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By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, Pso, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of 02 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By J. C. Yannopoulos

The quest for a continuous copper smelting and converting process, which has been going on for a long time, has not as yet reached its objective. The most recent efforts for the development of a continuous copper?making process started about two decades ago. Among the contending proposed processes, four have been piloted and three of them are currently in operation: the WORCRA process., the NORANDA process, the MITSUBISHI process, the OUTOKUMPU process. The WORCRA process, after some long pilot plant tests, failed to develop as an industrial process: The NORANDA process, as currently operating, is a smelting process and not a continuous copper?making reactor as initially conceived. The MITSUBISHI, although the only continuous process, has not been widely accepted. The OUTOKUMPU process can be applied only to a low iron concentrate feed and co?produces blister and high in copper slag. The thermodynamics of these "continuous" systems and the practical problems of their industrial application are reviewed and discussed. The achievement of efficient and inexpensive environmental control should' be the primary objective of any new process development. A review of the environmental problems of the copper industry indicates that the quest for a continuous smelting and converting furnace should be intensified.

Jan 1, 1983

By Jorge D. Vier, Raúl B. Rebak, Alicia E. Ares, Natalia S. Zadorozne

Recent worldwide demand has driven nickel and molybdenum prices to record high values. Alloys containing significant amounts of nickel and molybde- num, such as the austenitic and duplex grades, have experienced significant price increases and some spot shortages have resulted in some regions. With low or no nickel content and reasonable molybdenum content, super-ferritic stainless steels are now proving to be the most cost effective corrosion resistant materials. The electrochemical behavior APMT® (Fe–21Cr–5Al–3Mo–0.04C) and 4C54® (Fe–26.5Cr–0.8Mn–0.5Si) super-ferritic stainless steel in NaCl solutions has been studied using open circuit potential measurements, potentiodynamic polarization curves, and electrochemical impedance spectroscopy. The aim is to compare the behavior of these materials with austenitic stainless steel alloy 316 (Fe–18Cr–10Ni– 2.5Mo). The results indicate that the APMT alloy presents a better performance than the AISI 316 stainless steel, while 4C54® does not, especially at anodic potentials. The good behavior of APMT® may be attributed to Al and Mo content in its composition.

Mar 1, 2017

By George S. Dulikravich

An advanced semi-stochastic algorithm for constrained multi-objective optimization has been adapted and combined with experimental testing and verification to determine optimum concentrations of alloying elements in heat-resistant and corrosion-resistant H-Series austenitic stainless steel alloys. The objective was to simultaneously maximize a number of alloy's mechanical properties. This research will result in a rigorous tool for the design of high-strength H-Series steels and other types of alloys unattainable by any means existing at the present time. Such a material-by-design tool will also be able to reduce or minimize the need for the addition of expensive elements such as Cr, Ni, Co, Nb, Ti, V, etc. and still obtain the optimum properties of an alloy.

Jan 1, 2003

By J. E. Dutrizac

Fracture-exposed surfaces of sphalerite samples having five different solid solution iron contents ranging from 0.0 wt% to 14.8 wt% Fe were leached for 15 to 120 s at 100°C in 0.3 M Fe(S04)1.5 -0.3 M H2S04 media. The reacted samples were examined using X-ray photoelectron spectroscopy (XPS) which provides chemical state information on the first few nanometers of the solid surface. Surface compositions show that the leaching rate increases with increasing solid solution iron content of the sphalerite. Detailed evaluation of high resolution S2p spectra show that the leaching progresses via the formation of polysulphide species. Disulphide species were not detected in any of the experiments. Examination of the Zn2p and Fe2p spectra indicate little change in the chemical states of these elements over the duration of the experiments. Longer leaching times resulted in the generation of elemental sulphur. The ratios of elemental sulphur to dissolved ferrous ions and zinc suggest that less than 5% of the sulphide is oxidized to sulphate. Morphological studies showed that the elemental sulphur commonly formed at a few isolated sites, such as the grain boundaries. Furthermore, euhedral sulphur crystals were often identified. These observations suggest that at least part of the elemental sulphur forms via dissolved sulphide species which are oxidized in solution by ferric sulphate.

