KTH Industrial Engineering and Management Sulfur and Nitrogen in Ladle Slag
Sweden Akademisk avhandling som med tillstånd av Kungliga Tekniska Högskolan i Stockholm, framlägges för offentlig granskning för avläggande av Teknologie Doktorsexamen, fredagen den 1 april 2016, ABSTRACT The present work deals with some aspects of slags related to secondary metallurgy in the steelmaking process. More specifically the focus is given to sulfur and nitrogen in ladle slags. Even though slags have been fairly well–researched in the past, the available data for these elements in typical ladle slag compositions is rather scarce. In some cases the available data is in discordance. There are also inconsistencies between the literature data and what is commonly observed in the industrial processes. Sulfide capacities were measured at steelmaking temperatures, 1823–1873 K, in ladle slags. The data was found to be in reasonable agreement with the industrial process norms. The sulfide capacity was found to increase with the basic oxides CaO and MgO; and decrease with the acidic components Al 2 O 3 and SiO 2. The sulfide capacity was also found to increase with temperature. The dependence of sulfide capacity on the oxygen partial pressure, for slags containing multivalent elements, was investigated experimentally at 1873 K with a slag containing vanadium oxide. A strong dependence of oxygen partial pressure was observed. The sulfide capacity increase by more than two orders of magnitude when the oxygen partial pressure was increased from 4.6×10-16 atm to 9.7×10-10 atm. The nitrogen solubility and the effect of carbon was investigated in typical ladle slags and the CaO–MgO–SiO 2 system at 1873 K. Carbon increases the nitrogen solubility substantially. In the absence of carbon, the nitrogen solubility is extremely low. Low concentrations of cyanide was detected in the carbon saturated slag. This was much lower than the total nitrogen content and formation of cyanide cannot explain the large increase. The possibility of removing sulfur with oxidation from used ladle slag was investigated experimentally at 1373–1673 K. The sulfur removal of mostly solid slag was found to be a slow process, and would not suitable for industrial practice. At 1673 K the slag was mostly liquid and more than 85% of the sulfur was removed after 60 min of oxidation in pure oxygen atmosphere. ii ACKNOWLEDGEMENTS
Thermodynamic Model and Database for Sulfides Dissolved in Molten Oxide Slags
A thermodynamic model has been developed in the framework of the modified quasichemical model in the quadruplet approximation to permit the calculation of solubilities of various gaseous species (sulfide, sulfate, nitride, carbide, water, etc.) in molten slags. The model calculates the solubilities solely from knowledge of the thermodynamic activities of the component oxides and the Gibbs energies of the pure liquid components (oxides, sulfides, sulfates, etc.). In the current article, it is shown that solubilities of sulfur as sulfide in Al2O3-CaO-FeO-Fe2O3-MgO-MnO-SiO2-TiO2-Ti2O3 multicomponent slags, which are predicted from the current model with no adjustable model parameters, are in good agreement with all available experimental data. The article also provides a thorough review of experimental sulfide capacity data for this system. The model applies at all compositions from pure oxides to pure sulfides and from basic to acidic slags. By coupling this database with other evaluated databases, such as those for molten metal and gaseous phases, and with general software for Gibbs energy minimization, practically important slag/metal/gas/solid equilibria can be computed such as S-distribution ratios.
Experimental investigation of the geotechnical properties and microstructure of lime-stabilized saline soils under freeze-thaw cycling
Abstract The Song-Nen Plain in northeastern China holds one of the three largest expanses of soda saline-alkali soil in the world. Due to its disadvantageous geotechnical properties, the saline soil in this area is unable to meet the needs of construction projects. This study evaluates the stabilizing effect of adding lime to such soils. Specifically, it investigates how the physicochemical and mechanical properties and microstructure of soda saline-alkali soil are altered by lime and how these changes are affected by both freeze-thaw cycling and the duration of curing. The results reveal that adding lime to saline soil transforms clay particles into sand and silt particles and causes the pore size distribution (PSD) to become bimodal, with small-pore and macropore populations. An increase in lime content leads to an increase in the unconfined compressive strength (UCS) but a gradual decrease in both the cation exchange capacity (CEC) and plastic index. Freeze-thaw cycles break up coarse particles and aggregate finer particles, increasing the diameter of macropores and decreasing the USC; however, the effect on specimens with >9% lime is negligible. It is further shown that the geotechnical properties of the soil change immediately after the addition of lime, indicating that the cation exchange reaction takes place very quickly. Furthermore, the pozzolanic reaction leads to an increase in the percentage of sand-sized particles and a decrease in porosity after 28 days of curing. Overall, these results indicate that it is feasible to use lime to improve the engineering properties of soda saline-alkali soil in this area.