CN110204322B - 一种莫来石隔热耐火砖及其制备方法 - Google Patents
一种莫来石隔热耐火砖及其制备方法 Download PDFInfo
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Abstract
本发明属于耐火材料技术领域,提出了一种莫来石隔热耐火砖,由以下重量份的组分组成:莫来石57~78份,石英砂3~9份,硅酸铝纤维6~14份,贝壳粉2~5份,壳聚糖1.5~3.6份,纳米高岭土5~12份,硼纤维2~6份,正硅酸乙酯0.5~1.5份,聚丙烯酸0.3~1.5份,氨丙基三乙氧基硅烷0.15~0.5份,聚酰亚胺0.6~1.1份,松香0.3~0.8份,聚乙二醇1.2~2.5份,莲蓬壳粉0.35~1.72份,本发明还提出了其制备方法,具体为先将莫来石、石英砂、贝壳粉、纳米高岭土混合后粉碎,再加入聚乙二醇、聚丙烯酸、聚酰亚胺、壳聚糖、松香、氨丙基三乙氧基硅烷的混合液中,加入硅酸铝纤维、硼纤维、莲蓬壳粉、正硅酸乙酯,混合均匀后压制、烘干、烧制成型。通过上述技术方案,解决了现有技术中莫来石砖导热率高、热震稳定性差的问题。
Description
技术领域
本发明属于耐火材料技术领域,涉及一种莫来石隔热耐火砖及其制备方法。
背景技术
随着近些年有色冶炼技术和化工工业的快速发展,我国相继建成大型现代化的有色金属冶炼窑炉和大型化工生产基地,对满足冶炼窑炉和化工生产用耐火材料也提出了苛刻的要求。由于高温物料会和作为内衬的耐火材料直接接触,对耐火材料的耐高温、耐侵蚀和抗热震性能都有较高的要求。莫来石质砖因其耐高温、耐腐蚀、高耐磨、抗热震等优良性能,适用于冶金、石化、建材、陶瓷、机械等领域的各种工业炉热面衬里和背衬,可与火焰直接接触,能最大限度的满足现代有色金属冶炼和化工生产苛刻的使用环境。
现有的莫来石砖均采用高铝原料进行制备,原料成本高,制备得到的莫来石砖的导热率高,由于热量的大量散失而造成能源的严重浪费,使得生产和使用成本居高不下,并且其热震稳定性差,使用过程中往往会因急冷、急热而出现剥落破裂的现象,使用寿命短。
发明内容
本发明提出一种莫来石隔热耐火砖及其制备方法,解决了现有技术中莫来石砖导热率高、热震稳定性差的问题。
本发明的技术方案是这样实现的:
一种莫来石隔热耐火砖,由以下重量份的组分组成:
莫来石57~78份,石英砂3~9份,硅酸铝纤维6~14份,贝壳粉2~5份,壳聚糖1.5~3.6份,纳米高岭土5~12份,硼纤维2~6份,正硅酸乙酯0.5~1.5份,聚丙烯酸0.3~1.5份,氨丙基三乙氧基硅烷0.15~0.5份,聚酰亚胺0.6~1.1份,松香0.3~0.8份,聚乙二醇1.2~2.5份,莲蓬壳粉3.5~7.2份。
作为进一步的技术方案,由以下重量份的组分组成:
莫来石69份,石英砂6份,硅酸铝纤维11份,贝壳粉3份,壳聚糖2.5份,纳米高岭土8份,硼纤维4份,正硅酸乙酯1份,聚丙烯酸0.8份,氨丙基三乙氧基硅烷0.3份,聚酰亚胺0.9份,松香0.5份,聚乙二醇1.7份,莲蓬壳粉5.2份。
