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By Animesh Jha, Catherine Davey

"Carbothermic reduction and nitridation reactions using synthetic kaolinite mineral were investigated for the formation of silicon based nitrogen ceramics. The temperature dependence of the reaction rate and its effect on phases formed are reported. The effect of the reactivity of carbon on the kinetics of formation of AIN and ShN4 is discussed. Using the standard Gibbs free energy values for the formation of nitrides and oxides of aluminium and silicon, a log po2 verses I/T diagram is constructed. The experimental data results are discussed and compared with the predicted phase equilibria. We also report the influence of sub-oxide gaseous species on the microstructure of the ceramic phases produced.IntroductionSynthetic kaolinite is a clay containing alumina, silica and water of crystallisation, and has a chemical formula 3(Al2O 3.2SiO2.2H2O). This mineral is relatively inexpensive and, is therefore an ideal candidate for use in the production of ceramic powder mixtures for example silicon nitride and aluminium nitride for composite material formation, When the mineral is heated, the water of crystallisation from the crystal lattice is lost via the 3(Al2O 3.2SiO2.2H2O) = 3(Al2O3.2SiO2) + 6H2O reaction. It has been shown [1·2j that on further heating to 1673K, the anhydrous kaolinite decomposes to a mixture of mulllte and silica, 3(Al2O3.2SiO2) = 3Al2O 3.2SiO2 + 4SiO2 which is consistent with the alumina-silica phase diagram, shown in figure 1.The binary alumina-silica phase diagram has a well-defined sub-eutectic immiscibility dome and this characteristic dernixing behaviour is reflected in the thermal decomposition of anhydrous kaolinite consequently the microstructural features resemble the spinodal decomposition process. It is well established that the spinodal decomposition process raises the nucleation frequency due to their low free energy barrier, (?G). The small magnitude of this barrier consequently promotes the evolution of a very fine microstructure. The process of spinodal decomposition is therefore expected to be influential during the reduction-nitridation of kaolinite minerals."

Jan 1, 1996

By Xinghui Meng

The leaching behavior of platinum powder in .iodide solutions under oxygen pressure in an autoclave was investigated. Ammonium salts were added to the leaching solution at neutral pH as a key lixiviant for platinum. The effect of temperature, partial pressure of oxygen, concentration of iodide and of arttmonium salts on the dissolution rate of platinum was examined. Under experimental conditions, the leaching behavior of platinum powder exhibited a complex reaction mechanism. A precipitate was found during the leaching process and was identified to be platinum ammine iodide, Pt(NH3hI4. The dissolution rate was controlled by a series of chemical reactions, the equilibrium concentration of the platinum ammine iodide being responsible for the ultimate limit to the recovery.

Jan 1, 1996

By Liow Jong-Leng

A survey of the interactions of large gas bubbles formed from top and bottom injection of gases into melts was carried out. Spherical cap bubbles were found not to produce much splash when they break through the bath free surface except for that formed by plunging of the-spout at its edges. In contrast, the bursting of balloons produces cavities which give rise to liquid jets being ejected from the bath free surface. The position of the balloons relative to the bath free surface is an important parameter in the formation of the liquid jet. It is found that the interactions of multiple bubbles close to the free surface is important in determining the splash behaviour of gas injected systems.

Jan 1, 1996

By Barry J. Welch

The production of primary aluminium can potentially lead to metal that, with minimum treatment, meets a high purity standard. Smelters that can achieve a significant proportion of their production in this manner have a competitive edge which is of growing importance as the use grows for such items as compact discs and the like. Superimposed on the desire to produce high quality metal are stringent environmental requirements that the industry must adhere to. The environmental 'legislation focuses on fluoride emissions and the approach adopted is towards a zero waste management philosophy. The fluoride recycling process does, however, result in volatile impurities being captured and recycled to the cell. Aluminium has an extremely high reduction potential and this results in a significant proportion of the recycled impurities being reduced at the electrolyte metal interface and thus contaminating the metal. This paper reviews sources of impurities and the impact of the operating procedures adopted on metal treatment.

