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1.
Equilibrium studies between CaO-SiO2-10 pct MgO-Al2O3-TiO1.5-TiO2 slags, carbon-saturated iron, and a carbon monoxide atmosphere were performed at 1773 K to determine the activities of TiO1.5 and TiO2 in the slag. These thermodynamic parameters are required to predict the formation of titanium carbonitride in the blast furnace. In order to calculate the activity of titanium oxide, the activity coefficient of titanium in carbon-saturated iron-carbon-titanium alloys was determined by measuring the solubility of titanium in carbon-saturated iron in equilibrium with titanium carbide. The solubility and the activity coefficient of titanium obtained were 1.3 pct and 0.023 relative to 1 wt pct titanium in liquid iron or 0.0013 relative to pure solid titanium at 1773 K, respectively. Over the concentration range studied, the effect of the TiO x content on its activity coefficient is small. In the slag system studied containing 35 to 50 pct CaO, 25 to 45 pct SiO2, 7 to 22 pct Al2O3, and 10 pct MgO, the activity coefficients of TiO1.5 and TiO2 relative to pure solid standard states range from 2.3 to 8.8 and from 0.1 to 0.3, respectively. Using thermodynamic data obtained, the prediction of the formation of titanium carbonitride was made. Assuming hypothetical ‘TiO2,’ i.e., total titanium in the slag expressed as TiO2, and using the values of the activity coefficients of TiO1.5 and TiO2 determined, the equilibrium distribution of titanium between blast furnace-type slags and carbon-saturated iron was computed. The value of [pct Ti]/(pct ‘TiO2’) ranges from 0.1 to 0.2.  相似文献   

2.
Perovskite phase was successfully separated from CaO-TiO2-SiO2-Al2O3-MgO melt by super gravity. Under the hypothesis that the titanium exists in the slag in terms of TiO2, with the gravity coefficient G = 600, time t = 5 minutes, and temperature T = 1563 K (1290 °C), the mass fraction of TiO2 in the concentrate is up to 52.94 pct, while that of the tailing is just 5.88 pct. The recovery ratio of Ti in the concentrate is up to 81.28 pct by centrifugal separation.  相似文献   

3.
《钢铁冶炼》2013,40(1):20-25
Abstract

Three high basicity slags (A, B and C) were used in laboratory to refine Al killed steel to target high oxide cleanliness and low melting temperature inclusions. Inclusions were of CaO–MgO–Al2O3–SiO2 system after 90 min reaction, parts of which were MgO based. Total oxygen were in the range of 0·0007–0·0010 and 0·0005–0·0010% respectively when slag A (CaO/SiO2, 6–8; Al2O3, ~40%) and slag B (CaO/SiO2, 6–8; Al2O3, ~30%) were applied, with inclusions all in spherical shape and mainly <5 μm. Inclusion composition concentrated in or around the lower melting point region (<1500°C) under slag A, while it became more scattered under slag B. Total oxygen varied between 0·0008 and 0·0011% under slag C (CaO/SiO2, 3–4; Al2O3, about 20–25%). Many of the inclusions were in larger size, irregular morphology and located far away from the lower melting point region. Formation of MgO based inclusions closely related to solubility behaviour of MgO in the slag.  相似文献   

