CN111377723A - 低成本环保型刚玉莫来石质蜂窝陶瓷蓄热体及制备方法 - Google Patents
低成本环保型刚玉莫来石质蜂窝陶瓷蓄热体及制备方法 Download PDFInfo
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Abstract
本发明公开一种低成本环保型刚玉莫来石质蜂窝陶瓷蓄热体的制备方法,其中使用的粘结剂是用三种不同粘度的羟丙基甲基纤维素复合而成,还使用具有润滑和减水作用的水溶液,其包含聚乙烯醇、聚乙二醇、聚丙烯酰胺和聚氧化乙烯中的一种或者多种和一种电解质减水剂。陶瓷材料的组成基本由下述材料组成:2~5%的滑石,3%~10%的粘土,其选自苏州土、高岭土、膨润土和黑泥,40%~70%的煅烧矿物料,其选自煅烧高岭土、煅烧焦宝石和煅烧低铝矾土,以及20%~50%的工业氧化铝或95瓷废瓷粉。本发明的制备方法环保,还允许使用易得原料获得莫来石‑刚玉质陶瓷蓄热体。
Description
技术领域
本发明属于无机材料领域,具体涉及无机非金属材料制备领域,更具体涉及陶瓷蓄热体的生产方法。
背景技术
蓄热燃烧技术是目前广泛应用于钢铁冶金、机械、石化、建材、和有色冶金等行业高温燃烧工业炉上的一种节能环保燃烧技术。陶瓷蓄热体是蓄热式燃烧器完成烟气余热回收利用的中间载体,通过陶瓷蓄热体周期性的蓄热与释热,将高温烟气的热量传递给常温助燃空气或煤气,实现烟气余热的回收和助燃空气或煤气的高温预热,达到节能环保的目的。因此,蓄热燃烧系统温度效益及热效益的高低,直接取决于蓄热体的性能。
高温空气燃烧技术(High Temperature Air Combustion-HTAC)是20世纪90年代日本科学家开发成功的一项燃料燃烧领域中的新技术,广泛应用于钢铁、机械、建材、石化、有色金属冶炼等行业的各种加热炉、热风炉、热处理炉、裂解炉、烘烤炉、熔化炉、均热炉、油气锅炉等窑炉中。该技术通过换向装置使两个蓄热体交替吸热放热,最大限度的回收烟气的热量,再把炉内的助燃空气和煤气加热到1000℃以上,即使低热值的劣质燃料也能实现稳定着火和高效燃烧。应用证明,HTAC技术的应用的可节约燃料40%~70%,产量提升15%以上,钢坯氧化烧损下降40%以上,NOx排放小于100ppm,排放烟气温度低于150℃,大大降低了地球大气的温室效应。而HTAC技术的关键是能否研制出高性能的蜂窝陶瓷蓄热体。高性能的蜂窝陶瓷蓄热体必须具有高耐温、抗腐蚀、抗热震性好、强度高、蓄热量大、导热性能好等优点。
目前,蜂窝陶瓷蓄热体为满足1500℃以上环境使用要求,材质基本为耐火度很高的刚玉-莫来石质。CN102399082A披露一种刚玉莫来石蜂窝陶瓷蓄热体,是以刚玉、莫来石、氧化铝、滑石及粘土组成的粉末,再加入纤维素、甘油、胶水、水制备成可塑性泥料,通过混料、调泥、真空练泥、成型、烘干、高温烧结制备成刚玉莫来石质蜂窝陶瓷蓄热体。但莫来石及刚玉较难获得,生产成本相对较高;3%~5%的纤维素用量将占生产成本的20%以上;更重要的,为蜂窝陶瓷成型用使用的胶水、甘油、纤维素助剂总量超过陶瓷粉体干基重量的10%,烧成排胶阶段,有机废气会对环境造成污染,处理成本增加。
发明内容
本发明的目的在于提供一种低成本、环保型的刚玉莫来石蜂窝陶瓷蓄热体制备方法,该蜂窝陶瓷蓄热体,具有高耐温、抗腐蚀、抗热震性好、强度高、蓄热量大、导热性能好等优点,使用温度超过1600℃,可满足钢铁、冶金等工业窑炉的余热回收利用。
