Effect of Basicity and Al2O3 on Viscosity of Blast Furnace Slag and Thermodynamic Analysis

With the increased use of laterite nickel ore, the impact of high Al2O3 slag on blast furnace smelting has gradually increased. In this paper, the effects of slag basicity and Al2O3 content on slag viscosity and enthalpy change under constant temperature conditions was investigated. The changes in slag structure were analyzed by activation energy and Fourier Transform Infrared (FT-IR) spectroscopy. The relationship between slag components and slag temperature and viscosity when slag heat is reduced was investigated. The results showed that the viscosity first slightly decreased and then significantly increased with increasing basicity at constant temperature. With the addition of Al2O3 content, the viscosity of the slag increases. The activation energy increases with increasing slag basicity and Al2O3. With increasing basicity, the [SiO4]4- tetrahedral unit trough depth becomes shallow, the [AlO4]5- asymmetric stretching band migrates to lower wave numbers, and the slag structure depolymerizes. With the increase of Al2O3 content, the trough of [SiO4]4- tetrahedra deepens and the center of the symmetric stretching band moves to a higher wave number. The [AlO4]5- asymmetric stretching band becomes obvious, indicating the complexity of the slag structure. When the heat decreases, the slag temperature increases as the basicity increases, and the slag thermal stability is better at the basicity of 0.95-1.05. As the Al2O3 content increases, the thermal stability of the slag becomes worse.

Direct microalloying of steel with cerium under slags of СаО–SiO 2 – Ce2O3– 15 % Al2O3 –8 % MgO system with additional reducing agents

An assessment of the possibility of steel direct microalloying with cerium was performed using thermodynamic modeling of cerium reduction from slags of CaO– SiO2– Ce2O3 system containing 15 % Al2O3 and 8 % МgO, additional additives of reducing agents (aluminum or ferrosilicoaluminium), at temperatures of 1550 and 1650 °C using the HSC 6.1 Chemistry (Outokumpu) software package. Depending on the additional additives of aluminum or ferroglycoaluminium, metal temperature, slag basicity and content of cerium oxide, 0.228 to 40.5 ppm of cerium transfers into the metal. With an additional additive of aluminum from slag (Y1) containing 1.0 % of cerium oxide, 0.228 ppm of cerium is transferred to the metal at 1550 °C. An increase in the system temperature to 1650 °C is accompanied by a slight increase in cerium content, reaching no more than 0.323 ppm. When added to ferrosilicoaluminium metal, cerium content in the metal is higher and amounts to 0.402 and 0.566 ppm at 1550 and 1650 °C, respectively. When concentration of cerium oxide in the slag (Y2) increases to 7.0 %, more signifcant increase in cerium content in the metal is observed, reaching in temperature range of 1550 – 1650 °C, 1.65 – 2.31 ppm with aluminum additives and 2.90 – 4.05 ppm with ferrosilicoaluminium additives. The most noticeable increase in cerium content in the metal is observed with an increase in slag basicity. During formation of slags with basicity of 2 – 3, containing 1 – 7 % Ce2O3, the equilibrium concentration of cerium in the metal varies from 0.5 to 4 ppm with aluminum additives and 1 – 7 ppm with ferro­silicoaluminium additives at 1550 °C. Slags transfer to the increased (up to 3 – 5) basicity is accompanied by an increase in the equilibrium content of cerium in the metal to 4 – 12 ppm with aluminum additives and 7 – 20 ppm with ferrosilicoaluminium additives at Ce2O3 content of 3 – 7 % and, as a result, an increase in efciency of cerium reduction process.

Theoretical and Experimental Studies of Sulfur and Boron Distribution between the Slag of the CaO-SiO2-B2O3-MgO-Al2O3 System and the Metal

