Search Documents

By R. N. O'Brien, E. Peters

"It has been discovered that copper concentrates can be leached in strong (40-60%) sulfuric acid with nitric acid, or with oxygen if nitric acid is present as a catalyst. Chalcopyrite is rapidly decomposed at temperatures well below the boiling temperature of the lixiviant (-150 C.) and the resulting copper and ferric salts are precipitated as CuS04.H20 and FeH(S04)z.4H20. Other metal sulfides such as zinc, lead, nickel, etc. are also converted to sulfates that are nearly insoluble. Sulfur is partially converted to elemental and partially to sulfuric acid. Reduction products of nitric acid can be recovered from the distillate with good recovery. Conversion of as-received copper concentrates is largely complete in about 1 hour. Introduction9 molar sulfuric acid is an unusual hydrometallurgical lixiviant: it has a boiling point of about 150 C. and a low solubility for base metal sulfates. Below about 6 molar acid, the boiling point falls below 120 C. and yields much higher sulfate salt solubility, while above 12 or 13 molar acid and at higher temperature sulfuric acid becomes an oxidizing agent, yielding gaseous S02' Thus, sulfuric acid within this range of concentration is capable of acting well above the temperature of boiling water without requiring autoclave conditions, and if typical oxidative leaching conditions are applied to suspended mineral sulfide concentrates, it is possible to obtain a conversion of these sulfides into 'crystalline sulfates. Thereafter, the sulfates can be separated by filtration or by solid - bowl centrifuge and the solution can be recirculated to the reactor vessel. Meanwhile, the solid sulfates can be treated in a typical hydrometallurgical circuit, i.e., dissolved in a return stream that is essentially water, separated from each other by, for example, solvent extraction, and recovered as metals by electrowinning."

Jan 1, 1997

By Shoukun Wei, Cong Wang, Lin Cheng, Zhiyu Qiao, Jingkui Liang, Weidong Zhuang

"The subsolidus phase relations in the Sm2O3-CeO2-CuO ternary system sintered at 1000°C in air have been investigated by X-ray powder diffraction. The system can be divided into two ternary phase regions and three binary phase regions. Solid solution Sm2-xCexCuO4-y is the only ternary phase in the system. The maximum solid solubility was confirmed to be x = 0.2. The crystal structure, oxygen content and superconductivity of the solid solution Sm2-xCexCuO4-y have been investigated.I. INTRODUCTIONAfter the first discovery of the superconducting ceramic system La-Ba -Cu-O[l] with Tc = 30 to 40K, other families of cuprate-based ceramics have been synthesized with higher critical temperature. These oxides include the R-Ba-Cu-O (R: rare earth) systems (Tc=90K or so)[2,3], the Pb-Sr-(R,Ca)-Cu-O systems (T c = 50 to 100K), the Bi-Sr-Ca-Cu-O systems (Tc=80 to 105K)[4], the T1-Ba-Ca-Cu-O systems (Tc=85 to 125K)[5], the Hg-Ba-Ca-Cu-O systems (Tc=90 to 150K)[6,7], and some others. The improvement of Tc is very rapid. The measurement of the Hall and Seebeck coefficients shows that they all are p-type superconductors. In 1989, Tokura et al.[8] discovered the superconductors R2_XCexCU04_y(R = Nd, Pr, Sm) with Tc=20 to 24K (onset) and found that the charge carrier is electron in contrast to their hole doped counterparts. This discovery increases the fundamental understanding of the cuprate-based superconductors by comparing their characteristics and mechanisms to those of the p-type superconductors.One of the outstanding features of these n-type superconductors is the difficulty in obtaining samples in good charactors, such as the difficulty in obtaining zero resistivity state in single crystal or bulk samples; the semi-conductivity of bulk samples in ordinary state (opposite to the superconducting state) and a reducing reaction involved before the superconductivity has been found[9]. Therefore, it is necessary to optimize the sample preparation of the n-type superconductors. All the n-type superconductors have been found· considerable solid solubility. The compositional variations play a governing role in the carrier doping of the superconducting phases. Also, it is vital to the ceramic processing of superconductors to identify the compatible phases in the phase diagram. Finally, there is always the possibility of finding additional compounds, both superconducting and non-superconducting, in an unexplored system."

