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By Liu Chunpeng

The new technological process developed is by means of thermal plasma arc smelting to obtain high grade Ni matte directly from Ni-Cu concentrates containing 6-7% nickel and 3-8% sulfur. In comparising with conventional smelting and converting processes the plasma arc smelting process has many advantages over conventional processes, such as lower energy consumption, lower capital investment and free from SO, pollution by transforming the sulfides into elemental sulfur with microwave irradiation under controlled oxygen potential, moreover, the process is simple and easily controlled due to less magnetite troubles in the operation. Therefore, this new technological process can be used as an alternative way to conventional process for Ni-Cu concentrate smelting. The main economical technical index is summarized in Tabal 1. Table 1 Main Ecnomic-technical Index

Jan 1, 1993

By Harvey Alter

National attention in, recycling focuses on municipal solid waste (MSW), even though only about 50'million tons or so of MSW can be recycled, including grass, leaves and other yard wastes. The scope and value of the recycling of industrial "wastes" is much greater. It is possible to account for some 240 million tons of material recycled at the industrial scale annually, which is likely a conservative estimate. Some of this recycling reduces what would otherwise be hazardous waste to 'comrnodities and non-hazardous residue. Global trade in recycled commodities is outlined, as well as the-effect of the Basel Convention on the Trans boundary Movement of Hazardous Wastes A recent Decision under the Convention can, diminish the trade; deny developing countries needed secondary raw materials, and put world markets in chaos. Current U.S. government policies and activities toward ratification of the Convention, and possible new regulation of industrial recycling activities, will be discussed. There are federal proposals that would regulate industrial recycling differently for on-site and off-site facilities and judge legitimate or "sham" recycling according to the concentration of so-called "toxics along for the ride."

Jan 1, 1995

By Duan Xin-hui, Wang Xin, Peng Jin-hui, C. Srinivasakannan, Zhang Li-bo

The work attempts to optimize the process of preparation of modified semi-coke from semi-coke using phosphoric acid (H3P04) as the activating agent using the response surface methodology (RSM). The influences of three major dependent variables, the impregnation ratio, activation time, and activation temperature were assessed on the independent variables yield and the iodine number. The empirical relationship between the dependent and the independent variables were established using the quadratic response surface models, which were utilized to optimize the process parameters. The significance of each of the parameters and interaction among the parameters on the independent variable was assessed based on analysis of variance (ANOVA). The process variables were varied within the range of impregnation ratio (IR) from 1.5 to 4, activation time from 30 to 90 min and activation temperature from 550 'C to 650 'C. The optimized process conditions were estimated to be an IR of 2.29, activation time of 32 min, and an activation temperature of 605°C respectively using the process optimization tool. The BET surface area of modified semi-coke of the optimized sample was estimated to be 915m2/g, with the pore volume of0.71cm3/g, with an average pore diameter of 3.09 nm, with micropore volume fraction being 52.36%. The scanning electron microscope (SEM) images were utilized to visualize the surface pore structure.

Jan 1, 2013

By Henrik Gudbrandsen, Geir Martin Haarberg, Ana Maria Martinez, Karen S. Osen, Sverre Rolseth

