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By Eiki Ono, Atsushi Yamatodani, Shigeru Sunagawa, Yasushi Takasaki, Atsushi Shibayama, Yasunori Higuchi

"During metallurgical processing of non-ferrous metals, smelting residue (inc. smelter slag, flue gas and so on) is inevitably generated as secondary product.In this research, some experimental feasibilities were investigated to recover/remove Cu and As from the residue. Primarily, the removal of As and volatilized materials from the residue was examined by pyrometallurgical treatment (dry-process). In the second stage after treating the residue with a dry-process, leaching and solvent extraction as hydrometallurgical treatments (wet-process) were also investigated by using H2SO4 solution as a two stage leaching treatment, to dissolve various metals from the leach residue. Then, solvent extraction was examined by using LIX-84I as an extractant to recover and separate Cu from impurities from the final (2nd) leached solution. For the leaching stages, the removal of 90 % As and the leaching rate of 85 % Cu could be achieved by 0.25 mol/l and 1.0 mol/l H2SO4 solution, respectively. On the other hand, the extraction of over 90 % Cu and stripping was carried out by solvent extraction. 1. IntroductionIn metallurgical process for non-ferrous metals, smelting residue (inc. smelter slag, flue gas and so on) is inevitably generated as secondary product, i.e., flue dust, slug and so on. The smelting residue includes some useful metals and undesired toxic materials; Cu, Pb, Ca and As, etc.In Japan there is one undisclosed place stockpiled with 10,000 ton of smelting residue from abandoned smelters about 25 years ago. Therefore it is necessary to reduce the residual amount for space and environmental protection including water treatment by separating and removing toxic materials."

Jan 1, 2008

By Ibrahim Yusufoglu, Cem Kahruman, Sedat Ilhan, Ahmet Orkun Kalpakhi

"Scheelite is the main raw material in tungsten production. In hydrometallurgical processes, extraction of tungstate ions into solution is very important. During the leaching of scheelite in oxalic acid solutions, tungsten dissolves as a chelate complex. Scheelite includes impurities along with calcium tungstate. Determination of the dissolution of these impurities is important in the subsequent tungsten production stages. In this study, scheelite was dissolved in oxalic acid solutions and the dissolution of impurities was investigated. The quantities of dissolved impurities were determined by ICP - OES and characterization of the undissolved impurities in the leach residues was carried out by SEM - EDS analysisIntroductionScheelite and wolframite ores are used for the industrial production of tungsten. Both ores are dissolved in acidic or basic solutions, and ammonium paratungstate is obtained as an intermediate product. Prior to crystallisation of ammonium paratungstate, all the impurities must be removed. Among these, Fe, Si, P, Mn, Mg and Mo are classified as ""harmful"" elements and different methods are used for their removal [1]. During purification, solvent extraction, ion exchange, etc. methods are used.Potashnikov et al. [2] studied the dissolution of scheelite in acidic solutions and the effects of stirring speed, temperature and oxalic acid concentration on the dissolution kinetics.There are no works in the literature about the removal of impurities from scheelite ores in oxalic acid solutions. Therefore, the aim of this work was to investigate the dissolution mechanisms of impurities during the leaching of scheelite in oxalic acid solutions. The effects of temperature and oxalic acid concentration on the dissolution were also investigated. In addition, the characterization of the impurities which were not dissolved was studied."