Jan 1, 1996

By Sergey Komarov, Manuela Diaz, Sano. Masamichi

"Mixing time, bubble behavior and absorption rate of gas injected into a liquid bath through rotary L-shaped lances have been studied by cold models with an effort to improve refining characteristics of metallurgical processes. Two kinds of the rotary lances were tested, namely the single-hole lance and the multi-hole lance. The effects of gas flow rate, bath depth and rotation speed were examined.It is found that when gas is injected through the rotary lances, the mixing intensity and the gas absorption rate are larger than that for the gas injection through stationary lances. The effect of rotation speed decreases as the bath depth and the gas flow rate increase.The multi-hole lance produces much smaller bubbles, which lead to an increase in the volumetric mass transfer coefficient by 3-4 times as compared with the single-hole lance. However, the effect of rotation speed is smaller for the multi-hole lance. The obtained results are explained in terms of the bubble coalescence and fragmentation, the rate of which depends on the departure bubble size and the power supplied to the liquid bath.IntroductionIn recent years, there has been a growing interest in the development of gas injector for metallurgical processes. The majority of the previous work was focused on modification to the injector design to improve mixing and to increase the of chemical reaction rate. These two goals can not be necessarily achieved by the same way. Bottom nozzles and stationary immersed top lances, which have been widely applied to steelmaking processes, are effective for the bath mixing, but have a limit to decrease in the bubble size. This results from a vigorous coalescence occurring between the bubbles when they rise in the molten bath as a bubble swarm.One of the ways to ensure the small bubble size and the effective bath stirring is the gas purging through rotary injectors. A number of studies have been undertaken to improve the refining characteristics by using rotary injectors. All of them are related to aluminum refining. The SNIF equipment (The Spinning Nozzle Inert Flotation) has significantly improved the quality of aluminum products at National Luxemburg Aluminum [1]. Rotary injectors made in the form of a disc have been applied to the Alcoa 622 [2] and the GBF processes [3]. A study of the gas injection by a rotary impeller has been carried out by C. Leroy and G. Pignacelt [4]. All researchers note the significant improvement in removal of sodium, calcium, hydrogen and non-metallic inclusion."

Jan 1, 1996

By M. Nilmani, J. Sofra

The transverse distributions of the solids discharge velocity and mass flux at the discharge end of vertical and inclined lances were measured in order to detennine the transverse distributions of the axial momentum flux, which is a dominant factor influencing the penetration behaviour of particles into melts during submerged injection. The effects of gas velocity (10 - 30 m/s), solids loading (5 - 10), lance length (0.15 - 1.0 m), lance inclination (vertical downward - horizontal) and particle density (2500 - 8900 kg/m3 ) were investigated, while the lance diameter and particle size were fixed at 10 mm and 220 µm respectively. The particle velocities and mass fluxes were measured by image analysis of particles illuminated in a laser-generated light sheet aligned vertically through the axis of the lance at the discharge point. The particle discharge velocity profiles for vertical downward flows were synunetrical about the centre-line of the lance, with the maximum velocities occurring at the centre-line. The velocities increased with increasing gas velocity, increasing lance length and decreasing particle density in accordance with previous observations. The transverse mass flux profiles were also synunetrical for vertical downward flows, however at the lower gas velocities the peaks in the profiles were displaced from the centre-line of the lance by a fractional diameter of about 0.15. The particle discharge velocity profiles become increasingly asynunetric as the lance orientation was changed from vertical to horizontal, with higher particle velocities present near the top wall of the lance. The mass flux profile also became asyrrunetric as the horizontal orientation was approached, however in this case, the profile became biased towards the bottom of the lance. The effect was much more pronounced for a gas velocity of 10 m/s than for 30 m/s, showing the relatively stronger gravitational influence as the velocity was reduced.

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 che1ation-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, B-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.IntroductionSupercritical fluid extraction (SFE) offers several advantages over conventional solvent extraction including the minimization of organic liquid waste generation and exposure of personnel to organic vapors.[1] The high diffusivity, low viscosity, and T-P dependence of solvent strength are some attractive properties which make supercritical fluids excellent candidates for extraction and recovery of organic compounds from solid materials [2] Carbon dioxide is a gas of choice for SFE because of its moderate critical constants (Tc = 31 °·C and Pc = 73 atm), inertness, and availability in purified form. After extraction, the fluid phase is depressurized to separate organic solutes from CO2 gas and the gas can be recycled for repeated use. The SFE technology has been applied to industrial scale operations such as the preparation of decaffeinated coffee and hop extracts."

