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By Terence Makanyire, Animesh Jha

The dissolution and chemical properties of vanadium, zirconium, and niobium in rutile lattice are analyzed by comparing the octahedral site preference energies, with respect to Ti4+ ion in the solvent phase. The oxides are often present in rutile lattice and interfere in achieving the quality of pigment grade TiO2 due to favourable Gibbs energy for dissolution in the solvent rutile matrix. Binary mixtures of V2O5 { TiO2; Nb2O5 { TiO2 and ZrO2 { TiO2 with compositions of 80, 85, 90, 95 and 97 wt% TiO2 were made, pelletized and sintered at 1100 °C for 24 hours. The solidsolution mixtures were then cooled and leached in 2M NaOH for 3 hours at 60 °C. Phase and lattice parameter characterizations, and microstructural and compositional analyses were then carried out using X-ray diraction and SEM/EDX, respectively. The leachates were analysed by Atomic Absorption Spectroscopy (AAS), using which the solute dissolution model for oxides were investigated.

Jan 1, 2014

By F. J. J. van Loo, J. K. Kivilahti, M. Paulasto

"Activation mechanism and interfacial reactions in brazing of ShN4 with different AgCuTi filler alloys has been investigated thermodynamically and experimentally. During brazing the AgCuTi filler alloy is divided into two liquids Ll and L2, where the (Cu,Ti)-rich liquid L2 gathers at the ShN4 interface and reacts with it. The concentration of Ti in L2 is high, but due to the strong attractive interaction between Cu and Ti, the activity of Ti in L2 is considerably low. In reaction between ShN4 and Cu-containing brazes a Ti-Cu-Si-N compound is typically formed at the interface. In absence of Cu, in joints brazed with AgTi based filler alloys, extremely Ti-rich solution reacts with ShN4 and as reaction products TiN and TisSh[N] are formed. IntroductionAdvanced ceramics like silicon nitride are increasingly used as structural components in demanding applications as well as in electronics industry. Complex, multicomponent structures for engineering applications generally require interconnections and therefore joinability of ceramics largely determines the possibilities of metal-ceramic structures to enable demanding functions. Brazing with active filler metals, most of which are based on the Ag-Cu-Ti system, has been commonly employed for joining of ShN4 to other ceramics and metals. The interfacial microstructures formed when ShN4 is brazed with Ag-Cu-Ti braze alloys have been discussed in several recent studies [1-7]. However, some inconsistencies exist in the reported results. The formation of layers of TiN and titanium silicides, possibly TisSh, next to the ShN4 has been reported in several studies [1-5], while in another investigation, a layer of an orthorhombic TiSi- Cu-N phase was found beyond the TiN layer [6]. In few investigations the thermodynamics of the ShN4-Ti system has been considered, but no detailed thermodynamic analysis of the chemical interactions between the braze and ShN4 has been provided. In order to resolve which chemical reactions are possible under various joining conditions and thereby to be able to control the brazing of ShN4 the reactions in brazing has to be studied using both microstructural and thermodynamic analysis."

Jan 1, 1996

By Mala Nath, Atjit Mallick, Asheesh Kumar

"The present research work is aimed to focus on the development of chemically stable light weight microporous carbonaceous material, such as activated charcoal incorporated either with titanium n-butoxide, titanium diisopropoxide bis(2,4-pentanedionate), vanadium 2,4-pentane-dionate or zinc 2,4-pentanedionate having varying wt% of the metal (2-8%) using ethanol as solvent at 40--50 oC followed by calcinations at 100, 150 and 200 cC, except the samples with titanium diisopropoxide bis(2,4-pentanedionate) which are calcinated at 80 oC. Atomic absorption studies along with FESEM revealed that the maximum incorporation of metals (Zn, V and Ti) in activated charcoal was observed with 4 wt% of zinc 2,4-pentanedionate calcinated at 150 oC , 4 wt% of vanadium 2,4-pentanedionate at 100 oC, 2 wt% of titanium n-butoxide at 100 oC and 2 wt% of titanium diisopropoxide bis(2,4-pentanedionate) at 80 oC, and equilibration time of 20-24 h was used in each case. Hydrogen sorption behavior in these carbonaceous materials has also been studied at 77.4 K and low pressure up to I bar. The highest hydrogen uptake obtained was 1.45 wt% (164.5 cm3 (STP)/g at P/Po = 1.0) for activated charcoal incorporated with 4 wt% of zinc 2,4-pentanedionate calcinated at 150 oC.IntroductionTwo of the major challenges for humanity in the next twenty years are the shrinking availability of fossil fuels, the global warming and potential climate changes that result from their ever-increasing use. So it is necessary to fmd an energy source that is convenient, flexible and controllable. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store hydrogen in electric power plants and vehicles. Hydrogen storage is the bottleneck for the breakthrough of hydrogen as energy carrier in automotive applications [1]."