作为进一步的技术方案,所述莲蓬壳粉由新鲜莲蓬壳晒干后粉碎得到。
作为进一步的技术方案,所述石英砂的粒径为0.5~1mm,所述硅酸铝纤维的直径为2mm,所述硼纤维的直径为0.2mm,所述纳米高岭土的粒径为500nm。
一种莫来石隔热耐火砖的制备方法,包括以下步骤:
S1.按照上述的一种莫来石隔热耐火砖的配方,称取各个组分备用;
S2.将莫来石、石英砂、贝壳粉、纳米高岭土混合均匀后粉碎,过200目筛,得到干混料;
S3.将聚乙二醇、聚丙烯酸溶解在水中,加入聚酰亚胺、壳聚糖、松香、氨丙基三乙氧基硅烷,混合均匀后得到混合液;
S4.将步骤S2得到的干混料加入步骤S3得到的混合液中,加入硅酸铝纤维、硼纤维、莲蓬壳粉、正硅酸乙酯,超声混合均匀,得到湿混料;
S5.将步骤S4得到的湿混料压制成型,得到半成品;
S6.将步骤S5得到的半成品烘干后烧制成型,得到一种莫来石隔热耐火砖。
作为进一步的技术方案,步骤S4超声时间为20min。
作为进一步的技术方案,步骤S5中压制成型时压力为85MPa。
作为进一步的技术方案,步骤S6中烘干具体为在60℃烘24小时,烧制成型具体为在1450℃烧制12小时。
本发明的工作原理及有益效果为:
1、本发明中,制备的莫来石隔热耐火砖具有良好的理化性能:荷重软化温度高达1680℃,体积密度小于3.35g/cm3,重烧线收缩低至0.5%,常温耐压强度高达3.6MPa,导热系数低至0.16w/m.k,热震稳定次数达到100次,说明本发明的莫来石隔热耐火砖的耐火度高,体积密度小,导热系数小,热震稳定性好,有效解决了现有技术中莫来石砖导热率高、热震稳定性好而使生产成本高、使用寿命短的问题。
2、本发明中,原料中莲蓬壳与松香配合,使得莫来石砖内部气孔小且分布更加均匀,气孔率更高而使体积密度更小、导热系数更。与传统的生物填料锯末相比,莲蓬壳体轻、质松软如海绵,与松香配合,烧制后在莫来石砖内部形成均匀分布的气孔,从而降低了莫来石砖的导热率,提高了莫来石砖的隔热能力,实用性强。
3、本发明中,原料中加入的聚乙二醇与聚丙烯酸相互协同,改善了莫来石砖内部各组分之间的固定效果,加强了莫来石砖内部晶体之间的相互作用,有效避免了莫来石砖在烧制成型过程中产品开裂现象的出现,有效降低了莫来石砖的重烧线收缩,提高了莫来石砖的热震稳定性。
4、本发明中,原料中贝壳粉、纳米高岭土、氨丙基三乙氧基硅烷协同作用,显著提高了莫来石砖的耐火度、耐压强度和热震稳定性。贝壳粉、纳米高岭土、氨丙基三乙氧基硅烷与硼纤维、硅酸铝纤维通过分子间作用力形成有机-无机杂化材料,填补了莫来石基体在外力作用下形成的裂缝,阻止了裂纹的增长,从而提高了莫来石砖的耐火度和耐压强度。氨丙基三乙氧基硅烷与壳聚糖、聚酰亚胺、聚乙二醇、聚丙烯酸配合,改善了硼纤维、硅酸铝纤维、贝壳粉、纳米高岭土与莫来石、石英砂的界面结合,从而提高了各组分间的协同作用,显著提高了莫来石的热震稳定性。
