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By Chu Yong Cheng

Manganese is one of the main impurities in the recovery of base metals from their ores. This is especially true when laterite ores are processed using the pressure acid leach (PAL) process. The use of intermediate precipitation, solids/liquid separation and re-leach in the three Western Australian nickel laterite plants to separate nickel and cobalt from manganese and other impurities makes these processes complicated and costly in capital and operation. The research work carried out by the solvent extraction (SX) group at the A J Parker Cooperative Research Centre for Hydrometallurgy (CSIRO Minerals) has led to the development of direct solvent extraction processes to separate nickel and cobalt from manganese and other impurities. The simplicity of the process flowsheets and the expected savings in capital and operating costs are the major advantages of the new direct solvent extraction processes over the existing processes. By using a new synergistic organic system, Versatic 10 / dccyl-4-pyridinccarboxylatc ester, with a pilot plant leach solution from BHP¬Billiton (after iron precipitation), the metal values (Ni and Co) together with zinc and copper were separated from manganese and other major impurities (Mg, Ca and Cl) in the first SX circuit. The co-extracted manganese, magnesium and calcium were easily scrubbed out. The extraction and stripping kinetics of the metals with the new synergistic organic system were very fast and the synergistic system was found to be chemically stable. pH-extraction isotherms of metals with D2EHPA showed that the extraction order as a function of pH50 was Zn2+ > Ca2+ > Mn2+ > Cu2+ > Co2+> Ni2+> Mg2+. Semi-continuous test work with a cobalt pilot plant leach solution from Peko Rehabilitation Project Pty Ltd and a synthetic solution to simulate a concentrated laterite leach solution from BHP-Billiton showed that manganese, together with calcium, copper and zinc can be separated from nickel, cobalt and magnesium. This led to the development of another direct solvent extraction process to separate manganese and other impurities from nickel and cobalt and to recover nickel and cobalt from leach solutions. A project was initiated by HiTec Energy Ltd to recover manganese from waste laterite leach solutions using SX technology and to further purify it to produce high purity electrolytic manganese dioxide (EMD) for the high quality alkaline battery industry. Batch tests were conducted to select a suitable organic system for the extraction of manganese in terms of selectivity and extraction and stripping kinetics. A total of eight organic systems were tested using waste laterite processing solutions. A Versatie 10 / synergist system showed very promising results. By using the synergistic system, high manganese recovery would be obtained, fewer SX stages would be required and a higher A:O ratio could be used in extraction, resulting in a smaller organic inventory and lower capital costs. The risk of gypsum formation is also minimised with the synergistic system. Keywords: Solvent Extraction, Manganese, Laterite, Synergist

Jan 1, 2004

By Joo Hyun Park, Kyu Yeol Ko

The viscosity of the CaO-SiO2-xMnO-yCaF2 slags (C/S=1.0; x=10, 40%; y=0 to 15%) was measured to clarify the effect of CaF2 on the viscous flow of molten slags at high temperatures. Furthermore, the Raman spectra of the quenched glass samples were quantitatively analyzed to investigate the structural role of CaF2 in a depolymerization of silicate networks. The critical temperature of the slags abruptly increased at 15%CaF2, which was confirmed to originate from a crystallization of cuspidine using XRD analysis. The viscosity of the slags continuously decreased by CaF2 addition in the 10%MnO system, whereas the viscosity of the 40%MnO system was not significantly affected by CaF2 addition. The effect of CaF2 on the viscosity of the slags was quantitatively analyzed using micro-Raman spectra of quenched glass samples accompanying with a concept of silicate polymerization index, Q3/Q2 ratio. A polymerization index continuously decreased with increasing content of CaF2 in the 10%MnO system, whereas it was not affected by CaF2 in the 40%MnO system. Consequently, the bulk thermophysical property of the CaO-SiO2-MnO-CaF2 slags was quantitatively correlated to the structural information.

Jan 1, 2014

By Shengli Wu, Laixin Wang, Minyin Kou, Xinliang Liu, Weidong Zhuang, Yujue Wang

COREX process has obvious advantages in environment protection but still has some disadvantages, for example, it has a higher sulfur content of hot metal than blast furnace. In this paper, the thermodynamics and dynamics of desulfurization have been investigated to obtain the main operation parameters related to the mass fraction of sulfur in the hot metal. In addition, statistical analyses have been carried out to study the relationship between operating parameters and sulfur content of COREX hot metal based on actual plant data. It has been found that the mass fraction of sulfur in hot metal is significantly influenced by the C content in hot metal, MgO/Al2O3 in slag, the concentration of MgO in slag, the temperature of hot metal and binary basicity (R2).A linear model has been developed and subsequently used for reducing the mass fraction of sulfur in hot metal, improve the quality of hot metal and contribute to low carbon ironmaking.