4.
For carbothermal reduction (CTR) to be an economic and clean process for magnesium metal production, operational challenges must be overcome. Strong and reactive precursor pellets are necessary to effectively and selectively produce Mg(g) from any feedstock. In this study, the effects of ore (magnesia and dolime), carbon (petroleum coke, charcoal, algal char, and carbon black), and binder (organic and inorganic) on pellet strength and reactivity, product yield and purity, and reduction selectivity were analyzed. Theoretically and experimentally, the CTR of dolime (MgO·CaO) favored MgO reduction over CaO reduction; however, with enough carbon and heat, both oxides could be reduced. CaO carbothermal reduction produced CaC2 and Ca(g). The selectivity to CaC2 remained constant (7 ± 4 pct) for all C/MgO·CaO ratios analyzed, while the selectivity to Ca(g) increased (5 pct → 40 pct) when C/MgO·CaO was increased from 0.5 to 2.0. As the overall metal yield decreased (77.6 pct → 59.7 pct) with increasing CaO reduction (38.2 pct → 78.1 pct), Ca(g) reverted faster than Mg(g). Heavy metal impurities primarily remained in the residue (< 30 pct volatilized) and, when volatilized, condensed at high temperatures (700 °C to 1450 °C), relative to light metal impurities (350 °C to 1000 °C, > 78 pct volatilized). Organic binders added reducing power to the pellets but produced frail pellets (radial crush strength = 9.1 ± 0.7 N) after pyrolysis, relative to pellets with inorganic binders (15.1 ± 3.2 N). Kinetic parameters were determined for extruded pellets to predict the reaction rate as a continuous function of pressure and temperature.  相似文献   

5.
The effect of TiOon the grain growth kinetics of MgO prepared from MgCl2·6H2O was studied by the tradition phenomenological rate equation. The results showed that the addition of TiOdecreased the activation energy of MgO grain growth, accelerated the growth rate of MgO grain, and markedly promoted the sintering of MgO. Without TiOaddition, the MgO grain growth exponent $ n $ was 3, the grain growth activation energy $ Q $ was 556.9 kJ·mol?1, and the process was considered as volume diffusion controlled. With 0.2 wt pct TiOaddition, the MgO grain growth exponent $ n $ was 2, the grain growth activation energy $ Q $ was 272.8 kJ·mol?1, and the process was considered as interface diffusion controlled. The apparent and closed porosities of MgO-0.2 wt pct TiOsample were decreased significantly, and the bulk density increased to 3.49 g·cm?3 (relative density is 97.5 pct). The main mechanism of TiOpromoting the sintering of MgO was that TiOsolubilized in MgO to form unequivalence substitutional solid solutions and cation vacancies that were favorable to cation diffusion.  相似文献   

6.
The viscosity of smelting slags from the Glogow copper plant in Poland was measured using a concentric cylinder viscometer. These slags contain typically 45 pct SiO2, 16 pct CaO, 8 pct MgO, 11 pct Al2O3, and only 5 to 7 pct total iron. The viscosity was measured as a function of the CaO, MgO, SiO2, Cu2O, Cr2O3, and Fe3O4 contents in the temperature range from 1473 to 1623 K. Silica and chromium oxide additions increased the viscosity, while small additions of the other oxides decreased the viscosity. However, at large additions of CaO or MgO, cooling resulted in a rapid increase in the viscosity upon reaching the transition temperature. This critical transition temperature increased with increasing additions of CaO and MgO. This was explained by the precipitation of solid particles upon reaching the saturation limit. Depending on the slag composition, the activation energy for viscous flow was found to be in the range from 200 to 370 kJ/mol.  相似文献   

7.
A new sodiothermic reduction process of TiO2 in CaCl2 melt was proposed aimed at fine Ti powder preparation. The chemical analysis and direct potentiometric methods were used to investigate the reaction pathway of sodiothermic reduction in CaCl2 melt. The as-prepared samples were characterized by X-ray diffraction and scanning electron microscopy. It was found that when reductant of Na was added into the CaCl2 melt, Ca2+ was reduced to Ca by Na and Ca dissolved in the CaCl2 melt. The whole melt would have the reducing power with dissolved Ca. Using this melt as a reaction medium, fine and uniform Ti powder with a purity of around 99 mass pct was successfully produced at 1173 K (900 °C). In addition, as the CaCl2 melt could dissolve about 20 mol pct CaO, it was found that the molar ratio of TiO2 and CaCl2 should be 1:20 to eliminate the by-product CaO from the reaction interface within the experimental period to continue the reduction.  相似文献   