Jan 1, 2003

By Lauri Holappa

Copper converting is mostly performed in Peirce-Smith converters. The process is still very similar to the original one developed in the early 20th century. It is a batch process in a horizontal cylindrical reactor with air blowing via tuyeres along the length of the reactor side. The Peirce-Smith converter has its roots in Bessemer's inventions in the 1850's as he tested both horizontal and vertical vessels for steel converting. However, for steel making a vertical pear-shaped converter with air bottom-blowing was established. In the course of time, there was a distinct necessity for oxygen usage instead of air due to harmful effects of nitrogen to steel properties and its cooling effect. In-bath blowing of oxygen did not succeed, however, and top-blown oxygen converter with oxygen lance (LD or BOF) was first developed in he 1950's and emerged rapidly to a dominating position. Somewhat later oxygen bottom-blowing via special shrouded tuyeres was developed (OBM or Q-BOP) but has attained only fractional share. Bottom-blowing technique had, however, impact on the current combined blown converters which adopted the benefits of both top and bottom blowing. In copper converting Peirce-Smith type converters have kept their position until today although new processes have been introduced and at least few of them seem to be emerging. In one respect copper converting has a clear leading position i.e. in the progress of continuous converting processes (Mitsubishi, Ausmelt). These processes utilise top-blowing lances instead of in-bath blowing tuyeres. A different principle for continuous converting is flash converting by Kennecott Outokumpu, which makes smelting and converting independent of each others. Solid ground matte is used as a feed for flash converting in a reactor shaft similar to Outokumpu matte flash smelting. A comparable process has been presented by Inco too. The paper discusses principal physico-chemical and process technical similarities and differences in copper and steel converting. Although these processes are metallurgically quite different it seems that during the modem history of ferrous and non-ferrous metallurgy, starting from the 1850's, the exchange of knowledge between these disciplines has been quite intensive. In long-term perspective, many similarities in the development can be found but also divergences due to different ambient circumstances.

Jan 1, 2003

By D. Papazoglou

This work was undertaken to investigate the thermodynamic and kinetic feasibility of using hot sulfur dioxide bearing gases from smelting processes to selectively sulfate the nickel in nickel laterite ores for subsequent extraction in water. The environmental benefits ofthis approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the S02 rather than converting it to sulfuric acid are strong drivers for such a process. A thermodynamic analysis indicated that selective sulfation of the nickel could be feasible under appropriate conditions and these were explored through a series of laboratory scale experiments. Laterite samples were reacted at temperatures between 500 and 800°C with an equilibrated mixture of sulfur dioxide, oxygen and nitrogen in a fixed bed reactor. Tests were conducted on saprolitic ore from Bulong, Western Australia, limonitic ore from New Caledonia and garnieritic ore from Indonesia. Nickel extractions were highest from the limonite and relatively low from the other ores. The maximum selective extraction of nickel from the limonite in a single stage sulfation was 73%. Sulfation of other elements present in the laterites was also examined. A two-stage process was also identified which involved sulfation using a strong sulfation potential followed by weaker sulfation potential to attempt to convert ferric sulfate formed in the first stage to ferric oxide. This increased the extraction for the limonite ore to around 84% Ni, 95% Co and 2% Fe. Direct sulfation of laterite could be feasible in locations where sulfide smelting or roasting operations are relatively close to laterite deposits.

Jan 1, 2003

By George S. Dulikravich

An advanced semi-stochastic algorithm for constrained multi-objective optimization has been adapted and combined with experimental testing and verification to determine optimum concentrations of aJ10ying elements in heat-resistant and corrosion-resistant H-Series austenitic stainless steel alloys. The objective was to simultaneously maximize a number of alloy's mechanical properties. This research will result in a rigorous tool for the design of high-strength H-Series steels and other types of alloys unattainable by any means existing at the present time. Such a material-by-design tool will also be able to reduce or minimize the need for the addition of expensive elements such as Cr, Ni, Co, Nb, Ti, V, etc. and still obtain the optimum properties of an aJ1oy.

