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By Kosei Morita, Osamu Nakano, Katsuhiko Nagai, Kazuhiro Mori

"The Sumitomo Toyo Smelter and Refinery commenced its operation in 1971 with three Peirce- Smith (PS) converters. “2 hot – 1 blowing” operation was practiced, that is one of two available converters was blowing and the other was standby in a hot state while the third converter was under repair. After several improvements, the stack time ratio reached around 90%; and processing 5 batches a day became possible.As a result of the expansion program of the Toyo smelter and refinery that started in 2001, the converter operation pattern was shifted from “2 hot – 1 blowing” to “2 hot – 2 blowing” with the installation of second converter blowers and an additional ladle crane.In 2005 a, the fourth converter was installed and “3 hot – 2 blowing” operation began. Also, with improvements experienced in the anode furnaces and the anode-casting wheel operation, today, the number of cycles has been increased up to more than 8.5 a day.The treatment techniques of fugitive gas containing sulfur dioxide from converter furnaces have been gradually reinforced, and the fixation rate of treated sulfur is currently being maintained at more than 99.9%. This paper introduces the operations described above, and the improvements in environmental management techniques for the Toyo PS converter operation."

Jan 1, 2009

By David K. Melgaard

Electroslag Remelting (ESR) is a complex process used to produce high quality specialty alloy materials. The quality can be directly correlated to variances in melt rate and immersion depth. Conventional ESR furnaces control these quantities using two independent control loops using proportional changes in current for melt rate and driving the electrode up and down to match a voltage set point for immersion depth. However it is well known that the control loops are highly coupled, i.e. changing the current to account for melt rate deviations changes the voltage depth relationship and vice verse. In addition the noise in measurements of the ESR process can be considerable, forcing conventional controllers to use highly damped responses. A new model-based controller has been developed to embody the coupling and improve responsiveness by using estimates from a reduced-order linear ESR model and the typical process measurements to control melt rate and immersion depth simultaneously. Kalman filtering is used to optimally combine the model estimates of eight process states and the measurements of voltage, current, position and mass to estimate the instantaneous melt rate and immersion depth. Several ESR melts under steady state and transient conditions were conducted to evaluate the performance of the new controller. This paper will discuss the design of the new ESR model and controller and will present experimental results demonstrating its much improved control and responsiveness. While this controller was developed for the ESR process, the effectiveness of model-based control in managing such a complex process with relatively simple equations suggests the approach could be employed for many other processes as well.

Jan 1, 2006

By R. G. Reddy

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

Jan 1, 1996

By S. 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 Xuyang Liu, Xuewei Lv, Yu Zhang, Xiaolong Wu, Chunxin Li

Titanium nitride is a broad-spectrum specific functional material because of its many superior properties. Therefore, it is necessary to investigate synthesis methods of TiN and alloys containing TiN reinforcement. In the current study, with the increase of nitrogen gas pressure and the optimization of routine ball milling parameters, the conventional mechanical ball-milling method can be improved, the nanometers TiH2-TiN composite powder can be synthesized successfully in a shorter time. Nitrogen gas filled in ball mill jar in which the pressure was 0.6 MPa. TiH2 powder was milled under nitrogen atmosphere at a spinning rate of 250 rpm. The results show that the stable TiN is formed after grinding for 2.5 h according to the X-ray diffraction pattern. DSC (differential scanning calorimetry) curves also indicate that milled compound powder adsorbs certain nitrogen gas. The gas adsorbed in TiH2-TiN composite can exist stably below 200 °C.

Mar 1, 2017

The direct removal of lead ions from D2EHPA-kerosene using metallic zinc as the reducing agent was evaluated. The electrochemical process, called galvanic stripping, is a potential alternative stripping technique when standard chemical methods are not adequate. Four parameters found to be important in the rate of lead removal were studied in a factorially designed experiment. The variable evaluated included D2EHPA concentration, temperature, zinc surface area and solution agitation. Temperature and surface area were found to be the most significant, while agitation and D2EHPA concentration had less influence on the reaction. An activation energy of 22.5 Kcal/mole was calculated indicating a chemically-controlled process. The reaction was also sensitive to the concentration of oxygen in the system. The zinc required was considerably in excess of stoichiometry, possibly due to the dissolution and redeposition of lead: In general, the results were encouraging and demonstrated that lead impurities could be removed from D2EHPA using cementation type reactions.

