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By D. Gu, R. G. Anthony, C. V. Philip, M. E. Huckman

"In this paper, we review the equations needed to construct an ion exchange column model. These models contain three major components: 1) a differential material balance around the column, 2) a differential material balance around an ion exchange particle, and 3) a constitutive equation for diffusive flux. We then examine the ability of a fairly simple mathematical model to predict ion exchange column experimental data. This model contains the traditional absorption theory equations and is used to predict the behavior of a column filled with a hydrous crystalline silico-titanate and which is removing trace amounts of Cs+ from a high pH, complex electrolyte solution. Finally, we propose replacing Fick's law with the Nemst-Planck equation as the constitutive equation for diffusive flux. We use a NemstPlanck type model to predict batch experimental data, then evaluate it by comparing it's ability to predict experimental data to that of a more traditional Fick's law type model. The data from this comparison suggests that the Nemst-Planck type model yields better results.IntroductionMillions of gallons of strongly basic, radioactive waste are currently stored in underground storage tanks at Hanford and Savannah River and several locations within the United States. Due to the limited life expectancy of the tanks, there is a pressing need to remediate these wastes. This need has prompted the recent development of new ion-exchange materials for removing radioactive elements from aqueous solutions. A novel material called TAM-5 has been developed jointly by Texas A&M University and Sandia National Laboratories. TAM- 5, a crystalline silico-titanate, is highly selective for Cs + in the complex electrolytic solutions typical of these wastes. It is stable in very basic solutions and in radioactive environments [1, 2 ,3]. In laboratory testing to determine the selectivity of various materials, TAM-5 was superior to other candidate ion exchangers [4, 5]. The selectivities were determined by measuring a distribution coefficient, Kd, which is defined as the concentration, gig or mmols/g of Cs in the solid phase divided by the concentration, mg/L or mmols/mL, of Cs in the liquid phase. The units of Kd are ml/g or L/kg. Table 1 shows Kd values for TAM-5 compared to 9 other candidate materials in a typical waste solution [6]."

Jan 1, 1996

By Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450 °C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

By Jan Vrestal, Josef Tomiska, Pavel Broz

"Thermodynamic investigations on fcc solid ternary Fe-Ni-Cr alloys have been performed by means of the computer-aided Knudsen cell mass spectrometry. Ternary T.AP.-series (Thermodynamically adapted power series) are used for the algebraic representation of the thermodynamic excess properties. At 1650 K the molar excess Gibbs energy GE is negative over the whole field of stable fcc phase. The molar heat of mixing HE is exothermic in the predominant part of the fcc phase field. Only between the section with a constant ratio of mole fraction Xcr/XNi = 0.64 and the fcc phase field boundary the HE values are slightly endothermic. The results of this work can be used successfully for phase diagram calculations.IntroductionThermodynamic investigations on multicomponent alloy systems such as the Fe-Ni-Cr ternary system including the three binary boundary systems are very time-wasting and usually beset with considerable experimental difficulties. Additionally, the required experimental equipment is very expansive and the obtained results are not always satistying. Therefore it is understandable that many phase diagram calculations are based only on few experimental values of the molar excess free Gibbs energy GE. Consequently, Kundrat and Elliott [1] as well as Hillert and Qiu [2] used in their reassessments of the phase diagram of the Fe-Ni-Cr system thermodynamic data mainly assumed and/or optimized by means of various reasoning.Lee [3] reported recently, a revision of the used thermodynamic description of the Fe-Ni liquid phase is necessary to obtain a better agreement with the experimental data on the bcc/liquid or fcc/liquid tie lines and liquidus temperatures in the Fe-rich region of the Fe-Ni-Cr ternary system than in the previous assessments. This is 'in full agreement with mass spectrometric investigations of Fe-Ni alloys in the liquid and in the fcc solid phase, published earlier [4,5]. Indeed, phase diagram calculations based upon the molar excess free Gibbs energies GE obtained in these studies yield liquidus and solidus lines in excellent agreement with experimental phase diagram data [5]. Nevertheless, these experimental data have not been considered later on any more, not even in the revision by Lee [3]."

