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By A. Siegmund, Gerhard Martin

The recycling of metal containing scrap is a common practice in the industry and has a long tradition. . In rec~nt years, this philosophy has been transferred to organic materials, in particular to thermoplastic polymers. BSB . Recycling GmbH, a company with a long experience in the treatment and recovery of lead from battery scrap,· had recognized this exploitation at an early stage and challenged it by a consequent continuation of the idea to recycle materials other than metals without degradation and maintaining the quality. These efforts resulted in an economic and environmentally acceptable solution producing high quality polypropylene compounds at BSB beside lead and lead alloys from battery scrap. The raw material fair the production of polypropylene compounds is shredded plastics from the separated casings of spent lead-acid batteries. The production of polypropylene with specific physical and mechanical properties is carried out by the accurate dosing of organic as well as inorganic additives. The result of the procedure is a novel product group "Seculene PP", a registered trademark of BSB Recycling GrnbH.

Jan 1, 2000

By R. Padilla

In most of the Chilean copper and gold concentrates, arsenic is present mainly as enargite, Cu3AsS4, which at the conventional roasting or smelting temperatures decomposes liberating arsenic as gaseous compounds. The objective of this investigation was to study the decomposition reaction of enargite in an inert atmosphere in the range of 500 °C - 750°C. The results obtained indicated that the decomposition begins at about 525 °C. Two distinct regions in the temperature dependence of the decomposition rate were observed: a low temperature region between 525 °C to 650°C and a high temperature region between 650 °C to 725 °C. The X-ray diffraction analysis suggests that the decomposition of enargite occurs through the formation of intermediate tenantite, according to the following sequential reactions: 4Cu3AsS4(s) ? Cu12 As4S13(s)+ 3/2S2(g) Cu12 AS4S13(s) ? 6Cu2S(s) + 2As2S3(g) + 1/2S2(g) The decomposition kinetics was analyzed by using the model for a topochemical reaction of spherical particles: 1-(1-X) 1/3 = kt, which represented well the data. Apparent activation energies of 113 kJ/mol and 60.5 kJ/mol were found for the low and high temperature regions, respectively.

Jan 1, 1999

By Anil Saigal, Jr. Fuller, Said Jahanmir

"All-ceramic crowns, including glass-infiltrated spinel composites, are coming into widespread use because of their superior aesthetics and chemical inertness. This study investigates the residual stresses that are developed in these composites as a result of cool down from the glass-infiltration temperature to room temperature due to slight mismatch in the coefficients of thermal expansion and its effect on the mechanical behavior of these composites. Two-dimensional finite element simulations were performed using an object oriented finite element program OOF. The OOF program is a combination of two programs. The first program, PPM200F, is designed to read an image file such as a micrograph. The individual pixels that constitute the micrograph may be collected into groups and their material properties assigned. PPM200F is then used to create the finite element model/mesh that OOF then reads. The average residual stresses are found to be tensile in the spinel matrix and compressive in the infiltrated-glass. There is large variation in residual stresses and strains from location to location with presence of locations at which the glass is under tensile stress. The crack initiation and initial propagation in glass-spinel composites is at the glass-spinel interface in both the glass and the spinel. The presence of residual stresses can lead to lower crack initiation stresses and degrade the mechanical properties of the composites.IntroductionGlass-infiltrated spinel ceramics are in clinical use as core materials in all-ceramic crowns and as inlays and onlays (1-3). Advantages of ceramic composites include near net-shape forming with high strength in the infiltrated state. Besides, spinel is quite translucent and may potentially be used without a veneer. However, these ceramic composites are subject to damage accumulation from repeat oral contact loading and often fail after a few years of use (4). This paper examines the residual stresses that are developed in these composites, after cooldown from the glass infiltration temperature to room temperature, due to the slight mismatch in the coefficients of the thermal expansion of the two phases."