Jan 1, 2012

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of873 OK is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composItion formed under roasting of concentrates with particle sizes less than 0.02 J..lm (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CufeSz) each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forehamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By E. T. White, Dean Ilievski

"The population balance is one of the basic relations for analysing particulate mineral processing operations. It is an exact relation. The principles of the population balance are reviewed and applications in the minerals industry discussed.IntroductionMathematical modelling has proved to be a very successful approach for improving the design and performance of mineral processes, particularly since the availability of computers to handle the complexity usually necessary to give a useful model.Mineral processes almost invariably involve particles, as either solid fragments, liquid drops or bubbles. Process performance usually is highly dependent on the behaviour of these particles. In modelling particle behaviour, the basic relation to be used is the population balance. This paper discusses the role of the population balance and the range of its applications in minerals processing.The Population BalanceThe population balance was developed for demographic studies, ego predicting the change in the population (numbers) of, say, school children between one census and the next. The first sustained application to the processing industries appears in the 1960s for crystallization. However it was recognised almost immediately that it had application to all particulate processing."

Jan 1, 1996

By Florian Kongoli

"Lime ferrite" slag with limited silica content has proven to be a valuable choice in the modem processes of copper smelting and converting due to several advantages that this slag offers compared to classical silicate slags. Nevertheless the liquidus surface of this slag has been experimentally measured only at low oxygen potentials such as in equilibrium with iron or near it and in air. Although most of the smelting and converting processes that use this slag occur at intermediate oxygen potentials, the liquidus surface of this slag is not known at these conditions and the effect of oxygen potential and silica has not been correctly understood. This has brought some confusion in literature as well as in the industrial practice. In this work the liquidus surface of the calcium ferrite slags has been quantified by the means of a new thermophysicochemical model and a new type of liquidus surface diagrams which are very convenient for any industrial process that uses calcium ferrite slags. These diagrams can be easily used to select the lowest liquidus temperature of calcium ferrite slags at a minimum cost and can help design several fluxing strategies in copper smelting and converting processes. The effect of the oxygen potential and silica is also quantified and important industrially related conclusions are drawn.

Jan 1, 2003

By Fumitaka Tsukihashi

Increasing amounts of steel scrap are being used as resources for steelmaking. Therefore. there has been a growing interest in the removal of handful tramp elements such as antimony, zinc, tin, arsenic, bismuth, lead and copper from the molten steel. The problem that should be solved is the economic removal treatment of residual tramp elements in the steelmaking processes and the production of high quality steel by reducing the effect of the contaminated tramp clements and satisfying the environmental regulations. In this paper, the available thennodynamic data of the residual tramp elements in the molten steel are summarized and the possibility of the removal of residual tramp elements from the molten steel is thcnnodynamieally estimated.

Jan 1, 2003

By René Winand

A new process was studied at large laboratory scale at Université Libre de Bruxelles, under contract with Metallurgie Hoboken-Overpelt. A two cathodes (1m long ; 0.2 m high) channel cell was used at 2000 A/m2, with an electrolyte flow rate up to 1.8 m/sec. The main results may be summarized as follows : cathodes are electro¬refined grade in analysis ; metallographic structure and surface roughness are kept under control up to 1.3 cm (one side deposits) ; silver in cathode is controlled by CI and Br ions in solution ; organics must be used at very low concentrations (in the range of 0.1 mg/1, with a consumption of about 0.01 mg/lh).

