Search Documents

By K. Osseo-Asare

Rate laws for the hydrogen reduction of metal ions are typically of the form: [r = -d[M(II)]/dt = k[M(II)]xPy2H] where k is an apparent rate constant, [M(II)] and PH2 represent dissolved metal concentration and hydrogen pressure respectively, while x = 0 - 1 and y = 0.5 - 2. Half-order dependences have been reported for some M(II)/H2 systems; however, no satisfactory explanations have been offered. In an effort to bridge this gap in our understanding, the published precipitation rate data (for M(II) = Cu(II), Ni(II), and Co(II)) are reviewed (with emphasis on the reported reaction orders) and compared with the corresponding but limited electrochemical polarization data. Based on the available literature on the electrochemical kinetics of the M/M(II) and H2/H+ systems it is demonstrated theoretically that, under certain conditions (e.g., in the presence of electron-conducting solids), the rate of the M(II)/H2 reaction can be expressed as: [-d[M2+]/dt = k[M2+]2/1P2/12H] It is concluded that electrochemical processes probably play an important role in the hydrogen reduction of metal ions, especially for systems that involve heterogeneous catalysis.

Jan 1, 2003

By Richard D. Hagni

The techniques of reflected light microscopy and cathodoluminescence microscopy are uniquely suited to the study of the products from many important industrial problems. Ref1 ected 1 ight microscopy provides the means to rapidly identify the mineralogy of an industrial sample, determine the abundance of each phase, and examine the mineral intergrowths or textures. Cathodoluminescence microscopy is a relatively new instrument that provides the means to cause many minerals to cathodoluminescence under the microscopy. The cathodoluminescence of a mineral allows it to be readily distinguished from other phases that differ in cathodoluminescence but are similar in optical properties. Cathodoluminescence microscopy is especially useful to detect cathodoluminescence minerals that are present in only small quantities. Reflected 1ight microscopy and cathodoluminescence microscopy have been successfully applied in studies of beneficiation products, prediction of beneficiation and leaching problems, phosphatic iron ores and mill products, pyrometallurgical products, roasted refractory gold-bearing sulfides, ceramic build-ups, electric arc furnace and smelter dusts, and other industrial products.

Jan 1, 1993

By Jewel Gomes

Produced water (PW) is salty water trapped in the reservoir rock and brought up along with oil or gas during production. It subsists under high pressures and temperatures, and usually contains hydrocarbons and metals. Therefore, it must be treated before being discharged to surface water. Different techniques are being used to treat PW through phase separations, system control and design, and chemical treatments. In this paper, we discuss our experimental results on treating PW through electrocoagulation (EC). The performance of EC was investigated for the reduction of chemical oxygen demand (COD) and metal ions. Effects of different electrodes, residence time, current density, and pH were also studied to optimize the treatment conditions. Different kinds of cleansing agents, such as lime and borax were used to break the buffering effect encountered during treatment. FTIR, SEM/EDS, and XRD were used to characterize the EC-floc and thus to elucidate removal mechanisms.

