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By T. Nagano

Mitsubishi Metal Corporation started the development work of a new process for continuous production of copper in 1961. After a series of experimental and semi-commercial operations, the first commercial plant of the Mitsubishi Continuous Copper Smelting and Converting Process was put into operation in March, 1974. The new plant, which has a design capacity of 4,000 metric ton copper per month, was built within the premises of Naoshima Smelter, replacing the old No.1 reverberatory smelter there. The SO2-rich exhaust gas from this new plant is blended with the off-gas of the No.2 reverberatory furnace for production of sulfuric acid and the overall emission of sulfur at Naoshima has been greatly reduced. The operation of the continuous plant has been satisfactory and several advantageous features of the Mitsubishi Process have been proven on a commercial scale. This paper first gives a brief description of the history of the development work and the characteristic features of the process. The paper then describes the new commercial plant and operating data obtained so far.

Jan 1, 1976

By Zhigan Deng

Cooling crystallization was used to separate iron (III) and nickel (II) from acidic sulfate solution produced by leaching of molybdenum-nickel black shale. The effect of K2SO4 concentration, crystallization temperature, solution pH and crystallization time on recovery of nickel (II) and precipitation of iron (III) was investigated, in order to obtain effective separation of nickel and iron. The optimum parameters determined were as follows: 200 g/L K2SO4, 10 °C crystallization temperature, solution pH of 0.5 and 24 h crystallization. Under these conditions, 97.6% nickel (II) was recovered as K2Ni(SO4)2, 6H2O crystals and only 2.0% of the total iron (III) was precipitated. Recrystallization yielded K2Ni(SO4)2, 6H2O crystals with a purity of 98.4%.

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 Francois Reizine

Infrared sensors will include scanning detectors and positioning sensors. The focus will be on 1, 2, and 4-color wavelength pyrometer systems which allow the accurate measurement of emissivity and, consequently, of the true temperature even in the presence of scale, slag, and fumes. Such sensors are being used in blast furnaces, BOF's, and galvanizing lines. Laser sensors will be presented using different principles of physics, mainly time-of-flight, pulsed infrared lasers for level measurement and dimensional measurement; triangulation lasers for width and thickness measurements; and laser Doppler velocimeters for velocity and length measurements, including mass flow, elongation, and tension control, cut-to-length applications. These sensors and systems are based on state-of-the-art technical developments to improve productivity and quality and reduce maintenance and downtime.

Jan 1, 2001

By James C. Foley

In-situ characterizations of green state part density and sintering state have long been desired in the powder metal community. Recent advances in non-contact electromagnetic acoustic transducer (EMAT) technology have enabled in-situ monitoring of acoustic amplitude and velocity as sintering proceeds. Samples were made from elemental powders of Al (99.99%), Al (99.7%), Ag, (99.99%), Cu (99.99%) and Fe (99.9%). The powders were pressed in a uniaxial die and examined with acoustic waves for changes in velocity and amplitude during sintering. The changes in acoustic properties were correlated with mechanical properties. Evolution of a series of reverberating echoes during sintering is shown to provide information on the state of sintering, changes in sintering kinetics as well as having the potential for detection of interior flaws.

Jan 1, 2001

By Miao Tian

Large quantities of copper complex resources are produced globally and urgent to be cleanly processed. This article presents a thermodynamic analysis of mixed smelting process including low-grade polymetallic copper sulfide concentrates, high copper content sulfide concentrates, metallurgical by-products (copper removal slag from lead metallurgy), and copper powder from electronic waste. A top blown smelting reactor to simulate mixed smelting process is developed using a metallurgical process simulator, METSIM. Reactor parameters, heat loss and phase distributions are estimated from actual plant data. The proper proportion between complicated primary and secondary copper resources is determined by analyzing the influence of the feed rates of various resources, oxygen, silica flux and revert on the smelting performance. Autogenous smelting process is built by optimized matching materials of copper complex resources, in terms of the reactor temperature, copper content in matte and slag, and the percentage of magnetite in slag.

