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By S. Seetharaman, Du Siehen

"In the processing of molten metals, it is extremely important to monitor continuously the concentration levels of various minor elements. In the production of common metals like copper, iron and aluminium electrochemical sensors involving solid as well as liquid electrolytes are being increasingly used to measure the concentrations of minor elements. The present paper deals with the electrochemical principles underlying these measurements and the possible errors involved. One of the major difficulties in the case of the solid electrolytes is to correct for the consequences of the electronic contribution to the conduction of the electrolyte.The application of the electrochemical sensors for molten metals processing involves designing of these probes to withstand the industrial operating conditions. In this respect, significant achievements have been made with respect to the design of oxygen probes for liquid metals in general and liquid copper in particular. Some of the salient design features are discussed in the paper. The application of auxiliary electrodes for impurities in molten metals like phosphorus in copper and silicon in iron are taken up. The development of oxygen sensors for slags is given special attention. Recent developments in the field of sensor technology, as applied to metals processing are highlighted.1. IntroductionThe rapid technological advancement today require precise control of the process parameters and the impurity levels. Most of the molten metals processing in industrialized countries are often steered by suitable computer models, either phenomenological or simulations based on theoretical principles. These models often require that the process parameters are continuously monitored so that the progress is followed and modified suitably as and when required. It is common practice to measure temperatures by incorporating temperature sensors at the various strategic points of the reactor. In the case of monitoring the composition changes in the various phases, the method of sampling followed by routine chemical analysis involves a time lag as well as uncertainties in sampling and analysis. In this respect, electrochemical sensors have the advantage of generating accurate data when properly applied and increasing attention is being paid in the development of electrochemical sensors for various common species in molten metals processing. In the present paper, the developments in this area over the years are outlined and typical process applications are discussed. A greater emphasis will be laid on sensors based on oxygen conducting electrolytes and their application to the production of common metals like iron and copper."

Jan 1, 1996

By Zhi-biao Yin

Copper smelter flue dusts often cannot be directly recycled to the smelting process and accumulate as hazardous wastes requiring environmentally acceptable disposal. Because of the limited amount of flue dust, a separate copper extraction process must be simple and require-a small plant investment. A flue dust process has been developed, consisting of the following steps: (1) roasting a pelletized mixture of hydrated lime and flue dust to fix arsenic and sulfur as insoluble calcium salts, (2) heap leaching the roasted pellets with a buffered ammonia/ammonium salt solution to extract copper as an ammine complex in a lined cell that is the final repository of the leached pellets, and (3) boiling ammonia from the lixiviant to precipitate copper. Condensed ammonia and the filtered solution are returned to leaching. Heap leaching in the final repository cell lowers the capital investment significantly compared with competing extraction processes. Chemistry with respect to arsenic, sulfur and copper is discussed.

Jan 1, 1992

By Timothy W. Skszek, Adrian S. Sabau, Hebi Yin, Gerard M. Ludtka, Xiaoping Niu

"A constitutive model has been developed to predict the yield strength aging curves for aluminum casting alloys during non-isothermal age-hardening processes. The model provides the specific relationship between the process variables and yield strength. Several aging heat treatment scenarios have been investigated using the proposed model, including two-step aging recipes. Two-step aging heat treatments involve a low temperature regime to promote nucleation of secondary phases and a second step at higher temperature for the growth of the secondary phases. The predicted results show that a yield strength of approximately 300MPa might be obtained in a shorter aging time, of approximately 30 minutes. As a result, better mechanical properties can be obtained by optimizing the time-temperature schedules for the precipitation hardening process of heat treatable aluminum alloys.IntroductionA356 is one of the commercially heat treatable aluminum casting alloys, and T6 is one of the heat-treated conditions to improve mechanical properties. The first stage of a T6 temper is solution treatment at an elevated temperature, generally in the range of 480 - 540°C. After solution treatment, the cast part is typically quenched in water/air to retain the solute-rich homogeneous matrix chemistry at room temperature. Subsequent ageing treatment stages capitalize on this super-saturated solid solution to generate controlled dispersions of very small strengthening precipitates within the matrix of Al grains [l]."