Jan 1, 2009

By Maria D. Salazar-Villalpando, Anthony Cugini, Bryan Reyes

"The electrochemical reduction of CO2 was performed in a laboratory-made, divided Htype cell. A copper electrode was used as the cathode. An Aldrich Nafion 117-type ion exchange membrane (0.18mm thickness) was used as the diaphragm. NaHCO3 and KHCO3 were studied as the catholytes. Hydrogen evolution from water reduction and products from CO2 electrochemical conversion were recorded. Higher CO2 reduction enhancement was observed by KHCO3 as compared to NaHCO3. The main conclusion of this work is that in fact CO2 can be electrochemically reduced with copper electrodes.1.-INTRODUCTIONThe direct electrochemical reduction of CO2 may allow for a simple process and, by avoiding high temperature reactors, would enable the process production rate to be quickly varied to follow the time of day availability of surplus electricity [1]. Temperature has a major effect on the electrochemical conversion of CO2 since its solubility increases when temperature decreases [2]. The electrical potential applied to the electrochemical reacting system will have an influence on the product distribution, as well. For example, a narrow potential range during cyclo-voltagraphic studies will determine the detection of a lower number of products. A recommended potential range to study the electrochemical reduction of CO2 is -2V to 2V. Moreover, the reaction rate on the electrode is governed by various processes, such as the kinetics of electron transfer, adsorption/desorption at the electrode surface, and diffusion of CO2 to the Cu electrode. The availability of active species, CO2 for electro-reduction, is extremely low at the vicinity of the electrode surface and it seriously interferes with the rate of mass transfer. In batch type electrolytic reactors, depletion of CO2 at the surface takes place first. CO2 from the bulk then has to diffuse to the electrode surface, resulting in mass transfer controlled kinetic phenomena. During the above process, several other competitive side reactions could suppress the primary reaction even though the cathode has good electro catalytic properties for reduction of carbon dioxide. When the dynamic supply of specific active species is ensured to electrode surface, the mass transfer effects are minimized to certain extent. Hence it is envisaged that a continuous flow reactor is more efficient for the electro-reduction of CO2 in CO2 saturated aqueous electrolytes. The primary reactions that occur at the copper electrode during the reduction of CO2 are listed below (with the standard potentials calculated using formation energies [1] :"

Jan 1, 2010

By Kimio Itagaki

"As a contribution to understand the smelting of copper or nickel matte by blowing oxygen or oxygen-enriched air, the phase equilibrium and the distribution of minor elements between the iron-silicate based slag and the Cu2S-FeS or Ni3S2-FeS matte at 1573K were investigated in a magnesia crucible under controlled partial pressures of SO2 at 0.1, 0.5 and 1.atm. At a given matte grade, the solubility of copper in the slag was found to be independent of p5O2 while that of nickel was dependent on pSO2 and these behaviors were analysed thermodynainically based on a concept of oxidic and sulfidic dissolution of the components in the slag. When the matte grade was specified, the distribution ratios of X, defined as (wt pct X in slag)/(wt pct X in matte}, for As, Sb and Bi increased with increasing p5O2 while that for Ag was constant against p5O2.IntroductionA combination of intensive reactors with the use of oxygen or oxygen-.enriched air as the blowing gas has provided a number of improved copper and nickel smelting processes such as INCO-Flash, Outokumpu-Flash, Mitsubishi-Continuous and IBRC (top blown rotary converter) processes. Phase equilibrium and thermodynamic studies for the slag and the copper matte or the nickel matte under high partial pressure of SO2 are of practical importance for evaluating the behaviours of the related components in the oxygen-smelting.A series of experimental studies have been already conducted in a limited range of conditions for Pso2 around 0.1 atm, which corresponds to the smelting with air-Stowing [1-5]. However, there remain very few data on the phase equilibrium in the matteslag systems under higher partial pressures of SO2. Tavera and Davenport studied the phase equilibrium between the copper matte and fayalite slag phases under the partial pressure of SO2 controlled at 0.1 - 1 atrn but without controlling the partial pressures of sulfur and oxygen [6]. A potential diagram for the Cu-Fe-S-O-SiO2 system at 1523 - 1573K suggests that the partial pressure of S2 equilibrated with the matte and the fayalite slag with saturated SiO2 under the high SO2 pressure is considerably high at 10-4 - 10-2 atrn [7]. This condition must require controlling of p52 as well as Pso2, in the equilibrium experiments, otherwise, the equilibrium condition may be hardly attained due to the continuous flushing of sulfur from the system."

Jan 1, 2000

By Min Chen, Lei Xu

Sintering behavior and performance of high alumina refractory based on the ternary subsystem MgAl2O4-CaAl4O7-CaAl12O19 were investigated using ZrO2 as an additive up to 8 wt.% by solid state reaction sintering. It was found that the added ZrO2 could dissolve in the CA6 grains in the form of a solid solution, which enhanced the isotropic growth of CA6 grains and then improved the sintering. As a result, the densification process was improved and areas with enrichment of ZrO2 showed a more compact structure. With further increase of ZrO2 addition, tetragonal ZrO2 were found to locate in the grain boundaries for exceeding the solid solubility limit, which enhanced the thermal shock resistance, indicating that addition of ZrO2 exhibited a positive effect on sintering behavior and performance of this refractory. In addition, it is considered that the optimal amount of ZrO2 addition was about 4% considering the performance together with the cost.

