scrap, ash, consumed batteries, flue dust, slag, sludge and slime, pickling solutions, spent acids; plating rinse solutions, spent etchants, waste water from synthetic fibre manufacture and from tanneries etc. These wastes constitute a source of a variety of non ferrous metals. In the processing of secondary resources like these, the techniques of hydrometallurgy such as solvent extraction play a pivotal role. This paper outlines the efforts made to use solvent extraction to recover(1) base metals. such as copper, zinc, nickel and cobalt from a number of secondary resources like cake, and sludge(2) refractory metals like molybdenum and vanadium from sulphidic byproducts and spent catalyst and (3:) nuclear metal like uranium from phosphoric acid. In the case of base metals, process flowsheet involving the use of acidic extractants such as DEHPA and PC88A have been optimised. The problem of iron removal from the leach liquor, "which influences the metal recovery process significantly, has drawn a special emphasis. hi the case of refractory metals, basic extractants .like Alamine 336 has been pressed into service to produce kilogramme. quantities of pure salts of molybdenum and vanadium, Finally, the paper gives a brief account of plant experience in recovering uranium from phosphoric acid, using 'a solvent system comosed of DEHPA and TOPO.

Jan 1, 1996

By Luiz A. Teixeira

This paper reports the results of kinetic studies involving the precipitation of arsenic from aqueous solutions as FeAs041 Fe(OH)3' using FeS04 as source of Fe ions, and Air or H202 as oxidizing agents. Both systems lead to an efficient removal of arsenic. The differences in oxidants performances are in the precipitation reaction rate -much faster using hydrogen peroxide. Mechanisms of reactions were suggested based on the following main steps:

Jan 1, 1996

By Liping Li

A comprehensive three-dimensional two-phase mathematical model was developed to represent a channel type reactor with intense bottom gas agitation. Tracer dispersion and particle tracing methods were used to conduct the analysis based on the solution of the Navier-Stokes equations. Different operational parameters, such is gas volume flow rate. bubbler separation aspect ratios and liquid Input flow rates, were investigated for the purpose of reactor optimization. The numerical calculations were compared with experimental results obtained at the University of Missouri and a good general agreement was observed. Relatively low longitudinal mixing was observed characterizing the system as a "plug-flow" type reactor, in contrast to the intense vertical mixing, under the conditions investigated. Some general mixing characteristics are also discussed In connection to the behavior of other metallurgical reactors.

Jan 1, 1996

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 M. E. Huckman

In this paper, we review the equations needed to construct an ion exchange column model. These models contain three major components: 1) a differential material balance around the colunm, 2) a differential material balance around an ion exchange particle, and 3) a constitutive equation for diffusive flux We then examine the ability of a fairly simple mathematical model to predict ion exchange column experimental data. This model contains the traditional absorption theory equations and is used to predict the behavior of a column filled with a hydrous crystalline silico-titanate and which is removing trace amounts of Cs+ from a high pH, complex electrolyte solution. Finally, we propose replacing Fick's law with the Nernst-Planck equation as the constitutive equation for diffusive flux We use a Nernst-Planck type model to predict batch experimental data, then evaluate it by comparing it's ability to predict experimental data to that of a more traditional Fick's law type model? The data from this comparison suggests that the Nemst-Planck type model yields better results.