"The Several approaches were tried for developing an electrochemical route for producing high purity silicon from molten salts. K2SiF6 and metallurgical grade silicon were used as the source of silicon. Molten LiF-KF and pure KF with additions of K2SiF6 were used as electrolytes at temperatures from 550 - 900 oC. Silicon was cathodically deposited and anodically dissolved in the fluoride electrolytes. High electrorefining efficiency was obtained for many elements after electrolysis experiments at constant potential or constant current. The main challenge was to reduce the contents of boron and phosphorus. Another difficulty was to remove inclusions of solidified electrolyte. The lowest energy consumption was estimated to be ~ 3 kWh/kg Si, while the best current efficiency for Si deposition was found to be ~ 95 %.IntroductionSilicon is the most important material for photovoltaic power generation devices because of high feasible efficiency, low ecological impact and slow degradation. Development of a new and less expensive route for producing silicon of the desired quality is necessary in order to make solar cells competitive. Electrochemical routes may be an alternative possibility, and many laboratory studies have been reported over the past few decades. Most of the studies have been performed in molten salts, chloride or fluoride, at moderate temperatures so that solid silicon was deposited at the cathode. The production of high purity silicon has shown an annual increase of about 25 %, due to the increasing demand of solar grade silicon (SoG-Si). For future increased use of solar energy it is important to develop alternative, more energy efficient and cheaper processes for SoG-Si production compared to the Siemens process.Common silicon sources have been SiO2 and K2SiF6 for electrowinning and MG-Si in the case of electrorefining. A serious challenge is to find an oxygen evolving anode for electrolytes containing dissolved oxides. Especially at moderate to high temperatures and in molten fluoride electrolytes this is a difficult task.Many experimental results have been reported in molten chloride electrolytes. Nohira et al. [1-3] and Chen et al. [4] cathodically deposited silicon by electrodeoxidation of solid SiO2 in molten CaCl2 by potentiostatic electrolysis. An alternatice approach is to use electrorefining of low-cost metallurgical grade silicon (MGSi) to produce SOG-Si. In previous studies [5], an MG-Si anode was used, and silicon was successfully electrodeposited on a molybdenum wire in a CaCl2 based melt. It was found that the anode was strongly passivated due to the precipitation of silicon. Also, some deposits detached from the molybdenum wire because of the poor adherence to the cathode.Considering the Cu-Si alloy which has a good segregation effect for some impurities, and should not passivate, could be a good candidate anode for electrorefining. [6]."

Jan 1, 2014

By Guillermo A. Vidal

With the introduction of monitoring technologies, process computers and Web services on Industrial Facilities the need for electrolytic processes automation has been set. Recently designed facilities have substantially improved plant layouts, automated cathode processing and copper harvesting. Despite these advancements only limited progress has been accomplished on the electric current distribution of the process. Lately a number of proposals focused on preventing short circuits and balancing cathode currents have emerged. Among these are the AZSA intercell, the Outokumpu double contact, and the Optibar InterCell Plus. Although these intercell bars are clearly superior to the conventional bar, little or conflicting data is available about their merits relative to each other. Consequently, selection of the best intercell bar for most applications is accompanied by uncertainty, which can lead to less than optimum results. A critical evaluation of the performance of the aforementioned bars on the basis of the application is provided, thereby giving the framework and guidelines for the selection of the best bar for each application.

Jan 1, 2003

By Hector M. Henao

To provide thermodynamic data for converting nickel matte to liquid nickel at high temperature, an experimental study was conducted on the phase equilibrium between the Ni-S alloy and the FeOX-SiO2, FeOx-CaO, and CaO-A12O3 base slag in a magnesia crucible and the CaO-Al2O3-MgO slag in an alumina crucible. All experiments were carried out at 1773 K under controlled pso2 of 0.1 atm and po2 in a range between 5x10- and 10-5 atm by using CO-CO2-SO2 gas mixtures. The dissolution of nickel in the slag was found to be minimum for the CaO-Al203¬-MgO slag with a molar ratio of NCaO/NA1203=1.7. The solubility of nickel in this slag at p02 of 6x10 atm (just before the precipitation of solid NiO) was 4 mass%. This result suggests that a CaO-A12O3 base slag could be used in converting Ni-S melt to nickel while minimizing nickel losses to the slag.