Jan 1, 2015

By Juan Hernández Ávila

This work studies the Molybdenum effect on the microestructure, mechanical properties of an as-cast ductile iron. For this study five ductile irons with different amounts of Molybdenum each were made in an induction furnace. In this material nodule count and nodularity is affected by the Molybdenum additions; The iron´s matrix, nodules and the phase were analyzed using scanning electron microscopy detecting Molybdenum only in the matrix. Mechanical properties such as hardness, microhardness, tensile strength and yield strength show increments as the Molybdenum amount is increased. In the same way, ferrite and pearlite phases display a variation in their percentage as the contents of the alloy element increase. This element has a marked influence on the pearlite interlaminar spacing. From the obtained results we conclude that Molybdenum in these quantities dissolves in solid ferrite solution during the solidification process, improving the material´s mechanical properties.

Jan 1, 2009

By Shulan Wang, Xuan Liu, Li Li

"Electrochemistry of Fe(III) in 69CaCl2-12CaF2-19KF and 81CaCl2-19KF (mole percentage, %) was investigated at 827 oC on molybdenum electrode by cyclic voltammetry, chronoamperometry and galvanostatic electrolysis using Fe2O3 as the Fe(III) source. The reduction of Fe(III) to Fe was conducted in one step and controlled by diffusion process. Fe(III) shown greater reduction rate and diffusion coefficient in molten 81CaCl2-19KF than in 69CaCl2- 12CaF2-19KF. Galvanostic electrolysis of Fe was performed in both molten salts with a cylindrical cathode rotating at 200 r/min and dendritic iron deposit was obtained.Keywords: iron; electrolysis; electrochemistry; molten saltIntroductionThe production of iron and steel causes huge emissions of CO2. Iron electrowinning in molten salts with dissolved Fe2O3 using an inert oxygen evolving anode is an alternative process to reduce or eliminate the formation of CO2. Research on novel process of producing metal has been reported recently [1-2] by using CaCl2 as the main electrolyte and dissolving CaO in CaCl2 due to the high solubility of CaO in the melt. This process has been used in preparing many active metals and alloys [3-14]. In the present work, the electrochemical behavior of iron in CaCl2-KF was studied and transport property of iron ion in the melt was discussed.ExperimentalCaCl2,CaF2 and KF (in analytical purity) were dried in air for 48 h. Mixed salts used in experiments were placed in a graphite crucible (??58 mm inner diameter). The graphite crucible together with the salts was heated at 473 K for 12 h in a furnace with flowing Ar (99.99%) before further heating. Temperature inside the furnace was measured by an S type thermocouple. Electrochemical measurements, such as cyclic voltammetry and chronocoulometry, were performed in a three electrode cell by EG&G PAR273A potentiostat/galvanostatand. Galvanostatic electrodepositon of iron was conducted in a two electrode cell. Molybdenum (??2 mm) and iron (??5 mm) were used as the working electrode (WE) and the reference electrode, respectively. A graphite crucible and a magnetite rod (??25 mm ) consisted of 100% magnetite and sintered at 950 oC in argon atmosphere for 2 h with electrical conductivity of 366 O-1m-1 at room temperature were used as the counter electrodes in the galvanostatic electrolysis experiment. Carbon (??10 mm) was used as the counter electrode in electrochemical measurement. The deposits were washed in distilled water bubbled with argon and dried in air before being characterized by X-ray diffraction (PW3040/60 diffractometer) and scanning electron microscope (SEM, SSX-550)."