8.
We investigated the effect of flux (lime) addition on the reduction behavior of iron oxide in copper slag by solid carbon at 1773 K (1500 °C). In particular, we quantified the recovery of iron by performing typical kinetic analysis and considering slag foaming, which is strongly affected by the thermophysical properties of slags. The iron oxide in the copper slag was consistently reduced by solid carbon over time. In the kinetic analysis, we determined mass transfer coefficients with and without considering slag foaming using a gas holdup factor. The mass transfer of FeO was not significantly changed by CaO addition when slag foaming was ignored, whereas the mass transfer of FeO when slag foaming was considered was at a minimum in the 20 mass pct CaO system. Iron recovery, defined as the ratio of the amount of iron clearly transferred to the base metal ingot to the initial amount of iron in the slag phase before reduction, was maximal (about 90 pct) in the 20 mass pct CaO system. Various types of solid compounds, including Mg2SiO4 and Ca2SiO4, were precipitated in slags during the FeO reduction process, and these compounds strongly affected the reduction kinetics of FeO as well as iron recovery. Iron recovery was the greatest in the 20 mass pct CaO system because no solid compounds formed in this system, resulting in a highly fluid slag. This fluid slag allowed iron droplets to fall rapidly with high terminal velocity to the bottom of the crucible. A linear relationship between the mass transfer coefficient of FeO considering slag foaming and foam stability was obtained, from which we concluded that the mass transfer of FeO in slag was effectively promoted not only by gas evolution due to reduction reactions but also by foamy slag containing solid compounds. However, the reduced iron droplets were finely dispersed in foamy and viscous slags, making actual iron recovery a challenge.  相似文献   

9.
Attempts were made to elucidate the formation mechanism of CaO-SiO2-based inclusions in saw wires by both laboratory experiments and industrial trials. The key point was to make clear the origin of CaO in such oxide inclusions. Probable origins of [Ca] in steel were first discussed, which can be taken into steel from the steel-slag reaction or ferrous alloy. As a result, slag-steel chemical reaction equilibrium was carefully evaluated at 1873 K (1600 °C) to classify the changes of dissolved aluminum ([Al]), total magnesium (Mg), and total calcium (Ca) in steel and the caused composition variations of inclusions. With the rise of slag basicity from 0.5 to 1.8, [Al] was remarkably increased from 0.00045 to 0.00139 mass pct, whereas Mg varied in the range of 0.00038 to 0.00048 mass pct. By contrast, Ca was constantly kept below 0.00003 mass pct. Accordingly, Al2O3 and MgO in inclusions witnessed obvious rises from 5 to 23 mass pct and from 2 to 8 mass pct, respectively. By contrast, inclusions were free of CaO when slag basicity was below 1.5. With slag basicity further increased to 1.8, CaO witnessed a negligible rise to only 1.0 mass pct on average. This phenomenon agreed well with thermodynamic calculations, which revealed that chemical reaction between steel and CaO in slag (for example, between [Si] and CaO) was weak to hardly supplying sufficient [Ca] to steel to increase CaO in inclusions. Ca contained in ferrous alloys as contaminations was not the cause of CaO-SiO2-based inclusions, either. The industrial trial results indicated that CaO-SiO2-based inclusions have been readily produced in short time just after BOF tapping. Also, a percentage of them changed slightly with the proceeding of refining. Based on the good agreement of laboratory, industrial, and thermodynamics calculations results, it can be reasonably concluded that CaO-SiO2-based inclusions in saw wire were exogenous particles from entrapped/emulsified top slag, but not products of slag-steel-inclusion chemical reactions.  相似文献   

