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By S. Ajima

The Naoshima Smelter and Refinery is the most important copper operation of Mitsubishi Materials Corporation. There are a Mitsubishi Continuous smelter and a conventional type of copper tankhouse. The continuous smelter with 240,000 mtpy of anode production was commissioned in May 19914 replacing two existing smelters, i.e an original Mitsubishi Process line and a conventional reverberatory furnace line. In July 1992, the copper tankhouae was expanded for the purpose to close the gap of production capacity between the smelter and the tankhouse. The cathode production capacity was increased from 13,800 to 15,800 mtpm. By these plant modifications, the distribution of minor elements was significantly changed and the impurities load is getting on increase reflecting recent shortage of clean copper concentrates supply. The paper discusses the distribution of minor elements and the impurity control strategy at the smelter end the refinery.

Jan 1, 1995

By F. -Z. Ji

Carbon injection into metallurgical slag is important in electric arc furnace (EAF) steelmaking for foamy slag practices and in nonferrous slag cleaning operations. The current publication presents kinetic data for coal injection into EAF slag to understand the interaction between injected carbon and metallurgical slag. Coal particles were injected into EAF slag and the kinetics were followed by gas and slag analysis. The results were analyzed, in terms of fundamental rate equations for each possible reaction step, as a function of temperature and slag composition.

Jan 1, 2003

By L. M. Abrantes, A. P. Paiva

"A brief review of some innovative methods for the direct recovery of metals from loaded organic phases is presented; emphasis is given to electroreductive stripping and cementation, which are described and illustrated by examples: of current research. The recovery of silver using a two-phase electrolysis - by direct application of an electrical potential to a mixture of a metal loaded organic phase· containing Cyanex 471X, obtained by solvent extraction, and a stabilized sodium thiosulfate solution - is more extensively discussed. The overall efficiencies are analyzed and compared with data obtained by conventional stripping procedures. Some preliminary results achieved for the recovery of the precious metal using galvanic stripping, applied directly to similar organic solutions and involving zinc and iron powders as reducing agents, are also evaluated.Introductory ReviewThe application of hydrometallurgical methods to the recovery of metal values from ores and concentrates has been receiving a growing interest, either from researchers or from the mining industry [1].For the concentration / purification of the relatively low concentrated metallic solutions resulting from the leaching of those raw materials, solvent extraction (SX) is a well established technique [2]; the loaded organic solvent is then conventionally contacted with a suitable aqueous solution, the metal in its final form being usually recovered from this solution by electrowinning.As an efficient and / or selective stripping is sometimes difficult to achieve, depending on the specific characteristics of the system under consideration, some alternative procedures have been analyzed in order to overcome this problem. One of the chosen routes, mainly developed by Hirai and Komasawa, is to promote the reduction of the desired metal species in the organic phase, in such a way that the stripping stage becomes feasible; for the selective stripping of vanadium from a solvent containing a mixture of vanadium and molybdenum, the authors successfully used reductive [3], electro-reductive [4,5] and photo-reductive [6] techniques. The two latter methodologies have also been applied to the recovery of europium from a solvent containing europium, samarium and gadolinium [7,8].However, further processing is necessary to recover the metal in its solid state; therefore, methods causing the direct reduction of the metal species in the organic phase to their fmal metallic form would be of interest, as an intermediate step would be avoided"

Jan 1, 1997

By J. Méndez-Nonell

The thermodynamic and chemical properties of SrSO4 and SrS in a gaseous flow of CO and CO2 at high temperature are discussed. The thermodynamic analysis of the system was made using data from the literature. The results obtained from the thermodynamic analysis were experimentally verified using the thermogravimetric technique. The experimental results suggest the formation of a complex compound between SrO and SrSO4. It was also found a change in the chemical mechanism of the process between SrSO4 and CO-CO2 and in the chemical mechanism of the process between SrS and pure CO2.