Jan 1, 2014

By Yu Yamashita

There have been increasing in melting recycled scraps in copper smelting processes, and thus growing interests in the chlorine behavior. In this study, chloride dissolution in FeO-Fe2O3-SiO2slag (SiO2sat.) at 1523 K has been measured with varying in PCl2 from 1.13x10-8 to 1.30x10-7atm. and the oxygen partial pressures encountered in typical copper smelting furnace, i.e. PO2=10-8 to 10-10 atm. Discussion is made on the chloride capacity of FeO-Fe2O3-SiO2 slag in terms of its characteristics and the dissolved chlorine species. It has been shown that the mostreasonable dissolution reaction and chloride capacity can be expressed by the following reactions, where chlorine dissolves in the form of Cl-; here, aO2-, oxygen ion activity, is shown a function of oxygen partial pressure in the atmosphere. [ ]

Jan 1, 2006

The oxidation of zinc vapour plays a very important part in the operation of the Imperial Smelting Process. The kinetics of the reoxidation of zinc vapour by carbon dioxide and water vapour onto quartz and zinc oxide substrates is qualitatively understood and this pertains to the conditions found as the gases are being transferred from the furnace to the splash condenser. However, re-oxidation also occurs in the shaft of the furnace where the solid substrates are sinter and metallurgical coke. It was found that there was a threefold increase in the rate of oxidation on sinter, compared to quartz and a 30 to 300 increase in rate on the coke. This was attributed to the high surface area offered by these materials.

Jan 1, 2003

By Broggi Andrea

Condensates produced by SiO(g) and CO(g) have a crucial importance in silicon production. Condensation will follow the reactions 3 SiOðgÞ+COðgÞ→ 2 SiO2 + SiC and 2 SiO ðgÞ→Si+SiO2. Solid compounds generated during silicon production contain Si, SiO2 and SiC in different microstructures and amounts. In industrial systems, condensates limit the SiO(g) escape to the off-gas system. On the other hand, they can block the gas flowing from the high temperature zone, hence the necessity of studying an optimized condensation process. This review discusses SiO(g) condensation and its interaction with CO(g). The report gives an overview of the condensates found both at laboratory and at industrial scale. The two main compounds are the Si–SiO2 and the SiOx–SiC mixtures. The hypothesis on the mechanism of formation of SiC–SiOx condensates is presented through a wide selection of performed works. The advantages and disadvantages of the former experimental procedures are discussed.

By Krzyszof Borowiec

With the aim of determining the thermodynamic conditions for sulfation of impurity elements, in particular magnesium, in titaniferous slags the equilibrium gas composition for the sulfation reaction: MO + so2 + 1/2 02 = MS04 has been studied by an EMF technique with a solid zro2 + Cao electrolyte. Here M denotes the impurity elements: Mg, Ca and Mn, and the following _oxide systems have been studied: Ti02-MgO-Fe2 o 3 , Ti02-MnO-Mn2 o 3 , and Ti02 -CaO-Si02 , all in the . temperature range 700-1000ºc. Reproducible EMF values were obtained by adding small amounts of -Na2so4 to the oxide-sulfate mixture. From the observed results the Gibbs energy of formation of the phases Mg 2Ti04 , MgTi03 , MgTi 2o 5 , MnTi03 , CaTi03 , and CaTiSio5 , as well as the activity of MgTi05 in the solid solution with Fe2Ti05 have been calculated. The results show that, from a thermodynamic viewpoint, sulfation of these impurities in titaniferous stags i:s favorable- at around and below 800ºC.

Jan 1, 1985

By W. D. Keller

Scanning electron microscopy (SEM) accompanied by X-ray energy dispersive analysis (XES) is a useful tool in process clay mineralogy. The texture of kaolin, illustrated by SEM, gives a clue to its mode of genesis and probable industrial application. One type of kaolin, originating dominantly by weathering, has an open texture, slakes readily, and is used for filling and coating paper. Another type, in contrast, originates by diagenesis of Al-silicate sediments, and spectacularly resists slaking, thereby enabling it to maintain its bulk density and controlled size and shape of particles after crushing and moistening; this meets an important requirement for the manufacture of refractories. Ratios of elemental Al:Si that may be rapidly determined by SEM and XES yield information on the origin and purity of bauxite and bauxitic clays, and aid in quality control and processing of them. SEM of dissimilar textures of quartz, as in chert and novaculite, are evidence for geothermometry on a stratigraphic scale that is potentially useful in delimiting thermally favorable or unfavorable areas for hydrocarbon exploration, and possibly for unexposed metallic ore deposits.

