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By Masao Miyake, Eiichiro Matsubara, Tetsuji Hirato, Yasuhiro Awakura

"Zn-Cr alloy coating with around 15 wt% Cr has been found to have much higher chemical corrosion-resistance to steel than conventional zinc plating, while· its structure has not been clarified. The Zn-Cr alloy plating is performed at high current densities around 1 A cm-2 and for 10 to 20 sec using acidic aqueous sulfate solutions with some additives in the iron-steel industry. Due to the high current densities, it seems reasonable to consider that the Zn-Cr alloy plating proceeds under an unsteady-state condition and that the resulting coatings have a non-equilibrium phase and have a structure change in the .direction of thickness. In this research, the crystal structure of the Zn-Cr alloy coating electrodeposited at high current densities and change of the structure in the direction of thickness were examined by X-ray diffraction. The coatings containing under 20 and 35-40 wt% Cr had hcp and bee structure, respectively, while the coatings containing 20-35 wt% Cr comprised two phases with the hcp and the bee structure. The structure of the coating varied in the direction of thickness; both the hcp and bcc phases coexisted in the vicinity of the substrate, while the hcp phase became predominant with increasing distance from the substrate.IntroductionRecently it has been reported that Zn-Cr alloy coating containing around 15 wt% Cr has much higher corrosion-resistance to steel than conventional zinc plating.1-3) The corrosion-resistanc·e of Zn-Cr alloy plated steel sheet with a plating amount of 20 g m·2 is, for example, superior to that of Zn plated steel with a plating amount in the range 60 to 90 g m·2 , which is widely used for automotive bodies today.4l The Zn-Cr alloy plating is obtained by electrodeposition at current densities over 0.5 A cm·2 from a sulfate solution containing zinc and trivalent chromium ions and some additives.5•6) The deposition current densities mentioned above are much higher than those for usual electroplating processes, e.g., Zn, Cu and Ni plating, carried out about 0.05 A cm·2 • Therefore, the time required for plating is very short; around 10-20 sec. Due to the high current densities, it seems reasonable to consider that the· Zn-Cr alloy plating proceeds under an unsteady-state condition and that the resulting coatings do not have a phase expected from equilibrium diagrams; no phase diagram of the Zn-Cr system with a full composition range has been available. 7). In other words, the alloy phase plated would be a non-equilibrium phase with unknown structures."

Jan 1, 2000

Accretions of dust on the walls of the offtakes from furnaces and in the waste heat boiler are a cause of significant operating and maintenance problems in non-ferrous smelters. The dust originates from entrained solids in the gas stream and vaporised species that condense during gas cooling. Control of dust formation is very important for minimising the formation of accretions and reducing the severity of environmental problems caused by toxic species, such as those containing arsenic, in the dust. The present paper discusses the formation of accretions and the condensation of dust in copper smelting from a thermodynamic viewpoint. Changes, in gas composition and the amounts and identities of the condensed species in the dust are calculated using computational thermodynamics. Interactions between dust species to form accretions are considered in the light of appropriate phase equilibria. The results show that the nature of the dust formed varies greatly, depending on the temperature and the amount of oxygen present during cooling. Control of the amount of oxygen is required if offtake and waste heat boiler accretion problems are to be minimised.

Jan 1, 2002

By Wu Liu

A modified falling ball technique for measuring the viscosity of liquids is described. It consists of recording the weight vs. time of a crucible holding the liquid of unknown viscosity, as a solid ball, or liquid drop, is let to fall through the liquid. This method does not require measurements at constant terminal velocity, as the conventional falling ball technique. Also, measurements do not depend on visual observation, which is not possible in opaque liquids or containers. The effect of process parameters on the utility of this method and its potential application to liquid systems of metallurgical interest were analyzed theoretically. The paper also com- pares the gravimetric method to the conventional falling ball technique for measuring viscosity.

