环保型高磷铁水预脱磷渣的脱磷性能研究

实验室条件下采用间接测量法,测定了CaF2系和B2O3系脱磷渣的磷分配.即首先测量磷在液态渣和固态铁间的分配比,再通过计算得到磷在液态渣和铁水之间分配比,同时根据渣系成分和光学碱度计算了磷容量.同时采用了扫描电镜、能谱分析与X射线衍射分析技术对脱磷渣进行了研究.实验结果表明,B2O3系预脱磷渣的磷容量远大于CaF2系预脱磷渣的磷容量,因此可以用B2O3全部替代CaF2作为助熔剂进行高磷铁水的预脱磷处理,2种渣系的磷分配均随渣中有效CaO含量的升高而升高.用B2O3作为助熔剂时,B2O3能与渣中高熔点物质2CaO·SiO2和3CaO·P2O5反应生成低熔点物质,从而起到助熔的作用.且w(B2O3)/w(CaO)比值为0.16时,磷分配比为最高值,即该渣脱磷能力最强.     

锰硅合金沉淀脱磷工艺制度的优化

选用钙系脱磷剂、CaO—CaF2渣,对锰硅铁合金进行沉淀脱磷,着重研究脱磷剂加入量和锰硅铁合金中硅含量增量对脱磷效果的影响。结果表明：当脱磷剂加入量由2．5％增加到7．5％时,脱磷效果增加5．56％,而合金中硅含量由19％增加到25％时,脱磷效果将至少增加23．22％,说明锰硅合金中硅含量增加对脱磷效果的作用远大于单一增加脱磷剂的作用。合金熔体中硅含量的增加降低了氧势,同时提高了磷的活度,这将有助于脱磷剂中的钙以Ca2P3而非CaO形式进入渣中;此外,采用沉淀脱磷工艺的锰硅合金熔体中碳含量也有明显下降,有利于中、低碳锰铁生产中碳含量的控制。     

CaO基含TiO_2和Al_2O_3半钢渣系脱磷能力的热力学

以共存理论和冶金脱磷原理为基础,建立了脱磷热力学模型,并对CaO基含TiO_2、Al2O3半钢渣系的脱磷能力进行热力学研究,得到CaO基含TiO_2、Al2O3半钢脱磷渣系的磷分配比和磷容量热力学模型。研究结果表明,渣中TiO_2和Al2O3均会使炉渣的脱磷能力降低,尤其是在低温低碱度条件下影响较为明显,两种氧化物在质量分数相同的情况下,TiO_2比Al2O3的影响更大;随着炉渣碱度的增加,炉渣的磷分配比和磷容量均先升高而后持平;随着渣中w((Fe O))的增加,炉渣的磷分配比和磷容量均先升高而后降低;随着w((Mg O))的降低,炉渣的磷分配比和磷容量逐渐降低。采用半钢化渣球冶炼半钢,渣中w((TiO_2)+(Al2O3))和w((Fe O))升高,w((Mg O))稍有降低,在Fe O和Mg O的共同作用下,半钢渣系的磷分配比和磷容量有所升高。控制炉渣碱度为4.0左右,w((Fe O))≤20.0%时,炉渣不仅具有较高的磷分配比和磷容量,并且可以弱化TiO_2和Al2O3对磷分配比和磷容量的影响,确定半钢化渣球的加入比例为总渣量的15.0%~20.0%。     

硅锰合金选择性氧化脱磷的研究

讨论了硅锰合金氧化脱磷的热力学条件,用硅钼棒炉,CaO—SiO_2—Mno—CaF_2渣系对硅锰合金进行了氧化脱磷实验,取得了较高的脱磷率和脱硫率。     

锰铁合金用BaO-卤化物渣系脱磷的实验

通过BaO-卤化物渣系和锰铁合金之间磷的分配平衡实验,测定了实验渣系的磷酸盐容量.结果表明,脱磷剂中不同卤化物的加入对增大渣系脱磷能力的影响程度不同,按大小顺序为BaF2＞BaCl2＞CaF2＞CaCl2,实验得到CaO替代BaO,MnO2替代BaF2时对渣系脱磷能力的影响关系.在此基础上,用BaO-BaF2系熔剂对锰铁合金进行氧化脱磷工艺性实验,实验发现,采用56 %BaO-24 %BaF2-10 %Fe2O3-10 %MnO2熔剂,熔剂添加量为10 g/100 g合金,温度1573 K,脱磷率达到62 %,温度升高到1673 K,脱磷率降低到30 %.     

