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By Taufiq Hidayat

Accurate description of complex phase equilibria provide the foundations for the improvement of non-ferrous pyrometallurgical smelting and recycling processes. Recent advances in microanalysis and experimental techniques enable accurate phase equilibria characterisation. Quantitative microanalytical techniques including Electron Probe X-ray Microanalysis and Laser Ablation ICP-MS enable the concentrations of major and minor elements present in different phases in samples to be accurately measured providing data that cannot be obtained using bulk chemical analysis techniques. High-temperature equilibration experiments coupled with the subsequent analysis of elementary reactions at micro- and macro-scales ensure the attainment of equilibrium conditions, and therefore, ensure true phase equilibria information is obtained. Examples of the application of the improved methodology on the investigation of phase equilibria of low-order and complex, multi-component gas/slag/matte/metal/solids Cu2O–PbO–ZnO–Al2O3–CaO–MgO– FeO–Fe2O3–SiO2–S systems and the distribution of minor element are provided. The experimental study is closely integrated with thermodynamic database development for the above system. Example of implementation of the research outcomes into industrial operations is demonstrated.

By Ken-ichi Machida

"Surface modification of R-Fe-N intermetallic compounds was made to improve their magnetic property and nitrogenabsorbing ability, arid high-performance resin-bonded magnets and nitrogen storage materials were developed: Surface coating for Sm2Fe11Nx by the zinc metal produced via photodecomposition of Zn(C2Hs)2 was effective to avoid the further oxidation in the molding process of the fine powders for bonded magnets and the resulting (BH)max values were improved to -186 kJm-3. Meanwhile, R2Fe17 as the mother compounds for RzFe11Nx was highly active for decomposition of NH3 molecule and subsequent nitrogen absorption as metal nitrides. Furthermore, even inert Nz molecule was dissociated on them by impregnating Ru metal and the resulting nitrogen atoms were absorbed in the crystal lattice of R2Fe17. These results demonstrated that the nitrogen storage system was established by cycling the nitrogenation and hydrogenation of RzFe11/R2Fe11Nx materials.IntroductionProcessing for rare earth metals and intermetallic compounds requires well-controlled conditions in order to avoid the oxygen contamination involved in it due to their high reactivity, as causes the serious damage for materials such as magnets, metal hydride for hydrogen storage, and so on. Rare earth-iron intermetallic compounds, R2Fe17, provide the corresponding metal nitrides (R2Fe11Nx) by heating in N2 or a mixed gas stream ofNH3-H2 [l] and, among them, Sm2Fe11N3 has been particularly noted as one of the promising materials for high-performance permanent magnets such as bonded ones [2- 6]. Usually, the nitrogenation for Sm2Fe17 is made in Nz, but it needs the much more hard conditions of reaction pressure (-10 MPa), temperature (-550°C) and time (-72 h) than the nitrogenation in the NH3-H2 mixture [l]. In the latter case, a significant amount of nitrogen can be interstitial introduced in· the R2Fe17 crystal lattice (x=-7) under the more moderate conditions than in N2 (at 0.1 MPa and -450°C for -3 h) [3-6] and then, in a similar manner as metal hydride systems [7], the excess nitrogen in RzFe1 7Nx (x>3) is reversibly desorbed by heating at a temperature around 500°C in Ar to form the RzFe11N3 compounds. This behavior of nitrogen absorption and desorption has a close relation to the sites for nitrogen in the crystal lattices."

Jan 1, 2000

By Yotamu Stephen Rainford Hara, Animesh Jha

The investigation focuses on a low temperature recovery of Cu and Co from a 40 wt% SiO2-(30 wt%Fe,6 wt%Al)2O3-10wt% CaO-7wt%CuO-7wt%CoO slag over a temperature range of 1173K to 1323K. The alloy phases containing Cu-Co and Fe-Co alloy formed via the carbothermic reduction of oxides: MO + C = M + CO(g), where M represents metallic copper, cobalt or iron. In the direct reduction of oxides, the recovery of metallic phase was well below 90% at 1323K, due to the kinetic barrier which was analysed and attributed to oxygen and metal-ion transport in the slag. This barrier was overcome by adding CaSO4 and carbon, which yields a matte (MS) phase via MO + CaSO4 + 4C = MS + CaO + 4CO reaction. Lime thus produced in situ participates in metal oxide/metal sulphide reduction reactions, which are analysed with the help of X-ray powder diffraction, scanning electron microscopy, and thermogravimetric analysis.

