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By V. Ramachandran

In view of the increasing environmental regulations that have been promulgated in the last 30 years, non-ferrous smelters and refineries have learnt to handle effectively the process waste streams that need to be bled from the system for impurities' control. The cations of concern are copper, lead, zinc, cadmium, mercury, thallium, nickel, silver, sodium and potassium. Anionic species of arsenic and selenium also need to be addressed, Sulfates and chlorides-not a major concern at present-have come under scrutiny in the recent past. The current paper reviews several treatment options with reference to a) types of waste streams processed b)process chemistry c )discharge options and recovery of treated water and d) sludge disposal. The long term goal of any smelter and/or refinery should be to achieve zero liquid discharge from the plant. Methods to obtain zero discharge are discussed.

Jan 1, 2003

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 O. Ryosuke Suzuki

A new metallurgical process via sulfide is proposed: a sulfide is produced at a high temperature from its metallic oxide using gaseous CS2, and this sulfide is electrochemically reduced to its metallic state using molten salt. This combined process via sulfide is effective to obtain high purity of metallic powder, even if the metal in its oxide is strongly combined with oxygen. For example, it is not easy to reduce stable oxide TiO2, and only Ca can remove oxygen to form α-Ti. However, a fairly large amount of oxygen remains as Ti–O solid solution. Because the solubility of S in Ti is very small, this proposal was examined experimentally both on the conversion of TiO2 to TiS2 and on the successive reduction of TiS2 to Ti. TiO2 powder was exposed to CS2 gas flow at 1073 K, and the conversion to TiS2 was confirmed. TiS2 could be reduced to Ti powder either by calciothermic reduction or electrolysis in a CaCl2 melt. By Ca reduction at 1133 K in CaCl2 melt, sulfur concentration decreased to 0.03 mass%S when the amount greater than twice the stoichiometric calcium amount is added. By electrochemical reduction at 1173 K in CaCl2–CaS melt, S concentration significantly decreased to 0.01 mass% S when four times larger amount of electric charge was supplied.

By Rafael Padilla

In the production of copper from chalcopyrite (CuFeS2) concentrates by the smelting and converting technology, the ambient pollution with gaseous S02 and toxic metals such as arsenic compounds is still a serious problem, especial1y in the converting step due to the batch nature of the conventional Peirce Smith process. Non-SO2 emitting alternatives are leaching processes. However, few of them have had a limited industrial application and they are not very effective in discarding safely the toxic impurities. A combination of pyro-hydrometal1urgical methods: the sulfidation of chalcopyrite and subsequent leaching of the sulfidized material is a non-polluting alternative to treat not only clean chalcopyrite concentrates but also complex chalcopyrite-enargite concentrates. In this article, this alternative is discussed concerning the thermodynamics and kinetics of the sulfidation of chalcopyrite with gaseous sulfur. The kinetics of the leaching of the sulfidized concentrate in an H2SO4-NaCI-O2 system is also discussed.

Jan 1, 2003

By E. B. Freidina

We have investigated a new electrochemical process for preparing lead-calcium alloys. Calcium metal, reduced fiom a molten chloride mixture, forms an alloy with liquid lead cathode. The addition of calcium carbonate to conventional CaC12-NaCl electrolyte enables us to avoid chlorine production on the anode and replace it with oxygen and carbon dioxide. The ternary system CaClz-NaC1-CaCO3 has a range of melt compositions, where the electrolysis can be held below 650°C. In order to prevent the side reaction of carbon deposition on the cathode we have separated the anolyte from the catholyte with alumina diaphragm. The factors, which affect the level of impurities and the current efficiency of the process, are discussed.