CaO-SiO2-FeO-Al2O3-Na2O-TiO2-P2O5渣系的脱磷热力学模型

基于分子离子共存理论(IMCT)建立了 CaO-SiO2-FeO-Al2O3-Na2O-TiO2-P2O5渣系的磷分配比预测模型,并讨论了组分变化对磷分配比的影响以及各碱性组元对磷分配比的贡献.结果表明,该模型计算的磷分配比与实测值吻合度较好;随着w(CaO)增加,磷分配比先增加后趋于平缓,其中30％是较合适的CaO含...     

CaO-FeO-SiO2-Al2O3/Na2O/TiO2渣系与碳饱和铁水间磷分配行为

 为了研究Al2O3、Na2O和TiO2作为铁水预处理渣的助熔剂对铁水预处理脱磷的影响,借助FactSage热力学软件绘制了CaO-FeO-SiO2渣系1 573 K液相区。随着Al2O3和Na2O质量分数的增加,该渣系液相区明显扩大,TiO2对渣系液相区影响不大。实验室研究采用纯铁箔替代碳饱和铁水进行热力学平衡试验,间接测定了1 573 K时铁水预处理脱磷渣与碳饱和铁水间的平衡磷分配比。结果表明,渣铁磷分配比随渣中Al2O3和TiO2质量分数的增加而减小,TiO2对磷分配比的影响相对较小;渣铁磷分配比随渣中Na2O质量分数和碱度的增加而增加,Na2O可显著提高渣的脱磷能力;渣铁磷分配比随渣中FeO质量分数的增加先增加后减小,最合适的FeO质量分数为35%～40%。     

Li2O、Na2O、K2O、BaO对CaO基钢包渣系性能影响的实验研究

为改善钢包渣性能以控制钢包中钢液回磷,以Li2O、Na2O、K2O、BaO作添加剂替代模拟的CaO基钢包渣系中等质量的CaO，研究添加剂对渣系的熔点、粘度和脱磷能力的影响，并推荐Li2O作为CaO基钢包 渣系的添加剂。     

环保型高磷铁水预处理脱磷剂的试验研究

为开发高效环保的高磷铁水预脱磷剂,利用FactsageTM软件绘制了Fe3O4-CaO-B2O3和Fe3O4-CaO-K2O三元相图,根据相图确定出B2O3系和K2O系脱磷剂成分的质量分数,然后在实验室进行脱磷试验,并与以CaF2为助熔剂的高磷铁水预脱磷试验结果进行了比较。结果表明:B2O3能够完全替代CaF2作为助熔剂进行高磷铁水的脱磷预处理,控制w(P)<0.1%,此时w(B2O3)/w(CaO)=0.16,用此种脱磷剂进行脱磷时,化渣良好且不产生泡沫渣,脱磷率也最高。而K2O系脱磷剂的脱磷效果较差。     

向CaO基熔剂中添加Li2O,Na2O,K2O和BaO对钢水回磷控制效果的影响

在1853K温度下,用强碱性氧化物Li2O,Na2O,K2O和BaO分别替代CaO-SiO2-Fe2O3-MnO2-MgO-P2O5系熔剂中的部分CaO,进行钢水回磷控制实验.结果表明,上述添加剂影响钢水脱磷效果的强弱顺序为Li2O＞Na2O＞K2O＞BaO.推荐Li2O作为CaO基实验熔剂的首选添加剂.确定钢水回磷控制用CaO基熔剂的优化组成为W(CaO+Li2O)/WSiO2=2.5,WLi2O=15%,W(Fe2O3+MnO2)≥2%.当W(Fe2O3+MnO2)=2%时,采用上述组成的熔剂可获得48.1%的脱磷率.向CaO基熔剂中添加10%～30%的Li2O后,其磷酸盐容量lgCp为20.32±0.22,比未添加Li2O时CaO基熔剂的最大磷酸盐容量值增加了0.5～1.0个数量级.     