Jan 1, 2001

By Rzyman Michal, Nakamura Takashi, Shibata Etsuro, Grabda Mariusz, Oleszek-Kudlak Sylwia

"Tetrabromobisphenol A (TBBPA) and many systems based on the synergistic effect of brominated organic compounds with Sb2O3 are extensively used as effective brominated flame retardants (BFRs) in many materials such as plastics and textiles. Thermal degradation of BFR containing plastics leads to the formation of hydrocarbons and gaseous compounds such as HBr and SbBr3. Our thermodynamic considerations indicate that these gases can act as bromination agents for metallic oxides such as ZnO, Cu2O, CuO, PbO and FeO. Moreover, these metallic oxides have the thermodynamic tendency to brominate easier than does Sb2O3. The aim of this study was to investigate experimentally the reactivity of ZnO with 1) HBr originating from the thermal decomposition of TBBPA and 2) SbBr3, which is formed during thermal degradation of brominated flame retardant plastics. The thermal treatments of the mixture of compounds of interest were investigated by thermogravimetry coupled with mass spectrometry.IntroductionTetrabromobisphenol A (TBBPA) and many systems based on the synergistic effect of brominated organic compounds with Sb2O3 are extensively used as effective brominated flame retardants (BFRs) in materials such as plastics and textiles. For instance, 4.5 million tons of flame retardant plastics containing BFRs are produced in Japan each year. Thus, in thermal treatments such as the incineration and melting of solid wastes, BFR containing plastics are intentionally or unintentionally included in the wastes. Thermal degradation of BFR-containing plastics leads to the formation of hydrocarbons and gaseous compounds such as HBr and SbBr3 [1-5]. Our thermodynamic considerations [6] indicate that heavy metal oxides such as ZnO, Cu2O, CuO, PbO and FeO should easily react with HBr prior to Sb2O3 and also with SbBr3, the main gaseous product in the thermal decomposition of TBBPA, forming low boiling point metallic bromides suitable for the volatile separation of heavy metals. The metal oxides are also expected to qualitatively and quantitatively affect debromination and decomposition of the flame retardant."

Jan 1, 2008

By A. Vahed

The Goro Nickel Project is situated in the Southern Province of New Caledonia. Inco Limited and Goro Nickel S.A. have developed a process that features the use of pyrohydrolysis to produce nickel oxide. The process treats a blend of laterites by Pressure Acid Leaching followed by solvent extraction of nickel and cobalt using Cyanex 301®. Purified nickel chloride solution is converted to high purity NiO product and 6M hydrochloric acid, which is recycled back to the SX circuit. In co-operation with Andritz AG, spray roaster and fluid-bed pyrohydrolysis technologies were examined for this purpose. Tests were conducted at the Andritz AG pilot plant in Vienna, Austria, and at Goro in larger scale installations. The latter served to establish process engineering design parameters for scale-up. Several process variables were investigated in both technologies and the off-gas characteristics were established. Fluid-bed pyrohydrolysis was selected for the Goro commercial plant, primarily because it produced a granular nickel oxide. The main focus of this paper is to outline the results obtained in pilot plant studies of liquid fueled fluid bed pyrohydrolysis for the Goro Project. Keywords: lnco Goro Nickel, Fluid Bed Pyrohydrolysis, Pilot Plant Tests

Jan 1, 2004

The 15m high Inco flash furnace uptake was designed as a reaction chamber with the objective of destroying the H2S contained in the furnace off-gas by combustion with oxygen at about 1300°C. Until recently, the oxygen required for this purpose was injected through afterburners located at the bottom of the uptake. An undesirable side effect of this practice was the formation of build up accretions on the inside walls of the uptake. This buildup had a negative impact on both the furnace on line time and the control of the flash smelting process. In late 200 I, the afterburners were relocated to the roof of the uptake. As a result, about 80% of the uptake accretion buildup disappeared with obvious beneficial effects for the operation of the furnace. This paper discusses key flash smelting aspects that affect the operation of the flash furnace uptake such as the dusting rate, the formation of H2S in the freeboard of the furnace, and the impact of using coke to supply some of the heat required by the process. The mechanism of buildup formation and its dependence 'on uptake afterburners location are also examined. Prof. Yazawa's sulfide smelting thermodynamic relationships proved instrumental in understanding the conditions that influence the formation and the elimination of H2S and uptake buildup.

