CN107235741A - 一种新型轻质耐火材料 - Google Patents

一种新型轻质耐火材料 Download PDF

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CN107235741A
CN107235741A CN201710528086.9A CN201710528086A CN107235741A CN 107235741 A CN107235741 A CN 107235741A CN 201710528086 A CN201710528086 A CN 201710528086A CN 107235741 A CN107235741 A CN 107235741A
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refractory material
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佘建锋
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Changxing Hongkuang Furnace Burden Co Ltd
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Abstract

本发明提供了一种新型轻质耐火材料，包括以下重量份的组份：氧化铝空心球50～70份，电熔刚玉粉7～13份，碳酸钙1～3份，改性白炭黑3～6份，氧化锆0.5～1份，二氧化锰2～5份和金属钼0.5～1份。本发明的新型轻质耐火材料具有良好的耐压强度和热震稳定性能，通过多种助剂与氧化铝空心球发生协同作用，提高新型轻质耐火材料的强度和使用周期，从而延长了使用寿命。

Description

一种新型轻质耐火材料
技术领域
本发明涉及耐火材料技术领域，尤其涉及一种用于氧化铝空心球砖的稳定性好、耐热震性高的新型轻质耐火材料。
背景技术
轻质耐火材料为气孔率高、体积密度小、热导率低的耐火材料。在工业窑炉和其他热工设备上用作隔热材料。与一般耐火砖比较，抗渣蚀性、力学强度、耐磨损性较差，高温下体积收缩较大。氧化铝空心球砖因具有氧化铝含量高、体积密度小、高温强度大、使用温度高、导热系数小、节约能源等优点被广泛应用于石化行业高温窑炉，它既可用作隔热保温材料，也可用于高温工作衬里材料。基于现有氧化铝空心球砖中部分组份性能不稳定，使得现有氧化铝空心球砖存在易破碎、耐热震性不高的缺点，导致其使用周期短，浪费材料的后果，大大阻碍了氧化铝空心球砖的广泛应用。
中国专利文献上公开了“一种新型的氧化铝空心球砖”，其公告号为CN105294024A，该发明通过引入碳酸钙在基质中形成CA6结合相，可有效减少或避免材料使用过程中硅迁移的发生，同时还可提高材料的使用温度，可有效减少热量散失，节能环保。但是，该发明并没有解决氧化铝空心球砖易破碎、耐热震性不高的缺点。因此，如何对传统氧化铝空心球砖的配方进行改性提高其耐热震性是本领域技术人员亟待解决的技术问题。
发明内容
本发明为了克服传统氧化铝空心球砖易破碎、耐热震性不高的问题，提供了一种稳定性好、耐热震性高的新型轻质耐火材料。
为了实现上述目的，本发明采用以下技术方案：
一种新型轻质耐火材料，所述新型轻质耐火材料包括以下重量份的组份：氧化铝空心球50～70份，电熔刚玉粉7～13份，碳酸钙1～3份，改性白炭黑3～6份和氧化锆0.5～1份。
本发明的新型轻质耐火材料的配方中加入了少量的氧化锆，可以对氧化铝空心新型轻质耐火材料产生明显的增韧效果，其原理如下：该体系中的氧化铝空心球的热膨胀系数大，弹性模量高，烧结冷却后对氧化锆颗粒的束缚作用强，临界直径Dc较大，四方氧化锆颗粒可以更多更有效地保留下来，因此，对新型轻质耐火材料的增韧效果也比较明显，从而达到提高其耐热震性的效果，得到的增韧新型轻质耐火材料的强度大，不易破碎，使用周期长。
加入碳酸钙和改性白炭黑，可以在烧结过程中形成CaO+SiO2体系，不但产生液相，而且在基体中产生具有平直晶粒的片状晶体，可以大大提高新型轻质耐火材料的耐热震性。
作为优选，所述新型轻质耐火材料还包括二氧化锰2～5份和金属钼0.5～1份。
金属钼，作为一种难熔金属与氧化铝热膨胀系数接近，相差仅2.3×10-6，具有良好的热稳定性，其烧结性能也与氧化铝接近，相互适应性良好；体系中同时加入金属钼和二氧化锰具有以下的协同作用：在烧结过程中，二氧化锰与氧化铝空心球发生化学反应生成MnAl2O4，与金属钼形成含有孔隙的糊状体，此时，熔融状的二氧化硅可以润湿并填充这些孔隙，将Mo、MnAl2O4、Al2O3三者牢固粘结在一起，大大降低了新型轻质耐火材料的气孔率，增大了体积密度，从而实现了强度和耐热震性的大幅度提升。