Jan 1, 1996

By Yasuo Ojima

The mainstream of copper smelting processes in the world today is a combination of Outokumpu type Flash smelting and PS (Pierse Smith) converting process. Presently it can be estimated that about 50% of the worldwide copper production is produced by the Flash smelting process and 80% by the PS converting process. PS converting process due to its operational flexibility and despite its batch character of operation has been widely used in many smelters for more than 100 years. However, an environmental issue has been pointed out related to this process because of the difficulty of handling the fugitive gases. Recently several copper smelters in the world have been newly constructed and others have executed major modification and modernization, The continuous converting process has been applied in many of them instead of PS converting process. This paper compares PS to the emerging continuous converting process and makes a prospect of the future of the copper converting process.

Jan 1, 2003

By Esher Hsu

In Taiwan, around 8,000 tons of batteries are consumed per year but only 17% of which were collected and transported to oversea for recovery. The dumping used batteries have become a potential environment problem. How to increase the collection efficiency of used batteries is an important issue for EPA in Taiwan. Besides, some treatment plants are on process to get permission for recovering used batteries. The objective of this study is to estimate the recycling cost of spent consumer battery and explore the feasibility of recovering used consumer batteries in Taiwan based upon the principle of cost-efficiency. The recycling cost including collection cost and recovery is estimated based on a survey. Results would provide some suggestions to Taiwan EPA regarding feasibility of recovering used batteries in Taiwan.

Jan 1, 2006

By Asmo Vartiainen

Background of Direct-to-Blister Flash Smelting is discussed; especially slag chemistry relating to copper solubility, slag fluidity and impurity behavior. In December, 2000, Mini-pilot Flash Smelting test runs were carried out at Outokumpu Research Oy to produce blister copper from Chilean concentrate and white metal and from a mixture of them. Tested slag types were iron silicate slag, ferrous calcium silicate slag and calcium ferrite slag with different slag compositions and different concentrate/white metal ratios. The test runs were successful. The fluxing effect of copper oxide was clearly demonstrated and ferrous calcium silicate slags remained fluid on a very wide liquidus range. The distribution of arsenic between ferrous calcium silicate slag and blister copper is much higher than between iron silicate slag and blister copper. This successful test run with the new slag type offer new possibilities in Direct- to-Blister process design.

Jan 1, 2003

By Ivan Imris

The common problem of new and conventional technology of copper production is the copper losses in the slags, which may be divided into mechanical and physico-chemical losses. In the first group can be included particles of mechanically entrained or floated unsedimented matte particles which coexist with slag. On the other hand, the physico-chemical losses are caused by solubility of copper in the slag in the form of sulphide and oxide. The copper losses in the slags from different processes has been predicted by calculation from thermodynamic data and compared with those determined by microscopic examination and quantitative electron microprobe analysis. Depending on the forms of copper losses in the slag the reduction of copper losses in the slag or the slag cleaning process could be suggested.

Jan 1, 2003

By J. Antrekowitsch

Keywords: residues, fluorides, chlorides, zinc, steel mill dust The recyclability of various nonferrous metal wastes often suffers from a relatively high fluorine and chlorine content. Both are inserted in most cases by the use of plastic contaminated scrap and a wide variety of different coatings. These halogens lead to poor product qualities and off gas contamination. Especially the history of zinc recovery from steel mill dusts shows, that the today common hydrometallurgical options are on their limit and therefore are not sufficient in most cases. This thermochemical study should give more information about different pyrometallurgical options, that offer both a chlorine and fluorine reduction and efficient zinc recovery, preferably in one process step. Selective evaporation in different atmospheres and conversion with the use of hydrogen are the main parts in this study. The results combined with the relatively small information available from literature should provide a basis for further investigations in this field.

Jan 1, 2005

By Keith M. Axler

This report addresses issues specific to the generation of hydrogen fluoride via reaction of calcium fluoride with sulfuric acid. This process has been established on a commercial scale and is under consideration for treatment of calcium fluoride residues from uranium processing. Magnesium fluoride slags are also available as a product of uranium processing. The technique of using sulfuric acid for the production of hydrogen fluoride from magnesium fluoride is also under consideration as a residue processing scheme. In the current study, thermodynamic modeling was used to investigate these chemical processing systems. The results presented herein reveal information relevant to the selection of processing temperatures and conditions. Details include predicted effects in system composition based on operating temperatures for both the calcium fluoride and the magnesium fluoride systems.