Jan 1, 1996

By John R. FitzPatrick

The separation and purification of uranium from either nitric acid or hydrochloric acid media tan be accomplished by using either solvent extraction or ion-exchange. Over the past two years at Los Alamos, emerging programs are focused on recapturing the expertise required to do limited, small-quantity processing of enriched uranium. During this period of time, we have been investigating ion-exchange as a method for extraction/purification of uranium from acidic media. In addition, waste stream polishing is associated with this effort in order to achieve more complete removal of the uranium prior to recycle of the acid. Extraction chromatography has been demonstrated' to further polish the uranium from both nitric and hydrochloric acid media thus allowing for a more complete recovery of the actinide material and creation of less waste during the processing steps. We will discuss contact experiments for evaluation of eleven different resins for uranium removal from nitric acid, the evaluation (again by contact experiments) of uranium elution from the ion-exchange media by various chemicals, and small-scale experiments for the removal of 235U from nitric acid. Larger-scale (100-gram) flow experiments using depleted uranium, were done after the small-scale evaluation Of the selected resin. A discussion is also included concerning the shortcomings of the contact experiments and how the flow experiments were modified in order to overcome these problems. We will also discuss the application of ion-exchange for some specific process needs at Los Alamos Contact experiments were used to evaluate some commercially available solvent-impregnated resins in addition to evaluation of several resins of this type synthesized in our laboratory. These experiments' involved both nitric and hydrochloric acid media. The data from these experiments will be used to determine the column size and' amount of resin required to polish the waste stream produced by the ion-exchange process described above. Small-scale flow experiments will be described and data given on the mass balances achieved using this two step process. Future work for evaluation of new ion-exchange and solvent-impregnated resins as well as the search for new eluants will be discussed. Other future experiments for both processes, including large-scale experiments, will be discussed in detail.

Jan 1, 1996

By Donald R. Sadoway

Molten salt electrolysis is a proven technology for the extraction of metals -- all the world's primary aluminum is produced in this manner. The unique properties of molten salts, also make them excellent media in which to treat a variety of forms of waste. Of special .note in this regard is electrolysis in molten oxides, a .concept put forward by. the author, initially as a ."clean technology" for producing primary metal. However, in the context of waste treatment, electroly-sis in molten oxides is a process offering the prospect of changing the. valence of dissolved heavy metals while making pure oxygen gas as the main by-product .Laboratory tests conducted at a temperature of 1550°C on chromate sludge dissolved in an melt composed of Al2O3 and MgO have confirmed electrochemical production of oxygen on a carbon-free anode.

Jan 1, 1996

By I-Min Lu

An electric field was applied to a metal-bearing kaolinite specimen to investigate the efficiency of electro-osmosis in removing heavy metals from contaminated soils. The electric field induces a flow of water through the porous medium, called electro-osmosis, which is superimposed on the hydraulic flow. Because the electro-osmotic flow is relatively stronger in smaller pores, it can enhance the displacement of contaminated solution by fluid convection. Furthermore local changes in pH caused by the electrode reactions can affect adsorption equilibria and the distribution of solutes between the solution and the solid surfaces. The electro-osmosis experiments were conducted by applying either a constant current or a constant voltage across 8-cm inside diameter, 25 to 30-cm long specimens of kaolinite clay with graphite electrodes. Samples of the pore fluid and of the clay were analyzed to determine metal content, pH, and conductivity as functions of time and position. Results show that removal of heavy metals from soil can be accomplished effectively by electrokinetic treatment of sufficient duration. Approximately 95% of the lead was removed after 189 days.

Jan 1, 1996

By F. D. S. Marquis

An investigation of the mechanisms of formation of two types of porosity-primary and secondary-their characterization, evolution during processing, and effects on the mechanical behavior (fracture, fatigue, and failure) of 7X50 and 2X24 alloys has been conducted. The mechanisms of formation of three forms of primary or cast porosity were investigated, and each form was characterized: (a) macroscopic shrinkage porosity-MSP); (b) microscopic interdendritic porosity (MIP); and (c) hydrogen gas porosity (HGP) or primary hydrogen porosity (PHP). The mechanisms of formation of four forms of secondary or thermal/thermomechanical porosity were investigated, and each form of porosity was characterized: (a) high temperature oxidation (HTO). internal hydrogen precipitation (IHP), or secondary hydrogen precipitation (SHP); (b) preheating blistering porosity (PBP); (c) eutectic melting porosity (EMP);and, (d) dissolution micro void formation (DMF). The evolution and interactions of the primary and secondary types of porosity (w.ith special emphasis on PHP and SHP) during industrial and laboratory processing and their effects on the fracture and failure behavior of both types of alloys (with special focus on fatigue crack initiation and propagation) were investigated.

