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Effects of Slag Composition on H{sub 2} Generation and Magnetic Precipitation from Molten Steelmaking Slag–Steam Reaction
In this paper, the effects of slag composition (slag basicity CaO/SiO{sub 2} and FeO concentration) on the amounts of H{sub 2} gas generated and the magnetic spinel phase precipitated as a result of the reaction between synthetic steelmaking slag and steam at 1873 K (1600 °C) were studied by thermodynamic simulation (using Thermodynamic Package FactSage 7.0) and laboratory experiments. The thermodynamic calculation showed that, upon increasing slag basicity (CaO/SiO{sub 2}) from 1.0 to 2.5, for the reaction of 100 g of slags with 100 g of H{sub 2}O gas, the accumulated amount of the produced H{sub 2} gas increased from 0.17 to 0.27 g, while the amount of magnetic spinel phase first increased and then decreased, with the maximum precipitation of 16.71 g at the basicity of 1.5. When the FeO concentration increased from 15 to 30 pct for the slag with basicity of 2.0, the accumulated amount of the produced H{sub 2} gas increased from 0.17 to 0.28 g, and the amount of magnetic spinel phase increased from 5.88 to 10.59 g. The laboratory experiments were conducted in confocal laser scanning microscope to verify the reaction between 0.2 g of slag and 3.75 L of H{sub 2}O-Ar gas (P{sub H{sub 2O}} =0.2 atm). The results indicated that, for 100 g of slags, upon increasing slag basicity (CaO/SiO{sub 2}) from 1.0 to 2.5, both the produced H{sub 2} gas and magnetic spinel phase first increased and then decreased, with the maximum amounts being 0.09 g of gas and 37.00 g of magnetic spinel phase at the slag basicity of 1.50. For the FeO concentration increasing from 15 to 30 pct, the amounts of both the produced H{sub 2} gas and magnetic spinel phase increased from 0.04 to 0.10 g and from 18.00 to 27.00 g, respectively. The reaction rate between the molten CaO-SiO{sub 2}-FeO-MnO-Al{sub 2}O{sub 3}-MgO slag and the moisture (P{sub H{sub 2O}} =0.2 atm) increased with the increasing FeO activity in the slag. The dependence of the reaction rate (mol/cm{sup 2}/s) on FeO content can be expressed as r =(7.67(a{sub FeO})−2.99)×10{sup −7}.
Numerical Simulation of Slag Eye Formation and Slag Entrapment in a Bottom-Blown Argon-Stirred Ladle
A transient mathematical model is developed for simulating the bubble-steel-slag-top gas four-phase flow in a bottom-blown argon-stirred ladle with a 70-ton capacity. The Lagrangian discrete phase model (DPM) is used for describing the moving behavior of bubbles in the steel and slag. To observe the formation process of slag eye, the volume of fluid (VOF) model is used to track the interfaces between three incompressible phases: metal/slag, metal/gas, and slag/gas. The complex multiphase turbulent flow induced by bubble-liquid interactions is solved by a large eddy simulation (LES) model. Slag eye area and slag droplet dispersion are investigated under different gas flow rates. The results show that the movement of bubbles, formation and collapse of slag eye, volatility of steel/slag interface and behavior of slag entrapment can be properly predicted in the current model. When the gas flow rate is 300 L/min, the circulation driven by the bubble plume will stir the entire ladle adequately and form a slag eye of the right size. At the same time, it will not cause strong erosion to the ladle wall, and the fluctuation of the interface is of adequate intensity, which will be helpful for improving the desulfurization efficiency; the slag entrapment behavior can also be decreased. Interestingly, with the motion of liquid steel circulation, the collision and coalescence of dispersed slag droplets occur during the floating process in the vicinity of the wall.
