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CN116655360B - 一种rh精炼炉用复合耐火材料及其制备方法 - Google Patents

一种rh精炼炉用复合耐火材料及其制备方法 Download PDF

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CN116655360B
CN116655360B CN202310585028.5A CN202310585028A CN116655360B CN 116655360 B CN116655360 B CN 116655360B CN 202310585028 A CN202310585028 A CN 202310585028A CN 116655360 B CN116655360 B CN 116655360B
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马晨红
李勇
仝尚好
刘雷
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University of Science and Technology Beijing USTB
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Abstract

一种RH精炼炉用复合耐火材料及其制备方法，属于耐火材料领域。所述耐火材料包括如下原料组成：50～85wt.％刚玉、5～20wt.％铬铝合金粉、10～30wt.％镁砂，外加2～5wt.％结合剂。将上述原料与结合剂混合均匀后压制成型并干燥，得到AlCr‑MgO‑Al2O3复合坯体，于1200℃～1700℃空气气氛下烧成，制得MgAl2O4、MgCr2O4和MgAlON原位复合增强的Al2O3复合耐火材料，即MgAl2O4‑MgCr2O4‑MgAlON‑Al2O3复合耐火材料。本发明设计了无碳AlCr‑MgO‑Al2O3复合新体系，在高温下AlCr合金与O2、N2、MgO和Al2O3细粉发生反应，原位转化为MgAl2O4、MgCr2O4和MgAlON增强相，改善气孔结构，降低气孔孔径，提高了材料的抗侵蚀性能和抗介质渗透性能。