根据本发明,制备该提供的一种低成本环保型的刚玉莫来石质蜂窝陶瓷的原料主要是由滑石、粘土、煅烧矿物料、工业氧化铝或95瓷以上的废瓷粉组成。其中,粘土选自苏州土、高岭土、膨润土和黑泥中一种或多种,煅烧矿物质为煅烧高岭土、煅烧焦宝石、煅烧低铝矾土中的一种或多种,按照下述比例:
滑石 2~5%
粘土 3~10%
煅烧矿物料 40~70%
工业氧化铝或95瓷废瓷粉 20~50%。
尽管本发明没有给出实施例,仍不排除在上述成分之外少量使用其他成分的可能性,该少量其它成分的使用是为了赋予蓄热体新的或者提高的性能,但是其仍然属于本发明的构思范畴内。本发明的制备方法中使用一种同种复合粘结剂,所谓“同种复合粘结剂”是指采用相同成分不同粘度的羟丙基甲基纤维素(HPMC)混合而成的粘结剂。各组分的重量份(百份计)为:
羟丙基甲基纤维素A(HPMC)5~20份,粘度4000mPa·s~6000mPa·s;
羟丙基甲基纤维素B(HPMC)60~100份,粘度8000mPa·s~12000mPa·s;
羟丙基甲基纤维素C(HPMC)5~20份,粘度20000mPa·s~40000mPa·s。
优选的配比为:羟丙基甲基纤维素A,10-15份;羟丙基甲基纤维素B,70-100份;羟丙基甲基纤维素C,10-20份。
本发明的这种选择具有优势,不同粘度的羟丙基甲基纤维素均优选为粒径小于150微米(100目筛余≤1%)的粉状固态物料。将各组分在混料机中充分混合均匀,即制得蜂窝陶瓷成型用同种复合粘结剂。所述同种复合粘结剂的用量为蜂窝陶瓷原料干基总重量的1.0~5.0%,优选地,1.0~4.0%,在更优选的实施例中,用量不超过3.0%。
本发明的制备方法还使用具有润滑和减水作用的水溶液。所谓“具有润滑和减水作用的水溶液”是指将具有直链结构的高分子聚合物润滑剂、陶瓷用有机/无机电解质减水剂溶解于40℃~60℃温水中,配制而成的水溶液。
其中,具有直链结构的高分子聚合物润滑剂由聚乙烯醇(PVA)、聚乙二醇(PEG)、聚丙烯酰胺(PAM)、聚氧化乙烯(PEO)中的一种或多种组成。在使用聚乙烯醇和/或聚乙二醇时,水溶液的浓度可以在3-10%之间,优选5-8%之间。当使用聚丙烯酰胺和/或聚氧化乙烯的时候,浓度是0.2-3%,更优选0.2-0.3%的浓度。这种方式更有利,其可以将有机物的引入量进一步降低,进一步降低型坯的干燥线收缩率和烧成线收缩率。
本发明中,可以在复合助剂的水溶液中引入适量减水剂,可用的减水剂如柠檬酸钠、三聚磷酸钠,质量百分比为1-5%。作为本发明的改进之一,用木质素磺酸钙替代前述减水剂。可以避免引入钠离子而降低陶瓷制品的耐火度。木质素磺酸钙在组分II中的含量为2-4%。为配制上述水溶液,将上述各组分按重量精确称量,加入到40℃~60℃的部分水中充分溶解,再补足水量配置成水溶液密封备用。
所述的具有润滑和减水作用的水溶液在蜂窝陶瓷粉料混合工序、捏合工序过中的加入总量为蜂窝陶瓷粉料干基总重量的11%-20%,优选12%~18%。
本发明采用煅烧高岭土、熟焦宝石、低铝矾土为原料,采用上述比例,在较低的温度下即可反应合成针棒状莫来石,从而提高了产品的耐火度及抗热震性能。
现有技术中,蜂窝陶瓷蓄热体多采用油脂类高分子作为粘结剂、增塑剂及润滑剂,如桐油、液压油、大豆油、菜油等。油脂类高分子在烧结过程中发生不完全氧化,产生有害气体,对环境造成污染。本发明经过反复实验,采用不同粘度的羟丙基甲基纤维素(HPMC)配制成复合粘结剂和增塑剂,采用水溶性的直链高分子聚合物作为润滑剂,水溶性有机/无机电解质作为减水剂,将上述粘结剂、润滑剂、减水剂配置成水溶液。