转炉生产低磷钢的脱磷反应热力学

 为实现磷质量分数小于0.010%的低磷钢批量生产,系统研究了转炉脱磷反应热力学。分析了影响转炉渣-金间磷分配比LP的主要因素,研究了P2O5活度系数和脱磷反应氧分压的定量确定方式,以及碳、磷选择性氧化问题。研究结果表明：LP主要受氧分压、P2O5活度系数和温度的影响;P2O5活度系数采用修正的柯热乌罗夫规则离子溶液模型计算较为准确;脱磷反应氧分压受炉渣氧分压控制,炉渣氧分压主要取决于钢中碳含量、炉渣碱度和温度。对传统复吹转炉生产磷质量分数小于0.010%低磷钢的工艺条件是：终渣碱度w(CaO)/w(SiO2)≥3.0,终渣w(MgO)≤9.0%,终点碳w(［C］)≤0.065%,终点温度控制在1873～1923K范围。     

二元碱度和Al_2O_3对CaO-SiO_2-FeO-Fe_2O_3-P_2O_5-Al_2O_3-MgO-MnO钢渣中磷酸盐富集的影响

以八元CaO-SiO_2-FeO-Fe_2O_3-P_2O_5-Al_2O_3-MgO-MnO钢渣体系为研究对象,结合热力学计算和实验检测,分析了二元碱度B和Al_2O_3含量对八元钢渣系中磷酸盐富集行为的影响。结果表明:钢渣二元碱度和Al_2O_3含量直接影响钢渣中f-C2S的生成量,进而影响磷酸盐富集相nC_2S-C_3P内P_2O_5的含量。随着二元碱度从1.3提高至2.5,磷酸盐富集率增大,磷酸盐富集相nC2S-C3P中的P_2O_5含量呈现先迅速增大(B从1.3至1.7),然后逐渐减小(B从1.8至2.5)的趋势。当二元碱度和Al_2O_3质量分数分别控制在1.7和12%时,即当满足四元碱度R为1.23时,此八元钢渣体系有较好的磷酸盐富集效果,磷酸盐富集相nC_2S-C_3P内的P_2O_5的质量分数可以达到24.23%。     

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In order to effectively protect the hearth lining of the blast furnace by using materials containing titanium, the corrosion behavior of slags containing TiO2 to Al2O3 ceramic cup was experimentally investigated through slag resistance test in static crucible and calculation of slag quantity by mass conservation of CaO. The effect of temperature, reaction time and slag binary basicity on the corrosion behavior was studied, and the corrosion mechanism was discussed. The results show that increasing temperature and prolonging reaction time can lead to an increase of corrosion of Al2O3 ceramic cup by the slags with TiO2, whereas the corrosion shows a decrease trend with the increase of slag binary basicity. The corrosion mechanism can be summarized as that: CaO and SiO2 in slag will react with Al2O3 from ceramic cup to form CA6, C2AS and CAS2; the formed CA6, C2AS and CAS2 will dissolve into slags?? some high-melting-point minerals such as MA and CA2 near the original brick layer of ceramic cup will be formed to make slag more viscous.     

Effect of B_2O_3 on Melting Temperature of CaO-Based Ladle Refining Slag

B2O3 is selected as fluxing agent of CaO-based ladle refining slag to decrease the melting temperature as well as to improve the speed of slag forming and the refining efficiency.The effects of B2O3 on the melting temperature of two series of refining slags including the low basicity slags(the mass ratio of CaO/SiO2 is 3-4)and the high basicity slags(the mass ratio of CaO/SiO2 is 5-8.75)were investigated.The slag melting temperature was measured using the hemisphere method.The results indicate that the fluxing action of B2O3 is better than that of CaF2 and Al2O3.For the CaO-based refining slag with low basicity,the melting temperature is decreased effectively when B2O3 is used to substitute for equal mass of CaF2,Al2O3 and SiO2,respectively.For the CaO-based refining slag with high basicity,when CaF2 is substituted by B2O3,the melting temperature can be decreased remarkably.Especially,when the mass ratios of CaO/Al2O3 and CaO/SiO2 are in the range of 1.1-4.0 and 5.25-8.0,respectively,the slag melting temperature is lower than 1300 ℃.Therefore,the B2O3-containing refining slags with high ratios of CaO/Al2O3 and CaO/SiO2 have ultra low melting temperature.     

高炉渣钾容量的试验研究

为降低碱金属对高炉的危害,提高炉渣的排碱能力,采用气-渣平衡法测定了1 723 K时高炉渣的钾容量.依据广钢实际高炉渣成分,用纯化学试剂配制炉渣,用一定组成K(g)-CO-CO2-Ar混合气体提供一定的氧分压和钾分压.研究表明:试验条件下,w(MgO)和w(A12O3)一定时,钾容量随w(CaO)/w(SiO2)的增大而减小;在w(CaO)/w(SiO2)和w(A12O3)一定时,钾容量随w(MgO)的增大而增大;在w(CaO)/w(SiO2)和w(MgO)一定时,钾容量随w(A12O3)的增大而增大;当[w(CaO) w(MgO)]/w(SiO2)和w(A12O3)固定不变时,增加w(MgO),降低w(CaO),钾容量明显增大.广钢炉渣的合理成分为:w(CaO)/w(SiO2)保持在1.0,w(MgO)保持在12%～15%,w(A12O3)不超过15%.     

