中性气氛下钒钛磁铁矿高炉渣系研究

以钒钛磁铁矿现场高炉渣为基础,纯化学试剂调制渣样,在中性气氛条件下研究了炉渣二元碱度及Mg O,Al2O3,Ti O2,V2O5含量对实验渣系冶金性能的影响.结果表明:增加碱度和Mg O含量,炉渣熔化性温度(tm)、初始黏度(η0)和高温黏度(ηh)呈先降低后升高趋势;增大Al2O3含量,炉渣tm升高,η0先降低后升高,ηh呈上升趋势;增大Ti O2含量,炉渣tm升高,η0和ηh逐渐下降,炉渣黏流活化能升高,热稳定性变差;增大V2O5含量,炉渣tm先降低后升高,η0和ηh逐渐增大.高炉冶炼钒钛磁铁矿适宜渣系为:二元碱度1.15,Mg O,Al2O3,Ti O2,V2O5质量分数分别为13%,13%,7%,0.30%.     

Effect of TiO2 on the viscosity and structure of low-fluoride slag used for electroslag remelting of Ti-containing steels

The viscosity of CaF2–CaO–Al2O3–MgO–(TiO2) slag was measured using a rotating crucible viscometer. Raman spectroscopy analysis was performed to correlate the viscosity to slag structure. The viscosity of the slag was found to decrease with increasing TiO2 con-tent in the slag from 0 to 9.73wt%. The activation energy decreased from 95.16 kJ/mol to 79.40 kJ/mol with increasing TiO2 content in the slag. The introduction of TiO2 into the slag played a destructive role in Al–O–Al structural units and Q4 units by forming simpler structural units of Q2 and426TiO- chain. The amount of Al–O–Al significantly decreased with increasing TiO2 content. The relative fraction of4Q units in the [AlO4]5?-tetrahedral units shows a decreasing trend, whereas the relative fraction of2Q units and426TiO- chain increases with increasing TiO2 content accordingly. Consequently, the polymerization degree of the slag decreases with increasing TiO2 content. The varia-tion in slag structure is consistent with the change in measured viscosity.     

Effect of the CaO/SiO2 mass ratio and FeO content on the viscosity of CaO–SiO2–"FeO"–12wt%ZnO–3wt%Al2O3 slags

An effective process for recycling lead from hazardous waste cathode ray tubes (CRTs) funnel glass through traditional lead smelting has been presented previously. The viscous behavior of the molten high lead slag, which is affected by the addition of funnel glass, plays a critical role in determining the production efficiency. Therefore, the viscosities of the CaO–SiO2–"FeO"–12wt%ZnO–3wt%Al2O3 slags were measured in the current study using the rotating spindle method. The slag viscosity decreases as the CaO/SiO2 mass ratio is in-creased from 0.8 to 1.2 and also as the FeO content is increased from 8wt% to 20wt%. The breaking temperature of the slag is lowered sub-stantially by the addition of FeO, whereas the influence of the CaO/SiO2 mass ratio on the breaking temperature is complex. The structural analysis of quenched slags using Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy reveals that the silicate network structure is depolymerized with increasing CaO/SiO2 mass ratio or increasing FeO content. The [FeO6]-octahedra in the slag melt increase as the CaO/SiO2 mass ratio or the FeO content increases. This increase can further decrease the degree of polymerization (DOP) of the slag. Furthermore, the activation energy for viscous flow decreases both with increasing CaO/SiO2 mass ratio and increasing FeO content.     

Effect of TiO<Subscript>2</Subscript> on the viscosity and structure of low-fluoride slag used for electroslag remelting of Ti-containing steels

The viscosity of CaF₂-CaO-Al₂O₃-MgO-(TiO₂) slag was measured using a rotating crucible viscometer. Raman spectroscopy analysis was performed to correlate the viscosity to slag structure. The viscosity of the slag was found to decrease with increasing TiO₂ content in the slag from 0 to 9.73wt%. The activation energy decreased from 95.16 kJ/mol to 79.40 kJ/mol with increasing TiO₂ content in the slag. The introduction of TiO₂ into the slag played a destructive role in Al-O-Al structural units and Q4 units by forming simpler structural units of Q2 and Ti₂O₆4- chain. The amount of Al-O-Al significantly decreased with increasing TiO₂ content. The relative fraction of Q4 units in the[AlO₄]5--tetrahedral units shows a decreasing trend, whereas the relative fraction of Q2 units and Ti₂O₆4- chain increases with increasing TiO₂ content accordingly. Consequently, the polymerization degree of the slag decreases with increasing TiO₂ content. The variation in slag structure is consistent with the change in measured viscosity.     

