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

"Thermodynamic considerations indicate that heavy metal oxides should easily react with HBr, the main gaseous product from the thermal decomposition of tetrabromobisphenol A (TBBPA), forming low boiling point metallic bromides suitable for volatile separation. Mechanisms and kinetics of the bromination reactions must be well recognized prior to developing of a new treatment for the simultaneous recycling of plastic waste containing brominated flame retardants (BFRs) and metal oxides (printed circuit boards, automotive shredder residue, plating sludge, metallurgical dusts). In this work, a differential scanning calorimeter and laboratory-scale furnace were used to investigate the possibility and conditions of the bromination of ZnO by product of thermal decomposition of TBBPA. The formed solid, condensed and gaseous products were analyzed by X-ray diffraction analysis, electron probe microanalysis, inductively coupled plasma analysis, ion chromatography and gas chromatography coupled with mass spectrometry. Introduction Tetrabromobisphenol A (TBBPA) is the largest volume brominated flame retardant (BFR) in production today and is used in more than 70% of the world’s electronic and electric (E&E) appliances [1]. The growth in the production of E&E products and the fact they become obsolete so quickly cause significant problems in the safe disposal and recycling of the electrical and electric waste (E-waste) and other BFR-containing waste [2]. Among various treatment processes, thermal methods are most useful since they allow the recycling and recovery of both the organic and inorganic fractions of the waste. However, incineration of the BFR-containing wastes results in the emission of hazardous organobromine compounds, while the main portion of bromine released from decomposed BFRs is present in flue gas as hydrogen bromide (HBr) [3]. HBr, which is known to damage incineration systems, seems to be a very effective bromination agent for many metallic oxides present in waste. The concept of this study is to take advantage this of its property."

Jan 1, 2008

By E. A. Trillo, L. E. Murr, R. D. Flores, J. C. McClure, B. M. Nowak

Complex vortex and swirl-like solid-state flow phenomena have been observed in the residual microstructures characterizing the friction-stir welding (FSW) of copper to 6061 aluminum; 2024 aluminum to 6061aluminum,2024 aluminum to 1100 aluminum, 2024 aluminum to 7039 aluminum and 2024 aluminum to 2195 aluminum. These flow phenomena are characterized by intercalation lamellae composed of dynamically recrystallized grain structures of the dissimilar metals which provide a super-plastic-like mechanism for the FSW flow in the solid state; there is no melting and temperatures at the weld center do not exceed about 0.8 TM (where TM is the absolute melting temperature (K)). In experiments to be described and illustrated, optical or light metallography (LM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques are utilized in examining residual FSW microstructures corresponding to tool rotation (stirring) speeds ranging from 400 to 1200 rpm, and traverse (or actual welding) speeds of 1 to 2 mrn/s.

Jan 1, 1999

By Elli Nurminen

Sulphate decomposition was studied in the conditions of a typical copper flash smelting heat recovery boiler. The aim was to determine the kinetics of the copper sulphate decomposition reactions and to find out if they are likely to take place in the process conditions prevailing in an industrial HRB. The information is essential in CFD-modelling of the reactions taking place in the boiler and for optimising the process. Thermal decomposition of sulphates was studied by thermogravimetry. The experiments were conducted with a commercial copper sulphate, a partially sulphated copper oxide and an actual process flue dust. The main variables studied were temperature and gas composition of a N2-O2-SO2-mixture. The samples were characterized with SEM, optical microscope and XRD. Temperature affected the decomposition rate strongly but the gas composition had a minor effect on the kinetics. The decomposition was fastest in the partly sulphated oxide and slowest in commercial copper sulphate. Keywords: Sulphate decomposition, flash smelting, heat recovery boiler, flue dust

Jan 1, 2004

By Gavin Beer

The Chelopech Copper/Gold Mine, located in west-central Bulgaria, has been in operation since 1953 producing a low-grade copper/gold concentrate containing up to six percent arsenic by weight. The penalties and restrictions imposed on smelting this concentrate, have seen the past operators of the mine strive to find a balance between achieving acceptable metal returns from the smelters and installing novel or unproven technologies in the face of changing political and economic climates. This paper documents the colourful history of the concentrate processing alternatives that have been investigated and implemented over the 45 year life of the Chelopech Mine, culminating in the high pressure oxidation option that is now the focus of a Definitive Feasibility Study (DFS) presently being undertaken by GRD Minproc Limited. The fundamental chemistry of the preceding alternatives is outlined followed by a discussion as to why each was ultimately not employed. A detailed description of the technology proposed in the DFS is given including: pressure oxidation, arsenic fixation, SX/EW copper recovery, CIL gold recovery and AVR/SART cyanide/copper recovery processes. Keywords: Arsenic, Scorodite, HPOX, Chelopech, Dundee

