Activity coefficients of NiO and CoO in CaO-Al2O3-SiO2 slag and their application to the recycling of Ni-Co-Fe-based end-of-life superalloys via remelting

To design optimal pyrometallurgical processes for nickel and cobalt recycling, and more particularly for the end-of-life process of Ni-Co-Fe-based end-of-life (EoL) superalloys, knowledge of their activity coefficients in slags is essential. In this study, the activity coefficients of NiO and CoO in CaO-Al₂O₃-SiO₂ slag, a candidate slag used for the EoL superalloy remelting process, were measured using gas/slag/metal equilibrium experiments. These activity coefficients were then used to consider the recycling efficiency of nickel and cobalt by remelting EoL superalloys using CaO-Al₂O₃-SiO₂ slag. The activity coefficients of NiO and CoO in CaO-Al₂O₃-SiO₂ slag both show a positive deviation from Raoult's law, with values that vary from 1 to 5 depending on the change in basicity. The activity coefficients of NiO and CoO peak in the slag with a composition near B=(%CaO)/(%SiO₂)=1, where B is the basicity. We observed that controlling the slag composition at approximately B=1 effectively reduces the cobalt and nickel oxidation losses and promotes the oxidation removal of iron during the remelting process of EoL superalloys.     

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.     

CaO-Al2O3和CaO-SiO2-Al2O3渣系中组元活度的计算

根据分子和离子共存理论,建立了CaO-Al2O3和CaO-SiO2-Al2O3渣系的活度计算模型,并利用模型对渣中各组元的活度进行了计算,分析了w(CaO)对渣中组元活度的影响.结果表明,在CaO-Al2O3渣系中,当w(CaO)小于45%时,随着w(CaO)的增加,3CaO·Al2O3和12CaO·7Al2O3的活度不断升高,而CaO·Al2O3的活度变化不大;当w(CaO)大于45%时,随着w(CaO)的增加,CaO·Al2O3和12CaO·7Al2O3的活度不断降低,而3CaO·Al2O3的活度则略有升高.在CaO-SiO2-Al2O3渣系中,12CaO·7Al2O3的活度低于其在CaO-Al2O3渣系中的活度,随着w(CaO)的增加,CaO和3CaO·Al2O3的活度不断升高,2CaO·SiO2的活度则不断降低,CaO·Al2O3的活度呈现先升高后降低的趋势.     

低碳含铝钢20Mn2精炼渣系CaO-SiO2-Al2O3-MgO-CaF2的优化

通过对低碳含铝钢20Mn2精炼过程的取样分析,得出精炼渣的熔化温度偏高,渣中存在大量固相CaO,并导致钢中含有CaO类夹杂物,精炼渣吸附夹杂物能力差. 利用FactSage热力学计算,从渣的低熔点区域控制和渣-钢反应这两个方面对渣系进行研究与优化. 结果表明,CaO/Al2 O3 质量比在1. 5左右添加质量分数为3% CaF2 可以有效降低渣的熔化温度,渣的熔化温度随着CaF2 含量的升高呈现先降低后升高的趋势,MgO的质量分数控制5%左右低熔点区域面积达到最大. 在SiO2 质量分数大于30%区域,钢中氧含量大体上随着CaO/Al2 O3 质量比的增加而降低,在SiO2 的质量分数低于30%区域随着CaO含量的升高而降低,钢中酸溶铝含量在SiO2 含量高的区域随着Al2 O3/SiO2 质量比的增加而升高,在SiO2 含量低的区域随着CaO/SiO2 质量比的增加而增加. 根据热力学分析结果得出合理的渣系范围:CaO 50% ~60%, Al2 O3 20% ~35%, SiO2 5% ~10%, MgO 5% ~8%, CaF2 0~5%. 优化渣系的实验结果表明,优化后渣系熔化温度降低,钢中夹杂物数量、面积和平均尺寸均有明显下降.     