TiO2对含铬高钛熔分渣熔化性能和黏度的影响

A study on the melting and viscosity properties of the chromium-containing high-titanium melting slag (CaO–SiO₂–MgO–Al₂O₃–TiO₂–Cr₂O₃) with TiO₂ contents ranging from 38.63wt% to 42.63wt% was conducted. The melting properties were investigated with a melting-point apparatus, and viscosity was measured using the rotating cylinder method. The FactSage 7.1 software and X-ray diffraction, in combination with scanning electron microscopy–energy-dispersive spectroscopy (SEM–EDS), were used to characterize the phase equilibrium and microstructure of chromium-containing high-titanium melting slags. The results indicated that an increase in the TiO₂ content led to a decrease in the viscosity of the chromium-containing high-titanium melting slag. In addition, the softening temperature, hemispheric temperature, and flowing temperature decreased with increasing TiO₂ content. The amount of crystallized anosovite and sphene phases gradually increased with increasing TiO₂ content, whereas the amount of perovskite phase decreased. SEM observations revealed that the distribution of the anosovite phase was dominantly influenced by TiO₂.     

Rheological behavior and constitutive equations of heterogeneous titanium-bearing molten slag

Experimental studies on the rheological properties of a CaO–SiO₂–Al₂O₃–MgO–TiO₂–(TiC) blast furnace (BF) slag system were conducted using a high-temperature rheometer to reveal the non-Newtonian behavior of heterogeneous titanium-bearing molten slag. By measuring the relationships among the viscosity, the shear stress and the shear rate of molten slags with different TiC contents at different temperatures, the rheological constitutive equations were established along with the rheological parameters; in addition, the non-Newtonian fluid types of the molten slags were determined. The results indicated that, with increasing TiC content, the viscosity of the molten slag tended to increase. If the TiC content was less than 2wt%, the molten slag exhibited the Newtonian fluid behavior when the temperature was higher than the critical viscosity temperature of the molten slag. In contrast, the molten slag exhibited the non-Newtonian pseudoplastic fluid characteristic and the shear thinning behavior when the temperature was less than the critical viscosity temperature. However, if the TiC content exceeded 4wt%, the molten slag produced the yield stress and exhibited the Bingham and plastic pseudoplastic fluid behaviors when the temperature was higher and lower than the critical viscosity temperature, respectively. When the TiC content increased further, the yield stress of the molten slag increased and the shear thinning phenomenon became more obvious.     

Effect of the CaO/SiO2 mass ratio and FeO content on the viscosity of CaO-SiO2-“FeO”-12wt%ZnO-3wt%Al2O3 slags

An effective process for recycling lead from hazardous waste cathode ray tubes (CRTs) funnel glass through traditional lead smelting has been presented previously. The viscous behavior of the molten high lead slag, which is affected by the addition of funnel glass, plays a critical role in determining the production efficiency. Therefore, the viscosities of the CaO-SiO₂-"FeO"-12wt%ZnO-3wt%Al₂O₃ slags were measured in the current study using the rotating spindle method. The slag viscosity decreases as the CaO/SiO₂ mass ratio is increased from 0.8 to 1.2 and also as the FeO content is increased from 8wt% to 20wt%. The breaking temperature of the slag is lowered substantially by the addition of FeO, whereas the influence of the CaO/SiO₂ mass ratio on the breaking temperature is complex. The structural analysis of quenched slags using Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy reveals that the silicate network structure is depolymerized with increasing CaO/SiO₂ mass ratio or increasing FeO content. The[FeO₆]-octahedra in the slag melt increase as the CaO/SiO₂ mass ratio or the FeO content increases. This increase can further decrease the degree of polymerization (DOP) of the slag. Furthermore, the activation energy for viscous flow decreases both with increasing CaO/SiO₂ mass ratio and increasing FeO content.     