Jan 1, 1992

By Ramana. G. Reddy, Haoxing Yang

The electrodeposition of zinc from zinc oxide using urea and choline chloride mixture in a molar ratio 2:1 is investigated in different experimental variables, namely, the concentration of added [BMIM]HSO4, temperature, and applied cell voltage. The additive, [BMIM]HSO4, was determined to have beneficial effect on the current efficiency, energy consumed in the process and surface morphology of the deposits. The highest current efficiency (92.6%) and lowest energy consumption (2.92kWh/kg) was obtained for solution with 20mg/mL [BMIM]HSO4. The morphology showed the formation of absorbed additive layer on the cathode at higher concentration of additives. Experiments were conducted at different temperatures between 343K and 388K and at various applied cell voltages between 2.7V to 3.6V to determine the best experimental conditions. By varying temperature, highest current efficiency (91.3%) and lowest energy consumption (2.69 kWh/kg) was obtained at 373K. The electrodeposition process is enhanced between the applied voltage 3.0-3.3V by achieving lower energy consumption (2.75~3.06kWh/kg) and higher current efficiency (88.4~89.7%). SEM images showed grain size is significantly increased in higher applied voltages. While at higher temperatures, it seemed to generate particle growth as clusters at the outer deposit layer.

Jan 1, 2014

By Yoshiaki Suzuki

In 1996, Saganoseki smelter & refinery successfully shifted to a single flash smelting furnace operation and increased the copper production capacity to 450,000mtpy in 1998. As the next step, Saganoseki planned to further increase the productivity in the smelting process. Applying the latest technology and carrying out technological innovations the throughput of the flash smelting furnace has been increased to 195 tons per hour and the matte grade has been raised to 68%. In 2005, six PS converters have been successfully consolidated into four by maintaining the production capacity. This paper introduces recent operation conditions and results of implementation of technological improvements.

Jan 1, 2006

By Fuming Wang, Xin Lu, Hao Bai, Hebin Zhu

"In this study, CO2 emissions and carbon footprint of a typical steel works with integrated process and iron and steel industry in China was calculated and analyzed by a carbon footprint method based on the model of process CO2 emissions in iron and steel making. The carbon footprint of iron and steel industry from 1991 to 2010 in China showed a rapid increasing tendency. In 2008, the CO2 emissions of iron and steel industry in China was 1.289 billion tons, 19.71% of the national total CO2 emissions, and the corresponding carbon footprint was 159.13 million hm2 of green area. Carbon deficit of iron and steel industry also go up gradually if considering the carbon storage by green vegetation. Thus, the internal carbon reduction strategy, such as energy structure optimization and energy saving technology, was mainly encouraged for the sustainable development of iron and steel industry in China.IntroductionThe Global Warming resulting from the increase of Greenhouse Gases (GHGs), in particularly CO2, in the atmosphere has become the main reason of global climate change, and large emission reductions are required for sustainable development [ 1]. The iron and steel industry is the largest energy consuming manufacturing [2] in the world and the largest emitter of CO2 emissions. In 2005, it accounted for about 20% of global industrial energy use and 30% of energy and process CO2 emissions from industry [3]. In China, the crude steel has firmly been ranking at first of the world recent years and kept growing tendency year by year. With the production growth, the CO2 emissions of iron and steel industry also increased significantly and hence the steel industry has become one of the most sources of CO2 emission in China [4], which has attracted more and more attention to seek the carbon reduction strategies.Carbon footprint is an important and useful concept originating from Ecological Footprint, which was used efficiently to quantitatively analyze the impact of the human activities on ecological system, in particularly impact of the human energy activities [5]. In the view of Life Cycle, the carbon footprint is efficient to analyze the direct and indirect CO2 emission in the whole life of various products used in human activities. As to the iron and steel, the important materials and products in the human life, the carbon footprint analysis is quite necessary to evaluate the CO2 emission impact on the corresponding ecological system and global environmental."

Jan 1, 2013

By David G. Dixon

A mathematical model is derived in dimensionless form which simulates the effluent concentration response of reagents from spent heaps under both fresh and recycled water rinsing. The model is based on dispersion from isochoric pathways distributed in length and cross-section, oriented normal to convection channels in ideal plug flow. The effects of heap height, rinsate flow, and initial reagent concentration are examined. It is shown that the rinsing cycle undergoes a distinct shift between fast and slow rinsing at a certain time depending on the amount of stagnant solution in the heap, and the distribution of dispersion pathways. Results of preliminary column rinsing tests on both agglomerated and unagglomerated ores are presented which partially validate the model.

