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By Edouard Asselin, Guikuan Yue

"In the present study, electrochemical measurements, especially cathodic potentiodynamic polarization (CPC) and cyclic potentiodynamic polarization (CPP), have been employed to study the kinetics of ferric reduction on chalcopyrite in aqueous Fe( II )-Fe(III)-H2S04 solution at 25°C and 70 °C. Results from the calculation ofspeciation in the above solution reveal that, at both 25 °C and 70 °C, the real Fe3+/Fe2+ ratio is much lower than the nominal ratio, which leads to smaller values for the reversible potential of the ferric/ferrous couple based on the Nemst equation. Exchange current densities of the ferric/ferrous couple were obtained by extrapolating the cathodic linear Tafel line to the reversible potential and are on the order of 10-7·10-6 A/cm2 at 25°C and 10·6-10-5 A/cm2 at 70 °C, respectively. The transfer coefficients were about 0.35-0.38 at 25°C and 0.35-0.45 at 70 °C. Polarization plots of CPC and CPP under different nominal Fe3+/Fe2+ ratios are in good agreement at 25 ·c and at 70 °C. Based on the obtained exchange current densities, the rate constant k, was calculated and is on the order of 10-1 cm/s at 25 °C and 10 1 cm/s at 70 °C.IntroductionChalcopyrite is the most abundant copper mineral in nature, accounting for about 70% of copper reserves in the world [I]. In recent years, the metallurgical industry has been searching for a hydrometallurgical process as an alternative to pyrometallurgical treatment due to high emissions of S02 and capital costs associated with smelting. Activity in this area has increased recently due to some inherent advantages associated with hydrometallurgical processing, such as the possibility of treating low-grade ores (increasingly more abundant in the case of copper) and easier control of waste, with the attendant benefits to the environment [I]. Chalcopyrite is highly refractory under most hydrometallurgical conditions, owing to the formation of an anodic passivation layer on the chalcopyrite surface which renders the process kinetics very slow. Most of the currently proposed processes are based on sulfuric acid with ferric ions and/or dissolved oxygen as oxidants. Sulfuric acid is preferred over all other leaching reagents in terms of cost, environmental friendliness, and ease of its regeneration during electro-winning. Some of these processes have been piloted in attempts to implement these technologies on an industrial scale,"

Jan 1, 2012

By Jingwei Lou, Bing Li, Suzhen Li, Miao Shen, Jianguo Yu

"As a main impurity in primary lithium metal, magnesium is difficult to remove because of the very close relative volatility of the two metals. Electrochemical refining provides a possibility to completely remove Mg in the LiCl-KCl melt prior to Li reduction. MgCl2 reduction processes in LiCl-KCl- MgCl2 melt were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry and chronopotentiometry. Then potentiostatic electrolysis was carried out and Mg (II) ion was reduced onto a liquid lead cathode from the LiCl-KCl-MgCl2 melt at the Mg deposition potential. The results show that Mg ( II ) is reduced in one step with two-electron transfer. The reduction potential of Mg ( II ) was well defined. The reduction of Mg( II) results in Li ( I ) underpotential deposition at 0.2V more negative potential than that of Mg( II) reduction. Therefore, in order to prevent Li ( I ) from codeposition with Mg, accurately controlling Mg ( II) reduction potential during the potentiostatic electrolysis was necessary. Ninety three to 99 % removal rate of MgCl2 was achieved after 8-12 h electrolysis when liquid lead was used as cathode.IntroductionMetallic Li has been widely used in batteries, light weight alloys and in fusion reactors because of its excellent properties. Currently, the only way in industry to produce metallic Li is by electrowinning from molten LiCl-KCl at about 450 °C [l-5]. LiCl-KCl is the only electrolyte used, because they presents a lower eutectic temperature and KCl shows a slightly higher theoretical decomposition voltage than LiCl, as shown in Table l .The produced metallic Li generally contains 1-2 wt% impurities including Na, K, Al, Ca, Mg, Si, etc. [6l, which are derived from the corresponding metal chloride compounds or metal oxide compounds existing in the LiCl and/or KCl raw materials. These impurities have to be removed by subsequent vacuum distillation at high temperatures to meet the requirements for metal Li purity in the final products. Separation of Mg from Li by vacuum distillation is difficult because their relative volatilities are very close, as shown in Table 2."

