CN110723963B - 一种含纳米氧化铝的高炉出铁沟浇注料及其制备方法 - Google Patents

一种含纳米氧化铝的高炉出铁沟浇注料及其制备方法 Download PDF

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CN110723963B
CN110723963B CN201911053471.8A CN201911053471A CN110723963B CN 110723963 B CN110723963 B CN 110723963B CN 201911053471 A CN201911053471 A CN 201911053471A CN 110723963 B CN110723963 B CN 110723963B
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何见林
邵荣丹
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Wuhan Research Institute of Metallurgical Construction Co Ltd
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Abstract

本发明涉及一种含纳米氧化铝的高炉出铁沟浇注料及其制备方法。该浇注料按质量份数计，由以下组分组成：电熔棕刚玉50～70份，电熔致密刚玉5～15份，碳化硅10～20份，水泥1～3份，硅微粉1～3份，碳黑1.5～3份，活性氧化铝微粉5～8份，纳米氧化铝粉1～3份，抗氧化剂1.5～3份，复合防爆剂1～3份，复合减水剂0.1～0.3份，其中纳米氧化铝粉粒径为50～80nm。该浇注料生产及施工工艺简单，纳米氧化铝粉在浇注料中均匀分散，所得浇注料具有良好的耐高温冲刷性能、耐渣铁化学侵蚀性和抗热震稳定性能，使用寿命高，易于推广。