Jan 1, 2005

By Mari Naess, Jan Erik Olsen, Gabriella Tranell

"Fume, also known as dust, is produced during metal refining. Exposure to fume is damaging to the health of plant operators. A mathematical model has been developed to study the different factors governing the fuming mechanism. It is shown that natural convection is the main driving force of the phenomenon, and that the fuming rate is highly sensitive to the area of the exposed metal surface. A new feature introduced in the modeling concept is the ability to include a gas flux of unconsumed process gas flowing up through the metal surface. This reduces the fuming rate, and should normally not be neglected.IntroductionFormation of fume from the ladle in which metal is refined into its final specifications is an environmental issue of importance for the working environment in the production plant. In layman-term fume is often known as dust. It is formed when metal reacts with oxygen. As an example of a fuming process, we will focus on ladle refining of silicon. Note that many of the principles and conclusions will apply to other metal refining processes. For silicon production, silica fume (S1O2) is produced when silicon metal (Si) reacts with oxygen (O2).Silicon is produced in a submerged arc furnace. The metal is tapped from the furnace into a ladle for refining. The refining is conducted by injecting a mixture of air and pure oxygen at the bottom of the ladle. The oxygen reacts with the metal and the impurities, and the amount of impurities is reduced according to product specification. At the ladle surface, metal also reacts with oxygen present in the air surrounding the ladle. This reaction produces silica fume as illustrated in Figure 1."

Jan 1, 2012

By Reza Rahimi, M. Nili Ahmadabadi

"Because of high cost and shortage of primary resources of Ni-base superalloys, revert alloys can be used as a part of charging materials for production of superalloys ingots. The current study is based on recycling of IN738LC, a Ni-base superalloy, using 30% and 50% reverted alloy and balanced amount of virgin raw materials. Therefore, it has been attempted to cast an alloy with references to standard chemical composition and mechanical properties. After charging and casting in vacuum melting furnaces, chemical composition verification and non-destructive tests (i.e. Penetration and Radiography Tests), quality of samples were evaluated at elevated temperature by stress-rupture test. Results acquired from chemical composition and mechanical test indicate that cast ingots using 30% and 50% reverted alloy is reliable and consistent with the quality control requirements.IntroductionIn recent years, there have been many fluctuations in cost and availability of raw materials which are extremely determining in Ni-base superalloys production. Accessibility to the high purity metals such as Cobalt, Molybdenum, Tantalum, Niobium and etc. have been problematical during the past decades. Therefore, shortages of critical raw materials beside the economical considerations motivated the alloy suppliers and investigators to study and find alternate sources such as reclamation and recycling of scraps [1].There are a lot of reasons for the necessity of recycling; perhaps the most justifiable one is that consumers themselves produce scraps. For example, the weight of a finished superalloy product could be less than one-third of the cast alloy weight and in the case of complicated machined parts; this portion may reach to one-tenth [2]. High values of constituents, reduction of energy consumption and environmental concerns have all strengthened the obligation of recycling in Ni-base superalloys.Because of the high degree of risk in usage of improper materials for production of turbine blades, a delicately controlled program for recycling is needed. Depending on the type of scraps, this program can define the recycling procedure, required instruments, allowable percentage of scrap for usage and finally confidence level of the process."

Jan 1, 2012

By C. Koopman

During the production of phosphoric acid from phosphate ore and sulfuric acid, large amounts of calcium sulfate are formed, in which impurities from the feedstock are incorporated. To use the calcium sulfate in, for example, the building industry, a lower concentration of impurities is desired. Mercury, copper, lead, and cadmium were extracted from clear industrial recrystallization acid (0.8-3.9 mol/kg H3PO4, 0.2-0:5 mol/kg H2SO4) by supported solvent extraction with the extracting agent Cyanex 302 in kerosene in a transverse flow hollow fiber module. The permeability for the mercury ion was 1.4.10-6 m/s, whereas that for the copper ion was calculated to be 1.5.10 m/s. Cadmium, lead, and copper were extracted during the recrystallization of calcium sulfate hemihydrate to dihydrate, an existing step within the ,phosphoric acid production process, by solvent extraction with the same extracting agent. The concentrations of cadmium and zinc in the newly formed calcium sulfate were proven to be decreased. Unfortunately, concentrations of mercury and lead were too low for analysis.