Jan 1, 2011

By Sridhar Komarneni

"Microwave-hydrothermal processing is a novel technique which combines the conventional hydrothermal processing with microwave field and we previously showed for the first time, that ceramic powders can be rapidly produced by this technique. This review paper deals with the synthesis of unary oxides such as Fe203, Ti02, Zr02, etc., binary oxides such as BaTiO3, SrTiO 3, PbTiO 3, SrZrO 3, KNbO3, etc., and ternary oxides such as NaTi2 (PO4)3 and pyrochlore phases of Pb(Mg1/3Nb2/3)O3, Pb(Zn1/3Nb2/3)O3 etc. and metal powders such as Cu, Ni, etc. below 195°C. This method can be adopted to the synthesis of a large variety of powders by the appropriate control of pH, Eh, temperature/pressure and concentration of chemical species. The main advantages of this method compared to conventional hydrothermal processing are (a) it increases the kinetics of reaction by one to two orders of magnitude, and (b) it can lead to novel phases especially those with layered structures.IntroductionConventional hydrothermal processing is a well-established synthesis technique which has been extensively used in the preparation of fine ceramic powders [1-5], large single crystals [6-8] and massive cement blocks [9]. Technologically important ceramic powders such as BaTiO 3, Al203 etc. made by the hydrothermal process are now commercially available. Although there are numerous methods for materials synthesis, hydrothermal method is truly a low temperature and environmentally benign process. For example, ZrSi04 (Zircon) which is extensively used in ceramic industry can be prepared hydrothermally at 150·C [10] compared to sol-gel or solid-state method [11,12] which require a temperature of about 1000·C. The hydrothermal method is environmentally benign because hydrothermal reactions are carried out in closed systems at low temperatures and the contents can be recovered and recycled after cooling to the ambient conditions. One of the disadvantages with any low temperature processing method is slow kinetics. For this reason we have combined the hydrothermal method with microwaves to enhance kinetics and we named this method as ""Microwave-hydrothermal"" processing [13- 16]. Although the combination of microwave and hydrothermal techniques has been used in the past few years to dissolve all kinds of inorganic (e.g. alumino silicate rocks) and organic materials rapidly for chemical analysis, we were the first to show its potential value for the synthesis of various ceramic powders [13-16]. In this paper, I show that this novel method is applicable to the synthesis of all unary, binary and multinary oxides by the appropriate control of pH, Eh, temperature, pressure and concentration of chemical species. In addition, this method is also found to be useful for the preparation of metal powders."

Jan 1, 1994

By C. D. Chapman

Current regulations regarding the landfill disposal of asbestos containing wastes are inadequate to ensure there are no ground water or airborne emissions. Accordingly, there is growing recognition that asbestos wastes can only be safely disposed of by using techniques that destroy the hazardous fibres. An innovative high-temperature plasma arc technology (The MAGRAM Process) is being developed for the recovery of magnesium metal from asbestos together with supplementary magnesia containing feedstock. The furnace will operate in. open bath mode with aluminium and/or ferrosilicon being employed as reductant. An important advantage of the process is that magnesium vapour within the furnace will be generated close to atmospheric pressure rather than at reduced pressure under which existing processes operate. Thermodynamic modelling work has been undertaken to define the range of slag composition and furnace temperature under which magnesium production at atmospheric pressure is feasible. The effect of slag chemistry, reductant addition, and temperature on product quality and yield have also been investigated and key aspects have been tested on bench scale. A 300 kW pilot plasma furnace unit has been employed for the treatment of calcined asbestos wastes. Aspects of design and operation of the unit are detailed. Acknowledgement: This work is substantially financially supported by the European Communities under the Industrial and Materials Technologies (Brite EuRam H) Research and Development programme.

