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By C. M. Wai

"Metal species in solid and liquid materials can be extracted by supercritical carbon dioxide containing a suitable ligand. This in situ che1ation-supercritical fluid extraction technique offers several advantages over conventional solvent extraction including minimization of organic liquid waste generation and exposure of personnel to organic vapors. One unique feature of this technique is that metal species can be removed from solid materials directly using supercritical carbon dioxide as a solvent. Several ligand systems including dithiocarbamates, B-diketones, organophosphorus reagents, and macrocyclic compounds have been tested for metal extraction in supercritical carbon dioxide. This novel extraction technique may have important applications for metal recovery and mineral processing.IntroductionSupercritical fluid extraction (SFE) offers several advantages over conventional solvent extraction including the minimization of organic liquid waste generation and exposure of personnel to organic vapors.[1] The high diffusivity, low viscosity, and T-P dependence of solvent strength are some attractive properties which make supercritical fluids excellent candidates for extraction and recovery of organic compounds from solid materials [2] Carbon dioxide is a gas of choice for SFE because of its moderate critical constants (Tc = 31 °·C and Pc = 73 atm), inertness, and availability in purified form. After extraction, the fluid phase is depressurized to separate organic solutes from CO2 gas and the gas can be recycled for repeated use. The SFE technology has been applied to industrial scale operations such as the preparation of decaffeinated coffee and hop extracts."

Jan 1, 1996

By J. F. White

An experimental study was undertaken to evaluate the feasibility of a selective chloridizing roasting pre?treatment process for the elimination of impurities from zinc feed?stocks prior to recovering zinc by conventional unit operations. In this investigation, a number of chemistries that might serve as a basis for such a pre? treatment process were examined. A variety of chloridizing agents were admixed with EAF dust to promote the selective removal of lead and cadmium by the formation of volatile metal chlorides, he results of the experimentation firmly establish that selective chloridizing roasting is a technically feasible means of eliminating lead and cadmium from EAF dust. Excellent extraction efficiencies were accomplished with a number of chloride additives; as high as 98 percent lead extraction and 88 percent cadmium extraction were attained with minimal zinc losses, Continuous pilot?scale tests reinforced the trends established by laboratory?scale experimentation, Attempts of chlorine elimination using pyrohydrolysis were less successful. The extent of chlorine elimination was found to be highly dependent upon EAF dust sample type and treatment temperature.

Jan 1, 1996

By Z. Smieszek, J. Botor, Z. Miczkowski, S. Sobierajski

"From 1978, the direct process for the smelting of chalcocite concentrates in a flash furnace by the Outokumpu method has been applied at the Glogów II copper smelter. The chemical composition of these concentrates make it necessary to control the process very strictly. In this paper, the method for controlling and measuring the main technological parameters of the copper production by flash smelting is being presented. It includes the determination of the chemical composition of the concentrate, its grain structure, the temperature of liquid products of the process, oxygen content in process gases, as well as lead concentration in copper and copper concentration in slag.The main process parameters are determined from the mass and energy balances. The relations between parameters, such as an effect of grain structure of a concentrate on oxygen and oil consumption, and dependence of chemical composition of a concentrate on capacity and products quality are discussed. 1. IntroductionThe Polish copper concentrates, as most concentrates occurring worldwide, contain from 18% to 30% Cu, and less sulphur (7-11%) and iron (2-5%). The main copper-bearing mineral contained in the concentrates is chalcocite, while bornite and chalcopyrite are present in smaller quantities. Moreover, the organic carbon (5-7.5%), arsenic (0.05-0.3%) and lead (1.2-3.0%) are also contained in the concentrates. The gangue consists mainly of silica, aluminosilicates, calcium carbonate and magnesium carbonate. Their proportions make the addition of slag-forming agents unnecessary.The composition of Polish concentrates, especially their low iron content, allows their application in the direct flash smelting process for blister copper production. Low sulphur content is the factor which determines the necessity of oxygen application in this process."