Jan 1, 1995

By W. Dutton, D. Simms

"The clearing of tuyeres on copper and nickel converters or similar metallurgical, vessels has, for many years, been done using mainly a manually- operated ""puncher"". One such device is the ""Gaspe Puncher"" developed in 1962 at Noranda's Gaspe Smelter. In an attempt to remove the operator from the cab of the Puncher, and to relieve him of a tedious, uncomfortable job, Noranda's Horne Division, in cooperation with Heath & Sherwood (1964) Limited and the Noranda Research Centre, undertook to automate the Gaspe Puncher used on the Noranda Continuous Smelting Process Reactor.The automated puncher is controlled by a Texas Instruments Model 530C Programmable Controller (PLC). Position measurement and control is done using non-contact position measuring equipment from the Tele-Controls Division of Geodimeter Inc. The entire automation system was installed on an existing Gaspe Puncher with minimum disruption to the operation of the smelting process. The operator's panel allows the user to ""block out"" any individual tuyere, and to select any of a variety of operating modes.The development of the automated puncher is described, and the results of several months operation are given.IntroductionThe tuyeres of copper and nickel converters and similar metallurgical vessels become blocked with solidified material formed by the cooling action of the blowing air. This restricts the converting operation. Clearing these blocked tuyeres has for many years been done mainly using a manually-operated ""puncher"" which uses a hydraulic or pneumatically-operated piston to drive a steel bar into the tuyere. The Gaspe Puncher, developed at Noranda's Gaspe Smelter in 1962 is one such device. It is currently being built and sold by Heath & Sherwood (1964) Limited, under license to Noranda. There are over 200 units in operation world-wide.In an attempt to remove the Puncher operator from the cab of the Puncher, and to relieve him of a tedious, uncomfortable job, and to increase productivity, Noranda's Horne Division, in cooperation with Heath & Sherwood (1964) Limited and the Noranda Research Centre, undertook to automate the Gaspe Puncher used on the Noranda Continuous Smelting Process Reactor. This paper describes the development of the automated Gaspe Puncher, its installation at the Horne Smelter, and the results of its operation after several months."

Jan 1, 1989

By S. K. Shaha, A. Gryguc, S. B. Behravesh, B. Williams, M. Wells, H. Jahed

Warm forging to near final product geometry shows promising benefits in terms of microstructure refinement and texture modification. In the present study, Semi-closed die forging was performed on extruded AZ80 magnesium alloy at a forging temperature of 400 °C and various forging ram speeds. Compression tests were performed to investigate the influence of forging at various deformation rates on the performance of extruded AZ80 magnesium alloy. The microstructural analysis showed that the extruded AZ80 possesses a grain structure typical in wrought magnesium alloys, with sharp basal texture. In contrast, the forged samples had a recrystallized microstructures and a spatially varying textures and crystal orientations resulting from the complex flow behaviour within the closed die forging. Furthermore, once forged, a significant increase in the material isotropy, homogeneity as well as failure elongation were observed. An increase in UCS of 9% was observed in the forging direction, while the UCS in the extrusion direction was similar to that before forging. The changes in UCS can be attributed to both the refined grain microstructure and crystal reorientation. Successful microstructure recrystallization occurs for strain rates which traverse several orders of magnitude, and in general, UCS isotropy increases with increasing strain rate. It is believed that forging cause’s grain refinement and texture modification which act to enhance the mechanical performance (UCS, fracture strain and superficial hardness) for the forging conditions investigated in this study.

Mar 1, 2017

By Patrick R. Taylor

The synthesis of high-purity ultra-fine barium strontium titanate powders (BST: BaO6Sro.4TiO3) has been performed in a non-transferred are D.C. thermal plasma reactor. Slurries of aqueous solutions of dissolved barium and strontium nitrates and solid titanium dioxide powders were used as precursors. Oxygen and argon were used as carrier gases, and pure argon and combinations of argon and nitrogen were used as plasma gases. The plasma torch power was varied, as well as the oxygen flow rate and the total molar concentration of the precursors. A graphite plate was designed to protect the torch electrode and lower the level of impurities in the product. A thermochemical analysis of the Ba(NO3)2-Sr(NO3)2-TiO2-H2O-O2 system was performed to predict the conditions for the formation of BST and the feasibility of the reaction, The powders collected from the different sections of the reactor were characterized using Transmission and Scanning Electron Microscopy, X-Ray Diffraction, and ICP chemical analysis. The powders produced showed high conversion to BST, ultra-fine particle size (< 30 rim) and high purity, which makes this a potential process to produce ceramic materials for electronic devices.