Jan 1, 1999

By A. Valenzuela

During the last years, Chile has been the largest copper producer, either as concentrates or cathodes. Copper obtained via pyrometallurgy is produced by seven smelters, which have carried out modernization plans to increase smelting capacity or to achieve environmental regulations established in the Chilean legislation. Thus, the present work updates technological innovations in smelters, environmental regulations and presents solutions for S02 handling, particulate matter and arsenic. Also, the authors emphasize the important role of CODELCO Chile, the most important state-owned copper company, in developing technologies such as El Teniente Converter and El Teniente Slag Cleaning Furnace.

Jan 1, 2003

By C. W. Vierrether

Mineralogical analysis contributes directly to the selection of applicable beneficiation techniques for a given site. Tentative remediation methods for use on the Sharon Steel tailings in Midvale, Salt lake County, UT, were determined in part by mineralogical characterization. A systematic characterization scheme was employed to identify mineral species, mineral associations, and grain size. This paper presents the mineral content and distribution data collected for site characterization. This data was used to determine areas that were representative of the total tailings at the Sharon Steel site. Although this was the main focus of characterization, other useful information was obtained. The approximate location of "old jig tails" was identified and insight on possible arsenic, mobility through the pile was also obtained from the mineralogical study.

Jan 1, 1991

By Gunnar Eriksson

Computer simulation has become an everyday practice in thennodynamic and materials research. Advanced thennochemical algorithms take into account heat transfer effects and salient reaction kinetics when applied for process models. In particular, the combination of mass transfer or overall reaction rates with multi-component Gibbs energy minimisation provides an effective tool for simulation of industrial thennochemical processes and processing of materials. In this work the combination of rate factors with the Gibbs energy technique was studied by using the novel program ChemSheet, which operates through Microsoft's Excel® spreadsheets. Such processes as, for example, CVD of pure silicon production, titania pigment manufacturing, vapour pressure of Mercury in amalgams (in Hg-Iamp manufacturing) and melting behaviour of low-temperature alloys have been modelled. Provided that the thennochemical data is available simulations can be performed with any thennodynamic system. The calculation can be performed as an affinity study without a particular reactor model or with a specific reactor scheme.

Jan 1, 2001

By Maneesh Singh

During the various stages of iron & steel production a number of iron-rich by-products are generated. The traditional way to recycle them back to the blast furnace has been the balling - sintering process. These by-products can also be made into cement-bonded agglomerates for use as burden material for blast furnaces. In order to improve the quality of agglomerates the effects of various processing parameters on the properties of cement-bonded briquettes have to be controlled. This paper looks into the various aspects of producing cement-bonded agglomerates and using them as burden material for blast furnaces.

Jan 1, 2003

By A. Warczok

The heat transfer coefficient between liquid slags and solid surfaces is important for the design and operation of metallurgical reactors. An experimental technique developed for the purpose of measuring the heat transfer coefficient between liquid slags and solid metals is described. During the initial heating up of a Ni cylinder upon immersion in a liquid slag, a layer of frozen slag initially forms, then melts. The heat transfer coefficient measured during the initial rapid heat-up of the Ni cylinder, is approximately twice as high as the heat transfer coefficient measured during the final heat-up of the Ni cylinder subsequent of the liquidus temperature of the slag. The technique was tested in various melts i) NaNO3, ii) NaCl, iii) Na3AlF6 and iv) 2FeO*SiO2, giving consistent results. It was found that the heat transfer coefficient increases with increasing bath superheat and stirring. The heat transfer coefficient during the heating up following complete remelting of the frozen slag, is related to the slag superheat(AT) and the specific stirring energy(W) per kg of slag(E) as follows.