Description

一种RH精炼炉用复合耐火材料及其制备方法
技术领域
本发明属于耐火材料领域，尤其涉及一种RH精炼炉用MgAl2O4-MgCr2O4-MgAlON-Al2O3复合耐火材料及其制备方法。
背景技术
炉外精炼是钢铁生产，尤其是优质洁净钢生产过程中的关键工序。通过炉外精炼可以除去钢水中的杂质与夹杂物，同时调整钢水的化学成分并使其均匀化。RH真空精炼技术具有效率高，适应批量处理、装备投资少和易操作等优势，是炉外精炼中最为重要的方法之一，广泛应用于现代钢厂。RH精炼炉内衬用耐火材料服役环境苛刻，须承受长时间的高温(达1700℃)真空作用、钢水的冲刷和侵蚀作用、循环热震作用等，因此要求其耐火度高、强度高、耐磨损、耐侵蚀、抗热震性好、真空稳定性好等。
RH精炼炉衬用耐火材料的服役温度可能高达1700℃。目前，我国RH精炼炉内衬用耐火材料主要为镁铬砖(≥50％)，部分使用镁碳砖(～5％)耐火材料。RH下部槽是整个炉衬的高蚀区，主要使用电熔再结合镁铬砖。然而，在电熔再结合镁铬砖的气孔结构难以调控，抗化学侵蚀和抗铁水渗透的性能不理想。碳材料具有较高的热导率和不易被熔渣润湿性，在MgO材料中引入碳质原料开发的镁碳砖具有良好的抗渣和铁水渗透和侵蚀性能，以及较好的抗剥落性能，寿命相较普通镁铬砖提高了约15％。然而，在高温真空条件下，镁碳砖中的C会导致MgO发生还原反应，形成Mg(g)和CO(g)逸出，造成结构疏松。同时，碳会造成对钢水污染，因此镁碳砖不适宜低碳钢、洁净钢的冶炼。
公开的文献中《RH精炼炉用新型Al-Al2O3-MgO耐火材料应用性能研究》(仝尚好，北京科技大学博士论文)以及CN202111527731.8《一种RH精炼炉用多形貌共存的镁阿隆耐火材料制备方法》，提出以金属铝粉、氧化铝粉和镁砂颗粒为原料，于500-700℃保温2-10h，然后在1400-1700℃的烧结温度下保温2-6h，制得MgAlON结合的刚玉复合耐火材料。为满足工业应用的需要，此材料的高温稳定性和化学稳定性等性能还有待进一步提高，特别是在RH精炼服役过程中，抵抗碱性熔渣渗透和侵蚀的性能还存在不足，导致使用寿命不理想。研发一种RH精炼用高性能无污染的无碳耐火材料及其制备方法是本发明亟需解决的问题。
发明内容
为解决现有技术中RH精炼炉用镁铬砖(MgO-Cr2O3)气孔结构难调控导致抗渗透和抗侵蚀性能不佳，镁碳砖(MgO-C)中碳易溶于钢水，造成增碳污染的不足，以及MgAlON-Al2O3复合材料抗碱性渣侵蚀性能不理想等问题，本发明提供一种MgAl2O4-MgCr2O4-MgAlON-Al2O3复合耐火材料及制备方法，以进一步提高耐火材料的使用性能。
本发明采用的技术方案如下。
一种RH精炼炉用复合耐火材料，包括如下质量分数的原料组成：50～85wt％的刚玉、5～20wt％的铬铝合金粉、10～30wt％的镁砂，2～5wt％的结合剂。
进一步地，所述刚玉包括粒度为3～1mm和<1mm的刚玉颗粒和<5μm的活性氧化铝细粉；所述镁砂的粒度为<0.5mm。
进一步地，所述铝铬合金中的Cr含量按质量百分比为2％～60％。
进一步地，所述刚玉中刚玉颗粒的质量百分比为80％～95％，氧化铝细粉的质量百分比为5～20％。
进一步地，所述结合剂为热固性酚醛树脂结合剂。
上述RH精炼炉用复合耐火材料的制备方法，包括如下步骤：
(1)将刚玉、铝铬合金粉、镁砂和结合剂按照一定的比例混合搅拌,制成泥料；
(2)将所述泥料压制成复合坯体，并对所述坯体进行干燥；
(3)将所述复合坯体进行高温烧结后制得MgAl2O4-MgCr2O4-MgAlON-Al2O3复合耐火材料。
所述步骤(1)中刚玉、钛铝合金粉、镁砂和结合剂的质量分数比例如下：50～85wt％的刚玉、5～20wt％的铬铝合金粉、10～30wt％的镁砂，外加2～5wt％的结合剂。
进一步地，步骤(2)中所述干燥是将坯体在120～200℃温度范围内干燥10～50小时。
进一步地，步骤(3)中所述的高温烧结是在窑炉中空气气氛条件下以3～20℃/min速率升温至1200℃～1700℃，保温1～8小时。
进一步地，所述窑炉包括隧道窑、梭式窑、电窑。
本发明还提供了一种MgAl2O4-MgCr2O4-MgAlON-Al2O3复合耐火材料在RH精炼炉中作为内衬的应用。
本发明的反应原理：在空气气氛中，当体系温度达约800℃时，AlCr-Al2O3-MgO复合坯体中的AlCr合金颗粒吸收气氛中的O2开始显著氧化，生成高活性Al2O3和Cr2O3，伴随一定的体积膨胀，填充孔隙，细化气孔；随着气氛中O2的消耗，坯体内部的氧分压降低，AlCr合金进一步与N2发生反应，生成AlN；随着温度进一步升高，新生的高活性Al2O3、Cr2O3和AlN进一步与体系中的MgO反应原位生成高性能的MgAl2O4、MgCr2O4和MgAlON增强相。
有益效果：本发明以铝铬合金粉、氧化铝粉、氧化镁粉和刚玉颗粒为原料制得无碳的AlCr-MgO-Al2O3复合坯体，通过高温烧成制得MgAl2O4、MgCr2O4和MgAlON原位复合增强的Al2O3复合耐火材料，即MgAl2O4-MgCr2O4-MgAlON-Al2O3复合耐火材料。本发明采用高熔点的AlCr合金为原料作为合成Al2O3、Cr2O3和AlN中间相的前驱体，通过气-固反应、固-固反应的二步反应机制降低MgAl2O4、MgCr2O4和MgAlON多元化合物原位合成所需克服的势垒，从而降低了反应温度，同时实现了其高效合成和均匀分布，细化气孔，优化了材料的组成和显微结构。MgAlON具有优异的抗钢水\熔渣侵蚀性能和抗热震性能，MgAl2O4、MgCr2O4具有优异的抗碱性渣侵蚀性能和抗氧化性能，三者协同作用可大大提高了RH精炼炉内衬耐火材料的使用寿命，同时满足超低碳钢、洁净钢等高品质钢的冶炼需求。
具体表现如下：