Jan 1, 2013

By Stephen C. Britten

An in-situ amperometric slag sensor for measuring the concentration of easily dissociable oxides in slags at temperatures between 1200-1600°C is being developed. The sensor provides the same information as potentiometric sensors while also providing data on the concentration of the transition metal species and the diffision kinetics within the slag. The electrochemical technique utilized in the sensor is similar to methods utilized in aqueous voltammetry.

Jan 1, 1998

By S. q. Honingh, G. Van Weert

Currently produced zinc-enriched blast furnace dust is stored on site at CORUS IJmuiden. To end this practise, a research program was started in 1996. Four technologies were studied: oxidative autoclave leaching in a chloride medium, fluid bed pyrohydrochloridisation (pyrohydrolysis) to yield lead-zinc-free (hematite) calcine, EAF (plasma) smelting/zinc fuming, and incorporation of the dust in 'iron foundry cupola charges. All aim to remove zinc and lead, recycle the iron residue internally, and produce a saleable zinc-lead product.

Jan 1, 2000

By Takashi Araki

In this work, we have elucidated the two-step oxidative reaction mechanism of 2,4,5-trichlorophenol by adsorbing oxygen atom for oxidative decomposition reaction of 2,4,5-trichlorophenol on oxide catalyst surface using ab initio molecular orbital calculation. In the first oxidation, total energies of reaction products have been shown extremely stabilized at all oxidation positions. This reaction occurs due to charge transfer from benzene ring to adsorbing oxygen atom. As a result, 1£ bonding of benzene ring are weakened. However, the benzene ring of 2,4,5-trichlorophenol does not perform cleavage reaction. In the second oxidation, the benzene ring of2,4,5-trichlorophenol can perform cleavage reaction, since the second oxidation obtains larger stabilized energies than the first oxidation.

Jan 1, 2003

By Junfu Chen, Jiann-Yang Hwang, Yong Zhou, Lijun Lu, Likun Lia, Jixiong Liu

The sheet-like NiS-ZnS heterostructured composites were prepared by the microwave hydrothermal. The fabrication of the heterojunctions broadened the range of light response of ZnS. The photoexcited electrons of ZnS migrated to the redox potential of NiS/Ni2S under visible light irradiation, which can facilitate the effective separation of photogenerated electrons and holes in space. The visible photocatalytic activity towards hydrogen production for NiS/ZnS nanosheet heterostructed composites without co-catalyst achieved 0.28 mmol h–1, and the quantum efficiency was up to 18.6% under the wavelength with 420 nm visible light irradiation.

Jan 1, 2015

Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

By Chonghe Li, Xionggang Lu, Wei Xiao, Xingli Zou, Weizhong Ding

The reduction degree and rate of the initial ilmenite concentrate and pre-oxidation samples by hydrogen were investigated by using thermogravimetric analysis system. H2-TPR was used to detected reduction properties of the pre-oxidation products which were oxidized at different temperatures. The phase transformations and micromorphology changes during pre-oxidation and hydrogen reduction were identified by XRD and SEM. The FeTiO3 was decomposed into TiO2 and Fe2O3 at the temperature below 900 oC. With the temperature rising, Fe2TiO5 was the only stable phase in high temperatures. The reduction of pre-oxidation ilmenite concentrate was faster than the natural sample, which was attributed to the micropores generated on the surface of ilmenite concentrate during oxidation. The main phases of the reduction product were metallic iron, ferrous pseuodbrookite.