Jan 1, 2016

By ChuanJie Cai, Zemin Zhuang, Jing Chen, Xuebin Hao, Shaobo Zheng

"Carbon which was used as heating and reducing agent in traditional iron and steel making process at present brought us large amounts of greenhouse gas harmful gases and dust seriously leading to the fog and haze condition. As one of ideal global new energies, Hydrogen has good features such as rich resource, high heat efficiency, cleanness, renewable and transportation. With the commercialization of hydrogen energy, the world energy structure will be changed greatly. Although many scholars have done a lot of researches and long-term exploration on hydrogen metallurgy, researches on the formation of metal iron phase in the process of hydrogen reduction of iron oxides in slag was rarely reported, which had important theoretical significance on the development of hydrogen smelting reduction process. Based on the thermodynamics and kinetics calculation, A laboratory experiment has been designed to research the iron phase formation during hydrogen reduction of iron oxides in the molten slag in this paper. SEM and EDS techniques were also used to observe and analyze the iron morphology. According to detection results, the influence of temperature, reaction time and surface tension on the morphology of the iron phase reduced were showed.IntroductionWith the increasingly severe global warming greenhouse effect, governments are paying more attention to no-carbon and low-carbon energy development and utilization. Hydrogen has received widespread attention around the world, which has rich resources, high thermal efficiency, large energy density, use clean, transportation, storage, renewable etc [1].The development of the hydrogen economy is new competition areas of the world economy for the 21st century. China should assess the situation, and achieve the important strategy of peaceful development as the realization of new industrialization, by establishing a ""hydrogen economy"" industry revolution which replaces fossil energy. The current hydrogen metallurgy process includes hydrogen direct reduction, smelting reduction and direct steelmaking process. Hydrogen plasma hydrogen metallurgy is the use of hydrogen as a reducing agent to replace carbon reductant, to reduce carbon dioxide emissions, and to ensure the sustainable development of ironmaking industry."

Jan 1, 2014

By T. C. -M. Cheng

Iron removal and disposal in zinc plants has imposed a major environmental challenge to the industry. Among the existing options of precipitating iron as jarosite, goethite, and hematite, the Hematite Process seems to be the best candidate for the future development of a waste-free technology, because of its potential of producing saleable iron oxide residues for feed in iron-steel making industry. Unfortunately, under the current practice of the Hematite Process, it is not possible to produce iron residues clean enough to meet the specifications of the said industry. In this paper, the practice of industrial hematite precipitation and the relevant technical literature are reviewed with the objective to identify the critical processing parameters which are responsible for the contamination of hematite, particularly with sulfur and zinc. The analysis is conducted from a crystallization theory standpoint with emphasis given to the role of supersaturation with respect to the cleanliness of hematite precipitates.

Jan 1, 1997

By Kazuteru Tozawa

Surface tension, density and viscosity coefficient of acidic copper sulfate solutions simulating electrolyte solution for electrolytic production of copper have been measured and are summarized as a function of the solution composition and temperature. Nickel sulfatc is taken to be a representative coexisting sulfate that affects the physical properties of the copper sulfate electrolyte solution. The sulfates in the solutions, including sulfuric acid, increase the physical properties under consideration. Gelatin, representing organic additives for electrolyte solution, was found to sensitively affect the surface tension of the solution at low concentration of up to 200mgIL. The surface tension was markedly lowered by the addition of gelatin and the increasing concentration of gelatin led to a more pronounced decrease in the observed values. The surface tension gradually increases with time after addition of gelatin and the increase is enhanced by higher acid concentration and higher temperature. The observed change in the surface tension is considered to reflect the preferential adsorption of gelatin to the bubble-solution interface and the decomposition of gelatin due to hydrolysis to form various molecules having smaller molecular weights.

Jan 1, 2003

By Nan Wang

Based on the commercial computational fluid dynamics software, Fluent, a three dimensional finite-volume model has been established, and the fluid flow and heat transfer in the super-wide slab mold (cross section 3250mm×150mm) of Nanjing Iron and Steel Company has been simulated. The basic feature of flow and temperature field in a super-wide mold has been analyzed, and the effects of mold width, the submergence depth of SEN, outlet angle of SEN, casting speed, superheat and cooling rate on the flow and temperature field have been investigated. The results by comparing several simulated calculations for 3250mm×150mm slab show that a more proper fluid flow and temperature field in the super-wide mold can be obtained with 15°outlet angle, 120~150mm submergence depth of SEN and 1.2~1.4m/min casting speed. The results through numerical simulation provide a theoretical basis for optimizing the configuration design of SEN and choosing reasonable processing parameters for the continuous casting mold of super-wide slab.