5、本发明中,原料中聚酰亚胺与正硅酸乙酯相互配合,显著提高了莫来石砖的热震稳定性,降低了莫来石砖的导热系数。聚酰亚胺与壳聚糖配合,营造了碱性环境,正硅酸乙酯在碱性环境以及聚乙二醇的作用下缩合形成二氧化硅凝胶,从而与纳米高岭土、贝壳粉配合,填充耐火砖内部部分孔隙,使得莫来石砖内部孔隙分布更加均匀,增加了莫来石砖表面的密实性,从而提高了莫来石砖的热震稳定性,延长了莫来石砖的使用寿命,形成的均匀内部孔隙降低了莫来石砖的导热系数,从而增强了莫来石砖的隔热能力,减少了热量损耗,降低了使用成本。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种莫来石隔热耐火砖,由以下重量份的组分组成:
莫来石57份,石英砂3份,硅酸铝纤维6份,贝壳粉2份,壳聚糖1.5份,纳米高岭土5份,硼纤维2份,正硅酸乙酯0.5份,聚丙烯酸0.3份,氨丙基三乙氧基硅烷0.15份,聚酰亚胺0.6份,松香0.3份,聚乙二醇1.2份,莲蓬壳粉0.35份,其中,莲蓬壳粉由新鲜莲蓬壳晒干后粉碎得到,石英砂的粒径为0.5~1mm,硅酸铝纤维的直径为2mm,硼纤维的直径为0.2mm,纳米高岭土的粒径为500nm,
其制备方法,包括以下步骤:
S1.按照上述的配方,称取各个组分备用;
S2.将莫来石、石英砂、贝壳粉、纳米高岭土混合均匀后粉碎,过200目筛,得到干混料;
S3.将聚乙二醇、聚丙烯酸溶解在水中,加入聚酰亚胺、壳聚糖、松香、氨丙基三乙氧基硅烷,混合均匀后得到混合液;
S4.将步骤S2得到的干混料加入步骤S3得到的混合液中,加入硅酸铝纤维、硼纤维、莲蓬壳粉、正硅酸乙酯,超声20min至混合均匀,得到湿混料;
S5.将步骤S4得到的湿混料在85MPa下压制成型,得到半成品;
S6.将步骤S5得到的半成品在在60℃烘24小时,烘干后在1450℃烧制12小时,烧制成型。
实施例2
一种莫来石隔热耐火砖,由以下重量份的组分组成:
莫来石78份,石英砂9份,硅酸铝纤维14份,贝壳粉5份,壳聚糖3.6份,纳米高岭土12份,硼纤维6份,正硅酸乙酯1.5份,聚丙烯酸1.5份,氨丙基三乙氧基硅烷0.5份,聚酰亚胺1.1份,松香0.8份,聚乙二醇2.5份,莲蓬壳粉1.72份,其中,莲蓬壳粉由新鲜莲蓬壳晒干后粉碎得到,石英砂的粒径为0.5~1mm,硅酸铝纤维的直径为2mm,硼纤维的直径为0.2mm,纳米高岭土的粒径为500nm,
其制备方法同实施例1。
实施例3
一种莫来石隔热耐火砖,由以下重量份的组分组成:
莫来石65份,石英砂5份,硅酸铝纤维40份,贝壳粉3份,壳聚糖2.1份,纳米高岭土7份,硼纤维3份,正硅酸乙酯0.8份,聚丙烯酸0.7份,氨丙基三乙氧基硅烷0.25份,聚酰亚胺0.8份,松香0.4份,聚乙二醇1.5份,莲蓬壳粉0.75份,其中,莲蓬壳粉由新鲜莲蓬壳晒干后粉碎得到,石英砂的粒径为0.5~1mm,硅酸铝纤维的直径为2mm,硼纤维的直径为0.2mm,纳米高岭土的粒径为500nm,
其制备方法同实施例1。
实施例4
一种莫来石隔热耐火砖,由以下重量份的组分组成:
莫来石75份,石英砂7份,硅酸铝纤维12份,贝壳粉4份,壳聚糖2.8份,纳米高岭土9份,硼纤维5份,正硅酸乙酯1.2份,聚丙烯酸1.1份,氨丙基三乙氧基硅烷0.35份,聚酰亚胺1份,松香0.6份,聚乙二醇2.1份,莲蓬壳粉1.5份,其中,莲蓬壳粉由新鲜莲蓬壳晒干后粉碎得到,石英砂的粒径为0.5~1mm,硅酸铝纤维的直径为2mm,硼纤维的直径为0.2mm,纳米高岭土的粒径为500nm,