Jan 1, 1989

By Gerhard Bayer

X-ray and thermoanalytical studies were carried out on the formation and stability of Ca-, Mg-and Mn-tungstate, and of the corresponding minerals scheelite and wolframite. The tungstates were synthesized by different methods: precipitation from solution, solid state reactions, displacement reactions with solutions and in the solid state. The reactivity of natural scheelite and wolframite with different salt solutions and in mixtures with other minerals was investigated.

Jan 1, 1989

By C. -S. Jiang

In most copper refineries, addition agents are added at predetermined rates with no further monitoring of their activity or concentration in the electrolyte. Increasingly stringent cathode quality requirements, and a desire for better process control in tankhouse operations, have recently directed a number of refineries to search for a better addition agent control strategy. Extensive development work has been carried out at the Noranda Technology Centre for the monitor in of glue and thiourea in copper refinery electrolyte using cyclic voltammetry (cv~. Data from both synthetrc and commercial electrolytes are presented, showing the ability of CV to produce reliable and easily identifiable fingerprints of addition agent concentrations in copper refinery electrolyte.

Jan 1, 1991

By Musa Karakus

Reflected light microscopic (RLM) examination of dust particles from lead and copper smelters can effectively characterize their mineralogy, texture, and origin. Scanning electron microscopic-energy dispersive spectroscopic (SEM-EDS) analysis provides confirmation of the optical identifications and chemical data on the phases. Studied lead smelter dust samples were from the: I) blast furnace, 2) sinter plant scrubber, 3) sinter plant crusher, 4) dross furnace, and 5) refinery. Phases identified included galena fragments, melted PbS, metallic Pb and Cu, Cu-Ni, Cu-Zn, Zn-Ag, Zn-Cu-Ag, Ni-Cu-Sb, and Ni-Cu-Zn-Ag metal alloys, Ni-sulfide, Cu-sulfide, and Cu-Pb-sulfide dross .phases; slag and sinter particles, coke fragments, unreacted original feed phases: pyrite, chalcopyrite, sphalerite, siegenite, bravoite; and oxidized particles: iss, bornite, chalcocite, covellite, magnetite, hematite, and goethite. Dust from a secondary copper refinery were found by RLM and SEM to consist of tenorite, cuprite, cassiterite, two silicate phases. Magnetite, hematite, Fe-Al-Cr-Mg spinel, periclase, forsterite, and wollastonite were derived from the furnace linings during initial cleaning.

Jan 1, 1992

By Ryokichi Shimpo

Much amount of sludge is produced from the wastewater treatments in surface finishing industry. There are many problems for the abandonment of the sludge because of the high water content and heavy metals included. It is often observed that hexavalent chromium, which is toxic, is generated in the course of heat treatments of the sludge for reducing its amount by dispersing water. In this study, conditions of the sludge calcinations for reducing water contents have been examined. Maximum hexavalent chromium generation was observed in the temperature range around 773 K, at which most of the crystallization water decomposed from the sludge. When the heating temperature became higher than 1173 K, the amount of the hexavalent chromium extracted from the calcined sludge became as low as 10 mg/kg sludge. When the sludge was heated with iron oxides, FeO or Fe203, iron ferrite has been synthesized which may be used as a magnetic material. The amounts of hexavalent chromium generated in the heat treatment with iron oxides were not much different from those without iron oxides.

Jan 1, 2003

By John J. Mortvedt

Application of some by-products of the metals industry which contain plant nutrients to agricultural lands could constitute resource recovery instead of costly disposal. Some industrial by-products contain appreciable concentrations of heavy metal contaminants, such as Cd, Cr, Ni, and Pb. After land application, these metals may be absorbed by plants and enter the human food chain or be leached to groundwaters. Plant uptake of these heavy metals varies with plant species:, soil pH, soil texture, and the particular metal. Certain leafy vegetables can absorb significant amounts of heavy metals, while absorbed metals are usually poorly translocated to cereal grains. Allowable heavy metal concentrations in fertilizers now are not regulated, but EPA is considering such regulations. Heavy metal impurities in animal feed supplements are regulated by the states; so some by-products may not be permitted for this use.