Dripping and evolution behavior of primary slag bearing TiO<Subscript>2</Subscript> through the coke packed bed in a blast-furnace hearth

To investigate the flow of primary slag bearing TiO₂ in the cohesive zone of blast furnaces,experiments were carried out based on the laboratory-scale packed bed systems.It is concluded that the initial temperature of slag dripping increases with decreasing FeO content and increasing TiO₂ content.The slag holdup decreases when the FeO content is in the range of 5wt%-10wt%,whereas it increases when the FeO content exceeds 10wt%.Meanwhile,the slag holdup decreases when the TiO₂ content increases from 5wt% to 10wt% but increases when the TiO₂ content exceeds 10wt%.Moreover,slag/coke interface analysis shows that the reaction between FeO and TiO₂ occurs between the slag and the coke.The slag/coke interface is divided into three layers:slag layer,iron-rich layer,and coke layer.TiO₂ in the slag is reduced by carbon,and the generated Ti diffuses into iron.     

MgO含量对CaO-Al2O3-MgO-FexO-SiO2-K2O系熔体性质的影响

研究了MgO含量变化对CaO-Al2O3-MgO-FexO-SiO2-K2O系熔体黏度和熔化特性的影响,结合X射线衍射和扫描电镜分析熔渣冷却过程中的物相析出,并通过FactSage软件计算了该体系的黏度、熔点和冷却过程中析出相的含量与温度的关系,并与实验结果进行了对比和分析.结果表明,MgO含量的增多会造成熔渣熔化温度的升高,黏度随温度变化时会出现黏度骤增的转折点,高于转折点温度时,熔渣黏度随MgO含量变化不大,同时该转折点温度随MgO含量的增加而升高.在熔渣冷却过程中析出相主要为固溶的橄榄石相和Fe3O4尖晶石相,MgO含量的增大可以促进橄榄石相的析出,熔体黏度骤增主要由于橄榄石相的析出造成的.     

Effects of Fe content on the microstructure and properties of CuNi10FeMn1 alloy tubes fabricated by HCCM horizontal continuous casting

Heating-cooling combined mold (HCCM) horizontal continuous casting technology developed by our research group was used to produce high axial columnar-grained CuNi10FeMn1 alloy tubes with different Fe contents. The effects of Fe content (1.08wt%–2.01wt%) on the microstructure, segregation, and flushing corrosion resistance in simulated flowing seawater as well as the mechanical properties of the alloy tubes were investigated. The results show that when the Fe content is increased from 1.08wt% to 2.01wt%, the segregation degree of Ni and Fe elements increases, and the segregation coefficient of Ni and Fe elements falls from 0.92 to 0.70 and from 0.92 to 0.63, respectively. With increasing Fe content, the corrosion rate of the alloy decreases initially and then increases. When the Fe content is 1.83wt%, the corrosion rate approaches the minimum and dense, less-defect corrosion films, which contain rich Ni and Fe elements, form on the surface of the alloy; these films effectively protect the α-matrix and reduce the corrosion rate. When the Fe content is increased from 1.08wt% to 2.01wt%, the tensile strength of the alloy tube increases from 204 MPa to 236 MPa, while the elongation to failure changes slightly about 46%, indicating the excellent workability of the CuNi10FeMn1 alloy tubes.     

B2O3对高铝钢连铸保护渣理化性能的影响

高铝钢连铸过程中,为了避免或减轻钢液中Al与保护渣中SiO2发生反应,设计了低SiO2、高Al2O3含量的高铝钢连铸保护渣,通过添加适量的酸性氧化物B2O3协调熔渣酸碱性,利用实验分析了B2O3含量对高铝钢保护渣熔融特性、黏度特性及渣膜传热特性的影响。结果表明,B2O3含量在4%～10%时,随着B2O3含量增加,保护渣熔化温度、黏度、黏流活化能均降低,渣膜热流密度增加;保护渣的等温转变曲线(TTT曲线)向孕育时间增加的方向移动,晶体生长速率降低;实验条件下,增加B2O3含量可抑制保护渣中CaF2的析出。     

Electrorheological effect of Ti-bearing blast furnace slag with different TiC contents at 1500℃

The electrorheological properties of CaO–SiO2–Al2O3–MgO–TiO2–TiC slags were investigated to enhance understanding of the effect of TiC addition on the viscosity, yield stress, and fluid pattern of Ti-bearing slags in a direct-current electric field. The viscosities and shear stresses of 4wt% and 8wt% TiC slags were found to increase substantially with increasing electric field intensity, whereas virtually no rheological changes were observed in the 0wt% TiC slag. The Herschel–Bulkley model was applied to demonstrate that the fluid pattern of the 4wt% TiC slag was converted from that of a Newtonian fluid to that of a Bingham fluid in response to the applied electric field; and the static yield stress increased linearly with the square of the electric field intensity.     