Jan 1, 1996

By C. Pereira

Spent nuclear fuel (SNF) can be treated in a molten salt electro refiner for conversion into metal and mineral waste fonns for geologic disposal. The fuel is dissolved in molten chloride salt. Non-transuranic fission products in the molten salt are ion-exchanged into zeolite A, which is subsequently mixed with glass and consolidated. Zeolite was found to be effective in removing fission product cations from the molten salt. Breakthrough of cesium and the alkaline earths occurred more rapidly than was observed for the rare earths. The effluent composition as a function of time is presented, as well as results for the distribution of fission products along the length of the column. Effects of temperature and salt flow rate are also discussed.

Jan 1, 1996

By Milton Manrique, Edgar E. Vidal, Patrick R. Taylor

"Ultrafine zirconium carbide powder has been synthesized using zircon concentrate and methane in a thermal plasma reactor. The effect of several experimental variables, such as power used and zircon particle size, on the conversion has been studied. A thermodynamic analysis of the possible reactions and stable compounds was performed. A mathematical model that describes the in-flight decomposition of zircon particles was developed based on a description of the temperature and velocity profiles calculated in the reactor. It was shown that the formation of zirconium carbide from zircon and methane is thermodynamically possible. Complete 'vaporization of zircon in the reactor is predicted when the particle size is below 45flm and the effective power entering the reactor is 15 kW. The powders were collected and characterized by XRD, SEM, TEM and chemical analysis using ICP. Results of the product analysis indicated the presence of zirconium carbide, zirconium oxide, silicon carbide and silicon oxide.IntroductionIn recent years there has been an increased interest in the production of nanometric sized powders of ceramic materials for use in advanced materials applications. One possible method to produce these powders is with a thermal plasma reactor, which offers high temperatures and fast quenching rates. This technology has been called - Thermal Plasma Synthesis - [1].Zirconium Carbide (ZrCx) has typical properties of transition metal carbides: elevated hardness - between alumina and diamond - a high melting temperature of 3420°C and high chemical stability at room temperature [2]. ZrCx has a Bl crystal structure with deficiencies in the number of carbon atoms in the cell with x between 0.6 and 1 [3]. Different methods have been used to produce ZrC, one method is by direct reaction of zirconium hydride or halide with carbon. Other methods used are direct reduction and carburization of zirconium oxide (Zr02) and reaction of metallic zirconium with a caburizing gas such as acetylene [3]. Recently small films of ZrC have been obtained using a sputtering device [4,5]. ZrC has been used in nuclear plants as a low neutron absorbing and high mechanical resistant refractory material and also as a constituent in cathodes made of UC-ZrC [6]. It is also used in the form of tubes, boats and crucibles to handle molten metals and as part of electronic devices used for thermoionic transducers. Recently ZrC has been used along with zirconium diboride (ZrB2) to produce composite materials [7,8]."

