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By Guohui Zheng

The ever increasing quantities of solid wastes generated by various industries are at the source of the growing need for proper waste disposal methods. Thermal treatment of combustible wastes is a proven technology which permits the reduction of hazardous material having to be landfilled. However, this method is not universally applicable to waste disposal. For example, the transferal of heavy toxic metals into the thermal remediation products is a major issue of public concern. This paper focuses on the analysis of morphology changes from solid sludge to ash which is a product of the sludge combustion. The morphological parameters analyzed were particle size and external surface. They were determined using Jeol 840 Super Probe. The experiments were conducted in a computer-controlled high-temperature combustion system consisting of the thermogravimetric furnace coupled with Fourier transform infrared spectrometer (TGA-FTIR). Sludge particles were made of complex fibers trapped in the aluminosilicate matrix. At low temperatures, up to 680 K, the solid residue looked similar to the initial sludge. Between 680 K and 1180 K the sludge underwent intensive burning and steadily changed into powdered ash. At the temperature of 1050 K the ash was composed of separate, flat flakes with sizes ranging from 5 to 20 um. At 1470 K the flakes aggregated into large particles. The surface observed at 1670 K was a mixture of mullite crystals. Such structure could result from the solidification of the ash material after its melting. Morphological changes influenced the distribution of metals in the solid residue. For example, Cr was concentrated in small aggregates. Such distribution should allow for recovery of valuable metals from the solid waste residue.

Jan 1, 1996

By Y. W. Chung, W. I. Chia

"The interaction of water vapor with single crystal Ni3(Al,Ti) and polycrystalline Ni3Fe, with and without the presence of oxygen, has been studied with Auger electron spectroscopy, photoemission spectroscopy, thermal desorption and isotope exchange. Water dissociates to produce atomic hydrogen above 200 K on both Ni3(Al,Ti) and Ni3Fe surfaces. For Ni3(Al, Ti), the reaction is structure-sensitive. Pre-adsorbed or co-adsorbed oxygen on Ni3(Al,Ti) and Ni3Fe significantly suppresses hydrogen production due to water dissociation. This suppression process occurs more efficiently on Ni3Fe than Ni3(Al, Ti).IntroductionOrdered intermetallic compounds such as aluminides, silicides and titanides are very attractive for structural applications at high temperatures. This is because these intermetallics tend to form adherent oxides in oxidizing environments which protect the base materials from excessive oxidation and corrosion. In addition, they have low density, relatively high melting points and good high-temperature strength. However, the moisture in air severely embrittles many ordered intermetallics such as FeAl [1-3], Fe3A1 [4,5], C03Ti [6,7], (Co,Fe)) V [8], Ni3Si [9], Ni3(Si,Ti) [10], Ni3(AI,Mn) [Ill, and Ni3A1 [12-14], resulting in low 'ductility and brittle fracture at room temperature. Recent studies by Liu and coworkers (see review by George and Liu [15]) provide a qualitative description of the mechanism for this moisture-induced embrittlement. During elongation testing, cracks are formed, thus exposing fresh alloy surfaces. One or more active components of the alloy react with water vapor in the environment to produce atomic hydrogen which penetrates into crack tips and causes hydrogen embrittlement. This is similar to that proposed for moisture-induced embrittlement of aluminum alloys [16]."

Jan 1, 1996

By S. M. McDeavitt

Waste form alloys are being developed at Argonne National Laboratory for the disposal of remnant metallic wastes from an electrometallurgical process developed to treat spent nuclear fuel. This metal waste form consists of the fuel cladding (stainless steel or Zircaloy), noble metal fission products (e.g., Ru, Pd, Mo and Tc), and other metallic wastes. The main constituents of the metal waste stream are the cladding hulls (85 to 90 wt%); using the hulls as the dominant alloying component minimizes the overall waste volume as compared to vitrification or metal encapsulation. Two nominal compositions for the waste form are being developed: (1) stainless steel-IS wt% zirconium for stainless steel-clad fuels and (2) zirconium-8 wt% stainless steel for Zircaloy-clad fuels. The noble metal fission products are the primary source of radiation in the metal waste form. However, inclusion of actinides in the metal waste form is being investigated as an option for interim or ultimate storage. Simulated waste form alloys were prepared and analyzed to determine the baseline alloy microstructures and the microstructural distribution of noble metals and actinides. Corrosion tests of the metal waste form alloys indicate that they are highly resistant to corrosion.