Jan 1, 2003

By Steven Wright

The extent and the rate of reduction of slags produced from the smelting of recycled lead batteries were investigated under laboratory conditions using graphite as reductant. Simultaneous reduction of PbO, Fe2O3, Sb2O3 and As2O3 occurred at temperatures of 1180 and 1200°C, with Sb and As reporting to the metal phase while the PbO content of the slag was above 2 wt%. Fuming of As from the metal occurred at lower concentrations of lead in the slag. Discard slags with low levels of As, Pb and Sb were produced. Arsenic levels were reduced to less than accurately measurable by ICP analysis, and Sb levels in the final slags were in the range of 0.1 to 0.2 wt%. The kinetic data obtained were analysed and compared with other measurements on lead oxide containing slags. The results showing a dependence of the reduction rate on the oxidation state and the basicity are consistent with other studies on well characterised industrial and. synthetic lead slags. These results indicate that when carbonaceous reductants are used, the rate of interfacial reactions play an important role in enabling the production of environmentally acceptable discard slags.

Jan 1, 1994

By Wen-Ming Chien, Vamsi Krishna Kamisetty, Amrita Mishra, Ivan Gantan, Prathyusha Mekala, Dhanesh Chandra

"The phase equilibrium and characterization studies by using high temperature X-ray diffraction (XRD) and differential scanning calorimetric (DSC) methods have been performed for binary organic thermal energy storage materials. The organic thermal energy storage materials undergo a solid-solid state phase transition before melting which stores large amounts of thermal energy. Two materials [tris(hydroxymethyl)aminomethane(TRIS) and 2-Amino-2-methyl-l, 3- propanediol(AMPL)] were used for this study. Binary samples of AMPL-TRIS were prepared to perform high temperature XRD characterization and DSC studies and the binary AMPL-TRIS phase diagram was developed. The high temperature solid-state phases of AMPL and TRIS were characterized as a disordered BCC structure. It was found there is virtually no solubility of TRIS in AMPL or vice versa below -75 °C. The maximum solubility of TRIS in AMPL is 11% TRIS at 75 °C. The eutectoid transformation was shown at 19%TRIS-81%AMPL composition and at a temperature of 75°C. Lattice expansion calculations on single phase of TRIS and AMPL have been performed.IntroductionThermal energy storage materials can store a large amount of heat due to the presence of thermal transitions from the orientationally ordered to disordered phases occurring before melting. These molecules (such as amine and alcohol derivatives of neopentane) can reorient as a whole about the central carbon atom to form orientationally disordered crystals (ODIC) and their spherical shape makes them reorient relatively easier. Thermal energy storage materials are becoming increasingly important as a renewable energy resource. These molecules undergo large changes in enthalpies at solid-solid transitions. The presence of these compounds with large enthalpy changes are identified as potential thermal energy materials and some of die applications are solar cell systems [1-3]. Binary mixtures have been found as a way to adjust the transition properties in addition to pure compounds [4]. Tris(hydroxyrnethyl)aminomethane (TRIS, C(CH2OH)3NH2) and AMPL, CH3C(CH2OH)2NH2) are two important thermal energy storage materials."

