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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

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