Jan 1, 2014

By Zhengjie Chen, Wenhui Ma, Jijun Wu, Kuixian Wei

The gasification reactivity of PC (petroleum coke), strengthened by addition of different potassium carbonate proportions using different grinding medium, was investigated by using thermogravimetric analysis (TGA). Results showed that the gasification reactivity of PC not only increased with the increase of catalyst-loaded, but also showed the effective improvement by anhydrous alcohol. The PC was mixed with potassium carbonate [K2CO3] catalyst at 0.5%, 0.8%, 1.0% and 1.5%, and then ground wet with distilled water. The CO2-gasification rate of PC was only 77.35%, 80.55%, 84.07% and 85.88% under the gasification temperature 1100 °C and holding time 120 min, at different K2CO3 respectively. However, when the PC was ground in anhydrous alcohol at the same condition of catalyst-loading, the gasification rate of PC reached 95.43%, 96.63%, 95.50% and 95.61% at the holding time of 108 min, 101 min, 74 min and 35 min, respectively. It was shown by FTIR, SEM and EDX determinations that the anhydrous alcohol used as the grinding medium can further improve the gasification reactivity of PC when compared with the distilled water.

Jan 1, 2016

By Ikuhiro Sumi

A new steelmaking process, in which manganese ore was intentionally reduced, was developed to achieve a higher manganese Yield using a combined blowing converter. In this study, manganese behavior was discussed through the introduction of a model. Apparent reduction rates of manganese were calculated by the two terms that were determined experimentally, with SOkg and 2S0ton combined blowing converters. The model calculated manganese changes during the operation. We applied the model to the actual operation and found that manganese behavior was predicted fairly well by this model.

Jan 1, 1996

By Bingguo Liu, Daifu Huang, Jinhui Peng

"The conditions to prepare U3O8 by calcination from ammonium diuranate were optimized, and the response surface design method was applied to analyze the influence on the total uranium and U+4 of calcination temperature, calcination time and mass of sample. A quadratic equation model for the total uranium and U+4 of U3O8 was built and the effects of main factors and their corresponding relationships were obtained. The analysis of variance shows that calcination temperature and calcination time significantly affected the value of total uranium and U+4 of U3O8. The optimal calcination conditions were as follows: calcination temperature 931.83 K, calcination time 24.32 min and 43.89 g. Under these conditions the value of total uranium and U+4 of U3O8 was 84.78% and 28.02%, respectively. The validity of the model was confirmed experimentally and the results were satisfactory.IntroductionNuclear energy is clean, effective, and a sustainable from of energy. It plays an important role in overcoming the impending global energy crisis, and in reducing energy vulnerability. In addition, nuclear energy is a possible cheaper and cleaner source of energy compared to fossil fuels, with no not really, mining of uranium produces CO2 contribution to green house gases [1]. Uranium dioxide, one of the most important fuel pellets used as nuclear fuel in light water reactors, is manufactured by calcining ammonium diuranate to triuranium octaoxide, followed by its reduction to uranium dioxide using cracked ammonia at 700°C [2]. Earlier attempts to optimize the important calcination process through several common techniques have not yielded desirable results [3]. These techniques either rely on the classical one parameter at a time approach that ignores the combined interactions between physicochemical parameters, or are theoretical in nature. Furthermore, these techniques also require large number of experimental data to be generated [4]. In order to produce triuranium octaoxide in an optimized manner, which considers the interaction of different process parameters [5], there is a need to adopt a multivariate statistical technique."