Jan 1, 1996

By T. Shimizu

In Japan, the emission standard of selenium in effluent was set at a maximum of20 mgll in Feb. '94 for the first time, and it is scheduled to be further decreased to a maximum of 0.1 mg/I from Feb. '97 due to tightening of the Water Pollution Prevention Act. Selenium (IV) and (VI) are generally found in effluent from precious metals refineries. Although selenium (IV) can be easily eliminated by some reducing agents, selenium (VI) is more difficult to be reduced. Therefore, many smelters are having difficulty in complying with the new emission standard. At Mitsubishi Materials' Naoshima smelter, the behavior and the elimination of selenium in effluent have been extensively investigated. As a result, it was found that two strategies were particularly effective. One of them is improving the overall operation of precious metals refinery, that is, feeding uniformly the effluent to the waste-water treatment plant, reducing the effluent volume by recycling and recovering more selenium (IV) in the effluent. The other is eliminating selenium (VI) in the effluent from the precious metals refinery. It was found that selenium (VI) can be effectively reduced by using hydrazine under high? sulphuric acid concentration and high temperature conditions. By using these measures, it is considered that Naoshima Smelter will be able to comply with the new emission standard.

Jan 1, 1996

By S. A. Platias

Large amounts of dunile tailings can be recycled for olivine produdion from the existing beneficiation adivity of chromite ore in northern Greece. This olivine production aims at the preparation of a material suitable for the substitution of the environmental hazardous quartz sand in the foundries of Europe In smelting of chromite ore the losses that occur ore usually of the order of 6-8% Cr that report in the slag. Most of this is in the form of oxides that cannot be recovered, but usually 30-35% is in the form of FeCr alloy that can be recovered by gravity methods. About 90% of the produced slag is sold for road construdion after crushing to a desired grain size. Finally, recycling of chromites sludges from the ferrochrome produdion plant, through the preparation of pellets, improved the total chromite yield by 2%.

Jan 1, 1996

By D. Gu, R. G. Anthony, C. V. Philip, 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 column, 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 Nemst-Planck equation as the constitutive equation for diffusive flux. We use a NemstPlanck 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.IntroductionMillions of gallons of strongly basic, radioactive waste are currently stored in underground storage tanks at Hanford and Savannah River and several locations within the United States. Due to the limited life expectancy of the tanks, there is a pressing need to remediate these wastes. This need has prompted the recent development of new ion-exchange materials for removing radioactive elements from aqueous solutions. A novel material called TAM-5 has been developed jointly by Texas A&M University and Sandia National Laboratories. TAM- 5, a crystalline silico-titanate, is highly selective for Cs + in the complex electrolytic solutions typical of these wastes. It is stable in very basic solutions and in radioactive environments [1, 2 ,3]. In laboratory testing to determine the selectivity of various materials, TAM-5 was superior to other candidate ion exchangers [4, 5]. The selectivities were determined by measuring a distribution coefficient, Kd, which is defined as the concentration, gig or mmols/g of Cs in the solid phase divided by the concentration, mg/L or mmols/mL, of Cs in the liquid phase. The units of Kd are ml/g or L/kg. Table 1 shows Kd values for TAM-5 compared to 9 other candidate materials in a typical waste solution [6]."

Jan 1, 1996

By E. T. White, 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.IntroductionCrystallisation operations, including precipitation, are widely used in a number of hydrometallurgical processes to recover a desired component or to remove an undesired impurity. The goals of industrial precipitation processes are to maximise the recovery while maintaining product quality (generally product crystal size distribution, purity and morphology and product handling properties). Knowledge of the precipitation mechanisms and kinetics is invaluable for designing new precipitators or for improving existing units. The mechanistic and kinetic information is generally incorporated into mathematical precipitator models, which are then used for process design and optimisation."

