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By M. Nilmani, H. Pham

"A mathematical model was developed for the dissolution of particles in gas-stirred liquid baths, linking the hydrodynamic flow field of the bath, the average particle trajectory and liquid-side mass transfer controlled dissolution kinetics. The model was validated by comparison with experimental data for the dissolution rates of urea particles in gas-stirred aqueous CaCl2 solutions measured during this study. The dissolution rates of urea. particles were measured using an image analysis system.The effects of operating conditions on the dissolution rates of urea particles were investigated. It was found that the key operating parameters influencing the utilisation efficiency of particles were the gas flowrate, particle diameter and lance submergence. An optimisation of the operating conditions for the model urea-aqueous CaCl2 system indicated that the utilisation efficiency increased with decreasing gas flowrate and decreasing particle size for a given lance submergence.IntroductionThe utilisation solid reagents in molten baths varies from one process to another, depending upon the rates and mechanisms of the reactions between the particles and melts, as well as the trajectory and residence time of the particles in the melts. Previous studies have not attempted to predict the utilisation efficiency of injected solids by coupling the motion of the particle with its dissolution rate. Instead, the particles have usually been assumed to remain suspended in the bath until completely dissolved, and the mass transfer coefficients were based on the average specific mechanical energy dissipation rates in the bath. Investigations of this nature relevant to the present study have been undertaken by Apelian et al. [1], Brucato et al. [2] and Langberg and Nilmani[3]. The objective of the present study was to develop a mathematical model, incorporating both the reaction kinetics between the particles and liquid and the particle motion simultaneously, to predict the dissolution rates and times of the particles. The mathematical model was validated by comparison with experimental dissolution rates of a cold model analogue system measured using an image analysis technique, and then applied to optimise the operating conditions in the model system."

Jan 1, 1996

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 Kirsi M. Riihilahti

The oxidation characteristics of solid copper matte particles under simulated Kennecott-Outokumpu Flash Converting conditions are presented. This project is concerned with the determination of the effects of operating variables on the reaction of the particles. Experiments were carried out in a large laboratory-scale flash furnace with 72 wt-% Cu matte by varying initial particle size, temperature, oxygen partial pressure, oxygen-to-matte mass ratio and residence time. Chemical analysis was used to study the oxidation extent and copper volatilization. Particle fragmentation was examined. Fractional conversion and sulfur removal slightly decreased with initial particle size, while a higher oxygen-to-matte mass ratio mainly resulted in higher fractional conversion and more efficient sulfur removal. The fractional conversion values represented the overall extent of oxidation more closely than degree of sulfur removal.

Jan 1, 1997

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 Mahesh C. Meyer Jha

AMAX has developed a chloride refining process to produce pure nickel and cobalt metals from mixed sulfide .precipitates, Metal chloride solutions, generated in a hydrochloric acid leaching step and purified in a solvent extraction circuit, are converted to metal oxides .and HCI gas by pyrohydrolysis. A pilot plant consisting of a 30-inch diameter fluidized bed reactor and other ancillary units was designed, constructed, and operated for over one year. Process design was aimed at minimizing energy consumption, maximizing conversion efficiency, and achieving simplicity of operation and control. The operation provided valuable information on process scale up parameters, process control strategies, and materials of construction., Several process variables such as bed temperature, solution composition, solution feeding system, bed particle size distribution, and fines recycle system were investigated to determine their effects on process efficiency and the physical and chemical characteristics of the product.

Jan 1, 1985

By V. D. Tathavadkar

Chromite ore is of immense importance for the extraction of metallic chromium and chromium chemicals. The mineralogy and crystal structure of chromite phase are therefore important part of our investigation on the extraction chemistry of chromium species. In this investigation, we have studied the effect of the processing parameters, i.e., the temperature and the oxygen potential on the microstructure and composition of mineral phases formed in the Cr2O3 ?Al2O3 -FexOy -MgO system. In particular the importance of the spinodal decomposition reaction is emphasized in the extraction of chromium as sodium chromite and sodium chromate. Experiments were carried out in order to study the differences in the crystallography of different chromite minerals. Phase equilibria in natural chromite minerals were investigated by calcining chromite mineral in air, argon, and 5% hydrogen + argon atmospheres over a temperature range from 200 to 1200 °C. The effect of the oxygen partial pressure and temperature on the phase constituents of the calcined product has been discussed. The microstructural changes were examined using scanning electron microscope (SEM) and the changes in elemental composition in different phases were analysed by electron probe micro analyser (EPMA). The results obtained from EPMA studies were used to calculate lattice parameter of the spinel lattice, and these values were compared with the values obtained from X-Ray powder diffraction data. On the basis of the experimental data, the mechanism of the spinodal decomposition of complex spinel phases is described under the influence of oxygen partial pressure and temperature.