Jan 1, 2012

By Sergei A. Degterov

A thermodynamic database for the slag, matte and liquid copper phases in the Cu-Ca-Fe-Pb-Zn-Si-O-S system has been developed for the ranges of compositions of importance to the production of copper. When used with the Gibbs energy minimization software and other databases of the F*A*C*T thermodynamic computing system, this database will permit the calculation of matte-slag-copper-gas phase equilibria that take place during copper smelting and converting. The calculations reproduce within experimental error limits all available experimental data on phase diagrams, activities of components, enthalpies of mixing, matte - alloy miscibility gap and tie-lines. The calculated solubilities of Cu in both S-free slag and slag equilibrated with matte are also in good agreement with experiment under all studied conditions, such as at SiO2 saturation, in equilibrium with Fe, Cu or Cu-Au alloys, at fixed oxygen or SO2 partial pressures and at different contents of Pb, Zn and CaO in the slag. Sulfide contents (sulfide capacities) of the slags are predicted within experimental error limits. The distribution of Pb and Zn among matte, slag, copper and gas has been calculated. The calculations are in good agreement with experimental data and predict the distributions under conditions which are difficult to study experimentally, such as at magnetite saturation or under various oxygen partial pressures and iron to silica ratios in the slag.

Jan 1, 1999

By Jae-Chun Lee

Di-2-ethylhexyl phosphoric acid (D2EHPA) is widely used for separating rare-earth elements. In commercial plants, rare-earths are usually stripped from loaded extractant streams using mineral acid, then precipitated as oxalates. Many rare-earth uses demand specific powder characteristics, which are obtained by secondary processing. This paper demonstrates the feasibility of combining the stripping, precipitation and powder processing stages, thereby achieving considerable savings. MEHPA solutions were loaded with yttrium, then emulsified with oxalic acid-HC1 solutions to precipitate yttrium oxalate, which was readily calcined to yttrium oxide. The precipitation kinetics and yield were sensitive to process conditions. The morphology and size of the yttrium oxalate powders varied with the concentrations of D2EHPA and oxalic acid, and the presence of SPAN 60, which affected nucleation, growth, and the emulsion characteristics.

Jan 1, 1992

By Chai Liyuan

Chromium-containing slag was detoxified by the method of microbial treatment using Ch-1bacteria isolated from nature by our research group, belonging to achromobacter sp. and with the characteristic of reducing high concentration of Cr(VI) in alkaline solution. The detoxifying process of Ch-1 to chromium-containing slag was studied by column-leaching techniques respectively. The results indicate that Cr(VI) in leachate can not be detected when chromium-containing slag has been column-leached for 7 days, and Cr(OH)3 content in precipitate is up to 32.8% with great value of resource recycling. Flowchart of engineering experimentation was ascertained based on the parameters of column-leaching experiments. Using the technique of pelletization of chromium-containing slag heap-leaching by Ch-1,the leaching rate of water-soluble Cr(VI) existing in chromium-containing slag reaches up to 100%, while the leaching rate of full chromium is up to 90%, when the process has been operated for 7-10 days under the conditions of 25-40C and consecutive spray by circular leachate. The content of Cr(VI) in chromium-containing slag after detoxified meet the national identification standard for extraction procedure inxicity for hazardous wastes(GB5085-1996) in China, moreover approximately 90% of Cr(VI) existing in chromium-containing slag has been recycled.

Jan 1, 2006

By Pertti Pekkala

Outokumpu has 25 years of experience in the SX area. The development of the solvent extraction plants responds to an ever increasing demand for lower operational costs wd for adaptability to process disturbances with minimized risks. In this paper the features of the VSF ("Vertical Smooth Flow") SX technology are described, such as the separated pumping and mixing, the homogenous gentle mixing, the droplet coalescence and the ultra pure settling. A major advantage of the mixing technology is the high stage efficiency of above 99 per cent. The connection between this and some features of the settler front section is clarified. The present design of VSF plants is based on experience of existing operations at, for example, Zaldivar, Radomiro, Morenci, Kokkola and Harjavalta. These production plants cover a unit capacity range of 60 to 3,600 m3/h expressed as a total flow. It is evident that there are no restrictive factors to increase the total flow up to 5,000-6,000 m3/h by introducing the VSF technology. The copper SX technology has a long history reflecting many individual features of the separate copper SX plants. Still it is necessary to verify all actual running parameters by pilot tests taking into account impurities, chemicals used etc. The design of SX plants is not only about the delivery of equipment but also a process concept, and it is best tailor-made and adapted to specific local requirements.