Jan 1, 1996

By Y. A. Chang, L. M. Pike, C. R. Kao

"Knowledge of the site preference of ternary solute additions is essential to developing an understanding of how these solutes affect the properties of B2 intermetallic compounds. A quasichemical model will be presented which is able to predict the site preferences of dilute solute additions to tliple defect B2 compounds. The only parameters required are enthalpies of formation at the stoichiometric composition. General equations are developed which can be used to determine site occupations and defect concentrations for dilute as well as non-dilute solute additions. These equations use atom pair bond enthalpies as the parameters. It is found that the site preferences of dilute additions are not always in agreement with predictions based on the solubility lobes in ternary Gibbs isothelms. Predictions for dilute additions to NiAl and FeAl are compared to expel1mental results found in the literature. Satisfactory correlation is found between the model and the experimental results. In addition, the predictions from the model on vacancy concentrations in Fe doped NiAl are compared to recent experimental results by the authors.1.0 IntroductionIntennetallic compounds with the B2 crystal structure such as NiAl and FeAl have been investigated recently for possible use as structural materials in high temperature, oxidizing, and/or corrosive environments. The major limiting property of these materials has been a lack of sufficient room temperature ductility. Attempts to improve the ductility have often been made through ternary or higher order alloying. For B2 compounds, substitutional alloying additions can occupy either of the two sublattices and this site occupancy can be crucial in determining how the alloying addition affects the properties of the alloy. In this manuscript we will discuss the use of thelmodynamic modeling to predict the site occupancies of ternary alloying additions in B2 compounds with the triple defect structure."

Jan 1, 1996

By M. Yoshida, S. Hanada, T. Takasugi

"A study has been conducted to examine the effect of ternary alloying elements on high temperature deformation of the C15 NbCr2 based intermetallics in Nb-Cr-X (X=V, Mo and W) alloy systems, which have attractive properties as high temperature structural materials. The high temperature deformation of the C15 NbCr2 intermetallics can be improved by two alloying methods. One method is based on geometrical consideration for site occupation and atomic size factor of component elements and additive elements in the single phase C15 lattice; addition of Mo and V can promote dislocation movement without introducing significant hardening. The other method is based on microstructural modification through ternary alloying; moderate addition of these elements results in a variety of duplex microstructure consisting of the C15 phase and bee solid solution without forming any intermediate phases, and can enhance the high temperature deformability. Particularly, alloys with duplex microstructure equilibrating with Cr-rich bee solid solution is shown to exhibit superior deform ability. Also, lattice property of the additive atoms in the C15 structure and phase relation between the C15 structure and the bee solid solution are investigated by OM, XRD, TEM and ALCHEMI observations and then discussed in association with observed mechanical behavior.IntroductionLaves intermetallics with AB2 stoichiometry belong to the largest group in a large number of intermetallics with various kind of crystal structures, and have a variation of the cubic CIS, the hexagonal C14 and the dihexagonal C36 structures, depending on stacking sequence of XYZ type, each of which consists of four interpenetrating atomic layers (1-3). Some of the Laves intermetallics have good functional properties and therefore are considered to be used as, for instance, magnetic materials, magneto-optical materials, hydrogen storage materials and superconducting materials (2). Also, the Laves intermetallics are considered to be good candidate as high temperature structural materials operating at high temperatures and in severe environment because they have high melting point, low density, and potential resistance to corrosion and oxidation. However, the Laves intermetallics are very brittle at low temperatures because they consist of complex crystal structures similar to many other intermetallics."

Jan 1, 1996

By Hui Zhang

The leaching behavior of palladium powder in aqueous solutions containing NaCI or N'H4Cl was investigated. Cupric ion was used as an oxidant for the dissolution reaction. The effect of a number of leaching parameters such as temperature, concentration, stirring speed and surface area on the leaching rate was studied. The leaching system containing chloride and cupric ion was found to be very effective for the dissolution of metallic palladium. Based on the experimental results the overall leaching rate was believed to be controlled by a chemical reaction step. The dissolution rate of palladium was found to be first order with respect to the concentration of cupric ion and second order with respect to the concentration of chloride.

Jan 1, 1996

By Ravi Vancheeswaran

The consolidation of ceramic fiber reinforced metal matrix composites is a key process step in the synthesis of high performance composite systems. A simulation tool has recently been developed for predicting the evolution of the composites internal state microstructural variables (eg. relative density, fiber microbendinglfracture, and chemical reaction layer thickness at the fiber-matrix interface) during the consolidation processing of spray deposited composite mono-tapes. A Generalized Predictive Control (GPC) scheme is used in conjunction with the simula-tion tool to design near optimal process paths that minimize fiber damage and reaction product thickness while simultaneously maximizing the composites relative density. The microstruc-tural evolution depends nonlinearly on the process conditions and therefore the scheme uses a constantly updated linearization of the model to optimize the input process variable vector. A control simulation is presented to illustrate the performance of the design scheme and to assess the feasibility of its use for the achievement of goal state microstructures at the completion of consolidation cycles.

