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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 Heikki K. Jalkanen

Thermodynamic properties of copper-iron mattes and slag-matte distribution of copper and some minor matte constituents (Ni, Co, Mo, As, Sb and Bi) are discussed on? the basis of equilibrium measurements: a change from. oxidic to sulfidic solubility as the predominant form of dissolution of copper takes place as matte grade decreases. Distribution coefficients of minor matte constituents are complex functions of sulfur and/or oxygen potentials?. The distribution behaviour of different? metals can be qualitatively derived from their affinities to copper and stabilities. of their sulfides and oxides. The equilibrium results are compared with commercially observed values. from Outokumpu.Oy flash smelting furnace.

Jan 1, 1983

By John A. Clark, Danylo Oryshchyn, Casey Carney, Stephen Gerdemann, Cathy Summers, Thomas Ochs

"Limited analysis of combustion gas streams where carbon capture is not of interest is done mainly to ascertain operation parameters. Stringent regulations on acid gases and particulates promote careful flue gas analysis. Unregulated components are typically not analyzed. Typically not more than four points (two in the boiler, and one each in the flue and the stack) are sampled. A successful oxy-fuel process with carbon capture and compression is anticipated to require as many as 12 sample points with analysis for water, nitrogen, oxygen, argon, NOx, SOx, and carbon monoxide. Carbon dioxide captured for beverages produces a high value product and the cost associated with analysis is warranted. However, carbon capture for disposal must keep all costs to a minimum. This paper will compare alternative approaches for cost-effective sampling and analysis of the carbon dioxide product streams from oxy-fuel combustion, through all stages of production through compression and pipeline/vessel delivery.IntroductionAnalysis of gases in an oxy-combustion process with carbon capture is essential to the operations of the oxy-fired boiler and the subsequent collection, compression, and purification of carbon dioxide. The process is charged with pure oxygen and not-so-pure carbon in the form of coal at the front end, generating a product of mainly carbon dioxide with traces of argon, nitrogen, sulfur compounds, nitrogen compounds, oxygen, hydrogen, and mercury. It is possible that hydrogen chloride and hydrogen sulfide may also be present in trace amounts [1]. The trace components primarily come from impurities contained in coal such as water, sulfur, nitrogen, and volatile organic compounds. Coal also contains a good deal of mineral matter that is transformed into ash during combustion, becoming particulates that can complicate the analysis regimes utilizing standard analytical equipment."

Jan 1, 2010

By J. Brent Hiskey

The global copper industry faces a technological challenge to develop processing schemes for more complex and impure ores and concentrates. Group 15 elements (As, Sb, and Bi) represent impurities that are troublesome both in terms of environmental impact and metallurgical processing. The so-call "dirty" copper concentrates are either unacceptable for smelting and refining or incur high penalties. The behavior of the Group 15 elements is of critical importance in maintaining product quality and process performance. During copper electrorefining, these impurities are released to the electrolyte by electrochemical dissolution of the anode. Depending mainly on temperature, concentration, and oxidation state these elements can spontaneously coprecipitate from the electrolyte. Some of these precipitates are referred to as floating slimes and their formation can have extremely detrimental effects on cathode purity. In this paper, the mechanism of floating slimes formation will be discussed and the fundamental thermochemistry will be reviewed and analyzed in relation to solubility properties.

Jan 1, 2012

By Jan Smit

Sulphidic copper concentrates are generally processed by pyrometallurgical means; while oxidative pressure leach processing of such materials has been shown to be technically feasible, there has traditionally been little incentive to choose this route in favour of a smelting option. However, for concentrates with elevated arsenic levels, oxidative pressure leaching offers distinct advantages, as smelter air emission standards and restrictions on concentrate importation have tightened. The current state of pressure leach technology allows for high copper extractions from arsenical copper concentrates, while producing an environmentally stable process residue, without atmospheric emissions of sulphur dioxide or arsenic. In its studies on pressure leaching of copper concentrates, Sherritt has shown that arsenical feed materials can be converted into environmentally stable residues, with excellent copper extractions. The results of recent batch and pilot plant test work are discussed, including the deportments of copper, arsenic and precious metals.