Jan 1, 1996

By B. W. Lightfoot, Neill F. Arthur

"The AusIron process is a new development of the well established Ausmelt bath smelting technology(l). The development of this technology has been tied to the South Australian Steel and Energy (SASE) project which brings dedicated coal and iron resources together with this new technology. SASE is a joint venture between Ausmelt (40%), Meekathara Minerals (40%) and the South Australian Government through Mines and Energy South Australia (MESA) (20%). It will use a multiple lance furnace to process iron ore using steaming coal for both fuel and reductant.It is intended to build the simplest plant economically possible. Refinements such as preheating and prereduction of the ore are compatible with the technology but are not expected to be necessary in the first generation plant.The joint venture is negotiating with suitable partners for funding of the project through to commercial implementation at a target scale of2.5 mt/a of pig iron.ObjectivesAusIron aims to produce pig iron directly from steaming coal and from any of a variety of iron sources in a simple furnace system with a minimum of pre-processing of either coal or iron ore. Preheating and prereduction of ore are compatible with the technology but may not be necessary. The immediate aim is not to be the technology that uses the least quantity of coal to produce iron metal but rather the technology that uses the least number of dollars to produce metal.The chemistry of iron making is well known, probably better known than that of smelting of any other metal. Iron has been made for thousands of years and it is possible to make iron from charcoal and ore in a simple blast furnace the size of a beer barrel. The focus is therefore not making iron but rather making it more cheaply than it is made by current technologies. Large blast furnaces now set the standard and new technologies must perform better if they are to gain market share. It is still the cost of iron, energy units and capital going into these mega blast furnaces which ultimately set the market price for pig iron."

Jan 1, 1996

By Y. Z. Zhang

Cyanide has generated environmental concerns because of its toxicity, and it may not respond to the treatment of complex and refractory gold ores. Gold leaching by thiourea is one of the most promising substitutes of cyanide. However, the high reagent consumption has hindered thiourea from its commercial application in gold extraction. The process chemistry and mechanism of thiourea degradation has been discussed on the basis of chemical bonding theory, thermodynamics and electrochemistry in this paper. Progresses on the decreasing of thiourea consumption have been summarised. The potential application of thiourea in gold extraction has been evaluated.

Jan 1, 1996

By Howard K. Worner

"In a rewarding career spanning nearly two thirds of a century, the author has worked at the frontier of such diverse fields as the creep of metals, structure properties and production of novel dental and surgical materials, molten salt electrolysis for titanium production, greatly improving the productivity of large iron blast furnaces and of oxygen steelmaking. While each of these has given great satisfaction, special thrills have derived from the development of new methods for the continuous production or refining of both ferrous and non ferrous metals. A rewarding segment was the evolution of various aspects of WORCRA technology. Unfortunately, several of these inventions have been ""ahead of their time"". Introduction""I am greatly honoured by the convening of this meeting to recognise my contributions to pyrometallurgy. My appreciation is the greater because this is the third Howard Worner Symposium; the first took place in the University of Newcastle in 1988, close to my 75th birthday. It was arranged by the local branch of The Australasian Institute of Mining and Metallurgy with the theme, ""Frontiers in Pyrometallurgy"". The second was organised by the University of Wollongong in conjunction with the Australian Academy of Science and the Australian Academy of Technological Sciences and Engineering; it celebrated my 80th birthday and, at my request, covered a broad range of topics under the heading of ""Recent Advances in Science and Technology"". Now, this very international meeting on ""Injection in Pyrometallurgy"" has been convened by the G K Williams Co-operative Research Centre for Extractive Metallurgy in my alma mater. I am both delighted and honoured that the cosponsors are the TMS (USA) and ISIJ (Japan).Dr Madhu Nilmani consulted me about the field to be covered and I readily concurred because ""injection"" has been of keen interest to me since the beginning of the 1960s when I began my pioneering work on sequential oxygen (or air) injection into flowing streams for both refining of blast furnace hot metal to steel and for the continuous smelting-converting of copper and nickel."

Jan 1, 1996

During electrowinning of nickel chloride, hydrochloric acid was regenerated instead of chlorine in a two membrane cell, by segregating the chloride catholyte with an anion exchange membrane, and the sulphate anolyte with a cation exchange membrane from the middle electrolyte (ampholyte) compartment. Successful operation of such a cell depends on controlling chloride leakage through the cation exchange membrane to the anolyte. Small amounts of chlorine gas could be detected in the oxygen evolved at the anode. In this paper, the chloride. leakage as a function of various types of cation exchange membrane and different composition of the anolyte is reported and discussed. Ag+ was added to the anolyte to eliminate chloride leakage to the anode. The cell voltage, electrode potential and voltage drop over the membrane as a function of current density has also been investigated.