Modification of Inclusions in Molten Steel by Mg-Ca Transfer from Top Slag: Experimental Confirmation of the ‘Refractory-Slag-Metal-Inclusion (ReSMI)’ Multiphase Reaction Model
High-temperature experiments and Refractory-Slag-Metal-Inclusion (ReSMI) multiphase reaction simulations were carried out to determine the effect of the ladle slag composition on the formation behavior of non-metallic inclusions in molten steel. Immediately after the slag-metal reaction, magnesium migrated to the molten steel and a MgAl{sub 2}O{sub 4} spinel inclusion was formed due to a reaction between magnesium and alumina inclusions. However, the spinel inclusion changed entirely into a liquid oxide inclusion via the transfer of calcium from slag to metal in the final stage of the reaction. Calcium transfer from slag to metal was more enhanced for lower SiO{sub 2} content in the slag. Consequently, the spinel inclusion was modified to form a liquid CaO-Al{sub 2}O{sub 3}-MgO-SiO{sub 2} inclusion, which is harmless under steelmaking conditions. The modification reaction was more efficient as the SiO{sub 2} content in the slag decreases.
Optimization of Mineralogy and Microstructure of Solidified Basic Oxygen Furnace Slag Through SiO{sub 2} Addition or Atmosphere Control During Hot-Stage Slag Treatment
Valorization of basic oxygen furnace (BOF) slag is of significant importance for mitigation of the steel production’s environmental impact. The present work aims to investigate the influence of SiO{sub 2} addition and oxygen partial pressure on the mineralogical modification of a typical industrial BOF slag. The slag basicity (mass ratio of CaO/SiO{sub 2}) was varied from 1.8 to 4.4 by mixing specific amounts of SiO{sub 2} with the master BOF slag. The original and modified slags were remelted and solidified under argon or air atmosphere followed by slow cooling. The experimental observations were then compared with the results of thermodynamic modeling to achieve a thorough understanding. With decreasing the basicity, free lime was eliminated, as it forms dicalcium silicate (Ca{sub 2}SiO{sub 4}). With increasing oxygen partial pressure, wustite was oxidized to hematite, which combined with free lime to form calcium aluminoferrite (C{sub 2}AF). The effects of SiO{sub 2} addition and oxygen partial pressure were finally evaluated with respect to the energy consumption for the BOF slag valorization. The modified slag is suitable as a precursor for construction applications as binders.
Interaction of Pure Alumina Refractory with FeO–SiO 2 and FeO–SiO 2 –CaO Slags Relevant to the Novel Flash Ironmaking Technology
Not provided.
The Effect of Propellant Variables on Slag in Subscale Spin Motors: Design and Qualification of a Slag Discrimination Motor - Part 1
The formation, collection, and expulsion of aluminum oxide slag is known to affect the performance of many solid rocket motor systems. Slag expulsion, in particular, is believed to be capable of causing pressure and thrust perturbations. Propellant combustion studies, performed and documented by many investigators, have shown that variations in propellant raw materials and processing affect the nature of alumina droplets at the burning propellant surface, and hence, may affect the quantity of slag retained in the motor chamber, available for expulsion. Thiokol has completed an experimental and analytical evaluation to determine the effects of several material and process variables on Space SHuttle propellant and its propensity to 'slag'. This paper describes the test article, a small scale spin motor with special nozzle, designed and qualified as a slag discriminating tool for use in the evaluation.
Iron speciation in blast furnace slag cements
Slag-containing pastes and concretes were analysed by element-specific synchrotron-based techniques to determine the speciation of iron on crushed materials through spatially resolved micro-spectroscopic studies. The investigated cement samples were hydrated either in the laboratory, or exposed to river or sea water. Metallic iron, along with minor proportions of iron sulphide and magnetite was detected in the laboratory sample. Iron sulphide, goethite, and siliceous hydrogarnet were discovered in the blended slag cements hydrated in contact with river water for up to 7 years. In contrast, no Fe(0) was observed in blended concretes exposed to sea water. Instead, iron sulphide, iron(II)-hydroxide and -oxide, hematite, magnetite, siliceous hydrogarnet, and goethite were detected as well as ilmenite (FeTiO{sub 3}) in the aggregates. The strong acceleration of Fe oxidation in samples exposed to sea water and the long-term passivation observed in the other samples indicate comparable processes as those occurring on steel bars.