Jan 1, 2012

By Caisa Samuelsson, Sina Mostaghel, Theo Lehner

"Rönnskär smelter of Boliden Mineral AB, Sweden, is well known for recycling of base and precious metals. Slag from the electrical furnace is processed at the fuming plant to produce zinc clinker. The granulated slag is a by-product used as e.g. construction material. In this paper, influences of Al2O3 on mineralogy of the slag, which can affect its chemical and physical properties, are investigated. Different mixtures of Al2O3/fumed slag were prepared. Re-melting was carried out in a Thermo-Gravimetry (TG) furnace with an inert atmosphere. Scanning electron microscopy (SEM) and X-ray diffractometer (XRD) were then applied for the analyses. Investigations depict that addition of alumina to slag, results in an increase in the number of spinels and a transformation from iron rich to aluminum rich spinels. Anorthite (CaAl2Si2O8) will also be formed.IntroductionRönnskär smelter of Boliden Mineral AB is located in north of Sweden; the main products of this smelter are: Copper, Zinc clinker, Lead, Gold, and Silver, while sulphuric acid, liquid sulphuric dioxide, and Iron sand are some of the by-products. Reducing the energy consumption and decreasing the usage of finite natural resources are becoming more and more important for the Rönnskär smelter; this result in use of different recycling and scrap materials. Metal residues, from brass foundries, steel mills, and electronic scrap are recycled at Rönnskär smelter [1]. Most of the electronic scraps contain mixtures of various metals together with plastics and ceramics, which can affect the composition and properties of the slag considerably [2]. At the same time, treatment of slag and controlling its composition and properties are of much interest for Base Metals producers from different aspects. Composition of slag influences the physical properties such as: 1) Liquidus temperature [3-4] 2) Viscosity, which controls separation of valuable metals, especially copper by gravity separation [2] and also heat and mass transfer [5] 3) Electrical conductivity [6]."

Jan 1, 2008

By Zhang Libo, Wang Xin, Peng Jin-hui, Ju Shaohua, Guo Sheng-hui, Xu Lei, Huang Meng-yang

"China is lacking high grade titanium ores. This work intends to leach impurities such as Fe, Ca and Mg from a low grade titanium ore, to increase the grade. The original material contained 65% TiO2 , 16.12% Fe, 9.4% CaO + MgO, 4.2% SiO2, 1.25% A12O3, and the particle size is between 0.053-0.045mm. Microwave energy was used to enhance the leaching effect. The results showed that when normal heating was used to leach the mineral, the extraction of impurities Fe, Ca and Mg was very low. However, when microwave energy is introduced, the extraction of Fe, Ca and Mg increased dramatically. The optimized conditions are: relative power 5W/g, the ratio of concentrate to HC1 isl5%, leaching at 160°C for 20 min with a ratio of liquid to solid 12:1 mL/g. The material obtained under these conditions contains 92.73% TiO2, 0.207% Ca + Mg, 0.8% Fe, with 94.6% Ti recovery. The poduct meets with the quality for boiling chlorine.IntroductionThe resources of titanium are very abundant, and are distributed all over the world. There are almost 140 minerals containing TiO2 with a content of more than 1%. However, there are only several minerals which can be used for producing sponge titanium. They are mainly rutile and ilmenite. The grade of nature rutile concentrates is higher than 95% TiO2, and it is a high quality raw material. But the resources of nature rutile are relatively low; after mining for many years, its resources are exhausting gradually. Although ilmenite reserves are great, ilmenite cannot be used as a raw material because of its low content of TiO2, only 45-70%; also it has a high impurity content of Ca, Mg and Fe. In these years, there is a tendency for titanium industry to use high grade concentrate."

Jan 1, 2012

By S. Seetharaman

The present paper presents. the concept of micro-models and illustrates the application of the same in the simulations metallurgical processes. Development of micromodels requires access to accurate thermodynamic, thermophysicaland kinetic information for the relevant systems with suitable models to extrapolate the data as functions of temperature and composition. Experimental measurements and modelling of the thermodynamic properties, sulphide capacities and viscosities of oxide melts carried out in the department are presented. The incorporation of these models in process models, with special reference to ladle refining of steel is illustrated. Typical example of micro-modelling of solid-gas reactions is also presented.

Jan 1, 1999

By Giuseppe Bonifazi

Minerographic and petrochemical research was carried out on crude ore samples from the complex polymetallic Zn-Cu-Pb sulfide ores of , Sotiel in Huelva province west of Seville, Spain. A computerized image analysis system was used to define the structural and textural characteristics of the ore to obtain information on the degree of liberation of the different minerals (i.e. pyrite, sphalerite, galena, chalcopyrite). Techniques of digital multispectral image processing of reflected light microscopy images were used. Particular structures were identified by means of mineral associations and numerically quantified to obtain useful information for designing beneficiation processes.