Jan 1, 1996

By K. Gao, R. Dry

"Carbon boil, which results in excessive spitting and even complete destruction of a metal drop, could significantly influence the efficiency of direct smelting processes. Carbon boil has been studied as a function of some key parameters such as melt sulfur content, oxygen partial pressure, and melt area/volume ratio. The time of carbon boil was determined using a CCO camera coupled with a time/date generator connected in parallel to a video recorder and a computer. The time of carbon boil was in the range ~5 - 15 seconds under the conditions in this study. A mechanism for carbon boil has been proposed.IntroductionThe occurrence of carbon boil in molten iron drops can result in excessive spitting and sometimes even complete destruction of a metal drop. In direct iron smelting processes, this could significantly influence the decarburisation of liquid metal and the post combustion and hence may influence the efficiency of smelting processes. The generation and consequent ejection of metal droplets into the gas phase occurs due to the intense turbulence in the bath which results from the injection of gases and coal. The aim of this investigation is to understand the fundamentals governing the carbon boil phenomenon under direct iron smelting conditions to assist control of process efficiency.Carbon boil phenomenon has been studied as a function of some key parameters such as melt sulfur content, oxygen partial pressure and melt area/volume ratio. The time for the occurrence of carbon boil has been determined in this study at 1440 °C using a novel approach which includes utilisation of a CCD camera coupled with a time/date generator connected in parallel to a video recorder and a computer. This arrangement permits the capture of the entire sequence of events leading up to carbon boil and therefore the determination of time of boil which is in the range -5 - 15 seconds under the conditions in this study."

Jan 1, 1996

By S. K. Wu, Ray Y. Lin, Sunil Annaji

Infrared joining of TiAI using aluminum foils as the filler material was investigated at temperatures between 1050 °C and 1350 °C in a flowing argon environment for times varying between 15 and 60 seconds. Using aluminum foils, the attempt was to form the Al3Ti phase in the joint as a result of reaction between Al and TiAI at temperatures above the melting point of Al. It has been found based on X-ray diffraction and TEM analysis that, Al3Ti, indeed is the product of infrared joining of TiAI using Al as the joining alloy. Al3 Ti was detected even in the joint processed at 1050 °C for only 15 seconds. Since the aluminum foil used in this study contains 27 at% Si, the t 2 phase in the Ti-Al-Si ternary system is believed to have also formed at the joint/base TiAI interface. Cross sectional studies on the joined specimens have shown different degrees of reaction depending on the temperature and time of joining. Micro hardness evaluations across the joint show that the hardness near the center of the joint is typically smaller than that near the joint edge next to the base material. However, as the joining temperature and time increase, the increment of the hardness at the center of the joint is faster than that around the periphery of the joint.

Jan 1, 1996

By Jörg Wallner

In order to limit SO2 emissions, the Montanwerke Brixlegg AG has installed a desulphurisation plant with the primary aim of reducing the peak emissions from the copper converter that are of particular ecological concern. The author discusses the process requirements, the desulphurisation process selected and the results achieved.

Jan 1, 1996

By Peter R. Whiteley

"This paper discusses gaseous, solid and liquid injection technologies employed in the aluminium industry. The reasons for injection systems are presented, together with a description of the processes used. This includes a review of injection in crucibles, furnaces, launders, and into special purpose metal treatment boxes. The paper covers both the primary and secondary aluminium industries. IntroductionMany injection technologies are used in the aluminium industry and are in a rapid state of development. This paper provides a review of these systems and presents some thoughts on the possible future application of injection to further improve productivity and reduce losses associated with current applications.The Needs for InjectionThere are many issues facing the process metallurgist in the aluminium industry which call for the application of injection technologies now and in the future. In order to categorise these issues the industry may be broken into primary and secondary aluminium, although some of the concerns occur in both areas.The forementioned issues are variously concerned with improving metal quality, improving productivity, and reducing process problems.The use of injection techniques will be discussed under the heading of solid, gaseous and liquid injections, and the objectives and benefits of each covered briefly."