其制备方法同实施例1。
实施例5
一种莫来石隔热耐火砖,由以下重量份的组分组成:
莫来石69份,石英砂6份,硅酸铝纤维11份,贝壳粉3份,壳聚糖2.5份,纳米高岭土8份,硼纤维4份,正硅酸乙酯1份,聚丙烯酸0.8份,氨丙基三乙氧基硅烷0.3份,聚酰亚胺0.9份,松香0.5份,聚乙二醇1.7份,莲蓬壳粉1.05份,其中,莲蓬壳粉由新鲜莲蓬壳晒干后粉碎得到,石英砂的粒径为0.5~1mm,硅酸铝纤维的直径为2mm,硼纤维的直径为0.2mm,纳米高岭土的粒径为500nm,
其制备方法同实施例1。
对比例1
一种莫来石隔热耐火砖,由以下重量份的组分组成:
莫来石69份,石英砂6份,硅酸铝纤维11份,贝壳粉3份,壳聚糖2.5份,纳米高岭土8份,硼纤维4份,正硅酸乙酯1份,聚丙烯酸0.8份,氨丙基三乙氧基硅烷0.3份,聚酰亚胺0.9份,松香0.5份,聚乙二醇1.7份,锯末1.05份,其中,石英砂的粒径为0.5~1mm,硅酸铝纤维的直径为2mm,硼纤维的直径为0.2mm,纳米高岭土的粒径为500nm,
其制备方法对应的将步骤S4莲蓬壳粉改为锯末,其余步骤同实施例1。
对比例2
一种莫来石隔热耐火砖,由以下重量份的组分组成:
莫来石69份,石英砂6份,硅酸铝纤维11份,贝壳粉3份,壳聚糖2.5份,纳米高岭土8份,硼纤维4份,正硅酸乙酯1份,氨丙基三乙氧基硅烷0.3份,聚酰亚胺0.9份,松香0.5份,莲蓬壳粉1.05份,其中,莲蓬壳粉由新鲜莲蓬壳晒干后粉碎得到,石英砂的粒径为0.5~1mm,硅酸铝纤维的直径为2mm,硼纤维的直径为0.2mm,纳米高岭土的粒径为500nm,
其制备方法对应的将步骤S3中聚乙二醇、聚丙烯酸删除,其余步骤同实施例1。
对比例3
一种莫来石隔热耐火砖,由以下重量份的组分组成:
莫来石69份,石英砂6份,硅酸铝纤维11份,壳聚糖2.5份,硼纤维4份,正硅酸乙酯1份,聚丙烯酸0.8份,聚酰亚胺0.9份,松香0.5份,聚乙二醇1.7份,莲蓬壳粉1.05份,其中,莲蓬壳粉由新鲜莲蓬壳晒干后粉碎得到,石英砂的粒径为0.5~1mm,硅酸铝纤维的直径为2mm,硼纤维的直径为0.2mm,纳米高岭土的粒径为500nm,
其制备方法对应的将步骤S2中贝壳粉、纳米高岭土删除,将步骤S3中氨丙基三乙氧基硅烷删除,其余步骤同实施例1。
对比例4
一种莫来石隔热耐火砖,由以下重量份的组分组成:
莫来石69份,石英砂6份,硅酸铝纤维11份,贝壳粉3份,壳聚糖2.5份,纳米高岭土8份,硼纤维4份,聚丙烯酸0.8份,氨丙基三乙氧基硅烷0.3份,松香0.5份,聚乙二醇1.7份,莲蓬壳粉1.05份,其中,莲蓬壳粉由新鲜莲蓬壳晒干后粉碎得到,石英砂的粒径为0.5~1mm,硅酸铝纤维的直径为2mm,硼纤维的直径为0.2mm,纳米高岭土的粒径为500nm,
其制备方法对应的将步骤S3中聚酰亚胺删除,将步骤S4中正硅酸乙酯删除,其余步骤同实施例1。