By Jianxun Song, Hongmin Zhu, Qiuyu Wang, Jungang Hou, Shuqiang Jiao, Xiaobo Zhu

This work presents the results of a study on the Ti3+/Ti2+ couple redox potentials vs. Cl–/Cl2 at the temperature range (673 to 1073 K) in fused LiCl-KCl eutectic by direct potentiometric method. Initial concentrations of TiClx in solvents did not exceed 5.0 mol%. Basic thermodynamic properties of the reactions TiCl2+1/2Cl2(g)=TiCl3 were calculated using the temperature dependencies of apparent standard potentials of the couples E* Ti3+ /Ti2+.

Jan 1, 2014

By Demaerel. J. P.

Arsenic plays a major role during electroreflning of copper. Both the arsenic content in the anode and the arsenic concentration of the electrolyte have, in conjunction with other impurities such as lead, antimony, bismuth and oxygen, a direct influence on the quality of the cathode. The mechanisms are currently slime. inclusion and precipitation of insoluble compounds in the bulk of the electrolyte. Arsenic has also been reported to have a depassivating effect on the anode. An influence on the anode slime adhesion has also been found. A literature survey is given and these data are compared with and completed by our own results based on lab and pilot scale experiments as well as on Olen tank.house practice.

Jan 1, 1987

By Carlos Antonio da Silva

Steel refining reactors based on chemical heating are being used as an alternative to ladle furnaces, They show a high degree of flexibility in respect to heating rate in addition to carrying out refining reactions such as de-S, inclusion removal, alloying etc. IR-UT and CAS-OB are examples of such reactors. Their performance is dependent upon geometrical characteristics as well as operational conditions which determine the flow field inside the vessel. A physical model of the IR-UT process of the Companhia Siderúrgica de Tubarão, steel plant located in Serra, Espirito Santo, Brazil, was developed to assess the features of the flow field and its influence on the metallurgical behavior. Results of the physical model were used to optimize the process parameters in the industrial unit.

Jan 1, 2003

By Xin Wang, Hongmin Zhu, Shuqiang Jiao

"The behavior of electrochemically depositing silicon in a molten high-melting-point fluoride electrolyte was studied at 1300 °C. The cathodic product was characterized by XRD, SEM and EDS. Though the analysis of structure and composition of deposition, it could certify that silicon deposited on the Mo rod and alloyed with molybdenum. A series of tests had been performed on the cathodic behavior of Si4+ ions in BaF 2-CaF 2-Na2S iF 6 molten salt. The influence of electrochemical parameters on the cathodic deposition of silicon was also investigated. The electrochemical behavior of Si4+ ions in applied fluoride melts was observed to proceed according to one-step reaction.IntroductionGreenhouse warming has been a serious global issue. lt is increasingly urgent for clean and renewable energy. Effective utilization of clean and inexhaustible solar energy has become very important. Solar cell (especially poly-Si solar cell) production has significantly increased this decade, as there is a growing demand for clean energy. Since the early 1980s, the annual growth of the photovoltaic (PY) solar cell industry is more than 30%. More than 90% of the annual solar cell production is based on crystalline silicon wafers. This rapid growth leads to a shortage of silicon of the adequate quality and price for the continued growth of this industry [I , 2J. The most conunonly used technology to produce silicon is the so-called Siemens process. This technology, involves the forming of gaseous Si compounds such as trichlorosilane (SiHCli) or silane (SiH4) with subsequent thermal decomposition of these back to Si. This technology is associated with transformations from solid to gas, and then back to solid phase, which lead to high irreversible thermodynamic losses and subsequent high energy consumption, the energy cost being around 200kWh/kg Si [3l_ The purity of the material from this process is very high (9 to 11 N). In general, what is needed for solar cell purposes are reported to require 4 to 6 N quality. To promote continued growth of the silicon-based PY industry, there is need for a low-energy silicon production process which can produce large amounts of silicon with an acceptable quality and a lower price particularly."

