CN106699206B - 一种大中型高炉无水炮泥及其制备方法 - Google Patents
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Abstract
本发明涉及一种大中型高炉出铁口用无水炮泥及其制备方法,所述炮泥原料包括高铝骨料及细粉、碳化硅骨料及细粉、焦炭、可塑粘土粉、沥青粉及微粉添加剂,所述微粉添加剂按重量份包括:金属硅粉、金属铝粉、高碳树脂粉、氧化铝微粉、硅灰、羧甲基纤维素钠及六偏磷酸钠,生产搅拌过程中以焦油作为结合剂。本发明所述的无水炮泥能够实现炮泥中高温度快速烧结,增强了新旧炮泥的结合程度,提高了铁口泥包抵抗渣铁冲刷能力;炮泥材料气孔率低致密性好,增强了炮泥的抗渣铁液侵蚀渗透性能;有利于保持铁口深度和铁口孔径稳定,能很好地适应高炉大型化对铁口炮泥的性能要求。
Description
技术领域
本发明涉及冶金耐火材料技术领域,具体包括一种大中型高炉无水炮泥及其制备方法。
背景技术
无水炮泥是用于封堵高炉出铁口的一种耐火可塑料。高炉铁口区域是渣铁侵蚀和冲刷最严重的部分,影响着高炉的使用寿命。无水炮泥压入高炉内部,可以在铁口区域形成泥包,抑制高炉内部铁水环流对铁口区域冲刷侵蚀,保护铁口区域的炉缸,因此对高炉长寿起着关键性的作用。
每天高炉的出铁口都要反复多次被打开和充填,炽热的铁水和渣液对铁口炮泥产生物理和化学侵蚀。一般来讲,需要炮泥作业性好能够充分填充铁口、较高的耐火度;较强的抵抗渣、铁溶液冲刷的能力和抗氧化的能力;适宜的可塑性,便于打泥操作和形成铁口泥包;良好的体积稳定性;较好的烧结性能、快速烧结性和具有快干速硬及较高的中高温强度;良好的开口性能。
为满足高炉大型化、高强冶炼的生产要求,所采用的新技术使得出铁口内衬承受的恶劣化学侵蚀、高温热冲击、铁水溶液强力冲刷的综合作用越加严重,炮泥在铁口孔道温度梯度区域、炉缸炉口区域的使用性能必须更加优良。
目前广泛使用的无水炮泥,大多以焦油、沥青、可塑粘土等为结合剂,采用绢云母作为中温烧结剂;低温状态下,焦油碳化结焦构成网状结构,将骨粉料结合在一起,但这种粘合强度一般较低,其抗冲刷性较差;焦油及沥青中的挥发份逸出,气孔率增大,不利于材料抵抗熔渣的渗透;绢云母能够实现炮泥的快速烧结,但过多的加量会导致炮泥在高温阶段抗侵蚀性能下降。而炮泥质量差,使用时就会出现潮铁口、浅铁口、断铁口、跑大流等一系列问题,影响正常生产,甚至造成人身伤害事故。
因而迫切需要提供一种增大炮泥材料,从而在中高温阶段的烧结程度,强化填充铁口后新旧炮泥的结合强度,有利于材料抵抗其渣铁溶液冲蚀,维持足够铁口深度保护炉缸,保证铁口孔道稳定,延长出铁时间,降低出铁次数,确保高炉安全运行。
发明内容
本发明提供了一种大中型高炉无水炮泥及其制备方法,将微粉添加剂加入到Al2O3-SiO2-SiC-C体系的炮泥中,能够有效改善炮泥在铁口孔道各个部位的使用性能,炮泥的烧结性、致密性、新旧炮泥粘结强度、抗冲刷性和抗侵蚀性得到大幅度提高,能够满足高炉大型化高强冶炼时出铁口愈加严苛的工作环境要求。