Jan 1, 1995

By Stig Petersson

Slag from the converting of copper matte is usually recirculated to the smelting furnace. This recirculation generally causes disadvantages as magnetite-build-up in the furnace, accumalation of impurities as antimony, lead, nickel etc in the process. The treatment of converter slag in a separate furnace in order to recover the copper and nickel content would be of advantage from several points of view. At the Mining and Metals Division, Boliden, testwork has been carried out to treat converter slag from the PS-converters in a separate furnace. The tests have been performed in laboratory and pilot plant scale. The pilot plant tests have been carried out in a TBRC with charges of 5 tons. Based on these tests a full scale TBRC has been projected in order to treat the slag from the PS-converters. This slag will be reduced with copper concentrates to give a matte and a final slag low in copper and nickel. The background and data from the testwork are presented. Also the lay out, technical data and flowsheets for the projected process are shown as well as some production data from the Rönnskär smelter.

Jan 1, 1976

By I. Goy D. Gaballah

Decontamination of synthetic K2Cr2O 7 solutions containing 10 to 1000 ppm of hexavalent chromium using chemically treated barks have been studied at a laboratory scale. Metal removal from solutions depends on the pH, the initial concentration and the bark species. The use of a pulp density of 2 % in an agitated flask at the optimum pH for 2 hours leads to a percentage chromium removal of about 95 of the initial metallic ions content. Other trials conducted by column percolation permit the determination of the maximum retention capacity of the treated bark. Depending on the bark species, oak or pine, the rate of saturation is 110 and 215 mg of Cr per gram of bark respectively. The incineration of the metal charged barks gives recyclable, ashes containing 36 and 54 % of chromium metal for the oak and pine barks respectively. Experiments, of Cr6+ removal from industrial effluents containing up to 1800 ppm have been carried out on the semi-pilot plant scale. They have lead to the elimination of about 90 % of hexavalent chromium from this industrial waste solution. Further studies are conducted in order to define the hexavalent chromium binding mechanisms on bark constituents.

Jan 1, 1992

By Baozhong Zhao

Laboratory experiments have been conducted on the removal of As, Sb and Bi from molten copper by SF 6 injection. The results showed that the impurities can be removed by SF6 injection in the? sequence of Sb >As >,Bi and the rate of Bi removal is affected significantly by the concentration levels of As and Sb in the copper melt. Analysis of the experimental data indicates that the impurity removal process is under chemical reaction control rather than by mass transfer of impurity through the molten copper phase. On the basis of experimental results, a kinetic model was developed and the order of chemical reaction and the volumetric chemical reaction rate coefficients of impurity removal were determined.

Jan 1, 1996

By Gaballah I.

Elimination of arsenic, mercury and zinc from synthetic solutions containing H;\A.sD4. HgCI2 and ZnCI2 using modified barks was investigated. The pH range was varied from ?1 to 10. The initial concentrations of individual element were 10,100 and 1000 ppm. More than 99 % of mercury and 65 % of zinc cations were removed by the modified bark .. In this case, the modified bark reacts as a cation exchanger leading to the release of ' two protons for every HgII or ZnII fixed by this material. About 30 % of arsenic was eliminated from the solution. This 'low efficiency could be attributed to? the presence of arsenic ,as. anion. Decontamination of a treated industrial effluent containing 4 ppm of ion? metals was performed on a pilot plant scale by the modified bll(k. More than 70'% of these ion metals were eliminated.