By Satu Strömberg

Four different nickel concentrates were oxidized in a laboratory scale laminar flow furnace in simulated flash smelting conditions. The major nickel- and iron-bearing minerals in the con- centrates were pentlandite, violarite, gersdorffite, and pyrite and pyrrhotite, respectively. Thermal decomposition, ignition and oxidation behavior of nickel and iron sulfides were examined by using optical and scanning electron microscopy. General reactivity of the concentrates was monitored with sulfur removal which was most effective in violarite-based concentrate. Pentlandite-concentrates needed higher experimental temperatures for complete desulfurization and gersdorffite-based concentrate contained 5 - 10 % of the original sulfur even in the most oxidizing conditions studied (1 100°C, 50 vol-% 02). The reactivity of the iron minerals was found to depend on the other minerals present in the concentrate. In this paper, the observed re- action products and mineralogical changes are presented and preliminary conclusions of possible reaction mechanisms of nickel-bearing minerals are discussed.

Jan 1, 1997

By D. F. Suarez

Spontaneous nodulation leading to growth of well developed glossy spheroids (generally hemispheres) of up to 0.06 cm width in 120 min has been observed during copper electrodeposition with certain levels of glue, thiourea and C1-. Thiourea alone can produce spontaneous nodulation but addition of glue and/or Cl- is required for rapid and sustained growth. In most cases once the glossy nodules develop they consume the majority of the copper deposited; thus, the specific current densities (and hence copper electrodeposition rates) on the glossy nodules are about an order of magnitude or, more greater than on the adjacent planar surfaces. The texture of the adjaoent planar surfaces is not glossy in appearance but is well faceted showing the usual deposition grain structure for such additives. Cathode potentials when spontaneous nodulation occurs are about TOO my more negative than with usual copper electroplating. This fact associated with evidence of extremely high levels of cathode surface passivation based on cyclic voltammograms indicates that the conditions which lead to spontaneous nodulation result from a very tightly adsorbed additive surface film. This film breaks down in specific points initiating the glossy nodules which then grow at extremely rapid rates. Current density is also important in spontaneous nodulation. At equal deposition times a current density of 21.5 mA/cm produced much larger glossy nodules than at 48 mA/cm2. The surface concentration of the glossy nodules was much greater in the latter case, however. The role of current density is still not well understood. The role of it as well as the relative roles of the three additives, thiourea, glue and Cl- in spontaneous nodulation is presented. Preliminary results and some possible correlations of these to help explain spontaneous nodulation are presented. It is believed that tankhouse upsets where cathode nodulation occurs may be related to this phenomenon.

Jan 1, 1987

By Grégory Miette

The paper deals with a process that allows the recycling in a cupola of EAF dusts with 18 % Zn. It produces dusts with zinc grade higher than 50 - 55 % and commercial cast iron with less than 200 ppm Zn, 50 ppm Pb, 0.15 % S. The paper focuses mainly on lab tests made with the aim to develop an effective formulation of self reducing - melting pellets. With such a formulation, agglomerates develop a breaking load higher than 125 - 150 kg without any thermal treatment. Zinc and lead are volatilized in the cupola with yields higher than 95 % at 1200 OC, before any melting. Sulphur is transfemed into gas and slag. All these conditions allow to lower zinc, lead and sulphur grades below the cast iron specifications. Results of first bench scale tests performed at Fonderie Piret to validate the process will be presented.

Jan 1, 2002

By Wen-Ming Chien, Vamsi Krishna Kamisetty, Amrita Mishra, Ivan Gantan, Prathyusha Mekala, Dhanesh Chandra

"The phase equilibrium and characterization studies by using high temperature X-ray diffraction (XRD) and differential scanning calorimetric (DSC) methods have been performed for binary organic thermal energy storage materials. The organic thermal energy storage materials undergo a solid-solid state phase transition before melting which stores large amounts of thermal energy. Two materials [tris(hydroxymethyl)aminomethane(TRIS) and 2-Amino-2-methyl-l, 3- propanediol(AMPL)] were used for this study. Binary samples of AMPL-TRIS were prepared to perform high temperature XRD characterization and DSC studies and the binary AMPL-TRIS phase diagram was developed. The high temperature solid-state phases of AMPL and TRIS were characterized as a disordered BCC structure. It was found there is virtually no solubility of TRIS in AMPL or vice versa below -75 °C. The maximum solubility of TRIS in AMPL is 11% TRIS at 75 °C. The eutectoid transformation was shown at 19%TRIS-81%AMPL composition and at a temperature of 75°C. Lattice expansion calculations on single phase of TRIS and AMPL have been performed.IntroductionThermal energy storage materials can store a large amount of heat due to the presence of thermal transitions from the orientationally ordered to disordered phases occurring before melting. These molecules (such as amine and alcohol derivatives of neopentane) can reorient as a whole about the central carbon atom to form orientationally disordered crystals (ODIC) and their spherical shape makes them reorient relatively easier. Thermal energy storage materials are becoming increasingly important as a renewable energy resource. These molecules undergo large changes in enthalpies at solid-solid transitions. The presence of these compounds with large enthalpy changes are identified as potential thermal energy materials and some of die applications are solar cell systems [1-3]. Binary mixtures have been found as a way to adjust the transition properties in addition to pure compounds [4]. Tris(hydroxyrnethyl)aminomethane (TRIS, C(CH2OH)3NH2) and AMPL, CH3C(CH2OH)2NH2) are two important thermal energy storage materials."