Jan 1, 1994

By Singareddy R. Reddy, Ramana G. Reddy

"The Margules equation is used for interpreting excess Gibbs energy of several ternary systems. An expression for the activity coefficient of a dilute solute, 2(oxygen), in a binary solvent 1-3 is derived. It is used to calculate the logarithmic activity coefficient of oxygen in Pb-O-Gu, Pb-O-Bi, AgO- Sn, Pb-O-Sn and Ag-O-Pb metallic systems. Self interaction parameter of the solute is derived from the partial Gibbs energy of solute using constant compositional path. The derived equation is used successfully to deduce the self interaction parameter of oxygen in Pb-O-Gu and Pb-O-Bi metallic systems. The predicted thermodynamic parameter data i.e activity coefficient and self-interaction parameters are in an excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.1 IntroductionThe nature of solute interactions such as oxygen, nitrogen and sulfur with the metallic solutions are important for a number of chemical and metallurgical processes. Several theories [1-23] have been developed to evaluate fundamental thermodynamic properties of solutes constituting two elements. The activity of solutes has been calculated using statisticalor quasi- chemical approach.Wagner's [4] Ideal Solvent Model is based on one energy parameter to describe the compositional dependencies of the activity coefficient of nonmetallic solutes such as oxygen in binary metallic solutions. This model depends on a constant energy of interaction for the exchange of atoms from the coordination shell of an oxygen atom to the shell of an interstitial site and cannot account for properties of strongly interacting systems [4]. Therefore, several attempts have been made to improve the Wagner's model for the strongly interacting systems. [10-16]."

Jan 1, 1996

By Guohui Zheng

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

Jan 1, 1996

By A. V. Tarasov, A. D. Besser

A processing flowsheet has been developed for treating substandard lead-containing polymetallic bulk concentrates and intermediate flotation products containing precious metals, which comprises oxidizing roasting in a calcination kiln and electrothermic smelting generating low volumes of off-gas. The proposed flowsheet also incorporates a dust collection system and sulfur dioxide recovery from off-gas. It is proposed to implement this process by using a reaction smelting technique. For this purpose, the charge to be fed to the smelting furnace after its calcination in a drum-type rotary kiln must have a ratio of sulfide sulfur to sulfate sulfur of at least 1 :2. Electric smelting makes it possible to produce lead bullion that also collects the precious metals contained in the feed, as well as copper-lead matte and slag containing zinc. The recovery of lead into lead bullion and into matte is approximately 83% and 14%, respectively (thus the overall recovery is 97%); the total recovery of gold and silver into lead bullion and matte is 98%; th\lt of copper into matte is 89%; the recovery of zinc into slag is 96%; and that of sulfur into sulfuric acid or gypsum is 90%. After the recovery of zinc from slag, the latter can be utilized in the construction industry.

Jan 1, 2000

By Bo Jiang, Lianyun Liu, Hongmin Zhu, Kai Huang

"Watermelon peel is selected as a novel adsorbent to remove Pb(II) from aqueous solution. A simple saponification process is proposed to modify the peel and the adsorbent is characterized by SEM and FTIR. The effects of pH, contact time, initial concentration of Pb(ll), biosorbent dosage and temperature on adsorption of Pb(II) are investigated. Different models are used to fit experimental data. These models indicate that the adsorption process follows the Langmuir model and pseudo-second-order model. The maximum adsorption capacity obtained from Langmuir model is 1.05mol kg-1 for the prepared sorbent. Equilibrium time is attained in 5-10 min for the studied concentrations. The watermelon peel can be used as an effective and low-cost biosorbent for removal of Pb(ll) from aqueous solution.IntroductionRecently, removal of heavy metal ions from industrial effluents by biosorption has become a very attractive topic, since the more serious pollution issues caused by heavy metals emerge frequently, and more strict requirements for its control are called upon by society [1,2]. In this case, most conventional purification technologies are not suitable due to poor cost-effectiveness [3]. For example, chemical precipitation by alkaline reagents usually can not decrease the metal ion concentration below the permissive levels, and also it will produce a large amount of sludge containing toxic metals. Membrane separation techniques can realize deep purification of wastewater easily, although its operating cost is usually high. Thus, considering the high effectiveness, low cost and free-sludge operation, bisorption has become a promising technique in water treatment [4]. The most important thing for this technology is the synthesis of a suitable biosorbent, whose adsorption properties will determine the removal efficiency and economic cost for the whole process. Watermelon is one of the most popular fruits for mankind for its delicious flavor. Usually, the watermelon is consumed mainly for its edible pulp, and its peel is discarded or only used as feed for livestock. Considering the pectin contained in the watermelon peel, just like that in orange wastes in the reported literatures [3], the idea of using it as the raw material to prepare the biosorbents for heavy metal ions removal from the aqueous solution was evaluated in this study."