Jan 1, 1993

By M. J. Bagshaw, J. D. Hunt, R. M. Jordan

"Continuous casting processes, and the roll casting process in particular, offer considerable potential to the Aluminium industry, both meatallurgically and economically.The three major limiting process problems that occur during roll casting are Centre Line Segregation', 'Sticking' where metal adheres to the rolls during casting, and 'Heat Line' formation. 'Heat Lines' are localised semi-continuous longitudinal defects, usually a few cms in width, where the cast metal leaves the roll bite partially molten. These defects occur at relatively low casting speeds when the mean slab exit temperature remains several hundred degrees below the solidus temperature. The objective of the work described here is to develop a better understanding of the roll casting process in general, and in particular, to understand the phenomenon of 'Heat Line' formation.A steady state two dimensional finite difference model has been developed to describe the roll casting process, incorporating a variable heat transfer coefficient through the roll bite. In the model the difference equations are formulated using a control volume method and latent heat is incorporated according to the Scheil equation. A Gauss-Seidel type technique is used to obtain the solution. Because the rate of heat evolution is non-linear the temperature in each box is determined by using a Newton-Raphson method. The solution for a box can be multi valued and therefore lead to instability particularly near the vicinity of the front. A stability 'criterion is presented which shows that to obtain a stable solution it is better to have long narrow boxes rather than boxes with small dimensions in both directions.The model explains why heat lines form in terms of the variable slab/roll heat transfer coefficient.Experimental measurements of slab exit temperatures are also presented. These were obtained on a Hunter twin roll caster for the binary AI-Cu system, at two compositions over as wide a range· of casting speeds as possible. The experimental results are compared with the predicted ones."

Jan 1, 1986

By Batric Pesic

Adsorption of gold on activated carbon from gold bromide solutions was examined as a function of pH, particle size, carbon amount, initial gold bromide concentration, bromine concentration, temperature, and various cations and anions. pH did not have any effect below pH=6. Above pH=6, pH had dramatically negative effect. The adsorption results satisfied a first reaction order model. The reaction rate constant was proportional to the inverse of carbon particle radius. It was also proportional to the amount of carbon, and independent of initial gold concentration. Temperature had a very little effect at pH=l. At pH=8, the activation energy was a function of the extent of a reaction, increasing with the extent of a reaction. Cu, Fe, Ca, Mg, and Na cations and sulfate, chloride and bromide anions did not have any effect on gold adsorption. Bromine had a very negative effect on gold uptake.

Jan 1, 1991

By Scott R. Giese, Lucas Dix

"Recently, there is a growing trend in the aluminum foundry industry to develop· improved melting and casting processes to produce lightweight, high-strength, and thin-wall castings for the aerospace and transportation industry. One casting method that has demonstrated industrial potential for producing clean, thinwall castings is vacuum-assisted, counter gravity casting. This process has the benefit of expeditiously and quiescently filling the casting cavity with a dramatic reduction of furnace related and reoxidation inclusions. Additionally, lower casting temperatures can be utilized because the application of vacuum during filling overcomes the resistive internal cavity pressure resulting in a finer, as-cast microstructure. The paper explores and discusses the processing and design conditions in improving the mechanical properties of A206 casting alloy using the vacuum assisted, counter gravity casting process.IntroductionThe process of metal casting has been, over the centuries, the chief production technique for components used in everyday life. However, the casting process has certain inherent problems that can adversely effect the properties of a finished product. These problems are directly attributable to the gravity pouring technique used to transfer molten metal to the mold and to fill the mold cavity.A recent study for the American Metalcasting Consortium demonstrated reoxidation products created during the casting process are five times more likely to cause product rejects than entrapped molding aggregates, melt slag, or furnace lining materials1. Formation of nonmetallic and intennetallic compounds are more prevalent in aluminum and titanium alloys because of their reactiveness to furnace lining materials and their high affinity for oxygen. The incorporation of undesirable compounds can be attributed to four areas of the casting operation. The sources are charge materials, melting technique, pouring methodology, and casting cavity filling. Aluminum foundry men have addressed the first three areas by selecting high quality melt stock, non-stirring melting equipment, and the use of porous ceramic filters. Unfortunately, little consideration is given to the last, but yet tl.1e most important part of the casting operation, the actual fill mg of the casting cavity.The generation of inclusion defects during the casting process can be described by two methods. As the liquid metal flows in the gating network and casting cavity, abrupt changes in flow d1rect10n cause the metal to become agitated. This mechanism liquid metal splashing, is generated by instability of the advancing liquid metal interface from turbulence effects as schematically illustrated in figure 1a2 . The surface oxide film bursts under high velocity conditions, folds over, and becomes dispersed and incorporated in the bulk liquid. Additionally, fragmented liquid droplets ejected from the disturbed interface oxidize and become dispersed in the metal stream."