Jan 1, 1995

By B. G. Thomas

"Mathematical process models can be applied in several different ways to serve industry by inducing beneficial changes to process operation. This paper attempts to summarize the different uses, types, and attributes of these models, and to offer some ideas to consider when developing, using, and reporting on them. Process models range from empirical to mechanistic in nature and vary in complexity from simple analytical solutions to coupled, 3-D transient numerical simulations. They are classified here according to the way in which they are implemented in practice, viz. fully-online models, semi-online models, off-line models, and literature models. The purpose of the model should dictate how choices are made during its development. Ways to validate and compare the model with experiments are suggested. Examples are taken in the context of the author's experience in modeling the continuous casting of steel.IntroductionThe objective of this paper is to provide a partial introduction for this symposium by discussing some basic aspects of the application of mathematical process models in industry. Essentially, the aim is to explore how process models are used to benefit industry, and to offer some general comments and suggestions, based on the experience of the author, on how models can best meet this goal.This work is concerned with process models, which consist of systems of mathematical equations and constants that are solved on a computer to make quantitative predictions about some aspect(s) of the process. The specific variables required as input data and generated as output data are important features of the model. The equations often derive from a numerical solution to one or more differential equations and their boundary conditions. The model also includes the constants, which represent material properties, empirical relationships, and other knowledge about the process, and usually require considerable effort to obtain. Thus, general purpose commercial software packages, (ie. finite-element or finite-difference based codes), are not models in this context. They are useful tools, however, serving as frameworks for the development of process models."

Jan 1, 1994

By Larry G. Twidwell, Jannette L. Chorney, Bryce D. Ruffier, Katelyn M. Lyons, Daniel W. Gaede, Ryan J. Foy, Jerome P. Downey

The Army Research Laboratory (ARL) has an interest in the recovery and processing of rare earth elements. At Montana Tech, elevated temperature chlorination of rare earth oxides is presently being investigated as a potential methods leading to the selective separation and recovery of rare earth elements from mineral ores and concentrates. After preliminary evaluation, ytterbium oxide was selected as a representative surrogate material for more extensive chlorination studies. Methods used to determine the conversion and recovery include X-ray diffraction (XRD) and inductively coupled plasma (ICP) analysis. These data have been used to establish and confirm process conditions that consistently yield high conversion efficiencies. Based on the promising results, further experimentation is underway to ascertain the metallurgical response of other rare earth oxides and carbonates to the roasting process. The end goal is to create a robust process for industrial application that has greater efficiency and reduced costs as compared to current practice.

Jan 1, 2015

By Pinakin C. Chaubal

Today?s steel industry is in a vibrant and resurgent mode. This transformation has been in the making for some time now. Over the last few decades, the industry was steadily transforming itself into becoming a high tech industry. New technology was adopted, efficiencies were enhanced, lean manufacturing concepts were brought in and a strong customer focus was developed. Today?s mills employ sophisticated instrumentation, computerized monitoring, on-line smart systems etc. driving processes that are producing at rates of many tons/minute. All this is not possible without judiciously using the latest available technologies in various fields and developing a more sophisticated work force. Prof. Sohn has been a pioneer in driving the concept of process engineering in process metallurgy. In this paper the focus is on some aspects of process engineering ? primarily process modeling - as applied to iron and steelmaking processes. Examples are shown to demonstrate how problems have been addressed. Some thoughts on future directions are presented.

Jan 1, 2006

By Bin Xu, Qian Li, Yong-bin Yang, Tao Jiang, Jian-jun Hu

It could significantly increase the leaching rate of refractory gold concentrate containing sulfur and arsenic by roasting pretreatment with adding certain amount of sodium sulfate, and the mechanism of that was systematically researched with DSC, XRD and SEM in this paper. Results indicated that the mechanism of Na2SO4 on double refractory gold concentrate at roasting pretreatment can be summed up in the following three aspects：Firstly, Na2SO4 can react with SO2 and SO3 which is produced by the oxidation of sulfides and generate Na2S2O7(l), which plays buffer effect on sulfides exothermic oxidation, avoiding the secondary-encapsulated of gold. Secondly, the liquid phase of Na2S2O7 can cover mineral particles' surface that possesses a sintering effect, it leads to internal cracks of the particles. Finally, mineral particles will gather with sodium sulfate particles as the center that can improve the permeability of the layer.