Jan 1, 1987

By R. C. Hubli

A chemical model has been developed to investigate the dissolution of sulphide minerals in brine solutions containing copper and iron chlorides. The model has been employed to study the dissolution .of synthetic NiS using different initial concentrations of Cu(II), Cu(I), Fe(III) and temperature. The speciation of copper with particular reference to the formation of hydroxy-chlorides as a function of total chloride and H+ has been computed. The model predictions are in agreement with experimental results. It has been found that addition of Fe(III) results in the maintenance of a high Cu(II)/Cu(I) ratio leading to enhanced rates of dissolution and suppresses the loss of Cu(II) due to the formation of hydroxyl-complexes.

Jan 1, 1997

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 Laurence Whitty-Léveillé

Proper handling of the radioactive fraction associated with the production of rare earth elements (REEs) in the mining industry is essential for a sustainable environment and human health. Actinides, such as uranium and thorium, have similar chemical properties to REEs, and are often co-dissolved in current hydrometallurgical processes. This causes radioactive contamination of the infrastructure through the extraction cycle. The present study optimizes, through experimental design, a sequential leaching procedure with Na2CO3/NaHCO3 and HCl for the rapid and selective dissolution of REEs and actinides. Optimization focuses on the main operating parameters (time, temperature, and concentration); different types of minerals, REE composites, and ores; on achieving maximal leaching yield; and on minimizing dissolution of the gangue metals (Fe, Si, and Ca). The final sequential procedure was rapid (1 h), effective, and led to the segregation of Th, U, and REEs with limited dissolution of the gangue metals.

By Robert M. Leary

The Kennecott Utah Copper smelter operates two Outokumpu flash furnaces: a smelting furnace for production of high-grade matte and a converting furnace for production of blister copper. Flash furnaces typically possess several characteristic features that must be considered in process control development such as long lag times associated with settler volume, non-linear input and output responses, large process gains, and unmeasured disturbances. Additionally, the Kennecott smelter possesses certain unique characteristics which must be considered such as single mine concentrate source, limited concentrate blending capacity, and feed preparation facilities that inevitably cause significant lags between furnace control parameters and manipulated set points. In order to improve furnace control and on-line time, a process control system was developed to address these issues. The feed forward control module provides predictive control and operates in response to furnace feed input changes. The feed back control module provides responsive control and is based on furnace output deviations. To provide regular feed back information to the control room supervisors, new sampling methods were developed which provide the operators with molten metal and bulk material samples at regular intervals to provide information for control. The control system was implemented on the Flash Converting Furnace in May 1999 and on the Flash Smelting Furnace in August 1999.

Jan 1, 2000

By Florian Kongoli

Slags and fluxes are important interchangeable dimensions of pyrometallurgical processes. They can increase the efficiency of the smelting, converting and refining processes and improve the quality of the final products. A good slag should have appropriate physicochemical properties such as low liquidus temperature, optimal viscosity, maximum ability to attract undesirable elements, minimum potential of attracting valuable elements, etc .. A good flux, on the other hand, when properly used, can considerably improve the physicochemical properties of the slag since by modifYing its chemical composition it could decrease the liquidus temperature, improve viscosity etc.. Consequently, the choice of a good slag and the corresponding fluxing strategies has become indispensable in most of industrial processes. However, the properties of multi component slags as well as the effect of several fluxes are known only empirically and confusion exists in the literature and in the industrial practice. In today's reality of frequent changes in the composition of raw materials and that of the fluxes themselves, in the existing or new developing technologies, the quantification of the thermophysicochemical properties of multicomponent slags and the effect of fluxes becomes indispensable. This paper reviews some of the work carried out by the author's group during the last ten years on the quantification of the thermophysicochemical properties of multicomponent slags and on the effect of fluxes in several smelting and converting processes in close relation to their individual characteristics. Several examples have been given in order to demonstrate the fact that when taken outside the context some fluxes can become in fact anti-fluxes.