Jan 1, 1992

By Bart Blanpain, Muxing Guo, Zhuangzhuang Liu

In order to stabilize free lime in the basic oxygen furnace (BOF) slag to achieve high value products, quartz sand and other additives are injected into slag. However, the current hot stage slag stabilization does not work in case of slag (before treatment) with a liquid fraction lower than 90%, where the slag containing solid particles is too viscous. Therefore, it is essential to understand how solid phases affect the viscosity of the slag system. In this study, the industrial BOF slags were investigated with respect to the correlation between volume fraction of solid phases and its viscosity. Slag viscosity was measured with a rotating type viscometer at temperatures below the liquidus. The volume fraction of solid phases was quantitatively calculated with FactSage. The Einstein-Roscoe equation was employed to predict the viscosity of BOF slag.

Jan 1, 2016

By Jong-Jip Kim, J. G. Byrne, W. Kim, In-Ok Shim, John E. Flinn

"Two rapid solidification processes for 304 stainless steel were studied: centrifugal atomization (CA) in a helium atmosphere and atomization by exposing argon-containing melt to vacuum (VGA). Positron annihilation and x-ray line broadening measurements of explosively consolidated monoliths were used to clarify microhardness measurements as a function of annealing temperature. Interesting differences in positron response between CA and VGA materials are ascribed to more carbide formation in the CA material than in the VGA material in the 600 0C range. In addition, hot isostatic pressing of the CA material was examined as to the relations between mechanical behavior, pore shape, and relative density. A variable stress concentration factor is introduced into the theory to allow for changing pore shape as relative density increases.IntroductionThere are many potential advantages of rapid solidification processing (RSP), such as a high degree of matrix supersaturation, finely dispersed microstructures, improved chemical homogeneity, and retention of metastable phases, which have been studied extensively. To consolidate rapidly solidified material which is in powder form into useful shapes often requires subjecting the material to elevated temperature for extended periods of time under mechanical forces, as in hot isostatic pressing or hot extrusion. In such cases, some of the characteristics of the rapid-cooling step can be strongly affected. An alternative is dynamic consolidation (1), for example by explosive forming, where the time frame at least is extremely short.In the present work, effects of the consolidation processes of hot isostatic pressing (HIP) and explosive forming in a die are examined. The particular material is 304 stainless steel. The characteristics of both RS and VGA 304 stainless-steel powders were described by Wright, Flinn, and Korth (2) earlier."

Jan 1, 1988

By Masayuki Kudoh, Tohru Maruyama, Yohichi. Ito

When hypo-peritectic carbon steel is quenched during unidirectional solidification, the region of fine columnar grain is observed. It is classified into two coexisting phases. One is coexisting phases of liquid, delta and gamma in the upper part of the region, and the other is coexisting phases of delta and gamma in the lower part of the region. To form the coexisting part of the three phases means that solidification in this experiment proceeds in non-equilibrium state. The size of the narrow side of one fine columnar grain coincides with the arm spacing of a primary dendrite and this result is the same as the hyper-peritectic carbon steel. However, the boundary of the fine grain in the hypo-peritectic carbon steel is formed in different location from that of the hyper-peritectic carbon steel. The former is formed in the skeleton of the dendrite, while the latter is formed in the interspacing of the dendrite. The region of the fine grain changes suddenly to that of the coarse grain when the delta phase in the coexisting part of two phases disappears completely. Therefore, the delta phase in the hypo-peritectic carbon steel might prevent the growth of gamma grain. In order to recognize it, ferrite formers such as Mo, V and Ni are added in the sample. Then, the longitudinal length of the fine columnar grain extends in the sequence of the no addition, Mo, V and Nb.