Jan 1, 1996

By U .. C. Rojas, J .. C. Gomez

"Fire Refined Copper (EI Teniente Three Stars) has been produced at Caletones Smelter of Codelco Chile since almost the beginning of its operations.Due to changing features of the copper market, together with the targets on technical efficiency and productivity, it has become more and more relevant for copper industry to reach both, good final product quality and a proper environmental control.At present, copper refining process at Caletones Smelter takes place in two cylindrical tilting furnaces, where solid fluxes are injected through horizontal tuyeres into the molten bath. (Fig. N2 1)Solid reagents are pneumatically conveyed and injected into the liquid copper bath attaining excellent solid - liquid contact, so the impurities removal efficiencies are found to be high. Same injection tuyeres are used to introduce both oxidising agent (normal air) and reducing agent (reformed gas) into the molten bath. Air or nitrogen is used as conveying gas for solid reagents, depending on the process stage.This pap~r gives a fundamental description of the process and industrial results related to the injection of blend of sodium and calcium carbonates to remove arsenic and antimony, silica and granulated reverberatory slag to remove lead and a mixture of calcium carbonate and mineral coal to reduce the selenium content of the fire refined copper."

Jan 1, 1996

By José R. de Tenorio

The aim of the present work was to investigate the reduction process of MnO~FeO-Si02 slags by carbon-saturated liquid iron. The effect of the initial Mn content in the bath was explored. The initial Mn content was in the range of 0 up to 40 wt. %. The MnO content in the slag was kept constant at 40 wt. %. Tests were performed in laboratory apparatus. Samples of slags and bath were taken. In the first 5 minutes, it was observed a very strong reduction of FeO. This first step promoted a MnO-Si02 enrichment of the slag and a formation of CO bubbles, which increases the slag level. The increase ofMn content decreases the MnO reduction rate.

Jan 1, 1996

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

By B. Mishra

The application of various bydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, eg. 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 [EMI' and decontamination and decommissioning [D&D].

Jan 1, 1996

By J. R. Parga

A shortage of landfill space and growing environmental concerns in Mexico are renewing interest in the recyclability of scrap from automobiles. This work describes a pyroumetallurgical process for the recovery of metallic lead from waste lead paste. Argentopyrite concentrate is commingled with lead paste residue and smelted in a fuming process thereby transferring the precious metals into lead bullion. The process consists of smelting lead paste and argentopyrite, sodium carbonate, and metallic iron at smelting temperatures of about 1100 T. The reaction products are slag and molten lead bullion enriched with precious metals. A major feature of this process is the removal of precious metals from the bullion by means of zinc, whereby a silver-zinc intermetallic compound is formed and floats out of the lead. The recoveries of precious metals are about 98%.

Jan 1, 1996

By Nagy El-Kaddah

"One of the emerging technologies for the production of ultra-clean metals is electromagnetic filtration. The theory and the mechanism of electromagnetic separation of inclusions from molten metal are briefly reviewed along with basic electromagnetic separation systems. This paper focuses on inclusion removal in the induced current separators, with specific reference to a new separator developed at the University of Alabama. A simple analytical model is presented for the analysis of particle separation in such a system. The role of the applied magnetic field on inclusion removal will be discussed. It is shown that particle velocity increases exponentially with increasing magnetic field strength. At moderate field strengths, the velocity of 50 to 100 u. inclusions· are an order of magnitude larger than those achieved by buoyancy. The separator developed at the University of Alabama is described together with experimental results of laboratory and large scale experiments on purification of molten aluminum. These results demonstrate the capability of the system for producing super-clean metals.IntroductionThe nature of extraction, refining and processing of metals is such that oxides and other non-metallic particles will always be present. This is due to the highly reactive nature of metals with oxygen and other non-metallic elements. The presence of these type inclusions in metals, even in minute amounts, can seriously flaw the reliability and performance of the final product. They not only reduce the strength and the stiffness of the metal/1/, they are the reason behind many of manufacturing defects such as porosity in castings, surface and internal cracks in continuously cast ingots and rolled products, etc., which act to cause premature failure of manufactured parts. In fact, for critical applications such as turbine blades, there is virtually no tolerance for inclusions above ten microns in size /2/. Therefore, removal of inclusions from the liquid metal is an essential processing step.The demand for cleaner metals has brought major changes in the technology and practice of metal refining and casting. Inclusion removal from the melt is currently achieved by passing the melt through a series of melt treatment systems, including induction stirring furnaces, argon-stirred ladle, and ceramic foam and deep-bed filters /3,4/. These systems are generally capable of removing all inclusion particles above 50 microns in diameter, which meets current cleanliness requirements for most applications. However, they may not be able to meet the projected cleanliness levels for critical applications due to kinetic and operational limitations of these systems in removing smaller particles /5/."