(1)在RH精炼服役环境下，现有技术中MgO-C材料中的C易溶于钢水中，污染钢液。本发明中AlCr-MgO-Al2O3复合耐火材料高温烧成后为TMgAl2O4、MgCr2O4和MgAlON协同原位增强的Al2O3复合材料，是一种新型无碳耐火材料，且化学稳定性优异，不会污染钢液；同时，增强相原位合成，可填充气孔，细化气孔，优化材料结构，从而进一步提高材料的抗渗透和抗侵蚀性能。
(2)本发明采用铝铬合金为原料，其熔点远高于金属铝(如图1所示)，当温度达800℃时，固态的铝铬合金与气氛反应(气-固反应)更具有动力学优势，反应速度比较快，有利于Al2O3、Cr2O3、AlN中间相的高效大量生成与均匀分布，从而促进了MgAl2O4、MgCr2O4、MgAlON在较低温度下的可控合成；
(3)本发明通过添加AlCr合金，在空气气氛中烧成，原位合成MgAl2O4、MgCr2O4、MgAlON增强相，其中MgAlON具有优异的抵抗钢水冲刷侵蚀的性能；MgAl2O4尖晶石合成伴随一定体积膨胀，可有效细化气孔，优化结构，进一步提高抗侵蚀介质渗透性能；MgCr2O4尖晶石具有优异的抗碱性渣的性能，可大大提高单一MgAlON-Al2O3复合材料的抗碱性渣侵蚀性能，三者协同发挥作用可大大提高材料的使用寿命。
附图说明
图1是本发明的Al-Cr二元相图。
具体实施方式
实施例1
将50wt.％的刚玉(其中刚玉颗粒的质量百分比为95％，氧化铝细粉为5％。)、30wt.％的镁砂、20wt.％的铝铬合金粉混合，外加上述混合料4wt.％的酚醛树脂结合剂，混炼均匀，压制成型制得AlCr-MgO-Al2O3复合材料坯体，并在120℃干燥24小时。将干燥后的AlCr-MgO-Al2O3坯体以10℃/min的升温速率升温至1400℃保温4h烧成。在空气气氛中，当体系温度达约800℃时，AlCr-Al2O3-MgO复合坯体中的AlCr合金颗粒吸收气氛中的O2开始显著氧化，生成高活性Al2O3和Cr2O3；随着气氛中O2的消耗，坯体内部的氧分压降低，AlCr合金进一步与N2发生反应，生成AlN；随着温度进一步升高，新生的高活性Al2O3、Cr2O3和AlN进一步与体系中的MgO反应生成高性能的MgAl2O4、MgCr2O4和MgAlON增强相。最终制得MgAl2O4、MgCr2O4和MgAlON原位复合增强的Al2O3复合耐火材料。
所得MgAl2O4、MgCr2O4和MgAlON原位复合增强的Al2O3复合耐火材料经检测，物相组成为Al2O3、MgAl2O4、MgCr2O4和MgAlON，显气孔率为11.2％，常温耐压强度为276MPa。
实施例2
将85wt.％的刚玉(其中刚玉颗粒的质量百分比为90％，氧化铝细粉为10％。)、5wt.％的铝铬合金粉、10wt.％的镁砂粉混合，外加上述混合料4wt.％的酚醛树脂结合剂，混炼均匀，压制成型制得AlCr-MgO-Al2O3复合材料坯体，并在200℃干燥12小时。将干燥后的AlCr-MgO-Al2O3坯体以5℃/min的升温速率升温至1600℃保温3h烧成，制得MgAl2O4、MgCr2O4和MgAlON原位复合增强的Al2O3复合耐火材料。
所得MgAl2O4、MgCr2O4和MgAlON原位复合增强的Al2O3复合耐火材料。经检测，物相组成为Al2O3、MgAl2O4、MgCr2O4和MgAlON，显气孔率为12.8％，常温耐压强度为206MPa。
实施例3
将65wt.％的刚玉(其中刚玉颗粒的质量百分比为95％，氧化铝细粉为5％)、20wt.％的铝铬合金粉、15wt.％的镁砂粉混合，外加上述混合料5wt.％的酚醛树脂结合剂，混炼均匀，压制成型制得AlCr-MgO-Al2O3复合材料坯体，并在150℃干燥48小时。将干燥后的AlCr-MgO-Al2O3坯体以15℃/min的升温速率升温至1200℃保温8h烧成，制得MgAl2O4、MgCr2O4和MgAlON原位复合增强的Al2O3复合耐火材料。
所得MgAl2O4、MgCr2O4和MgAlON原位复合增强的Al2O3复合耐火材料经检测，物相组成为Al2O3、MgAl2O4、MgCr2O4和MgAlON，显气孔率为10.1％，常温耐压强度为197MPa。
实施例4
将55wt.％的刚玉(其中刚玉颗粒的质量百分比为95％，氧化铝细粉为5％)、15wt.％的铝铬合金粉、30wt.％的镁砂粉混合，外加上述混合料4.5wt.％的酚醛树脂结合剂，混炼均匀，压制成型制得AlCr-MgO-Al2O3复合材料坯体，并在120℃干燥50小时。将干燥后的AlCr-MgO-Al2O3坯体以20℃/min的升温速率升温至1700℃保温2h烧成，制得MgAl2O4、MgCr2O4和MgAlON原位复合增强的Al2O3复合耐火材料。
所得MgAl2O4、MgCr2O4和MgAlON原位复合增强的Al2O3复合耐火材料经检测，物相组成为Al2O3、MgAl2O4、MgCr2O4和MgAlON，显气孔率为11.6％，常温耐压强度为319MPa。
实施例5
将80wt.％的刚玉(其中刚玉颗粒的质量百分比为92％，氧化铝细粉为8％。)、10wt.％的铝铬合金粉、10wt.％的镁砂粉混合，外加上述混合料3.5wt.％的酚醛树脂结合剂，混炼均匀，压制成型制得AlCr-MgO-Al2O3复合材料坯体，并在200℃干燥10小时。将干燥后的AlCr-MgO-Al2O3坯体以3℃/min的升温速率升温至1500℃保温1h烧成，制得MgAl2O4、MgCr2O4和MgAlON原位复合增强的Al2O3复合耐火材料。
所得MgAl2O4、MgCr2O4和MgAlON原位复合增强的Al2O3复合耐火材料经检测，物相组成为Al2O3、MgAl2O4、MgCr2O4和MgAlON，显气孔率为14.1％，常温耐压强度为282MPa。