Jan 1, 1982

By Kathryn C. Sole

A novel solvent-extraction process for the refining of gold was recently commercialised, with the commissioning in May 1997 of a 24 t a-' refinery at Harmony Gold Mine in Virginia, South Africa. The MinataurTM Process (Mintek Alternative Technology for Au Refining) uses solvent-extraction technology to produce gold of 99.99% purity from the cathode sludge arising from a conventional carbon-in-pulp / electrowinning circuit. Implementation of this process introduces significant cost benefits compared with the conventional dore smelting / toll-refining route previously followed. This paper outlines the process, presents selected operating results obtained during the first few months of operation, and provides some details of the associated techno-economic advantages.

Jan 1, 1998

By Claudio Toro, Alex Moyano, Jonkion Font, Carlos Caballero, Pedro Morales

"Codelco-Chile in the last decade has carried out industrially-oriented research as an alternative to the traditional batch-type converting process. In a first stage carried out preliminary evaluations in a rearranged Peirce Smith (PS) converter, and then an exploratory test in a “Convertidor Teniente” (Teniente converter, TC) for the Codelco-Chile Continuous Converting Process. However, the validation test for this process in the TC was delayed up to the second quarter of 2007 where the validation studies were done satisfactorily.Thus, the objective of this paper is to present the results of the campaign tests validating the Codelco-Chile Continuous Converting Process in the TC1 of the Codelco Norte smelter.The results of charging the solid or liquid matte or high grade matte (“white metal”) by Garrgun, or by mouth of the 22 m x 5 m TC1 are presented. Some features of the industrially validated process are discussed, and the pilot test results of the matte injection are also presented."

Jan 1, 2009

By Wentao Guo, Xuefeng She, Qingguo Xue, Jingsong Wang

By the coke gasified reaction device and online measurement high-temperature compressive strength apparatus, the variation of pore structures of coke after gasified reaction with CO2 and H2O was investigated. Research illuminating the influences of solution loss rate, temperature, and carbon species on compressive strength of coke was also carried out. The results showed that the total compressive strength was higher than for the reaction with CO2. The high-temperature compressive strength of coke decreased with the increasing of solution loss ratio or temperature after reacting with CO2 and H2O. At the same solution loss ratio, the damage of pore structure to coke strength after gasified reaction with H2O was relatively smaller and the deformation resistance was stronger when compared with that in CO2.

Jan 1, 2016

By S. E. Khalafalla

A method for preparing ferrochromium alloys containing less than 2 pct carbon has been devised in a single vacuum furnace reactor. This method can conserve chromium and should reduce the capital and energy requirements relative to chromite electrothermal reduction. Reduced products containing less than 2 and as low as 0.01 wt pct carbon were obtained by reacting pellets of chromite and carbonaceous reductant mixtures at pressures of 0.1 to 1 ton and temperatures of 1,230° to 1,320° C. The extent of reduction increased with increased temperature and decreased pressure; however, operating conditions were limited due to the onset of significant chromium vaporization at higher temperatures and lower pressures. Foundry coke, anthracite, and carbon black were found to be superior to graphite as reductants. The reduction of chromite to metallics was found to proceed via the carbide intermediates Fe3C or Cr3C2. Lime accelerates the. rate of solid state reduction of chromite and can shorten the furnacin1r time at 1,3000 C under vacuum from 13 hours to less than three hours. Additional lime and silica are added to the hot reduced chromite after releasing the vacuum and raising the furnace. temperature to 1, 700° C. Soaking the charge for about 20 minutes gave a button of low carbon ferrochromium alloy beneath a well-defined slag layer.