10.
The crystallization behavior of a calcium-aluminate system with various MgO content from 2.5 to 7.5?wt pct and CaO/Al2O3 ratios between 0.8 and 1.2 has been examined using a confocal laser scanning microscope (CLSM). CCT (continuous cooling transformation) and time temperature transformation (TTT) diagrams were constructed to identify the primary crystal phase of slag at different compositions and at cooling rates between 25 and 800?K/minutes. In the slag at a CaO/Al2O3 ratio of 1.0, crystallization temperature increased during isothermal and continuous cooling with higher MgO content, and the shortest incubation time was observed at 5?wt pct MgO. When MgO content was fixed to be 5?wt pct, crystallization temperature increased with lower CaO/Al2O3 ratio. According to the slag composition, cooling rates and temperature, the primary phase could be CA, or C5A3, or C3A, or C3MA2, or MgO, and the crystal morphology changes from dendrites to faceted crystals to columnar crystals in this composition range.  相似文献   

11.
Blast furnaces are encountering high Alumina (Al2O3 > 25 pct) in the final slag due to the charging of low-grade ores. To study the viscosity behavior of such high alumina slags, synthetic slags are prepared in the laboratory scale by maintaining a chemical composition of Al2O3 (25 to 30 wt pct) CaO/SiO2 ratio (0.8 to 1.6) and MgO (8 to 16 wt pct). A chemical thermodynamic software FactSage 7.0 is used to predict liquidus temperature and viscosity of the above slags. Experimental viscosity measurements are performed above the liquidus temperature in the range of 1748 K to 1848 K (1475 °C to 1575 °C). The viscosity values obtained from FactSage closely fit with the experimental values. The viscosity and the slag structure properties are intent by Fourier Transform Infrared (FTIR) and Raman spectroscopy. It is observed that increase in CaO/SiO2 ratio and MgO content in the slag depolymerizes the silicate structure. This leads to decrease in viscosity and activation energy (167 to 149 kJ/mol) of the slag. Also, an addition of Al2O3 content increases the viscosity of slag by polymerization of alumino-silicate structure and activation energy from 154 to 161 kJ/mol. It is witnessed that the activation energy values obtained from experiment closely fit with the Shankar model based on Arrhenius equation.  相似文献   

12.
The solubility of TiO2 in cryolite-alumina melts at 1020 °C was measured; it decreased with increasing alumina concentration up to ∼3.5 wt pct total oxide and then increased at higher alumina concentrations. The solubility was found to be 3.1 wt pct Ti in cryolite, and 2.7 wt pct Ti in an alumina-saturated melt. Modeling indicated that the most probable titanium species are TiOF2 and Na2TiO3, which coexist in the solution; the former dominates at low alumina concentrations and the latter at high alumina concentrations. Additional unknown amounts of fluoride may also be associated with these species. Determination of the solubility of TiO2 in alumina-saturated melts as a function of temperature showed that the solubility increased from 1.9 wt pct Ti at 975 °C to 2.8 wt pct Ti at 1035 °C, the apparent partial molar enthalpy of dissolution of TiO2 being 88±4 kJ mol−1.  相似文献   

13.
The effects of CaO, Al2O3, and MgO additions, singly or in combination, on the copper solubility, the Fe3+/Fe2+ ratio in slag, and on the minor-element behavior of silica-saturated iron silicate slags were examined at 1250 °C and a p O2 of 10−12 to 10−6 atm. The results indicated that copper solubility in slag was lowered with the addition of CaO, MgO, and Al2O3, in decreasing order. The Fe3+/Fe2+ ratio in the slag decreased with the additions, but this effect was smaller at lower oxygen potentials. The presence of small amounts (about 4 pct) of CaO, Al2O3, and MgO in the slag resulted in increased absorption of Bi and Sb into molten copper, but had a smaller effect at large additions (about 8 to 11 pct). The distribution behavior of Pb was a function of oxygen partial pressure, which indicates the oxidic dissolution of Pb in the slag as PbO, while the behavior of Bi, Sb, and As was found to be independent of oxygen potential, supporting the atomic (neutral) dissolution hypothesis of these elements in the slag. The distribution behavior of Pb and As was not significantly affected by the additions. The activity coefficients of Bi and Sb in the slags were determined to be as follows: (1) for no addition, γ Bi=40 and γ Sb=0.4; (2) for small additions (about 4.4 pct), γ Bi=70 to 85 and γ Sb=0.8; and (3) for large additions (about 8 to 11 pct), γ Bi=60 to 75 and γ Sb=0.5 to 0.7.  相似文献   