Jan 1, 1996

By R. G. Reddy

The Margules .equation is used for interpreting excess Gibbs energy of several ternary systems. In the present study activity coefficient of 'a dilute solute, 2, in a binary solvent 1-3 was derived. The derived expression is used to interpret logarithmic activity coefficient of oxygen and sulfur in several metallic systems. Self interaction parameter of the solute is derived from the partial function of solute using constant compositional path. An expression for logarithmic activity coefficient and self - interaction parameter of solute is also derived using Maclaurin infinite series. The derived equation is based on Maclaurin infinite series used successfully to deduce thermodynamics of self interaction of oxygen as a interstitial atom in two metallic systems. The predicted thermodynamic parameters values using Maclaurin infinite series and Margules. equations, are in excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.

Jan 1, 1996

By S. Seetharaman, Du Siehen

"In the processing of molten metals, it is extremely important to monitor continuously the concentration levels of various minor elements. In the production of common metals like copper, iron and aluminium electrochemical sensors involving solid as well as liquid electrolytes are being increasingly used to measure the concentrations of minor elements. The present paper deals with the electrochemical principles underlying these measurements and the possible errors involved. One of the major difficulties in the case of the solid electrolytes is to correct for the consequences of the electronic contribution to the conduction of the electrolyte.The application of the electrochemical sensors for molten metals processing involves designing of these probes to withstand the industrial operating conditions. In this respect, significant achievements have been made with respect to the design of oxygen probes for liquid metals in general and liquid copper in particular. Some of the salient design features are discussed in the paper. The application of auxiliary electrodes for impurities in molten metals like phosphorus in copper and silicon in iron are taken up. The development of oxygen sensors for slags is given special attention. Recent developments in the field of sensor technology, as applied to metals processing are highlighted.1. IntroductionThe rapid technological advancement today require precise control of the process parameters and the impurity levels. Most of the molten metals processing in industrialized countries are often steered by suitable computer models, either phenomenological or simulations based on theoretical principles. These models often require that the process parameters are continuously monitored so that the progress is followed and modified suitably as and when required. It is common practice to measure temperatures by incorporating temperature sensors at the various strategic points of the reactor. In the case of monitoring the composition changes in the various phases, the method of sampling followed by routine chemical analysis involves a time lag as well as uncertainties in sampling and analysis. In this respect, electrochemical sensors have the advantage of generating accurate data when properly applied and increasing attention is being paid in the development of electrochemical sensors for various common species in molten metals processing. In the present paper, the developments in this area over the years are outlined and typical process applications are discussed. A greater emphasis will be laid on sensors based on oxygen conducting electrolytes and their application to the production of common metals like iron and copper."