Jan 1, 1996

By George A. Calboreanu

In order to overcome drilling and tapping of high hardness wear resistent material in slurry pumps, most of time mild steel inserts are mounted in the mold and after pouring they become an integrated part of the casting. This process is limiting the size and design possibilities of slurry pumps and efforts were made to drill and tap the hard iron itself. The paper will present practical results obtained in drilling and tapping Cr-Mo wear resistent material with hardness in excess of 700 HBN. The life time of the slurry pump parts used in hazardous waste fuel transportation with high slurry velocity and 15% solid loading some of it being quartz, increased 2.5 to 6 times.

Jan 1, 1996

By L. L. Tavlarides, N. V. Deorkar

"Recovery/Recycling of metal ions from industrial process waste streams is a preferred alternative to disposal by conventional techniques. This paper presents methods for preparation of inorganic chemically active adsorbents to be used in fixed bed adsorbers. Methods for immobilization of chelating agents on the inorganic supports are discussed. The prepared adsorbents are characterized to determine coverage density of functional groups, effect of pH on metal ion removal efficiency, regeneration efficiency and uptake capacity. Results from the laboratory scale and bench scale experiments are presented here.IntroductionRemoval of heavy metal ions from processing wastes in various industries is an important problem. Waste streams in electroplating, electronic, catalyst preparation and hydrometallurgical industries contain metal ions such as copper, nickel, chromium, lead, tin, cadmium, silver, gold and platinum. One major concern for the non-ferrous metal industry is secondary recovery of precious metals and cyanide from cyanide leachate from smelter residue and hydrometallurgical waste streams.Recovery methods recently considered include evaporation, electrolyte metal recovery, reverse osmosis (1), adsorption, ion exchange (2,3), membrane separation (4,5) and Solvent extraction. These processes have met with various levels of limited success. The use of liquid ion exchange molecules to selectively extract metal ions for on-site treatment of these waste streams is currently receiving substantial interest (6,7). This interest seems from an awareness of the advances made in the development of commercial extractants for metal ion separation in hydrometallurgical industries (8). However, separation by solvent extraction processes is generally considered to be economical in the range of aqueous metal ion concentrations from 0.01 to 1.0 mol/lit (9). In order to exploit the selectivity of chelating agents, the idea of immobilizing chelating agent into a solid matrix has attracted growing attention in recent years. Many supports such as inorganic oxides, organic polymers, cellulose powder and polyurethane foam can be used for immobilization of chelating agents. Over the last decade, considerable efforts have been directed toward attachment/introduction of chelating agents into a polymer matrix (10,11). Inorganic supports as compared to polymer supports provide high mechanical strength, chemical and thermal stability, and high reaction rates due to open pore structure. On the contrary, organic resins shrink and swell, thus affecting mass transfer (12). Many of the disadvantages of polymer supports can be excluded by the use of inorganic supports. Innovative use of immobilization techniques can produce inorganic chemically active adsorbents with comparable capacity, stability and reaction rates. Consequently, the objective of our program is the development of inorganic chemically active adsorbents to be used in a fixed-bed unit operation as an alternative heavy metal ion recovery process. Methods of preparation of inorganic chemically active adsorbents, (ICAAs) characterization and applications are discussed in this paper. A brief summary of the results from laboratory scale studies and bench scale studies is presented."

Jan 1, 1996

By Cecil Harriss

Philip Environmental Services Corporation's (Philip's) innovative fluidized bed thermal desorption system recovers mercury from contaminated soil. Referred to as the Thermal Recycling System, Philip has constructed a mobile thermal desorption system that has a processing rate up to five tons per hour. The system includes a continuous-feed system, all radiant heat, inert gas atmosphere, hot gas filter, two-stage cooling, and a water treatment system. Based on treatability studies, the processed soil can meet cleanup objectives as low as two milligrams per kilogram and passes the mercury toxicity characteristic leaching procedure test.

