Sulfur distribution in preparation of high titanium ferroalloy by thermite method with different CaO additions

Ferrotitanium is used as a deoxidizer and alloying agent during steelmaking process,which has a high demand for sulfur control.Sulfur was introduced from raw materials in the process of producing ferrotitanium by thermite method,where CaO was used as fluxing agent.At the same time,CaO has a great desulfurization capability.Effects of CaO addition on the distribution of sulfur in high titanium ferroalloy prepared by thermite method were studied in this work.The equilibrium diagram of Ti-AlFe-S system was calculated by FactSage 6.4 software package with FactPS and FTmisc database.The alloy and slag samples were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),inductively coupled plasma atomic emission spectrometer(ICP-AES),X-ray fluorescence(XRF)and high-frequency infrared ray carbon sulfur analyzer.The result indicates that the sulfur in the alloy firstly exists in the form of liquid FeS,thereafter TiS(s)and eventually Ti2 S(s)during cooling.The sulfur is mainly distributed in the alloy,and only a small amount of sulfur remains in the slag.Moreover,it is noted that the sulfur in the alloy does not distribute homogeneously,and it exists in the form of solid solution phase,(Ti,Al,Fe)S.S content in the slag,the sulfur capacity of the slag and the sulfur distribution ratio(LS)all increase with the increment of CaO addition,while S content in alloys decreases.

Oxygen content of high ferrotitanium prepared by thermite method with different melt separation temperatures

High ferrotitanium prepared directly by the thermite method has a disadvantageously high O content(≥10 wt%)because of the short slag-metal separation time.In this study,CaO and CaF2 are added to the melt to improve the basicity of the slag and melt separation under heat preservation is performed to strengthen slag-metal separation.The thermodynamics of the step-by-step reduction process of TiO2 in the Ti-Al-Fe-Si-O system whose composition is close to the alloy after melt separation were calculated.Samples of alloys and slags before and after melt separation were systematically analyzed.The result indicates that the reaction that TiO is reduced by Al to Ti is the limited step in the reduction process of TiO2.The O content of the alloys slightly decreases with temperature from 1873 to 2023 K,which agrees with the changes in the law of deoxidation limit.It is mainly attributed to the movement of chemical reactions in the alloy melt at different temperatures and slag-metal interfacial reaction.The addition of Al2 O3-CaO-CaF2 slag and high temperature promote the removal of Al2 O3 and titanium suboxides.The minimum contents of O and Al in the alloy reach 1.84 wt% and 3.26 wt%,respectively.

Mechanism of fluidized chlorination reaction of Kenya natural rutile ore

In this paper, the thermodynamics and kinetics of nature rutile carbochlorination in a fluidized-bed were investigated. The thermodynamic calculations of TiO2-C- C12 system show that when C is excess in the solid phase, titanium tetrachloride and carbon monoxide can exist sta- bly. At high temperature, the reaction with CO as the product is the dominant reaction. The appropriate reaction conditions are as follows： reaction temperature of 950 ℃, reaction time of 40 min, carbon ratio of 30 wt% of rutile, natural rutile particle size of -96 μm, petroleum coke size of -150 μm, and chlorine flow of 0.036 m3.h-1. Under the above conditions, the reaction conversion rate of TiO2 can reach about 95 %. This paper proposed a reaction rate model, and got a rutile chlorination rate formula, which is generally consistent with the experimental data. For the TiO2-C-C12 system, the reaction rate is dependent on the initial radius of rutile particle, density, and the partial pressures of C12. From 900 to 1,000 ℃, the apparent activation energy is 10.569 kJ.mo1-1, and the mass diffu- sion is found to be the main reaction-controlling step. The expression for the chlorine reaction rate in the C-C12 sys- tem is obtained, and it depends on the degree of reaction, the partial pressure of C12, and the size of rutile particle.