Jan 1, 2000

By L. Filip

The roast-leach-electrowinning (RLE) process for zinc was modified to treat two typical complex concentrates containing zinc, lead, copper, gold and silver. Laboratory testwork results indicated that the optimum roasting temperature ranged from 700 to 800°C, in order to produce acceptable residual sulfur levels. The calcined concentrate was subjected to a three-stage leach sequence. The resulting leach solution was purified by hematitic precipitation and directed to the recovery of copper and zinc by solvent extraction and electrolysis. Alkaline smelting and subsequent electrolytic purification recovered the lead and precious metals from the leach residue. A flowsheet was developed based on the laboratory testwork results, and demonstrated in a large-scale pilot plant. The recoveries produced during the pilot plant operation ranged from 90 to 92% for zinc and copper, 85% for lead and 90% for gold and silver, respectively.

Jan 1, 1999

By R. Padilla

A thermogravimetric study has been conducted to follow the decomposition and volatilization of arsenic from enargite concentrate in nitrogen and slightly oxidizing atmospheres. Temperature has a large effect on the rate of volatilization of arsenic. Fractional volatilization of arsenic as high as 98% were obtained in less than 60 min at 650°C in nitrogen atmosphere, while in slightly oxidizing atmosphere the same volatilization could be achieved in 30 min. It was found that arsenic volatilizes as sulfide in nitrogen atmosphere and as 4xture of sulfide and oxide in atmospheres containing 1% oxygen. By using the pore blocking and the first order kinetic models, apparent activation energies of 213 and 200 kJ/mol for the temperature range of 780 - 900 K and 205 and 184 kJ/mol for the temperature range of 900 - 985 K were determined for enargite and copper concentrate, respectively.

Jan 1, 1997

By Melinda Channel, Alan W. Weimer, Jonathan R. Scheffe

"There is a need to develop cost effective renewable energy processes for the production of clean fuels that can simultaneously mitigate the U.S. energy/global environmental security issue. If H2 can be obtained cost effectively via the splitting of water using concentrated sunlight, then it’s possible to operate a fuel cell using renewable H2 or to synthesize other fuels based on renewable H2 for generating electricity or for running internal combustion engines. For example, H2 can be reacted with sequestered carbon dioxide (CO2) to produce syngas (H2/CO) via reverse water gas shift (RWGS), i.e. H2 + CO2 ? CO + H2O. The syngas can be catalytically methanated to form synthetic natural gas (SNG) or it can be catalytically reformed to produce liquid fuels such as “green” gasoline via the MTG process (syngas? methanol ? gasoline). The desert SW United States is home to world class sunlight. Fundamental ferrite thermodynamics will be reviewed, an example of the beneficial effect of ferrite surface area on reaction kinetics will shown, and process economics will be investigated for a 100,000 kg/day facility to produce H2.Introduction and Background ThermodynamicsSpinel ferrites of the form MxFe3-xO4, where M generally represents Ni, Zn, Co, Mn, or other transition metals, have been shown to be capable of splitting water according to the two step cycle shown below:MxFe3-xO4 + solar thermal energy ? xMO + (3-x)FeO + 0.5 O2 (1)xMO + (3-x)FeO + H2O ? MxFe3-xO4 + 2H2 (2)This is an inherently clean and sustainable process, as the only net inputs are solar energy and water, and the net outputs are hydrogen and oxygen. Ferrite water splitting cycles are advantages compared to other high temperature water splitting cycles, such as the ZnO/Zn and Mn2O3/MnO cycles, because thermal reduction has been demonstrated at significantly lower temperatures[1, 2]. As a result, overall efficiency may be increased due to the fact that radiation losses increase as the fourth power of temperature, and material considerations for reactor design should be more flexible. Additionally, cycle repeatability has been demonstrated with relative ease as compared to other thermochemical cycles [3-6]. However, the amount of hydrogen per mole that is generated is significantly less than for other high temperature thermochemical cycles due to the fact that only Fe3+ is capable of being reduced at the temperatures of interest[6]. In addition, water oxidation kinetics appear to be very slow, likely due to diffusion or surface area limitations created by near surface oxidation [6, 7]."

