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By E. Salinas-Rodriguez, J. Hernández-Ávila, E. O. Ávila-Dávila, A. Romero-Serrano, M. Perez-Labra, G. Juárez-López

"Single phase rubidium jarosite was synthesized by precipitation from aqueous solution. X-ray diffraction and SEM-EDS analyses showed that the synthetic rubidium jarosite formed in subspherical particles with an average particle size of about 35 µm. The chemical analysis showed an approximate composition of Rbo9432Fe3(SO4)2 1245(OH)6. The decomposition behaviour of the jarosite in terms of solution pH was thermodynamically modeled using FACTSage by constructing the potential-pH diagram at 298.15 K. The E-pH diagram showed that the decomposition of jarosite leads to goethite (FeOOH) together with Rb+ and SO42- ions. The experimental decomposition of the Rb-jarosite was carried out in alkaline solutions with five different Ca(OH)2 concentrations. The decomposition process showed an ""induction period"" followed y a progressive conversion period where the Rb+ and SO42- ions formed in the aqueous solution. In contrast, calcium was incorporated in the solid residue and iron was transformed into amorphous ferrihydrite. The kinetic analysis showed that this process can be represented by the unreacted-core chemically controlled model. The reaction order with respect to Ca(OH)2 is 0.4342 and the calculated activation energy is 98.70 kJ mol-1. IntroductionJarosite type compounds are hydrous sulfate minerals containing alkalis and ferric ions, MFe3(SO4)2(OH)6, where M can be H3O+· Na+, K+, Rb+, Ag+, NH4 +, Tl+, ½ Pb2+ or ½ Hg2+. Jarosite-type compounds were formed by the natural ""in situ"" oxidation of pyritic ores leading to the replacement of the original iron sulfides and iron oxides (Dutrizac and Kaiman) [1]. The great interest in jarosites is due to its ability to eliminate or diminish the iron concentration of the acid leach solutions produced in the hydrometallurgical zinc process, with relatively low losses of divalent metals such as Zn2+, Cd2+, Cu2+ or Co . However, the losses of the metal values demand a careful study of the conditions under which the jarosite compounds are formed together with their chemical properties."

Jan 1, 2012

By Xuerong Wen

The oxidation behavior of TiAl3 intermetallics was investigated as a hnction of time at 1273K in pure dry oxygen. The oxidation experiments were carried out using TGA method. The oxidation scales were analyzed using SEM, EDS and X-ray diffraction methods. The structures of oxides formed at the different oxidation times were analyzed. The mechanism of oxidation of TiAl3 intermetallics was discussed.

Jan 1, 1998

By R. Cavanagh

Studies relating to the fixation of sulfur by reaction of 4 to 8 mm diameter cylinders of calcined limestone or dolomite with high strength sulfur dioxide in the temperature range 880°C to 1020°C were undertaken. Dolomites are far superior in sulfate capacity and reactivity than dense limestones even at high strength SO2. The sulfation reaction was first order with respect to SO2 concentration below 100 percent. Zero reaction rate at 100 percent SO2 concentration indicates that sulfate was the exclusive reaction product and that sulfite had no role in the reaction. At relatively low SO2 concentrations gaseous diffusion through the reaction product layer has a marked effect on the rate. As SO2 concentrations were increased up to 100 percent more complex rate controlling mechanisms unfold. By sectioning partially reacted dolomitic limestone pellets a moving interface was observed. Reaction ceased because of pore plugging for dense non-porous limestones at 30% conversion. With dolomitic material virtually complete sulfation of the calcium was observed. S.E.M. analysis showed that the average atom ratio Ca:S was 1.01, thus supporting the argument that little if any of the magnesium was sulfated.