14.
The thermal conductivities of some synthetic slags containing Al2O3, CaO, and SiO2 have been determined in the temperature range between 1623?K (1350?°C) and 1823?K (1550?°C) by applying a front-heating front-detection laser-flash method. In this method, the temperature response curve is measured in the short initial time period immediately after irradiating a laser pulse. The resultant values obtained by this method are unaffected by the radiative heat transfer. The temperature dependence of the thermal conductivity values were found not to be significant for all slag samples currently investigated. The thermal conductivity (??) of samples is represented with standard deviation less than 2?pct of its value as a function of compositions as follows: $$ \lambda = - 0.48\left[ {{\text{Al}}_{ 2} {\text{O}}_{ 3} } \right] - 0.57\left[ {\text{CaO}} \right] - 0.55\left[ {{\text{SiO}}_{2} } \right] + 57.1{\text{ W m}}^{ - 1} {\text{ K}}^{ - 1} $$ where [Al2O3], [CaO], and [SiO2] are molar percent of Al2O3, CaO and SiO2, respectively. The equation is suggested to cover the region of the following compositions: 8.0?mol pct < Al2O3 <21.0?mol pct, 31.5?mol pct < CaO <41.5?mol pct and 43.0?mol pct < SiO2 <58.1?mol pct. The addition of Al2O3 to slags with a constant CaO/SiO2 molar ratio resulted in an increase in thermal conductivity. In contrast, the effects of addition of SiO2 and CaO are found to be insignificant.  相似文献   

15.
The slag composition plays a critical role in the formation of inclusions and the cleanliness of steel. In this study, the effects of FeO content and the C/A (CaO/Al2O3) ratio in the slag on the formation of inclusions were investigated based on a 10-minute slag–steel reaction in a MgO crucible. The FeO content in the top slag was shown to have a significant effect on the formation of MgO·Al2O3 spinel inclusions, and critical content exists; when the initial FeO content in the slag was less than 2 pct, MgO·Al2O3 spinel inclusions formed, and the T.O (total oxygen) was 20 ppm; when the initial FeO content in the slag was more than 4 pct, only Al2O3 inclusions were observed and the T.O was 50 ppm. It was clarified that the main source of Mg for the MgO·Al2O3 spinel inclusion formation was the top slag rather than the MgO crucible. In addition, the cleanliness of the steel increased as the initial FeO content in the top slag decreased. As regards the effects of the C/A ratio, the MgO amount in the observed inclusions gradually increased, whereas the T.O content decreased gradually with the increasing C/A ratio. Slag with a composition close to the CaO-saturated region had the best effect on the inclusion absorption.  相似文献   

16.
Liquidus in the Al2O3(25 mass pct)-CaO-MgO-SiO2(<20 mass pct) and Al2O3(35 mass pct)-CaO-MgO-SiO2(<20 mass pct) systems were determined experimentally in the high-CaO-containing region at 1873 K (1600 °C). For the Al2O3(35 mass pct)-CaO-MgO-SiO2(<20 mass pct) system, liquidus data were also determined for 1773 K (1500 °C). The equilibrating and quenching technique with subsequent electron probe microanalyzer (EPMA) microanalysis were employed. Based on the data, liquidus lines were constructed for the 25 and 35 mass pct alumina planes at silica contents generally below 20 mass pct. The current results showed a slightly lower solubility of CaO and a higher solubility of MgO at 1873 K (1600 °C) for the 25 mass pct Al2O3 section compared with the existing phase diagram. At 1773 K (1500 °C), the result showed a slightly lower solubility of both CaO and MgO in the 35 mass pct Al2O3 section compared with the existing phase diagram. In addition, the activities of MgO, CaO, and Al2O3 were estimated at 1773 K and 1873 K (1500 °C and 1600 °C) using the phase diagram information.  相似文献   

