Search Documents

By Matthew John M. Krane

"The macrosegregation patterns and convective behavior of a Pb-5wt%Sb-35wt%Sn alloy are studied using new numerical treatments of solid particle motion and of transport phenomena occurring during the solidification of ternary metal systems. At this composition, the solidification which occurs while the local liquid composition is in the (Pb)-(SbSn) binary eutectic trough has a significant effect on these phenomena. The effects of this solidification path on fluid flow and macrosegregation are compared to the more familiar binary alloy patterns and the effect of solid particle transport is evaluated. The final predictions of macrosegregation are compared to measured composition profiles. IntroductionThe macroscopic maldistribution of alloy constituents during solidification, commonly called macrosegregation, is a defect which occurs in real metal processing systems. This nonuniformity of species distribution, especially when it forms a high composition gradient or a poor distribution of secondary phases, can lead to areas of high stress concentration, which contribute to cracking during extrusion or forging of wrought alloys or when an as-cast piece is severely loaded in service [1, 2]. Macrosegregation studies in binary systems have become quite common since the introduction of single-domain numerical models which feature one set of conservation equations and boundary conditions for an entire, fixed computational domain containing solid, liquid and multiphase regions. A complete review up to 1995 has been presented by Prescott and Incropera [3]. However, most commercial alloys generally have more than two species in amounts significant enough to affect the convective flows which lead to macrosegregation and other defects. The formation of secondary solid phases, including eutectic and peritectic reactions, also may occur in commercial metal alloys and should be treated using appropriate thermodynamic models."

Jan 1, 1999

By L. J. Lutz

The U.S. Bureau of Mines has developed an electrorefining process to recover Ni, Co, Cr, and other metals from mixed and contaminated superalloy scrap. The superalloy scrap is cleaned then directly electrodeposited as a Ni -Co deposit. The process recovers approximately 90 pct of the Ni-Co available from the scrap as a 99t pct pure Ni-Co alloy. During electrorefining the electrolyte undergoes a purification process which results in Cr and other refractory metals reporting to the purification residue. Operating data is given for a 3-L compartmented electrolytic cell. Techniques for the removal of Fe, Cr, and trace impurities from the recycled electrolyte are outlined. The economics of a facility producing 15 mt/d of a Ni-Co alloy are also discussed.

Jan 1, 1993

By T. Ueno

Naoshima Smelter & Refinery of Mitsubishi Materials Crop. commissioned a new Mitsubishi continuous copper smelter in May 1991. Process offgas volume of the conventional reverberatory furnace line, one of the previous smelters having been shut down, was very large and thus two acid plants had been operated. It was expected that the offgas volume would, be reduced at the new smelter to about a half of the sum of those from previous two smelters and the sulfur dioxide strength would be increased. So various alternatives were studied to minimize the operation cost. And it was decided to utilize both of the plants with minor modifications by diluting the gas either with air or with dilute gases. The acid plants now receive off gases from the new copper smelter, a sintering machine of a lead smelter and a decomposer of waste acid. The paper discusses plant design, operation, improvements and modifications realized in relation with the retrofitting of the copper smelter.

Jan 1, 1992

By G. Haesebroek

In L969 Metallurgie Hoboken-Overpelt started an industrial plant for the separation of iron and zinc from a concentrated CoCL2 solution. Iron and zinc are extracted in column contactors by a solvent containing 12 vol % of tertiary amines in xylene. The extracted metals are stripped from the pregnant organic phase by precipitation with a NaOH solution at pH LL. In this paper an overview is given of the industrial process. In order to overcome some drawbacks of this process (low flash point of the diluent, reagent consumption, batchwise stripping) an alternative solvent extraction process has been examined. In this alternative process, iron and zinc are extracted with an or¬ganic phase containing 50 vol % of TBP in Escaid 110. The pregnant solvent is stripped with water in conventional mixer settlers. Despite the ability of this process to overcome most of the inconveniences due to the use of tertiary amines, it suffers from the poor stability of TBP in concentrated chloride solutions, resulting in unavoidable and inacceptable precipitation phenomena in the stripping section.