Effect of Al2O3 on the viscosity of CaO-SiO2-Al2O3-MgO-Cr2O3 slags

We investigated the effect of Al2O3 content on the viscosity of CaO-SiO2-Al2O3-8wt%MgO-1wt%Cr2O3(mass ratio of CaO/SiO2 is 1.0,and Al2O3 content is 17wt%-29wt%)slags.The results show that the viscosity of the slag increases gradually with increases in the Al2O3 content in the range of 17wt%to 29wt%due to the role of Al2O3 as a network former in the polymerization of the aluminosilicate structure of the slag.With increases in the Al2O3 content from 17wt%to 29wt%,the apparent activation energy of the slags also increases from 180.85 to 210.23 kJ/mol,which is consistent with the variation in the critical temperature.The Fourier-transform infrared spectra indicate that the degree of polymerization of this slag is increased by the addition of Al2O3.The application of Iida’s model for predicting the slag viscosity in the presence of Cr2O3 indicates that the calculated viscosity values fit well with the measured values when both the temperature and Al2O3 content are at relatively low levels,i.e.,the temperature range of 1673 to 1803 K and the Al2O3 content range of 17wt%-29wt%in CaO-SiO2-Al2O3-8wt%MgO-1wt%Cr2O3 slag.     

Al2O3对高炉渣物化性能影响的理论分析

随着优质铁矿资源的消耗,钢铁企业可利用的铁矿原料品位逐渐降低。因此,高铝质铁矿资源越来越受到钢铁企业的关注,但高铝原料在高炉冶炼过程中会带来渣铁黏稠、炉温偏低、冶炼安全等一系列问题。本研究中采用FactSage热力学软件分析Al₂O₃质量分数对高炉渣平衡物相、熔化温度、相析出温度的影响以及高铝渣液相区变化和黏度变化,旨在为高炉冶炼高铝原料提供一定的基础支撑。研究发现：炉渣为低铝（5%～10%）含量时,随着Al₂O₃含量增加,炉渣熔化温度升高,析出相为黄长石相和纯物质相,高炉渣黏度变化不大,炉渣中SiO₂含量高,炉渣黏度过高,不适合高炉冶炼;炉渣为中铝（10%～15%）含量时,随着Al₂O₃含量增加,炉渣熔化温度升高,析出相为尖晶石相、黄长石相和纯物质相,高炉渣黏度增加幅度略有提高,Al₂O₃含量对高炉渣性质影响较小,增加炉渣二元碱度对炉渣黏度降低效果较明显;炉渣为高铝（15%～30%）含量时...     

镁铝比对高炉渣脱硫能力的影响

利用双层石墨坩埚,模拟铁液滴下穿过炉渣的过程,主要研究渣中Mg O,Al2O3质量分数对炉渣硫质量分数的影响,探索镁铝比与高炉渣硫质量分数的关系.结果表明渣中Mg O质量分数由6%提高到12%时,炉渣脱硫能力逐渐提高,由12%提高到14%,脱硫能力逐渐降低;渣中Al2O3质量分数由9%提高到15%时,炉渣脱硫能力逐渐降低,但降低幅度较小,当Al2O3质量分数由15%提高到17%时,炉渣脱硫能力大大降低;Mg O质量分数小于12%,Al2O3质量分数小于15%,提高炉渣镁铝比可以显著提高炉渣脱硫能力.     