Jan 1, 2011

By M. Hashimoto

The equilibrium distribution ratios of sulfur between molten copper and CaO-fluxes containing caF2 and caC12 were determined in the range of 1300° to 1400° C under carbon monoxide. The rate of approach to equilibrium is rapid and increases with increasing CaCll concentration. In CaO-CaFl-CaCl2 fluxes, the distribution ratio varies in a complex way with temperature and CaFl concentration. The results are compared with those obtained with the binary fluxes of CaO with BaFZ and MgFl ?

Jan 1, 1983

By R. G. Reddy

Viscosities of alkaline metal oxide-silicate melts were estimated using our previously developed mathematical model. The structural based model considers depolymerization effects and related breakdown of the silicate network structure, on the addition of metal oxides to the melt. The developed expression: n =4.9x10 9 NO 0 T ½ exp(E/RT) poise was used to calculate the viscosities of various binary silicate systems such as, CaO-SiO,, MgO-SiO, and MnO-SiO,, as a function of temperature and composition. Excellent agreement was obtained between the calculated and experimentally determined viscosities.

Jan 1, 1991

By Herbert H. Kellogg

A model of the ISF is described. which reproduces with accuracy the "normal" operation of three industrial furnaces. The model, written in Fortran, is based on detailed heat and material balances, and the concept that the ascending gases reach equilibrium with zinc oxide and with the water-gas shift reaction. "Solution loss" of carbon in the lower shaft, and partial reoxidation of zinc vapor in the upper shaft are also essential features. For prediction of furnace behavior under altered operating conditions (blast rate, temperature, moisture content, oxygen enrichment, or injection of oil or coal through the tuyeres) the model modifies the heat loss, temperature of slag and bullion, amount of reoxidation in the upper shaft and the condenser efficiency to reflect the altered operating parameters. Model predictions for such operating conditions are in reasonable agreement with plant experience.

Jan 1, 1990

By E. M. Weenink

A proposed alternative to the conventional zinc extraction processes is the flash reduction of zinc calcines. As part of an overall study of this process, the kinetics of single zinc oxide pellets were investigated. Pellets, compacted from Outokumpu zinc calcine (60.9% zinc, 9.6% iron), were suspended in a flow of CO/CO, mixtures and reduced at temperatures between 1000 and 1200°C and atmospheric pressure. The pellet weight loss with time was recorded and analyzed. It was found that the reduction of calcine pellets (0.9 cm height and 1.36 cm diameter) was controlled by chemical reaction. This paper includes an analysis of the experimental results of two previous investigations of ZnO reduction.

Jan 1, 1992

By Rolando Campos

In August 1993, the operation of Refimet Chile's copper custom smelter commenced at La Negra, near Antofagasta in northern Chile. Design smelter throughput corresponded to 235 000 tonnes of concentrate, calcines and copper cements arising from suppliers in the north of the country to produce 90 000 t/y of blister copper. Refimet had initially gained experienced in building and operating leaching, roasting and a blast furnace facility at Rungue, near Santiago, followed by Roasting at La Negra. The initial smelter project was based on conventional reverb- smelting and Peirce-Smith converting and the majority of equipment was 'purchased second-hand and rehabilitated or modified. After only 3 years in production, the treatment capacity was significantly improved by introduction of technical improvements to the original plant operating scheme. Recently, the plant was further expanded to an annual smelting capacity in excess of 400 000 t/y feed, corresponding to around 160 000 t/y copper production. This expansion, referred to as Phase 2, was achieved by modification of the reverb to oxy-fuel firing, addition of a further (second-hand) acid plant, fire refining and anode casting facilities. Parallel development of concentrate injection into enlarged converters-also took place. Following successful commissioning of Phase 2 expansion, initial engineering studies for a third expansion phase have been completed. This aims to use leading technology based on bath smelting of bone-dry concentrates in a Continuous Reactor. This paper provides an overview of the relatively short plant history, its development and improvements together with operating indices achieved.

