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By Louis J. Mittoni

"It is well known that gas injection systems can exhibit a wide range of dynamical behaviours, ranging from linear periodic bubbling through to highly complex turbulent jetting. Recently, it has been observed that an important intermediate regime exists under certain system conditions, where the dynamics are complex in nature yet predictable for short time periods. This paper reviews the evidence to support the above hypothesis, and discusses the invariant quantitative measures such as density, return maps, Lyapunov exponent and dimension which may be used as pattern recognition features in a mOnitoring and control strategy.INTRODUCTIONThere has been a great deal of research on the submerged injection of gases into liquids. This interest is primarily due to the large number of applications in the pyrometallurgical and chemical engineering industries. Gases are typically injected into liquids to achieve goals such as heat and mass transfer, or physical mixing and agitation. Only recently though has the possibility of using the evolution of the gas dynamics as a probe to internal system conditions been raised [1, 2].At very low gas injection rates and small upstream chamber volumes, gas normally disperses in the form of stable bubbles of constant volume [3]. With increases in gas flow rate, the dynamics become more complex, bifurcating into double bubbling, multiple bubbling and complex coalescence behaviour. Irregularities measured in pressuretime series acquired upstream of the injection port under these complex conditions have usually been treated as bothersome noise or contamination to be filtered from the signal and ignored in the analysis. These irregularities, however, may contain physically interesting and useful information on the system from which they were produced if the system may be classified as deterministically chaotic [4]."

Jan 1, 1996

By Sui Xue

A process has been developed from laboratory-scale experiments for the aqueous processing of various lead-bearing wastes. The process exploits the limited solubility of lead in sulfate-rich solutions to effectively separate lead from other metals. The lead sulfate is then completely converted to lead carbonate using sodium carbonate and ammonium carbonate. The effectiveness of this conversion was observed to be sensitive to the solution pH and carbonate concentration. The final stage of the process uses low temperature calcination of the lead carbonate to form PbO. Yellow lead oxide (massicot) is readily formed if calcination is conducted at a temperature at or iibove 50G°C, wlule red iead oxide (iitharge) is formed at temperatures near 450°?C. A complete economical analysis of the process will be discussed.

Jan 1, 1996

By Gudrun A. Saevarsdotti

For decades tile aluminium industry has been practicing gas treatment of aluminium melts. This treatment is of great importance because of its influence on 'impurity" and inclusion removal from the melt. The gas-melt interaction is greatly influenced by the gas composition, melt temperature etc. This paper gives an overview of the interaction between argon-chlorine gas mixtures and the aluminium melt. It covers the thermodynamics of the reaction between the chlorine and a number of different elements commonly found in liquid aluminium, and discusses the behaviour of reaction products in the melt. The paper reports an experimental study of the behaviour of the chlorine-molten aluminium interface, using sodium contaminated aluminium melt with and without the addition of grain refiner.

Jan 1, 1996

By Kazutaka Kunii

It is invariably certain that after punching for IC Leadframes, scrap metal were generated. These seraps were re-dissolved and in order to use as raw material for leadframes, it is necessary to remove the Ni plating. In this study a simple method was developed for the removal of Ni plating by surface oxidation of Ni plating. For this purpose a fundamental study was carried out on the oxidation behavior of Ni plating. Results showed that by controlling the oxidation condition, a considerably high rate of Ni could be removed.

Jan 1, 1996

By Ralph H. Nafziger

The Bureau of Mines, in cooperation with the Idaho National Engineering Laboratory, has electroslag melted a V-5Ti-5Cr alloy using a fused CaF2, flux. The alloy is a candidate for use in future fusion reactors. One objective of this research was to evaluate the feasibility of the electroslag melting process in separating simulated radioactive isotopes from the V alloy to demonstrate recyclability. Small amounts of Ca, Y, and Mn were added as surrogates for radioactive isotopes. Results showed that this vanadium alloy can be electroslag melted satisfactorily. The impurities added intentionally were removed or decreased successfully. Among the major alloying constituents, Cr was retained but there were some Ti losses. The latter may be controlled with process refinements. This research suggests that the electroslag melting process could be a suitable method for recycling V alloys after use in future fusion reactors, or for processing other reactive metal alloys with more immediate applications.