Jan 1, 1985

By L. Katgerman, H. J. Brinkman, J. Duszczyk

"The phase formation sequence in the in-situ synthesis ofTiB2 in A1 from elemental A1, Ti and B powders is identified with a combination of DSC and XRD. After the melting of A1, A1B2 and A13 Ti are formed at the contact areas between A1-B and A1-Ti. The influence of variations in starting composition on the reaction kinetics is explained in terms of there effect on the different processes in the formation sequence. Parameters in the starting composition that were investigated are; fraction ofTiB2 forming reactants, non stoichiometric Ti:2B ratio's, and addition of alloying element Cu.It was found that a liquid Al phase is necessary for the in-situ TiB2 forming reaction from the intermediate A1B2 and A13 Ti phases. If all Al is consumed by the formation of A1B2 and A13 Ti the TiB2 formation is halted until the decomposition of A1B2 and A13 Ti .Overstoichiometric amounts of B are needed for complete conversion of the Ti, present in A13Ti, into TiB2 This is explained by the fact that some of the stable A1B12 phase is formed after the decomposition of A1B2•The addition of Cu leads to an increasing reaction rate in the A1-Ti reaction. A possible explanation for this is that the A1-Cu liquid penetrates more easily between the Ti and its surface oxide than the unalloyed A1 liquid."

Jan 1, 1998

By Elizabeth M. Ho

Oxidants are added in uranium leaching in acid media to convert iron(II) in solution to iron(III). Iron(III) has an important role in the leaching of uranium by acting as an electron transfer agent for the oxidation of uranium(IV) to uranium(VI). The oxidation of iron(II) to iron(III) in sulfate solutions using sulfur dioxide/oxygen (SO2/O2) was carried out under typical uranium leaching conditions (pH 1-2, 20-50°C) to confirm literature trends and this work was then extended to the use of SO2/O2 in the leaching of uranium ore. The oxidation rate was found to be dependent on the initial SO2/O2 volumetric ratio and the oxygen mass transfer rate, but was independent of the initial iron(III) concentration above about 200 ppm at pH 2. The presence of 55 ppm organic extractant (Alamine 336) decreased the reaction rate. The oxygen mass transfer coefficient (kLa) for the mixing tank system was measured and was found to decrease with increasing solids density in a 1 g L-1 MgSO4.7H2O solution.

Jan 1, 2003

By D. Lui, B. G. Thomas, B. Ho

"Results from mathematical models and plant experiments are combined to quantify the effect of transverse depressions and oscillation marks on heat transfer in the continuous casting mold. A heat transfer model has been developed to calculate transient heat conduction within the solidifying steel, coupled with the steady-state heat conduction with the continuous casting mold wall. The model features a detailed treatment of the interfacial gap between the shell and mold, including mass and momentum balances on the solid and liquid powder layers. The model predicts the solidified shell thickness down the mold, temperature in the mold and shell, thickness of the resolidified and liquid powder layers, heat flux distribution down the mold, mold water temperature rise, ideal taper of the mold walls, and other related phenomena. The important effect of non-uniform distribution of superheat is incorporated using the results from previous 3-D turbulent fluid flow calculations within the liquid cavity. Results from plant experiments confirm that transverse surface depressions and oscillation marks form at the meniscus and move down the mold. Measurements of mold thermocouple temperatures and breakout shell thickness were used to calibrate the models. The results indicate that the surface depressions and oscillation marks are filled with mold flux, but still have a significant effect on decreasing heat transfer. The predicted mold temperature fluctuations are consistent with measurements. If the depressions become filled with air, their effect is greatly increased. These results should be useful in the difficult task of interpreting transient mold thermocouple signals for on-line quality monitoring.IntroductionMany different types of intermittent surface defects on steel slabs arise during initial solidification in the mold of the. continuous casting machine. These defects include deep oscillation marks, surface depressions, and cracks. They may lead to quality problems, such as slivers, in the final rolled product. In severe cases, breakouts may occur, where liquid steel bursts through a thin section of the shell and drains over the casting machine below the mold."

Jan 1, 1997