Jan 1, 1995

By K. Murayama, M. Kawakami, T. Takenaka, S. Yokoyama

"Cokes play an important role of spacer in blast furnace. However, they degenerate during Boudouard reaction. Blast furnace cokes are reacted with pure C02 at I 072 to 1673 K. Reaction rate was obtained by the weight change of spherical specimen. The specimen after reaction was examined by microscopic observation. The reaction rate increased with temperature and was expressed by two Arrhenius type lines. The activation energy was 126 KJ/mol at higher temperature than 13 73 K and 202 KJ/mol at lower temperature range. At the higher temperature range, the reaction proceeded from the surface leaving unreacted core, whereas homogeneously whole inside at lower temperature. The porosity increased from the center to surface at higher temperature, whereas it was almost constant at lower temperature.IntroductionThe cokes have the function of fuel, reductant and spacer to keep gas and liquid flow in the blast furnace. Thus, the reaction mechanism of coke with several gas and the strength after the reaction should be important factor to control the blast furnace operation. The reaction mechanism of coke with C02 has been studied extensively. The rate equations were derived by Gadsby[ I], Ergun[2] and Turkdogan and Vinters[3]. They were compared and discussed by Kobayashi and Omori [ 4]. Effect of crystallization degree on the reaction rate was examined by Kashiwaya and Ishii[5]. Catalytic enhancement effect of ash componets have been clarified by Kashiwaya et. al. [6]. Although degradation of coke in blast furnace has been examined recently[7], however, the degradation of coke after the reaction with C02 has not been well clarified yet. In the present work, the metallurgical coke specimen was heated in N2 and C02 and the reaction mechanism and degradation behavior after the reaction was investigated."

Jan 1, 2000

By R. L. Nyirenda

One of the problems with ammoniacal-ammonium carbonate leaching of EAF carbon steelmaking flue dust is that zinc present in spinel phases is not leached. This paper presents results of test work in which prior to leaching, EAF dust was reduced with CO containing gas to decompose the spinels into zinc oxide and iron bearing phases, mainly metallic iron and wustite. From such reduction products, the amount of zinc leached increases but the iron co-leached becomes extensive. The effect of various leaching parameters such as liquor concentration and redox potential on zinc and iron dissolution has been investigated. Supplementary experiments utilizing pure zinc oxide and pure iron phases were also carried out. Results show that the co-dissolution of iron from severely reduced EAF dust cannot be prevented. This is because the wustite phase contains zinc which can only be leached when iron also dissolves. Further, the zinc bearing wustite phase is not totally soluble so that the residue cannot be made zinc free. In the absence of air, dissolution of metallic iron hardly occurred, though in leaching experiments of a long duration its transformation to a spinel structure was observed.

Jan 1, 1992

By Takeshi Nagano

Copper pyrometallurgy in Japan has experienced quite fundamental changes in last fifteen years. The severe environmental restriction coupled with increase of energy costs accelerated the development work of the new continuous process in Mitsubishi Metal Corporation. After several years of pilot plant test work the commercial plant was put into operation at Naoshima Smelter in 1974, the design capacity of which was 4,000 tonnes of copper per month. Many modifications and improvements have been incorporated into the process and 7,200 tonnes per month of copper production was achieved in 1983, proving that continuous process was much more economical than conventional process. It is now possible to design and operate the continuous process in wide range of capacity. This paper will review the process and describe the progress of the process in these 10 years. 311

Jan 1, 1985

By Yang Jian-guang, Deng Zi-xiang, Zhang Xu-liang, Li Jun-yuan

"Hyperaccumulator biomass harvested after heavy-metal phytoremediation must be considered as hazardous waste that should be contained or treated appropriately before disposal or reuse. As a potential method to detoxify the biomass and to convert this material to a suitable bio-energy resource, the hydrothermal upgrading process was applied to remove heavy metals and upgrading crude bio-oil from Pteris vittata stems and leaves harvest. Parameters such as material granularity, temperature, Liquid/Solid (L/S, ml/g), pressure, duration and catalysts were examined for their effect on the removal efficiency of heavy metals and upgrading efficiency of crude bio-oil. Maximum heavy metal removal efficiency of>99% and crude bio-oil upgrading efficiency of 83% were attained with an 200 mesh (75 µm) granularity, LIS 40:1and23 MPa at 380°C in the presence ofO.l mol L-1 K2C03 for 30 min. GC-MS analysis results show that the resulting bio-oil mainly consists of benzene 11 %, ketone 42%, alcohols 14%, alkene 15% and ester 11 %, etc., and the relative molecular weight distribution lies in 94-282, carbon number distribution lies in 6-18, calorific value is 32MJkg-1.IntroductionPhytoremediation of soil or water with hyperaccumulator has been extensively explored in recent years [1-4]. Living plants can clean up soils or waterways. This approach exploits the ability of various plant species to thrive in high metal environments where large amounts of toxic elements are accumulated, such as heavy metals, and is particularly appropriate when slow remediation of relatively low metal concentrations is acceptable. Advantages compared with existing remediation methods include the minimal site destruction and destabilization, low environmental impact, and favourable aesthetics; advantages compared with biosorption include continuous in situ regeneration of the biomass, and the ability of living plant cells to supplement passive sorption of metals with metabolic mechanisms of metal uptake and detoxification [5-8]."