Jan 1, 2015

By T. Shibaraki

A new larger, more efficient and economical Mitsubishi furnace line at Naoshima was put into operation in May 1991. Naoshima Smelter had produced previously about 230,000 mtpy anode copper with two smelter lines, i.e., a conventional reverberatory furnace line and Mitsubishi furnace line, which had been shutdown at the same time of the start up of the new smelter. At the beginning of the operation, there were several initial problems at the area of off gas trains and feeding system. By overcoming them now the process has been continuing satisfactory operation at the design rate. The paper describes about the design concepts and the actual operation of the new smelter.

Jan 1, 1993

By Shengfan Zhou, XUEWEN WANG, Bianfang Chen, Mingyu Wang

Vanadium was leached from roasted stone coal by NaOH solution, and the effect of leaching temperature, leaching time, addition of NaOH, liquid to solid ratio, the grinding fineness of stone coal, and stirring speed on the vanadium leaching rate was studied. The kinetics analysis for the process is presented by the shrinking core model. The results show that the vanadium leaching ratio of roasted stone coal can be beyond 75% at the 6% NaOH addition, leaching temperature of 95°C, leaching time of 7h, liquid to solid ratio of 1.2mL/g, and grinding fineness of 0.111mm. The leaching process is controlled by interfacial reaction kinetics and the apparent activation energy was 59.36kJ/mol.

Jan 1, 2016

By Brian G. Thomas

Quality problems in continuous casting of steel can be identified as they occur by monitoring mold signals (level sensor, thermocouples in the mold walls, friction etc.) and taking appropriate action (such as slowing casting speed, changing taper, changing a clogged nozzle, or later visual inspection of the surface for possible downgrading. Surface depressions and groups of deep oscillation marks form at meniscus and reduce local heat transfer as they move down the mold at the casting speed. This slows shell growth, increases shell surface temperature, and causes characteristic dips in mold thermocouple signals. More importantly, they are also associated with longitudinal cracks. Characteristic thermocouple signatures have been identified for many defects, including sticker breakouts, transverse depressions and deep oscillation marks, narrow-face bleeds, transverse comer cracks, longitudinal cracks, mold level fluctuation defects, and other problems. With the help of computational models, these mold signals should be used to troubleshoot defects, and to take appropriate corrective action. Keywords: Continuous casting, defect detection, thermocouple signals, on-line control

Jan 1, 2003

By Leiting Shen

The thermodynamics of tungsten ore decomposition in mineral acid and alkaline solutions were studied. The published thermodynamic data of tungsten minerals were collected and assessed. The Gibbs energies of CaWO4 (−1538.43 kJ/mol), FeWO4 (−1053.91 kJ/mol), MnWO4 (−1206.08 kJ/mol), H2WO4 (−1003.92 kJ/ mol), and Na2WO4 (−1455.58 kJ/mol, aq) at 25 °C were adopted in the calculation using HSC software. The results show that CaWO4 is decomposed more readily in Na2CO3 solution than in NaOH,while FeWO4 andMnWO4 aremore reactive inNaOH solutions. Froma thermodynamic point of view, tungsten ore decomposes easily in acid solutions despite most ΔGo T increasing slightly with temperature. Oxidizing Fe2+ to Fe3+ in acidic solutions facilitates decomposition of FeWO4, and the reaction of CaWO4 in H2SO4 solution occurs more easily than in other mineral acids, due to the formation of sparsely soluble CaSO4. The results fit well with the experimental data and industrial experience previously reported in the literature.

