CN107954747A - 耐腐蚀耐火砖及其制备方法 - Google Patents

耐腐蚀耐火砖及其制备方法 Download PDF

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CN107954747A
CN107954747A CN201610897316.4A CN201610897316A CN107954747A CN 107954747 A CN107954747 A CN 107954747A CN 201610897316 A CN201610897316 A CN 201610897316A CN 107954747 A CN107954747 A CN 107954747A
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corrosion
adobe
proof fire
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张微微
计富宝
吉飞虎
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Henan Haina New Material Co Ltd
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Abstract

本发明提供一种耐腐蚀耐火砖,包括耐火砖基体和喷涂在所述耐火砖基体表面的耐高温涂层;其中,所述耐火砖基体的制备原料包括:铝硅酸盐耐火纤维7%~18%、红柱石大颗粒15%~25%、膨胀石墨3%~5%、钛白粉10%~18%、六铝酸钙小颗粒5%~8%、粉煤灰5%~10%、硅藻土15%~20%、高铝矾土熟料6%~11%、余量为纸浆水;所述耐高温涂层的制备原料包括:聚硅氧烷40%~58%、Mo粉3%~10%、刚玉微粉5%~10%、氮化硅微粉2%~5%、余量为乙醇。本发明还提供一种耐腐蚀耐火砖的制备方法,该方法步骤简单、易于自动化生产。