Jan 1, 2014

By Guoqiang Lv, Xi Yang, Wenhui Ma

Cast multicrystalline silicon ingots are widely used in photovoltaic manufacturing. A key issue to achieve high solar cell efficiencies is to attain an optimized temperature field during directional solidification (DS) process. This paper reports numerical investigation of multicrystalline silicon (mc-Si) ingot production using two major types of DS furnace. Specific examination is made on thermal distribution, interface shape and stress field. Evaluation is performed for the applicability of thermal system design to reduce thermal stress, improve crystal quality and enhance energy efficiency. The effects of procedure parameters and geometric configuration on temperature distribution are discussed as well to provide the viable solutions for systems optimization.

Jan 1, 2015

By J. D. Law

The presence of long-lived radionuclides presents a challenge to the management of radioactive wastes. Separation of the radionuclides from the waste solutions has the potential of significantly decreasing the costs associated with the immobilization and disposal of the waste by minimizing waste volumes. Several solvent extraction processes have been developed at the Idaho National Engineering and Environmental Laboratory for the separation of transuranic elements (TRUs), 90 Sr, and/or 137 Cs from acidic radioactive waste solutions. The TRUEX and POR processes for the separation of TRUs, the SREX process for the separation of 90Sr, the cobalt dicarbollide process for the separation of 137Cs and and a universal solvent extraction process for the simultaneous separation of TRUs, 90Sr, and 137Cs have all been developed in centrifugal contactors using actual liquid radioactive waste solutions and simulated dissolved calcine waste solution. In addition, the behavior of metals with each of the solvent extraction processes was evaluated. This article summarizes the most recent results of the each of the flowsheet demonstrations and provides Information on the centrifugal contactor equipment used for the testing.

Jan 1, 1999

By Geoffrey Brooks, Ben M. Ekman, M. Akbar Rhamdhani

"Concentrated solar collectors including solar simulators have been studied to concentrate solar radiation to flux levels capable of reaching temperatures of 3000K. Currently, there are no industrial scale solar reactors used for material processing and only small research units have been tried. Various laboratory scale solar reactor designs are reviewed including their operating temperature and heat transfer efficiency. Solar reactor designs can be classed into directly or indirectly irradiated and single or double cavity construction. Thermal efficiencies of up to 40% have been achieved in experimental units while operating at 1500K. Problems are encountered that relate to the transfer of high heat flux. Hybrid reactor system should be considered in the future to overcome some of the practical issues associated with solar thermal reactors.I. INTRODUCTIONIn the high temperature processing of materials, such as the production of metals, cement, refractory or glass, the reactions are typically performed in the range of 500° to 2000°C. Metals are produced from minerals, which maybe oxides, sulphides, chlorides or silicates, and to recover the metals, these compounds have to undergo chemical reaction to liberate the metal. The thermodynamic stability of these compounds found in minerals necessitates the use of high temperatures to break down the bonds between the metals and other elements. Normally, the raw metals produced from smelting require refining, which is often carried out in the molten state. As new energy sources have been established, new furnace designs have evolved to incorporate the latest technology. Although solar energy has existed longer than all the current energy sources, it has not yet been incorporated into any industrial smelting; refining or melting processes. The solar radiation reaching the earth’s atmosphere, called the “Solar Constant” (SC), is defined as the rate at which solar energy is incident on a surface normal to the sun’s rays at the outer edge of the atmosphere when the earth is at its mean distance from the sun. The currently accepted value is 1367 W/m2 [1]. The earth intercepts only a small amount of this and 30% is reflected back into space, 47% is converted to low-temperature heat and reradiated into space and 23% powers the evaporative and precipitation cycle of the biosphere [2]. As a result, the solar energy reaching the earth’s surface is weakened considerably to about 1000 W/m2 or one sun, on a clear day and much lower on cloudy or smoggy days [3]. The thermodynamic limit for solar concentration is determined from the inverse square law [4] by the factor sin2? = 46,764 sun’s [5] where ? is the angular size of the sun and equals 0.0093 radians [7]. This would produce a steady state temperature equal to that of the sun’s surface of approximately 5800oC. In practice however much lower concentrations are achieved due to geometrical and optical imperfections, shading effects and tracking inaccuracies. Optical configurations based on parabolic-shaped mirrors are commercially available for large-scale collection and concentration of solar energy for the generation of electrical power. The most common configurations used for concentration of the sun’s energy in solar thermal applications are parabolic troughs, solar towers and parabolic dishes [8,9]."