Jan 1, 2012

By Carlos Antonio da Silva

Steel refining reactors based on chemical heating are being used as an alternative to ladle furnaces. They show a high degree of flexibility in respect to heating rate in addition to carrying out refining reactions such as de-S, inclusion removal, alloying etc. IR-UT and CAS-DB are examples of such reactors. Their performance is dependent upon geometrical characteristics as well as operational conditions which determine the flow field inside the vessel. A physical model of the IR-UT process of the Companhia Siderurgica de Tubarao, steel plant located in Serra, Espirito Santo, Brazil, was developed to assess the features of the flow field and its influence on the metallurgical behavior. Results of the physical model were used to optimize the process parameters in the industrial unit.

Jan 1, 2003

A novel, low-pressure adaptation of Praxair?s coherent jet technology utilizing CoJet lances was developed for application at Inco&apos;s Copper Cliff Smelter where oxygen is available in large tonnage quantities but only at relatively low supply pressures (< 193 kPa header pressure). The project objectives were to evaluate the effect of coherent jet technology on controlling oxygen lance accretion (?horn?) formation and to increase oxygen efficiency in the Inco Oxygen Top-Blowing Nitrogen Bottom Stirring (TBBS) MK Reactor used for converting nickel- contaminated chalcocite to semi-blister copper. This paper describes the development and subsequent implementation and testing of two CoJet lances in this application.

Jan 1, 2005

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 M. Ramprecht, M. Wu, A. Kharicha, A. Ludwig, H. Holzgruber

"The influence of the frequency of AC power supply on the magneto-hydrodynamic during the electroslag remelting process is studied. The focus is on the electrodynamic field and its resulting mechanical effects on the flow and liquid interfaces. The possible influence of the electrochemistry on the droplet formation is qualitatively discussed.IntroductionThe electroslag remelting (ESR) process is a secondary melting technique which can be used for a variety of metals and alloys, provided appropriate fluxes (slags) and melting parameters are employed. The ESR process is presently operating mostly with AC current of about 50 Hz. However for reasons primarily of inductive losses in the electric circuit, furnaces for ingots larger than 1 m, use or are projected to use current of very low frequency (< 5 Hz). Effects of lower frequencies (2.5-5Hz) on macrostructure and non-metallic inclusions were recently studied by Chang [1]. Most of investigations were performed either with DC power or with AC of 50-60 Hz [2-4]."

Jan 1, 2012

By M. Z. Mubarok

Effect of single addition of a lignin-based biopolymer additive, DP 2782, at various dosages as well as in combination with thiourea on cathode polarization during copper deposition was investigated by performing potentiodynamic and galvanostatic measurements using a potentiostat. The result of electrochemical measurements was compared with the behaviour of cathode deposition with glue and thiourea additives. Surface micro-appearance of the copper deposit after 1 h galvanostatic scan under current density of 330 A/m2 and various additive type and dosage was evaluated by scanning electron microscopy (SEM) examination. It was found that the addition of 2.5 mg/l biopolymer gave sufficiently polarizing effect of copper deposition. SEM examination of the cathode surface after galvanostatic scan revealed that the combination of the biopolymer with thiourea (2.5 and 3.5 mg/l) resulted in a compact deposit which is comparable with that resulted from the test with glue and thiourea.

By W. G. Davenport

Chapter 6 examined autotherrnal smelting of pure chalcopyrite concentrate with 50 mass% O2-50 mass% N2 blast. It showed that production of 1500 K products with this blast requires: 181 kg of pure oxygen 337 kg of air per tonne, of concentrate. It also showed that the grade of matte produced with this blast is 58% Cu. This chapter re-examines autotherrnal smelting by asking: (A) WHAT COMPOSITION BLAST (MASS% 02 -MASS% N2), 298 K, WILL AUTOTHERMALL Y PRODUCE 65% Cu MATTE 1500 K FROM PURE CHALCOPYRITE CONCENTRATE? (B) HOW MUCH PURE OXYGEN AND AIR WILL BE NEEDED? These are important questions for flash? smelting because furnace operators usually want to send specific composition matte to converting. This chapter shows how a specified matte can be produced autotherrnally with 298 K oxygen-air blast. Later chapters show how it can be done with hot blast, hydrocarbon combustion, different concentrates etc.