Jan 1, 2012

By T. Innmi

The potential of the nickel matte anode was measured during the matte electrolysis in the commercial cell. The slime layer consists of elemental sulfur and was found to greatly influence the potential of anode. The measurements of porosity and permeability of the slime suggest that the voltage drop of the slime layer dominates the potential. Furthermore, the diffusion of the electrolyte through the slime layer is also one of the factors to determine the potential. In addition, the copper content of the nickel matte anode was found to affect the change in the anode potential during the electrolysis. The role of copper on the anodic dissolution of nickel matte is discussed in this work.

Jan 1, 1988

By Hector M. Henao

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

Jan 1, 2002

By Jorge Alberto Soares Tenório, Viviane Tavares de Moraes, Denise Crocce Romano Espinosa, Franco Alves Lavacchini Ramunno

"The traditional process for recovery of metals from waste electric and electronic equipment (WEEE) usually involves pyrometallurgical processing. However, the application of this technology to processing waste printed circuit boards (WPCBs) might lead to the formation of dioxins and furans, due to thermal degradation of flame-retardants and polymeric resins present in the board substrate. Therefore, this paper proposes a hydrometallurgical route for the recovery of copper. The acid leaching behavior of copper has been investigated at three different temperatures (25°C, 50°C and 75°C) with and without the addition of an oxidizing agent (hydrogen peroxide - H202). The dissolution kinetics for acid copper leaching was calculated based on chemical analysis by ICP-OES (Inductively Coupled Plasma - Optical Emission Spectroscopy). At 50°C with 1 mol/L H2S04 added 10 mL H202 (30%) each half hour under pulp density of 1 g I 10 mL, 100% of copper was extracted after 3 hours. The dissolution kinetics of copper with H2SO4-H2O 2 followed 1 - (1 - X)113 =Ket, i.e. chemically controlled reaction model.IntroductionThe information regarding the generation of waste electric and electronic equipment (WEEE) are still difficult to obtain because the estimates should take into consideration the historical production and sale of various products and the rate at which they reach the end of their life cycle, whose duration depends on the behavior of consumers [1]. Thus, the estimated overall WEEE generation varies between 25 and 50 million tons each year, which corresponds to more than 5% of all municipal waste generated [2], and this amount will increase at a rate of 3 to 5% per year, approximately three times faster than other individual types of waste [3].Printed circuit boards (PCBs) are essential parts of electric and electronic equipment (EEE), being found in virtually all electronic products, as well as in weapons systems [4]. A PCB is a basic component, which consists of a board where copper tracks are deposited. While the board behaves as an electrical insulator, the tracks connect electrically the various components attached to the board [ 5]. In addition to glass fibers, paper and resins, the PCBs contain significant amounts of metals, such as copper, iron, nickel, lead, stain, silver, gold and palladium [6]. In general, the weight fraction of metal is around 28% and the remainder of the boards is composed of plastic (19%), bromine (as flame retardant - 4%) and ceramic material (49%) [7]."

Jan 1, 2014

By Gunther Schimmel

Ag exudation in four different alloys (Ag-Cd, Ag-Sn, Ag-Sn-In and Ag-Zn) is characterized. The amount of exuded material is correlated with the volume increase due to oxide formation in dependence of the alloy concentration and different densities of the oxide and matrix phases. It is shown that all four alloys show similar amounts of volume increases, but different amounts of exuded material. It is concluded that internal stresses due to the volume increase cannot be the dominant driving force for Ag exudation. A gradient in the chemical potential of Ag that originates from the O concentration gradient inherent to internal oxidation is suggested as driving force. The exudation behavior is thus governed by the variation of the activity of Ag in the Ag fcc phase in the Ag-Me-O system that differs between the alloying systems.