Jan 1, 1996

By Zbigniew Zurecki

The selection of atmosphere composition is critical for controlling surface quality of reactive aluminum alloys during solution treatments. An improper selection of annealing atmosphere can result in surface blistering in AI-Mg and sub-surface depletion of lithium in AI-U ingots. To determine optimum atmosphere compositions for homogenizing A1-Mg and Al-Li alloys, Ii number of exploratory experiments were carried out in air, nitrogen, and carbon dioxide based atmospheres including reactive impurities or additive such as moisture and sulfur hexafluoride. This paper describes the influence of these atmospheres on high-temperature oxidation and sub-surface defects. The results are discussed in terms of the change in Pilling-Bedworth ratio.

Jan 1, 1996

By H. Fukuyama

The wetting behavior of single crystalline MgO by fayalite-type slag melts has been studied by the sessile drop technique incorporated with high temperature X-ray radiography. The experiments were performed under oxygen partial pressures of 10-6 and 10-4 Pa at 1473 K. Mass ratios of iron to silica, Fe/Si~, in the slag employed were 1.4 and 2.0. To investigate the interfacial reaction, experiments using high density MgO crucibles were also conducted. The reactions at the interfaces were examined by Electron Probe Microanalysis. The contact angles between the slag melts and the MgO substrates were found to be relatively low, ranging from 30 to 10 degrees. The surface tension of the slag was 0.4 N/m for a slag of Fe/Si02 = 2.0. Two phases, magnesiowiistite and olivine, were observed at the interface. Interdiffusivity in magnesiowiistite solid solution was determined as a function of iron oxide content. Phase relations between magnesiowilstite and olivine, and the growth rates of both phases, are also discussed

Jan 1, 1996

By Tom McCullough

The purpose of this paper is to discuss the implementation and results derived from installing oxy-fuel burners in a l80 ton copper reverbatory melting furnace. Specific results will be discussed in the areas of melt chemistry, furnace modifications, productivity, process enhancements, and the combustion system capabilities.

Jan 1, 1996

By Lev Levin, Sergei Lesokhin

"The formation of titanium carbide during hot filament assisted carburizing of NiTi alloy was investigated. Phase content and morphology of the diffusion zone were examined by X-ray diffraction, X-ray microanalysis, SEM, and Auger electron spectroscopy. The growth of stable and adherent TiC film was observed. A non-planarity of interphase boundary was noticed. The applicability of the chemical diffusion approach to the analysis of the experimentally observed interface instability is discussed. A criterion, taking into account the influence of growth stresses on the stability of the flat interface, is developed by means of linear perturbation analysis.Introduction.Equiatomic intermetallic NiTi belongs to a class of materials exhibiting the shape-memory effect. The unusual property of this compound promotes its application in many fields, from aerospace technologies to medicine. The relatively high ductility ofNiTi also permits its use as a matrix material in metal-ceramic composites. The objective of this work was to investigate the possible incorporation of a ceramic material (titanium carbide) into NiTi by gas carburizing.Free energy calculations indicate the potential to obtain TiC by carburizing Ni-Ti binary phases. The main obstacle to such a process is the high affinity of titanium to oxygen. At moderate temperatures the formation of TiC is preferable to titanium oxidation only if the partial pressure of oxygen is extremely low [1]. This problem was overcome in this work by the use of hot filament assisted gas carburizing. Due to chemical reactions occurring near the hot filament, the gas mixture, initially consisting of methane and molecular hydrogen, was enriched by atomic hydrogen [2], drastically decreasing the content of free oxygen in the carburizing atmosphere.The second part of this article concerns the theoretical analysis of reasons that lead to the development of the experimentally observed morphology of the diffusion zone. In particular, the influence of the growth stresses on the morphology of an interphase boundary is investigated."

Jan 1, 1996

By Rolf R. von Oppenfeld

Onsite hazardous waste processors often find obtaining a Treatment Storage and Disposal (TSD) permit one of their first major challenges. Some processors may spend the time and money required by the permitting process, only to find out later that a permit was not necessary. This paper will present and analyze four strategies that processors may use to avoid obtaining a TSD permit. Some facilities will be able to remove their waste streams from RCRA's oversight by ensuring the material is not "hazardous" waste. Parties that treat waste while it is in process may be able to avoid generating "waste" altogether. Certain treatment facilities have been specifically exempted by EPA. Finally, treatment of waste while it is in generator storage tanks may be allowed without a RCRA TSD permit. Hazardous waste point of generation, an important determination relating to these strategies, will also be discussed. Generators and processors will find this paper useful when evaluating their permit exemption potential

Jan 1, 1996

Physical and chemical properties of the salt flux phase play a significant role in the recycling of UBC in Aluminum melting processes. Particularly knowledge of several properties such as salt vapor pressure, melting temperature, loss of aluminum, corrosion of refractories are useful for the process control decisions in order to attain a good quality of aluminum produced. A literature review and analysis of several salt flux systems for the selection of a flux for the Aluminum melter (low temperature natural gas bath melting) process were made. Based on these analysis two salt flux systems are recommended for further studies. These are NaCl?KCl?LiF system and NaF?LiF?KCl system with small amounts of other salt additives. Application of these fluxes to Al industrial processes are discussed.