Jan 1, 1996

By Timothy W. Ellis

"This paper presents the basic theory of operation, physical chemistry and phase equilibria which allow the development of liquid-liquid extraction circuits based on metallic solvents. The incorporation of reduction and reduction/diffusion processes into the process scheme is discussed and a detailed description of several liquid-liquid extraction schemes are developed. A synopsis of experimental results obtained using this method to separate rare earth and other metal based materials will be given.IntroductionConcerns over the effects of waste materials in the environment has been one of the significant social hallmarks of the late 20th century. Essentially every industrialized country has had to incorporate the cost of waste material into the equation of production. Legislative initiatives have led to the passing of very tough laws, by historical standards, which govern the environmental impact of materials processing.Liquid-Liquid extraction is a very common unit operation normally using aqueous and/or organic based solvents. Early work at the Ames Laboratory focused on the use of this technique for the reprocessing of spent fuel from liquid metal breeder reactors by the use of metallic solvents. Recently, we have revisited this area as a means to recycle/reprocess several emerging rare earth based materials, although this method has a much wider range of application. The reinvestigation of this technology is particularly timely as hydrometallurgical based processes are coming under increasing scrutiny in the U.S.A. by the Environmental Protection Agency (EPA). Although technology currently exists to remove contaminants from aqueous based waste streams, often the application of such methods is expensive. With proper design and judicious selection of reagents liquid metal extraction can achieve a high recovery along with a benign waste stream.This process has several possible advantages over other technologies. First is the elimination of aqueous solvents. Therefore, problems associated with disposal or reprocessing of the aqueous carrier are eliminated. Second, with proper system design, very high separation coefficients can be obtained thus limiting the number of stages required. Third, metals are extracted from metals with a metallic product, thereby eliminating the need to re-reduce metal for oxides or other compounds which are the common output for aqueous based extraction procedures."

Jan 1, 1996

By Guo Xian Jian

In this paper, an alternative process to recover the value metals from polymetallic gold ore by FeCh leaching was proposed. In the process, gold was recovered by direct cyanidation from the leaching residue, the isolative electrolyte in chloride solution was selected to recover lead, the cementation with copper powder was used to recover silver and the solvent extracting was applied to recover copper and zinc. The total recovery of gold, lead, copper, silver and zinc in the process is 90.8%,96.05%,84.3%,81.98% and 54% to the bullion of gold, lead and silver and sulfate of copper and zinc, respectively. The process conditions selected for FeCh leaching are the temperature of 104°C, leaching time of 6 hours, Fe3+ content of 140 g/l and stoichiometry of FeCl3.

Jan 1, 1996

By J. K. Brimacombe

"Nearly all the easy things have been investigated in injection metallurgy. Water models have been used exhaustively to study mixing, gas distribution and flow in submerged jets. Mathematical models have been developed with their restrictive boundary conditions to quantify submerged gas jet behavior. While being valuable tools to our understanding of injection metallurgy, there is an obliqueness to their application. What we need now are measurements and modelling on the actual systems, hot and unfriendly, where gas meets liquid at temperatures above l000°C. This is where the challenge lies.AN APPRECIATONThere are those who follow the trail and there are those few who blaze new trails in search of novel concepts and processes. With his restless, inventive mind, Howard Womer is a trail blazer without doubt. Decades ago, he was a pioneer in the pursuit of continuous steelmaking with the WORCRA Process and, today, he is developing new processes for the treatment of waste. He is not only an inventor but has been a professor at the University of Melbourne and was the first Director of Research at BHP. He has influenced the lives of many people, including myself; with his achievements and humanity. Therefore it is most fitting that this symposium should be held in honour of Howard Womer, a luminary in the metallurgical world for over half a century.BACKGROUNDGas injection has been an integral part of pyrometallurgical processes since the early days of Bessemer, then of Pierce and Smith. Today, of course, one cannot imagine pyrometallurgical processes without submerged gas injection to effect reactions for metal extraction and refining, to provide mixing and to inject solids into molten metal, slag or matte. Spurred on by new developments like tonnage oxygen and argon production, the Savard-Lee concentric tuyere and porous plugs, new steelmaking processes have emerged; and now solids injection is changing copper extraction processes. The ingenuity of the extractive metallurgists who drove these developments is inspiring for they have applied gas injection to transform pyrometallurgical processes. Humankind has been the beneficiary.' Today these processes are safer, more efficient, cost effective, less energy intensive and more environmentally friendly."

Jan 1, 1996

By S. R. Reddy, 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.1 IntroductionIn most of the pyrometallurgical high temperatures processes, interactions of solutes such as oxygen, nitrogen and sulfur, with the solvent atoms are most important during refining processes. There are numerous theories are developed [1-25] to interpret the thermodynamics of solutes in multicomponent alloy systems. Which are mainly developed using statistical or Quasichemical equations.Wagner [4] developed one energy parameter ideal solvent model based on activity coefficient of solutes compositional dependency. He used one energy interaction term which is not able to account for interaction energy parameters for the same solute concentration at different solvent compositions and also it is ineffective model to predict for strong interacting systems."