Claims (10)

1.一种RH精炼炉用复合耐火材料，其特征在于，包括如下质量分数的原料组成：50~85wt%的刚玉、5~20 wt%的铝铬合金粉、10~30 wt%的镁砂，2~5 wt%的结合剂，原位合成MgAl2O4、MgCr2O4和MgAlON增强相，化学分子式为MgAl2O4-MgCr2O4-MgAlON-Al2O3。
2.根据权利要求1所述的RH精炼炉用复合耐火材料，其特征在于，所述刚玉包括粒度为1~3 mm和<1mm的刚玉颗粒和< 5 μm的活性氧化铝细粉；所述镁砂的粒度为<0.5mm。
3.根据权利要求1所述的RH精炼炉用复合耐火材料，其特征在于，所述铝铬合金粉中的Cr含量按质量百分比为2%~60%。
4.根据权利要求1或2所述的RH精炼炉用复合耐火材料，其特征在于，所述刚玉中刚玉颗粒的质量百分比为80%~95%，氧化铝细粉的质量百分比为5~20%。
5.根据权利要求1所述的RH精炼炉用复合耐火材料，其特征在于，所述结合剂为热固性酚醛树脂结合剂。
6.权利要求1-5任一项所述的复合耐火材料，其特征在于，应用于RH精炼炉中的内衬。
7.权利要求1-5任一项所述的RH精炼炉用复合耐火材料的制备方法，其特征在于，包括如下步骤：
（1）将刚玉、铝铬合金粉、镁砂和结合剂按照一定的比例混合搅拌,制成泥料，其中50~85 wt%的刚玉、5~20 wt%的铬铝合金粉、10~30 wt%的镁砂，2~5 wt%的结合剂；
（2）将所述泥料压制成复合坯体，并对所述坯体进行干燥；
（3）将所述复合坯体进行高温烧结后制得MgAl2O4-MgCr2O4-MgAlON-Al2O3复合耐火材料。
8.根据权利要求7所述的制备方法，其特征在于，步骤（2）中所述干燥是将坯体在120~200oC温度范围内干燥10~50小时。
9.根据权利要求7所述的制备方法，其特征在于，步骤（3）中所述的高温烧结是在窑炉中空气气氛条件下以3~20oC/min速率升温至1200°C~1700°C，保温1~8 小时。
10.根据权利要求9所述的制备方法，其特征在于，所述窑炉包括隧道窑、梭式窑、电窑。
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