Jan 1, 2012

By S. Seetharaman, Du Siehen

"In the processing of molten metals, it is extremely important to monitor continuously the concentration levels of various minor elements. In the production of common metals like copper, iron and aluminium electrochemical sensors involving solid as well as liquid electrolytes are being increasingly used to measure the concentrations of minor elements. The present paper deals with the electrochemical principles underlying these measurements and the possible errors involved. One of the major difficulties in the case of the solid electrolytes is to correct for the consequences of the electronic contribution to the conduction of the electrolyte.The application of the electrochemical sensors for molten metals processing involves designing of these probes to withstand the industrial operating conditions. In this respect, significant achievements have been made with respect to the design of oxygen probes for liquid metals in general and liquid copper in particular. Some of the salient design features are discussed in the paper. The application of auxiliary electrodes for impurities in molten metals like phosphorus in copper and silicon in iron are taken up. The development of oxygen sensors for slags is given special attention. Recent developments in the field of sensor technology, as applied to metals processing are highlighted.1. IntroductionThe rapid technological advancement today require precise control of the process parameters and the impurity levels. Most of the molten metals processing in industrialized countries are often steered by suitable computer models, either phenomenological or simulations based on theoretical principles. These models often require that the process parameters are continuously monitored so that the progress is followed and modified suitably as and when required. It is common practice to measure temperatures by incorporating temperature sensors at the various strategic points of the reactor. In the case of monitoring the composition changes in the various phases, the method of sampling followed by routine chemical analysis involves a time lag as well as uncertainties in sampling and analysis. In this respect, electrochemical sensors have the advantage of generating accurate data when properly applied and increasing attention is being paid in the development of electrochemical sensors for various common species in molten metals processing. In the present paper, the developments in this area over the years are outlined and typical process applications are discussed. A greater emphasis will be laid on sensors based on oxygen conducting electrolytes and their application to the production of common metals like iron and copper."

Jan 1, 1996

By R. A. Spitz, R. Leiby, M. Bricker

Electrochemistry plays a significant role in minimizing wastes at East Penn's secondary lead smelter. East Penn has been recovering spent battery acid for reuse in new batteries since 1992. East Penn also produces a fertilizer feedstock from sulfur dioxide in the smelter stack gases. The success of these processes is, in large part, due to the installation of electrochemical cells. The cells in the acid recovery plant allow the waste from this process to be concentrated into less that 10% of the original spent acid. The cells in the fertilizer plant treat the solution to remove dissolved metals prior to sale to fertilizer manufacturers.

Jan 1, 2000

By Jinfu Xu, Youqing Cao, Yuting Lv, Hang You, Peng Jiang

"In present work, we reported the fabrication of composites consisted of M42 powder metallurgy high speed steel and 45 steel at one step via spark plasma sintering (SPS) technology. The interface microstructure, compositions and microhardness with the interface forming mechanism were investigated. The results show that the morphology and microhardness within the M42/45 steel interfaces exhibit a gradient distribution. The interfaces possessed a transition layer up to 10.2 ?m with few distortions and microcracks. The formation of M42/45 steel interfaces were driven by both fusion and diffusion processes. The former one was primary at the early sintering process, while the later one becomes dominant over the followed sintering process.IntroductionPowder high-speed steels have been widely used in cutting tools, cold-hot tools and dies, as well as in cut materials and structure parts with wear resistance and high-temperature resistance, due to its high hardness, good wear resistance, desirable cutting toughness and favorable hot hardness [1-2]. For materials of some parts in practical production, not only the favorable toughness is required to resist the impact action, but also the high hardness and exceptional wear resistance are demanded. According to the functional requirements and working conditions, bimetal composite materials are prepared in a certain mode, proportion and distribution, by designing two metals with different chemical and physical properties [3-6]. Considering the composites exhibit different properties in different positions of the parts with a combination of the advantages of two metals, they can obtain enhanced properties that the single one can not achieve."