Jan 1, 1996

By R. C. Hubli

Copper (II) chloride has proven to be an efficient lixiviant for copper sulphide ores and secondary sources of copper such as scrap. Nickel sulphides are generally associated with copper ores and copper-nickel matte is an intermediate product of processing mixed sulphides. While the copper species in aqueous chloride media are present as chlorocomplexes, the presence of nickel as Ni++ offers effective separation between the two by solvent extraction techniques. Oxidation of millerite by cupric chloride in sodium chloride solutions has been studied as a function of rate of agitation, leaching time, temperature, acid concentration and total initial cupric concentration. The reaction has a 1/2 order of dependence on initial cupric concentration in the range of 0.0 to 0.5M. The activation energy for the temperature range 333 -363 K has been found to be 59.2 kJ/mol with chemical reaction at the unreacted mineral surface as the rate controlling step. The rate expression, according to the shrinking-core model, for initial cupric concentrations between 0.0 to O.5M, is evaluated as

Jan 1, 1996

By Gordon A. Irons

"Powder injection for melt refining is widely practiced in the steel industry, and is gaining acceptance in the non-ferrous industries. In these commercially-important systems, the thermodynamics and kinetics may be very complicated. More than one element may be removed by refining, and often the refining agents are not just one compound. In this paper, the thermodynamic and kinetic aspects of these processes are reviewed. A number of examples are given, such as the desulphurization of iron with a variety of reagent mixtures, and selenium removal from copper with several different reagent combinations.IntroductionI am very pleased and honored to present a paper at this Symposium recognizing the many contributions of Professor Howard Womer. Even at the time I was an undergraduate student, the WORCRA process was part of the curriculum. I remember at the time that I was fascinated by the concept, and due to it and the many other rapid developments in Process Metallurgy, I chose it as my field of study. I think the Symposium is testimony that Professor Womer has touched the lives of many others as well.My original assignment was an overview of the basic aspects of gas and solids injection. However, I reviewed most of this material at the Savard/Lee Symposium [1]. In the present paper, I will present some of the basic issues related to refining with powder injection, using work that we have recently completed in both ferrous and non-ferrous systems."

Jan 1, 1996

By Baozhong Zhao

Experimental results have shown that fluxing with soda ash (Na:zC03) can remove As and Sb from molten copper at the rate of As>Sb, but is relatively ineffective in removing Hi. The rate of impurity removal is controlled by impurity mass transfer in the metal phase. In this paper, a mathematical model was developed to describe the impurity removal phenomena. The model incorporates the effects of molten bath mixing intensity, soda ash feeding rate, oxygen content in the molten copper and soda ash fluxing by surface addition and injection. The model predictions are in good agreement with experimental results and may be used in designing large scale tests.

Jan 1, 1996

By Mark Kramer

This paper is limited to treatment of bottom and fly ash waste resulting from WTE and RTE Cogeneration plants, commonly known as trash burners. The body of the paper defines waste generation and conventional treatment schemes. This paper does not identify a best treatment, however, it does offer a general perspective of the treatments to lead the reader to further investigation. Advantages and disadvantages of the ash treatments Is discussed in each treatment section.

Jan 1, 1996

By P. Thapliyal

The petroleum refining industry generates over a million tons of spent catalyst per year, containing valuable metals. Currently, these materials are recycled to smelting furnaces, but the fundamental mechanisms controlling the recovery processes are poorly understood. Furthermore, submerged injection of finely divided materials is potentially a means to obtain high recoveries of pay metals. In this study, a catalyst containing 10% Ni and 1% Co was injected into 45 kg heats of matte. A copper matte was chosen so that the nickel and cobalt recoveries were measurable. It was found that the recovery ranged from 40 to 700Al, increasing with catalyst feed rate, decreasing with catalyst particle size and decreasing with the oxygen content of the carrier gas. A mathematical model was developed to account for the results, and to permit extrapolation to nickel mattes. The industrial implications are discussed.

Jan 1, 1996

By Ikuhiro Sumi

A new steelmaking process, in which manganese ore was intentionally reduced, was developed to achieve a higher manganese Yield using a combined blowing converter. In this study, manganese behavior was discussed through the introduction of a model. Apparent reduction rates of manganese were calculated by the two terms that were determined experimentally, with SOkg and 2S0ton combined blowing converters. The model calculated manganese changes during the operation. We applied the model to the actual operation and found that manganese behavior was predicted fairly well by this model.

Jan 1, 1996