Jan 1, 2003

By Rui-Qing Li, John G. Peacey, Peter J. Hancock

"Noranda has been investigating a pyrometallurgical process for the direct recovery of zinc from zinc concentrate and zinc and iron containing residues. The process consists of injecting dry zinc concentrate and secondary zinc materials into a molten iron oxysulphide bath, volatilizing metallic zinc into furnace off gas essentially free of sulphur or S02, fixing sulphur contained in the feed materials as iron oxysulphide matte which is disposed, and recovering metallic zinc in an ISP type lead splash condenser. Combustion of petroleum coke with air or oxygen enriched air inside the oxygen containing matte supplies part of the heat, and the products of combustion dilute the zinc-laden gas to a desired level.This paper describes the process concept, thermodynamic background, experimental tests, mass and heat balance calculation for a conceptual flowsheet, environmental stability of the residue and advantages and disadvantages of the process. Experimental tests have successfully proved the process concept and thermodynamic predictions. Direct smelting of zinc concentrate and residues inside an iron oxysulfide bath has a great potential to become a cost effective and flexible zinc smelting process.1. INTRODUCTIONZinc is mainly produced by a roast-leach-electrowinning process route, which accounts for about 80% of the world primary zinc production. This process produces high quality zinc with very high zinc recovery (>95%) but suffers from several major drawbacks such as using high cost electricity as reductant, producing environmentally problematic iron containing leach residue (jarosite or goethite) and the difficulty in treating secondary zinc feed materials containing high impurity levels, such as electric arc furnace dusts from the steel industry, and other complex sources. Also in some areas, markets for sulphuric acid are distant resulting in negative realizations on acid sales.The Imperial Smelting Furnace (ISF) process is the major pyrometallurgical process to treat zinc-lead concentrate. The advantage of this process over the electrolytic zinc process is its flexibility in treating high-lead, bulk concentrates with high recoveries of lead, copper and precious metals. However, this is a two-stage process involving sintering of Zn-Pb concentrates followed by blast furnace reduction. The process requires large amounts of high-quality coke which is a major operation cost, and the sintering process which results in serious environmental problems."

Jan 1, 1996

By R. Nilsson

In the present work, an assessment of the sulphide capacities of a number of binary and ternary slag systems have been carried out in the light of a sulphide capacity model. The model is based on the expression: {CS- exp (-A G °/R T) ? ao2 / fs2-} where AGO is the standard Gibbs energy change for the above reaction, ao2 is the activity of oxygen ions and f, is the activity coefficient of the sulphide ion in the slag. In the present model, the ratio (ao2/fs2) is optimized for the experimental data available in literature. The systems assessed are the binaries MnO-SiO2, CaO-SiO2, Al2O3-CaO, as well as the ternaries CaO-Al2O3-SiO2 and CaO-MnO-SiO2. In the case of all these systems, the experimental data available in literature were complemented by measurements carried out at the Division of Theoretical Metallurgy. The sulphide capacities of some FeO- containing binary, ternary and quaternary slags are also examined. The potentiality of the model to estimate the sulphide capacities of complex slag systems from binary and ternary data is demonstrated.

Jan 1, 1996

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 Xie Zhang, Jiang Diao, Xin Qiu, Lu Jiang, Bing Xie, Hong-Yi Li

"Duplex converter process, in which the first converter is used for removing phosphorus from hot metal (De-P), is an important way to produce low P-content and ultra-low P-content steels. In order to improve phosphorization removal and formation of slag with high basicity at relatively low temperature during dephosphorization converter process, effects of temperature, silicon content in hot metal and varied compositions of the De-P converter slag on phosphorus distribution between the slag and hot metal were investigated with thermodynamic calculations and by laboratory scale experiments in present work. Results showed that phosphorus distribution ratio between slag and metal was varied in 10.6~26.6 when basicity of the slag was in the range of 1.5~2.1 at 1370, and the distribution ratio was increased with increasing basicity and Fe10 content in the slag.IntroductionIt is known that phosphorus exists in steel in the form of solid solution, which can significantly improve strength and hardness of steel at room temperature. However, the plasticity and toughness of steel, especially the low temperature plasticity is sharply reduced and leads to high ductile-brittle transition temperature. This phenomenon is commonly known as cold brittleness of steel [1~3]. Hence, phosphorus should be removed as much as possible in the steelmaking process, because it is generally harmful to the iron and steel products."