Jan 1, 2003

By Vladimir Lobanov, Pritchinm Alexander, Nikifor Ageev

"Sulfuric anhydride is one of the most voluminous technological emissions. The possibility of high-temperature SO2 oxidations without catalyst in presence of calcium-bearing filling materials (CaO, Ca(OH)2 and CaCO3) with obtaining of binding material on the basis of waterless calcium sulfate is studied. Due to application package HSC-4 the thermodynamic analysis of the specified interactions is made and following conclusions are drawn: 1) Reactions are feasible in the all range of investigated temperatures (400 – 1000 °?); 2) The best results should be expected at use of ???; 3) The heat of reaction does possible autogenous behavior of process. The researches have shown: 1) Practical possibility of the process; 2) SO2 oxidation without the catalyst is feasible in presence of ???, Ca(OH)2 and CaCO3; 3) The optimum temperature range is 600-800 °?; 4) The content of waterless calcium sulfate in a product reaches 48% that makes it possible to use as the binding material; 5) At excess of ??? the degree of SO2 collection is nearer to 100%. Introduction At processing of sulfide raw materials in metallurgical furnaces the significant amount of sulfur, mainly in the form of sulfuric anhydride is escaped. Rich gases (SO2>3 %) are used for the sulfuric acid or element sulfur production. Chemism of sulfuric acid manufacturing is based on catalytic high-temperature oxidation of anhydride. Poor gases of metal works (SO2 =2,5 %) and power combustion units (SO2 =0,5 %) after clearing discharge into the atmosphere. Commonly, to recovery of weak sulfuric anhydride the chemical and physicochemical methods are applied. A few chemical ways of recycling sulfur dioxide are applied practically. In a number of methods for SO2 recovery a pulp of metals oxides (magnesium, zinc, etc.) with formation of sulfites is used. In other case sulfuric anhydride is catch by weak sulfuric acid in the presence of an oxidizer (pyrolusite ore). Methods of absorption SO2 by solid sorbents, (carbon fibers, silica gels, zeolites) are known and put into practice. Regeneration of the saturated sorbents is realized by thermal decomposition or extraction. Obtained as a result high-concentrated solutions are a commercial product."

Jan 1, 2008

By H. Masuda

The lijima Zinc Refinery started operation in 1972, and has today an annual capacity of 200,000t-Zn. The hematite process was employed for the first time and the ideal of waste-free refinery has been pursued for 30 years. In recent years, however, only half of the hematite produced would be sold to the cement industry and hence a reduction of arsenic level has been necessary in order to sell the entire amount produced. The arsenic cementation process with zinc powder, developed through a long time laboratory research was found among some options as the best for the hematite process. The construction work started in 2000 and the facility was put into operation in 2001, As a result in the same year all hematite were sold to the cement industry. The outline of this project, present operations and technical issue are reported in this paper.

Jan 1, 2003

By J. D. Zhu, T. Ohmichi, H. Yasuda, S. Kashiwai, I. Ohnaka

"Since the casting process affects the properties of castings, its computer simulation has been greatly developed in the last decades. This paper presents our recent works, especially on mold filling simulation, because most casting defects such as porosities and inclusions that greatly affect the properties originate during mold filling. The first topic is the mold filling simulation with consideration of cavity pressure change during mold filling, including direct observation of flow phenomena with X-ray and pressure measurement. The second .one is the mold filling simulation in the lost foam process, in which gasification of polystyrene pattern and gas outflow through the coating and mold have been considered. The simulation can predict not only the mold filling sequences but also periodical vibration of the gas layer between the melt and pattern. The third one is the comparison of simulation of Al melt flow in a metallic runner and direct observation through a transparent mold, showing that the entrapped gas or inclusions is expelled ahead through the melt and its simulation needs very fine meshes. These examples show that the comparison of simulation and observation is very important to develop the numerical simulation further.IntroductionThe mechanical properties of castings are greatly affected by casting defects such as porosities and inclusions, and solidification structure. Although recently the structure simulation has greatly progressed [1-4 ], the application in plants is very limited, because the structure is mostly determined by chemical compositions and cooling rate, enabling us to estimate it from the structure of past similar castings without simulation.On the other hand, the casting defects often vary with each casting or time. Among the defects, porosities and inclusions are main causes to deteriorate the properties and mostly originate during mold filling. Therefore, a lot of efforts to simulate the mold filling and estimate those defects have been made in the last decades [l,5,6]. These efforts have been mostly to develop numerical techniques to solve the Navier-Stokes equation. However, the flow phenomena in molds have not been well understood, because the direct observation of the flow phenomena in mold is not easy. This means the accuracy of the simulation is still not clear."