采用同种复合粘结剂及具有润滑减水作用的水溶液的优势表现在以下几个方面:第一,干燥过程中,羟丙基甲基纤维素(HPMC)无挥发,无气味,利于操作,且烧结过程中羟丙基甲基纤维素(HPMC)全部氧化,无有害气体放出,有利于环境保护;第二:通过多粘度粘结剂的复合,高粘度的粘结剂提供较高的粘结力和强度,低粘度的粘结剂提供很好的分散性,在与陶瓷材料捏合时与高粘度粘结剂发生缠接(连接),形成高分子网络,使得只使用少量羟丙基甲基纤维素就达到所需的粘结力。不同粘度的复合粘结剂同时起到增塑作用,降低成本;第三:水溶性润滑剂和减水剂配置成水溶液使用,简化了工艺流程,降低了劳动强度,兼具润滑性的同时,由于减水剂的引入,大大降低了用水量,提高了坯体强度及致密度。
该刚玉莫来石质蜂窝陶瓷蓄热体的制备工艺及同种复合粘结剂、具有润滑和减水作用的水溶液具体使用方法如下:
将滑石、粘土、煅烧高岭土/熟焦宝石/煅烧低铝矾土、95废瓷粉/工业氧化铝按配方比例称量,球磨1.5~3小时后,过100目振动筛备用;
将占蜂窝陶瓷原料干基总重量的一般1.0%~4.5%、优选1.0-3.0的同种复合纤维素粘结剂与陶瓷原料粉末通过强力混料机混合均匀,与此同时,为避免粉尘飞逸,以喷雾方式引入陶瓷粉末干基重量的6%~9%的具有润滑和减水作用的水溶液,配制成半湿性混合料;
将混合料再加6%~9%的水,在捏合机中充分捏合,得湿性泥料;
将泥料在练泥机中充分混练2遍,得粗炼泥料;
将粗炼泥料在室温25℃,湿度≥80%的陈腐室内陈腐24~48小时,得陈腐泥料;
将陈腐后的泥料经真空练泥机练泥2次,得真空泥料;
将真空泥料通过立式液压挤出成型机经模具挤出成型,得蜂窝陶瓷蓄热体湿坯;
蜂窝陶瓷蓄热体湿坯经微波定型、微波干燥,得蜂窝陶瓷干坯;
将蜂窝陶瓷干坯经切割机、倒角机、吹灰机预加工成蓄热体规定形状;
将蓄热体干坯在1380℃~1450℃温度下烧成,得蜂窝陶瓷蓄热体制品。
本发明制备的蜂窝陶瓷蓄热体耐火度可达1750℃以上,使用温度超过1600℃。
具体实施方式
下面通过具体实施例例举说明本发明的构思和达到的技术效果。在下面的实施例中,羟丙基甲基纤维素A是购买自石家庄冠翔建材有限公司的低黏度羟丙基甲基纤维素,黏度4000-6500mpa·s。羟丙基甲基纤维素B是购买自石家庄冠翔建材有限公司生产的黏度为8000-12000mpa·s的羟丙基甲基纤维素。羟丙基甲基纤维素C是购买自石家庄清泉纤维素有限公司,黏度范围18000-30000mpa·s。聚丙烯酰胺是购买自的分子量为800万-2200万的阴离子聚丙烯酰胺,聚氧化乙烯购自日本住友化工株式会社
实施例1:
按照45:48:5:3重量比,将煅烧高岭土、工业氧化铝、水洗高岭土、滑石球磨2小时,过100目振动筛;
将羟丙基甲基纤维素A、B、C分别10、75、15份按重量配比称量,混料机中充分混合均匀,得复合粘结剂。将聚乙二醇3份、聚乙烯醇3份、木质素磺酸钙2份、水92份加入到40℃~60℃的温水中,充分溶解定量后得具有润滑减水作用的水溶液,备用。
将陶瓷粉末、复合粘结剂、水溶液按照100:3:7的重量比在强力混料机中混合,水溶液通过喷雾装置喷洒于物料上,强力混合1小时,混合均匀,制备成半湿性混合料;