Jan 1, 1999

By E. J. Peuraniemi

Recently commissioned Kennecott-Outokumpu flash converting was developed to replace the approved but environmentally outdated Peirce-Smith -converting to satisfy the globally tightening emission regulations. In the present study, dust formation and reaction mechanisms of two copper mattes with different experimental parameters were studied in lean suspension conditions. Both mattes had very high copper content of approximately 75 wt% and low iron content of 4.5 wt% and 1.2 wt% Fe. A laboratory scale, vertical laminar-flow furnace with a low feeding rate was used to simulate the phenomena taking place in the reaction shaft of a flash converter. Experimental conditions included temperature of 1300 °C with reaction gas oxygen contents of 20 vol%, 50 vol%, and 75 vol%. In the experiments, sieved particle fractions were fed to the furnace and sampled after short reaction time intervals by quenching them into a water film. Collected particles were analysed chemically for their main elements to define their removal rates. Also, optical and scanning electron microscopy with EDS-analyser were applied to determine phenomena occurring during reactions. Kinetics of oxidation as well as ignition of particles are discussed. Changes in particle morphology, size, and composition are reviewed to describe dust formation and reaction mechanisms.

Jan 1, 1999

By V. A. Luganov

During the treatment of raw materials containing arsenic and antimony, problems in the distribution of these elements in the process products occur. In a number of cases in processing of copper-bearing materials, it is possible (or necessary) to obtain speiss. The purpose of the present research is to study the theoretical aspects and analyze the technological possibilities of producing copper-bearing speiss and the subsequent electrometallurgical processing with copper extraction as well as arsenic and antimony utilization. Copper arsenide (Cu3As) and copper antimonide (Cu3Sb) are the main components of the speiss. A thermodynamic analysis of the electrochemical oxidation of Cu3As and Cu3Sb, carried out using Pourbaix diagrams, showed that in a pH range from 0 to 2, oxidation potential 0.45-0.55V, ions of copper and arsenic and antimony trioxide are in the equilibrium. The kinetic study has shown, that with an increase in the polarization potential, the dissolution process changes from chemical to diffbsion control. An increase in temperature stabilizes the electrolysis process due to dissolution of arsenic trioxide forming on the anode. Electrolysis of speiss using a cathode diaphragm with the solution pH = 1-2, current density 150-200 A/m2 and temperature 60-70°C makes it possible to obtain cathode copper with a current efficiency of 95-96% and to remove the arsenic from the process during the electrolyte cleaning process. The arsenic content in the cathode copper did not surpass 0.002%. As the result of the research, a technological flowsheet for copper-lead speiss processing was developed. At the present time this technology is undergoing pilot testing.

Jan 1, 1999

By N. Solak

CrN, TiN and Ti-B-N coatings were deposited onto H13 hot-working tool steel and alumina substrates by arc-PVD. The coatings were characterized with respect to their mechanical and structural properties. Oxidation behavior of the coatings on alumina substrates was investigated by TG/DTA. Samples coated on H13 substrates were oxidized in a tube furnace under atmospheric conditions at specific temperatures determined from TG/DTA tests of the same coatings deposited on alumina substrates. The oxide scale morphology was characterized by scanning electron microscopy and X-ray diffraction. Oxide scale thickness change and TG data were used to calculate oxidation reaction activation energies. It was determined that boron addition into TiN coating improves not only mechanical properties but also oxidation resistance. Depending on the substrate material different oxidation activation energy values for the TiN and Ti-B-N coatings were determined revealing the importance of film morphology on oxidation resistance.