Jan 1, 2000

By Andre Thess, Oleg Zikanov

"Direct numerical simulation methods are applied to study the influence of a constant magnetic field on turbulent flows of liquid metals. The flow is assumed to be homogeneous and the problem is reduced to the classical case of the turbulent flow in a 3D box with periodic boundary conditions. The main subject of the study is the anisotropy developing in a liquid metal flow affected by constant magnetic field.To investigate the long-time evolution of initially isotropic flow the large-scale forcing is applied to maintain the flow energy at a statistically steady level. It is found that the flow evolution depend strongly on the magnetic interaction parameter (Stuart number). In the case of small Stuart number, the flow remains three-dimensional, turbulent, an approximately isotropic. At large Stuart number (strong magnetic field) the turbulence is suppressed rapidly and the flow becomes two-dimensional and laminar. Very interesting is the intermittent flow evolution at moderate Stuart number. Long periods of almost two-dimensional, laminar behavior are interrupted by strong turbulent three-dimensional bursts.The influence of a constant magnetic field on scalar transport properties of liquid metal turbulence is investigated using the simplified formulation of homogeneous flow driven by an imposed mean temperature gradient. Such a flow consists primarily of two turbulent antiparallel jets providing an effective mechanism for heat transfer. It is shown that the magnetic field parallel to the mean temperature gradient stabilizes the jets and, thus, enhances heat transfer considerably."

Jan 1, 1999

By Andreas Weber

Batrec operates a plant for the recycling of used dry batteries with a capacity of 3000 tons per year. The plant Is situated In a tourist area of Switzerland and has complied with all the strict emission restrictions. The process yields four products: FeMn. Zn, Hg and slag. No hazardous waste Is produced. All types of batteries can be treated.

Jan 1, 1995

By Heinz Giegerich

This paper deals with a new development in recycling second generation catalytic converters, namely metal substrate converters (MSC). It describes a patented dismantling process, whereby the MSC is segregated into it's three components outer steel shell, metal substrate carrier foil and ceramic W8shcoat with embedded precious metals.

Jan 1, 1995

By Noriaki Kurita, Norihiko Fulcatsu, Teruo Ohashi

"An electrochemical sensing device for hydrogen in molten metal has now been available owing to the development of the proton conducting solid electrolyte made of ceramics of metal oxide. The structure of the sensor and the theoretical limitations of its applications are discussed based on the electrochemical properties of the electrolyte used. The practical performance of the sensor is reviewed from the results of test measurements at the plants of aluminum and copper melting industries. The effectiveness of the sensor to the process control of continuous casting of copper is also discussed.IntroductionSince the in-line monitoring of the amount of oxygen dissolved in molten metal was realized by using the oxygen concentration cell based on zirconia solid electrolyte a similar method has been expected to be developed for sensing of hydrogen, which is a very important element of gas species in liquid metals, especially, in aluminum and copper. In 1981; Iwahara and coworkers found the dominant proton conduction at a high temperature in some perovskite-type oxide (1). Since then, the effort has been made to apply this proton conducting material as the electrolyte of the hydrogen concentration cell for high temperature use. The hydrogen sensor for liquid aluminum of this kind was first produced in 1991 (2) and released commercially from TYK Co., Ltd. Recently, we have developed the mother one usable at higher temperature such as copper and silver melting processes (3). In this note we discuss their structure, design and applicable limitations based on the electrochemical properties of this new type electrolyte. The performance of the sensor and benefit to use it to control the melting process is also discussed"