Jan 1, 2002

By R. Boom, B. Kraaijveld, H. Kuntzel, Y. Meteleva-Fischer

"Alloying refining with rare earth elements followed by acid leaching was examined for the potential of upgrading of metallurgical grade silicon. Microstructure study of silicon alloyed with small additions of rare earths showed behavior relatively similar to the influence of calcium addition. After alloying with neodymium the phosphorus content was detected in various intermetallic silicides containing neodymium and iron. The content of lanthanum and neodymium in refined silicon was by several times lower than that of aluminium and calcium. Alloying with lanthanum and neodymium at smaller additions than calcium reduced the phosphorus content down to the same level. The efficiency of lanthanum and neodymium in removal of boron and phosphorus at the 1-2 wt% of their additions and their low solubility in silicon make the alloying with these metals followed by acid leaching an attractive option for the refining route of metallurgical grade silicon up to solar grade.IntroductionA striving for a cheap ""green"" energy directs the research interests in silicon solar cells towards new efficient refining routes for metallurgical grade silicon (MG-Si, -98% purity). The silicon price determines up to high extent the solar module's price, so that cheap and efficient metallurgical process is awaited. The research challenge is to fulfil the purity requirements of solar grade silicon (SoG-Si, 6N) by competing with the energy-consuming and environmentally unfriendly Siemens process. Most difficult impurities to remove are boron and phosphorus, so technologies dedicated to their efficient removal attract an attention of industry and academia.Alloying refining (also known as solvent refining) is one of the most promising refining options, which is based on a principle of solid-liquid extraction using limited solubility of impurity elements in solid silicon [ 1]. Various elements were proposed for alloying refining: aluminium [2], calcium [3], tin [4], iron [5], copper [6] etc. The attractiveness of the alloying refining is in decreasing a melting point of the metal mixture and an affinity of the alloying element to the most harmful impurities, especially to boron and phosphorus. However, the difficulties are still faced due to self-solubility of the alloying elements, their low affinity to boron and/or phosphorus, silicon losses and necessity of removal of the silicide impurity phases in an additional step, using acid leaching [7], fractional melting [ 8] etc."

Jan 1, 2013

By Ann E. Visser

Aqueous Biphasic Systems (ABS) form upon the admixture of certain water-soluble polymers or polymers and salts above critical concentrations, and thus represent liquid/liquid extraction systems whose nature is entirely aqueous. We are currently investigating the utility of ABS (and its solid phase analogs) as "green" alternatives to the use of volatile organic diluents in separations of metal ions. Chaotropic (water-destructuring) metal ions with small negative AGhyd (e.g., Tc04) tend to partition quantitatively to the PEG-rich phase of an ABS, but even hydrated metal cations can be partitioned to the PEG-rich phase if a suitable extractant (e.g., halide, dye, crown ether, etc.) is used to produce a more chaotropic ion-complex.

Jan 1, 1999

By Guohui Zheng

The ever increasing quantities of solid wastes generated by various industries are at the source of the growing need for proper waste disposal methods. Thermal treatment of combustible wastes is a proven technology which permits the reduction of hazardous material having to be landfilled. However, this method is not universally applicable to waste disposal. For example, the transferal of heavy toxic metals into the thermal remediation products is a major issue of public concern. This paper focuses on the analysis of morphology changes from solid sludge to ash which is a product of the sludge combustion. The morphological parameters analyzed were particle size and external surface. They were determined using Jeol 840 Super Probe. The experiments were conducted in a computer-controlled high-temperature combustion system consisting of the thermogravimetric furnace coupled with Fourier transform infrared spectrometer (TGA-FTIR). Sludge particles were made of complex fibers trapped in the aluminosilicate matrix. At low temperatures, up to 680 K, the solid residue looked similar to the initial sludge. Between 680 K and 1180 K the sludge underwent intensive burning and steadily changed into powdered ash. At the temperature of 1050 K the ash was composed of separate, flat flakes with sizes ranging from 5 to 20 um. At 1470 K the flakes aggregated into large particles. The surface observed at 1670 K was a mixture of mullite crystals. Such structure could result from the solidification of the ash material after its melting. Morphological changes influenced the distribution of metals in the solid residue. For example, Cr was concentrated in small aggregates. Such distribution should allow for recovery of valuable metals from the solid waste residue.

Jan 1, 1996

By Kenji Monden

"The creep properties of tin-based lead-free solders Sn3.0AgO.5Cu and SnO.7CuO.1Ni and lead solders 10Sn90Pb and 50Sn50Pb were investigated at temperatures between 298 K and 398 K. The creep-rupture time decreases with increasing initial stress and temperature. The analysis of the solder creep curves uses the Omega method. The creep rate E is expressed by following formula: 1n ? = 1n ?0 + O?, where ?0 and O are experimentally determined. The parameter Eo increases with increasing initial stress and temperature. The activation energy for ?0 is 108 kJ/mol for Sn3.0Ag0.5Cu and 85 kJ/mol for SnO.7CuO.INi. These energies suggest that the lattice diffusion of tin is dominant. The energy of 1OSn90Pb is 37 kJ/mol and that of 50Sn50Pb is 67 kJ/mol. The creep-rupture time is calculated using the parameters, ?0 and O. The calculated creep-rupture time is in good agreement with the measured creep-rupture time.IntroductionLead-free solders are replacing traditional tin-lead solders as part of a major trend toward protecting the earth's environment. However, tin-lead solders are currently needed for a high temperature range. Since creep is the main deformation mechanism in solder joints, understanding a constitutive model for creep and examining creep data for solders are important for reliability analysis of solder joints. A steady-state creep equation is generally used for solders [1,2], and it supposes that the secondary-, or minimum-, creep rate occupies the entire creep life. However, secondary creep accounts for only about 15 % to 40 % of the entire creep life for solders. Thus, the equation may not represent the entire creep life."