Jan 1, 2003

By Ryosuke O. Suzuki

A new cell concept for calciothermic reduction is proposed in which the titanium dioxide instead of TiCl4 is used as the raw material for reduction, Metallic calcium is needed as the reductant of a thermochemicaily stable oxide, such as TiO2. CaCl2, is selected as the solvent of Ca and simultaneously as the solvent of CaO. The reduction system consists of a single cell where both the reduction reaction and the electrolytic reaction for recovery of reducing agent coexist in the same molten CaCl2 bath. A few mol%Ca dissolves in the melt and gives the media a strong reducing power. Sufficiently deoxidized metallic titanium deposits and forms a slightly sintered granular sponge. Both mechanisms of the halide flux deoxidation and the electrochemical deoxidation work efficiently for these fine precipitates, The reducing agent is in situ recovered by electrolysis of CaO because the molten CaCl2 he a relatively large solubility for CaO Some cell designs and modifications are proposed for industrial applications.

Jan 1, 2003

By J. E. Dutrizac

A mineralogical study of a weak acid leach residue from the Clarksville zinc plant of Savage Zinc Inc. was carried out. The study focused on Pb and Cd as these elements most significantly impact on the environmentally acceptable disposal of the residue. The residue consists of major amounts of bassanite, zinc ferrite and various Zn-Pb-Fe-Cd silicate species. Also present are lesser quantities of PbSO4, sphalerite, Fe2O3 quartz, Mn-Pb-Fe oxides, SrS04, (Pb,Sr)SO4 iron gel-silica gel, jarosite and Ti oxide. The principal Cd carriers are the zinc ferrite, which contains up to 9.00% Cd and likely accounts for -45% of the total Cd content of the residue, and the various silicate species which contain up to 6.97% Cd and account for about 45 % of the total Cd. The sphalerite is a minor Cd carrier containing an average of 0.35 % Cd and accounting for -5 % of the total Cd; the other carriers contribute only trace amounts to the total Cd content. The major Pb carriers are PbS04, Pb-bearing silicates and Mn-Pb-Fe oxides. Minor proportions of the total 1.09% Pb content of the residue are carried by SrS04 and (pb,Sr)S04' Trace Ph carriers include the iron gel-silica gel, Fe-Zn-AI oxide and bassanite. The residue after the toxicity characteristic leaching procedure (TCLP) is mineralogically very similar to the initial weak acid leach residue; the amounts of calcium sulphate are approximately the same in the two products. The principal Cd and Pb carriers are also the same as those noted in the initial residue, except that some dissolution and reprecipitation of Pb-Sr sulphate takes place. That the residue fails the TCLP test is likely a consequence of the superficial dissolution of Pb and Cd from species such as PbS04 or Zn-Pb-Fe-Cd silicate.

Jan 1, 1995

By D. E. Larson

In cooperation with the National Institute of Environmental Health Science and the National Institute for Occupational Safety and Health the U.S. Bureau of Mines conducted grinding research on non-asbestiform tremolite. The goal of this effort was to prepare ground tremolite samples containing a considerable percentage of acicular grains with aspect ratios (approximately = 8um long with widths = 1 um) similar to those of asbestos particles suspected of causing cancer, Optical-and electron-microscopic examinations were used to monitor the size and shape of the grains in the ground products. Although customized milling techniques do have noticeable effects in producing acicular grains, the prismatic nature of fracturing in the non-asbestiform tremolites limited the number of acicular grains that could be purposely produced, and indicates that the likelihood of high concentrations of acicular particles occurring under normal mining and milling conditions is small.

Jan 1, 1991

By John M. Gaines

Lead concentrates from the Viburnum Trend in Southeast Missouri are sintered, prior to smelting, to bind the particles together, homogenize the feed, and reduce the sulfur content. About 20% of the sinter at some plants is classified as bad sinter. A total of 130 samples of good and bad sinters were studied by reflected light microscopy, scanning electron microscopy-energy dispersive analysis, and electron microprobe analysis to characterize their differences in mineralogy and textures. Good sinters consist predominantly of hardysonite, franklinite, lead silicate matrix, and large crystals of calcium-magnesium-iron silicate, together with minor amounts of lead oxides, lead-zinc silicate, metallic lead, specular hematite, magnetite, lead-iron-bearing zincite, and zinc-lead-magnesium-bearing wustite in a tightly intergrown mesh of crystals and with an evenly distributed porosity of about 15-20%. Bad sinters contain larger amounts of lead silicate matrix, galena, metallic lead, and lead oxides, but smaller amounts of hardysonite, franklinite, and calcium-magnesium-iron silicate, lack intimate intergrowth of the phases, and have lower (0-5%) and unevenly distributed porosity.