Jan 1, 2000

By Tomás Vargas

The catalytic influence of a pure strain of Thiobacillus ferrooxidans (ATCC 19859) on the dissolution of natural pyrite crystals was studied using electrochemical techniques. The results showed that this microorganism catalyze the leaching of pyrite by both, oxidizing ferrous iron in solution and depolarizing the reduction of ferric ion on this sulfide. In addition, studies of bacterial corrosion under applied potential showed that pitting on the pyrite surface centers on weak sites of the sulfide structure in which bacteria has attached, but occurs only when the ferric iron in solution induces an adequate level of anodic polarization on the mineral.

Jan 1, 1992

By Toshia Suzuki, Keiji Kakudate, Yoshihiro Adachi

"A macro model for the steel usage pattern in Japan is proposed. The steels are classified into four types; converter steel for machinery and for construction and electric furnace (EF) steel for machinery and for construction. The steels are assumed to be discharged from the society in accordance with lifetime distributions of each usage. The amount of EF steel and the accumulation in society are calculated using a population balance model. The comparison with the calculated results and statistics ensures the validity of the model. Since the amount of EF steel for construction will increase and be oversupplied, EF steel will have to be used for machinery. The required and available amounts to supply EF steel for machinery are considered from the point of allowable· copper concentration for machinery use. Copper contaminates steel used for machinery during recycling process and contamination ratio is evaluated with the model. Copper concentration in EF steel is predicted for various scenarios.IntroductionThe amount of CO2 emission from Japanese steel industry is 48.0 million C-ton in 1990 and it occupies 15.1% of the total amount in Japan. In order to reduce the C02 emission and to save the natural resources, it is strongly required to promote the recycling of steel. However, the impurity contaminates steel in recycling process and lowers its quality. The copper concentration in EF steel is analyzed by Toi et al. using a macro model with the assumption that steel is discharged in proportion to the accumulation amount [1]. However the discharged amount of products is dependent on their age for service and usage pattern and not on the accumulation amount. In addition, the degree of copper contamination is different depending on the usage of steel. Therefore a precise model that contains the age for service within the society as a parameter and distinguishes the usage· of steel is necessary in order to clarify the problems in the recycling of steel."

Jan 1, 2000

By G. A. Irons, D. Guo

"The average spout height and width produced by bottom gas injection in a water model of a steel ladle were measured with an image processing technique. It was revealed that the spout height could be described by a Gaussian curve. A combined SIMPLE -VOF model was developed to simulate the liquid surface and flow. The results showed that, though the model produced reasonable velocity distributions and free surface positions, the spout height due to the dynamic head of the rising liquid was substantially lower than observed, indicating that the bubble dynamics at the bath surface play an important role in spout height.IntroductionDue to the enormous importance of gas injection and stirring in metallurgical processes, there have been numerous publications on water and numerical modeling of such vessels. The free surface of the bath has received considerably less attention, despite its importance. At the free surface there are often important chemical phenomena occurring that require a good understanding of the fluid flow; these would include reoxidation of steel, metal splash and fume formation. Furthermore, to understand the details of slag-metal interactions such as slag entrainment, metal losses to slag and the transport phenomena associated with refining reactions, it is necessary to understand the plume and spout interactions first.There have been few experimental studies of the free surface of liquid in gas-injected ladles [1- 3], and even fewer on numerical modeling. Brimacombe and co-workers [1] studied the gas void fraction in the spout region, using a double-tip electrical resistance probe. This sensor cannot distinguish between gas in bubbles about to break and gas in the freeboard. Thus, it is a matter of judgement as to the position of the free surface. Schwerdtfeger and co-workers [2] used a single probe configuration with a wire and a counter electrode in the liquid, so that the height of the continuous liquid phase was unambiguously determined. Irons and co-workers [3] measured the spout height by ultrasonic and electrical capacitance techniques. These techniques were as reliable as the resistance techniques, but were restricted to low flow rates."