Variation and optimization of acid-dissolved aluminum content in stainless steel

As a key step in secondary refining, the deoxidation process in clean stainless steel production is widely researched by many scholars. In this study, vacuum oxygen decarburization (VOD) deoxidation refining in a 40-t electric arc furnace + VOD + ingot casting process was analyzed and optimized on the basis of Al deoxidation of stainless steel and thermodynamic equilibrium reactions between the slag and steel. Under good stirring conditions in VOD, the deoxidation reaction reaches equilibrium rapidly, and the oxygen activity in the bulk steel is controlled by the slag composition and Al content. A basicity of 3–5 and an Al content greater than 0.015wt% in the melt resulted in an oxygen content less than 0.0006wt%. In addition, the dissolved oxygen content decreased slightly when the Al content in the steel was greater than 0.02wt%. Because of the equilibrium of the Si–O reaction between the slag and steel, the activity of SiO₂ will increase while the Si content increases; thus, the Si content should be lowered to enable the formation of a high-basicity slag. A high-basicity, low-Al₂O₃ slag and an increased Si content will reduce the Al consumption caused by SiO₂ reduction.     

精炼渣中FeO的活度模型

根据熔渣结构的分子离子共存理论,建立了SiO2-Al2O3-CaO-MgO-FeO-MnO六元渣系的活度计算模型。计算得到了LF精炼渣中FeO的活度值,并分析了炉渣成分Al2O3、FeO以及碱度w(CaO)/w(SiO2)对FeO活度的影响,为帘线钢精炼变渣过程中控制回硫提供指导。     

CaO-SiO2-Al2O3-FeO-CaF2-La2O3-Nb2O5-TiO2渣系的活度计算模型

根据熔渣结构的分子离子共存理论,建立了CaO-SiO2-Al2O3-FeO-CaF2-La2O3-Nb2O5-TiO2八元渣系的活度计算模型.利用该活度模型,计算和分析了此渣系中铌、稀土、钛相关组元的活度变化规律.实验结果表明,模型计算结果与实际测量值能较好吻合;在本实验渣系条件下,含铌组元主要为FeO·Nb2O5,含...     

六元熔融还原渣黏度的分析

结合高效脱磷能力的熔融还原冶炼惠民高磷铁矿工艺及HIsmelt熔融还原炼铁技术的特点选取CaO-MgO-FeO-Al2O3-SiO2-P2O5六元熔渣作为研究对象其熔渣成分为：二元碱度R(CaO/SiO2)0.8～1.4Al2O3质量分数为6.4%～15.4%P2O5质量分数为0～3%、MgO、FeO质量分数分别为4%、6%采用纯化学试剂配制熔渣。借助扫描电子显微镜对炉渣矿物组成和微观结构进行研究采用RTW-10熔体物性综合测试仪研究熔渣成分的变化对黏度产生的影响。研究表明：该熔渣矿相结构主要以黄长石(钙铝黄长石、钙镁黄长石)为主呈方形状、粗大骨架状结构。当P2O5或Al2O3质量分数一定时随着碱度的提高熔渣的黏度降低;当碱度或P2O5质量分数一定时熔渣的黏度随Al2O3质量分数的增加而增大;当碱度或Al2O3质量分数一定时黏度均随着P2O5质量分数的增加而提高。     

保护渣组分对部分稳定氧化锆原料高温稳定性的影响

选择CaO稳定氧化锆、CaO-Y2O3复合稳定氧化锆、Y2O3稳定氧化锆和MgO稳定氧化锆原料为研究对象,借助X射线衍射仪和扫描电子显微镜分析Al2O3、SiO2、Fe3O4、MnO2及3种不同组分的结晶器保护渣对这些原料高温稳定性的影响。结果表明,部分稳定氧化锆原料的高温稳定性主要取决于其稳定剂与渣组分的反应程度;高碱度渣有利于保持部分稳定氧化锆原料的稳定性。     

CaO-SiO_2-Na_2O-CaF_2-Al_2O_3-MgO渣系的粘度和结晶温度

采用CaOSiO2Na2OCaF2Al2O3MgO渣系,用差热分析仪测定熔渣的结晶温度,用粘度测定仪测定熔渣的粘度,研究结晶温度和粘度与碱度、w(Na2CO3)、w(CaF2)、w(Al2O3)和w(MgO)之间的关系,并得到相应的回归方程·利用这两个回归方程,可以预测连铸保护渣的结晶性能和粘性特征·化学成分通过改变粘度,来影响晶核形成速度和晶体成长速度,从而决定了熔渣的结晶性能·结晶温度随着粘度的减小而升高·渣系中只有MgO可以在减小粘度的同时降低结晶温度     