Jan 1, 2014

By I. A. Ibrahim, A. K. Ismail, A. A. I. Afifi

"Synthetic rutile for paints industry is conventionally produced by a combined smelting and leaching process. Smelting process is an energy intensive step and represents economic burden in view of the increasing energy costs. Egyptian ilmenite ore containing 40% TiO2 and 38% total Fe was thus directly leached with sulphuric acid to produce eventually synthetic rutile. The process-involves digestion of the ore with sulphuric acid whereby both TiO2 and Fe are dissolved. The solution was then treated with iron powder to convert Fe3+ to Fe2+ to avoid co-precipitation of iron during the hydrolysis step. After solid/liquid separation and clarification, Fe was crystallized as ferrous sulphate hydrate by chilling. The titanium pregnant liquor was concentrated by evaporation and then hydrolyzed to precipitate hydrated titanium dioxide which was then calcined to produce synthetic rutile containing 98.6 TiO2 and 0.58% Fe2O 3. The optimum conditions of all the processing stages were determined.IntroductionSynthetic rutile for paints, welding rods and other industries could be produced from ilmenite ore by sulfuric acid leaching process. This process is a batch process and nearly 80% of all TiO2 produced in the world is made by this process [1]. Figure l shows simple block flowsheet of the process. The process involves the following stages.Digestion: In this stage, ilmenite ore is treated with concentrated sulfuric acid where both iron and titanium are converted to their respective sulfates according to the following equations:"

Jan 1, 2000

By Pan Gu, Zhen Zhang, Jiang Diao, Bing Xie, Hongyi Li

Furnace refractories are in most cases chemically incompatible with smelter slag, which leads to a steady erosion in their thickness over time. Once too thin, refractory walls become mechanically unstable and catastrophic failure can result. Historically, external shell cooling was applied to generate a freeze lining of slag and thus prevent refractory erosion. Many modern high intensity smelting furnaces instead maintain their physical integrity by the use of internally cooled wall panels, plates or finger coolers. An initial refractory lining is often installed inside of the coolers, such that the furnace originally operates with a temperature (insulated) rather than a heat flux (freeze lined) boundary condition. This paper examines the change in slag-wall heat transfer coefficient and slag superheat as a function of process intensity. The implications of the changes in heat transfer on residual brick thickness are explored using analytical modelling.

Jan 1, 2016

By J. S. Becker

Technology developed and first implemented in the United Kingdom enables very low grade aluminum scraps containing oils, organics, plastics and ferrous metals to be directly charged, without pretreatment, into a unique melting furnace. The system has been in full scale production for four years. The oxy-fuel-based furnace design incorporates internal afterburning in the furnace's hot zone, producing excellent thermal efficiency and very low emissions. The furnace is inherently low in NOx. This paper will provide both theoretical background and extensive operating results for this new melting concept. Applications describing both purpose built new furnaces and retrofits of existing reverberatory furnaces will be presented. Extensive operating emissions data will be presented.

Jan 1, 1997

By Akira Yazawa, Kazuo Koike, Mitsuhisa Hino

"The vapor pressures of MS (PbS, SnS and Sb2S3) in the molten Cu2S-MS, FeS-MS pseudo-binary and Cu2S-FeS-MS ternary systems were measured by means of a transportation method in the temperature range of 1323 and 1423K to calculate MS activities in the sulfide melts. The activities of MS in these systems show negative deviation from ideal behavior except the FeS binary systems which exhibit nearly ideal behavior in the homogeneous melts. The activities of the Cu2S-FeS pseudobinary system, which is fundamentals of the copper matte, were estimated from the activity values in the ternary systems and exhibit negative deviation from ideality.The distribution behavior of tin between the ·matte and silica saturated fayalite slag was investigated under the controlled partial pressures of S02 at l 523K. It was found that, in general, tin is distributed in the both phase, while tin is concentrated to the slag phase with increasing copper content in the matte. The activity coefficient of SnO in the slag was calculated based on the distribution ratio combined with the activity coefficient in the Cu2S-FeS system.IntroductionThe thermodynamic properties related to the Cu2S-FeS system and the Cu2S-FeS-MS systems (where MS can be PbS, SnS, Sb2S3, As2S3, Bi2S3, etc.) is required to be better understanding of the copper smelting process. However, thermodynamic analysis such as the distribution of impurities among the gas, slag and matte phases is difficult due to lack of thermodynamic data. In this study, the vapor pressures of MS (PbS, SnS and Sb2S3) in the Cu2S-MS, FeS-MS. and Cu2S-FeS-MS systems were measured by a transportation method. The distribution behavior of tin between the matte and silica saturated fayalite slag was also investigated. The results in the present experiments are useful to analyze thermodynamically the behavior of component in the copper matte smelting."