作为优选，所述改性白炭黑的制备方法是：先将白炭黑在450～600℃条件下活化5～10h，加入无水乙醇，配置成4～10wt％的白炭黑溶胶；再在50～60℃条件下滴加吐温20到白炭黑溶胶中，搅拌反应15～30min，超声振荡5～30min，得到改性白炭黑。
本发明采用的改性白炭黑为多孔性物质，其组成可用SiO2·nH2O表示，能均匀并良好地分散于新型轻质耐火材料的配方体系中，从而可提高酚醛树脂的残炭率和抗氧化性，使新型轻质耐火材料的性能得到提高；改性后的白炭黑呈球形，能在新型轻质耐火材料中均匀良好地分散，分散效果好，此外，白炭黑的价格比其他纳米二氧化硅低，降低了生产成本，利于工业化生产。本发明对白炭黑进行改性的过程所选用的改性剂为吐温20，由于吐温20中聚山梨酯分子中有较多的亲水性基团一聚氧乙烯基，故亲水性强，为一种非离子型表面活性剂，可以修饰白炭黑，使得白炭黑中环氧基团具有较高的活性，容易发生开环加成，在烧结过程中与碳酸钙形成CaO+SiO2体系，不但产生液相，而且在基体中产生具有平直晶粒的片状晶体，可以大大提高新型轻质耐火材料的耐热震性。本发明改性白炭黑的制备工艺加单、易于推广。
作为优选，所述氧化铝空心球的颗粒度为5～3mm、3～1mm和0.5～0.1mm。
坯料的颗粒组成对坯体的致密度有很大的影响，在大颗粒的组成中加入一定数目尺寸较小的颗粒，填充于大颗粒的间隙，可以使得坯体的气孔率下降，体积密度增大，使胚体变成具有一定尺寸、形状和结构强度的制品，使得材料的体积密度、耐压强度以及高温性能均得以提高，显著提升新型轻质耐火材料的理化性能。
作为优选，所述电熔刚玉粉的颗粒度不大于500目，颗粒越细，就越容易烧结，烧结温度也就越低，可以降低能耗，节约成本。
作为优选，所述碳酸钙的自然堆积密度小于0.2g/cm3。
本发明具有如下有益效果：通过多种助剂与氧化铝空心球发生协同作用，提高新型轻质耐火材料的强度和使用周期，大大增强了其耐热震性，从而延长了使用寿命。
具体实施方式
下面通过具体实施例，对本发明的技术方案作进一步具体的说明。
在本发明中，若非特指，所有设备和原料均可从市场购得或是本行业常用的，下述实施例中的方法，如无特别说明，均为本领域常规方法。
实施例1：
(1)制备改性白炭黑备用：先将白炭黑在450℃条件下活化5h，加入无水乙醇，配置成4wt％的白炭黑溶胶；再在50℃条件下滴加吐温20到白炭黑溶胶中，搅拌反应15min，超声振荡5min，得到改性白炭黑；
一种新型轻质耐火材料，包括如下组份：氧化铝空心球50g(5～3mm的氧化铝空心球30g，3～1mm的氧化铝空心球15g，0.5～0.1mm的氧化铝空心球5g)，电熔刚玉粉7g(颗粒度400目)，碳酸钙(自然堆积密度0.1g/cm3)1g，改性白炭黑3g，氧化锆0.5g，二氧化锰2g，金属钼0.5g。
实施例2：
(1)制备改性白炭黑备用：先将白炭黑在600℃条件下活化10h，加入无水乙醇，配置成10wt％的白炭黑溶胶；再在60℃条件下滴加吐温20到白炭黑溶胶中，搅拌反应30min，超声振荡30min，得到改性白炭黑；
一种新型轻质耐火材料，包括如下组份：氧化铝空心球70g(5～3mm的氧化铝空心球40g，3～1mm的氧化铝空心球20g，0.5～0.1mm的氧化铝空心球10g)，电熔刚玉粉13g(颗粒度350目)，碳酸钙(自然堆积密度0.15g/cm3)3g，改性白炭黑6g，氧化锆1g，二氧化锰5g，金属钼1g。
实施例3：
(1)制备改性白炭黑备用：先将白炭黑在550℃条件下活化8h，加入无水乙醇，配置成7wt％的白炭黑溶胶；再在55℃条件下滴加吐温20到白炭黑溶胶中，搅拌反应20min，超声振荡15min，得到改性白炭黑；
一种新型轻质耐火材料，包括如下组份：氧化铝空心球60g(5～3mm的氧化铝空心球25g，3～1mm的氧化铝空心球18g，0.5～0.1mm的氧化铝空心球17g)，电熔刚玉粉10g(颗粒度500目)，碳酸钙(自然堆积密度0.05g/cm3)2g，改性白炭黑5g，氧化锆0.7g，二氧化锰3g，金属钼0.7g。
对比例
对比例采用市轻质耐火材料，该轻质耐火材料的配方组分中未添加氧化锆、二氧化锰和金属钼的任意一种。
对实施例1-3和对比例的轻质耐火材料进行性能检测，结果如表1所示。
表1.理化指标检测结果
实施例1 实施例2 实施例3 对比例
体积密度(g/cm3) 1.4 1.55 1.45 1.65
耐压强度(MPa) 1700 1680 1650 1580
热震稳定性(1100℃，次) 28 26 35 18
由表1的理化指标结果可以看出，本发明的新型轻质耐火材料相对于市售轻质耐火材料具有良好的耐压强度和热震稳定性能，通过多种助剂与氧化铝空心球发生协同作用，提高新型轻质耐火材料的强度和使用周期，从而延长了使用寿命。

