CN108558418A - 一种轻量高强六铝酸钙耐火材料的制备方法 - Google Patents
一种轻量高强六铝酸钙耐火材料的制备方法 Download PDFInfo
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Abstract
一种轻量高强六铝酸钙耐火材料的制备方法,其特征在于:所述方法包括以下步骤:(1)将38~60wt%的碳酸钙质原料和40~62 wt%的氢氧化铝混合,之后加入上述原料之和80~120 wt%的水、0.02~0.05wt%的分散剂和1~4 wt%的结合剂,球磨3~5小时,得到混合浆料;(2)将混合浆料喷雾造粒,得到球形细颗粒;(3)将球形细颗粒在1000~1200℃条件下煅烧得到轻质多孔小球;(4)将15~30wt%的轻质多孔球和70~85 wt%的氧化铝质原料混合,之后加入上述原料之和2~6wt%的结合剂,搅拌均匀后,10~30MPa压力压制成型,在1600~1700℃的条件下煅烧6~8小时,得到轻量高强六铝酸钙耐火材料。
Description
技术领域
本发明属于耐火材料或多孔陶瓷技术领域,具体说是涉及一种轻量高强六铝酸钙耐火材料及其制备方法。
背景技术
高温行业具有能耗高,排放高的特点。随着社会对能源和环保的极大重视,降低能耗,绿色生产已是当前高温行业最为迫切的任务。高温行业中的热量大部分从耐火材料中散发和损失。开发导热系数低、使用温度高、高温性能好的隔热耐火材料是减少高温行业能源消耗,降低排放的关键。CA6(六铝酸钙)具有耐火度高(1875℃),在碱性环境下化学稳定性好,对金属的湿润性低的优良特点,是一种优良的耐火材料。同时,CA6具有片状或者板平状的结构,在高温下能够保持较大的比表面积,可在高温下表现出较好的隔热性能。这些特征使得轻量的CA6在高温隔热领域有着非常广泛的应用前景。
目前,六铝酸钙轻质耐火材料主要采用烧失或发泡法制备,如中国专利“一种六铝酸钙和刚玉复相多孔轻质隔热保温耐火材料及其制备方法”(CN 101928153 A)。该方法以碳酸钙和氧化铝等物质为主要原料,添加聚苯乙烯球和木屑等有机烧失物为成孔剂,煅烧后得到六铝酸钙轻质耐火材料。此类方法制备过程中烧失物生成气体并从材料内部排出,所形成的多为连贯的开口气孔,降低了耐火材料的性能。同时,有机烧失物会产生有害气体和大量CO2,对环境造成污染。中国专利“一种高强六铝酸钙轻质隔热材料及其制备方法”(CN 103496993 A),采用纳米碳酸钙和ρ-Al2O3微粉为主要原料,加入碱性泡沫剂的方法制备出了含微闭孔结构的六铝酸钙隔热材料,所得到的材料体积密度小,隔热性能好,但发泡法工艺控制较为复杂,易导致物料不均匀,且生产效率较低。
中国专利“一种高强微孔六铝酸钙轻质骨料及其制备方法”,(CN 105948772 A)以氧化铝水合物和碳酸钙为主要原料,采用氧化铝水合物和碳酸钙煅烧过程中原位分解的方法制备出了微孔结构的六铝酸钙轻质骨料,该方法工艺简单,生产过程中无污染,但化学反应速率不易控制,煅烧过程中易开裂。
发明内容
本发明的目的正是针对上述现有技术中所存在的不足之处而提供一种轻量高强六铝酸钙耐火材料及其制备方法,本发明所制备的轻量高强六铝酸钙耐火材料具有耐压强度高、使用温度高、高温体积稳定好的特点,本发明所采用的工艺简单易行,制备过程中不产生有害气体,有利于环境保护。
本发明的目的可通过下述技术措施来实现:
本发明所述轻量高强六铝酸钙耐火材料的制备方法包括以下步骤:
(1)将38~60wt%的碳酸钙质原料和40~62 wt%的氢氧化铝混合,之后加入上述原料之和80~120 wt%的水、0.02~0.05wt%的分散剂和1~4 wt%的结合剂,球磨3~5小时,得到混合浆料;
(2)将混合浆料喷雾造粒,得到球形细颗粒;
(3)将球形细颗粒在1000~1200℃条件下煅烧得到轻质多孔小球;
(4)将15~30wt%的轻质多孔球和70~85 wt%的氧化铝质原料混合,之后加入上述原料之和2~6wt%的结合剂,搅拌均匀后,10~30MPa压力压制成型,在1600~1700℃的条件下煅烧6~8小时,得到轻量高强六铝酸钙耐火材料。
本发明中所述的碳酸钙质原料取自纳米碳酸钙、轻质碳酸钙、普通碳酸钙或石灰石中的任意一种,原料的粒径均<0.074mm;所述的分散剂取自三聚磷酸钠、六偏磷酸钠或者木质素磺酸钠中的任意一种;所述的结合剂为亚硫酸纸浆废液、糊精、甲基纤维素、聚乙烯醇或硅溶胶中的任意一种。
本发明步骤(3)中所制备的轻质多孔球,堆积≤0.7g/cm3,粒径大小为0.044~0.3mm;步骤(4)中所述的氧化铝质原料取自工业氧化铝、α-氧化铝、电熔刚玉、煅烧刚玉中的任意一种或两种的组合,原料粒径≦0.088mm。
本发明所制备的轻量高强六铝酸钙耐火材料具有类球形的孔结构,体积密度为1.3~1.6g/cm3,耐压强度≥60MPa, 1600℃保温6小时的重烧线变化为-0.4%~+0.2%。
本发明首先以碳酸钙质原料和氢氧化铝为主要原料,采用原位分解的方法制备了高C/A(氧化钙/氧化铝)的多孔小球。然后,将高C/A的多孔小球与氧化铝质原料结合,采用反应扩散的成孔机理,制备出含有球形孔结构的CA6。
本发明与现有技术相比,具有以下有益效果: (1)所述的轻量高强六铝酸钙耐火材料,具有球形的孔结构,闭口气孔率高、且孔径大小可控;
(2)所述的轻量高强六铝酸钙耐火材料,耐压强度高、隔热性能好、使用温度高,能够满足高温窑炉工作层的使用的要求;
(3)所述的轻量高强六铝酸钙耐火材料,采用原位分解和反应扩散的成孔机制,生产过程中不添加烧失物和发泡剂,无有害气体排放、生产效率高,适合大规模工业化生产。
具体实施方式
本发明以下将结合实施例作进一步的说明。
实施例1
(1)将38 wt%的纳米碳酸钙和62 wt%的氢氧化铝混合,之后加入上述原料之和90 wt%的水、0.05wt%的三聚磷酸钠为分散剂和4wt%的糊精为结合剂,球磨3小时,得到混合浆料;
(2)将混合浆料喷雾造粒,得到球形的颗粒坯体;
(3)将球形的颗粒坯体在1100℃条件下煅烧得到轻质多孔球,多孔球的堆积密度为0.63g/cm3,粒径大小为0.044~0.3mm;
(4)将30wt%的轻质多孔球和70wt%的α-氧化铝细粉(原料粒径≦0.074mm)混合,加入上述原料之和的作为结合剂的糊精4wt%,搅拌均匀后,10MPa压力压制成型,在1600℃的条件下煅烧8小时,得到高强轻量六铝酸钙质耐火材料。
本实施例所制备的轻量高强六铝酸钙耐火材料技术指标为:
耐压强度为65.8MPa,体积密度为1.35 g/cm3,1600℃保温6小时的烧后永久线变化为率-0.3%。
实施例2
(1)将52 wt%的轻质碳酸钙和48 wt%的氢氧化铝混合,外加上述原料之和100 wt%的水、0.03wt%的木质素磺酸钠为分散剂和2wt%的甲基纤维素为结合剂,球磨4小时,得到混合浆体;
(2)将混合浆料喷雾造粒,得到球形的颗粒坯体;
(3)将球形颗粒坯体在1150℃条件下煅烧得到轻质多孔球,多孔球的堆积密度为0.52g/cm3,粒径大小为0.044~0.3mm;