Jan 1, 1996

By R. Cavanagh

Studies relating to the fixation of sulfur by reaction of 4 to 8 mm diameter cylinders of calcined limestone or dolomite with high strength sulfur dioxide in the temperature range 880°C to 1020°C were undertaken. Dolomites are far superior in sulfate capacity and reactivity than dense limestones even at high strength SO2. The sulfation reaction was first order with respect to SO2 concentration below 100 percent. Zero reaction rate at 100 percent SO2 concentration indicates that sulfate was the exclusive reaction product and that sulfite had no role in the reaction. At relatively low SO2 concentrations gaseous diffusion through the reaction product layer has a marked effect on the rate. As SO2 concentrations were increased up to 100 percent more complex rate controlling mechanisms unfold. By sectioning partially reacted dolomitic limestone pellets a moving interface was observed. Reaction ceased because of pore plugging for dense non-porous limestones at 30% conversion. With dolomitic material virtually complete sulfation of the calcium was observed. S.E.M. analysis showed that the average atom ratio Ca:S was 1.01, thus supporting the argument that little if any of the magnesium was sulfated.

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, electrolysis 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, SiO2; CaO, and MgO have confirmed electrochemical production of oxygen on a carbon-free anode. IntroductionMolten salt electrolysis is the electrolytic decomposition of a compound dissolved in an ionic melt. The prime example of this process can be found in the production of aluminum. The compound, alumina (Al2O3)' derived from the mineral bauxite, is dissolved in an ionic melt comprising a multicomponent solution of cryolite (Na3AlF6)' aluminum fluoride (AlF3)' and calcium fluoride (CaF2,). The products of electrolysis are molten aluminum and carbon dioxide, the latter due to the attendant consumption of the carbon anode. Primary aluminum is produced in a reactor known as the Hall cell.' Alternatively, the compound undergoing electrolytic decomposition can be derived from waste. Processing in molten salts, with their capacity to dissolve materials to very high concentrations compared to those attainable in aqueous solutions, can be rather advantageous. High solubilities lead to high limiting current densities, and this, in tum, results in high productivities: For a primer on molten salt electrolysis and a review of the basic literature in the field of molten salts the reader is directed to an earlier publication of the author (1)."

Jan 1, 1996

By Susumu Okabe

Top blowing lances are employed by the Mitsubishi Continuous Copper Converter for the continuous supply Of reaction gases into moken bath. In order to minimize the refractory wear caused by the interaction between the furnace lining and the melt splash. optimum furnace design and blowing condition are? required. An empirical equation obtained by the physical model study enables the estimation of the splashing rate on a vel1ical plane at a certain distance from the lance.

Jan 1, 1996

By L. Klinger, T. Werber, LA Levin, A Katsman

"The process of catastrophic carburization known as ""metal dusting"", whereby a solid metallic material is converted into fine particles in a carburizing atmosphere, was analyzed. It was shown that this conversion is the result of plastic deformation and subsequent fracture accompanying diffusional phase formation in the near-surface layer. The process is controlled by internal stresses arising during phase transformation. Competition between stress generation and relaxation may result in the attaining the ultimate strength in the near-surface layer and its fracture. Such a mechanism of metal disintegration may occur in a certain temperature interval depending on the kinetic and geometrical parameters of the system - the diffusivities of the alloy's components, the ratio between specific volumes of the new and the old phases, and the ultimate plastic strain. The temperature interval for disintegration of carbon steel, the rate of disintegration, and the period of the disintegration cycle, were evaluated and compared with experimental data. IntroductionCatastrophic carburization, known as ""metal dusting"", consists in conversion of a solid metallic material into fine particles. The process occurs in a carburizing atmosphere at elevated temperatures. The corrosion product, usually named ""coke"", consists of metallic particles dispersed in a loose carbon matrix. Under industrial conditions metal dusting takes place, for example, in a gas mixture of CO and H2 or in hydrocarbon environments. Steels, nickel- and cobalt alloys are susceptible to this kind of wastage in the temperature range 400-800°.A mechanism of metal dusting in steels was proposed by Hochman [1] and later developed by Grabke and coworkers [2-5]. According to the proposed model, the process consists of the following reaction steps:"