Jan 1, 1996

By Richard W. Lawrence

Leaching of copper from sulfide minerals using biooxidation offers a potential route for copper recovery. Oxidation of . sulfide sulfur can proceed either; to sulfate or to elemental sulfur depending on mineralogy and process conditions. The advances in commercial application of biooxidation for sulfidic gold ores has made available operating and cost data which allow the derivation of conceptual costs for copper ore processing for comparison with conventional processing routes. Although costs for copper biooxidation generally remain high relative to conventional smelting, application might be competitive in specific cases. Biooxidation becomes more competitive in the general case if the cost ofS02 emissions in pyrometallurgical processing were to be internalized to a greater degree than currently required. This paper describes the technical aspects of biological processing of copper sulfide ores and concentrates, specifically with respect to the fate of sulfur. The environmental and economic implications of the biooxidation route are discussed in relation to conventional processing.

Jan 1, 1996

By Brandon R. Ball

An investigation of the effects of ozone and ozone-induced hydroxyl radical on reducing whole effluent toxicity is described and discussed relative to the application of ozone for industrial water treatment. Results from operation of an ozone system treating industrial effluent from a lead and zinc mine in Colorado are presented. The mine discharges 1,000 gpm of wastewater into a tributary of the Arkansas River and has historically exceeded Whole Effluent Toxicity (WET) limits and on occasion has exceeded numeric limits for copper, ammonia, and cyanide. Based on results of a Toxicity Identification Evaluation (TIE) conducted on the effluent and individual process waste streams, the source of effluent toxicity is believed to be primarily associated with organic reagents used in the milling process. Based on test results, an applied ozone to COD ratio of 3: 1 by weight and a contact time of 30 minutes was found to be effective for reducing whole effluent toxicity at pH 11 but not at pH 7, indicating oxidation by hydroxyl radical to be the dominant mechanism responsible for toxic-ity reduction. At an applied ozone to COD ratio of 3:1 and a pH of 11, toxicity was improved from 0 percent survival to 100 percent survival for Ceriodaphnia dubia and fathead minnow (Pimephales promelas) based

Jan 1, 1996

By Marcelo B. Mourão

An experimental investigation was carried out to -study the rates of reduction of pellets containing iron oxides by carbon dissolved in liquid iron, at temperatures ranging from 1720 K to 1973 K. Several different pellet types were employed; the materials used in the pellet's manufacture were pure hematite, two kinds of commercial iron ores, and mixtures hematite/silica and hematite/lime: Reaction times were determined employing the constant volume pressure increase technique (CVPI). It has been observed that the reaction rate increases as the temperature and the pellet's specific surface area increases. The reaction rate is also affected by the oxide type: pellets made from commercial ores or from mixtures hematite/silica or hematite/lime show reaction rates lower than those made from pure hematite.

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 Y. W. Chung, W. I. Chia

"The interaction of water vapor with single crystal Ni3(Al,Ti) and polycrystalline Ni3Fe, with and without the presence of oxygen, has been studied with Auger electron spectroscopy, photoemission spectroscopy, thermal desorption and isotope exchange. Water dissociates to produce atomic hydrogen above 200 K on both Ni3(Al,Ti) and Ni3Fe surfaces. For Ni3(Al, Ti), the reaction is structure-sensitive. Pre-adsorbed or co-adsorbed oxygen on Ni3(Al,Ti) and Ni3Fe significantly suppresses hydrogen production due to water dissociation. This suppression process occurs more efficiently on Ni3Fe than Ni3(Al, Ti).IntroductionOrdered intermetallic compounds such as aluminides, silicides and titanides are very attractive for structural applications at high temperatures. This is because these intermetallics tend to form adherent oxides in oxidizing environments which protect the base materials from excessive oxidation and corrosion. In addition, they have low density, relatively high melting points and good high-temperature strength. However, the moisture in air severely embrittles many ordered intermetallics such as FeAl [1-3], Fe3A1 [4,5], C03Ti [6,7], (Co,Fe)) V [8], Ni3Si [9], Ni3(Si,Ti) [10], Ni3(AI,Mn) [Ill, and Ni3A1 [12-14], resulting in low 'ductility and brittle fracture at room temperature. Recent studies by Liu and coworkers (see review by George and Liu [15]) provide a qualitative description of the mechanism for this moisture-induced embrittlement. During elongation testing, cracks are formed, thus exposing fresh alloy surfaces. One or more active components of the alloy react with water vapor in the environment to produce atomic hydrogen which penetrates into crack tips and causes hydrogen embrittlement. This is similar to that proposed for moisture-induced embrittlement of aluminum alloys [16]."