Jan 1, 1996

By James A. Voigt

"The efficient separation of metal species from aqueous streams by precipitation techniques requires a fundamental understanding of the various processes that occur during precipitation. These processes include particle nucleation, particle growth by solute deposition, agglomerate formation, and agglomerate break-up. The application of the population balance approach has been used to develop a kinetic model that accounts for these competing kinetic processes. The usefulness of the model is illustrated through its application to the precipitation of yttrium hydroxynitrate, YHN. The kinetic parameters calculated from the model equations and system specific solution chemistry are used to describe several aspects of the effect of pH on the precipitation of the YHN. Implications with respect to the simultaneous precipitation of more than one cation type are also discussed through use of example systems. The effects of solution chemistry, precipitator design, and solvent choice are considered.IntroductionThe application of precipitation technologies to the separation of metals from solution is widely used. Regardless of its application, be it in such diverse areas as the preparation of metal oxide powders for use in commercial products or as a unit operation in the removal of trace metals during wastewater clean up, the fundamental processes involved are the same. These processes include: nucleation from solution, either homogeneous or heterogeneous; growth from solution with chemical reaction either in solution or at the precipitate/solution interface; growth by particle agglomeration; and particle break-up by collisional or shear forces. The effectiveness of the operation and the properties of the precipitate formed, or ""quality"" of the product, are determined by the competing kinetics of the different processes. The kinetics of the processes, in tum, are determined by system-specific solution chemistries and the conditions used to carry out the precipitation operation. For example, generally, when system conditions are such that the supersaturation driving force for precipitation is very high, growth species normally do not have the time to organize themselves with a high degree of crystallographic order and the precipitate is amorphous. In this case nucleation rates are invariably extremely high and the primary mechanism for growth is the agglomeration of nuclei. Conversely, when the supersaturation levels for the same system are reduced, the kinetics of the nucleation and growth processes also are greatly reduced, and a crystalline precipitate can be formed, since the growth species have time to order on particle surfaces."

Jan 1, 1996

By Thomas W. Chapman, Shi-Chern Yen, I-Min Lu

"An electric field was applied to a metal-bearing kaolinite specimen to investigate the efficiency of electro-osmosis in removing heavy metals from contaminated soils. The electric field induces a flow of water through the porous medium, called electro-osmosis, which is superimposed on the hydraulic flow. Because the electro-osmotic flow is relatively stronger in smaller pores, it can enhance the displacement of contaminated solution by fluid convection. Furthermore, local changes in pH caused by the electrode reactions can affect adsorption equilibria and the distribution of solutes between the solution and the solid surfaces.The electro-osmosis experiments were conducted by applying either a constant current or a constant voltage across 8-cm inside diameter, 25 to 30-cm long specimens of kaolinite clay with graphite electrodes. Samples of the pore fluid and of the clay were analyzed to determine metal content, pH, and conductivity as functions of time and position. Results show that removal of heavy metals from soil can be accomplished effectively by electrokinetic treatment of sufficient duration. Approximately 95% of the lead was removed after 189 days.IntroductionRemediation of soils contaminated with toxic chemicals is a difficult and expensive task. Washing or leaching are not particularly effective if the contaminate is sequestered in small pores; hydraulic flows of water pass through larger pores leaving the smaller pores relatively untouched. Electro-osmosis appears to be the most promising new technology for removing heavy metals and organic substances from contaminated soils (Segal, 1980; Hamed et al., 1991, Masliyah, 1994).Electro-osmosis is one of several electrokinetic phenomena that occur through the interactions among an electric field, fluid motion, solute adsorption, and the existence of a net charge on a solid-fluid interface (Newman, 1991, Masliyah, 1994). Electro-osmosis refers to the fluid flow in a porous medium that results when an electric field acts on the mobile region of the electrical double layer, the solution-side region of charge separation that exists at the pore walls."

Jan 1, 1996

By Germán Richter a

To comply with the chilean air quality regulation requirements, the Hernan Videla Lira Smelter which is a custom smelter having to cope with a wide variety of concentrates, has developed a two-step modernization plan. The main steps are: - A second acid plant of 80,000 Nm3/hr to be operating at the end of 1996. This will increase the sulphur capture from 43% to 701/o in association with the replacement of the Hoboken converter by a second PS-converter to reduce the operation problems resulting from the treating of high garde matte. - Oxygen enrichment, is going to be incorporated in 1998 in the Teniente Converter and PS-converters in association with tuyere injection of dry concentrates, increasing the sulphur capture to 90 - 93% of sulphur inputs. By this program, sulphur emissions will be decreased from 40,000 tpy today to less than 8,000 tpy and in this way to carry out the environmental regulations.

Jan 1, 1996