Jan 1, 1996

By Elli Nurminen

In this work the thermodynamics of the metallic sulphate decomposition reactions were studied through thermodynamical calculations and thermogravimetric methods. The decomposition temperatures and mechanisms were determined for cupric sulphate, ferric sulphate and also for industrial flue dust from a copper flash smelting process. The aim was to determine the thermodynamic conditions for sulphate decomposition and to estimate whether the reactions are kinetically likely to take place in the flash smelting process heat recovery equipment. The information is essential in CFD-modelling of the reactions taking place in the boiler and for optimising the process.

Jan 1, 2006

By Patricia Martínez Nicolás

Nickel and ferronickel are some of the major components in the production of special alloys; however, the energy consumption for their production greatly increases their price. A cheaper option could be to use NiO and a reducing agent. This work presents experimental and theoretical analysis to estimate the effect of slag basicity and amount of reducing agents on the NiO reduction from the slag which interacted with molten steel at 1600 °C in an EAF. The slag system contained CaO, SiO2, CaF2 and NiO together with a reducing agent, ferrosilicon or carbon. The NiO content in the slag was 25 mass%. The amounts of the reducing agents (Si and C) were 1 to 4 times the stoichiometric mass to reduce NiO. The CaO/SiO2 ratio was 1.5 and 2.5. The kinetics of the process was very fast since after few minutes the maximum nickel yield was obtained. The slag basicity had a negligible effect on the reduction of NiO.

Jan 1, 2006

By Taiping Lou

The effects of slag composition, additive agents, and heat treatment conditions on the perovskite (CaO ? TiO2) crystal morphology, the precipitation behavior, the crystal growth and the volume fraction (VF) in the Ti-bearing blast furnace slags were investigated. The morphology of perovskite is dispersed dendriform in molten slags. The crystal growth mechanism of the remelting of fine dendrites and the coarsening of larger grains exists throughout the solidification of molten slags. With the temperature decrease, the VF was increased and Perovskite transformed from fine dendrites to coarsening ones or equiaxed grains. The lower cooling rate can increase the VF and coarsen the grain obviously, while higher cooling rate will decrease the VF and reduce the average equivalent diameter (AED) of Perovskite. When .increasing the content of CaO and Fe20}, the VF can increase obviosly. However, high basicity will give rise to the increasing of viscosity of slag, which result in the reducing of the AED. The experimental results showed that additive CaF2 and MnO can efficiently decreased the viscosity of the slags, and obviously improved the morphology of perovskite and promote growth.

Jan 1, 2000

By Nam-Il Um

Bottom ash contains several ferrous materials (ferrous metals, Fe3O4, Fe2O3, FeS, etc.). In particular, ferrous metals contain heavy metal because Ni and Cr are chemically attracted to iron. Likewise, Cu is used to coat Ni and Cr metals as polish or to prevent corrosion. In this study, an Fe3O4-Fe2O3 double layer (similar to pure Fe) was found to have been formed in ferrous metal during air-annealing in an incinerator (1000°C). A strong thermal shock such as one that occurs during the water-cooling of bottom ash results in the breakdown of this oxidation layer, facilitating the degradation of ferrous metals and formation of corrosion products. Therefore, Fe-ion (heavy metal) oxides may be formed on ferrous metals and may be separated from bottom ash via magnetic separation. This study sought to investigate the separation ratio of heavy metals as magnetic separation and mineralogical formation of Fe-ion (heavy metal).

Jan 1, 2006

By Valery M. Paretsky

The effect of the degree of nickel oxide reduction and the reaction gas composition on the furnace productivity has been estimated by computations and the established relationship is in good agreement with the practical data obtained in the process of electric smelting at the Severonickel smelter. An increase in the reduction degree within a range of =0.65 - 0.9 results in an increase in the furnace productivity by 19% to 37% and in a decrease in the unit electric power requirement by 16% to 27% depending on the reaction gas composition. The agreement between the computed and practical data has confirmed that the decisive factor for the process of treatment of reduced nickel oxide in an electric-arc furnace under the given conditions is the specific heat absorption, which is dependent on the nickel oxide reduction degree and the reaction gas composition.

Jan 1, 2005

By N. E. Idenyi

The effects of compositions and firing temperatures on the physico-mechanical properties of blended Nsu fireclay and Nkalaha redbrick clay have been investigated. The clay samples were compounded according to the following ratios: 10:90, 20:80, 30:70, 40:60 50:50, 60:40, 70:30, 80:20 and 90:10 in the order Nsu: Nkalaha respectively, and test samples made and fired at 9000C, 10000C 11000C and 12000C. The properties tested for were the modulus of rupture, porosity, shrinkage, apparent density, water absorption and bulk density. From the results obtained, it is inferred that the blends have a maximum service temperature of 11000C, with the 30: 70 blend presenting the best characteristics. A conclusion is drawn to the effect that the blend could be adapted for the production of ceramic earthenware, electrical porcelain pin insulators, cement manufacture and for refractory linings where temperature requirements are less severe.