Jan 1, 1996

By Daudi R. Waryoba

Keywords: Wire Drawing, OFHC Copper, Recrystallization, Orientation imaging Microscopy (OIM), Texture inhomogeneity Textural inhomogeneities have been investigated in oxygen free high conducting (OFHC) copper wire drawn at room temperature to a true strain of 2.31, and isothermally annealed at 250°C and 750°C for annealing times ranging from 10 s to 1 hr. Local orientations were mapped by means of orientation imaging microscopy (OIM). The microtexture of the drawn wires showed a strong <111> + weak <100> duplex fiber texture at the inner core, whereas the mid and surface regions had a comparatively weak texture. Annealing at 250°C resulted into a recrystallization which originated from the mid section, proceed towards the surface regions and ends in the inner core. Recrystallization resulted into a strong<100>+weak<111> duplex fiber texture. A similar textural inhomogeneity was observed during short annealing at 750°C. However, prolonged annealing gave rise to abnormal grain-growth that proceed from the inner core to the outer surfaces with a dominant <111> fiber component at the inner region and mixed components of <111>, <100>, and <112> at the outer surfaces.

Jan 1, 2005

By C. Acuna

The standard procedure of fire refining consists of sulphur removal via air injected through tuyeres, arsenic slagging via soda-lime flux and oxygen reduction by air or oxygen deficient air or a steam fuel mixtures. The use of porous plugs to stir with an inert gas has been mainly considered as a surface renewing agent that increases the product quality and shorten the refining cycle. In the present study the effect of the bottom stirring by nitrogen gas injection through porous plugs for the treatment of the crude copper in the range of 400-150 ppm sulphur, 3,000?2,000 ppm arsenic and 14,000-7,000 ppm oxygen content was investigated. The combined effect stirring-reducing, by the use of air or a steam fuel mixtures through tuyeres for oxygen removal, follows a kinetics of first order where the constant, K, can be represented by the following polynomial expression: K = A .* R2 + B * R + C Where A, Band C are constants that depend on the nitrogen flow rate and R is the air-fuel ratio or the steam-fuel used in the reducing step. Depending on the optimization of the flow of nitrogen and the air-fuel or steam-fuel mixture and only if just the oxidation, complexing and reducing steps are considered, the process cycle might be shortened by 45%.

Jan 1, 2003

By Fiona J. Stevens McFadden, Gregory J. Hardie, Mark P. Taylor, William Uru

"Over 20 million tonnes of installed aluminium smelting capacity exists worldwide, with smelter energy con.sumption in the range 14-17 kWh/kg aluminium. In terms of the reduction cell technology itself, the lowest sustained energy consumption is just below 13DC kWh/kg, or 50% energy efficient.For 15 years Comalco Aluminium Ltd. in Australia has been engaged in developing and testing reduction cells that use a refractory hard cathode, composed of a TiBif carbon composite coating over a carbon cathode. This technology has the potential to reduce energy consumption significantly while simultaneously increasing the life of the cells, which is currently limited by wear rate of the conventional carbon cathodes used throughout the worldIntroductionThe successful development of an aluminium wettable cathode technology affords the opportunity to the cell designer and smelter operator to fundamentally change the physical operating characteristics of the Hall-Heroult process. With this revolutionary capability in hand, published papers and patents have indicated that the technology may be exploited in a wide variety of ways to improve the economic performance of aluminium smelting process. Comalco has been developing refractory hard cathode technology for more than 15 years and has been exploring a number of ways that the technology may be commercially applied in a smelter operation [l]."

Jan 1, 2000

The standard procedure of fire refining consists of sulphur removal via air injected through tuyeres, arsenic slagging via soda-lime flux and oxygen reduction by air or oxygen deficient air or a steam fuel mixtures. The use of porous plugs to stir with an inert gas has been mainly considered as a surface renewing agent that increases the product quality and shorten the refining cycle. In the present study the effect of the bottom stirring by nitrogen gas injection through porous plugs for the treatment of the crude copper in the range of 400-150 ppm sulphur, 3,000-2,000 ppm arsenic and 14,000-7,000 ppm oxygen content was investigated. The combined effect stirring-reducing, by the use of air or a steam fuel mixtures through tuyeres for oxygen removal, follows a kinetics of first order where the constant, K, can be represented by the following polynomial expression: K = A * R2 + B * R + C Where A, Band C are constants that depend on the nitrogen flow rate and R is the air-fuel ratio or the steam-fuel used in the reducing step. Depending on the optimization of the flow of nitrogen and the air-fuel or steam-fuel mixture and only if just the oxidation, complexing and reducing steps are considered, the process cycle might be shortened by 45%.