Jan 1, 2000

By M. C. Ruiz

The leaching behavior of chalcopyrite concentrate in acidic CuC12-NaCI-O2 solutions was investigated. Experiments were conducted under continuos flow of oxygen at atmospheric pressures. The results indicated that among the variables temperature has the largest influence on the dissolution of chalcopyrite in this medium, and high copper extraction can only be obtained at temperatures near the boiling point of the solution. It was also found that the stirring speed did not influence appreciably the dissolution of chalcopyrite. An increase in the oxygen flow rate up to 0.1 1/min increased the copper extraction. The total chloride concentration affects the dissolution of chalcopyrite up to about 4 M. Copper extraction of 93 % was obtained in leaching chalcopyrite of size fraction -400 # Tyler at 105 OC in 2 hours.

Jan 1, 1997

By Shengqin Zhang, Yousef Mohassab, Feng Chen, Hong Yong Sohn, Mohamed Elzohiery, Amr Abdelghany

A novel ironmaking process is under development at the University of Utah aimed at producing iron directly from iron oxide concentrate in a flash reactor. This process will reduce hazardous emissions and save energy. The kinetics of magnetite reduction with hydrogen was previously investigated in our laboratory in the temperature range 1150 to 1400 oC at large temperature increments (~100 oC increments). Due to the significant melting that occurs above 1350 oC, the reduction kinetics was measured and analyzed in two distinct temperature ranges of 1150 to 1350 oC and 1350 to 1600 oC (~50 oC increments). Experiments were performed using magnetite concentrate particles of different sizes under various hydrogen partial pressures and residence times. Reduction degrees of more than 90 % were achieved in a few seconds at temperatures as low as 1250 ºC. Different rate expressions were needed to obtain reliable agreement with experimental data.

Jan 1, 2016

By G. A. Brooks

Increasing interfacial area through gas injection is one of the main methods for accelerating reaction between slag, metals, and gases in modern pyrometallurgical reactors. In slag-metal reactors, the generation of a large number of metal droplets into the slag phase through high gas velocity has a much larger effect on the overall kinetics compared to the enhanced mass transfer through mixing. Top blowing technology generates large interfacial areas (>300 m2/tonne) through high impingement gas velocity at short distances between the exit of the injection lance and the metal-slag interface. Phase separation may become a limit at the case of very high interfacial areas, though there is still only limited understanding of the trajectories of metal droplets in slag-metal-gas emulsions.

Jan 1, 2003

By Jie E. Zhou, Yu U. Wang

"Development of crystallographic texture in polycrystals during templated grain growth process is studied by phase field modeling and computer simulation. To characterize the grain texture development, X-ray diffraction peak intensities are computed for the evolving grain structures as simulated by the phase field model, based on which Lotgering factor is further calculated as a quantitative measurement of uniaxial texturing. While the phase field modeling allows direct comparison between simulated grain structures and experimental microscopy observations, the computational diffraction allows convenient correlation between computer simulation and experimental X-ray diffraction characterization. The latter feature is especially desirable, since microscopy experiments normally require more efforts than X-ray diffraction, and diffraction is usually the preferred choice for material characterization.IntroductionThe properties of individual grains in polycrystals are generally anisotropic, while untextured polycrystalline materials with random grain orientations exhibit isotropic macroscopic properties that are independent of directions. In order to achieve anisotropic response in polycrystals, crystallographic texturing of grains is required [1]. Texture refers to the collective distribution of grain orientations towards preferred orientation in a polycrystal. To develop texture, special processing routes are needed, such as templated grain growth (TGG) for uniaxial texture [2]. TGG has been shown to provide uniaxial texture in wide variety of materials. For example, [001]-textured ferroelectric polycrystalline ceramics have been fabricated by TGG process, which exhibit enhanced piezoelectric properties [3]. Such highly textured polycrystalline materials offer better cost-performance ratio than single crystals. Thus, texture development in polycrystals is of technological importance for material applications.In this computational work, grain texture development in polycrystals during TGG process is studied. Grain structure evolution is simulated by phase field model, X-ray diffraction peak intensities for the evolving grain structures are computed, and Lotgering factor is calculated to quantitatively measure the development of uniaxial texturing. The phase field modeling allows direct comparison between simulated grain structures and experimental microscopy observations using imaging techniques such as scanning electron microscopy or optical microscopy. The computational diffraction allows convenient correlation between computer simulation and experimental X-ray diffraction characterization. The latter feature is especially desirable, because microscopy experiments normally require more efforts than X-ray diffraction, thus diffraction is usually the preferred choice for material characterization."