对实施例1~5及对比例1~4制备的莫来石隔热耐火砖进行如下性能测试:
1、荷重软化温度:按照GBT5989-2008《耐火材料荷重软化温度试验方法(示差升温法)》中规定的试验方法测试样品的荷重软化温度;
2、体积密度、气孔率:按照GB/T 2998-2015《定形隔热耐火制品体积密度和真气孔率试验方法》中规定的试验方法测试样品的体积密度;
3、重烧线收缩:按照GB/T 3997.1-1998《定形隔热耐火制品重烧线变化试验方法》中规定的试验方法测试样品的重烧线收缩;
4、常温耐压强度:按照GB/T 5072-2008《耐火材料常温耐压强度试验方法》中规定的试验方法测试样品的常温耐压强度;
5、导热系数:按照YB/T 4130-2005(2012)《耐火材料导热系数试验方法》中规定的水流量平板法测试样品的导热系数;
6、热震稳定性:按照YB/T 376.1-1995《耐火制品抗热震性试验方法(水-急冷法)》中规定的试验方法测试样品在1100℃水冷条件下的热震稳定性;
测试结果见下表:
表1实施例1~5及对比例1~4制备的莫来石隔热耐火砖的性能测试结果
从表1中数据可以看出,本发明实施例1~5制备的莫来石隔热耐火砖具有良好的理化性能:荷重软化温度高达1680℃,体积密度小于3.35g/cm3,重烧线收缩低至0.5%,常温耐压强度高达3.6MPa,导热系数低至0.16w/m.k,热震稳定次数达到100次,说明本发明的莫来石隔热耐火砖的耐火度高,体积密度小,导热系数小,热震稳定性好,有效解决了现有技术中莫来石砖导热率高、热震稳定性好而使生产成本高、使用寿命短的问题。
与对比例1相比,实施例5制备的莫来石砖的体积密度更小,重烧线收缩更低,导热系数显著降低,对比例1与实施例5的区别在于对比例1将实施例5的莫来石原料中莲蓬壳替换成锯末,说明与传统的生物填料锯末相比,莲蓬壳的加入,与松香配合,使得莫来石砖内部气孔小且分布更加均匀,气孔率更高而使体积密度更小、导热系数更低,起到了意料不到的效果。
与对比例2相比,实施例5制备的莫来石砖的重烧线收缩更低,热震稳定性显著提高,对比例2与实施例5的区别在于对比例2的莫来石原料中未添加聚乙二醇、聚丙烯酸,说明聚乙二醇与聚丙烯酸相互协同,改善了莫来石砖内部各组分之间的固定效果,加强了莫来石砖内部晶体之间的相互作用,有效避免了莫来石砖在烧制成型过程中产品开裂现象的出现,有效降低了莫来石砖的重烧线收缩,提高了莫来石砖的热震稳定性。
与对比例3相比,实施例5制备的莫来石砖的荷重软化温度更高、耐压强度更高、热震稳定性更好,对比例3与实施例5的区别在于对比例3的莫来石原料中未添加贝壳粉、纳米高岭土、氨丙基三乙氧基硅烷,说明原料中贝壳粉、纳米高岭土、氨丙基三乙氧基硅烷协同作用,显著提高了莫来石砖的耐火度、耐压强度和热震稳定性。贝壳粉、纳米高岭土、氨丙基三乙氧基硅烷与硼纤维、硅酸铝纤维通过分子间作用力形成有机-无机杂化材料,填补了莫来石基体在外力作用下形成的裂缝,阻止了裂纹的增长,从而提高了莫来石砖的耐火度和耐压强度。氨丙基三乙氧基硅烷与壳聚糖、聚酰亚胺、聚乙二醇、聚丙烯酸配合,改善了硼纤维、硅酸铝纤维、贝壳粉、纳米高岭土与莫来石、石英砂的界面结合,从而提高了各组分间的协同作用,显著提高了莫来石的热震稳定性。