Jan 1, 1998

By P. N. Anyalebechi

The effects of a cross-hatched grooved mold surface topography, casting speed, and superheat on the morphology of solidifying shells of aluminum alloy 3003 have been characterized by a series of immersion tests. The cross-hatched grooves were 0.232 mm deep with wavelength or spacing between 1 mm and 15 mm. The shells solidified at casting speed of less than 10 mm/s on the 1 mm spaced cross-hatched grooved mold surface were fairly uniform with little or no localized variations in thickness. However, the propensity for non-uniform shell growth morphology was exacerbated by an increase in casting speed, melt superheat, and the wavelength of the cross-hatched grooves. This is provisionally attributed to their effects on interfacial heat transfer and wetting of the mold surface by the molten metal.

Jan 1, 2008

By Mohamed Ahmed, A. Kawy

"Smelting of scrap copper and residual anodes and cathodes carried out in a reverberatory type furnace. In this, deoxidation process is carried out by wood, which acts as a resource of reduction gases such carbon monoxide, hydrogen and methane. Use of wood causes the formation of soot pollutants and efficiency of oxygen removal from copper is low leading to added costs in removing contaminants. This expensive problem was solved by using of reformed natural gas as a source of reduction gases (CO+ H2).IntroductionThree reverberatory furnaces were used for smelting of scrap copper and residual anodes and cathodes. Each furnace had a 7tpd capacity and was operated at 1183 °C.In this furnace, Step1-compressed air supplied by tubes from the side of the furnace to remove sulfur from copper matte by oxidation .The copper is also oxidized to copper oxide .[1]Step 2- copper from matte is deoxidized by a reductant. Typically deoxidation process is carried out using wood as a resource of carbon monoxide, hydrogen and methane which are the reduction gases. Use of wood causes the following:1- Forms soot pollutants2- Oxygen removal efficiency from copper is low; more contamination in copper matte increased energy in deoxidation3-the process is highly expensive.In the recent trends, this problem has been solved by using reformed natural gas as a source of reduction gases (CO+ H) .This results in 1-Reduced pollution during smelting.2- High efficiency in the removal of oxygen from copper to produce oxygen free copper. The surface of copper produced from this method is smooth which helps in forming and machining.3- Low cost and natural gas is more readily available in Egypt than wood."

Jan 1, 2010

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothemlic reduction, hydrometallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By QinGuo, Shenghui Guo, Jinhui Peng, Linqing Dai, Libo Zhang

This paper adopts a simple and novel preparation. Taking cellulose as a template, a tubular morphology structure of micro/nano ZnO crystals was obtained by microwave roasting at high temperature. The higher the microwave roasting temperature, the larger the degree of crystallization. The experiments indicate that the best photo catalytic effect can be obtained at 850 : At this temperature, the oxidation of cellulose is complete. Large quantities of hexagonal shaped ZnO crystal can be observed, specifically the (0001) crystal face. Under ultraviolet-visible irradiation, taking long arc mercury lamp as light source, the material had good photocatalytic activity. The decomposing efficiency of methylene blue reaches 97% in 60min, which is superior to that of preparations without templates at the same temperature.

Jan 1, 2016

By Bhagyadhar Bhoi, Chitta Ranjan Mishra, Pravas Ranjan Behera

Red mud of Indian origin contains around 55% plus of Fe2O3 and is considered as a hazardous waste for the alumina industry. For production of one tone of alumina employing the Bayer’s Process, around two tones of red mud is generated from three tones of Bauxite. Conventional process of steel making is not devoid of environmental pollution. In the present investigation, efforts have been made to produce steel from red mud by adopting reduction roasting, magnetic separation and hydrogen plasma smelting route. Magnetic fraction, containing enriched iron oxide and minimal content of alumina, is produced following the first two stages which is then subjected to hydrogen plasma smelting process for production of steel. This novel concept follows a green path way for production of steel free from pollution and is termed as green steel. Further, the only by-product that is produced in the process, is water, which is eco-friendly and recyclable.