Jan 1, 2006

By Kaixi Jiang, Bangsheng Zhang, Lei Zhang, Haibei Wang, Xiaoping Zou

"China plays an important role in the global molybdenum industry; in fact, both China's molybdenum mine and smelter production ranked first in the world. The characteristics of China's molybdenum resources are quite complex, and moly-nickel ores with carbon, coppermoly ores and wulfenite can be only found in China. This paper firstly introduces China's molybdenum resource/ reserve situation. Secondly, the status of molybdenum smelting technologies, especially roasting by rotary kilns and multiple-hearth furnaces, are discussed. The practices and the development of some new technologies, such as pressure leaching, solvent extraction, ion exchange, carbon adsorption for moly-nickel ores and low grade molybdenite concentrates, are also introduced.IntroductionMolybdenum is widely used in special steels, aviation, alloys, chemistry, electronic and medical industries because of its excellent physical and chemical characters [1,2].In nature, molybdenum exists mainly as molybdenite associated with copper ore which are the main material for smelting. About 99% of molybdenum is produced from molybdenite. In addition, wulfenite, molybdenum oxide ore and graphite shale containing Mo-Ni have also industrial value to extract molybdenum and other metals such as Ni, Re, Pb and Zn. The reserves of molybdenum in China are about 8.4 million tons metal; China is ranked as the second largest source in the world. The output in China is more than 40 kt in 2010. Ferromolybdenum is the main product and then ammonium molybdate. The consumption in China is about 20 kt and the rest is exported to overseas.The first molybdenum smelter in China was built in 1963. Today the main producers include Jinduicheng Moly Company, Luanchuan Moly Company and Jiangxi Copper Group Company. Technologies and equipment have changed greatly. Roasting and multi-hearth furnaces are widely used. Several new processes were developed such as pressure leaching, solvent extraction, ion exchange and carbon absorption [3-8]."

Jan 1, 2012

By Hideyuki Takahashi, Taro Aichi, Kazuyuki Tohji, Makoto Muramatsu, Rie Sato

"There are several ways to condition lead-based alloy anodes for zinc electrowinning: electrochemical treatment, chemical treatment and physical treatment. Two advantages of physical treatments are their productivity and variety. In this report, physical treatments, including blasting with silica, alumina, steel grit and cut zinc wire, were tested. The laboratory tests confirmed there were differences in the formation of anode scales during electrowinning and in the suppression of lead dissolution from the anodes. With an increase in the surface roughness, the misfit between the PbC""2 and the MnC>2 was mitigated and the anchor effect was promoted; these effects resulted in dense Mn oxide scales on the anode.IntroductionZinc is widely used for hot-dip zinc plating and for die casting alloys. As a supplier of materials, we have endeavored to produce zinc that is economical and contains as little impurity as possible. As a result of our efforts, a technology for consistently providing special high-grade (SHG) zinc has been established. However, as seen in the issuance of the Restriction of Hazardous Substances (RoHS) Directive, public awareness of the industrial impact of heavy metals on the environment has been heightened. Increasing efforts to control environmentally sensitive substances will be necessary for our production processes.Electrolytic SHG zinc is produced by electrodeposition in an acidic solution with a Pb-Ag or Pb-Ag-Ca alloy for the anode and an Al alloy for the cathode. Pb alloy anodes are widely used because of their excellent durability; however, they are a source of Pb, which is the main impurity of the product."

Jan 1, 2012

By Akira Yazawa

The composition of ferrous calcium silicate slag is located on the tie line between FeOx and calcium silicates in ternary FeOx-SiO2-CaO system. This slag has never been used as copper smelting slag because of high sulfidic copper solubility. However, when the dissolved copper in slag is just oxidic, as in direct white metal production or in converting process, this slag is quite attractive and can be regarded as the third copper smelting slag after fayalite and calcium ferrite slags. Based on the authors' studies on phase separation thermodynamics and laboratory experiments, it was clarified that the oxidic copper loss in this ferrous calcium silicate slag become the minimum not only %Cu in slag but also the total copper loss when the amount of slag is taken into account. It has been proven that calcium ferrite slag is suitable for continuous converting where the dissolved copper is oxidic, but there exist some drawbacks such as limited solubility of silica, low lead removability and too high fluidity. To overcome these difficulties accompanying traditional slags, ferrous calcium silicate slag is the hopeful alternative. In view of the general trends of modem copper smelting processes, the interesting features of this new slag system are discussed.