Description

一种含纳米氧化铝的高炉出铁沟浇注料及其制备方法
技术领域
本发明属于耐火浇注料领域，具体涉及一种含纳米氧化铝的高炉出铁沟浇注料及其制备方法。
背景技术
高炉出铁沟是高温铁水和熔渣自高炉炉内流出到铁水罐的通道，主要由主铁沟、支铁沟、渣沟、撇渣器及摆动溜槽组成。目前，高炉出铁沟工作层都是采用Al2O3-SiC-C质浇注料，Al2O3-SiC-C质浇注料具有强度高、耐冲刷、抗热震和使用寿命较长等特点，同时碳和碳化硅的高导热性、低膨胀率和渣非润湿性都赋予此材料体系良好的物理化学性能，从而广泛应用于高炉出铁沟系统。
近年来，随着高炉冶炼技术的发展，冶炼强度不断加大，高炉出铁沟耐火材料使用条件越来越苛刻，消耗量也越来越大，为进一步提高高炉出铁沟浇注料的使用性能，国内外学者纷纷通过优化基质来改善其使用性能。如专利号：CN201110044222.X“一种新型主铁沟浇注料”专利技术，公开了以改性纳米碳粉取代沥青，提高其抗氧化性能和残炭率，还能改善烘烤时抗爆裂性能，但其抗热震性能不太理想；专利号：CN201210281186.3“一种大于2500m3高炉主铁沟浇注料”专利技术，公开了加入锌铝尖晶石粉、纳米级硅酸锆、氧化锆空心球并以二氧化硅溶胶悬浮液做纳米结合剂，提高了浇注料的热震稳定性，但相应生产成本也提高不少，且抗氧化性能还没有得到很好的解决；专利号：CN101767999A“纳米Al2O3、SiC薄膜包裹碳的Al2O3-MA-SiC-C质耐火浇注料及其制备方法”专利技术，公开了用Al2O3和SiC薄膜包裹碳的并且用Al(OH)3和Mg(OH)2复合悬浮液作为纳米陶瓷结合剂制作的Al2O3-MA-SiC-C质耐火浇注料，通过原位反应生产尖晶石，提高了材料的抗氧化性及抗渣铁侵蚀性能，但其生产工艺、现场施工工艺均比较复杂，且原位反应生产尖晶石的量很难控制，如过多的生成尖晶石则对浇注料的抗渣铁性能不利。
随着冶炼技术进步的不断提高，通铁时间延长，出铁间隔时间短，增大了出铁沟耐火材料的侵蚀破坏程度，对高炉出铁沟用耐材提出了长寿命的要求。因此有必要对现有技术进行改进，研发出一种综合使用性能好，寿命长，制备方法简单的新型高炉出铁沟浇注料。
发明内容
本发明的目的在于提供一种含纳米氧化铝的高炉出铁沟浇注料及其制备方法，该高炉出铁沟浇注料具有良好的耐高温冲刷性能、耐渣铁化学侵蚀性和抗热震稳定性能，使用寿命长，其生产及施工工艺简单，易于推广。
为实现上述目的，本发明采用了如下技术方案：
提供一种含纳米氧化铝的高炉出铁沟浇注料，按质量份数计，由以下组分组成：电熔棕刚玉50～70份，电熔致密刚玉5～15份，碳化硅10～20份，水泥1～3份，硅微粉1～3份，碳黑1.5～3份，活性氧化铝微粉5～8份，纳米氧化铝粉1～3份，抗氧化剂1.5～3份，复合防爆剂1～3份，复合减水剂0.1～0.3份，其中纳米氧化铝粉粒径为50～80nm。
按上述方案，所述电熔棕刚玉中，Al2O3≥95％、C≤0.08％，分为8～5mm、5～3mm和3～1mm三个粒度等级，三个粒度等级对应质量比为35～47：25～30：28～35。
按上述方案，所述电熔致密刚玉中，Al2O3≥98％，分为1～0.075mm和0.075～0.04mm两个粒度等级，两个粒度等级对应质量比为40～60：40～60。
按上述方案，所述碳化硅由粒径中，SiC≥95％，分为1～0.075mm、0.075～0.046mm和0.046～0.02mm三个粒度等级，三个粒度等级对应质量比为50～60：25～35：15～25。
按上述方案，所述水泥为纯铝酸钙水泥，其Al2O3含量大于70％。
按上述方案，所述硅微粉中，SiO2≥96％。
按上述方案，所述碳黑中，碳含量大于99％，粒度小于2um。
按上述方案，所述活性氧化铝中，Al2O3含量大于99％，粒度小于2um。
按上述方案，所述纳米氧化铝中，Al2O3含量大于99％。
按上述方案，所述抗氧化剂为金属硅粉、碳化硼、硼化锆中的至少两种。
按上述方案，所述复合防爆剂为金属铝粉、乳酸铝、防爆纤维中的至少两种。
按上述方案，所述复合减水剂为三聚磷酸钠、萘磺酸盐、聚羧酸高效减水剂中的至少两种。
一种上述含纳米氧化铝的高炉出铁沟浇注料的制备方法，具体步骤如下：
a)将1～3份纳米氧化铝粉与1.5～3份碳黑进行预混，混合时间大于15min。
b)将步骤a)中的预混合粉与电熔棕刚玉50～70份，电熔致密刚玉5～15份，碳化硅10～20份，水泥1～3份，硅微粉1～3份，活性氧化铝微粉5～8份，抗氧化剂1.5～3份，复合防爆剂1～3份，复合减水剂0.1～0.3份投入到强制搅拌机中进行搅拌10-20min，使所有物料充分混合均匀即得含纳米氧化铝的高炉出铁沟浇注料。