Jan 1, 2009

By Liu Chunpeng

Under an inert atmosphere, the temperature enhancement of nickel bearing pyrrhotite irradiated by microwave was measured with a special metal-sheathed thermocouple and the non-isothermal rate equations were obtained. Under the controlled oxygen potential of the reacting gas in the microwave field, over 90% sulfur contained in the pyrrhotite is converted into elemental sulfur directly, the iron and the nickel are transformed into FeO,, NiO, NiFe,O, and FeSiO,. According to the experimental data the rate of the elemental sulfur produced is in diffusional control and the non-isothermal equation derived is

Jan 1, 1993

By Feng Liu, Bingji Yan, Zhiwen Shi, Hongwei Guo, Jianliang Zhang

During production of a large quantity of steel, slag is produced at the same time. This paper chooses blast furnace slag (BFS) as the main material for the research. The purpose of the research is to explore its optimal physicochemical properties and the use of BFS in building stone field. The paper elaborates the experimentation process of producing glass-ceramics and presents the results. The results show that SiO2 content in BFS and amount of Cr2O3 and Fe2O3 added as nucleating agents have certain effect on the properties of glass-ceramics. The results also show that the exothermic peak temperature of base glass is the lowest when adding 20% SiO2 to the BFS, and 2% Cr2O3 and 3% Fe2O3 as nucleating agents, which makes easy crystallization and optimal properties of the glass-ceramics.

Jan 1, 2015

By Nagy El-Kaddah

One of the emerging technologies for the production of ultra-clean metals is electromagnetic filtration. The theory and the mechanism of electromagnetic separation of inclusions from molten metal are briefly reviewed along with basic electromagnetic separation systems. This paper focuses on inclusion removal in the induced current separators, with specific reference to a new separator developed at the University of Alabama. A simple analytical model is presented for the analysis of particle separation in such a system. The role of the applied magnetic field on inclusion removal will be discussed. It is shown that particle velocity increases exponentially with increasing magnetic field strength. At moderate field strengths, the velocity of 50 to 100µ inclusions are an order of magnitude larger than those achieved by buoyancy. The separator developed at the University of Alabama is described together with experimental results of laboratory and large scale experiments on purification of molten aluminum. These results demonstrate ?the capability of the system for producing super-clean metals.

Jan 1, 1996

By Ruiling DU, Xiao YUAN, Keng Wu, Daan XU, Changyao CHAO

To utilize low grade coals to produce high quality semi-coke which can be used in blast furnaces, the pyrolysis of low grade coals was studied in this paper. According to the characteristics of coal pyrolysis process, the temperature range was divided into three parts. The interfacial chemical reaction model, random pore model and the internal diffusion model with the shrinking volume of resultant were established to describe the different ranges of pyrolysis process respectively. The results showed that the experimental data was fitted well, and all the correlation coefficients (r2) exceeded 0.97. Finally, the kinetic parameters for each temperature range have been calculated, which laid a necessary foundation for the simulation and expanded production.

Jan 1, 2016

By K. R. Barrett

The cupellation of dore/lead bullion to recover precious metals is one of the oldest metallurgical processes known to man. In recent times this has been carried out in small reverberatory furnaces but the process suffers from a number of disadvantages. A new process has been developed at the Northfleet refinery of Britannia Refined Metals Ltd, which gives much improved performance. The process depends upon the injection of oxygen through a nitrogen shrouded lance at the bottom of the furnace. The lance is consumable and of unique design. Reaction rates are high giving short process time; fuel consumption is low; oxygen efficiency is high and dore recirculation is low. The new process has resulted in substantially lower operation costs.

Jan 1, 1989

By Zhihe Dou, Guozhi Lyu, Liping Liu, Yi Luo, Ting-an ZHANG, Xijuan Pan, Zhuolin Liu

Due to the high energy consumption, long technical process, low usage rate of vanadium during the traditional smelting vanadium steel process, a new method for decarburization by CO2 to directly smelt vanadium-containing steel in blast furnace was proposed. In this paper, the thermodynamics of CO2 decarburization in molten iron process was calculated out by FactSage. The thermodynamic calculations indicated that in standard state, the transformation temperature of C and V was 1357 °C; the oxidation order of element was Si, C, V, Mn and S when using CO2 as oxidant. The experiment of blowing CO2 temperature showed that decarburization reaction temperature was 1550 °C, carbon content could be decreased to 0.676%, the decarburization rate was 88%. There was no effect on vanadium content in molten iron during the decarburization process, vanadium content was 0.323%, which meets the request of vanadium mould steel.