Jan 1, 1999

By Karel Verscheure

Reliable furnace cooling technology is a domain of increasing concern to the pyrometallurgical industry as it can significantly increase process intensities, productivity and campaign times of furnaces. Although there are many advantages in using cooling systems, they also impose a variety of problems mainly related to safety, heat losses and sustainability of the operations. The choice of cooling system is hence a matter of trade-offs and differs for every metallurgical application. This paper gives a review of different cooling designs used in the ferrous, non-ferrous and alloying industries. Additionally, the paper systematically reviews aspects of materials selection, manufacturing, installation, water quality and furnace monitoring when using water cooled refractories.

Jan 1, 2006

By Florian Kongoli

While calcium ferrite slags have been successfully used in continuous copper converting for the last 30 years, ferrous calcium silicate slag was proposed about 8 years ago as an additional alternative for copper smelting. Although both slags are normal extensions of each other their phase relations have not been completely clarified. In this paper the liquidus relations of both slags have been quantified at various areas that cover both of them. The existing experimental data have been first reviewed and discussed in relation to the solidification procedure. An original physical model is then used to predict various diagrams of the liquidus surface of both slags. It is shown that the ternary liquidus diagrams normally used for FeOx-SiO2-CaO system are not suitable for industrial slags. The new model diagrams of Fe/CaO versus SiO2 and Fe/SiO2 versus CaO as well as Fe/CaO versus Temperature and Fe/SiO2 versus temperature are proven to be much more convenient for ferrite and ferrous calcium silicate slags. Based on these diagrams the effect of SiO2 and CaO on the melting temperature is quantified. The effect of Cu2O is also quantified through the model. Some Fe/CaO versus Cu2O and Fe/SiO2versus CaO at various copper contents are predicted and the results show good agreement with the experimental data. It is also shown that in the presence of liquid copper, Cu2O is dissolved in the slag depending on the oxidation degree of the system and might lower the liquidus temperature. Some discussions are also presented taking into account plant observations and important conclusions are drawn for copper smelting and converting

Jan 1, 2006

By J. F. Leroux

The Gaspé smelter at Murdochville, Quebec, Canada introduced concentrate injection into elongated Peirce-Smith converters sized 1.96m x 12.5m (13 ft. by 41 ft.) in 1996, and commissioned a large, converter-like bath smelting vessel in April 1998. The new vessel, which is sized 4.27m x 16.1 5m (14ft. by 53ft.) has several interesting features designed to effectively utilize bath smelting technology for the requirements of the Gaspé smelter. For example, the vessel can operate on concentrate injection at upwards of 60-80 tph rate on an instantaneous basis, can operate as a large Peirce-Smith converter, while it is also fitted with matte and slag tapholes much akin to Noranda Process reactor, and includes a novel cold charge addition system. The new technology will eventually allow the capacity of the plant to increase from about 300,000 tonnes of concentrate per year to over 350,000 tonnes of concentrate per year while improving sulfur capture.

Jan 1, 1999

By Allan J. MacRae

A copper alloy to be used for coils in cast copper cooling blocks has been identified and samples prepared for metallurgical examination and destructive testing to compare with cast cooling blocks manufactured from copper and nickel-copper alloy pipes. The copper alloy allows for the formation of a metallurgical bond between the pipe and the cast copper during the casting process, which does not normally occur with pure copper or nickel-copper alloy pipes. The alloy's coefficient of thermal expansion is also much closer to that of pure copper compared with nickel-copper alloys, so there is less strain induced at the pipe-cast copper interface due to differential thermal expansion. It is expected that this new pipe coil alloy and associated casting techniques will allow for the production of cast copper cooling blocks that have greatly enhanced service life in high heat load applications compared to existing technologies.