Jan 1, 1992

By Jerome P. Downey

In the thermal treatment of electric arc furnace (EAF) dusts, zinc is reduced, volatilized, and ultimately recovered either as liquid metal in a splash condenser or as solid zinc oxide in bag filters. During the process, the duet's chlorine and fluorine content also enters the gas phase and condenses as dross in the splash condenser or as salts which contaminate the zinc oxide product. Pretreatment of EAF dust by pyrohydrolysis appeared to offer a means of minimizing the duet's halogen content. The primary research objectives were to experimentally verify the technical viability of pyrohydrolysis and delineate the process parameters requisite for efficient halogen removal. To this end, representative EAF duet samples were secured and characterized by x-ray diffraction, scanning electron microscopy, and Mössbauer analyses. Specific- experimentation focused on the response of halogen extraction to variations in temperature, retention time, water vapor partial pressure, and various additives. The experimental results proved that 97 to 99 percent chlorine extraction and 80 to 85 percent fluorine extraction are consistently achieved when EAF dusts are blended with silica and roasted at temperatures of 850°C or greater in a furnace atmosphere of 75% steam (diluted by air). A statistical analysis further established that more than- a single optimal point exists, thus affording flexibility in parameter selection (e.g., by increasing temperature, the necessary retention time and additive concentrations are decreased). The findings substantiate the feasibility of pyrohydrolysis roasting in reducing the chlorine and fluorine in the EAF dust to a level that will obviate industrial concerns about halogen contamination. The end-product of the pyrohydrolysis procedure is a de-halogenated, self-fluxing calcine which can be directly charged to a plasma or flame reactor. The paper includes design parameters and flow diagrams illustrating the pyrohydrolysis process integrated with the plasma and flame reactor technologies.

Jan 1, 1992

By Bo Björkman

Four different arsenic containing dusts from the Boliden plant, Boliden mineral AB, Sweden have been examined. A kinetic study of the As elimination was performed in a laboratory scale roasting furnace for roasting furnace ESP dust and smelting furnace ESP dust. Characterisation and thermodynamic calculations were carried out to determine the mineralogy, and the stability of compounds in the dusts studied. The characterisation methods used were chemical analysis, X-ray diffraction analysis and microprobe analysis. It was found in the experiments that a high degree of As elimination was obtained for roasting fumace ESP dust and a low degree for smelting fumace ESP dust. Derived kinetic models are given. A prediction of the As-elimation for settling furnace dust and converter ventilation dust is presented.

Jan 1, 1994

By D. Raghavan

In recent years, the environmental issues related to the landfill shortage received considerable importance. Many polymeric solid wastes have high resistivity to chemical and biological degradation, and options are sought by which these wastes can be recycled and reused, or reduced in volume. The present study investigated the biodegradation of polyethylene by Aspergillus niger, and biodesulfurization of rubber by pure and mixed cultures of Thiobacillus thiooxidans and Thiobacillus ferrooxidans. The fungus, A. niger, was found to metabolize portions of polyethylene. Quantitative calorimetric measurements revealed that the amorphocity of the sample decreased during biodegradation. Removal of sulfur from synthetic rubber samples containing 2 to 15% sulfur, was studied in shake flask experiments and the associated oxygen consumption was studied in Warburg respirometers. The mixed bacterial cultures were more effective in the desulfurization of rubber samples than the pure cultures of T. thiooxidans and T. ferrooxidans. The data obtained in these studies may have far reaching consequence for the development of new effective processes regarding the remediation and management of discarded polymeric packaging wastes and car tire rubber materials.

Jan 1, 1993