Mar 1, 2018

By Chikabumi Yamauchi, Mitsuru Tanahashi, Toshiharu Fujisawa

"Thermodynamic properties of impurities in molten silicon are of prime importance in developing economical production methods of solar grade silicon. In the present research work, thermodynamic properties of boron, the most difficult element to remove from molten silicon, were measured by chemical equilibration techniques at 1723 and 1773 K. Activity coefficients and self-interaction parameters of boron in molten silicon were determined by equilibrating the melt with solid BN under controlled nitrogen partial pressures. Interaction parameters between boron and nitrogen in molten silicon were also determined by equilibrating the molten Si-B alloys with solid Si3N4• Based on the data obtained, the stability diagram of the Si-B-N system was established.IntroductionPhotovoltaic power generation using a silicon solar cell is expected to be the most promising energy source, because it is inexhaustible, cleaner and more safety than conventional energy sources, such as thermal or atomic power generation. At present, expensive off-grade silicon for semiconductor (SEG-Si) is used for a solar cell production. However, if a large-scale photovoltaic energy conversion using silicon solar cell comes into wide use in the near future, silicon will be sure to be in short supply for the cell. Therefore, a development of a new large scale process for solar grade silicon (SOG-Si) production is definitely necessary, which can remove contained impurities from silicon.Among the impurities contained in silicon, boron is one of the most difficult ones to remove by a zone melting or an unidirectional solidification, because its segregation coefficient in silicon is close to unity (0.8). In addition, boron behaves as a p-type silicon semiconductor dopant and, therefore, its content in SOG-Si must be severely controlled. Although some attempts to remove boron by various metallurgical methods have been carried out [I -4], quantitative analysis has not been made due to lack in the information on the thermodynamic properties of boron in molten silicon. From this view point, the activity of boron in molten silicon was determined in the present study by chemical equilibration techniques at 1723 and 1773 K."

Jan 1, 1998

By A. W. Bryson, K. C. Lenthall

"With the growth in the use of cobalt in industry, interest in its extraction and recovery has increased. With this increased interest comes the need for a fundamental knowledge of the processes involved in the recovery of cobalt metal. This paper examines the effects of cobalt concentration, catholyte pH, operating temperature and current density on cobalt electrowinning with respect to the current efficiency, cell potential and nature of the cobalt deposit. It is found that the cobalt concentration and catholyte pH affect the current efficiency, while current density and temperature affect the cell potential and thus the specific power consumption. Pitting on the deposit is affected by the catholyte pH and the operating temperature. Furthermore, the effect of feed flow-rate on catholyte pH, and thus current efficiency, is investigated. A model to predict the cell performance, which includes the flux of hydrogen ions through the diaphragm, is proposed.IntroductionCobalt metal is a silvery transitional metal found between nickel and iron on the periodic table. Due to its resistance to corrosion and other properties under high temperatures and its good work-hardening characteristics, it is favoured in alloys used in high temperature applications. These include aerospace, aircraft and high speed tools. Other applications include its use as a colourant in glass and ceramics, a drying agent in paints, a nutrient for livestock, a catalyst in the petroleum industry and, in the medical field, in prosthetics and radiology.The main deposits of cobalt are found in Central Africa, specifically Zaire and Zambia, although deposits also occur in Morocco, Canada and Australia. The cobalt is generally associated with other transitional metals including nickel, iron and copper. It is generally extracted by hydrometallurgical means and recovered from solution by electrowinning or hydrogen reduction. Little data [1-2] exists in literature on the electrowinning of cobalt from aqueous solutions. This paper investigates the effects of various operating conditions on the current efficiency, cell potential and deposit nature under continuous operation."

Jan 1, 1997

By James P. Bennett

The successful reuse/recycling of refractory materials after removal from industrial service is limited because of contamination, the low value of spent materials, the low cost of virgin raw materials, the lack of driving forces such as regulations or taxes, and low disposal costs. Most spent refractory is disposed in landfills. Concerns over future liability for waste materials, corporate images, and IS0 14000 have helped to encourage recycling at some companies. The recycling practices and application for spent refractory materials at facilities successfully recycling used refractory materials will be discussed, with emphasis on similarities.