Jan 1, 1988

By F. R. A. Jorgenson

The ignition of chalcopyrite and pyrite was studied using laminar flow furnace and thermal analysis techniques which were supported by XRD and optical microscopic examination of the products. In air, chalcopyrite and pyrite ignited at temperatures of 400-500'C and 500-600?C respectively. The phase assemblages predicted from thermodynamic analyses were compared with those found by experiment, and the onset of ignition was correlated against changes in the phase compositions. Pyrite and chalcopyrite ignited when pyrrhotite and intermediate solid solution formed thus opening up the structure and allowing ready access of oxygen.

Jan 1, 1989

By Kuniaki Murase

Cadmium telluride (CdTe) semiconductor has been well investigated as a CdS/CdTe heterojunction solar cell material since its band gap is suitable for energy conversion from sunlight into electricity. In this paper a new electrochemical processing of thin-layered CdTe using basic aqueous electrolytes is reviewed from the standpoint of thermodynamics using a potential-pH diagram. The cathodic electrodeposition of the stoichiometric CdTe with a flat surface morphology took place at more positive potentials than that of the Nernst potential for the bulk-Cd deposition and at more negative potentials than that for the hulk-To. In this potential region deviation from the stoichiometric composition of eleetrodeposited CdTe was controllable by the Cd(II)/Te(IV) concentration ratio, pH, or concentration of complexing agent for Cd2+ ions of the electrolytes, The deposition behaviors for ammoniacal media were well accounted for by the potential-pH diagram of the Cd-Te-NH3-H2O system devised by a combination of those of the Cd-NH3-H20 and the Te-H2O systems, Diagrams for other complexing agents, ethylenediamine and diethylenetriamine, were also constructed to investigate and discuss the electrodeposition conditions regarding the corresponding media.

Jan 1, 2003

By R. S. Celmer

The distributions of cobalt, molybdenum, copper, and selenium between nickel matte and silica-saturated iron silicate slag have been determined in the region of the metallic saturation boundary, at 1523 K. Results are given as a function of the composition of the coexisting Fe-Ni alloy and the activity of iron in the system. Under strongly reducing conditions, these minor elements display a marked preferential accumulation in the sulphide phase. It is shown that the dissolution of cobalt and molybdenum in slag follows an oxidative mechanism, and distribution equilibria are correlated with the oxygen potential. From these data, the thermodynamic properties of cobalt in nickel matte are computed. Further, comparisons of minor element partitions are made between the nickel and copper matte smelting cases under metal saturation conditions.

Jan 1, 1988

By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

By F. J. J. van Loo, A. A. Kodentsov, J. A. van Beek, M. R. Rijnders

"A periodic layered morphology of the reaction zone has been observed in several annealed solid/solid diffusion couples, including metal/metal and metal/ceramic couples. This morphology is characterized by a regular array of alternating layers, which are either single-phase layers or bands of particles embedded in an intermetallic matrix phase. A description of several systems showing periodic layer formation is given. It is shown that the periodic layered structure with the single phase layers and the one with the bands of particles have a different mechanism of formation.IntroductionSolid state reactions in ternary systems can produce a variety of reaction zone morphologies if there are two or more reaction products. Three types of morphology have been described in detail: 1) simple layered; 2) isolated precipitates in a singlephase layer; 3) interpenetrating columnar (lamellar) or interwoven structure. Understanding the factors that govern the formation of different morphologies is of importance in many fields of engineering. For solid state displacement reactions the conditions governing the formation of these morphologies are well understood [1-4]. For example, the development of a layered or aggregate reaction zone depends on the relative diffusivities of the components through the reaction products.This paper is concerned with the periodic layered morphology which has been observed in various solid state systems. We consider this to be a fourth type of reaction layer morphology. Two manifestations of periodic layered morphology may be distinguished. One form consists of regularly spaced layers of particles of one reaction product embedded in a matrix phase (another reaction product). The other form consists of single-phase layers embedded in a matrix phase. It will be shown that each manifestation has its own mechanism of formation. In section A we consider a system (Ag/Ti-foil/Si) in which periodic layer formation will be explained as a special case of the Liesegang phenomenon. In section B we consider systems where the periodic layered structure has a different origin."