Jan 1, 1999

By Thomas M. Harris

Cation exchange is not sufficiently selective to be used for the removal of heavy metal ions from a general industrial wastewater. However, if the metals can be converted to polyvalent anions through complexation, they may be removed both selectively and efficiently by anion exchange. This approach, referred to as chelation-assisted anion exchange (CAAE), has been examined using industrial wastewater samples contaminated with Ni2+ and Cr3+. For this particular application, the Ni2+ is complexed with 8-hydroxyquinoline-5-sulfonic acid, and the Cr3+ with sulfosalicylic acid. Removal efficiencies and adsorption isotherms for both the complexants and the complexes were determined in batch-mode tests.

Jan 1, 1994

By H. Kurokawa

Sumitomo Metal Mining decided to expand copper production capacity of Toyo Smelter and Refinery to cope with the recent copper demand growth in Asia, and to survive by reducing cost. The expansion plan is promoted to increase electrorefined copper production capacity from 270,000 metric tons in 2001 to 450,000 metric tons in 2007. The major changes in smelting section are introduction of the rotary steam dryer, renewal of the feeding system for flash furnace, improvement of the concentrate burner, modification of the flash furnace cooling materials, renewal of the slag cleaning furnace, modification of the flash furnace waste heat boiler, installment of a new converter furnace, enlargement of two anode furnaces. In addition, the gas cleaning system was upgraded and the second acid plant was installed. In the refinery section, the existing tank houses have been operated at high current density of 300A/m2 using the conventional starting sheet cathode technology and moreover a new tank house utilizing the permanent cathode technology was constructed. Although the copper production capacity has been increased, SO2 emission has been kept the lowest in the world through consideration of influence on the environment by expansion project.

Jan 1, 2006

By Gabriel Riveros, Ariel Balocchi, Andrzej Warczok, Daniel Smith

Blister copper from converting of copper matte is processed by fire refining prior to electrorefining. The fire refining consists of two steps: copper oxidation with impurities slagging and copper reduction. The classical batch process is carried out in vascular or reverberatory furnaces called anode furnaces. A new process for continuous copper fire refining has been proposed. The copper flows through two reactors in cascade, where is oxidized and reduced. The flow of a liquid copper through a ceramic packed bed increases the surface area and the rate of oxidation as well as the rate of reduction in the packed bed of charcoal. Mathematical modelling allowed for the design of a laboratory scale demonstration installation and industrial-pilot installation in Hernan Videla Lira Smelter (Paipote). The results have demonstrated the process feasibility and flexibility in operation.

Jan 1, 2009

By Batric Pesic

Dissolution of gold with sodium bromate solutions of various compositions was studied by using a rotating disc technique. The role of bromide ion, acid and externally added bromine was examined. It was found that sodium bromate could not dissolve gold in the absence of either acid or bromide ion, or both. When acid was absent, no bromine necessary for gold dissolution could be produced. When bromide ion was absent, formation of soluble gold bromide species, AuBr,-, was not possible. Bromate concentration had a complex effect, and it was dependant on bromide ion concentration. For fixed initial bromide ion concentration, gold dissolution rate increased with sodium bramate concentration increase until certain level, beyond which further increase of bromate concentration decreased the gold dissolution rate. The negative effect of bromate was explained by the depletion of necessary bromide ion. Sulfuric acid concentration effect was a function of initially present bromine.

Jan 1, 1992

By William Petruk

An investigation was conducted to determine types of particles that tend to be recovered in concentrates by mineral beneficiation. It was found that, in concentrates of the same grade the proportion of desired mineral occurring as apparently liberated grains varies widely. In contrast the proportion is nearly constant when the grains considered are apparently liberated grains plus unliberated grains in particles composed largely of the desired mineral. It was also found that the types of particles which tend to be recovered in concentrates are dependent upon the concentrate grade. Hence it is much more important to determine the characteristics of recoverable particles and to measure the percentage of mineral that occurs in recoverable particles. than to measure the percentage of totally liberated mineral. A relationship between concentrate grade and type of particle that tends to be recovered in concentrates was established.

Jan 1, 1989

By Min Chen, Lei Xu, Liang-yu Jin, Xue-liang Yin

For the purpose to reduce the high cost and heat storage loss of Al2O3-MgO bricks used as ladle linings, Al2O3-MgO-CaO bricks with lower theoretical density were fabricated and the densification behavior as well as mechanical property of this refractory was investigated. With addition of CaO, the initial sintering temperature of Al2O3-MgO refractory was decreased from 1300 to 1100°C associated with the expansive formation of CA2, and the compressive strength was also enhanced owing to the formation of bond linkage between CA6 and spinel. At high temperature, brick with 4% CaO content showed poor sinterability with high porosity because of the formation of platelet structure of CA6 grains, whereas brick with 8% CaO content was well sintered with higher relative density but lower bulk density than Al2O3-MgO brick, indicating that the densification as well as lightweight of Al2O3-MgO refractory was effectively promoted.