Claims (6)

1.一种新型轻质耐火材料，其特征在于，所述新型轻质耐火材料包括以下重量份的组份：氧化铝空心球50～70份，电熔刚玉粉7～13份，碳酸钙1～3份，改性白炭黑3～6份和氧化锆0.5～1份。
2.根据权利要求1所述的一种新型轻质耐火材料，其特征在于，所述新型轻质耐火材料还包括二氧化锰2～5份和金属钼0.5～1份。
3.根据权利要求1所述的一种新型轻质耐火材料，其特征在于，所述改性白炭黑的制备方法是：先将白炭黑在450～600℃条件下活化5～10h，加入无水乙醇，配置成4～10wt％的白炭黑溶胶；再在50～60℃条件下滴加吐温20到白炭黑溶胶中，搅拌反应15～30min，超声振荡5～30min，得到改性白炭黑。
4.根据权利要求1所述的一种新型轻质耐火材料，其特征在于，所述氧化铝空心球的颗粒度为5～3mm、3～1mm和0.5～0.1mm。
5.根据权利要求1-4任一所述的一种新型轻质耐火材料，其特征在于，所述电熔刚玉粉的颗粒度不大于500目。
6.根据权利要求2或4所述的一种新型轻质耐火材料，其特征在于，所述碳酸钙的自然堆积密度小于0.2g/cm3。
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