Jan 1, 1996

By Jean P. Murray

The extractive metallurgical industry is a major consumer of high-temperature process heat. It is, consequently, a major contributor of C02 emissions and other greenhouse gases derived from the combustion of fossil fuels for heat and electricity generation, or from the process itself. These emissions can be substantially reduced by replacing fossil fuels with solar energy as the source of process heat. Concentrated solar radiation can supply a large amount of thermal energy to endothermic reactions at temperatures exceeding 2000 K. Another potential for C02 emission reduction exists as well. Thermodynamically, the total amount of energy required for metal production at any given temperature is the enthalpy change of the reaction, AH. Of this total, an amount equal to the Gibbs free energy AG must be supplied as high quality energy in the form of electrical work or by using a reducing agent. Many conventional metallurgical electrolytic processes and reducing furnaces are unable to add only the thermodynamically required electricaVchemical energy due to process inefficiencies. Electrical work in excess of AG for the reaction may be used to supply process heat, or excess chemical reducing agent burned to supply process heat. Besides the thermodynamic and economic drawback, this inefficiency results in excess C02 emissions derived from the combustion of fossil fuels. With these practices, energy becomes an important cost element of the metal produced. Highly-concentrated solar energy has the demonstrated potential to separate these two forms of process energies, allowing the addition of only the thermodynamically required high-quality energy while high-temperature solar process heat is provided to the reactor. Examples of metal oxide reduction processes that have been studied experimentally in solar furnaces include the production of Fe, Al, AI/Si alloy, Mg, Zn, Tic, Sic, CaC2, TIN, Si3N4, and AIN by carbothermic reduction of their oxides, and the high-temperature solar- electrothermal reduction of ZnO.

Jan 1, 1999

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 Boyd Davis, Vladimiros Papangelakis, Joshua LaMarre, Jan de Bakker

"HCl leaching using molten salt hydrates has the potential to improve the extraction of nickel from laterite ores. However, as in other HCl leaching applications, recovery of HCl is key to process economics. Spray pyrohydrolysis, which is used in current chloride-based flowsheets, is associated with a high energy cost. The authors have developed a proposed laterite leach circuit using an alternative HCl recovery route. The leach circuit envisions a leach by concentrated (33%) HCl in an MgCl2 molten salt hydrate (MSH) or brine medium, followed by Ni/Co recovery and iron precipitation. Magnesium and chloride are precipitated from solution as magnesium hydroxychloride; this hydroxychloride is thermally decomposed to produce HCl gas. The proposed flowsheet employs a chloride leach circuit with simpler equipment and lower energy cost than in the conventional practice of pyrohydrolysis. Laboratory work investigated key aspects of the flowsheet, including precipitation of magnesium hydroxychlorides and their composition; magnesium hydroxychloride thermal decomposition; and iron control.Introduction As sulphide nickel ores become harder to mine and more complex to process, laterite ores will increase in importance. Laterite ore deposits can be divided into two main mineralogies. Limonite ores consist mostly of hydrated iron oxide, FeOOH, with 1-3% nickel substituting for the iron. Saprolite ores consist of iron-magnesium silicates, (Fe, Mg)2Si04, again with some nickel substituting for the metal ions. Limonite ores can be treated using the HP AL (High Pressure Acid Leach) process, in which the ore is reacted with sulphuric acid at high temperature in an autoclave. HP AL, however, cannot in general be used to treat saprolite ores because the magnesium enters solution and consumes sulphuric acid, which results in excessive spending on lixiviant. It is therefore desirable to find a hydrometallurgical process specifically for saprolite ores that can provide better results than the treatment options currently available."

Jan 1, 2011

By Shenghui Guo, Ying Lei, Hao Niu, Huilong Luo, Jinhui Peng, Libo Zhang, Yu Li

"In this work, the combination of microwave drying (MWD) and heat pump drying (HPD) drying experiments were designed by response surface methodology (RSM) based on central composite design (CCD) using design expert software (Version 7.15), and the process parameters were optimized. The conditions given by software are: the MWD time is 4.6 or 4.4 min; the HPD time is 9.0 or 8.6 min; and the sample mass is 620 or 600 g. Under those conditions the moisture content is 1.0 10-2kg water/kg wet basis, and the effectiveness ratio is 0.70 kg water/kwh. The results of confirmatory experiments conducted under the optimized conditions show the combined drying have superiority of decrease of energy consumption and increase of handling capacity over the single MWD or HPD.1 IntroductionSilica sand is one of a silicate mineral with properties as hard, anti-friction and less reactive, commonly used as raw material for foundry and construction. The silica sand obtained from mineral dressing processes such as scrubbing, magnetic separation and flotation. Its moisture content is approximately 0.08~0.12 kg water/kg wet basis. The most common methods used for drying are solar drying and hot air drying. But these methods have some shortcomings: for example, the solar drying has longer process time due to low energy yield, [1] hot air drying has low-energy efficiency and a lengthy drying time. [2]Microwave is electromagnetic waves with frequency are 300MHz to 300GHz. The outstanding features of microwave heating are rapidity and selectivity. The water specific inductive capacity of 60~78 is much bigger than common materials, the moisture always quickly absorb electromagnetic wave and rapidly transfer to vapors. So, it can significant reduce the drying time. [3] Heat pumps (HPs) are devices for raising the temperature of low grade heat energy to a more useful level using a relatively small amount of high grade energy."