Jan 1, 2010

By Isıl Kerti, Sibel Daglılar, Sinem Yıldırım

In this study, effect of rolling and coiling temperature in thermo mechanical controlled process (TMCP), on the microstructure and mechanical properties of dual phase (DP) steel according to martensite volume fraction (MVF) rate was investigated. By using various finishing mill exit temperature and cooling conditions that is controlled laminar cooling system, the microstructural evolution of coil improves the mechanical properties with lower costs and higher productivities, in comparison to the heat treatment after rolling. The main part of the paper contains the result of tensile, yield and microstructure properties of DP600 steel produced on hot strip rolling plant and run- out table line. The results show that a higher MVF and an increasing cooling rate after the last deformation raised strength of the DP600 steel. The yield strength and ultimate tensile strength increase by decreasing coiling temperature.

Jan 1, 2015

By Xu Zhang, Xuewei Lv, Guibao Qiu

Slag foaming phenomenon is of vital importance to the mass and energy transfer in metallurgical processes. A considerable extensively studies carried out via out-gas in the past cannot simulate well the foaming phenomenon formed in the blast furnace where high TiO2 iron ore is used. A gas reaction was designed in the water-glycerol system to simulate the inner-gas system. This study investigated the influences of solution viscosity, particle concentration and particle size on foaming caused by endogenetic gas. The results show that the foaming height decreases with the increase of solution viscosity, which means reduced foaming ability, more difficult foaming elimination process and prolonged time for natural defoaming. With increasing the solid particle content, the foam height presents a trend which increases firstly and then decreases. Under a certain solid particle content, foaming height decreases with the increase of solid particle size, indicating a weak foaming ability.

Jan 1, 2015

By Akira Kaneda, Nozomu Hasegawa

"In the Mitsubishi Continuous Copper Smelting and Converting Process, slag/matte mixture overflowed from the smelting furnace is separated continuously in an electric furnace (slag cleaning furnace, CL-furnace). In order to improve the separation efficiency of slag and matte and to minimize power consumption, the design and the operating conditions of the CL-fumace should be optimized. In the previous study, the authors developed a mathematical model for simulating phenomena in the CL-furnace. The model consisted of 3 modules, electric field analysis, heat and fluid flow analysis and the particle tracking method. In this study, the model was partially modified: k -E. model was adopted, and the effects of various conditions, such as furnace shape (including accretion) and scale, electrodes configuration, immersion depth of electrodes, and thickness of slag layer, were evaluated. And the optimum design and operating conditions were discussed.IntroductionUnder the recent environmental restriction, advantageous features of the Mitsubishi process have attracted much attention. The process uses 3 furnaces connected by launders. Mixture of matte and slag formed in a smelting furnace flows continuously to a slag cleaning furnace (CL-furnace), where the matte is separated from the slag. The matte is continuously siphoned out to a converting furnace and converted to blister copper. The slag overflowed from the CL-furnace is discarded. Because the slag contains about 0.6 % copper, improving slag/matte separation efficiency and decreasing copper loss make a great profit. Moreover the process requires a large amount of electric energy, so reduction of electric power consumption brings in enormous benefit.The objective of this study is to optimize the design and the operating conditions of the process, especially the CL-furnace. This will be achieved by developing the mathematical model and clarifying relations between the design or the operating conditions and various phenomena in the furnace. Fig. 1 shows an outline of the CL-furnace. The mixture entering through an inlet is separated to slag layer and matte layer . In order to maintain the temperature of the melt at a predetermined level, 6 electrodes are immersed into the lag and Joule's heat is generated by 3-phase alternating current flowing."

Jan 1, 2000

By Hans Jürgen Maier, Hans-Bernward Besserer, Gregory Gerstein, Florian Nürnberger

The formation and development of voids in both the single-phase ferritic steel DC04 and the dual-phase ferritic-martensitic steel DP600 are discussed. Various mechanisms and kinetics of void formation are considered regarding the influence of dislocation glide, precipitates and other parameters. Different characteristic locations in the microstructure are investigated at which strain concentrations during plastic deformation can occur and cause the formation of voids and microcracks. For the specimen preparation ion slope cutting is applied. Voids and cracks revealing ductile damage are analyzed by Scanning Electron Microscopy (SEM). Stress concentrations in consequence of plastic deformation could be shown by extinction contours on images recorded by Transmission Electron Microscopy (TEM).