Jan 1, 2003

By Kazuaki Mita

There are various intermetallic compounds in the Zn-Fe system. We synthesized them at about 673K. A specimen was examined chemically and X-ray diffraction was applied to ensure the formation of intermetallic compounds. Material containing two phases was placed in a Knudsen type effusion cell and the mass spectrum studied to evaluate the vapor pressure of zinc. The thermodynamic properties of intermetallics was then evaluated through measured intensity.

Jan 1, 1999

By M. Soltanieh

The liquidus surface? and tie-lines in the nickel-cobalt-sulphur ternary system have been determined between 1<273-1573 K. The experiments were conducted by equlibrating the liquid sulphide with the metallic alloy phase. The liquid sulphide phase was sampled and chemically analyzed. The alloy was analyzed by electrol} microprobe. Combining the present results with the.avai1abl~ literature data, the thermodynamic properties of this system were calculated.

Jan 1, 1998

By George P. Demopoulos

n this study we have sought to highlight the critical linkage between individual reaction kinetic parameters (usually determined in small bench scale experiments) and large continuous reactor performance by focusing on the industrially significant zinc pressure leach process. To this end a comprehensive mathematical model previously developed for the description of this process was employed. In this paper we have examined in particular how small variations in key kinetic parameters impact on the autoclave&apos;s performance, i.e. attainment of autogenous steady-state temperature, zinc conversion and solution chemistry. The reaction parameters studied were: (i) stoichiometry of the marmatite leaching reaction; (ii) the activation energy of the same reaction, E,; (iii) the rate constant of the ferrous to ferric oxidation reaction, k,; and (iv) the apparent equilibrium constant for ferric precipitation, K,. This parameter sensitivity analysis was done under no oxygen mass transfer control limitations. Model predictions were found to be more sensitive to the kinetic parameters under certain conditions than others. The most dramatic finding was the one related to the small amount of sulfate produced during marmatite leaching. In connection to this it was found that the small percentage (< 5 %) of sulfate produced enhances the autothermal operational stability of the autoclave. The need for accurate kinetic parameter determination under conditions similar to those encountered in industrial zinc pressure leaching was demonstrated.

Jan 1, 1999

By H. J. Garcia

Biodegradation of cyanide by microorganisms isolated from solids previously exposed to cyanide has been investigated. Initial sodium cyanide concentration was 300 ppm at pH 10.5. The kinetics of biodegradation were found to be first order with respect to cyanide concentration, and the overall reaction rate constant is k = 0.102 day-1. The activation energy and the frequency factor were determined to be { A }Ea = 5.45 Kcal/mol and A = 1.28 x 10-2 sec-1, respectively. Based on these values, thermodynamic properties of an intermediate activated complex were assessed. All tests resulted in cyanide concentrations less than 0.1 ppm in about 35 days at 250C, whereas at 350C the time of biodegradation to reach this cyanide level was 30 days. Kinetic data were also established to relate biodegradation to amount of inoculum. The maximum theoretically-attainable rate, Vm , and the optimum amount of inoculum, K , were determined to be 4.8 x 10-4 M NaCN/day and 7.5 % of amount of inoculum. With respect to the mechanism of biodegradation, cyanide was shown to decompose to carbonate, bicarbonate and ammonia. Titrimetric analyses revealed concentrations of 5.6 x 10-3, 4.8 x 10-3 M, and 70.2 ppm for carbonate, bicarbonate and ammonia, respectively. The average cell population was determined to be 3.75 x 108 cells/mL.

Jan 1, 1994

By R. Padilla

In most of the Chilean copper and gold concentrates, arsenic is present mainly as enargite, Cu3AsS4, which at the conventional roasting or smelting temperatures decomposes liberating arsenic as gaseous compounds. The objective of this investigation was to study the decomposition reaction of enargite in an inert atmosphere in the range of 500 °C - 750°C. The results obtained indicated that the decomposition begins at about 525 °C. Two distinct regions in the temperature dependence of the decomposition rate were observed: a low temperature region between 525 °C to 650°C and a high temperature region between 650 °C to 725 °C. The X-ray diffraction analysis suggests that the decomposition of enargite occurs through the formation of intermediate tenantite, according to the following sequential reactions: 4Cu3AsS4(s) ? Cu12 As4S13(s)+ 3/2S2(g) Cu12 AS4S13(s) ? 6Cu2S(s) + 2As2S3(g) + 1/2S2(g) The decomposition kinetics was analyzed by using the model for a topochemical reaction of spherical particles: 1-(1-X) 1/3 = kt, which represented well the data. Apparent activation energies of 113 kJ/mol and 60.5 kJ/mol were found for the low and high temperature regions, respectively.