Jan 1, 2011

By David K. Melgaard

Electroslag Remelting (ESR) is a complex process used to produce high quality specialty alloy materials. The quality can be directly correlated to variances in melt rate and immersion depth. Conventional ESR furnaces control these quantities using two independent control loops using proportional changes in current for melt rate and driving the electrode up and down to match a voltage set point for immersion depth. However it is well known that the control loops are highly coupled, i.e. changing the current to account for melt rate deviations changes the voltage depth relationship and vice verse. In addition the noise in measurements of the ESR process can be considerable, forcing conventional controllers to use highly damped responses. A new model-based controller has been developed to embody the coupling and improve responsiveness by using estimates from a reduced-order linear ESR model and the typical process measurements to control melt rate and immersion depth simultaneously. Kalman filtering is used to optimally combine the model estimates of eight process states and the measurements of voltage, current, position and mass to estimate the instantaneous melt rate and immersion depth. Several ESR melts under steady state and transient conditions were conducted to evaluate the performance of the new controller. This paper will discuss the design of the new ESR model and controller and will present experimental results demonstrating its much improved control and responsiveness. While this controller was developed for the ESR process, the effectiveness of model-based control in managing such a complex process with relatively simple equations suggests the approach could be employed for many other processes as well.

Jan 1, 2006

By A. S. Rao

In the original roast-leach-electrowin (RLE) circuit at the Chambishi Cobalt Plant, commissioned in 1978, the separation of nickel and zinc from cobalt in aqueous streams was achieved by successive stages of precipitation using lime. However, this technique was not able to meet the increasingly stringent metal quality requirements of customers whilst maintaining acceptable process recoveries. Intensive process development work was carried out and, in July 1988, an ion exchange circuit for nickel removal was commissioned using DOW XFS 4195 resin and for the first time Z.C.C.M. produced high purity cobalt metal containing less than 0.10% nickel. Following further work, a solvent extraction circuit for zinc removal, using DZEHPA, was commissioned in February 1991 in order to enhance cobalt recovery by reducing co-precipitated cobalt losses. This paper outlines the process development, design, commissioning and subsequent operation of these nickel ion exchange and zinc solvent extraction circuits.

Jan 1, 1993

By V. D. Tathavadkar

Chromite ore is of immense importance for the extraction of metallic chromium and chromium chemicals. The mineralogy and crystal structure of chromite phase are therefore important part of our investigation on the extraction chemistry of chromium species. In this investigation, we have studied the effect of the processing parameters, i.e., the temperature and the oxygen potential on the microstructure and composition of mineral phases formed in the Cr2O3 ?Al2O3 -FexOy -MgO system. In particular the importance of the spinodal decomposition reaction is emphasized in the extraction of chromium as sodium chromite and sodium chromate. Experiments were carried out in order to study the differences in the crystallography of different chromite minerals. Phase equilibria in natural chromite minerals were investigated by calcining chromite mineral in air, argon, and 5% hydrogen + argon atmospheres over a temperature range from 200 to 1200 °C. The effect of the oxygen partial pressure and temperature on the phase constituents of the calcined product has been discussed. The microstructural changes were examined using scanning electron microscope (SEM) and the changes in elemental composition in different phases were analysed by electron probe micro analyser (EPMA). The results obtained from EPMA studies were used to calculate lattice parameter of the spinel lattice, and these values were compared with the values obtained from X-Ray powder diffraction data. On the basis of the experimental data, the mechanism of the spinodal decomposition of complex spinel phases is described under the influence of oxygen partial pressure and temperature.