Jan 1, 2014

By Guozhu Ye, Mikael Larsson, Eric Burström, Sten Ångström

"Increased use of scrap in steelmaking including scrap use in BOF has a high economic and environmental potential in terms of increased productivity, energy saving and reduced emission of CO2. Preheating and surface cleaning of steel scrap is a concept developed by MEFOS in a four year research program funded by MISTRA, Swedish Foundation of Strategic Environmental Research. The process concept consists of four major steps: 1) Combustion of ASR or other waste fuel and composing of the gas composition. 2) Scrap heating and cleaning in a shaft where the coated zinc is removed as ZnCl2 and scrap is heated to about 600 ºC. 3) Dust separation for recovery of metal zinc. 4) Gas cleaning. This paper will describe the process concept and highlight the major results from preliminary trials around the scrap heating and cleaning shaft.IntroductionSteel is often coated to increase the corrosion resistance. Share of coated and galvanized steel in the world marked is steadily increasing. This results in increased amounts of scrap with different types of coatings. Use of galvanized scrap in EAF plant results in an EAF dust with high content of zinc ferrite and many other impurities like Pb, Hg, Cd and halide. EAF dust is classified as hazardous waste in most of the developed countries and the steel plant has to pay for external treatment for zinc recovery. For use in BOF plant this will result in a BOF dust containing typically 1-5%Zn making it impossible for recycling to the blast furnace.Different approaches for surface cleaning have been investigated in past. Dapper et al. [1] examined the possibility to evaporate Zn, Ni, Cr, Sn from coated materials using chlorine. Chlorinated rinsing of non iron oxides and metals using HCl from combustion of PVC was discussed by Fray [2]. Further studies by Tee and Fray [3-5] have been concentrated on the possibility to vaporize coatings with an air and chlorine gas mixture. The O2:Cl2 ratio in the gas mixture was found to have great importance for control of the process. To avoid the chlorination of iron, this ratio should be kept at a level of 10:1.Scrap pre-heating up to about 600 ºC is a well known method and this alone could save up to 100 kWh per ton steel. The technology has been established since many years and efficient processes were developed in the 90’s. However, no process has fully gained the expected energy savings as the large quantity of the exhaust gas has to be reheated to over 1000 ºC again to destroy the hazardous components like dioxins."

Jan 1, 2008

By C. L. Lin

Multiphase, irregularly-shaped randomly-oriented PARGEN particles were grown to determine the breakage/liberation characteristics of such locked particles. The simulated locked particles were randomly broken to establish the liberation characteristics of the broken fragments. The progeny size distributions are consistent with Gilvarry's volume and surface flaw model for single particle breakage. The extent of liberation of both continuous and dispersed phases can be described from the conservation of interfacial area. In this regard the data can be normalized and liberation described for a wide range of dispersed phase grades and dispersion densities.

Jan 1, 1988

By I. M. S. Moraes

Caraiba Metais has a plant for the purification and the cristallization of the crude nickel sulfate removed from its copper electrolyte purification system. In November 1994, an interdepartmental group was formed to study the Q.F.D. method, through its application on the improvement of the quality of the nickel sulphate hexahydrate. The team, formed with representatives of the following areas : production, technology, marketing, sales, maintenance, laboratory and TQC office, had also the task of checking the applicability of the method to other products of the comp any. This paper describes the main steps such as the survey of customer's demands, the preparation o1 the quality matrix, stablishing the planned quality matrix, the planned and the designed quality, and the consequent identification of the engineering bottlenecks. It is also shown how these bottllenecks were studied and solved. The application of the method allowed the team to identify means of increasing the production capacity by 40%, to improve the intrinsic quality of the product (including packaging), and to increase the reliability of the process.

Jan 1, 1997