本发明在高炉出铁沟浇注料中添加粒径为50～80nm的纳米氧化铝粉，纳米氧化铝粉粒径小，比表面积大，一方面可以有效的填充颗粒间隙，促进烧结，降低浇注料的加水量，提高致密度和强度，大大改善浇注料的作业性能和使用性能；此外，在高温条件下，纳米氧化铝粉可与硅微粉或SiC氧化后生成的SiO2发生反应生成莫来石，改善浇注料的抗热震性及抗冲刷性能；纳米氧化铝粉还能为水泥水化提供较多的成核点，促进铝酸钙水泥的水化，这对浇注料在单铁口或双铁口的高炉进行快速热修非常有利，可以大大缩短浇注料的硬化时间，便于高炉快速投入生产。
本发明的有益效果为：
1.本发明提供的高炉出铁沟浇注料，含有粒径为50～80nm的纳米氧化铝粉，与浇注料中其他组分配合，使得浇注料具有良好的耐高温冲刷性能、耐渣铁化学侵蚀性和抗热震稳定性能，使用寿命高，易于推广。
2.本发明高炉出铁沟浇注料中纳米氧化铝粉掺入量小，成本低，对浇注料性能提升明显。
3.本发明采用碳黑替代球状沥青，球状沥青软化点低，在烘烤时易冒黄烟，而碳黑软化点高，烘烤时不易冒烟，可减少对环境的污染，起到了一定的环保作用。
4.本发明提供的高炉出铁沟浇注料的制备方法，其生产及施工工艺简单，其中将纳米氧化铝与碳黑预先混合，因纳米氧化铝粒径小、比表面活性大，可使其均匀吸附在碳黑颗粒表面，保护碳黑不被氧化，提高材料的抗氧化性，而纳米氧化铝可在碳黑表面均匀分布，不易团聚，最大限度的发挥了纳米氧化铝的改性作用，减少了纳米氧化铝掺入量，降低了成本；而碳素材料与渣的润湿性差，抗渣性能好，因而制备的浇注料抗渣性能也得到改善。
具体实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
以下各实施例中，所用原料指标为：
电熔棕刚玉中，Al2O3≥95％、C≤0.08％，分为8～5mm、5～3mm和3～1mm三个粒度等级，三个粒度等级对应质量比为45：27：28。
电熔致密刚玉中，Al2O3≥98％，分为1～0.075mm和0.075～0.04mm两个粒度等级，两个粒度等级对应质量比为55：45。
碳化硅中，SiC≥95％，分为1～0.075mm、0.075～0.046mm和0.046～0.02mm三个粒度等级，三个粒度等级对应质量为50：32：18。
水泥为纯铝酸钙水泥，Al2O3含量大于70％。
碳黑中，碳含量大于99％，粒度小于2um。
硅微粉中，SiO2≥96％。
纳米氧化铝粉中，Al2O3含量大于99％，粒径为50～80nm。
活性氧化铝微粉中，Al2O3含量大于99％，粒度小于2um。
抗氧化剂为金属硅粉、碳化硼两种物质混合而成。
复合防爆剂为金属铝粉、乳酸铝、防爆纤维三种物质混合而成，质量比为5：1：5。
复合减水剂为三聚、聚羧酸高效减水剂两种混合而成，质量比为1：3。
一种含纳米氧化铝的高炉出铁沟浇注料制备方法，具体包括如下步骤：
a)将纳米氧化铝粉与碳黑进行预混，预混时间大于15min；
b)将步骤a)中的预混合粉与电熔棕刚玉，电熔致密刚玉，碳化硅，水泥，硅微粉，活性氧化铝微粉，抗氧化剂，复合防爆剂和复合减水剂份投入到强制搅拌机中进行搅拌10min，使所有物料充分混合均匀即得含纳米氧化铝的高炉出铁沟浇注料。
实施例1
一种含纳米氧化铝的高炉出铁沟浇注料，各组分及其质量份数如下：
Figure BDA0002255931220000041
本实施例得到的含纳米氧化铝的高炉出铁沟浇注料具体性能测试参见表1。
实施例2
一种含纳米氧化铝的高炉出铁沟浇注料，各组分及其质量份数如下：
Figure BDA0002255931220000042
Figure BDA0002255931220000051
本实施例得到的含纳米氧化铝的高炉出铁沟浇注料具体性能测试参见表1。
实施例3
一种含纳米氧化铝的高炉出铁沟浇注料，各组分及其质量份数如下：
Figure BDA0002255931220000052
将上述实施例按照国标进行制样和检测，测得的含纳米氧化铝的高炉出铁沟浇注料具体性能测试参见表1。
表1 产品性能指标
Figure BDA0002255931220000053
Figure BDA0002255931220000061
具体性能测试参照标准如下：
按照YB/T5200-1993测试样的显气孔率和体积密度；
按照GB/T5072-2008测试样的常温抗折强度和常温耐压强度；
按照GB/T3002-2004测试样烘干后在1450℃保温0.5小时的高温抗折强度；
按照GB/T5988-2007测试样线变化率。
上述实施例是对本发明的说明，不是对本发明的限定，任何对本发明简单变换后的方案均属于本发明的保护范围。