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 Ralph H. Nafziger

The feasibility of smelting a Ni-Co-Cr-bearing laterite ore from southern Oregon was evaluated by the Bureau of Mines. The objective was to prepare a master alloy for subsequent stainless steel production. A mixture of the ore with suitable reductants and fluxes was smelted in a 50-lb-capacity single-phase ac electric furnace under sub- merged arc conditions. The smelting tests produced a metal in which most of the nickel was concentrated. High-chromium recoveries required an excess of carbon. The resulting metal alloys contain sufficient nickel for some stainless steels. Ferrochromium additions would be required to attain suitable chromium levels. This research was conducted under the Oregon Metals Initiative in cooperation with Walter B. Freeman.

Jan 1, 1993

By T. Ueno

Naoshima Smelter & Refinery of Mitsubishi Materials Crop. commissioned a new Mitsubishi continuous copper smelter in May 1991. Process offgas volume of the conventional reverberatory furnace line, one of the previous smelters having been shut down, was very large and thus two acid plants had been operated. It was expected that the offgas volume would be reduced at the new smelter to about a half of the sum of those from previous two 1 smelters and the sulfur dioxide strength would be increased. So various alternatives were studied to minimize the operation cost. And it was decided to utilize both of the plants with minor modifications by diluting the gas either with air or with dilute gases. The acid plants now receive offgases from the new copper smelter, a sintering machine of a lead smelter and a decomposer of waste acid. The paper discusses plant design, operation, improvements and modifications realized in relation with the retrofitting of the copper smelter.

Jan 1, 1992

Based on experimental and computer simulation results from our group, we report a systematic, atomic level analysis of carbon dissolution from carbonaceous materials in molten iron. Experimental results on graphite / Fe-C-S system were obtained using carbon dissolution studies, XRD and FESEM investigations and were supplemented with Monte Carlo simulations. Three basic mechanisms, namely carbon atom dissociation rate, interfacial phenomena and mass transfer in the melt were found to be responsible for the overall dissolution process. While mass transfer in the melt is governed by the concentration gradients, melt composition and temperature; impurities present in ash play a significant role in the interfacial phenomena. For less ordered forms of carbonaceous materials, carbon atom dissociation rate depends strongly on the degree of long-range order and is an important rate controlling mechanism in the overall dissolution process. A systematic comparison of dissolution rates for a variety of coal-chars, natural and synthetic graphites has been carried out in an attempt to identify rate-controlling mechanisms. The structure of the carbonaceous material appears to be an important underlying factor in the carbon dissolution process.