Description

耐腐蚀耐火砖及其制备方法
技术领域
本发明属于耐火材料技术领域,具体的说,涉及了一种耐腐蚀耐火砖及其制备方法。
背景技术
耐火材料由于对高温介质良好的抗侵蚀性,以及具有保温隔热的性能, 在冶金、石化、玻璃等高温行业被广泛使用。随着我国对节能降耗的重视程度不断提高,具有良好保温隔热效果的轻质耐火材料得到了更多的研究与发展。不定形耐火材料由于具有施工便利、生产成本低,以及衬体的整体结构性好等优势,而受到了特别的关注,其中尤以耐火浇注料应用得最为广泛。
通常使用的耐火浇注料主要为Al2O3-SiO2质材料,但这类耐火材料在石化等行业使用时,由于所处还原气氛环境的影响,会导致耐火材料的损毁加剧,从而使得材料的使用寿命降低。另外,由于传统的耐火骨料中气孔尺寸较大,孔径多处于毫米级,这样当该材料在高温环境中使用时,由于通过气孔内气体辐射传热与对流传热的加剧,会使耐火材料的导热系数升高,进而降低了耐火材料的隔热保温效果,增大了热能的流失,导致能源成本的上升。
为了解决以上存在的问题,人们一直在寻求一种理想的技术解决方案。
发明内容
本发明的目的是针对现有技术的不足,从而提供一种具有较高的抗热震性、较好的隔热保温效果的耐腐蚀耐火砖。
为了实现上述目的,本发明所采用的技术方案是:一种耐腐蚀耐火砖,它包括耐火砖基体和喷涂在所述耐火砖基体表面的耐高温涂层;其中,所述耐火砖基体的制备原料包括:铝硅酸盐耐火纤维7%~18%、红柱石大颗粒15%~25%、膨胀石墨3%~5%、钛白粉10%~18%、六铝酸钙小颗粒5%~8%、粉煤灰5%~10%、硅藻土15%~20%、高铝矾土熟料6%~11%、余量为纸浆水;所述耐高温涂层的制备原料包括:聚硅氧烷40%~58%、Mo粉3%~10%、刚玉微粉5%~10%、氮化硅微粉2%~5%、余量为乙醇。
基于上述,所述六铝酸钙小颗粒粒度小于0.074mm、所述红柱石大颗粒粒径为1 mm~3 mm。
基于上述,所述高铝矾土熟料粒度小于0.043mm、所述硅藻土粒度小于0.074mm。
本发明还提供一种耐腐蚀耐火砖的制备方法,包括以下步骤:
按照上述质量百分数的原料计算,将铝硅酸盐耐火纤维、红柱石大颗粒、膨胀石墨、钛白粉、六铝酸钙小颗粒、粉煤灰、硅藻土、高铝矾土熟料和纸浆水进行混碾制得预制泥料,将所述混碾泥料压制成砖坯;
将聚硅氧烷、Mo粉、刚玉微粉、氮化硅微粉与乙醇制得耐高温涂料,然后将干燥后的所述砖坯表面喷涂所述耐高温涂料,制得喷涂砖坯,所述喷涂砖坯经干燥、煅烧后制得所述耐腐蚀耐火砖。
基于上述,将所述混碾泥料压制成砖坯,并将所述砖坯在自然干燥24小时后置于干燥窑内,在100℃~200℃的温度条件下干燥24小时~48小时;然后将干燥后的所述砖坯浸渍在所述耐高温涂料中制得喷涂砖坯,并在1100℃~1250℃的温度下对其进行煅烧8小时~10小时,从而制得所述耐腐蚀耐火砖。
本发明所提供的耐腐蚀耐火砖原料中各成分的性能作用如下:
铝硅酸盐耐火纤维:硅酸盐中的SiO4四面体的一部分由AlO4四面体取代组成的铝硅酸盐,如正长石KAlSi3O8,也可写为K[(AlO2)(SiO2)3],表示四分之一的含氧四面体被铝原子所占据,还有钙长石CaAl2SiO8或Ca[(AlO2)2(SiO2)2],其中一半是AlO4四面体,另一半是SiO4四面体由其制成的铝硅酸盐耐火纤维具有性能稳定,纤维长、抗拉强度大,渣球少等特点。
红柱石大颗粒:晶体属正交(斜方)晶系的岛状结构硅酸盐矿物,红柱石在砖坯煅烧过程中会发生不可逆的晶体转化形成具有良好的莫来石网络的莫来石,从而使其具有1800℃以上的耐火性能,且耐骤冷骤热、机械强度大、抗热冲击力和抗渣性强、荷重转化点高,并具有极高的化学稳定性和极强的抗化学腐蚀性,从而使得制备的所述低蠕变红柱石复合耐火砖具有高荷软、低蠕变、高抗热震性能。
膨胀石墨:膨胀石墨是由天然石墨鳞片经插层、水洗、干燥、高温膨化得到的一种疏松多孔的蠕虫状物质。其除了具备天然石墨本身的耐冷热、耐腐蚀、自润滑等优良性能以外,还具有天然石墨所没有的柔软、压缩回弹性、吸附性、生态环境协调性、生物相容性、耐辐射性等特性。膨胀石墨遇高温可瞬间体积膨胀150~300倍,由片状变为蠕虫状,从而结构松散,多孔而弯曲,表面积扩大、表面能提高、吸附鳞片石墨力增强,蠕虫状石墨之间可自行嵌合,这样增加了它的柔软性、回弹性和可塑性。
钛白粉:主要成分为二氧化钛,化学性质极为稳定,是一种偏酸性的两性氧化物,广泛用于各类结构表面涂料。本文中其主要作为烧结助剂,降低耐火砖的烧结温度。
硅藻土:硅藻土是一种硅质岩石,是一种生物成因的硅质沉积岩,它主要由古代硅藻的遗骸所组成。其化学成分以SiO2为主。工业上常用来作为保温材料。同时由于具有孔隙度大、吸收性强、化学性质稳定、耐磨、耐热等特点,能为涂料提供优异的表面性能,增容,增稠以及提高附着力。
六铝酸钙小颗粒:是一系列由氧化钙和氧化铝在高温下烧结而成的无机化合物,由于其硬度大、熔点高的物理性质,被应用于水泥和灭火材料中。通式为mCaO·nAl2O3
高铝矾土熟料:是指铝矾土矿物经过煅烧后的物料,其主要成分为水铝石和高铝硅石,具有较高的耐烧性能,常用来制备各种高铝砖,是冶金工业和其它工业广泛使用的耐火或防腐材料。