Jan 1, 2014

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

By C. Flores

A novel process using solid metals for the direct reduction of more noble metal ions from solvent extraction organics has been developed. Base metals recovery has been the principal focus of investigations to date but feasibility tests have now also been made on galvanically stripping selected precious metals. In this study gold (III) was loaded from an aqueous HAuCI4 .3H20 solution into a mixed organic 40 vol.% TBP, 10 vol. % D2EHPA in kerosene. The direct precipitation of metallic gold from the loaded organic phase using zinc powder and iron, aluminum and copper slabs at 70 °C was successfully demonstrated. The gold reduction rates were relatively fast even though the conductivity of the organic solutions is very low. The reaction rates were studied as a function of the variables zinc particulate size, oxygen and nitrogen atmosphere, water content in the organic phase, organic ratios and temperature. The gold morphology was usually powdery or dendritic in nature but continuous films were obtained in some instances. Activation energies were calculated and possible reaction mechanisms are discussed. In general, the results obtained were very promising and showed that gold can be successfully cemented from selected organic solvents by galvanic stripping using less noble solid metal reductants.

Jan 1, 1995

By Xiao Y. Yan

A fused salt electrochemical process was investigated for the synthesis of non-oxide ceramic powders directly from metal oxides, boric oxide, and carbon powders by electro-deoxidation. Sintered pellets of the mixed powders were designed to act as a composite cathode in the electrolytic cell. Electrolysis was carried out in molten CaCl2-NaCl eutectic at 3.1 V and at 600-900 ºC under argon. The favoured cathodic reaction was the removal of the oxygen from the oxides to produce metal atoms that reacted with either the reduced boron atoms, forming a metal boride, or the carbon initially present in the sintered pellets to produce a metal carbide. The technical viability of the process was demonstrated by the electro-deoxidation of sintered pellets of TiO2/B2O3 and TiO2/C to produce TiB2 and TiC, respectively. Compared to existing carbothermic reduction process, this new electrochemical process may be less energy intensive and may lead to lower production costs. I

Jan 1, 2008

By S. Y. Tan

As CMOS devices are scaled down into nano-region, SiO2 dielectric is approaching its physical and electrical limits. High-k material has been investigated widely in recent years, and gate oxide take place growth oxide with Hf-based below 45nm gate length technology node has been shown. The phenomenon of interfacial property between bulk silicon and gate dielectric materials (HfO2 and HfSiO) was focused. A comparison of capacitance-voltage (C-V) characteristic of gate insulator was presented. Furthermore, the electrical property and thermal stability of high-k dielectric materials at various post deposit anneal (PDA) temperatures were established. The X-Ray diffraction technique was (XRD) utilized to analyze crystallization of the thin films, and the X-ray photoelectron spectroscopy (XPS) was applied for surface chemical bounding energy to identify the silicon and dielectric layers. Results show that HfSiO films have exhibited a superior performance on both thermal stability and electrical performance.

Jan 1, 2009