The equilibrium interfacial distribution of sulfur and boron was estimated using the HSC 6.1 Chemistry software package (Outokumpu) and the simplex-lattice planning method. Adequate mathematical models have been constructed in the form of III degree polynomial, which describe the effect of the composition of the studied oxide system on the equilibrium distribution of sulfur and boron between the slag and the metal. Generalization of the results of experimental studies and thermodynamic modeling made it possible to obtain new data on the influence of the basicity and content of B2O3 in the slag of the CaO-SiO2-B2O3-MgO-Al2O3 system on the interphase distribution of sulfur and boron. It was found that in the range of boron oxide concentration of 1.0-10%, an increase in slag basicity from 2 to 5 at 1600°C leads to an increase in the sulfur distribution coefficient from 1 to 20 and, as a consequence, a decrease in the sulfur content in the metal from 0.02 to 0.0014 %, i.e. an increase in slag basicity favorably affects the development of the metal desulfurization process. An increase in the B2O3 content from 2.0 to 10.0% in slags formed in the region of moderate basicity, not exceeding 2-3, is accompanied at 1600°C by a decrease in the boron interphase distribution coefficient from 450 to 150 and an increase in the boron concentration in the metal from 0.006 to 0.021 %, which indicates the progress of boron reduction from slag to metal. The shift of the formed slags to the area of ​​increased basicity up to 5.0 shows a high degree of boron reduction from slag to metal. The results of the laboratory experiment confirmed the results of thermodynamic modeling.

Mechanism of Phosphorus Enrichment in Dephosphorization Slag Produced Using the Technology of Integrating Dephosphorization and Decarburization

In order to better understand and develop the technology of integrating dephosphorization and decarburization in a single converter (abbreviated as IDDSC), the relevant thermodynamic issues were discussed by calculation. Based on the thermodynamic calculation, the bridges between the phosphorus distribution ratio, temperature, and slag composition were constructed. Besides, the connections between the dephosphorization behavior and the microstructure of slag were also established by investigating four heats of hot metal smelt using IDDSC technology. As a result, the mechanism of phosphorus enrichment in the dephosphorization slag was revealed. Also, the results show that the dephosphorization efficiency increases gradually with increasing slag basicity. While the dephosphorization efficiency increases first and then decreases with the increase of FeO content in slag. There is a competition relationship between P2O5 and FeO in reacting with CaO and SiO2. When CaO/FeO is relatively high, not enough FeO is provided. Thus P2O5 is in priority to react with CaO and SiO2 through [3n + 2](CaO) + 2SiO2 + n(P2O5) = n(3CaO·P2O5)-2CaO·SiO2(s), generating P2O5-rich nC2S-C3P solid solution which promotes the removal of [P] from the hot metal. When CaO/FeO is relatively low, FeO competes over P2O5 in reacting with CaO and SiO2 through a(CaO) + b(SiO2) + c(FeO) = aCaO·bSiO2·cFeO(s), generating CaFeSiO4 instead of P2O5-rich solid solution. As a consequence, the slag with low CaO/FeO shows a poor dephosphorization ability.

Analysis of possible ways to reduce sulfur content in pig iron

One of the ways to increase the energy efficiency and intensity of blast furnace smelting, especially when using pulverized coal fuel, is to increase the hot strength of coke. In the conditions of OJSC NLMK, an oil additive was introduced into the coal charge to improve the coke quality. At the same time, sulfur content in the coke increases, and, consequently, sulfur content in the cast iron increases as well. In this regard, the task of finding ways to improve the desulfurization of cast iron in blast furnace becomes urgent. The main factors determining the desulfurization of cast iron are slag basicity, content of MgO oxide in it, temperature of the smelting products, and the slag viscosity. The purpose of this work was to compare the efficiency of sulfur removal by increasing the slag basicity and MgO content. On the basis of wellknown equations, an algorithm was developed that allows the problem to be solved. It was established that an increase in MgO content in the slag promotes desulfurization of cast iron to a greater extent than a basicity increase. In addition, an increase in MgO content by 1 % is accompanied by an increase in slag yield by 3.0 – 3.5 kg/t of cast iron. At the same time, an increase in basicity by 0.01 leads to an increase in the slag yield by 4 – 5 kg/t of pig iron. Consequently, reducing the sulfur content in pig iron by increasing the slag basicity requires less heat. In terms of the specific consumption of coke, difference in heat demand is 0.4 – 0.5 kg/t of pig iron. It is shown that with an increase in MgO content in the slag, the slag viscosity at a temperature of 1450 °C increases to a lesser extent than with an increase in basicity.