Molecular structure of CaO?FeO[subscript x]?SiO[subscript 2] glassy slags and resultant inorganic po
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Synthesis of Titanium Oxycarbide from Titanium Slag by Methane-Containing Gas
In this study, reaction steps of a process for synthesis of titanium oxycarbide from titanium slag were demonstrated. This process involves the reduction of titanium slag by a methane-hydrogen-argon mixture at 1473 K (1200 °C) and the leaching of the reduced products by hydrofluoric acid near room temperature to remove the main impurity (Fe{sub 3}Si). Some iron was formed by disproportionation of the main M{sub 3}O{sub 5} phase before gaseous reduction started. Upon reduction, more iron formed first, followed by reduction of titanium dioxide to suboxides and eventually oxycarbide.
Effect of Slag Composition on the Crystallization Kinetics of Synthetic CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-MgO Slags
The crystallization kinetics of CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-MgO (CSAM) slags was studied with the aid of single hot thermocouple technique (SHTT). Kinetic parameters such as the Avrami exponent (n), rate coefficient (K), and effective activation energy of crystallization (E{sub A}) were obtained by kinetic analysis of data obtained from in situ observation of glassy to crystalline transformation and image analysis. Also, the dependence of nucleation and growth rates of crystalline phases were quantified as a function of time, temperature, and slag basicity. Together with the observations of crystallization front, they facilitated establishing the dominant mechanisms of crystallization. In an attempt to predict crystallization rate under non-isothermal conditions, a mathematical model was developed that employs the rate data of isothermal transformation. The model was validated by reproducing an experimental continuous cooling transformation diagram purely from isothermal data.
Slag Management of Carbon Feedstock Used in Gasification FY17 TCF between Eastman Chemical and NETL (Final Report)
NETL, in collaboration with Eastman Chemical Corp (Kingsport, TN), targeted the joint evaluation and refinement of a slag management program developed by NETL (NETL IP, patent applied for) to control gasifier slag properties formed from ash in individual or combinations of different coal-based carbon feedstock materials and specific slag modifiers used in gasification. Slag forms from mineral or organic-metallic impurities in the carbon feedstock that melt at the high temperatures of gasification, coalescing to form a liquid (slag) that must flow from the gasifier. Slag additives, also known as slag modifiers, are often added to the carbon feedstock to modify the ash chemistry and achieve desired slag flow properties at target temperatures used in gasification. If slag does not flow from a gasifier, its buildup within the gasification chamber will cause either gasifier shutdown to physically remove the slag (consuming time and damaging the protective refractory lining), or the gasification temperature must be increased to lower slag viscosity so it can flow from the gasifier, leading to greater refractory wear/corrosion, along with increased fouling and downstream component wear. Because of these issues, gasification is typically targeted at the lowest temperature possible where slag will flow in a controlled manner (a temperature range called T100 for the lowest temperature, with T250 being the highest temperature where the slag has achieved the desired fluidity). That temperature range also needs to yield a desired syngas composition, highlighting the importance of knowing and being able to control carbon feedstock slag viscosity and the temperature of thermal breakdown of the carbon feedstock. Slag viscosity varies with changes in the gasification chamber temperature, oxygen partial pressure, and slag chemistry. The slag model work with Eastman Chemical targeted predicting and controlling molten coal ash slag behavior at specific gasification conditions. The final goal of the refined model was to develop/refine the NETL slag model so a gasifier operator would be able to predict slag behavior prior to purchasing or using a carbon feedstock and control slag properties once a carbon feedstock is being gasified, allowing a gasifier user to determine what mineral additives or blends of different carbon materials would be needed to achieve desired slag properties at targeted gasification conditions. For a given carbon feedstock and desired gasification condition, the actual gasification cost and slag behavior would be able to be predicted using the slag management program in advance of purchasing or using the carbon feedstock – allowing accurate control of slag ash behavior in real time. As part of the TCF project work with Eastman Chemical, the viscosity of several ash compositions of interest to them would be measured and used to populate the slag model, along with a large database of historical slag temperature, chemistry, and viscosity information they possess – information that would in-crease the predictive accuracy of the slag management model with slag ash chemistry of interest to them. As part of the model evaluation and refinement, the predictive model and its database will be installed on computers at Eastman Chemical and used to manage slag properties in a gasifier during real-time operation of their gasifier. In summary, success of the slag management program at Eastman Chemical would support its use by other gasifier operators to manage slag chemistry and properties over other desired gasification temperature ranges, allowing greater process control and efficiency of their carbon feedstock conversion during gasification.