Jan 1, 2013

By Duclerc Fernandes Parra, Vijaya Kumar Rangari, Washington Luiz Oliani, Danilo Marin Fermino, Ademar Benevolo Lugao, Nilton Lincopan, Luiz Gustavo Hiroki Komatsu

Polyethylene is widely used for packing applications. Different grades of polyethylene, LLDPE and LDPE play a major role in the film blowing industry. The use of nanoclay in polymer matrices (non-polar) requires the use of a compatibilizer agent, ethylene graft maleic anhydride copolymer (PE-g-MA), which acts as a bridge for nanoclay-matrix-interaction. In our study, blown films of LLDPE, LDPE, and their blends were produced using a twin screw extruder. The combination of PEs as matrix, montmorillonite (MMT) and silver nanoparticles (AgNPs) intended to improve mechanical and thermal properties. Nanocomposites films with 1 wt% of montmorillonite and 0.5–1.0 wt% silver nanoparticles were prepared by blow extrusion and evaluated. Nanoclay intercalation/exfoliation degree was investigated by X-ray diffraction spectroscopy (XRD) and scanning electron microscopy (SEM). Mechanical and thermal properties were evaluated. The results showed optimum dispersion at intercalation/exfoliation levels for polyethylene nanocomposite (PENC), slight increasing in mechanical and especially improvement in thermal properties.

Mar 1, 2017

By A. E. Isaacson

The U.S. Bureau of Mines is studying the effect of supercritical water, at 400' C and 3,500 psi, and subcritical water, at lower temperatures and pressures, on mixtures of minerals and metals to determine the possible applications of water at high temperature and pressure for processing these materials. This research was conducted using a flow-through bench-scale system. Copper-bearing minerals studied were chalcocite, chalcopyrite, covellite, and cuprite. In general, mixtures of copper minerals and pyrite reacted to form bornite. Intermediate phases formed were chalcopyrite and digenite. Similar reactions occurred between pyrite and metallic copper. A mixture of chalcopyrite and pyrite was inert in supercritical water'. The reaction between cuprite and metallic zinc yielded metallic copper. The cuprite was reduced by hydrogen generated by the reaction between metallic zinc and water. None of the reactions occurred exclusively in supercritical water, but also occurred in water at high temperature and pressure below the critical point. 'Experimental results did show that a dual-reaction process, consisting of solid-state diffusion and fluid transport, was occurring.

Jan 1, 1989

By E. Oshima

In May 1991, a New Mitsubishi Continuous Copper Smelter Line started operation at Naoshima. Recently, it has been continuing steady operation and one and a half year campaign life has been achieved. In 1996, new records of on line time, the amount of copper concentrate treated and copper anode production were achieved. 1t proves the superiority of the process with respect to pollution control, energy efficiency, flexibility and easiness of the operation and over all economy including off gas handling cost. Furthermore, .plans are underway to prolong the campaign life for two years and to improve the process efficiency. This paper describes recent operation, improvements, and a future capability study.

Jan 1, 1998

By Huayi Yin, Wang. Dihua, Wei Xiao, Xuhui Mao, Diyong Tang

"The world production of crude steel reached 1.55 billion tons in 2012,which generated ~2.5 billion tons of CO2. Electrochemical metallurgy especially through high temperature molten salt electrolysis with renewable electricity stands for a great opportunity for producing “green” metals. In recent years, electrolytic production of iron without emission of CO2 in different molten salt systems has been reported. A cost-affordable inert anode is the key to produce acceptable eco-friendly iron by the novel molten salt electrolysis processes. Based on the authors’ research, this paper will discuss iron production by molten salt electrolysis using a nickel alloy inert anode. On the other hand, the paper also covers a novel molten salt CO2 capture and electrochemical transformation (MSCC-ET) process, in which CO2 is effectively converted to value-added carbon and oxygen in a molten bath using a cost-affordable nonconsumable SnO2 anode.1. IntroductionEnergy and materials are cornerstones to support the development of human society. The traditional primary metal production, especially iron and steel, and electricity production are mainly based on the reactions between carbon (coal) and oxygen (represented by equations (1) and (2) respectively), which produce huge amount of CO2.MxOy + 0.5y C = x M + 0.5y CO2 (g) + Q1 ( 1 )C + O2 (g) = CO2 (g) + Q2 ( 2 )In 2012, the world production of crude steel reached 1.55 billion tons, of which 46.3 %, ~0.7165 billion tons were produced in China. Based on the average level of 1.7t CO2 emission per ton steel, more than 1 billion tons of CO2 generated from steel industry in China in the year. Besides the iron and steel industry, thermal power plant leads the CO2 emission in both USA and China. The total consumed electricity in China increased to 4959 billion kWh in 2012, ~70% of it was from coal fired power plant. The average CO2 emission for electricity production in the typical thermal power plant in China is around 0.78 kg kWh-1. It accounts for ~ 3.868 billion tons of CO2 emission from thermal power plant in 2012 in China."