将混合料加入捏合机中,再加入陶瓷粉料干基总重量的7%的水,在捏合机中充分捏合,得湿性可塑性泥料;
将泥料在练泥机中充分混练2遍,得粗炼泥料;
将粗炼泥料在室温25℃,湿度≥80%的陈腐室内陈腐24~48小时,得陈腐泥料;
将陈腐后的泥料经真空练泥机练泥2次,真空度小于等于-0.092MPa,得真空泥料;
将真空泥料通过立式液压挤出成型机经蜂窝陶瓷蓄热体模具挤出成型,挤出压力控制在10MPa~15MPa之间,得蜂窝陶瓷蓄热体湿坯;
蜂窝陶瓷蓄热体湿坯经微波定型、微波干燥,得蜂窝陶瓷干坯,干燥线收缩率7.2%;
将蜂窝陶瓷干坯经切割机、倒角机、吹灰机预加工成蓄热体规定形状;
将蓄热体干坯在1420℃烧结2小时,自然冷却,得刚玉莫来石质蜂窝陶瓷蓄热体制品,烧成线收缩率4.1%,制品中氧化铝含量69.02wt%。
实施例2,采用与实施例1基本相同的材料和工艺,区别在于,水溶液是含有0.2%聚丙烯酰胺、0.1%聚氧化乙烯和2%磺酸木质素的水溶液。
将蓄热体干坯在1420℃烧结2小时,自然冷却,得刚玉莫来石质蜂窝陶瓷蓄热体制品,干燥线收缩为2.5%,烧成线收缩率1.2%,制品中氧化铝含量69.02wt%。
实施例3:
按照45:48:5:3重量比,将熟焦宝石、工业氧化铝、水洗高岭土、滑石球磨2小时,过100目振动筛;
将羟丙基甲基纤维素A、B、C分别15、75、10份按重量配比称量,混料机中充分混合均匀,得复合粘结剂。将聚氧化乙烯0.3份、木质素磺酸钙2份、水98份加入到40℃~60℃的温水中,充分溶解定量后得具有润滑减水作用的水溶液
将陶瓷粉末、复合粘结剂、水溶液按照100:2.5:6.5的重量比在强力混料机中混合,水溶液通过喷雾装置喷洒于物料上,强力混合1小时,混合均匀,制备成半湿性混合料;
将混合料加入捏合机中,再加入陶瓷粉料干基总重量的6.5%的水,在捏合机中充分捏合,得湿性可塑性泥料;
将泥料在练泥机中充分混练2遍,得粗炼泥料;
将粗炼泥料在室温25℃,湿度≥80%的陈腐室内陈腐24~48小时,得陈腐泥料;
将陈腐后的泥料经真空练泥机练泥2次,真空度小于等于-0.092MPa,得真空泥料;
将真空泥料通过立式液压挤出成型机经蜂窝陶瓷蓄热体模具挤出成型,挤出压力控制在10MPa~15MPa之间,得蜂窝陶瓷蓄热体湿坯;
蜂窝陶瓷蓄热体湿坯经微波定型、微波干燥,得蜂窝陶瓷干坯,干燥线收缩率3.25%;
将蜂窝陶瓷干坯经切割机、倒角机、吹灰机预加工成蓄热体规定形状;
将蓄热体干坯在1420℃烧结2小时,自然冷却,得刚玉莫来石质蜂窝陶瓷蓄热体制品,烧成线收缩率1.57%,制品中氧化铝含量69.53wt%。
实施例4:
按照62:30:5:3重量比,将煅烧低铝矾土、工业氧化铝、水洗高岭土、滑石球磨2小时,过100目振动筛;
将羟丙基甲基纤维素A、B、C分别15、75、10份按重量配比称量,混料机中充分混合均匀,得复合粘结剂。将聚丙烯酰胺0.3份、木质素磺酸钙2份、水98份加入到40℃~60℃的温水中,充分溶解定量后得具有润滑减水作用的水溶液。
将陶瓷粉末、复合粘结剂、水溶液按照100:3.5:8的重量比在强力混料机中混合,水溶液通过喷雾装置喷洒于物料上,强力混合1小时,混合均匀,制备成半湿性混合料;
将混合料加入捏合机中,再加入陶瓷粉料干基总重量的8%的水,在捏合机中充分捏合,得湿性可塑性泥料;
将泥料在练泥机中充分混练2遍,得粗炼泥料;
将粗炼泥料在室温25℃,湿度≥80%的陈腐室内陈腐24~48小时,得陈腐泥料;