聚硅氧烷与Mo粉在高温条件下会裂解反应生成Mo2C、Mo3Si等新相、氮化硅微粉会与刚玉微粉高温反应生成Sialon晶须,从而在耐火砖表面形成掺杂有晶须的非晶态SiOC陶瓷涂层,提高了耐火砖的表面抗腐蚀能力,产生的体积膨胀能有效降低陶瓷材料的孔隙率。
本发明相对现有技术具有突出的实质性特点和显著的进步,具体的说,本发明首先将不同粒度及长度的铝硅酸盐耐火纤维、红柱石大颗粒、膨胀石墨、钛白粉、六铝酸钙小颗粒、粉煤灰、硅藻土、高铝矾土熟料和纸浆水进行混合,使得制备的砖坯各个部位成分配比搭配一致,保证了煅烧所得的耐腐蚀耐火砖各部位性能的一致性,同时原料中含有大量棱角突出的粒度料,增大了临界粒度,为耐腐蚀耐火砖提供了牢固的骨架结构使其在使用过程中不易产生变形。本发明将所述砖坯喷涂由聚硅氧烷、Mo粉、氮化硅微粉、刚玉微粉和乙醇混合制备的耐高温涂料中,使得烧制后的砖坯表面形成一层耐高温陶瓷层,提升了产品的耐高温和表面抗腐蚀性能。
同时,本发明充分利用六铝酸钙小颗粒与上述原料混合,使得材料内部在多时间内存在大量微小气孔,且所述微小气孔不会随烧结过程的进行而聚集长大,最终在产品中形成微米级且均匀分布的气孔,使得制备的耐腐蚀耐火砖具有高荷软、低蠕变、高抗热震性能。
具体实施方式
下面通过具体实施方式,对本发明的技术方案做进一步的详细描述。
实施例1
本实施例提供一种耐腐蚀耐火砖,包括耐火砖基体和喷涂在所述耐火砖基体表面的耐高温涂层;其中,所述耐火砖基体的制备原料包括:铝硅酸盐耐火纤维7%、红柱石大颗粒25%、膨胀石墨5%、钛白粉10%、六铝酸钙小颗粒8%、粉煤灰10%、硅藻土15%、高铝矾土熟料11%、纸浆水9%。所述耐高温涂层的制备原料包括:聚硅氧烷40%、Mo粉3%、刚玉微粉5%、氮化硅微粉5%、乙醇47%。
其中,所述六铝酸钙小颗粒粒度小于0.074mm、所述红柱石大颗粒粒径为1 mm~3mm、所述高铝矾土熟料粒度小于0.043mm、所述硅藻土粒度小于0.074mm。各原料中的化学成分如表1所示。
表1、各原料主要化学成分
本实施例还提供一种所述耐腐蚀耐火砖的制备方法,具体制备步骤包括:
(1)按照上述质量百分数的原料计算,将铝硅酸盐耐火纤维、红柱石大颗粒、膨胀石墨、钛白粉、六铝酸钙小颗粒、粉煤灰、硅藻土、高铝矾土熟料和纸浆水进行混碾制得预制泥料;将聚硅氧烷、Mo粉、氮化硅微粉、刚玉微粉与乙醇制得耐高温涂料;
(2)采用压力吨位大于315吨的制砖机将所述混碾泥料压制成砖坯,并将所述砖坯在自然干燥24小时,然后置于干燥窑内,在200℃的温度条件下干燥24小时;然后将干燥后的砖坯浸渍在所述耐高温涂料中制得喷涂砖坯,并在1250℃的温度下对其进行煅烧8小时,从而制得所述耐腐蚀耐火砖。经检测,本实施例制得的所述耐腐蚀耐火砖密度为2.0g/cm3
实施例2
本实施例提供一种耐腐蚀耐火砖,包括耐火砖基体和喷涂在所述耐火砖基体表面的耐高温涂层;其中,所述耐火砖基体包括下述质量百分数的物料:铝硅酸盐耐火纤维18%、红柱石大颗粒15%、膨胀石墨3%、钛白粉10%、六铝酸钙小颗粒5%、粉煤灰10%、硅藻土15%、高铝矾土熟料11%、纸浆水13%。所述耐高温涂层的制备原料包括:聚硅氧烷58%、Mo粉10%、刚玉微粉10%、氮化硅微粉5%、乙醇17%。
本实施例所述的耐腐蚀耐火砖的制备方法与实施例1中的制备方法相同。经检测,本实施例制得的所述耐腐蚀耐火砖密度为2.1g/cm3
实施例3
本实施例提供一种耐腐蚀耐火砖,包括耐火砖基体和喷涂在所述耐火砖基体表面的耐高温涂层;其中,所述耐火砖基体的制备原料包括:铝硅酸盐耐火纤维18%、红柱石大颗粒15%、膨胀石墨3%、钛白粉18%、六铝酸钙小颗粒5%、粉煤灰5%、硅藻土15%、高铝矾土熟料6%、纸浆水15%;所述耐高温涂层的制备原料包括:聚硅氧烷50%、Mo粉8%、刚玉微粉8%、氮化硅微粉5%、乙醇29%。
本实施例所述的耐腐蚀耐火砖的制备方法与实施例1中的制备方法相同。经检测,本实施例制得的所述耐腐蚀耐火砖密度为1.8g/cm3
耐腐蚀耐火砖性能检测
分别对实施例1~3制备的耐腐蚀耐火砖中的体积密度、平均孔径、耐火度、常温耐压强度和1350℃高温抗折强度性能进行检测,检测结果如表2所示。
表2、耐腐蚀耐火砖性能检测
从上表中可以看出:实施例1~3提供的耐腐蚀耐火砖的耐火软化点大于1700℃、常温耐压强度大于39MPa、平均孔径介于8.5微米~9.0微米之间、体积密度介于1.8 g/cm3~2.2g/cm3之间,因此所述耐腐蚀耐火砖各项性能指标符合GB/T3994-2013规定的指标,所述耐腐蚀耐火砖内部存在均匀分布的微米级气孔,同时该产品具有载荷软化温度高、高抗热震的性能的优点。
最后应当说明的是:以上实施例仅用以说明本发明的技术方案而非对其限制;尽管参照较佳实施例对本发明进行了详细的说明,所属领域的普通技术人员应当理解:依然可以对本发明的具体实施方式进行修改或者对部分技术特征进行等同替换;而不脱离本发明技术方案的精神,其均应涵盖在本发明请求保护的技术方案范围当中。