(4)将22wt%的轻质多孔球和40wt%的煅烧刚玉细粉(原料粒径≦0.074mm)和38%的工业氧化铝分析混合,加入上述原料之和的作为结合剂的甲基纤维素3wt%,搅拌均匀后,20MPa压力下压制成型,在1650℃的条件下煅烧7小时,得到高强轻量六铝酸钙质耐火材料。
本实施例所制备的轻量高强六铝酸钙耐火材料技术指标为:
耐压强度为70.2MPa,体积密度为1.41 g/cm3,1600℃保温6小时的烧后永久线变化为率-0.1%。
实施例3
(1)将60 wt%的普通碳酸钙和40 wt%的氢氧化铝混合,外加上述原料之和100 wt%的水、0.05wt%的六偏磷酸钠为分散剂和4wt%的亚硫酸纸浆废液为结合剂,球磨5小时,得到混合浆体;
(2)将混合浆料喷雾造粒,得到球形的颗粒坯体;
(3)将球形的颗粒坯体在1200℃条件下煅烧得到轻质多孔球,多孔球的堆积密度为0.61g/cm3,粒径大小为0.044~0.3mm;
(4)将20wt%的轻质多孔球和80wt%的工业氧化铝细粉(原料粒径0.074mm)混合,加入上述原料之和的作为结合剂的甲基纤维素3wt%,搅拌均匀后,在15MPa条件下压制成型,在1650℃的条件下煅烧7小时,得到高强轻量六铝酸钙质耐火材料。
本实施例所制备的轻量高强六铝酸钙耐火材料技术指标为:
耐压强度为60.5MPa,体积密度为1.43 g/cm3,1600℃保温6小时的烧后永久线变化为率-0.2%。
Claims (7)
1.一种轻量高强六铝酸钙耐火材料的制备方法,其特征在于:所述方法包括以下步骤:
(1)将38~60wt%的碳酸钙质原料和40~62 wt%的氢氧化铝混合,之后加入上述原料之和80~120 wt%的水、0.02~0.05wt%的分散剂和1~4 wt%的结合剂,球磨3~5小时,得到混合浆料;
(2)将混合浆料喷雾造粒,得到球形细颗粒;
(3)将球形细颗粒在1000~1200℃条件下煅烧得到轻质多孔小球;
(4)将15~30wt%的轻质多孔球和70~85 wt%的氧化铝质原料混合,之后加入上述原料之和2~6wt%的结合剂,搅拌均匀后,10~30MPa压力压制成型,在1600~1700℃的条件下煅烧6~8小时,得到轻量高强六铝酸钙耐火材料。
2.根据权利1所述的轻量高强六铝酸钙耐火材料的制备方法制备方法,其特征在于:所述的碳酸钙质原料取自纳米碳酸钙、轻质碳酸钙、普通碳酸钙或石灰石中的任意一种,原料的粒径均<0.074mm。
3.根据权利1所述的轻量高强六铝酸钙耐火材料的制备方法制备方法,其特征在于:所述的分散剂取自三聚磷酸钠、六偏磷酸钠或者木质素磺酸钠中的任意一种。
4.根据权利1所述的轻量高强六铝酸钙耐火材料的制备方法制备方法,其特征在于:所述的结合剂为亚硫酸纸浆废液、糊精、甲基纤维素、聚乙烯醇或硅溶胶中的任意一种。
5.根据权利1所述的轻量高强六铝酸钙耐火材料的制备方法制备方法,其特征在于:步骤(3)中所制备的轻质多孔球,堆积≤0.7g/cm3,粒径大小为0.044~0.3mm。
6.根据权利1所述的轻量高强六铝酸钙耐火材料的制备方法制备方法,其特征在于:步骤(4)中所述的氧化铝质原料取自工业氧化铝、α-氧化铝、电熔刚玉、煅烧刚玉中的任意一种或两种的组合,原料粒径≦0.088mm。
7.根据权利1所述的轻量高强六铝酸钙耐火材料的制备方法制备方法,其特征在于:所制备的轻量高强六铝酸钙耐火材料具有类球形的孔结构,体积密度为1.3~1.6g/cm3,耐压强度≥60MPa, 1600℃保温6小时的重烧线变化为-0.4%~+0.2%。
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