Jan 1, 2001

By A. Slotwinski, R. E. Barry, M. M. Menon, P. T. Spampinato

"A coherent FM laser radar based sensor for remote metrology of plasma facing material surfaces in a fusion reactor is described. The sensor is capable of 3-D mapping of surfaces, based on a series of precise range measurements from large distances (up to 20 m). Other features include the ability to operate under adverse environmental conditions involving very high gamma radiation (3xI04 Gy/hr), ultra-high-vacuum (<I0-5 Pa), and high temperature (200°C). The paper describes the basic principles of the sensor, together with experimental results obtained with the sensor. The ability of the sensor for remote rendering of ""visual quality"" images without the need for any external illumination is also illustrated.IntroductionMeasurement of the features of large area surfaces (-1500 m2) to sub-millimeter accuracy, from relatively large distances (20 m), is necessary in the case of the International Thermonuclear Experimental Reactor (ITER -a 1500 MW fusion reactor that is currently in the design phase). Furthermore, the measurements may have to be performed after the reactor is temporarily shut down. During such shut-downs, the ITER in-vessel environment will be highly radioactive due to neutron activation of the reactor wall (gamma radiation field of 3xl04 Gy/hr), the vessel will be maintained under ultra-clean vacuum conditions (<10-5 Pa), and the plasma facing surfaces will be maintained at elevated temperature (200°C). Therefore, the precision measurements must be conducted remotely, and because of the large dimensions of the fusion reactor and the limited number of access ports, the measurements must be done from large distances. The reactor vessel is a large toroid. Fig. 1 shows the cross section of the toroidal vacuum vessel, and the location of the metrology probe. Because of the very large surface area involved, fast scanning capability is also needed to reduce the reactor down-time."

Jan 1, 1997

By Nobuyuki Higashiyama, Ikuo Yonezu

"Hydrogen-absorbing alloys containing rare-earth elements are used in high capacity nickel-metal hydride secondary batteries,' hydrogen storage systems for portable fuel cells, and refrigeration systems. New hydrogen-absorbing alloys containing rare-earth elements have also been developed and introduced into these applications. High performance in nickel-metal hydride secondary batteries is strongly demanded because of the remarkable advancements in portable electric appliances. A large hydrogen absorption capacity, high electrochemical reactivity and superior corrosion resistance in an alkaline solution are required for hydrogen-absorbing alloys used in nickel-metal hydride batteries. The aim of this investigation is to improve the performance of conventional LaNi5 type hydrogen-absorbing alloys. For example, Mm(Ni-Co-Al-Mn)„ type hydrogen-absorbing alloys with various non-stoichiometric compositions were developed. In addition, a new process of rapid quenching process was applied for preparing these hydrogen-absorbing alloys in order to improve their performance.IntroductionRecently, the trend in electronic appliances toward portability has increased the demand for high capacity of secondary batteries as power sources. Since nickel-metal hydride batteries were first commercialized in 1990 in Japan, they have become increasingly popular as power sources for cellular phones, portable computers, electric shavers, and other, products.The performance of a nickel-metal hydride battery, such as its discharge capacity, high rate capability, and charge-discharge cycle life, strongly depends on the characteristics of the hydrogen-absorbing alloy negative electrode. Many types of hydrogen-absorbing alloys have been developed so far. For a hydrogen absorbing alloy to be used as the negative electrode material, (1) it must allow a large amount of hydrogen to be absorbed and desorbed in an alkaline solution, (2) its reaction rate should be high, and. (3) it must have long term durability under repeated charge-discharge cycling. However, LaNi5, a typical rare earth-nickel type alloy, shows significant capacity deterioration during repeated charge-discharge cycling. Therefore the first step in its development was to obtain sufficient corrosion resistance of the LaNi5 alloy for its use as an electrode material. A partial replacement of nickel with cobalt and a substitution of the lanthanum- content with misch metal (Mm), a mixture of rare earth elements such as lanthanum, cerium, praseodymium and neodymium, were very useful in improving the charge-discharge cycle life. However, the discharge capacity of the alloy was still not sufficient for a practical battery. A study of the effect of the partial substitution of aluminum and manganese showed that the best alloy composition was Mm(Ni-Co-Al-Mn)x, as follows.The stoichiometry x of Mm(Ni-Co-Al-Mn)x largely affects the discharge capacity and cycle life. Theose alloys with non-stoichiometric alloys with the compositions of [Mm(Ni-Co-AMn)x: 4.7<x<4.8] have a large capacity and a long cycle life. Nogami' et al. reported that 'a non-stoichiometric alloy with a Mm(Ni-Co-Al-Mn)x (x=4.76) composition showed approximately 10% higher discharge capacity than the stoichiometric alloy (x=5) [1] and greater influence of x on the electrochemical properties of multi-component AB„ type hydrogen-absorbing alloys for batteries."