By Yuanyuan Wang, Yuhao Ding, Hao Bai, Kang Zhou, Guangwei Du

"In this paper, the list analysis of GHG emissions of aluminum industry was conducted based on the data from typical electrolytic aluminum plants of a China’s northwest province. The results show that under the conditions of average anode effect coefficient as 0.16 times/(cell• day) and anode duration as 5 minutes per day, equivalent emissions of CO2 reached 1.23 ton per ton of aluminum, in which PFC emissions accounted for about 71%. Compared with foreign advanced level, which is 0.87 ton per ton of aluminum under the conditions of average anode effect coefficient as 0.01 times/(cell•day) and anode duration as 0.46 minutes per day, there is much room for China’s aluminum industry to reduce GHG emissions. Since anode effect plays an important role on PFCs generation in electrolytic aluminum process, how to control anode effect strictly becomes the key factor for remarkable reduction of GHG emissions in China’s aluminum industry.IntroductionTechnology of aluminum electrolysis is a mature and efficient process of aluminum production. Due to the huge demand on aluminum worldwide, so resource consumption, energy consumption and pollutant emissions in the process of aluminum production are still large. The global output of aluminum reached 45193 kt in 2012. A large amount of CO2 and PFCs are produced in the process of aluminum production, and the greenhouse effect and environmental pollution caused by emissions of them is a concern. PFCs belong to a powerful greenhouse gas, thus emission reduction of PFCs is very important for aluminum electrolysis industry. At present, China's aluminum production accounts for about 33% of the world's aluminum production, and controlling PFCs emission has become the key point of pollution control of aluminum electrolysis industry in China [1].Taking the case of a typical electrolytic aluminum plant of a China’s northwest province, this paper studies the list analysis of GHG emissions of aluminum industry in China. GHG emissions of a China’s northwest province were calculated through investigating existing situation of aluminum electrolysis industry in the province, knowing capacity, output, main production technology and equipment level of aluminum electrolysis industry, and using the calculation framework and methods of GHG emissions of aluminum electrolysis industry, which were put forward by the intergovernmental panel on climate change (IPCC), the international aluminum association and other organizations at home and abroad. The list analysis of GHG emissions of aluminum electrolysis industry will offer useful information in promoting emission reduction of GHG in aluminum electrolysis industry, improve the efficiency of energy utilization."

Jan 1, 2014

By Pinakin C. Chaubal

Today?s steel industry is in a vibrant and resurgent mode. This transformation has been in the making for some time now. Over the last few decades, the industry was steadily transforming itself into becoming a high tech industry. New technology was adopted, efficiencies were enhanced, lean manufacturing concepts were brought in and a strong customer focus was developed. Today?s mills employ sophisticated instrumentation, computerized monitoring, on-line smart systems etc. driving processes that are producing at rates of many tons/minute. All this is not possible without judiciously using the latest available technologies in various fields and developing a more sophisticated work force. Prof. Sohn has been a pioneer in driving the concept of process engineering in process metallurgy. In this paper the focus is on some aspects of process engineering ? primarily process modeling - as applied to iron and steelmaking processes. Examples are shown to demonstrate how problems have been addressed. Some thoughts on future directions are presented.

Jan 1, 2006

By L. A. Neumeier

The Bureau of Mines, U.S. Department of the Interior, is investigating the feasibility of partitioning complex sulfide minerals to simpler sulfide .phases by sulfldation reactions. Such partitioning can afford opportunity to improve selective extraction of mineral constituents of value. This report describes initial research involving sulfidation partitioning of chalcopyrite concentrates. Small chalcopyrite samples were sulfidized with elemental sulfur in glass capsules sealed after evacuating and backfilling with helium, by heating for 1 to 24 h at specific temperatures in the range of 250° to 500° C. which extends from below to above the boiling point of sulfur (-445° C). Above the boiling point of sulfur, the overall reaction with adequate sulfur (13.9 wt pct of CuFeS2) is 5CuFeS2 + 4S g ? Cu5FeS6 + 4FeS2.

Jan 1, 1989

By Gaballah Djona M.

Spent hydrorefining catalysts contain about 5 % of CoO and/or NiO, 12 % of MoO3 and up to 10 % of V205. They are generally supported by alumina and contain up to 25 percent of C, S and hydrocarbons. Such materials are potentially hazardous to the soil and to water resources. Selective chlorination of raw unroasted samples with Cl2 + air gas mixture had been investigated. At temperatures lower than 600 °C, it was possible to recover more than 90 % of nickel and cobalt chlorides, about 99 % of the molybdenum and up to 75 % of vanadium chlorinated compounds. CoCl2 and Ni/Cl2 were extracted from the chlorination residues by their dissolution with acidified water. Molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The chlorination of Al2O3 could be limited to less than 6 %. The scale up of this treatment was successful and a flow-sheet is proposed.