Jan 1, 1999

Physical and chemical methods were investigated to tower thorium levels in Eneabba Ilmenite from the natural levels of 180-500 ppm to give Becher Process synthetic rutile with less than 100 ppm thorium. Chemlcal treatments, but not physical separations were successful. A pilot plant trial of a sodium hydroxide leach (25M NaOH at 75°C and 40 wt% solids for Ih) followed by a sulphuric acid leach (3M H2S04 at 90°C and 60 wt% solids for 211) confirmed that thorium could be removed to below 100 ppm. However, the activity of the ilmenite was not lowered to the same extent

Jan 1, 1996

By Yanlong Li, Lifeng Zhang, Ying Ren

In this work, a multiphase mathematical model for the fluid flow in argon-stirred steel ladles was established and validated by experimental measurement of wood's metal. Alloy dispersion in the molten steel was calculated. The melting and mixing of alloy was faster with smaller size of the alloy particles, larger superheat and bigger slip velocity. The current mixing time is approximately 300 s with 30 mm alloy diameter and 91.5 K superheat.

Jan 1, 2014

By Liwen Hu, Jianxun Song, Hongmin Zhu, Qiuyu Wang, Shuqiang Jiao

The subchloride titanium was prepared by sponge titanium and titanium tetrachloride in the CaCl2 at 1173 K. The species were detected are mainly titanium dichloride, and the average valent in the melt are 2.05. The accurate equilibrium constants were obtained for the reaction 3Ti2+ = 2Ti3++Ti after the accurate activities of titanium chloride were evaluated with emf method, and the observed deviations from ideal behavior are discussed.

Jan 1, 2015

By Y. Huang, P. B. Prangnell

"An Al-0.1Mg alloy was firstly deformed at room temperature by ECAE to a true strain of 10, where a steady state deformation was established and further processing had little effect on grain refinement. The ECAE samples, with an average grain size of ~0.55µm, were then compressed in a channel die at 77K- 473K to various reductions. Microstructures were characterized by electron backscatter imaging and EBSD in a FEGSEM. Grain refinement to the ECAE submicron structure occurred during deformation at cryogenic temperatures of 77 – 213K, whereas coarsening took place during deformation at elevated temperatures. A steady state deformation was observed at all temperatures where a constant grain structure was developed and maintained upon further straining due to dynamic recovery. The mechanisms of dynamic recovery during steady state deformation at cryogenic temperatures are discussed.IntroductionSevere deformation processing (SDP) has been successfully used to produce submicron grain structures, and in some cases nano-scale crystallite sizes, in a wide range of alloys. However, the rate of grain refinement becomes increasingly inefficient at high strains as a steady state grain structure is approached [1-3]. Steady-state grain sizes have also been reported in other ultra-high strain deformation processes, like cryogenic ball-milling [4]. There is thus a minimum grain size achievable in a material by a given SPD process under constant deformation conditions.It is well documented that a steady state subgrain size is observed in warm deformation of metals due to dynamic recovery (e.g. [5]). In severely deformed alloys a constant grain size at ultra-high strains has similarly been attributed to dynamic recovery [1-3]. Mechanisms have been proposed, for rapid deformation induced grain growth including stress driven boundary migration and breakaway from solute pinning [2]. However, as pointed out by Humphreys et al. [2] the restoration processes are currently poorly understood, particularly at low temperatures, where the boundary migration rates required to maintain a constant grain size are orders of magnitude higher than can be satisfactory explained from diffusion controlled migration. Similar to the subgrain size, the steady state grain size obtained during SDP is generally related to the temperature compensated strain rate [2, 6]. Thermally activated restoration processes are thus expected to be suppressed by lowering the deformation temperature and a smaller steady state grain size can be achieved."