Jan 1, 2015

By E. T. White, Dean Ilievski

"Mathematical modelling of the precipitation process requires that the kinetics of crystal growth, nucleation and agglomeration be known. This paper reviews the current state of knowledge on these precipitation sub-processes (ie. growth, nucleation and agglomeration) and describes a number of experimental techniques for estimating their kinetics. The experimental methods used to generate the precipitation data and the data analysis techniques used to extract the kinetics information from the data are discussed separately. There is no universal ""best"" technique for determining the kinetics. However, studies on multi-crystal systems are more reliable for modelling purposes than are single crystal studies. The selection of a technique will depend on which sub-processes are present. A problem with all kinetics studies is that there is generally a large uncertainty in the estimated kinetic parameters. This stems from the scatter in the experimental data being further propagated by the mathematical techniques used to extract the kinetic parameters.IntroductionCrystallisation operations, including precipitation, are widely used in a number of hydrometallurgical processes to recover a desired component or to remove an undesired impurity. The goals of industrial precipitation processes are to maximise the recovery while maintaining product quality (generally product crystal size distribution, purity and morphology and product handling properties). Knowledge of the precipitation mechanisms and kinetics is invaluable for designing new precipitators or for improving existing units. The mechanistic and kinetic information is generally incorporated into mathematical precipitator models, which are then used for process design and optimisation."

Jan 1, 1996

By Guo Xian Jian

In this paper, the effects of matte grade, flux grain size, blast flowrate and blast O2 content on the process of silica flux melting in a copper converter were investigated. The results showed that the blast flowrate and the blast 02 content were not significant factors in the melting process. However, with an increase in grain size of flux and grade of matte, the amount of the flux molten decreased. The data on the melt rate of process correspond well with the mathematical model which simulates the chemical reactions occurring at the interface. The kinetic equations of melting are as follow:

Jan 1, 1996

By Leiting Shen

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

By Phillip A. Armstrong, Charles A. Lewinsohn, John H. Gordon

"This paper describes the opportunity offered by employing systems based on mixed conductive ceramics, in particular, ceramics conductive to oxygen ions and electrons, in reducing CO2 emissions from metallurgical production. Membranes based on these mixed conducting properties enable commercial viability of several attractive metallurgical processes. One of these processes utilizes modular, ceramic-membrane structures for the generation of pure oxygen, in tonnage quantity. The membrane-based systems offer significant capital savings and operating efficiencies in various metallurgical processes. The current status of this technology is summarized below.IntroductionCryogenic oxygen supply technology is currently the state-of-the-art for applications that require large quantities of oxygen (hundreds to thousands of tons per day). Cryogenic technology, however, requires substantial energy inputs and, hence, adds significant costs and emissions to processes. Furthermore, cryogenic oxygen supply technology is mature and there is relatively little potential for substantial capital cost reduction or efficiency improvement in coming decades. Non-cryogenic technologies offer a means to reduce the environmental footprint and cost of the oxygen supply facility in various applications.Ion Transport membranesCommercially available non-cryogenic air separation technologies, such as adsorption-based and polymeric membrane-based methods, do not afford the economies of scale that the cryogenic distillation enjoys. Therefore, industrial gas industry researchers began searching for alternatives to the relatively inactive and unselective polymeric membrane materials available. In the late 1980’s, Air Products began developing a new class of highly selective membrane materials with exceptionally high activity for oxygen transport. The materials constitute a class of oxide ceramics, and conduct both oxygen (as oxygen ions) and electrons in the same membrane, separating oxygen from air electrochemically. Numerous detailed process economics studies have shown that, based on these ion-transport membranes (ITM’s), the cost of oxygen can be reduced by approximately one-third relative to that obtained from state-of-the-art cryogenic oxygen supply technology, through a combination of capital cost savings and efficiency improvements. [1,2,3]"

Jan 1, 2008