Jan 1, 2001

By Wang Dawan

During the process of arsenic bearing gold concentration biooxidation, the content of chloride ion in water is a very important factor to the activity of bacteria and the oxidation of sulfide minerals. In this paper, the influence of underground mine water with different chloride ion content to the biooxidation of arsenic bearing gold concentration and the limit of chloride ion content to bacteria were summarized. These results indicated if the content of chloride ion was less than 1.2g/L, the bacteria?s ability to oxidize sulfide minerals was little affected, and if the content of chloride ion were increased to 2g/L or more, the activity of bacteria was seriously restrained, and if the content of chloride ion were increased to 4g/L, the activity of bacteria was absolutely restrained. So, as the content of chloride ion in water was cumulated to 2g/L or more in biooxidation plant, the water must be refreshed to maintain normal production.

Jan 1, 2008

By M Kolbe

Co-Cu exhibits a metastable miscibility gap in the region of the undercooled melt. Specimens have been undercooled and solidified containerlessly into the metastable miscibility gap in an electromagnetic levitation facility (EML) and in drop tube (DT) experiments. Due to the high undercooling the velocity of the solidification front is very high and the microstructure is frozen in instantaneously. The microstructure of samples processed in the EML is influenced by the electromagnetic stirring due to the induction of electrical currents into the melt. A variety of microstructures has been observed. After undercooling below the binodal the liquid melt separates into the Co-rich L1-phase and the Cu-rich L2-phase. Two basic morphologies of the L1-phase can be observed, they can be attributed to the transition in dendrite growth from diffusionally and thermally controlled to only thermally controlled growth. Transient microstructures are observed after solidification in the vicinity of the binodal. Drop tube experiments, which lead to a rapid solidification of a distribution of droplets under reduced gravity conditions, in contrary allow for the observation of the early stages of demixing: the microstructure shows a homogeneous distribution of spherical particles of the minority phase in the droplets. The cooling rate of the droplets and its dependence on the droplet radius has been calculated. The solidification velocity as a function of undercooling has been measured in the EML for the composition Co-lB.Bat%Cu. The data are analysed in the framework of the LKTlBCT model with a velocity-dependent distribution coefficient as well as within a model of Galenko and Danilov using a kinetic growth coefficient of u=0.22 m/Ks.

Jan 1, 2002

By A. Navarra

Peirce-Smith converting (PSC) is applied for roughly 50% of primary nickel and 70% of primary copper production. PSC cycles produce batches of ironfree sulfide matte (or blister copper, in the case of copper smelters), that are subject to further processing. However, the number of cycles that can be performed simultaneously is limited by the offgas handling system. Moreover, PSC suffers from variation in the yield and duration of the cycles. This variation is managed by conventional smelter designs, in which the upstream smelting capacity exceeds the nominal converting capacity; PSC is thus a major bottleneck in conventional nickel and copper smelters. Stabilization and standardization of PSC operations can therefore increase smelter throughput. The current paper presents a discrete event simulation (DES) framework to assist in smelter debottlenecking. It features random number generation to represent cycle variability, and time-adaptive finite differences to represent thermochemical complexity. Preliminary computations are presented.

TiO2 and Ti/TiO2 thin films were deposited on a quartz substrate by laser ablation of Ti02 and Ti targets using Nd:YAG pulsed laser. After sulfurization of the Ti02 film in H2S or CS2 gas at 1273 K for 1 hour, the surface atomic structure was changed. Furthermore, the Ti/TiO2 film was successfully prepared by the subsequent ablation of Ti and TiO2 targets. The morphology and structure of the films were characterized by XRD, XPS and AFM analyses.

Jan 1, 2003

By T. Nakamura

TiO2 and Ti/TiO2 thin films were deposited on a quartz substrate by laser ablation of TiO2 and Ti targets using Nd:YAG pulsed laser. After sulfurization of the TiO2 film in H2S or CS2 gas at 1273 K for I hour, the surface atomic structure was changed. Furthermore, the Tirri02 film was successfully prepared by the subsequent ablation of Ti and Ti02 targets. The morphology and structure of the films were characterized by XRD, XPS and AFM analyses.

Jan 1, 2003