Effects of smelting parameters on the slag/metal separation behaviors of Hongge vanadium-bearing titanomagnetite metallized pellets obtained from the gas-based direct reduction process

Smelting separations of Hongge vanadium-bearing titanomagnetite metallized pellets (HVTMP) prepared by gas-based direct reduction were investigated, and the effects of smelting parameters on the slag/metal separation behaviors were analyzed. Relevant mechanisms were elucidated using X-ray diffraction analysis, FACTSAGE 7.0 calculations, and scanning electron microscopy observations. The results show that, when the smelting temperature, time, and C/O ratio are increased, the recoveries of V and Cr of HVTMP in pig iron are improved, the recovery of Fe initially increases and subsequently decreases, and the recovery of TiO₂ in slag decreases. When the smelting CaO/SiO₂ ratio is increased, the recoveries of Fe, V, and Cr in pig iron increase and the recovery of TiO₂ in slag initially increases and subsequently decreases. The appropriate smelting separation parameters for HVTMP are as follows: smelting temperature of 1873 K; smelting time of 30–50 min; C/O ratio of 1.25; and CaO/SiO₂ ratio of 0.50. With these optimized parameters (smelting time: 30 min), the recoveries of Fe, V, Cr, and TiO₂ are 99.5%, 91.24%, 92.41%, and 94.86%, respectively.     

Reduction-melting behaviors of boron-bearing iron concentrate/carbon composite pellets with addition of CaO

Although the total amount of boron resources in China is high, the grades of these resources are low. The authors have already proposed a new comprehensive utilization process of boron-bearing iron concentrate based on the iron nugget process. The present work de-scribes a further optimization of the conditions used in the previous study. The effects of CaO on the reduction–melting behavior and proper-ties of the boron-rich slag are presented. CaO improved the reduction of boron-bearing iron concentrate/carbon composite pellets when its content was less than 1wt%. Melting separation of the composite pellets became difficult with the CaO content increased. The sulfur content of the iron nugget gradually decreased from 0.16wt%to 0.046wt%as the CaO content of the pellets increased from 1wt%to 5wt%. CaO negatively affected the iron yield and boron extraction efficiency of the boron-rich slag. The mineral phase evolution of the boron-rich slag during the reduction–melting separation of the composite pellets with added CaO was also deduced.     

含氟烧结矿黏结相流动性的探讨

针对包钢含氟烧结矿黏结相的流动性进行了试验研究.通过改变黏结相的碱度(w(CaO)/w(SiO2))以及MgO,CaF2和FeO的含量并测得相应黏结相在熔融态下的黏度和表面张力,从而得出烧结矿黏结相物性的一般变化规律.结果表明,碱度为1.4时,黏结相的黏度最小和熔化性温度最低,但表面张力随碱度的升高而增大;适量的MgO能降低黏结相的黏度,而表面张力随MgO含量的增加而增大,当MgO质量分数为5%时,熔化性温度最低;添加CaF2能显著降低黏结相的黏度和表面张力;FeO含量增加,黏结相的黏度和表面张力变小.     

改进型蜡基粘结剂的喂料流变性能

研究了改进型蜡基粘结剂体系和Fe-2Ni粉混合制备的喂料的流变性能.结果表明,喂料是一种假塑性流体,其非牛顿指数n较大,150℃时n为0.52,恒剪切速率粘流活化能△Eη=53.8Kj·mol     

Dissolution of Al<Subscript>2</Subscript>TiO<Subscript>5</Subscript> inclusions in CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> slags at 1823 K

Al-Ti-O inclusions always clog submerged nozzles in Ti-bearing Al-killed steel. A typical synthesized Al₂TiO₅ inclusion was immersed in a CaO-SiO₂-Al₂O₃ molten slag for different durations at 1823 K. The Al₂TiO₅ dissolution paths and mechanism were revealed by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Decreased amounts of Ti and Al and increased amounts of Si and Ca at the dissolution boundary prove that inclusion dissolution and slag penetration simultaneously occur. SiO₂ diffuses or penetrates the inclusion more quickly than CaO, as indicated by the w(CaO)/w(SiO₂) value in the reaction region. A liquid product (containing 0.7–1.2 w(CaO)/w(SiO₂), 15wt%–20wt% Al₂O₃, and 5wt%–15wt% TiO₂) forms on the inclusion surface when Al₂TiO₅ is dissolved in the slag. Al₂TiO₅ initially dissolves faster than the diffusion rate of the liquid product toward the bulk slag. With increasing reaction time, the boundary reaches its largest distance, the Al₂TiO₅ dissolution rate equals the liquid product diffusion rate, and the dissolution process remains stable until the inclusion is completely dissolved.