Jan 1, 2003

By Wei Gao, Qing-cai Liu, Cun-fang Lu, Jian Yang, Hinmi Zheng

"The mode of occurrence of sulfur and mercury in 57 Chinese bituminous coals have been examined using X-ray fluorescence spectrometry (XRF), X-ray diffraction (XRD), and Zeeman atomic absorption mercury spectrometer. Mercury levels in coal are related to the geographic location of the coals and types of the coals. A synthesis of result indicated that most likely occurrence modes of mercury in high-sulfur and high-mercury coals are in solid solution in pyrite. Our study from 57 coal samples showed that most values of mercury concentration in coal varied from 100 to 1000 ng/g with an average of approximately 500ng/g, and mathematical model about correlation between mercury and sulfur was gained by mathematical statistics. This is apparent that mercury and sulfur vary concomitantly from coal data (table 3) , the high correlation between them in all coals at confidence of 95% ( a=0.05 ) .1. INTRODUCTIONThere contained about one trillion ton abundant coal resources in China. As a leading level of proven coal reserves in the world, the coals mainly distributed in north China and northwest China, especially in Shanxi, Guizhou, Shanxi provinces and Inner-Mongolia autonomous region. At the same time, China has the largest production and consumption of coal, and has the output of coal nearly accounted for 37 percent of the world's production. Coal-fired power plants are the major source of energy generation in China, and the proportion of coal combustion is up to 75 percent in the total energy configuration. Therefore, the mercury pollution caused by coal-fired has become a topic of wide-spread discussions since 1990. The contamination of mercury of human activities accounted for 10 to 30 percent [1], and the mercury emissions of coal-fired flue gas has made the greatest contribution to the pollution of atmosphere[2] In the past 30 years, the global increasing concentration of mercury pollutant in atmosphere maybe result from coal combustion[2]. The mercury emissions caused by coal-burning has become the main reason of China's mercury pollution, and the characteristics of mercury pollution is closely related to China's energy configuration, additionally, the features of mercury pollution have changed from the point pollution in 1970's to diffused pollution today[3]. Mercury can be found in various types of coals, and it is evaporated into gas phase during the combustion process."

Jan 1, 2011

By R. E. Sundell, S. M. Correa

"A mathematical model is developed for the fluid flow in tungsten-inert gas weld pools. The fluid is taken to be incompressible, viscous, electrically conducting, and confined within a pool of specified shape. The flow is driven by surface-tension gradient (thermocapillary), electromagnetic, and buoyancy forces generally in this order of importance. Analysis indicates that the electromagnetic field may be calculated a priori and so decoupled from the nonlinear fluid mechanics and heat-transfer problem. The resulting set of equations is solved numerically by a line relaxation process. Computational errors caused by truncation in finite-difference schemes and by inadequate grid distributions are considered. The model is used to study several cases of differing heat and current input to the pool with and without surfactant-induced thermocapillary forces. The principal conclusions are that the thermocapillary flow, when present, is dominant with surface velocities on the order of 1 m/s. The heat transfer, as deduced from isotherms within the pool, is crucially dependent on the flow. Also, flow velocities and weld-pool surface temperatures were measuredand agree well with the model.2. IntroductionThe requirements of improved control and of automation in the TIG (tungsten-inert gas) welding process have led to the development of mathematical models for the heat transfer to the workpiece. It is now widely recognized that the fluid flow in weld pools sufficiently distorts the conduction heat transfer pattern to warrant inclusion in a process model. The experiments of Woods and Milner (1), among others, demonstrated that TIG weld pools could be driven by the electromagnetic J x B body forces present, J being the current distribution and B the induced magnetic field. Atthey (2) calculated that in typical pools the buoyancy force was about an order of magnitude less important - despite the large temperature gradients present - and neglected it in a computational study of the magnetohydrodynamic (MHD) flow. This work also reviewed many earlier studies of MHD flow caused by a source of current at a fluid surface, including analytical studies by Shercliffe (3), Sozou (4), and Sozou and Pickering (5), and a numerical study by Andrews and Craine (6). These works establish the importance of the electromagnetic force in the weld-pool flow."

Jan 1, 1986

By Gennady I. Gulyayev

A mathematical model of plastic deformation occurring in cold plug drawing of mother tubes with initial cross-sectional wall thickness variations (CSWTV) has been developed. The main provision of the model is that eccentricity em is of such value that projection of all forces acting upon the plug in the deformation zone along the axis perpendicular to the drawing axis equals to zero. Calculations have proven that with other conditions being equal increase in the die cone angle and the deformation cycle number reduces CSWTV. Theoretical findings were confirmed by practical results. Keywords: cold, drawing, plug, die cone, plastic deformation.

Jan 1, 2003

By Takahiko Okura

Most non-ferrous raw materials are associated with sulphur. To extract the metals, the sulphur is recovered typically as sulphuric acid or liquid SOz, On the other hand, natural gas may contain over 20% of hydrogen sulphide (HzS) and a huge quantity of elemental sulphur is produced through oil and gas refining processes in the world. A large fraction of the sulphur mined from natural sources is eventually returned to the earth as fertilizers, by-products of desulphurisation and neutralisation processes, or as fugitives to the atmosphere. However, the supply and demand for sulphur are in imbalance. Such situation urges to develop a new smelting process without sulphuric acid production. This paper briefly reviews the global sulphur balance and the technologies for recovering elemental sulphur. The core of this paper is a proposal to convert SO2 gas to elemental sulphur by using organic materials. Some results of thermodynamic calculations and experiments are presented.