与对比例4相比,实施例5制备的莫来石砖的导热系数更低,热震稳定性更好,对比例4与实施例5的区别在于对比例4的莫来石原料中未添加聚酰亚胺、正硅酸乙酯,说明原料中聚酰亚胺与正硅酸乙酯相互配合,显著提高了莫来石砖的热震稳定性,降低了莫来石砖的导热系数。聚酰亚胺与壳聚糖配合,营造了碱性环境,正硅酸乙酯在碱性环境以及聚乙二醇的作用下缩合形成二氧化硅凝胶,从而与纳米高岭土、贝壳粉配合,填充耐火砖内部部分孔隙,使得莫来石砖内部孔隙分布更加均匀,增加了莫来石砖表面的密实性,从而提高了莫来石砖的热震稳定性,延长了莫来石砖的使用寿命,形成的均匀内部孔隙降低了莫来石砖的导热系数,从而增强了莫来石砖的隔热能力,减少了热量损耗,降低了使用成本。
以上仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (3)
1.一种莫来石隔热耐火砖,其特征在于,由以下重量份的组分组成:
莫来石57~78份,石英砂3~9份,硅酸铝纤维6~14份,贝壳粉2~5份,壳聚糖1 .5~3.6份,纳米高岭土5~12份,硼纤维2~6份,正硅酸乙酯0 .5~1 .5份,聚丙烯酸0 .3~1 .5份,氨丙基三乙氧基硅烷0 .15~0 .5份,聚酰亚胺0 .6~1 .1份,松香0 .3~0 .8份,聚乙二醇1 .2~2 .5份,莲蓬壳粉0 .35~1 .72份;
所述莲蓬壳粉由新鲜莲蓬壳晒干后粉碎得到;
所述石英砂的粒径为0 .5~1mm,所述硅酸铝纤维的直径为2mm,所述硼纤维的直径为0.2mm,所述纳米高岭土的粒径为500nm。
2.根据权利要求1所述的一种莫来石隔热耐火砖,其特征在于,由以下重量份的组分组成:
莫来石69份,石英砂6份,硅酸铝纤维11份,贝壳粉3份,壳聚糖2 .5份,纳米高岭土8份,硼纤维4份,正硅酸乙酯1份,聚丙烯酸0 .8份,氨丙基三乙氧基硅烷0 .3份,聚酰亚胺0 .9份,松香0 .5份,聚乙二醇1 .7份,莲蓬壳粉1 .05份。
3.一种莫来石隔热耐火砖的制备方法,其特征在于,包括以下步骤:
S1 .按照权利要求1~2任意一项所述的一种莫来石隔热耐火砖的配方,称取各个组分备用;
S2 .将莫来石、石英砂、贝壳粉、纳米高岭土混合均匀后粉碎,过200目筛,得到干混料;
S3 .将聚乙二醇、聚丙烯酸溶解在水中,加入聚酰亚胺、壳聚糖、松香、氨丙基三乙氧基硅烷,混合均匀后得到混合液;
S4 .将步骤S2得到的干混料加入步骤S3得到的混合液中,加入硅酸铝纤维、硼纤维、莲蓬壳粉、正硅酸乙酯,超声混合均匀,得到湿混料,超声时间为20min;
S5 .将步骤S4得到的湿混料压制成型,得到半成品,压制成型时压力为85MPa;
S6 .将步骤S5得到的半成品烘干后烧制成型,得到一种莫来石隔热耐火砖,烘干具体为在60℃烘24小时,烧制成型具体为在1450℃烧制12小时。
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