Jan 1, 1991

"Recycling of solid wastes plays an important role in environmental protection. However, solid wastes are often contaminated with some undesired components so that many of these solid wastes are hardly economically recycled. Therefore, effective and efficient separation of undesired components from solid wastes becomes a crucial step for sustainable recycling of the solid wastes. There exist three general strategies of separation of undesired components from solid wastes: before-process separation, post-process separation and in-process separation. In this paper, different separation strategies are discussed in terms of energy requirement and availability, implementation complexity and additional need for environmental protection. It is concluded that of all separation strategies, in-process separation has the least energy requirement, the least implementation complexity and the minimum need for additional environmental protection.IntroductionIn industries, solid wastes almost come with every production process. Multi-million tons, if not billion tons, of solid wastes are being generated globally each year. These solid wastes are lowvalue materials in general, and often have very limited markets. As a matter of fact, many of these solid wastes have been stored on site or have been disposed of at landfills for many years, not only occupying lands, but also polluting environment. Therefore, effective and efficient recycling of solid wastes has been a very challengeable task and has played a very important role in environmental protection.One of the major barriers which hinder recycling of solid wastes is contamination of the solid wastes with some undesired components. These undesired components are components which are not wanted by production processes or applications where the solid wastes are consumed or recycled, since the undesired components often degrade qualities of the solid wastes, imposing negative effects on operations, facilities and product qualities of the production processes or applications. Sometimes, the undesired components may also pose severe environmental concerns. When undesired components are present in solid wastes at over-limit levels, the solid wastes tum to become destructive, useless and non-recyclable. Consequently, effective and efficient separation of undesired components from solid wastes becomes a crucial step for sustainable recycling of the solid wastes."

Jan 1, 2014

By E. Yegan Erdem, Fiona M. Doyle, Alyssa A. Maich

"There is an expanding interest in synthesizing high quality magnetic nanoparticles, most notably for biomedical applications. Different processing routes have been reported for the synthesis of magnetite and maghemite. However, some ambiguity remains on their precise chemistry, intermediates, and final products, due to the structural similarity of maghemite and magnetite, and the relative ease of redox transitions during synthesis. Here we present the results of TEM, x-ray and electron diffraction, and SQUID studies aimed at characterizing the products from two different reaction systems, thereby clarifying the reaction chemistry. The first system hydrolyzed aqueous FeCh and FeCb chlorides with ammonia in a micro fluidic reactor at ambient temperature; although the reaction product displayed a uniform distribution, it included non-magnetic goethite and lepidocrocite. If the aqueous solutions contained dissolved oxygen, there appeared to be extensive oxidation of Fe(II). The second system thermally decomposed iron (III) acetylacetonate in ether. In prior studies, oleylamine has been reported to serve as both a reducing agent and capping ligand to control particle characteristics; however, our studies revealed little reduction, with maghemite dominating the reaction products.IntroductionMagnetite and maghemite nanoparticles are co=only used in ferrofluids, in medical applications, and in drug delivery. Superparamagnetic properties, along with low cytotoxicity, colloid stability and bioactive molecule conjugation capability, make these nanomagnets ideal for both in-vitro and in-vivo biomedical applications [1]. One of the major constraints on widespread adoption of nanoparticles for these applications is the amount needed. Typical batch synthesis methods produce polydispersed nanoparticles, which require further size selection procedures to isolate the mono disperse nanoparticle population needed for many applications. In order to maximize the yield of usable particles from a synthesis operation, the reaction conditions must be closely controlled. This requires full knowledge of how the reaction conditions control the various aspects of nanoparticle growth. Many methods have been used to synthesize iron oxides, including sonochemical reactions, mechanochemical synthesis, hydrolysis and thermal decomposition. This work examines the latter two methods, focusing on oxidation and reduction of iron."