Jan 1, 2000

By Kenneth S. Coley, Michael Pomeroy, Elaine Chen

Recent work on modeling of BOF steelmaking is reviewed, highlighting the critical aspects of each approach. It is concluded that the most successful models should be based on a deep understanding of the mechanisms and kinetics of the critical reactions. The importance of the decarburization mechanism is discussed with particular reference to its role in droplet swelling or bloating which has a profound influence on the droplet residence time in the slag. Conditions which cause bloating are discussed and the rate determining step is proposed to be primarily nucleation of CO bubbles inside the metal droplet with some influence from growth by reaction at the bubble/metal interface. The discrepancy in the super-saturation ratio required for classical nucleation is discussed and an approach using a surface tension modifying parameter is illustrated. Finally, the role of CO nucleation in controlling the driving force for dephosphorization is discussed.

Jan 1, 2014

By Nieves Iglesias

The removal of the refractoriness of a gold bearing pyrite- arsenopyrite ore is studied. Flotation concentrates were prepared and leached with a dilute acidic ferric sulfate solution. The elemental sulfur film which forms on arsenopyrite in the oxidation process is not responsible for the low rate of the arsenic dissolution observed. A positive effect on the leaching rate is observed when Ag' is added. This pretreatment eliminates the refractory nature of concentrates.

Jan 1, 1993

By Samson Adeosun, Sanmbo Balogun, David Esezobor

"Iron and steel making processes give rise to large amounts of usable and unusable materials, the latter generally being termed wastes. It is sometimes difficult to distinguish between re-usable by-products and wastes which cannot be sold or land-filled. Much depends on circumstances such as the local market for the material. This can itself vary from time to time with by-products which cannot be used or sold becoming wastes and vice versa. This paper defines the concept of “waste-free technology”, discusses its development in the steel industry and highlights the benefits of the technology to the manufacturing sector and the environment. The paper also articulates how the “waste-free” technology could be applied in the proposed Ajaokuta integrated steel plant in Nigeria.IntroductionIn the past, nature was considered an inexhaustible store. Its resources were consequently exploited and waste products therefrom were discarded. Today, attitudes have not changed appreciably even as raw materials cost rise by the year to pose a series of socio-economic problems, which, among others, may include the rational and optimum utilization of resources, environmental protection and reduction of waste formation. Consequently, industrialists now face unexpected regulatory pressure in areas of pollution prevention, waste minimization and hazardous waste disposal.Iron and steel making processes give rise to significant amounts of usable and un-usable materials, the latter generally being termed waste. It is sometimes difficult to distinguish between re-usable by-products and wastes which cannot be sold or land-filled. Much depends on circumstances such as the local market for the material. This can itself vary from time to time with by-products which cannot be used or sold becoming wastes and vice versa. In this paper, the term waste refers to those materials that are either irrationally utilized or, land-filled and part of the byproducts that are not utilized. It includes that part of used materials which is not incorporated into the products manufactured during a process stage and which in contrast to reuseable materials, is considered not suitable for any further use, owing to technical or economic factors. In general, these materials are inorganic and parts of them are either utilized or passed to the other processes; the other part should be disposed of using well-established waste disposal practices to avoid any environmental threat.Thus, creative methods must be developed to modify the manufacturing processes to reduce emissions and process wastes by fully utilizing all resources. One method of eliminating the negative effect of waste formation is the use of purification and cleaning structures (pollution control system, PCS). These are, however, quite expensive."

Jan 1, 2008

By F. Elgersma

A high purity electrolysis solution is essential for hydrometallurgical zinc winning processes. For this reason ferric iron containing compounds such as jarosite are precipitated as iron and impurity collector during the calcine leaching. Jarosite thus forms a chemical waste and creates environmental problems. This research contributes to the development of a wet jarosite treatment process, where less contaminated jarosite is produced which can act as an iron source. The present work studies jarosite precipitation kinetics and the uptake of zinc cations in batch and continuous experiments. The distribution coefficient for zinc in continuous experiments is constant for a wide ratio of zinc over ferric ions in the solution. Addition of NH, + ions in batch experiments accelerates the conversion rate equivalent to the driving force increment. Addition of 50,2-ions above the stoichiometric ratio increases the conversion rate less then could be expected from the increase in the estimated driving force. Zinc ions tend to retard the conversion rate. An increasing reaction temperature increases the conversion rate. Below 75 ?C the conversion rate approximates zero.

Jan 1, 1990