Jan 1, 2012

By Mototsugu Matsuno

A new process has been developed to treat fly ash generated from municipal incinerators, which contains not only toxic metals such as lead and cadmium, but also dioxins. The process includes the following steps; fly ash is formed into green pellets with some additives and the pellets are then roasted to eliminate or stabilize the toxic metals and to decompose dioxins. A pilot plant with a capacity of approximately 100 kg/hr was used to test the process, The tests verified that heavy metals were either volatilized or stabilized and dioxins were decomposed by high-temperature roasting. The pelletized ash was found to be non-toxic, so that it can be recycled as artificial lightweight aggregate. It was also found that volatilized metals collected as secondary ash can be recycled as smelting resources.

Jan 1, 2003

By Ker-Chang Hsieh

Four three-phase equilibria and one two-phase equilibrium in the FeNi- S-0 quaternary system in the vicinity of 1023 K and Pso2 = 1 atm were studied using the following emf cell 2 Pt,o2 (air)Zr02 .CaO/Pso2 = 1 atm, mixture of phases, Au The four three-phase equilibria are sp + (Fe,Ni )S + Ni 3s2, sp + Ni 3s2 + NiO, sp + NiO + N1S04 and Fe2 o3 + sp + (Fe,NOS04 -Y:he two-phase equilibrium is sp + (Fe,Ni)S. The two-.phase equilibrium was measured by using mixtures containing a major portion of one phase and a minor portion of the other. The results are presented in terms of oxygen potential as a function of YNi = nNi/(nN1+nFe) at constant temperature and pso2 = 1 atm. The stability diagram was also calculated using appropriate thermodynamic models for all the pertinent phases. The calculated diagram is in accord with the measured ones.

Jan 1, 1985

By A. E. M. Warner

Inco Limited has long and extensive experience in converting nickel-copper primary smelting mattes over a broad range of nickel/copper weight ratios and combined nickel-copper-cobalt contents. At the Copper Cliff Smelter, the composition of the converter product matte has to meet the requirements of the matte separation process; at the Thompson Smelter, converter matte of a different composition is cast into anodes for nickel electrorefining; and in Soroako, Indonesia, a very low copper product matte is granulated for the Japanese market. Recently, Inco has conducted pilot plant testing of three possible nickel-copper matte continuous converting routes, namely flash converting, oxygen top blowing-nitrogen bottom stirring, and tuyere blowing. This test work has generated substantial new information on nickel-copper matte converting chemistry. This overview paper reviews the metallurgy of nickel-copper matte converting, in particular the behaviour of cobalt and the operating conditions required to meet the iron and sulfur specifications of the product matte. The relevant thermodynamic information is used to discuss the industrial data.

Jan 1, 2003

By Bryn Harris

Chesbar Resources Inc.1 is developing a nickel-cobalt laterite project in Guatemala, Central America, by applying existing atmospheric chloride technology to a known resource. The tropical laterite project has an inferred resource of 133 million tonnes grading 1.51% nickel, which represents ~20% of Chesbar?s land holdings in Guatemala. Within its boundaries, the Sechol area has a measured resource of 14 million tonnes grading 1.46 % nickel and 0.08% cobalt, and an indicated resource of 23 million tonnes grading 1.34% nickel and 0.08% cobalt. Notwithstanding the impressive overall resource, the company has taken an innovative approach to a laterite project and is concentrating on El Inicio, a high-grade starter pit with five million tonnes grading 2.1% nickel and 0.08 % cobalt. The process flowsheet is based on atmospheric chloride leaching in a slightly acidic magnesium chloride brine, solution purification by recycled magnesia, precipitation of a mixed nickel/cobalt hydroxide intermediate product, and lixiviant regeneration by modified pyrohydrolysis technology. Initial results suggest that >90% of the contained nickel and cobalt in the non-magnetic fraction of the feed can be recovered, with <5% of the iron leaching. A metallurgical scoping study has established preliminary capital and operating costs for a production facility at a proposed rate of 20,000 tonnes per year of nickel as the intermediate mixed hydroxide. A preliminary assessment of producing a magnesium oxide by-product has also been carried out. This paper reports on the current development of the project and highlights the advantages of working in a chloride medium at atmospheric pressure and slightly elevated temperatures.