2CaO·SiO2-3CaO·P2O5固溶体形成机理

在1300℃下,通过向CaO-SiO2-FetO-P2O5系熔渣中浸入固相CaO的方法,分析了CaO-SiO2-FetO-P2O5渣系与固相CaO间的反应过程,利用分子离子理论计算了炉渣中各组元的活度,研究了2CaO·SiO2-3CaO·P2O5固溶体的形成机理.研究结果表明,CaO-SiO2-FetO-P2O5渣系中组元主要是以2CaO·SiO2和3FeO·P2O5化合物的形态存在;当固相CaO和炉渣接触时,渣中的2CaO·SiO2首先在固相CaO表面析出并形成2CaO·SiO2固相层;随着CaO组元和3FeO·P2O5化合物向反应界面的不断扩散,生成了2CaO·SiO2-3CaO·P2O5和CaO-FeO固溶体.     

CaO-SiO2-FetO-P2O5渣中磷的富集行为

通过考察不同温度下CaO-SiO2-FetO-P2O5熔渣中磷在2CaO·SiO2颗粒内部和表面以及熔渣本体中的浓度分布规律,对CaO-SiO2-FetO-P2O5熔渣中磷的富集行为进行了研究.结果表明:熔渣中存在的2CaO·SiO2固体颗粒为渣中磷富集提供了场所,磷向2CaO·SiO2颗粒富集并形成2CaO·SiO2...     

含碱高炉渣排碱、脱硫能力的实验研究

为探讨高炉渣排碱、脱硫能力间的关系,根据广钢实际高炉渣成分,通过实验研究了w(CaO)/w(SiO2),w(MgO),w(Al2O3)对炉渣排碱、脱硫的影响.结果表明:w(CaO)/w(SiO2)对炉渣的排碱、脱硫能力影响较大,二者相互矛盾;w(MgO)升高,炉渣排碱能力降低,含碱炉渣最佳脱硫对应的w(MgO)比普通炉渣低3%.w(Al2O3)升高,炉渣的排碱能力变化不大,而脱硫能力迅速降低.广钢高炉适宜的炉渣成分为:w(CaO)/w(SiO2)保持在1.0,w(MgO)保持在12%,w(Al2O3)保持在15%.     

红土矿半熔融态还原渣金界面分离的影响因素

红土矿半熔融态还原工艺中金属与渣相的界面分离及液渣从耐火材料表面的脱除是该工艺能否工程化的核心问题.针对该问题,考察了CaO和体系温度对渣铁分离行为的影响规律,同时实验研究了炉渣在不同耐火材料上的界面铺展行为.实验结果表明:不添加CaO时,1440℃金属聚集效果较好,磁选后“精矿”金属质量分数为61%;随着CaO质量分数的增加,液态金属易于团聚与长大,精矿金属的质量分数增加显著,在1400℃,15%CaO时可达937%;熔渣与Al2O3质耐火材料较易润湿,与碳质耐材较难润湿,在实验范围内随着炉渣碱度的增加其与耐材的润湿性变差.     

Recovery of iron and calcium aluminate slag from high-ferrous bauxite by high-temperature reduction and smelting process

A high-temperature reduction and smelting process was used to recover iron and calcium aluminate slag from high-ferrous bauxite. The effects of w(CaO)/w(SiO₂) ratio, anthracite ratio, and reduction temperature and time on the recovery and size of iron nuggets and on the Al₂O₃ grade of the calcium aluminate slag were investigated through thermodynamic calculations and experiments. The optimized process conditions were the bauxite/anthracite/slaked lime weight ratio of 100:16.17:59.37, reduction temperature of 1450°C and reduction time of 20 min. Under these conditions, high-quality iron nuggets and calcium aluminate slag were obtained. The largest size and the highest recovery rate of iron nuggets were 11.42 mm and 92.79wt%, respectively. The calcium aluminate slag mainly comprised Ca₂SiO₄ and Ca₁₂Al₁₄O₃₃, with small amounts of FeAl₂O₄, CaAl₂O₄, and Ca₂Al₂SiO₇.     