Jan 1, 2000

By R. Mehta, M. Misra, X. Su

"The conventional methods to assess Acid Mine Drainage (AMD) potential of the waste rocks and tailings are based on wet chemistry and leachability tests. These methods are time consuming and expensive. There is a growing interest to develop alternate techniques to establish the reactivity of acid mine tailings and stability of treated waste forms. The Electrochemical Impedance Spectroscopy (EIS) is a reliable non-invasive technique which can be used for quick estimation of reactivity of the potential acid generating tailings. In this paper the utilization of the EIS technique for the estimation of reactivity of tailings is discussed. EIS can also be used to predict the long term stability of different stabilized waste forms.IntroductionMetal contaminated mine drainage is one of the most persistent environmental problems facing the mining and mineral processing industries today. Of all the mine drainage pollutants, acid mine drainage has become a substantial concern because of the potential long-term environmental implications and the accompanying liabilities. The main source of acid mine drainage is the tailings containing sulfide-ores which are generated during the ore processing. When these sulfide minerals, particularly pyrite and pyrrhotite, are exposed to oxygen and water they begin to oxidize. The initial chemical reactions produce acid and the acid dissolves heavy metals present in the tailings. Rainfall and snow-melt flush the toxic solutions from the waste sites into the downstream environment [1-2]. In addition to mining tailings, several Department of Energy (DOE) sites contain wastes which are contaminated with radionuclides and heavy metals."

Jan 1, 1999

By J. R. Parga

A shortage of landfill space and growing environmental concerns in Mexico are renewing interest in the recyclability of scrap from automobiles. This work describes a pyroumetallurgical process for the recovery of metallic lead from waste lead paste. Argentopyrite concentrate is commingled with lead paste residue and smelted in a fuming process thereby transferring the precious metals into lead bullion. The process consists of smelting lead paste and argentopyrite, sodium carbonate, and metallic iron at smelting temperatures of about 1100 T. The reaction products are slag and molten lead bullion enriched with precious metals. A major feature of this process is the removal of precious metals from the bullion by means of zinc, whereby a silver-zinc intermetallic compound is formed and floats out of the lead. The recoveries of precious metals are about 98%.

Jan 1, 1996

By Xie Zhang, Chongyang Zhao, Qingyun Huang, Bing Xie, Xiaopeng Zhen

"Extracting vanadium from vanadium containing hot metal into vanadium slag by BOF is the main vanadium production process in China. In this paper, the influence of Si content in hot metal on the quality of vanadium slag is analyzed. Synthetic vanadium slag with different SiO2 content were melted at 1673 K and then cooled to 303K at the cooling rate of 3?/min. Optical microscopy, SEM, EDS and XRD were used to analyze the mineralogical phases and crystallization behavior of vanadium slag. The results show that vanadium slag mainly contains spinel phase and silicate phase; V is enriched in the spinel phases while Si is concentrated in Fe2SiO4 CaFeSi2O6 and (Fe,Mn)2SiO4 as silicate phase. The melting point of slag increases gradually with the addition of SiO2; whereas viscosity decreases with an addition of 15~19% SiO2 and increases with an addition of 19~27% SiO2.IntroductionVanadium is an important element which is used almost exclusively in ferrous and non-ferrous alloys. The major vanadium products include FeV, V2O5, V2O3, VN and Al-V-Ti alloy. Furthermore, vanadium slags are mostly produced by oxidizing the elements in V-containing hot metal during a duplex refining process. Therefore, the process of removing vanadium from hot metal has its significance on the subsequent process[1].The extraction of vanadium is greatly affected by the mineralogical composition of vanadium slag[2], the distribution of the elements between the spinel and silicate phases and its physic-chemical properties. These characteristics of vanadium slag have been studied in some details. It has been reported that Si mainly exists mainly in the form of silicate which wraps the spinel crystals while small amount of Si stands as phosphorus quartz or diopside[2]. Chen et al.[3, 4] points out, when SiO2 content in vanadium slag increased every 1%, V2O5 decreased 1.48%. Moreover, silicate phases would embarrass the oxidation of V-containing spinels through decreasing the exposing probability[5]. Meanwhile, melting point and viscosity of vanadium slag has been greatly influenced by the SiO2 content. Therefore, this work attempts to analyze the above-mentioned questions systematically."