Jan 1, 2012

By Dinesh Goyal

Industrial fly ash from (electro static precipitator) was mixed with soil at different levels on v/v basis for raising of pulpwood tree species. In field trials conducted on degraded soils increase in the plant growth of Eucalyptus tereticornis, Acacia auriculiformis and Casuarina equisetifolia by 10 %, was observed during the initial six months after plantation at 18-24% (v/v) fly ash concentration which was at par with chemical fertilizer treatment. Level of As, Se and Mo in flyash was 6.2, 3.6 and 4.0 ppm respectively. The radioactivity analyses 40K, soil and 28 fly ash showed that the activity levels of gamma emitting radionuclides K, Ra, Ac were within the permissible limits and mixing of fly ash with soil at tested concentration would have no deleterious effects. Available Co, Cr, Ni and Cd in rhizospheric soils were below detection limit. Fly ash at 10-20 % level (v/v) was also found to be a good potting mix material in forestry nurseries in terms of improving biomass production by 20 %, when tested in nursery seedlings of Eucalyptus tereticornis. Nursery addition of fly ash in soil decreased soil dehydrogenase activity and the soil bacterial population was negatively affected. These results indicate that use of fly ash in forestry sector involving nursery and plantations as a soil amendment agent upto 10-20 % v/v is a gainful utilisation of fly ash.

Jan 1, 2002

By Valery Kaplan

Sulfur emission in the form of SO2 in flue gases is one of the most serious atmospheric pollutants associated with coal combustion and non-ferrous metals production. The carbonate eutectic method for removing SO2 from flue gases at 723–923 K was initially proposed in the 1970s but despite its great efficiency (SO2 concentration in the flue gas after purification reached 0.003 volume %), it could not be implemented by industry due to the complexity of the carbonate melt regeneration stage. Earlier we proposed a method suited to coal-firing power stations where the melt was regenerated using CO as a reducing agent. However, most metallurgical plants do not use coal and therefore lack a large source of CO. Here we propose a method for removing sulfur from the carbonate eutectic melt by purging it with natural gas or a natural gas/air mixture, which are available in the vast majority of metallurgical plants. This reaction leads to the reduction of sulfate to H2S gas that leaves the melt. The experiments we conducted show that nearly complete sulfur removal from the melt is possible at 823 K and that the reaction rate is sufficiently high for a large scale process. One can foresee that this carbonate melt-based SO2 removal technique may become a practical and economically attractive method for limiting sulfur emission to the atmosphere from non-ferrous metallurgical processing plants.

By Li Yuhai

Kinetics of non-isothermal precipitate process and crystal growth of perovskite (CaO ? Ti02) phase in CaO-TiOz-Si02-AlP3-MgO system were studied. The experimental results show that the relative volume fraction can be described by the equation given by K. Matusita et at. and the experiential expression of average crystal radius was obtained. The particle coarsening in non-isothermal process has important effects on the crystal growth of perovskite phase.

Jan 1, 2000

By Yanhui Liu, Xuewei Lv, Chenguang Bai

A thermodynamic model for determining the surface tension of molten slag by considering the surface tension and molar volume of the pure oxide component, and their ionic radii was extended to the slag bearing high TiO2 (varying from 80 to 67%) at 1973 K. The iso-surface tension curves for the FeO-TiO2-Ti2O3 ternary system at 1973 K are almost parallel to the FeOTi2O3 line. TiO2 plays a role of surface-active solute, and its surface-active effect is attenuating with increasing the TiO2 content. The iso-surface tension curve shifts away from the TiO2 corner, indicating that the surface tension of the ternary slag decreases along with the addition of SiO2. The reasons include the addition of SiO2 with lower surface tension and the decrease of the total ion moment at the surface. Both CaO and MgO can bring about that the iso-surface tension curve shifts towards the TiO2 corner, indicating that the surface tension of the ternary slag increases along with the addition of CaO or MgO. CaO has a more pronounced effect on increasing the surface tension of the ternary slag than MgO at an equimolar amount addition. The increase of the surface tension results from both the compositional change and the variation of the slag structure.

Jan 1, 2015