Jan 1, 2015

By James C. Sever

Two green field magnesium reduction plants are under consideration using dolomite as the raw material. The Calix calciner was independently selected for both plants. The unique design of this calciner is detailed and the advantages defined for the specific application. The low carbon foot print of this unit combined with the ability to capture food grade carbon dioxide makes this an environmentally proactive approach to carboniferous ore calcination.

Jan 1, 2015

By Leah Penner, Thomas J. Ruth, Paul Schaffer, François Benard, Edouard Asselin, Stefan K. Zeisler, Thomas J. Morley

"This paper details the electrodeposition of metallic molybdenum from an aqueous, acetateelectrolyte containing molybdate ions. The deposition is carried out in a highly concentrated (up to I 0 M) acetate bath in the presence of a very low concentration of bone glue (60 µg/L). The molybdenum metal deposits are up to 20 µm thick and adherent. The deposits were characterized by XRD and XPS analysis. The deposition process is very inefficient, as up to 99% of the current is used to generate hydrogen during electrolysis. The effect of acetate concentration, pH, additives and current on the deposition efficiency and physical properties of the molybdenum deposit were investigated and optimized to obtain smooth, adherent coatings.IntroductionMolybdenum has increased thermal and wear resistance properties that are often utilized in material coatings [I]. These coatings are most often manufactured by sintering, pressing or spraying molybdenum powder at elevated temperatures, as a substitute method for standard metallurgical practices, such as electroplating [2, 3]. The lack of reports describing molybdenum deposition is most likely due to the highly oxophilic nature of molybdenum and the stability of its oxides, especially in water. Previous attempts to electrochemically reduce molybdenum from molybdate (Mool·) ions to molybdenum metal have reported the production of either a poorly adherent mixed oxide [4-6], or a thin(< 0.1 µm) metallic film [7-9]. Thick metallic molybdenum is capable of being co-deposited with one of the iron-group metals (Ni [10], Co [11] and Fe [12]) to produce an alloy [13, 14]. These alloys, however, may not be suitable for applications requiring pure molybdenum as they usually contain less than 50% molybdenum (often less than 30%)."

Jan 1, 2012

By Xiao Songwen

Based on the anion coordination polyhedron growth unit theory, the polymorph transformation mechanism of antimony white (Sb2O3) in hydro-process was investigated. The new findings had been verified in the commercial-scale test and it was shown that adding a small amount of tartrate ions was economical and effective for polymorph transformation of antimony white in hydro-process.

Jan 1, 2003

By James M. Lockwood

"Eureka Technology has developed and patented a technology for the recycling of EAFD. Through this process all constituents of the material become salable commodities or are returned to the steel making process. In transforming the EAFD ""waste"" stream into a ""process"" stream the Steelmaker eliminates potential liabilities and the uncertain future of current processes while further reinforcing its role as a recycler. This is a cost-effective and energy efficient technology that combines hydrometallurgic and electrolytic processes resulting in the recovery of salable metals. For instance, unlike pyrometallurgic processes, zinc is recovered in metallic form and no elements are volatilized. This on-site operation also eliminates expensive transportation costs. In summary this technology reduces the cost of dealing with EAFD by recycling material currently being landfilled.IntroductionWorld crude steel production reached a new record level in 2007 - 1.34 billion tons of which 31% was produced by EAF steel makers [1]. This resulted in the generation of over 6 million tons of EAFD. This steel byproduct contains significant amounts of lead, cadmium and other hazardous metals. In the United States the Environmental Protection Agency (EPA) has designated EAFD a hazardous waste (EPA waste code K061). With over 50% of steel production in the US coming from EAF steel making this byproduct represents the single largest source of solid hazardous waste generated."