Jan 1, 1995

By Versiane Albis Leão

This work aims at the selection of an appropriate eluant for cyanide recycling using ion exchange resins. Based on a literature review as well as on experimental results, the elution of resins loaded with copper and minor amounts of iron and nickel is discussed. The resins Imac HP 555s, Amberlite IRA 900 (Rohm&Hass) and Purolite A860S (Purolite Co) were eluted using either NaCI, zinc and nickel cyanides, hydrochloric acid, sulfuric acid or acid thiourea solutions. The results indicate that saline solutions are effective only with polyacrylic resins (Purolite A860S), failing to desorb the metals, specially the nickel cyanocomplex, loaded on polystyrene-based resins. Cyanide solutions of both zinc and nickel are capable of eluting over 90% of the loaded metals. In contact with pure acid' solutions, iron precipitates onto the resin beads, as Cu(II) ferrous cyanideCu2Fe(CN)6.xH20. Thiourea is able to elute all the three metal cyanocomplexes owing to the increased solubility of copper cyanocomplexes in the presence of this complexing agent. The results demonstrate that a universal eluant is not available and the selection of the most appropriate resin-elution procedure should be based on the specific features of the system under consideration

Jan 1, 1998

By H. K. Fouad, L. A. Guirguis

The starting mill strip solution· for this study· is an ammonium uranyl tricarbonate solution of pH 8.2 containing 20g uranium/liter, after a DEPA/TOPO extraction process from sulfuric acid leaching liquor. To the first portion of the concentrated acidified strip solution, hydrofuoric acid is added at 95°C in reduced condition to obtain uranium tetrafluoride. The second portion of the uranyl carbonate strip is subjected to a precipitation step by admixing 0.3 volume of non-solvent precipitating agent such as acetone per volume of uranium. ·Uranium oxide (U30 8) is obtained from this precipitate by calcination for half an hour at 800°C in air. The third portion of the strip solution is neutralized to a pH 6.5 with sulfuric acid to precipitate iron and other contaminants. The solution is further acidified to a pH 1.85 with continuous air bubbling to remove CO2, followed by H2Ch precipitation at pH 3.5 to obtain uranyl peroxide. The latter is reduced by stannous chloride to obtain uranium trioxide dihydrate UO3. 2H20. Identifications, characterization· and purity of these products are carried out by complete chemical analyses, Scanning electron microscope study, tap density determination, X-ray diffraction and infrared spectroscopic investigations. The achieved results agreed well with that of the published data for these nuclear grade purity products.

Jan 1, 2000

By Jean-François Boulanger

The production of rare earth elements from ore usually consists of three steps; the separation of a concentrate of REE bearing minerals; the cracking of the REE minerals to liberate the REE into an aqueous solution and separation of REE into individual elements. This paper describes the results of laboratory tests conducted on a carbonate-rich REE ore containing bastnaesite and monazite. The tests cover the whole processing sequence of beneficiation, preparation of the REE solution using a caustic leach followed by acid leach to break monazite and bastnaesite and liberate REE into an aqueous solution and the partial separation of the REE using solvent extraction. Details on the product quality and process performances (recovery and impurities removal) are given for each studied step. The paper also discusses the economic advantage of separating the REE rather than producing a mixed REO product to be sold to a refinery for REE separation. A mini-pilot plant version of the process is currently planned.

By T. T. Chen

Raw anode slimes consisting primarily of PbSO4, AgCuSe, Cu3Se2, Cu2-x Se, Cu2O, CuSO4.5H2O, Sn arsenate and Sb-Bi-As oxide are batch-leached with electrolyte-O2 to dissolve Cu. During this process, Cu2O and CuSO4.5H2O are solubilized and the Cu in the selenides is leached with the formation of Ag2Se and Se. A small amount of Cu remains in the Ag2Se, Sn arsenate and Sb-Bi-As oxide. The decopperized slimes are repulped in Na2CO3 solution to convert most of the PbSO4 to NaPb2(CO3)2(OH). The Sn arsenate and Sb-Bi-As oxide partly react, but the Ag2Se is not significantly affected by the Na2CO3 solution. The NaPb2(CO3)2(OH) intermediate phase is dissolved in acetic acid to leave a final product consisting of Ag2Se, Se, Sn arsenate and Sb-Bi-As oxide, together with small amounts of PbSO4, NaPb2(CO3)2(OH) and various gangue constituents.

Jan 1, 1993