Claims (10)

1.一种含纳米氧化铝的高炉出铁沟浇注料，其特征在于，按质量份数计，由以下组分组成：电熔棕刚玉50~70份，电熔致密刚玉5~15份，碳化硅10~20份，水泥1~3份，硅微粉1~3份，碳黑1.5~3份，活性氧化铝微粉5~8份，纳米氧化铝粉1~3份，抗氧化剂1.5~3份，复合防爆剂1~3份，复合减水剂0.1~0.3份；其中所述纳米氧化铝粉粒径为50~80nm，所述纳米氧化铝粉和所述碳黑预先混合。
2.根据权利要求1所述的含纳米氧化铝的高炉出铁沟浇注料，其特征在于，所述电熔棕刚玉中，Al2O3≥95%、C≤0.08%，分为8~5mm、5~3mm和3~1mm三个粒度等级，三个粒度等级对应质量比为35~47：25~30：28~35；所述电熔致密刚玉中，Al2O3≥98%，分为1~0.075mm和0.075~0.04mm两个粒度等级，两个粒度等级对应质量比为40~60：40~60。
3.根据权利要求1所述的含纳米氧化铝的高炉出铁沟浇注料，其特征在于，所述碳化硅中，SiC≥95%，分为1~0.075mm、0.075~0.046mm和0.046~0.02mm三个粒度等级，三个粒度等级对应质量比为50~60：25~35：15~25；所述硅微粉中，SiO2≥96%。
4.根据权利要求1所述的含纳米氧化铝的高炉出铁沟浇注料，其特征在于，所述水泥为纯铝酸钙水泥，其Al2O3含量大于70%。
5.根据权利要求1所述的含纳米氧化铝的高炉出铁沟浇注料，其特征在于，所述碳黑中，碳含量大于99%，粒度小于2um。
6.根据权利要求1所述的含纳米氧化铝的高炉出铁沟浇注料，其特征在于，所述活性氧化铝微粉中，Al2O3含量大于99%，粒度小于2um。
7.根据权利要求1所述的含纳米氧化铝的高炉出铁沟浇注料，其特征在于，所述纳米氧化铝粉中， Al2O3含量大于99% 。
8.根据权利要求1所述的含纳米氧化铝的高炉出铁沟浇注料，其特征在于，所述抗氧化剂为金属硅粉、碳化硼、硼化锆中的至少两种。
9.根据权利要求1所述的含纳米氧化铝的高炉出铁沟浇注料，其特征在于，所述复合防爆剂为金属铝粉、乳酸铝、防爆纤维中的至少两种；所述复合减水剂为三聚磷酸钠、萘磺酸盐、聚羧酸高效减水剂中的至少两种。
10.一种权利要求1所述的含纳米氧化铝的高炉出铁沟浇注料的制备方法，其特征在于，具体步骤如下：
a）将1~3份纳米氧化铝粉与1.5~3份碳黑进行预混，混合时间大于15min；
b）将步骤a）中的预混合粉与电熔棕刚玉50~70份，电熔致密刚玉5~15份，碳化硅10~20份，水泥1~3份，硅微粉1~3份，活性氧化铝微粉5~8份，抗氧化剂1.5~3份，复合防爆剂1~3份，复合减水剂0.1~0.3份投入到强制搅拌机中进行搅拌10-20min，使所有物料充分混合均匀即得含纳米氧化铝的高炉出铁沟浇注料。
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