Claims (5)

1.一种耐腐蚀耐火砖,其特征在于,它包括耐火砖基体和喷涂在所述耐火砖基体表面的耐高温涂层;其中,所述耐火砖基体的制备原料包括:铝硅酸盐耐火纤维7%~18%、红柱石大颗粒15%~25%、膨胀石墨3%~5%、钛白粉10%~18%、六铝酸钙小颗粒5%~8%、粉煤灰5%~10%、硅藻土15%~20%、高铝矾土熟料6%~11%、余量为纸浆水;所述耐高温涂层的制备原料包括:聚硅氧烷40%~58%、Mo粉3%~10%、刚玉微粉5%~10%、氮化硅微粉2%~5%、余量为乙醇。
2.根据权利要求1所述的耐腐蚀耐火砖,其特征在于,所述六铝酸钙小颗粒粒度小于0.074mm、所述红柱石大颗粒粒径为1 mm~3 mm。
3.根据权利要求1或2所述的耐腐蚀耐火砖,其特征在于,所述高铝矾土熟料粒度小于0.043mm、所述硅藻土粒度小于0.074mm。
4.一种耐腐蚀耐火砖的制备方法,包括以下步骤:
按照权利要求1~3任一项所述质量百分数的原料计算,将铝硅酸盐耐火纤维、红柱石大颗粒、膨胀石墨、钛白粉、六铝酸钙小颗粒、粉煤灰、硅藻土、高铝矾土熟料和纸浆水进行混碾制得预制泥料,将所述混碾泥料压制成砖坯;
将聚硅氧烷、Mo粉、刚玉微粉、氮化硅微粉与乙醇制得耐高温涂料,然后将干燥后的所述砖坯表面喷涂所述耐高温涂料,制得喷涂砖坯,所述喷涂砖坯经干燥、煅烧后制得所述耐腐蚀耐火砖。
5.根据权利要求4所述的耐腐蚀耐火砖的制备方法,其特征在于,将所述混碾泥料压制成砖坯,并将所述砖坯在自然干燥24小时后置于干燥窑内,在100℃~200℃的温度条件下干燥24小时~48小时;然后将干燥后的所述砖坯浸渍在所述耐高温涂料中制得喷涂砖坯,并在1100℃~1250℃的温度下对其进行煅烧8小时~10小时,从而制得所述耐腐蚀耐火砖。
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CN110498689A (zh) * 2019-08-01 2019-11-26 辽宁科技大学 一种六铝酸钙晶须增强钙铝质耐火材料
CN112159241A (zh) * 2020-10-09 2021-01-01 邢台德勤工矿工程有限公司 一种刚玉-铝硅酸盐复合耐火材料及其制备方法和应用
CN112174681A (zh) * 2020-10-09 2021-01-05 邢台德勤工矿工程有限公司 一种石墨-铝硅酸盐复合耐火材料及其制备方法和应用

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110498689A (zh) * 2019-08-01 2019-11-26 辽宁科技大学 一种六铝酸钙晶须增强钙铝质耐火材料
CN112159241A (zh) * 2020-10-09 2021-01-01 邢台德勤工矿工程有限公司 一种刚玉-铝硅酸盐复合耐火材料及其制备方法和应用
CN112174681A (zh) * 2020-10-09 2021-01-05 邢台德勤工矿工程有限公司 一种石墨-铝硅酸盐复合耐火材料及其制备方法和应用

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