Jan 1, 2000

By D. C. Foguel, J. L. R. Bravo

For several years, Caraiba Metais S.A. (CMSA) had to stock the arsenic sludge generated from the electrolyte purification process of its tankhouse. The amount stocked · reached approximately 3,500 tonnes, as the effects of its recycling during the smelting process and consequently in the sulfuric acid plant were unknown. Besides, it had as limiting factors the high content of arsenic in the copper concentrates supplied by foreign countries as well as the reduced capacity of the tankhouse's purification plant. The choice for selling the mentioned residue, which generally contains more than 50% of Cu, was attractive, but the environmental policies and regulations had not allowed this option. Other alternatives, such as the production of bicupric arsenic by means of a solvent extraction process or arsenic trioxide, were considered but the economic feasibility was not attractive due to the absence of a domestic market and a poor international market. After a study of the arsenic partition in the metallurgical process, it was verified that the residue could be recycled without causing any operational problems or damage to the environment. To make this possible, the capacity of the purification plant was increased and the way of removing the arsenic sludge from the cells was modified from manual to mechanical, therefore avoiding the direct contact of the workers with this poisonous substance. Moreover, procedures for recycling in the smelter were established and tolerance limits were set for both the smelter and the sulfuric acid plant. The main amount of arsenic to be recycled is released with the smelting furnace off-gas, which is washed during the purification stage of the sulfuric acid plant. The acid water, rich in arsenic, is then treated in the waste plant and the arsenic, in its stabilized condition, is confined in an appropriate area.

Jan 1, 2000

By T. Langthaler, H. W. Engl, H. Holl, K. L. Schwaha

"The trend towards near net shape casting requires the development of more complex design and control algorithms for continuous casting ""machines in particular with respect to the solidification process.Compared to conventional continuous casting the reduction in casting thickness allows to influence more directly the solidification rate by control variables like surface cooling and/or casting speed.In order to enable the determination of these control variables for a given solidification profile, an algorithm (inverse solidification analysis) has been developed based on nonlinear constrained optimization. The application of the model is illustrated by practical examples ranging from conventional continuous casting to advanced thin slab casting.IntroductionProcess development in the Iron and Steel Industry is directed towards the realization of continuous process sequences. Since the direct linkage of processes imposes some restrictions onto the individual process steps, more complex algorithms are needed for design of equipment and control of operation. In particular the recent trend to reduce casting thickness, i.e. to cast thin slabs, has made the direct coupling of continuous casting and rolling absolutely necessary. The prospective development in strip production is schematically shown in fig. 1."

Jan 1, 1988