Jan 1, 2006

By J. Y. Hwang

The relationship between coal characterization and physical cleaning has not been well understood due to the complex nature of coal. Therefore, it is difficult to apply the results of coal characterization to predict and evaluate the performance of a physical separation (e.g. flotation). Eight U.S. bituminous coals were analyzed and studied petrographically in conjunction with washability and flotation tests. The results show that grindability correlates to ash and fixed carbon contents; liberation determined directly by petrographic techniques is close to liberation determined indirectly by washability; and an ideal separation efficiency can be determined by measuring the inertinite content and the washability separation efficiency using a heavy liquid with a density of 1.4. The ideal separation efficiency was attained for most coals by packed column flotation. The ideal separation efficiency can be used for comparing process technologies and process parameters.

Jan 1, 1988

By David Arana

The use of gas-water dispersion of a molten material flow onto a vibrating surface is developed as a process to minimize water pumping requirements, minimize the risks of explosions, and minimize the post solidification dewatering and fines handling equipment requirements. The process uses existing vibration transport technologies and common plant utilities. Plant trials using the smaller footprint and the progressive molten particle cooling time have yielded encouraging results. The results are analyzed and reported.

Jan 1, 2006

By K. Narayana Swamy

The traditional approach to improving the operating efficiency of a metallurgical plant has been to study individual unit operations and focus on improving the poor-performing unit operations. The complex nature of most metallurgical plants call for a holistic approach that will consider the whole rather than just focus on the individual units of a plant. This holistic approach is part of the systems thinking principles. Numerous case studies highlight the importance of the need to apply systems thinking principles in improving the effectiveness of metallurgical operations. Improving the efficiency of one unit operation without considering its effect on the performance of other unit operations has in many cases lead to lower overall operational efficiency. Modeling and simulation are key to the application of the systems thinking principles. Standard flowsheet models are very useful in scenario analyses though they have to be supplemented with other models for useful predictions.

Jan 1, 2006

By Michael P. Sudbury

Non-ferrous slags are granulated and stockpiled as an alternative to pit cooling or transporting molten slag to a dump. The chemical composition of such slag is determined by the pyrometallurgical process in which it is produced, while the size distribution is set by safety concerns or a desire to reduce wear of pumps, pipelines and other equipment. Relatively few operations give consideration to the effect of granulation conditions on other properties of the granulate as the material is typically accumulated on the smelter site. It is becoming recognized that slag has many potential commercial uses and carries much of the energy applied to the smelting operation. This paper outlines the findings of extensive work to identify uses for granulated non-ferrous slag, the importance of preparation conditions on the properties, impediments to more extensive use of granulated slag, the real costs of slag stockpiling and the opportunities for further productive research.

Jan 1, 2006

By Hector Henao

To provide thermodynamic data for converting the nickel matte to liquid nickel, an experimental study was conducted in the phase equilibrium between the Ni-S alloy and the CaO-Ah03 based slag melted in a MgO crucible at 1873 K under controlled Pso2 of 10.1 kPa and pO;, in a range between 2.5x,IO,2 and 10.1 Pa by using CO-C02-S0Z gas mixtures. The content of nickel in the slag at POz of 10.1 Pa, above which solid NiO is expected to precipitate in the equilibrium state, was found to be 4.1 mass% and the contents of sulfur and oxygen in the nickel melt were 0.4 and 0.2 mass%, respectively. It was clarified that increase in the temperature reduces the solubility of nickel in the slag and the contents of sulfur and oxygen in the alloy. The distribution of minor elements such as gold, silver, copper, cobalt, iron, arsenic and antimony between the Ni-S alloy and the CaO-AI20) based slag was also studied. The distribution ratios of iron and cobalt, defined by (%X in slag)/[%X in alloy] where X is the minor element, are larger values than that of nickel, while those of copper, silver and antimony are similar to that of nickel. The distribution ratios of arsenic and gold are lower than that of nickel in the higher range of oxygen partial' pressure.

Jan 1, 2003