Jan 1, 2008

By Yotamu Stephen Rainford Hara

"The study focuses on the reduction mechanisms of copper, cobalt and iron during carbothermic reduction of copper-cobalt mineral sulphide concentrates in the presence of lime, in the temperature range of 1073K and 1273K. We have used three types of mineral concentrates which were derived from froth flotation from the Copperbelt region in Zambia. The reduction mechanisms were studied using thermogravimetric analysis in which selected reactions were stopped at different times for characterising the reaction mechanism using optical microscopy, XRD and SEM-EDX analyses. Using SEM-EDX analysis, we have analysed in details the stages of metallic phase formation during reduction process. Metallic cobalt and iron were embedded into copper, thereby permitting magnetic separation of the reduced metals even though copper is diamagnetic. Methods of preferential reduction of metal values were investigated by analysing the metallic phase formation.IntroductionIn conventional smelting or converting of copper sulphide minerals, metallic copper forms by giving off S02 gas on. Although in terms of overall energy balance the selective oxidation for metal production has major advantages, the process suffers from drawbacks in smelting complex concentrates containing copper, cobalt and iron sulphides minerals and these are: (i) cobalt and iron are oxidised, and consequently cobalt is lost into the slag phase. (ii) The volume of S02 gas produced is in low concentrations, which is insufficient for extracting sulphur or manufacturing sulphuric acid. The release of dilute S02 causes serious environmental pollution. The major cause for the loss of cobalt and iron into the slag, is due to that fact that the oxides of these metals are more stable than their sulphides. Since cobalt and copper are more valuable than iron, reducing conditions are required in a separate slag treatment reactor using electric arc melting for recovering the lost metal oxides from slag. This energy-intensive step makes metal making expensive.During chemical beneficiation of mineral sulphides (Cu2S, CoS, FeS) in the presence oflime (CaO), two types of equilibrium conditions may be set up either by forming CaS under reducing conditions, or by stabilizing CaS04 under oxidising conditions [l]. By comparison in the presence of carbon, CaS and metallic phases form, enabling the recovery of metals from sulphide minerals, which have been investigated by a number of authors [2-9]. During reduction of metal sulphide in the presence of lime and with carbon, it has been proven that the overall reaction le proceeds via two main steps: [5, 8, 9] (i) the anion exchange reaction between metal sulphides (MS) and CaO as shown in equation la, followed by (ii) the reduction of metal oxide (MO) via reaction lb."

Jan 1, 2013

By R. Boom, C. F. Balentina, J. H. L. Voncken

During vitrification of bottom ash generated from the combustion of municipal solid waste (MSW), a Fe-Cu based alloy phase with great value was formed. In order to find proper commercial use in metallurgical industry, it is necessary to separate Cu and Fe. The present study focuses on the sulfide treatment at temperatures of 1400 – 1500oC, in particular with FeS containing minerals. Various sulfide compounds such as Na2S, Al2S3 and Ni3S2 were added to promote the copper removal. Pyrite and zinc sludge (containing ZnS) as waste streams were studied with specific interests. The results showed that both zinc sludge and pyrite are effective for copper removal with the highest removal efficiency of 95% by using pyrite. The copper content drops from 12 wt% to about 2 wt%. However, it is still difficult to remove copper completely from the alloy in one step, and a multi-step operation is needed.

Jan 1, 2008

By Frank Field, Randolph Kirchain, Elisa Alonso, Richard Roth, Nathan Fleming

"High material prices and price uncertainty can be harmful to manufacturing firms. Increased use of recycled materials, industry-wide, can lower both material prices and price variability; moreover, increased recycling decreases the use of primary material, which mitigates price increases due to scarcity effects. These stabilizing and price lowering effects are explored using an Aluminum industry model. We show that (a) increased recycling leads to smaller price fluctuations in the presence of a primary metal supply perturbation, and (b) that the more substitutable the secondary metal is for the primary metal, the lower the overall material price is.IntroductionThe price of an industrial metal is expected to be a function of both the marginal cost of extraction and its scarcity[l-2]: where scarcity can be defined as the degree to which anticipated demand exceeds the known supply. Recycling end-of-life metal increases the apparent supply of the metal, or-in a functionally equivalent, but alternative conception-lowers the demand for primary metal; this lowers primary metal scarcity and should, theoretically, reduce its price. To the extent that this theoretical prediction holds true, recycling can provide benefits to consumers of industrial metals in the form of lower prices.Using a platinum industry model, prior work by Alonso[3] has shown that increased industrywide recycling can reduce metal price volatility because the secondary metal production (a) offsets virgin metal depletion, and (b) responds to supply-demand balance fluctuations more rapidly than the primary market. However, Platinum is not a typical industrial metal in the sense that secondary metal is perfectly substitutable for primary metal: Both primary and secondary platinum metal are functionally equivalent and have a common price. Other metals, such as secondary aluminum which is used as an example case in this study, contain varying degrees of other elements that were either intentionally added, or were inadvertently mixed in with the metal during the scrap recovery process. Consequently, different grades of scrap exist that have different profiles of elements in their composition. Depending on their particular profile of elements, more or less of a given grade can be used as a mass fraction of the final alloy-the secondary metal is not perfectly substitutable for the primary metal. For the purposes of this paper, the aluminum mass fraction of the final alloy that can be made up of secondary aluminum is termed the secondary substitutability of that grade in that alloy."

Jan 1, 2011