Crystallization Behavior of Liquid CaO-SiO{sub 2}-FeO-MnO Slag in Relation to Its Reaction with Moisture
To help maintain the sustainability of the steel industry, we are developing a novel process to recover thermal energy (in the form of hydrogen) and valuable metal elements contained in steelmaking slags by reacting molten slags with moisture. The process is dependent on the structure and properties of the slag, of which the crystallization tendency is key, since surface phases affect the slag reactivity with the gas and enable selective formation of solid phases containing transition metals. In this paper, the precipitated phases of the molten synthetic CaO-SiO{sub 2}-FeO-MnO slags after reacting with moisture were calculated by using thermodynamic package FactSage 7.0. Laboratory experiments were conducted to reveal the crystallization behavior of the targeted metal oxides in the slags with the aim of crystallization control. A hot stage-equipped confocal laser scanning microscope (CLSM) was used to in-situ observe the crystal precipitation on the surface of the liquid slag after reacting with moisture. Time temperature transformation (TTT) and continuous cooling transformation (CCT) diagrams were created from the precipitation behavior of crystals during cooling in the temperature range of 1873 K to 1173 K (1600 °C to 900 °C). The microstructures of the reacted slags were analyzed with a scanning electron microscope (SEM) equipped with an energy-dispersive spectrometer (EDS) and the phases present in the slag were characterized by X-ray diffraction (XRD). TTT curves of the reacted slags (with moisture) indicated that the nose temperature and critical time for nucleation located at 1473 K (1200 °C) and 89 seconds for the slag with basicity of 1.00. Further increasing the slag basicity to 1.25 and 1.50 increased the nose temperature to 1523 K and 1698 K (1250 °C and 1425 °C), respectively. CCT curves of the reacted slags (with moisture) indicated that the crystallization temperatures of precipitated phases increased with decreasing the cooling rate from 800 to 10 K/min, and the crystallization temperatures of primary phases increased with increasing slag basicity. Both magnetite (Fe{sub 3}O{sub 4}) and monoxide ((FeO){sub x}(MnO){sub 1−x}) phases were detected by SEM-EDS and XRD in the reacted slags (with moisture). The amount of magnetite in the reacted slags increased from 25 to 32 pct to 36 pct and that of monoxide decreased from 5 to 2 pct to 1 pct with the slag basicity increasing from 1.00 to 1.25 to 1.50.
Crystallization Characteristics and In-Mold Performance of Electroslag Remelting-Type TiO{sub 2}-Bearing Slag
The non-isothermal crystallization characteristics of the electroslag remelting (ESR)-type TiO{sub 2}-bearing slag were studied. The effect of crystallization characteristics of the slag on the in-mold performance was verified by ESR pilot trials operating in a static mode. The results showed that increasing TiO{sub 2} content decreased the crystallization temperature and liquidus temperature of the slag and suppressed the crystallization tendency of the slag. There is no change in the types of the crystalline phases in the slag with different TiO{sub 2} contents during cooling, i.e., 11CaO·7Al{sub 2}O{sub 3}·CaF{sub 2}, CaTiO{sub 3}, and CaF{sub 2}. The sequence of crystal precipitation during cooling was 11CaO·7Al{sub 2}O{sub 3}·CaF{sub 2} to CaTiO{sub 3}, and then CaF{sub 2} with increasing TiO{sub 2} content from 4.2 to 12.6 mass pct. With adding 16.8 mass pct TiO{sub 2} in the slag, the precipitation of 11CaO·7Al{sub 2}O{sub 3}·CaF{sub 2} and CaTiO{sub 3} took place simultaneously, followed by CaF{sub 2}. With the increase in the TiO{sub 2} content from 4.2 to 16.8 mass pct in the slag, the dominant crystalline phase changed from 11CaO·7Al{sub 2}O{sub 3}·CaF{sub 2} to CaTiO{sub 3}. The morphology of 11CaO·7Al{sub 2}O{sub 3}·CaF{sub 2} and CaTiO{sub 3} changed from faceted and bonelike to elliptically faceted and blocky, respectively. The morphology of CaF{sub 2} were spherical in all cases, irrespective of TiO{sub 2} contents in the slag. The decrease in the crystallization tendency of the slag with increasing TiO{sub 2} contents was attributed to the decrease in the activity of CaO in the slag. The increasing of TiO{sub 2} content in the slag are favorable for providing thin slag skin and stable heat flux across the slag skin, which improved the surface quality of the as-cast ESR ingot as demonstrated by ESR pilot trials operating in a static mode.