Jan 1, 1996

By H. Y. Sohn

A novel solvent extraction process in which the emulsion is generated by bottom gas injection rather than mechanical stirring has been developed. This process has a number of advantages over the mixer-settler unit or the spray column in terms of simple equipment configuration and the ease of cleaning and process control while providing a large interfacial area for mass transfer. The equipment consists of a horizontal cylindrical vessel in which the two immiscible liquids flow countercurrently. High-strength gas jets are injected from the bottom at certain intervals along the length of the vessel. The gas jet creates a plume zone consisting of an emulsion of the two liquids which contains a large interfacial area for rapid mass transfer. The two liquids then disengage and flow in the opposite directions before entering another plume zone. Thus, the process combines the simplicity of a cylindrical vessel, having no moving parts, with the contacting efficiency of a mixer-settler. The gas can be recycled in a closed loop, thus eliminating mist and other emission problems. These advantages would be especially significant for treating large-volume/low-value liquid streams which contain hazardous substances and/or suspended solid particulates.

Jan 1, 1996

By M. M. Monte

A method for removing metallic mercury from contaminated tailing, using the flotation process, is described. In order to define some relevant parameters for the mercury flotation system, microflotation and electrophoretic mobility tests were carried out on (pure) metallic mercury in the presence of several surfactants. Based on the results obtained from fundamental studies a series of bench scale flotation experiments with mercury containing tailings from two wetland sites in Brasil were done. The results of microflotation tests with mercury showed that by using cetyl trimethyl ammonium bromide, an increase in mercury flotability is observed in the acid pH range, whereas in the presence of potassium oleate the highest mercury flotability was found in the alkaline pH region. The mercury flotability using potassium amyl xanthate was improved by the addition at sodium dithionate as an activator. The bench scale flotation tests with contaminated tailings from Poconé (brazilian wetland site) showed a recovery of 70% when sodium dithionate was used as activator and potassium amyl xanthate as collector. The resulting coefficient of separation is around 60%. However, the results of the flotation experiments with fine fractions from amalgamation tailings from Peixoto de Azevedo (brazilian wetland site) showed a low mercury recovery (32%).The results from this work suggest that since in the Poconé site tailings, the metallic mercury is not completely associated to the finer particles, the flotation process to recover the metallic mercury seems very promisor.

Jan 1, 1996

By J. S. Becker

Technology developed and first implemented in the United Kingdom enables very low grade aluminum scraps containing oils, organics, plastics and ferrous metals to be directly charged, without pretreatment, into a unique melting furnace. The system has been in full scale production for over three years. The oxy-fuel-based furnace design incorporates internal afterburning in the furnace's hot zone, producing excellent thermal efficiency and very low emissions. The furnace is inherently low in NOx. This paper will provide both theoretical background and extensive operating results for this new melting concept. Applications describing both purpose built new furnaces and retrofits of existing reverberatory furnaces will be presented. Extensive operating emissions data will be presented.

Jan 1, 1996

By C. J. Malek

The CONTOP® smelting cyclone technology is a large-scale and time-proven method which in combination with other technologies (grinding, drying, pyrolysis, etc.) provides for a cost- efficient and ecological disposal of a wide range of waste materials from industry and households. In this report the basic principle of smelting cyclone technology will be explained first. Subsequently, the paper will discuss substantial concepts for the recovery of various remainders.

Jan 1, 1996

By Cyro Takano

An alternative use for recycling of waste from bag house of iron ore sinter plant was tested by producing and evaluating" at laboratory scale, the self reducing cold bonded pellets. This waste was characterized and the self-reducing pellets were produced using anthracite coal fines as reductant and Portland cement or hydrated lime/Blast Furnace slag as binder. It was used the molar ratio of Fe2O3/C (fix) equal to 3. Evolution of cold strength with curing time, for different contents of binder, was evaluated. Cold strength of 200N/pellet was obtained, for sinter dust, after 10 days of curing. Suitable hot strength was also presented and no decrepitation and swelling were observed. Good fractional reduction was obtained at 950°C and 1137°C. These results show that this material may be used by the Self-Reducing Processes for hot metal production, as an alternative route for this dust destination.

Jan 1, 1996