Jan 1, 2014

By Tuula Mäkinen

One of the latest applications of the Outokumpu Flash Smelting Technology is the direct smelting ,of nickel concentrates to metallised low-iron nickel mattes. Compared to the conventional nickel smelting, the new DON process needs a lower number of smelting vessels resulting in considerable economic and environmental benefits. Fundamentals of smelting nickel concentrates in one stage to low-iron mattes are presented. Properties of nickel. smelting slags with an emphasis of the slag fluidity at high MgO-levels are also discussed. Conditions prevailing in DON mattes at high oxidation degrees are presented as well as their influence on the behaviour of such mattes in the settler and on tapping the furnace. Distributions of elements in the direct smelting are presented and compared with the conventional process. A further comparison is made with pilot-plant data and the industrial scale.

Jan 1, 1998

By Zhuo Sheng

We have designed a high-temperature Raman micro-furnace and cell that is suited for the electrochemical process study of the NO3 − in molten NaNO3– KNO3 (fraction of NaNO3 50 wt%) salt. During the cycle voltammetry and constant potential electrolysis process, the Raman laser beam was focused near the electrode; subsequently, the Raman spectra are obtained and the reduction process of NO3 − is analyzed. In the CV cathodic scan process, the new peak attributed to the ν1 mode of NO2 − emerges, and the peaks assigned to superoxide ions (O2 −) and peroxide ions (O2 2−) are not found. In the constant electrolysis process, the peaks at 1130 and 800 cm−1 appear when the potentials are between −2.0 V and −3.2 V (vs. Pt). The results show that when the NO3 − is reduced in molten the NaNO3–KNO3 mixtures, the reduction product O2− cannot stably exist, and O2− will react with NO3 − to form of superoxide ions (O2 −) and peroxide ions (O2 2−).

By Stavros A. Argyropoulos

Exothermic mass transfer takes place in various areas involving metallic systems, ranging from liquid metal processing operations to the growth of thin films in microelectronics. The formation of intermetallic compounds plays an important role in the exothermic mass transfer of metallic systems. Two types of exothermicity are identified , namely , Microexothermicity and Macroexothermicity. The former is encountered when small amounts of metals are mixed, while the latter is exhibited when a solid metal in a lump form is added into liquid metal. In this paper two types of exothermic mass transfer in metallic systems will be presented and reviewed. Mathematical modelling work for these types of exothermic mass transfer will be analyzed.

Jan 1, 1993

By Chikabumi Yamauchi

The comprehensive scientific development of conventional industrial technologies stimulates the creation of new ones in the next generation. Prof. Akira Yazawa has just accomplished such an important work in the non-ferrous pyrometallurgical field. The results of his successful research are immortal. The research group of the author has conducted since 1985 fundamental studies on the application of sodium carbonate slag to copper fire refining. In the present paper, a calculation method for the distribution ratios of impurity elements between sodium carbonate slag and molten copper will be shown. The specific treatment by sodium carbonate slag will also be presented as an effective way for reducing each impurity content in the molten copper to 0.1 mass ppm, which is the level required for the production of high purity copper. The thinking-out of this evaluation method gets a hint from the Equation (2) in the text which was proposed by Prof. Akira Yazawa.

Jan 1, 2003