Jan 1, 2012

By X. J. Wu

Effects of various factors such as diaphragm materials, composition of electrolytes and current density on copper electrowinning from cupric chloride solutions was investigated. It is found that the crux of this process is to prevent the dissolution of copper by cupric ion and the formation of suspended CuCl precipitate. A process with high difference of copper concentrations between the feed solution and the spent electrolyte was selected. With this process, in which the feed solution contains 90 g/dm3 [Cu"], 3M NaC1, and 10mg/dm3 bone glue, and the spent electrolytes contains 10 g/dm3 [Cul, a very smooth and dense copper cathode can be produced with current efficiency above 93% and energy requirement less than 1.7 kwh/kg Cu at 25°C with N2 sparging. If a slightly higher energy requirement is permitted, smooth and dense copper cathodes can be produced at the current density up to 800 A/m2 with the identical solutions.

Jan 1, 1991

By Kazuyoshi Shimakage, Shinji Hirai, Kenji Wada

"An amorphous zirconium oxide coating was prepared by the sol-gel process using zirconium tetra-n-butoxide on the surface of aluminum to improve the corrosion resistance to salt, acid and alkaline attacks. The coating films formed on the smooth aluminum substrates under UV-irradiation indicated an excellent corrosion resistance for salt, acid and alkaline attack tests. For example, the corroded area of coating film in salt attack test for 3600ks in the order of sol-gel coating· film< chromate film <boehmite film, and the sol-gel coating film had the best corrosion resistance. The coating film prepared on the coarse aluminum substrate by a boiling treatment after heat treatment at 573K also had greater corrosion resistance, and a water-avid surface appeared a contact angle of approximately 3°.IntroductionAs given in a previous paper1; a composite film consisting of a porous layer of anodically grown aluminum oxide filled with amorphous zirconium oxide and an amorphous zirconium oxide coating layer deposited thereon via the sol-gel process utilizing the dip-coating technique, was prepared to improve the alkaline corrosion resistance of aluminum. The alkaline corrosion resistance of these composite films was increased in the range of 24 to 50 times those of conventional anodic oxide films anodized in sulfuric acid. As a result, it was proved that heat treatment at 573K after dip-coating was an important process to .remove organic component from gel film and to accelerate the densification of coating layer. Furthermore, the effect of ultraviolet (UV) irradiation at ambient temperature on the densification of coating layer was also examined to lower the heat-treatment temperature2.Then, a sol-gel film prepared by UV irradiation at ambient temperature indicated that alkaline corrosion resistance of aluminum was superior in the range of 2.4 times to 2. 6 times that of the conventional composite film heated at 573K."

Jan 1, 2000

By Karel Verscheure

Hydrometallurgical zinc leach residue, EAF dust and other Zn-bearing by-products pose potentially serious environmental problems that threaten the sustainability of the operations. A pyrometallurgical process designed for treatment of such residues is the high-temperature submerged plasma Zn-fuming process. The successful operation of this process requires high Zn fuming rates whilst retaining vessel integrity through stable freeze-lining. A Zn-fuming model has been developed and used to systematically investigate a range of operating scenarios and to identify potential fluxing parameters such as CaO/SiO2, Fe/SiO2, MgO/feed-ratios in the input and fluxing additions of dolomite for maximum fuming rates and stable freeze-lining.

Jan 1, 2006

By Matthew Jeffrey

Due to the increasing environmental and public concerns over cyanidation, there has been a large amount of research into viable alternative lixiviants. Despite these studies, there is little published data directly comparing the kinetics of gold leaching for each of these alternatives: most of the literature is concerned with gold extraction from ores. This paper presents a detailed kinetic study of gold leaching in cyanide, armmonia/thiosulfate and chloride/hypochlorite solutions. The gold leach rates were measured using a rotating electrochemical quartz crystal microbalance (REQCM). This instrument allows the mass of a gold sample to measured in?situ, with a sensitivity of less than 10 ng. From the results of these studies, it is possible to select experimental conditions where the leach rates of the alternative lixiviants are similar to that for the traditional cyanide system.

Jan 1, 1998