Thermodynamic Properties and Viscosities of CaO-SiO{sub 2}-MgO-Al{sub 2}O{sub 3} Slags
In this work, the effects of Al{sub 2}O{sub 3}, basicity, and MgO/Al{sub 2}O{sub 3} ratio on the heat capacity, enthalpy change, and viscosity of CaO-SiO{sub 2}-MgO-Al{sub 2}O{sub 3} slags at 1773 K, 1823 K, and 1873 K (1500 °C, 1550 °C, and 1600 °C) were investigated. The heat capacity of the slag increased with increasing Al{sub 2}O{sub 3}, basicity, and MgO/Al{sub 2}O{sub 3} ratio in the experimental temperature range. The enthalpy change increased with increasing Al{sub 2}O{sub 3} content and MgO/Al{sub 2}O{sub 3} ratio, and decreasing basicity. Under the fixed heat quantity of the slag, the addition of Al{sub 2}O{sub 3} would result in a decrease of slag temperature and increase of slag viscosity. The effect of decreasing temperature on the viscosity was more significant than increasing Al{sub 2}O{sub 3} content. Increases of slag basicity led to the increased slag temperature and the decreased viscosity which was due to the increased slag temperature. The viscosity change rate with different temperatures was more pronounced than that of different slag compositions. The change of the slag temperature at fixed heat quantity would be opposite due to different expressions of MgO/Al{sub 2}O{sub 3} ratio. In addition, when the heat decrement of the slag was fixed, the slag temperature rose first with the increase of MgO/Al{sub 2}O{sub 3} ratio and then decreased, while the viscosity decreased gradually. The viscosity fluctuation caused by different heat decrements reduced as well with increasing MgO/Al{sub 2}O{sub 3} ratio.
Development of Kinetic Model for Reactions Between Cu-Containing Multicomponent Slag and Liquid Sulfide Using Coupled Reaction Model
Copper smelting slag contains less than 2 mass pct of Cu oxide and 30–50 mass pct of Fe{sub x}O. Each year, the grade of copper ore decreases, while the amount of slag generated in the copper smelting process increases. In this study, a coupled reaction model to simulate the reaction between multicomponent slag and FeS-based matte was developed using reported thermodynamic data and double-film theory for the recycling of copper smelting slag. The activity coefficients of oxides in the multicomponent slag were calculated using a regular solution. The activity coefficients of Cu{sub 2}O in the slag and those of FeS, Cu{sub 2}S, and CaS in the FeS-based matte used previously reported data. The behaviors of Cu in slag and matte were confirmed by comparing the simulated results and the reported solubility of Cu in the slag in the temperatures ranging from 1473 K to 1573 K. In addition, the effect of the input amount of FeS on the copper content of the slag was verified by comparing the results of reaction model to experimental results. Using the reaction model, the influences of the initial ratio of FeO/SiO{sub 2} of the slag, temperature, and matte composition on the behaviors of Cu in the slag and matte were investigated.
Effect of Iron Phase Evolution on Copper Separation from Slag Via Coal-Based Reduction
Copper slag, a by-product of copper pyrometallurgy, inevitably contains a certain amount of copper. Oxygen-enriched smelting technologies increase the copper content in slag indirectly because of the production of higher-grade matte. The effect of iron phase evolution on the copper content in slag during the slag cleaning process in an electric furnace was investigated using the method of combining theory with experiments. Based on the analysis, the main factors that impede the separation of slag and copper/matte were determined. Subsequently, the properties of slag were analyzed after decreasing the magnetite content within the slag. The experimental results showed that decreases in magnetite content were beneficial for the separation of copper and slag because of the decrease of slag viscosity. Nevertheless, Cu-Fe alloys formed when magnetite was completely reduced to metallic iron, and the foaming slag was formed at 1250 °C. Furthermore, the distribution of copper in the reduced slags was studied in detail.