Jan 1, 2012

By Run Huang, Xuewei Lv, Songli Liu, Chenguang Bai

"Titanium alloy was prepared from titania-bearing blast furnace slag (Ti-BF slag) by aluminothermic process in an induction furnace. The effects of aluminum amount on the titanium silicon yield and titanium recovery ratio were studied. The phase transformation and chemical composition of the prepared alloy were investigated by X-ray diffractometry (XRD) and X-ray fluorescence (XRF) respectively. It was found that the mass fraction of silicon and aluminum increased with increasing the aluminum amount, however, the mass fraction of titanium increased first and then decreased with increasing the aluminum amount. Furthermore, both the titanium alloy yield and titanium recovery ratio increased with the increase of aluminum amount. The main phases of the alloy were TixSiy and AlTi3. The titanium alloy samples prepared in various conditions had a composition (wt.%): 38–50% Ti, 29-34% Si, 4-11 Al%, 1.6-2.2 Mn%.IntroductionPanzhihua and Xichang regions in the southwest of China are rich in vanadium-titanium magnetite containing iron, vanadium, titanium and gangue. According to the characteristics of the resource, iron and vanadium are successfully recovered with a blast furnace process and a converter process. However, most content of titanium are entered in the blast furnace slag with TiO2 22% -26% and metallic Fe 2%–6% called Ti-BF slag. Due to the dispersed distribution of Ti in various fine grained mineral phases with a complex combination between Ca, Al and Si, it is difficult to recover the Ti components[1]. This slag is generated at a current rate of 3.6 million tons per year, which adds to the existing 70 million tons of slag produced so far[2]. The slag has had to be piled as large as the mountains, which not only waste of resources but also cause a pollution of the environment. Therefore, the study of integrated utilizing Ti-BF slag has become very significant."

Jan 1, 2012

By Allan MacRae

Freeport-McMoRan Inc. operates an ISASMELTTM furnace for the smelting of copper concentrate at the Miami Smelter in Claypool, Arizona. In May 2017, the furnace was restarted after incorporating newly designed copper cooling elements from just above the tap hole to the underside of the roof. The objective of the improved cooling design was to extend campaign life by eliminating existing failure mechanisms with the wall refractory. In addition to upgraded bathline coolers and complete coverage of the gas offtake transition, or ‘kettle’, with plate coolers, a novel arrangement of coolers was installed in the remaining freeboard area. The shell required significant cutting and re-stiffening, as well as extensive modification of the cooling water piping. Based on performance observed to date, it is expected that smelter throughput will be increased due to extended ISASMELTTM refractory campaign life.

By Baozhong Ma, Qian Li, Yonggang Wei, Shiwei Zhou, Bo Li, Chengyan Wang, Hua Wang

The magnesium-rich nickel oxide ore (w (Ni) =1.09 %, w (MgO)=29.08 %) mixed with 6 % and 8 % anthracite were roasted at different temperatures. XRD and SEM/EDS techniques were utilized to characterize the phase and microstructure transformation of the ores. The results show that lizardite and chrysotile of raw ore were converted into forsterite and enstatite during reduction roasting process. Simultaneously, iron and nickel oxide were reduced and migrated from the initial magnesium silicate. Fe3Si were formed when the roasting temperature went up to 1300 ℃ and 1350 ℃, and a small amount of Ni was observed in it. Temperatures got too high were not benefit to the polymerization of ferronickel.

Jan 1, 2015

By Keizo Uematsu, Satoshi Tanaka, Nozomu Uchida, Yutaka Saito

"Effect of moisture content must be fully understood for controlling the granule compaction of ceramics. It changes the mechanical behavior of spray-dried granules applied for compaction process, and governs the structure and properties of .ceramics. To understand the time-dependent change in processing, the kinetics was examined for change of moisture content for granules placed in a die and the pressed compacts also. The results were explained in terms of apparent moisture diffusion coefficients. They varied non-linearly with the PVA content in the granules. The results were explained through the non-uniform PVA distribution in the granules.IntroductionMoisture must be controlled in compaction process to produce the green compacts having uniform structure. It affects glass transition temperature of binder and thus the deformation behavior of powder granules under an applied stress. Several studies [1-7] have clarified the effect of moisture content on the compaction behavior of granules and the structure of resultant compacts for both die pressing and cold isostatic pressing (CIP) of pre-formed compacts. In these studies, the moisture contents in the system were equilibrated with the humidity in the atmosphere before compaction. In practice, however, the moisture content in the system may vary with time if the relative humidity of surrounding atmosphere is different from what the granules were equilibrated previously. This is very likely case in real production processes. However, the kinetics of moisture change in the granules as well as in the pre-formed powder compacts have not been well studied. For controlling the microstructure in a system, it is necessary to fully understand the kinetics of moisture change and its relevance to packing structure of powders."