Equilibrium content of lanthanum in metal under the slag of СаО – SiO2 – La2O3 – 15 % Al2O3 – 8 % MgO system

Thermodynamic modeling results of lanthanum equilibrium content in metal under the slag of CaO – SiO2 – La2О3 – Al2O3 – MgO system corresponding to chemical composition of 16 points of local simplex plan are presented using the HSC 8.03 Chemistry (Outokumpu) software package in combination with the simplex planning lattice method. In the work, slag is represented by CaO – SiO2 – La2O3 – – 15 % Al2O3 – 8 % MgO oxide system in a wide range of chemical composition for temperatures of 1550 and 1650 °C, and metal contains 0.06 % C, 0.25 % Si, 0.05 % Al (in this expression and hereinafter in mass.%). The results of mathematical modeling are shown graphically in the form of composition - equilibrium content diagrams of lanthanum. There is significant effect of slag basicity on the lanthanum equilibrium content in metal. An increase in slag basicity from 2 to 5 at temperature of 1550 °C leads to an increase in the lanthanum equilibrium content from 0.2 ppm in the region of lanthanum oxide concentration of 1 – 5 % to 7 ppm in the region of increased concentration of lanthanum oxide to 4 – 7 %, hence the increase in slag basicity favorably affects development of lanthanum reduction. Increase in metal temperature also has positive effect on lanthanum reduction process. As temperature rises to 1650 °C, the lanthanum equilibrium content in metal increases from 0.2 ppm in the region of lanthanum oxide concentration of 1 – 3 % to 12 ppm in the region of increased concentration of lanthanum oxide to 4 – 7 %. In diagrams of chemical composition of slag containing 56 – 61 % CaO, 12 – 14 % SiO2 and 4 – 7 % La2O3 , the lanthanum content in metal at level of 7 – 12 ppm is ensured in temperature range from 1550 to 1650 °C. Therefore, there can be confirmed a decisive role of slag basicity, concentration of lanthanum oxide and temperature factor in development of lanthanum reduction from slags of the studied oxide system by aluminum dissolved in metal.

Features of ladle desulfuration of pipe steel with low sulfur content

At the present time the sulfur content in pipe steel is strictly regulated. Under conditions of PJSC “Magnitogorsk Iron and Steel Works” the metal is smelted in BOF shop with preliminary desulfurization of molten iron, treatment of tapping steel by a solid slag-forming mixture and final desulfurization in the “Ladle-Furnace” unit (LP-unit). In order to increase the efficiency of the sulfur removal process, the influence of the covering slag composition on metal desulfurization is considered. Statistical processing of production data array consisting of 14 melts of steel grade 10Г2ФБЮ with K60 strength class was performed. The dependences of the sulfur content in the metal after desulfurization in the LP-unit on the oxidizing ability, covering slag basicity and the content of magnesium oxide was established: it is shown that the amount of sulfur removed during the ladle treatment process increases with the increase of the covering slag basicity and with the decrease of the magnesium oxide content in slag. For describing this dependence, a new parameter was proposed – the ratio of slag basicity to MgO content in it, %–1. A high content of magnesium oxide in the “white” slag was revealed. This fact indicates a significant amount of converter slag getting into the ladle due to its poor cut-off in the process of metal tapping from the unit. The study of the influence of the coating “white” slag composition on the metal desulfurization process in the LP-unit showed, that for the effective sulfur removal, it is necessary to provide not only welldeoxidized slag with a total content of iron and manganese oxides of less than 1%, but also to ensure the ratio of its basicity to the magnesium content in this slag not less than 0.60–0.65%–1.

Determination of chromium valence state in the CaO–SiO2–FeO–MgO–CrOx system by X-ray photoelectron spectroscopy

The chromium valence states in the CaO–SiO2–FeO–MgO–CrOx system were investigated by X-ray photoelectron spectroscopy (XPS). The results indicated that the XPS peaks of Cr 2p3/2 and Cr 2p1/2 locate at the binding energy of ∼577 and ∼586 eV, respectively. There are three kinds of chromium ions such as bivalent Cr(ii), trivalent Cr(iii), and hexavalent Cr(vi) in the CaO–SiO2–FeO–MgO–CrOx slag. Cr(iii) is the dominant valence state, and more than 77.99% Cr is trivalent Cr(iii). The fraction of Cr(ii)/Cr is in the range of 11.24–17.22%. The fraction of Cr(vi)/Cr is below 4.80%. The fraction of Cr(ii)/Cr decreases with increasing slag basicity, Cr2O3 content, temperature, or oxygen pressure log(PO2), while the fraction of Cr(iii)/Cr increases with increasing basicity, Cr2O3 content, temperature, or oxygen pressure. The trend of change is opposite. Low log(PO2), high Cr2O3 content, and high temperature are beneficial to reduce the toxic hexavalent Cr(vi). The slag basicity has little influence on the fraction of Cr(vi)/Cr.