Rationale on composition of slags in oxygen steelmaking processes

Abstract

A study of plant analytical data on slags for the BOS and OBM processes revealed consistent interrelations between the concentrations of FeO, CaO, and SiO₂ in the slag at the end of the oxygen blow. Over a wide composition range, the amounts of CaO and SiO₂ decrease with increasing FeO, slag basicity increases with increasing FeO, and the amount of MgO decreases with increasing slag basicity. At all levels of lime and silica contents, the amount of FeO in the slag varies by 5–6% between the low and high contents. Consequently, the slag/ metal distribution ratios (%P)/[%P] and (%S)/[%S] as functions of basic and/or acidic oxide contents are within a composition range bordered by the equilibrium curves for the low and high FeO contents.     

Activity of MnO in MnO‐CaO‐MgO‐SiO2‐Al2O3 Slags at 1500 °C

A thermodynamic study was made on the MnO‐CaO‐MgO‐SiO₂‐Al₂O₃ slags that are typical of the production of ferromanganese in submerged arc furnaces. The Al₂O₃ content of the slags was kept constant at 5 per cent by mass. The activity‐composition relationship in Pt‐Mn binary alloys were re‐determined for calibration purposes at 1300, 1400 and 1500°C and po₂ values between 5.40×10^?6 and 4.54×10^?13 atm. A linear regression equation was derived to predict the activity coefficients of manganese, in Pt‐Mn alloys at 1500°C. The effect of concentration, basicity ratio and CaO‐to‐MgO ratio on MnO activities in above mentioned complex slags was investigated at 1500 °C and at two different po₂ values of 4.76×10^?7 and 5.80×10^?8 atm. It was found that a_Mno values increase with increasing MnO, and tend to increase with an increasing CaO‐to‐MgO ratio. The a_MnO values also increase with increasing basicity ratio. The activity coefficient of MnO increases with an increase in its mole fraction in the slag. Quadratic multivariable regression model equations which represent the activity data successfully and which can be used to predict the MnO activities in the compositional range of this study were developed. The MnO activity data was interpreted in terms of a slag model which describes the thermodynamic properties of the slag successfully.     

GCr15轴承钢中非金属夹杂物的转变

采用气体分析法、化学分析法、扫描电镜-能谱分析法,对GCr15轴承钢生产过程中的非金属夹杂物进行了研究。工业试验表明,GCr15轴承钢在LF-VD工序夹杂物转变规律为Al2O3→MgO·Al2O3→Al2O3·xCaO·yMgO→MgO·Al2O3或MgO;利用CaO-MgO-Al2O3三元相图对渣系进行优化,适当提高炉渣的wCaO/wAl2O3,提高渣中CaO含量,降低渣中w(FeO+MnO)含量,利于实现最终夹杂物向低熔点区(θm≤1500℃)转变。     

A thermodynamic model for calculation of sulfur distribution ratio between CaO- SiO2- Al2O3- Na2O- TiO2- (MgO) slags and carbon saturated hot metal

The ion and molecule coexistence theory (IMCT) indicates that the mass action concentrations of structural units or ion couples in slags can represent the chemical reaction ability as the traditional slags activity.By establishing the mass action concentrations equations of structural units or ion couples in the CaO- SiO2- Al2O3- Na2O- TiO2- (MgO) slags, the mass action concentrations were solved by Matlab, so as to build a thermodynamic model for calculating the sulfur distribution ratio between slags and carbon saturated hot metal under 1450??.The calculated sulfur distribution ratio of model agrees well with the experimental sulfur distribution ratio, which can help to predict the sulfur distribution ratio between slags and carbon saturated hot metal.The thermodynamic model can quantitatively determine the respective sulfur distribution ratio of CaO, Na2O and total sulfur distribution ratio in slags.Through the calculated results, the influencing factors on total sulfur distribution ratio were analyzed. In addition, the model can quantitatively calculate the contribution of CaO and Na2O on total sulfur distribution ratio, and qualitatively describe their trend affected by other factors.