将陈腐后的泥料经真空练泥机练泥2次,真空度小于等于-0.092MPa,得真空泥料;
将真空泥料通过立式液压挤出成型机经蜂窝陶瓷蓄热体模具挤出成型,挤出压力控制在10MPa~15MPa之间,得蜂窝陶瓷蓄热体湿坯;
蜂窝陶瓷蓄热体湿坯经微波定型、微波干燥,得蜂窝陶瓷干坯,干燥线收缩率3.65%;
将蜂窝陶瓷干坯经切割机、倒角机、吹灰机预加工成蓄热体规定形状;
将蓄热体干坯在1450℃烧结2小时,自然冷却,得刚玉莫来石质蜂窝陶瓷蓄热体制品,烧成线收缩率1.46%,制品中氧化铝含量为72.15%。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。
Claims (9)
1.一种低成本环保型刚玉莫来石质蜂窝陶瓷蓄热体的制备方法,在制备中使用一种具有增强增塑作用的同种复合粘结剂和一种具有润滑和减水作用的水溶液,其中,
所述同种复合粘结剂是采用三种不同粘度的羟丙基甲基纤维素按配比复合而成的纤维素粘结剂,
所述具有润滑和减水作用的水溶液的溶质由两部分组成,一是具有润滑作用的直链型高分子聚合物,其选自聚乙烯醇、聚乙二醇、聚丙烯酰胺和聚氧化乙烯中的一种或者多种;二是电解质减水剂,包括有机电解质和/或无机电解质,
陶瓷原料基本由下述材料组成:2~5%的滑石,3%~10%的粘土,其选自苏州土、高岭土、膨润土和黑泥,40%~70%的煅烧矿物料,其选自煅烧高岭土、煅烧焦宝石和煅烧低铝矾土,以及20%~50%的工业氧化铝或95瓷废瓷粉。
2.根据权利要求1所述的制备方法,其特征在于,所述减水剂选自柠檬酸钠、木质素磺酸钙和三聚磷酸钠,优选木质素磺酸钙。
3.根据权利要求1所述的制备方法,其特征在于,在蜂窝陶瓷挤出成型工艺的混料阶段引入所述同种复合粘结剂,并以喷雾方式引入50%的所述水溶液,经强力混料机混合成半湿性物料;在捏合阶段再加入剩余的50%水溶液捏合成可塑性泥料。
4.根据权利要求1所述的制备方法,其特征在于,所述同种复合粘结剂包括以下三种黏度的羟丙基甲基纤维素:
羟丙基甲基纤维素A:黏度4000mPa·s~6000mPa·s;
羟丙基甲基纤维素B:黏度8000mPa·s~12000mPa·s;
羟丙基甲基纤维素C:20000mPa·s~40000mPa·s。
5.根据权利要求1所述的制备方法,其特征在于,所述三种黏度的羟丙基甲基纤维素以质量计的配比为:
羟丙基甲基纤维素A,5-20份;
羟丙基甲基纤维素B,60-100份;
羟丙基甲基纤维素C,5-20份,
优选的比例为:
羟丙基甲基纤维素A,10-15份;
羟丙基甲基纤维素B,70-100份;
羟丙基甲基纤维素C,10-20份。
6.根据权利要求1所述的制备方法,其特征在于,所述具有润滑和减水作用的水溶液的溶质是聚丙烯酰胺和聚氧化乙烯中的至少一种,其质量百分比之和为0.2-3%,优选0.2-0.5%。
7.根据权利要求1所述的制备方法,其特征在于,所述同种复合粘结剂的加入量在蜂窝陶瓷粉体干基重量的1.0-5.0wt%以内,优选在蜂窝陶瓷粉体干基重量的4.0wt%以内,更优选在蜂窝陶瓷粉体干基重量的3.0wt%以内。
8.根据权利要求1所述的制备方法,其特征在于,所述具有润滑和减水作用的水溶液的加入量为蜂窝陶瓷粉体干基重量的12-20wt%。
9.权利要求1至8任一项所述方法制备的蜂窝陶瓷蓄热体。
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