Jan 1, 2010

By B. Bichel

For the last 70 years, molten blister copper has been transferred by rail in hot metal cars from the Copper Cliff Smelter to the Copper Cliff Copper Refinery (ex Ontario Refining Company) where it was processed in two (2) reverberatory anode furnaces by poling with logs, cast on four (4) wheels, and then electrorefined. This practice was modernized in 2001 with the installation of two (2) rotary anode furnaces at the. Copper Cliff Smelter which employ steam and. natural gas for reducing and which provide a significant reduction in emissions. A new casting shop with a single anode casting wheel is used to cast regular and stripper constant weight anodes which are transported by truck to the Copper Cliff Copper Refinery for anode preparation and electrorefining. This paper provides an overview of the copper circuit at the Copper Cliff Smelter and a description of the CDN$31 million capital project.

Jan 1, 2002

By S. Fitzel

The Betts process for electrorefining of lead has been in operation since 1902 in the Trail Operations Metallurgical complex. The Betts process allows production of high purity lead in a single electrochemical step. Process improvements and plant expansions have taken place over the many decades of operation of this process which has proven to be robust, flexible, and capable of successfully treating a large range of anode bullion compositions. This paper reviews the history of the Betts lead electrorefining process, the innovations and quick industrial adoption of new discoveries that took place at the end of the nineteenth century. The process was first implemented in Trail Operations and integrated very well with metallurgical needs then and now.

By Andreas Siegmund

Cast or rolled lead anodes employed in zinc electrowinning typically contain between 0.5?1.0% silver to decrease the overall corrosion rate. The production of cast lead-silver or lead-silver-calcium anodes often results in the formation of numerous holes, voids or laps in the anode surface that can initiate internal corrosion in localized areas. In rolled anodes the presence of internal porosity is significantly reduced, thus resulting in extended service life. The obtained grain structure of cast or rolled Pb-Ag anodes, however, requires a relatively long period of time to form a stable protective PbO2/MnO2 layer that can evolve oxygen without excessive lead contamination of the cathode. Therefore, these anodes are often mechanically, chemically or electrochemically conditioned prior to being placed in the electrowinning process. RSR Technologies has developed an improved anode for zinc electrowinning. The anode consists of a rolled Pb-Ag-Ca-alloy with controlled surface grain structure. The preferred calcium and silver content of the alloy is 0.05?0.08 % and 0.3?0.4%, respectively. Since May 2001, industrial-scale tests have been carried out at two zinc refineries in North America in industrial electrowinning cells. The controlled grain structure of these anodes allows forming an adherent protective oxide coating within a short period of several days when placed in an electrowinning cell without the necessity of being preconditioned. Anode sludge growth is evenly distributed. The anodes stay dimensionally stable and no short-circuits have been observed. Consequently, low corrosion rates and improved current efficiencies have been achieved.

Jan 1, 2003

By M. J. Adam

The U.S. Bureau of Mines is investigating the partitioning of selected complex minerals into simple phases using sulfidation reactions. Successful partitioning of complex mineralogy to simple phases may afford an opportunity to improve selective extraction of mineral constituents of economic value. The research has shown that complex minerals, such as chalcopyrite (CuFeS2) and pentlandite [(Fe,Ni)9Se]' may be partitioned to the simpler phases covellite (CuS) plus pyrite (FeS2) and vaesite (NiS2) plus pyrite (FeS2), respectively. Demonstrations of these reactions were verified through long-react ion-time (24 h or more) experiments, but basic rate investigations and modeling were not included in the previous research. This report describes research aimed at determining the rate at which the complex mineral CuFeS2 converts to the simple sulfides CuS plus FeS2. Small samples of CuFeS2 were blended with elemental S prior to thermal treating under an He atmosphere for time periods up to 4 h. Products from each treatment period were characterized using metallography, chemical analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Results of the investigation revealed a rapid conversion of CuFeS2 to CuS plus FeS2 early in thermal treatment periods. As the reaction occurred, a CuS rimming of particles was observed which separated the reacting species (CuFeS2 and S) and caused a considerable decrease in transformation rate.

Jan 1, 1991

By Arthur G. Hunt

Smelting using the direct-to-blister process commenced at Olympic Dam on 31 July 1988. The unique nature of the Olympic Dam ore body led to the selection of the direct to blister smelting process. Significant improvement in the design of the furnace and the understanding of the fundamentals of the process and its operation has occurred in the 10 years of operation. The paper will discuss the operation of the #1 Smelter and the design, preparation for start up and early operating experience of the #2 Smelter.

Jan 1, 1999