Jan 1, 2002

By Yuuki Hagio, Hiroyuki Tobo, Michihiro Kuwayama, Yasutaka Ta

"Reduction of CO2 emission is necessary to remedy global warming, however, promising approaches of CO2 separation require a large amount of energy. Molten slag, which is generated as by-product of steel production, has high temperature, but its energy has not been harnessed. To recover the thermal energy from the slag and to apply to separation of CO2 are economical and environmental conscious ways. We propose a new heat recovery system, in which, molten slag is solidified continuously on water-cooled roll and the solidified slag plates are charged into counter-current heat recovery equipment. In laboratory scale experiments, heat recovery ratio of more than 30% was acchived by controlling the thickness of slag.IntroductionThe steel industry in Japan has been working on the projects of ""Environmentally Harmonized Steelmaking Process Technology Development (COURSE50)"". COURSE50 aims at developing technologies to reduce CO2 emissions by approximately 30%. One of the main technologies is to capture and recover CO2 from blast furnace gas using chemical absorbents to regenerate CO2-laden chemical absorbents by separating CO2 from the absorbents. As one of the solutions, JFE Steel Corporation has been developing sensible heat recovery process from steelmaking slag. It is effective to recover and use unutilized high temperature waste heat within a steel plant as the thermal energy required."

Jan 1, 2012

By R. Padilla

In most of the Chilean copper and gold concentrates, arsenic is present mainly as enargite, Cu3AsS4, which at the conventional roasting or smelting temperatures decomposes liberating arsenic as gaseous compounds. The objective of this investigation was to study the decomposition reaction of enargite in an inert atmosphere in the range of 500 °C - 750°C. The results obtained indicated that the decomposition begins at about 525 °C. Two distinct regions in the temperature dependence of the decomposition rate were observed: a low temperature region between 525 °C to 650°C and a high temperature region between 650 °C to 725 °C. The X-ray diffraction analysis suggests that the decomposition of enargite occurs through the formation of intermediate tenantite, according to the following sequential reactions: 4Cu3AsS4(s) ? Cu12 As4S13(s)+ 3/2S2(g) Cu12 AS4S13(s) ? 6Cu2S(s) + 2As2S3(g) + 1/2S2(g) The decomposition kinetics was analyzed by using the model for a topochemical reaction of spherical particles: 1-(1-X) 1/3 = kt, which represented well the data. Apparent activation energies of 113 kJ/mol and 60.5 kJ/mol were found for the low and high temperature regions, respectively.

Jan 1, 1999

By Nils Eivind Kamfjord, Mari K. Næss, Halvard Tveit, Edin H. Myrhaug

"As a part of the FUME research programme being done by the Norwegian Ferroalloy Research Association (FFF), the SINTEF Group and NTNU, several measurements towards quantifying the gaseous and solid emissions from the draining of the silicon furnaces for metal have been carried out.Based on the measured size distribution of the formed fume particles and known particle growth theory, an estimate of the growth time for the given particles has been calculated. The formation time for the measured NO amount has also been calculated based on the fume measurements and a thermodynamic model of the furnace gases combusting with air. The two “formation” times are in the same order of magnitude and they are therefore used as parameters in a CFD model, modelling that the formed fume particles are heating up the surrounding air and thereby forming NO according to the Zeldovich mechanism. The measurements show an approximately equal constant NO formation per fume particle. The CFD model shows results in the same order of magnitude, supporting that the particle growth and NO formation happen under near stoichiometric conditions and are controlled by the formation of SiO2 fume.IntroductionNOx is the common notion for the two gases nitric oxide (NO) and nitrogen dioxide (NO2) formed during combustion of fuels. The main sources for human made NOx emissions is on-/offshore transportation industry, power generations based on fossil fuels, agriculture and other industries [1]."

Jan 1, 2012

By P. Hanniala, J. Sulanto

"The requirement for the reduction of sulphur dioxide emissions from copper smelters is becoming more and more important. Therefore, the most important question in smelting technology will be how to produce even, high strength SO2 gas in smelter and how to combine smelting and converting. The best sorution in certain cases is to eliminate converters totally.Outokumpu is already responding to this challenge. As a result of extensive research work, Outokumpu Oy has developed the Flash Smelting Process for direct smelting of blister copper from concentrates in one step.The newest process development is the Kennecott-Outokumpu Flash Converting process, where solidified copper matte is converted into blister copper. The production of low volume high SO2 content gases, separation of smelting and converting operations to allow increased on-line availability, and simplified process control are the major benefits of the process which translates to reduced smelter capital and operating costs.Also, it has been studied the use of the same Outokumpu furnace for smelting and converting alternately when the production capacity is low.In this paper, the developments and improvements of the Outokumpu Process are described from the operation and investment cost standpoints"

Jan 1, 1988