Jan 1, 2003

By Erik Olsson, Gunilla Hyllander, Stefan Schuster, Lena Sundqvist Ökvist, Maria Lundgren, Michael Hensmann, Olavi Antila

"Residual materials from the integrated steel plant itself or other sources often contain valuable compounds of e.g. C and Fe. Dust and sludge have to be agglomerated to be able to recycle to the blast furnace (BF) via top-charging. By injection of the materials, preparation methods in terms of e.g. drying and/or screening only, can be used. Alternative carbon materials (ACM) in terms of BF dust and sludge have been successfully injected up to levels of 60 kg/tHM in the LK.AB Experimental Blast Furnace (LKAB EBF®). Efficiency in recovery of valuable compounds as well as the behavior of undesired elements have been evaluated and are discussed.IntroductionTraditionally, recycling of steel in-plant fines is made via the sinter plant and blast furnace route. Steel plants operating with 100% pellet as ferrous burden and have no sinter plant. There are limited areas for land fill and costs are caused for preparation of landfills and deposit fees. Very fine paniculate dusts or sludges cause decreased productivity and increased coke rate in the sinter plant, and therefore other ways for recycling must be considered. Injecting them into the BF could be an economically and technically feasible alternative. Additionally, as the materials contain valuable compounds of e.g. C and Fe."

Jan 1, 2012

By Xiaodi Huang, Matthew Andriese, Zheng Zhang, Jiann-Yang Hwang, Zhiwei Peng

"The thermal decomposition and regeneration behaviors of wüstite were investigated by in situ high temperature X-ray diffraction (HT-XRD) under non-isothermal condition at heating rate of 4 K min-1 in vacuum ranging from 294 K to 973 K. Wüstite on heating decomposes to magnetite and iron up to 823 K, above which it exhibits marked tendency to regenerate. Investigation of thermal stability of the reaction system shows that the decomposition proceeds under kinetic reaction control while the regeneration is under thermodynamic control. Kinetics study based on the Coats-Redfern integral approximation method indicates that the decomposition reaction follows a Komatsu-Uemura model-based diffusion-controlled kinetics with activation energy of 32.860 kJ mol-1. The thermodynamics analysis of regeneration reaction demonstrates that wüstite regenerates at lower temperature than stoichiometric ferrous oxide.IntroductionOwing to its importance in preparing various magnetic ceramic/metal nanocompostites or nanocrystals with high values of coercivity for the application as recording media, wüstite (non-stoichiometric ferrous oxide) has been attracting the attention of scientists over a long period [1-6]. The thermal behavior of wüstite was investigated by several researchers and phase transformations due to thermal decomposition and regeneration of wüstite during the heating in a specific temperature range was observed [7-9]. In spite of wüstite being found to dissociate to magnetite and iron at temperatures lower than 848 K and then regenerates at higher temperature, a clear understanding of the reaction mechanisms is clearly lacking [9]."

Jan 1, 2012

By Luciano B. Oliveira, Angela O. Costa, Sergio N. Monteiro, Luis Guilherme C. Marques

"Biofuels are gaining a relevant role in today’s world not only as a solution for the decreasing petroleum reserves but mainly as a positive contribution to the efforts in global warming mitigation. In Brazil, since 1975, the replacement of gasoline by ethanol started a so-called PROALCHOOOL program, which is now being complemented with the replacement of petroleum diesel by biodiesel. This biodiesel program was officially created in 2005 with mandatory goals, supported by legislation, of 2% addition in 2008 and 5% addition in 2013 into all commercialized regular diesel. In this work, a critical analysis of the Brazilian biodiesel program is presented. The technical aspects related to the different raw materials, including wastes, available for biodiesel conversion as well as the economical conditions associated with production costs and market logistic are discussed. The environmental benefits associated with the retention of greenhouse gases are also discussed.IntroductionToday the commonly accepted fact that the petroleum world reserves are probably passing through a maximum and start declining in terms of the total amount that can be extracted by existing technologies is motivating significant changes in our society. The continuous increase in the price of gasoline and other liquid fuels is an immediate worrisome and visible consequence. However, more than an economical problem, our civilization is already facing the effects of global warming, due to CO2 emission from burning fossil fuels, mainly from coal and petroleum. It is now realized that a large scale solution for these problems demands the prompt substitution of non-renewable fossil fuels by others that, in addition of being renewable, have a relatively lower contribution to the greenhouse gases."