Jan 1, 2002

By Tejs Vegge

The lack of suitable means of storing hydrogen for use in the transport sector is generally viewed as a primary showstopper for a hydrogen economy. Recent developments within solid state hydrogen storage in complex hydrides and metal ammines have sparked new hope of a long term solution, but as of now, no materials fulfill all the DoE targets for onboard storage [1]. A detailed physical understanding of the ab-/desorption processes and the role of the essential catalytic additives is an essential prerequisite for the development of new optimized hydrogen storage systems. Here, we illustrate the potential of utilizing the synergy of combining state-of-the-art in theoretical methods and experimental techniques in the analysis and design of materials for hydrogen storage. Recent advances in computer hard- and software has made it possible to treat many of the essential problems in such materials, i.e. structural stability, hydrogen dissociation and diffusion, with high accuracy methods like density functional theory. We rely on such results to guide our synthesis of new materials, and to interpret our experimental results from, e.g. time dependant in situ x-ray diffraction, synchrotron/neutron experiments, and advanced materials testing. Through a continuous feed-back optimization loop between theory and experiments, the obtained nano-scale insight is used to expedite the design and development of novel materials for hydrogen storage.

Jan 1, 2006

By T. Ranki-Kilpinen

In the flash smelting technique, developed by Outokumpu Oyj, off-gases with dust load are directed into the heat recovery boiler (HRB). As the temperature decreases, metallic sulphates become thermodynamically stable. Sulphation of oxidic particles initiates. The release of heat causes an increase in particle temperatures, and soft sulphated particles can stick to the heat transfer surfaces. Dust accretion may form and cause operational problems. The objectives of the project are to study sulphation reaction mechanisms and kinetics of flue- dust particles under HRB conditions, and get more information for the flue-dust treatment possibilities. The sulphation behaviour of synthetic Cu2O particles (37-53 pm) was studied using a fluid-bed reactor of laboratory scale. The experimental parameters in the latest campaign were oxygen and sulphur dioxide contents of 2.5-10 vol-% 02 and 40-60 vol-% SO2 respectively and temperatures of 600-660°C. Samples were examined microscopically (SEM+EDS) and chemical analysis were conducted. The sulphation rate was found to have a maximum at the certain temperature, which was dependent on the gas SO2 content. Regardless of the level of SO2, a rise in oxygen content promoted sulphate formation.

Jan 1, 2002

By Bekir Karasu

Boron raw materials are amongst the most important natural sources for many industrial branches and their values become increasingly raised with the discovery of boron usage in many new technological fields. All the countries in the world are unfortunately not as lucky as Turkiye and USA where major boron deposits are mainly located. It is widely known fact that on one side, boron is very precious component with its technological importance, on the other; only its limited sources are available. Therefore, even its wastes have to be evaluated and regained. In the present work wastes of Etibor Kirka Borax Company of Turkiye were used in the production of opaque frits which was suitable for floor tile glazes. Standard and newly produced frit based glazes were applied on the pre-engobed floor tile bodies and single firing was employed. Final products were examined according to the certain standard tests and their microstructures were also investigated. All the results confirmed the evaluation of boron wastes in opaque floor tile glazes.

Jan 1, 2006

By Toshihiro Tanaka

The information on viscosity and surface tension of molten slag is indispensable to design new refining procedures in ferrous and non-ferrous processes. For example, the authors have tried to develop "Capillary Refining" to remove impurities in liquid metals by applying capillary absorption of molten slag with those impurities into solid fluxes which have a lot of small capillary tubes. It is necessary to adjust the above physico-chemical properties to adequate conditions on the capillary penetration. In the present paper, we discuss our recent trial to predict surface tension and viscosity of molten slag in multi-component systems. We have derived a thermodynamic model to predict the surface tension of molten slag by using ionic size, molar volume and surface tension of pure components. In addition, we have applied neural network computation to evaluate the viscosity of molten slag. We found good agreement of the calculated results with experimental values of the surface tension as well as the viscosity in various slag systems.

Jan 1, 2006