Jan 1, 2015

By Xiaobing Yang, Abhishek Lahiri, Animesh Jha

"In the FFC-Cambridge process, the cathodic dissociation of oxide and CO/CO2 production on carbon anode is the basis for metal production in a CaCl2 bath. By using an inert intermetallic anode, the CO2 evolution can be eliminated altogether with acceleration in the electro-reduction kinetics. At present the process suffers from slow reduction kinetics of TiO2 to Ti metal, which can be enhanced significantly by the incorporation of alkali species in the TiO2 pellet at the cathode and in the CaCl2 bath in the presence of an intermetallic inert anode. Nearly full metallization with greater than 99% of Ti metal containing 1500 ppm of oxygen is possible to achieve in less than 16 hours of electro-reduction. Analyses of phase composition and the microstructures morphology in fully metallized pellets revealed the presence of localized solidified Ti layer, indicating that fast reduction process also involved formation of liquid phase as middle stage reaction. In addition, in situ creation of porosity and maintain higher current level during electrolysis process were two key factors to fully reduction of TiO2.IntroductionDuring cathodic dissociation of TiO2 in a CaCl2 bath and anodic evolution of CO2 on a carbon anode, which is the basis for the FFC Cambridge process [1], the rate of metallization slows down due to the formation of CaTiO3 at the reaction interface. Calcium and alkaline earth perovskites are known for their poor electrical conductivity which adversely affects the overall electro-reduction. One of the ways to increase the porosity is via the addition of polyethylene precursors in the pellet or by directly starting from perovskite [2, 3]. The experimental evidences shown in the literature confirm although the speed of reaction increases, but a complete or near complete metallization is not possible by enhancing the in-situ porosity alone, as the insulating perovskite is very slow to decompose under the equilibrium that prevails in the cell. Plethoric evidences on carbon anode show with the current decrease gradually, and finally stabilize at a very low value between 0.2 and 0.4 A, which is a testimony of the presence of perovskite insulating barrier in the current path. Our aim in this paper is to demonstrate the mechanism of enhanced electro-reduction when alkali ions are present in the oxide pellet at cathode and in the bath. We also show for the first time the use of an intermetallic anode for Ti-metal production using the FFC Cambridge process."

Jan 1, 2009

By Du Sichen, S. Seetharaman, Wei Liu

"The viscosities of two-phase mixtures are of great importance in the modelling of the fluid flow in metallurgical processes. For example, in steel making and refining, the intimate mixing of metal droplets in the slag phase requires a consideration of the effective viscosities for the mixture. The present work was aimed at an understanding the phenomena underlying the viscous flow in a two-phase mixture with widely differing viscosities.Emulsions of silicone oils of known viscosities (345mPa.S and 1010mPa.S at 293K) with small amounts of water evenly distributed in the same were prepared by subjecting the mixture to uniform stirring using a magnetic stirrer. The viscosities of these emulsions were measured at constant temperature by rotating cylinder method using Brookfield Digital Rheometer. The uniformity of the preparation of the emulsions was confirmed by the reproducibility of the results. Th7 measured viscosities were generally found to be independent of the torque under the experimental conditions so that the two-phase mixture could be considered as a Newtonian liquid. The variation of viscosities with temperature and the effect of addition of a surface-active substance were also studied in this work.The measured viscosities were found to be· higher than those of both pure water and silicone oil. The experimental viscosities were found to increase with increasing concentration of water. The influence of surface tension on the viscosities was examined by adding surfaceactive agent to the mixtures. The result is discussed and compared with theoretical models developed by Einstein, Taylor and Oldroyd."

Jan 1, 2000