Jan 1, 2008

By Samuel Senanu, Benjamin Agyei-Tuffour, Lifeng Zhang, Eivind Øvrelid, Adegboyega Nathaniel Femi

"The solar grade silicon ingot produced from directional solidification process usually pushes the impurities to the top and finally cut off and discarded, which leads to material loss. The hard inclusions lead to wire breakages during the cutting of the ingot in wafers. The main kinds of inclusions found in solar grade silicon have been investigated using vacuum filtration: needle-like Si3N4 and lumpy SiC inclusions. Clusters of SiC inclusions and Si3N4 are also found. Surface observations of the scraps before polishing reveals that Si3N4 inclusions are usually bigger and in some cases can be about a few millimeters. SiC inclusions are usually smaller, ~200µm but can be ~500µm in some cases. Inclusions observed after filtration are mainly SiC with diameters ~10µm. Through the vacuum filtration, 99% inclusions can be removed 99%. The possible mechanisms of filtration are cake filtration for the larger sized Si3N4 and SiC inclusions and deep-bed filtration the SiC inclusions. For the directional solidified silicon ingot, an approximate distance of ~10mm gave an encouraging cutoff thickness. The inclusions sizes were below 10µm. Introduction The search for an alternative source of energy to fossil fuel has led to a dramatic increase in the demand for solar energy due to its high dependability (abundant in nature) and environmental friendliness 1). During the last 5 to 10 years, the annual worldwide production of solar cell by the photovoltaic industry has increased to an annual rate of 30 to 40 percent 2). A necessary condition for the maintenance and even an increase of this growth rate is a decrease in the cost of feedstock for the solar cell production 1). The total international production in 1997 was 130 MW worth more than $500 million. In 2004 the consolidated world total production of PV cells increased to 1146 MW or around. $7 billion (Figure 1) 3). Silicon is currently the most dominant semiconductor material used in the PV industry. As shown in Figure 2 3), solar cells consist of two types of material, often the p-type and n-type silicon. Light of certain wavelengths are able to ionize the atoms in the silicon (causing atoms to either gain or lose electrons) and the internal field produced by the junction separates some of the positive charges (“holes”) from the negative charges (electrons) within the photovoltaic device. The holes are swept into the positive or p-layer and the electrons are swept into the negative or n-layer. Although these opposite charges are attracted to each other, most of them can only recombine by passing through an external circuit outside the material because of the internal potential energy barrier. Therefore if a circuit is made, power can be produced from the cells under light because the free electrons pass through the load to recombine with the positive holes."

Jan 1, 2008

By J. C. Yannopoulos

The quest for a continuous copper smelting and converting process, which has been going on for a long time, has not as yet reached its objective. The most recent efforts for the development of a continuous copper?making process started about two decades ago. Among the contending proposed processes, four have been piloted and three of them are currently in operation: the WORCRA process., the NORANDA process, the MITSUBISHI process, the OUTOKUMPU process. The WORCRA process, after some long pilot plant tests, failed to develop as an industrial process: The NORANDA process, as currently operating, is a smelting process and not a continuous copper?making reactor as initially conceived. The MITSUBISHI, although the only continuous process, has not been widely accepted. The OUTOKUMPU process can be applied only to a low iron concentrate feed and co?produces blister and high in copper slag. The thermodynamics of these "continuous" systems and the practical problems of their industrial application are reviewed and discussed. The achievement of efficient and inexpensive environmental control should&apos; be the primary objective of any new process development. A review of the environmental problems of the copper industry indicates that the quest for a continuous smelting and converting furnace should be intensified.

Jan 1, 1983

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