Jan 1, 2012

By Bingchen Chen, Zhitong Sui, Junwei Ma

"In the blast furnace slag, titanium disseminated in various mineral phases Titanium could be concentrated mainly in perovskite, which could be selectively precipitated and grown by optimizing the operation factors like the slag composition, temperature of heat treatment and additive agents. This study aims at establishing the titanium slag mineralogy and its distribution in the treated slag and the as-received slag, as well as the methods of perovskite separation. After heat treatment, the grain size was grown from 5 - 20µm to 80 - 200µm, the distribution of Ti02 in perovskite was increased from 48% to 81 %, the morphology was changed from snow-shaped grain to coarsening dendrites or equiaxed crystals. A concentrate were produced by gravity separation analyzing 35.25% Ti02 with a recovery of 68.28% and a tailing analyzing 9.53% Ti02 , and a possibility of flotation upgrading was discussed. I INTRODUCTION CHINA is rich in mineral resources of titanium, 92.4% of which is vanadium-titanium bearing magnetite. About 53% titanium were in iron concentrate after mineral processing, by which the blast furnace slag containing about 25% TiO2 were produced[11 • The content of TiO2 in such slag is too low to separate titanium dioxide, and it is also too high to produce slag cement[21. It has been accumulated to 50 million tons so far, which is still increasing at a rate of 3 million tons per year, and results in a waste of titanium resources and pollution of environment. Due to the dispersed distribution of titanium component in various mineral phases, very fine grain(<10µm) and complex interfacial combination, it is very difficult to recovery titanium component from the slag by traditional separating technique. In this paper, a novel technique to recovery titanium from the waste slags was proposed [3H4l, on which three continuous processes were involved: selective concentrating, selective growing and selective separating. Perovskite was designed as a titanium-rich phase, in which the most titanium was concentrated promptly, then perovskite could be selectively grown and coarsened by optimizing the heat treatment and the appropriate additives [ 5l[6l. The grain size of perovskite phase was larger than 80 µm, and the crystals appeared as coarsening dendrites or equiaxial grains like lump."

Jan 1, 2000

By Dexter G. Mendoza

To analyze the behavior of minor elements in the copper smelting process, the phase relations and the activities of arsenic and antimony in the miscibility gap of Cu-Fe-S-X (X = As or Sb) system have been determined at 1473K by the quenching method and the double Knudsen cell- mass spectrometric method, respectively. The experiments have been conducted for the charges in the miscibility gap with different mass%Fe/mass%Cu ratios with varying arsenic or antimony content. The activity measurements indicate that the arsenic activities in both the metal and matte phases show extremely negative deviation from the ideal behavior. The Raoultian activity coefficients at infinite dilution in the metal and matte phases are found to be almost constant against the charges in the miscibility gap, and they are 4.3 x 10-3 and 5.5 x 10-2 for the metal and matte phases, respectively. Moreover, the activity measurements of antimony show an activity value larger than that of arsenic but it still deviates negatively from Raoult&apos;s law. The activity coefficients of antimony at infinite dilution are found to be 1.2 x and 2.2 x 10-1 for the metal and matte phases, respectively. The vapor pressures of the predominant As, AS2, AsS, Sb, Sb2, and SbS species in the gas phases of arsenic and antimony, respectively, equilibrated with the immiscible solutions have been calculated on the basis of the determined activity coefficients and they are very small at less than 1 Pa, even when their contents in the metal phase are increased up to 10 mass%.

Jan 1, 2002

By Mark C. Bronson

The feasibility of several pyrochemical approaches-for separating non-radioactive constituents from ICPP HLW calcine were examined. The removal of aluminum as AICI3 from aluminia calcine was successfully demonstrated. The examination of pyrochemical processes to remove non-radioactive constituents, primarily aluminium, zirconium, calcium and fluorine, from zirconia calcine showed that fluorine removal was required in order to chlorinate the calcine. A molten calcium chloride wash, a calcium reduction, and. a sulfuric acid treatment were examined as possible zirconia calcine pretreatment options for fluorine removal. Fluorine removal from simulated ICPP zirconia calcine was demonstrated by both a CaCl2 wash method and a sulfuric acid treatment method. X-ray fluorescence analysis indicated that greater than 97% of the fluorine can be removed by either method. Fluorine removal by a calcium reduction using an alloying agent, zinc, or a calcium reduction using, a filtration separation were also demonstrated, but the efficiencies of fluorine removal were considerably less ranging from 50 to 90%. Regeneration of CaCl2 from the salt and oxide residues of the CaCl2 wash experiments was also demonstrated &apos;by an aqueous dissolution method. From the salt residue, 85% or more of the CaCl2 was recovered and contained little if any CaF2 or CaO. From the oxide residue close to 100% of the CaC12 was recovered. Because of the overall success of the CaCI2 wash, it was determined to be the preferred fluorine removal process. The sulfuric acid treatment to remove fluorine is effective, but the proposed overall flowsheet has not&apos; been adequately demonstrated.

Jan 1, 1995