17.
The drop-quench technique was used to investigate the solubility of dense MgO in calcium ferrite-based slags (CaO 20 wt pct) under oxygen potentials from 10−8 to 10−4 atm at 1573 K. The effect of copper oxide in the slag on the solubility of MgO was also examined in a CO2 atmosphere. The results showed that MgO solubility in copper-free calcium ferrite slags was generally less than 2 wt pct and it increased with the addition of Cu2O (up to 28.5 wt pct). It was found that magnesiowustite or magnesioferrite may form at the slag-refractory interface depending on the prevailing oxygen potential. The activity of MgO was estimated through equilibrium between the slag and the solid solution phases. The activity coefficient of MgO was found to be essentially independent of the oxygen potential within the range studied and to decrease from approximately 15 for the copper-free slag to 7 for slags with 28.5 wt pct Cu2O.  相似文献   

18.
A high-accuracy, calibration-free technique to measure the electrical conductivity of molten oxides has been developed—the coaxial cylinders technique. Because the melt under investigation comes in contact only with metal and not with anything dielectric, the new technique enables the measurement of the electrical properties of liquids inaccessible by classical high-accuracy techniques. Two coaxial cylindrical electrodes are immersed in the melt to an arbitrary initial depth, and ac impedance is measured over a wide range of frequency. The electrodes are then immersed deeper, and ac impedance is again measured over the same range of frequency. This process is repeated at multiple immersions. The electrical conductivity is calculated from the change in measured conductance with immersion. The temperature dependence of electrical conductivity has been measured for two oxide melts: (M) 50.95 pct CaO, 12.51 pct MgO, 36.54 pct SiO2, 1733 K<T<1843 K; and (S) 24.59 pct CaO, 26.15 pct MgO, 49.26 pct SiO2, 1763 K<T<1903 K, where concentration is expressed in mole percent. Both melts exhibited behavior characteristic of ionic liquids.  相似文献   

19.
The chlorination of a titaniferous magnetite with low content in Ti and Fe has been studied between 1273 and 2273 K. Most of the hercynite and ilmenite initially present are decomposed during the gas-solid phase reaction between 1273 and 1823 K. Considerable ilmenite decomposition and FeCl3evolution already occur at 1273 K, leaving a residue consisting of TiO2, Fe2O3-TiO2 (pseudobrookite), and about 50 pct of each of the Cr and Mg initially present. X-ray diffractograms shown the formation of Al2TiO5 which contributes to the stabilization of TiO2 up to 1773 K, above which temperature significant decomposition of Al2TiO5 is observed. At the melting point of the titaniferous magnetite sample (around 1823 K), the presence of both solid and liquid phases result in a considerable decrease in the chlorination rate. In this respect, heating the sample under helium up to the melting point, so that liquid and solid phases are obtained at equilibrium, yields two structures replacing the magnetite present just prior to melting. One of these structures is of the spinel Fe2TiO4 type, while the other is a combination of the spinel types MgAl2O4, FeAl2O4, and MgCr2O4. When the sample is chlorinated, a high proportion of the initial Cr (90 pct) and Ti (80 pct) are found in the chlorination residue at the early stages of fusion, together with 13 pct of the initial Fe. Chlorination of the liquid phase between 1823 and 2273 K shows a steady decrease of Ti and Cr in the chlorination residue, associated with an increase of Fe content.  相似文献   

20.
《钢铁冶炼》2013,40(10):776-783
Abstract

A new approach to isothermal enriching combined with separating perovskite phase from CaO–TiO2–SiO2–Al2O3–MgO melt by centrifugal force was investigated. Using a two-stage centrifugal separation process, the recovery ratio of Ti in the second concentrate was 99·34% and the tailings were 0·66%, thus demonstrating excellent Ti separation. These materials can be considered as suitable raw materials for titanium white and cement respectively.  相似文献   

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