Jan 1, 2000

By Onder Guney, Erdem Demirkesenm

"In this study, the crystallization behavior and thermal expansion coefficient of a lithium disilicate (LS2) based glass-ceramic derived from SiO2-Li02-AhO3-K2O-ZrO2 system was investigated by using x-ray diffraction (XRD), high temperature x-ray diffraction (HTXRD), differential thermal analysis (DTA) and dilatometer techniques. Analytical reagent grade chemicals were chosen as raw materials for preparing glass batches. Nucleation and crystal growth heat treatments were planned according to DTA results. The amounts of the amorphous and crystalline phases developed during the heat treatments were determined by quantitative XRD. XRD results of crystallized samples showed simultaneous formation of lithium silicate (LS) and quartz in the early stage of the crystallization followed by formation of lithium disilicate (LS2) at higher temperatures. The thermal expansion coefficients of glassceramics were also measured depending on the applied heat treatments.IntroductionSignificant developments occurred in all ceramic materials provide the fabrication of high quality dental implants [1]. Glass ceramic based dental restorations like dental inlays, crowns, bridges and veneers are becoming increasingly popular with their reliable and durable performance [2,3]. In addition to their advanced functional properties, glass ceramic implants especially lithium disilicate glass ceramics also face the esthetics expectations of patients and dentists and in this way they are starting to take the place of metal based restorations today [1,3,4,5]. Lithium disilicate glass-ceramics derived from multicomponent glass systems have some superior mechanical and optical properties comparable to natural teeth [ 6]. In restorative dentistry, mechanical characteristics of biomaterials play very crucial role in order to resist the masticatory forces occurred during biting and chewing [7] According to three point bending test results of Roland, flexural strength of the lithium disilicate glass-ceramics were 400±40 MPa and their fracture toughness (K1c) are approximately 3,3 MPa m112 [2,6]. In addition to high mechanical strength, aesthetic appearance is another important prerequisite as material for dental restorative applications. Translucency and light transmission of the LS2 glass ceramics mimic enamel. Moreover, opacity of the material can also be adjusted depending on the restoration types [2,6, 7]. These superior properties of the LS2 glass ceramics are directly related with chemical composition of the base glasses and controlled crystallization heat treatments [ 4, 7]. The aim of the present work is to determine the effect of heat treatment schedules on the crystallization behavior and thermal expansion of the LS2 glass-ceramics."

Jan 1, 2011

By E. Charles Abbey

Manganese in electrolyte has both beneficial and detrimental effects in Zn electrowinning. Mn oxidizes to form MnO2 on Pb–Ag anodes, cell walls and pipes. MnO2 reduces anode corrosion but also leads to short circuiting and maintenance issues. MnO2 is thought to interact with chloride ions and produce oxidized chlorine species. The interactions between Mn and Cl are not well understood. Therefore, two sets of 45+ day bench scale experiments were conducted to investigate the effects of the manganese to chloride ratio on anode corrosion rate and electrolyte chemistry using rolled Pb–Ag anodes. Daily manganese and chloride losses from the electrolyte appeared to be correlated. Increasing the average Mn/Cl− ratio from ∼7:1 to ∼11:1 reduced the anode corrosion rate. Increasing the ratio above 11 did not reduce the corrosion rate further. Anode scales produced with Mn/Cl− ratios at and above 11:1 contained some γ–MnO2 while scales formed with ratios less than 11:1 did not.

By D. H. Magoon

The zinc smelter of Cominco Ltd. at Trail, B.C. Is the largest In the western world. A total of 550.000 tonnes of concentrate are proceed at the smelter annually. Approximately 80% of the zinc concentrate is roasted and the remainder Is treated by aqueous oxidation preaaure leaching. The zinc concentrate roasting and sulphur dioxide gas processing plants have undergone many changes over the years. This paper describes the processes and equipment currently used for concentrate roasting, S02 gas cooling and cleaning, mercury removal, sulphuric acid production liquid S02 production, and tall gas S02 scrubbing. The recent Installation of an advanced process control system for the operation of these Integrated processes Is also described.

Jan 1, 1990