Jan 1, 1996

By S. M. McDeavitt

Waste form alloys are being developed at Argonne National Laboratory for the disposal of remnant metallic wastes from an electrometallurgical process developed to treat spent nuclear fuel. This metal waste form consists of the fuel cladding (stainless steel or Zircaloy), noble metal fission products (e.g., Ru, Pd, Mo and Tc), and other metallic wastes. The main constituents of the metal waste stream are the cladding hulls (85 to 90 wt%); using the hulls as the dominant alloying component minimizes the overall waste volume as compared to vitrification or metal encapsulation. Two nominal compositions for the waste form are being developed: (1) stainless steel-IS wt% zirconium for stainless steel-clad fuels and (2) zirconium-8 wt% stainless steel for Zircaloy-clad fuels. The noble metal fission products are the primary source of radiation in the metal waste form. However, inclusion of actinides in the metal waste form is being investigated as an option for interim or ultimate storage. Simulated waste form alloys were prepared and analyzed to determine the baseline alloy microstructures and the microstructural distribution of noble metals and actinides. Corrosion tests of the metal waste form alloys indicate that they are highly resistant to corrosion.

Jan 1, 1996

By T. Shimizu

In Japan, the emission standard of selenium in effluent was set at a maximum of20 mgll in Feb. '94 for the first time, and it is scheduled to be further decreased to a maximum of 0.1 mg/I from Feb. '97 due to tightening of the Water Pollution Prevention Act. Selenium (IV) and (VI) are generally found in effluent from precious metals refineries. Although selenium (IV) can be easily eliminated by some reducing agents, selenium (VI) is more difficult to be reduced. Therefore, many smelters are having difficulty in complying with the new emission standard. At Mitsubishi Materials' Naoshima smelter, the behavior and the elimination of selenium in effluent have been extensively investigated. As a result, it was found that two strategies were particularly effective. One of them is improving the overall operation of precious metals refinery, that is, feeding uniformly the effluent to the waste-water treatment plant, reducing the effluent volume by recycling and recovering more selenium (IV) in the effluent. The other is eliminating selenium (VI) in the effluent from the precious metals refinery. It was found that selenium (VI) can be effectively reduced by using hydrazine under high? sulphuric acid concentration and high temperature conditions. By using these measures, it is considered that Naoshima Smelter will be able to comply with the new emission standard.

Jan 1, 1996

By S. A. Platias

Large amounts of dunile tailings can be recycled for olivine produdion from the existing beneficiation adivity of chromite ore in northern Greece. This olivine production aims at the preparation of a material suitable for the substitution of the environmental hazardous quartz sand in the foundries of Europe In smelting of chromite ore the losses that occur ore usually of the order of 6-8% Cr that report in the slag. Most of this is in the form of oxides that cannot be recovered, but usually 30-35% is in the form of FeCr alloy that can be recovered by gravity methods. About 90% of the produced slag is sold for road construdion after crushing to a desired grain size. Finally, recycling of chromites sludges from the ferrochrome produdion plant, through the preparation of pellets, improved the total chromite yield by 2%.

Jan 1, 1996