Al_2O_3-SiC-C砖基质组成对抗渣性影响

分析了Ａｌ２Ｏ３ＳｉＣＣ砖基质组成对抗渣性影响。实验结果表明,以莫来石为基质的Ａｌ２Ｏ３－ＳｉＣ－Ｃ砖,其抗渣性优于以刚玉为基质的制品,并用ＣａＯ－Ａｌ２Ｏ３－ＳｉＯ２三元系统相图给予了解释。     

82B硬线钢精炼渣和夹杂物研究

从A12O3活度和夹杂物成分两方面来研究精炼渣对夹杂物的影响．采用Factsage软件对CaO—A1203-SiO3-MgO（8％）-CaF2（8％）炉渣中A1203,活度进行了计算,并研究了碱度和（MgO）含量对A12O3度的影响．当炉渣碱度从1．0增加到2．0时,炉渣中A1203活度随着炉渣碱度的增加而降低;当炉渣碱度从2．0增加到3．8时,A1203活度变化幅度很小;（MgO）质量分数分别为5％和8％的渣,A1203活度差距较小;在碱度高的炉渣中[A1]。容易被从炉渣还原到钢水中．在使用高碱度精炼渣的盘条中发现许多含有MgO的硬性夹杂物,并对此进行了分析,最后得出最适宜的炉渣碱度为2．5—3．0．     

Fluoride evaporation and crystallization behavior of CaF2–CaO–Al2O3–(TiO2) slag for electroslag remelting of Ti-containing steels

To elucidate the behavior of slag films in an electroslag remelting process, the fluoride evaporation and crystallization of CaF₂–CaO–Al₂O₃–(TiO₂) slags were studied using the single hot thermocouple technique. The crystallization mechanism of TiO₂-bearing slag was identified based on kinetic analysis. The fluoride evaporation and incubation time of crystallization in TiO₂-free slag are found to considerably decrease with decreasing isothermal temperature down to 1503 K. Fish-bone and flower-like CaO crystals precipitate in TiO₂-free slag melt, which is accompanied by CaF₂ evaporation from slag melt above 1503 K. Below 1503 K, only near-spherical CaF₂ crystals form with an incubation time of less than 1 s, and the crystallization is completed within 1 s. The addition of 8.1wt% TiO₂ largely prevents the fluoride evaporation from slag melt and promotes the slag crystallization. TiO₂ addition leads to the precipitation of needle-like perovskite (CaTiO₃) crystals instead of CaO crystals in the slag. The crystallization of perovskite (CaTiO₃) occurs by bulk nucleation and diffusion-controlled one-dimensional growth.     

Synthesis of steel slag ceramics:chemical composition and crystalline phases of raw materials

Two types of porcelain tiles with steel slag as the main raw material (steel slag ceramics) were synthesized based on the CaO-Al₂O₃-SiO₂ and CaO-MgO-SiO₂ systems, and their bending strengths up to 53.47 MPa and 99.84 MPa, respectively, were obtained. The presence of anorthite, α-quartz, magnetite, and pyroxene crystals (augite and diopside) in the steel slag ceramics were very different from the composition of traditional ceramics. X-ray diffraction (XRD) and electron probe X-ray microanalysis (EPMA) results illustrated that the addition of steel slag reduced the temperature of extensive liquid generation and further decreased the firing temperature. The considerable contents of glass-modifying oxide liquids with rather low viscosities at high temperature in the steel slag ceramic adobes promoted element diffusion and crystallization. The results of this study demonstrated a new approach for extensive and effective recycling of steel slag.     

钙硅氧化物的质量比对10%Al2 O3高炉渣--尾矿--粉煤灰微晶玻璃性能的影响

利用高炉渣、尾矿和粉煤灰各自成分特点,在未添加任何晶核剂和其他化学试剂条件下,使用烧结法制得了不同CaO/SiO2质量比的10%Al2 O3(质量分数)矿渣微晶玻璃.通过差热分析、X射线衍射、扫描电子显微镜等分析手段,分析了CaO/SiO2质量比和析晶温度对高炉渣-尾矿-粉煤灰微晶玻璃样品的晶相变化规律、析晶行为和主要力学性能的影响.随着CaO/SiO2质量比增大,析晶活化能不断减小,Si-O四面体连接强度下降,质点移动加强,各组开始析晶温度和晶化温度逐渐减小.当玻璃样品中钙硅氧化物的质量比为0.4时,分别在886℃和982℃形核、析晶保温1 h 后,可以得到抗折强度103.59 MPa、显微硬度5.3 GPa、耐酸性0.25%(质量损失率)、耐碱性小于0.1%,主晶相为透辉石的最佳力学性能的微晶玻璃样品.