Jan 1, 2003

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

By J. S. Pitsillos

A new furnace tapping technique involving the simulation of a control valve at the exit to a furnace is being investigated. The purpose of this new tapping technique is to regulate the flowrate of liquid furnace products( slags, metals and mattes). Numerical modelling and experimental work has been carried out on tapping of slags leaving a SIROSMELT reactor and the results found to be in good agreement. Numerical modelling has also enabled prediction of the important industrial conditions for the onset of blockage from the shape of the pressure versus flowrate curves. Slag launder experiments have been carried out and a one-dimensional heat transfer model was used to evaluate the effectiveness of launder covers and different coolants. From the experimental results and mathematical model some launder design guidelines such as inclination angle, covers and coolants have been developed.

Jan 1, 1991

At its Copper Cliff Smelter, Inco Limited processes a bulk copper-nickel concentrate in two Inco oxygen flash furnaces, The furnace matte is converted to low iron matte for further processing, and the molten converter slag is recycled to the flash furnaces. The flash furnace slag is discarded. Natural gas or coke supplies a minor proportion of the process heat requirements, thus limiting the flash furnace matte grade to the target 45% CuNiCo. Coke addition to the furnace offers a potential means of establishing a reducing barrier on the surface of the molten bath. Such a practice would be conducive to producing sulfur deficient (partially metallized) matte. At the same iron content, the iron activity of sulfur deficient matte is higher than that of regular matte. A supernatant coke barrier could, therefore, be expected to lead to higher nickel and cobalt recoveries, reduction or even elimination of magnetite furnace bottom build-up and increased sulfur elimination as S02 in the flash furnace. Preliminary experiments were conducted in a miniplant flash furnace to investigate the effect on process metallurgy of the suggested modified scheme. This paper presents the experimental results and discusses key aspects of the possible operation of the Inco flash furnace with a coke barrier separating the freeboard from the molten bath.

Jan 1, 2003

By Liming Wang

One of the steps in the extractive metallurgy of lead is a refining process called drossing. Hot dross is mixture of impurity compounds that form on the surface during the cooling of lead blast furnace bullion, and in Missouri, the main impurities are copper and sulfur. The slow cooling of bullion throws out of solution all other minor impurity elements (or their compounds) which are much less soluble at lower temperatures (mainly nickel, arsenic, iron, and zinc). The transfer of bullion from the blast furnace to the refinery and the subsequent hot drossing step cause fugitive emission of lead-containing fume and dust, which creates a plant hygiene problem. One cause of the emissions is the high vapor pressure of lead and its compounds during transmission of = 1000 °C bullion to the drossing kettle. Another cause is the lifting of dross dust during manual skimming of dross. The environmental problems associated with the traditional hot drossing process provided an incentive to investigate a new drossing process that avoids contact between plant air and hot bullion or dross. A key aspect of the process development was a detailed mineralogical examination of dross from two different bullions. The bullion samples were cooled at different rates, and the dross filtered out and examined. The morphology, phase identification, and composition of the dross was examined by optical and SEM microscopy. The principal dross phases were copper and cuprous sulfide, galena, a complex sulfide containing copper, nickel and lead, and speiss (containing nickel, cobalt, iron, copper, lead, and arsenic compounds). The copper was acicular, with nickel and arsenic in solid solution. The cuprous sulfide was largely digenite in a granular or dendritic form. A substantial part of the dross was solidified matte with a eutectic microstructure, consisting mainly of CU2S and PbS. Small particles (some of which had a eutectic microstructure) never floated to the surface of the lead during the slowest cooling rate, thus indicating that flotation of tiny matte droplets and dross crystals is exceedingly slow. The success in separating dross and lead by centrifugal filtration suggests its application in industry as a replacement for traditional hot drossing.

Jan 1, 1995

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