Jan 1, 1996

By Jennifer Murphy, Brad S. Schake, Karol Holmes, John R. FitzPatrick, Mike H. West

"The separation and purification of uranium from either nitric acid or hydrochloric acid media can 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 (1 DO-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 Norbert Steiner

For the desulfurization of weak SO2 gas streams, Degussa developed a process using dilute H2SO4 solution containing H2O, instead of conventional gas scrubbing with all solid absorbent medium (limestone, MgO). The process is based on fast reaction of H2O, with SO2 yielding H2SO4 up to 70% strength, depending on off-gas temperature. Compared to the conventional systems with typically < 95% efficiency, independent on the raw gas SO2 concentration, residual SO2 concentrations of less than 20 mg/Nm3 can be easily achieved, corresponding to nearly 100% removal. These features render the H2O, process a very attractive, low capital cost technology to retrofit existing conventional desulfurization plants.

Jan 1, 1996

By David C. Lynch

FeCl3 particulate of 10 to 100 um in diameter was reacted with radicals produced in an oxygen plasma at pressures between 1 to 20 Torr. The particulate, in a fluidized bed, was positioned above the plasma to avoid over heating the oxide product which is known to lead to crust and clinker formation[ 1 ]. Reaction between the iron chloride and the gas phase occurred at temperatures between 66 and 226 °C. Oxygen radicals react with the surface material to a depth of approximately 2.5 4m. Surface material, analyzed with a x-ray technique, indicates that the maximum amount of FeCl3 reacted on a weight basis was found to be approximately 67%. More typically, 40 to 50 wt% of the chloride was reacted within 30 minutes to 1 hour.

Jan 1, 1996

By R. C. Hubli

A panial equilibrium model? to simulate the dissolution of millerite (NiS) in aqueous solutions containing copper(II) chloride as the oxidizing species has been developed. The predominant copper(I) and copper(II) species are CuQ3 and CUO2 respectively. The model computes the initial concentrations of the species present in the aqueous phase under the specified input conditions, prior to the simulation of dissolution. During the dissolution of millerite, nickel enters the leach liquor as NiH and it has been found that the H+ decreases as a function of NiS dissolution. The simulation has been accomplished under conditions prevailing during actual dissolution, with only one mineral undergoing dissolution. The model can be applied for the simulation of co-dissolution of two or more sulfides. Under the given conditions, the precipitation of Cu1(OH»)O is negligible but loss of Cu(1l) could be significant if the initial H+ is lower than 0.03 M. The results of the simulation compare favorably with experimental observations.

Jan 1, 1996

By H. Eccles

BNFL, an internationally acclaimed company noted for its nuclear fuel cycle services and waste management technologies, collaborated with Viridian BioProcessing Ltd, a small company acknowledged for developing environmental biological processes, and an internationally recognised professor of biological sciences, to develop an unique bioremediation process for treating toxic, heavy metal contaminated land. This paper describes the process, with particular reference to the problem and scope of land contamination with toxic, heavy metals and the current available technologies. The process technologies are based on using indigenous, soil micro-organisms which can be stimulated to produce acid or sulphide ions to mobilise or precipitate the heavy metals respectively. Laboratory studies have indicated metal removal efficiencies of greater than 90 % can be achieved, whilst recovery efficiencies from the metal loaded leachate are even higher at approximately 95%.

Jan 1, 1996

By J. Gartelmann, B. Zaslavsky, Y. Vojta, D. J. Chaiko, W. Mego, A. N. Rollins

"Aqueous biphasic extraction (ABE) processes offer the potential for low-cost, highly selective separations. This countercurrent extraction technique involves selective partitioning of either dissolved solutes or ultrafine particulates between two immiscible aqueous phases. The extraction systems that we have studied are generated by combining an aqueous salt solution with an aqueous polymer solution.We have examined a wide range of applications for ABE, including the treatment of solid and liquid nuclear wastes, decontamination of soils, and processing of mineral ores. We have also conducted fundamental studies of solution microstructure using small angle neutron scattering (SANS). In this chapter we review the physicochemical fundamentals of aqueous biphase formation and discuss the development and scaleup of ABE processes for environmental remediation.IntroductionAqueous biphasic extraction (ABE) is a highly adaptable separation technique that can be used in a wide range of applications. We have been evaluating various types of ABE systems for possible applications in the treatment of solid radioactive wastes (1,2), liquid nuclear wastes (3,4), and contaminated soils (5-7), and in the removal of organics from aqueous salt solutions (8). We have also conducted fundamental studies of the solution microstructure of ABE systems using small angle neutron scattering (SANS) (9).The extraction systems are generated by combining an aqueous salt solution and an aqueous polymer solution. This produces two distinct liquid layers that are as immiscible as oil and water, yet each liquid layer contains at least 70 to 80 wt % water. The biphasic systems that we have been working with consist of immiscible polyethylene glycol (PEG) and salt solutions. Some inorganic salts that promote biphase formation with PEG solutions include the sodium/potassium salts of sulfate, carbonate, phosphate, and hydroxide (10)."

Jan 1, 1996

By Guo Xian Jian

In this paper, the effects of matte grade, flux grain size, blast flowrate and blast O2 content on the process of silica flux melting in a copper converter were investigated. The results showed that the blast flowrate and the blast 02 content were not significant factors in the melting process. However, with an increase in grain size of flux and grade of matte, the amount of the flux molten decreased. The data on the melt rate of process correspond well with the mathematical model which simulates the chemical reactions occurring at the interface. The kinetic equations of melting are as follow:

Jan 1, 1996

By Günter Petzow, Hans Leo Lukas, Hans Jürgen Seifert

"The CALPHAD method (CALculation of PHAse Diagrams) has been extensively developed in the last 25 years and became a useful tool in materials science. Thermodynamic descriptions for the functions of state of unary, binary and ternary phases are derived by the optimization of phase diagrams. These functions are stored in computerized thermochemical databases and can be combined to extrapolate to multi component systems. Depending on special demand, the actually most advantagous presentations of the calculated results can be chosen: tables or in a clear graphical form as phase diagrams, phase amount diagrams or volatility diagrams. The method will be desribed by the system Ti-Si-C-N-O including the ceramic subsystem Si3N4-SiC-TiCi,N1_1,-C-N-O which is very important for the development of ceramic composites. The calculations give the thermodynamic stabilities of the condensed phases as function of temperature, concentration and partial pressure of different gas species. Adjusting the sintering conditions to these results the formation of unfavourable compounds or liquid phases can be suppressed.IntroductionThe CALculation of PHAse Diagrams (CALPHAD-method) of multicomponent systems provides the possibility to plan experiments very efficiently and avoid the experimental trial and error approach for the development of materials. The main problem for best use of calculated results is their interpretation with regard to the specific applications under consideration. Tables give the exact quantitative data for the treated phenomena. However, most important to make best use of these thermodynamic data is their graphical representation especially designed for the solution of specific problems, scientific as well as application oriented. Only well chosen graphical representations support a comprehensive understanding of the thermodynamic interrelationships and the transfer to the problem."

Jan 1, 1996

By John A. Herbst

Plantwide control of mineral processing operations has long been sought for its potential benefits. These benefits include minute-to-minute optimization, reacting to disturbances in ore characteristics and equipment status as they happen and the coordination of all unit operations in pursuit of the highest performance level. However several difficult challenges have kept us from fully realizing those benefits. One of these challenges has been to provide fairly complete quantitative descriptions of Unit operations to account for critical interactions within and &apos;between unit operations. In some cases we understand the physics and chemistry very well and can incorporate that &apos;knowledge into phenomenological models. In other cases our knowledge is incomplete, so we must rely on other forms of knowledge such as fuzzy logic or neural nets. Another challenge to be met has been to simultaneously compute a large number of manipulated variables. In the past this challenge was met by optimizing only unit-by-unit, rather than on a global basis to significantly reduce the number of variables. In this paper, a procedure that globally optimizes one or two important variables is outlined. This procedure comes much closer to true plantwide optimizing control while remaining computationally feasible. Finally, another major challenge is to choose a meaningful global objective that can be calculated With the models and can be effectively optimized. Financial goals seems to be the objectives of choice. This paper discusses recent progress In overcoming the challenges and illustrates a promising approach which is being pursued at :Mexicana de Cobre&apos;s &apos;La Caridad copper ore concentrator. At M de C, advanced ,control strategies have been &apos;installed one at a time in the crushing, grinding and flotation sections. During this period, the throughput of La Caridad, Mexico&apos;s largest copper concentrator, &apos;increased from 76;000 tpd to 90,000 tpd. Plantwide integration is expected&apos; to gain an additional 3% improvement in profitability.

Jan 1, 1996