根据本发明一个方面,一种大中型高炉出铁口用无水炮泥,一种大中型高炉出铁口用无水炮泥,所述炮泥原料包括高铝骨料及细粉、碳化硅骨料及细粉、焦炭、可塑粘土粉、沥青粉及微粉添加剂,所述微粉添加剂按重量份包括:金属硅粉、金属铝粉、高碳树脂粉、氧化铝微粉、硅灰、羧甲基纤维素钠及六偏磷酸钠,生产搅拌过程中以焦油作为结合剂。
优选地,所述的原料重量比例为,高铝骨料及细粉30~60%,碳化硅骨料及细粉5~20%,焦炭10~20%,沥青粉3~7%,可塑粘土粉8~15%,微粉添加剂8~20%。
优选地,所述微粉添加剂按重量份包括:金属硅粉1-4份、金属铝粉0~1份、高碳树脂粉1-5份、氧化铝微粉5~8份、硅灰1~3份、羧甲基纤维素钠0.1~0.3份、六偏磷酸钠0.2~0.5份。
优选地,所述的高铝骨料和细粉包括棕刚玉、高铝矾土或者均质矾土,骨料的粒度为3-1mm和1-0mm两种,细粉粒度小于0.088mm,高铝材料的Al2O3含量大于85%;所述的碳化硅骨料粒度为1-0mm,细粉粒度小于0.088mm,SiC含量大于90%;所述的焦炭粒度为2-0mm,残炭量大于80%;所述的沥青粉粒度小于0.1mm,软化点大于120℃,结焦值大于60%,粒度小于0.088mm;所述的可塑黏土粉粒度小于0.088mm。
优选地,所述的微粉添加剂中的金属硅粉的粒径小于0.088mm,纯度大于95%。
优选地,所述的金属铝粉的粒径大于150μm,纯度大于98%。
优选地,所述的高碳树脂粉的粒径小于0.088mm,含碳量大于80%。
优选地,所述的氧化铝微粉的粒径小于5μm,纯度大于99%。
优选地,所述的硅灰的粒径小于0.15μm,纯度大于92%。
优选地,所述的羧甲基纤维素钠和六偏磷酸钠为工业品级。
根据本发明另一个方面,大中型高炉出铁口用无水炮泥的制备方法,包括以下步骤:
(1)将金属硅粉、金属铝粉、高碳树脂粉、氧化铝微粉、硅灰、羧甲基纤维素钠和六偏磷酸钠,按照确立的比例进行混合均匀,制备成微粉添加剂;
(2)依据高炉出铁口无水炮泥配比,将高铝骨料及细粉、碳化硅骨料及细粉、焦炭、可塑粘土粉、沥青粉原材料先进行搅拌预混合,再加入(1)制备成的微粉添加剂继续搅拌形成均匀的混合粉料,加入焦油结合剂;经碾压、混炼获得可塑性良好的泥料后,挤压、成型后即得大中型高炉出铁口用无水炮泥。
本发明提供了高炉出铁口无水炮泥及其制备方法,与普通无水炮泥相比,具有如下优点和效果:
(1)能够有效强化无水炮泥中高温快速烧结,降低炮泥气孔率,提高烧结强度;增强炮泥材料的致密度,提高其抗侵蚀和抗冲刷能力。
(2)中低温烧结增强剂与中高温烧结剂协同作用,出铁口炮泥烧结速度合适,在温度的各个阶段都有适宜的强度;含微粉添加剂的无水炮泥能够在炉缸内形成良好的泥包,能够有效维持铁口深度以保护炉缸,具有良好的抗冲刷性、抗侵蚀性,开口无喷溅、铁口孔道无裂纹、孔径稳定,有利于延长出铁时间。
本发明的大中型高炉出铁口无水炮泥的制备方法,所涉及到的无水炮泥的原材料,在材料的主要作用机理如下:
棕刚玉、高铝矾土和均化矾土是无水炮泥的氧化铝成分的主要来源,粗颗粒起到骨架作用,粉料能提高炮泥的强度和高温性能。这些氧化铝骨料在炮泥中使用提高了炮泥的强度,增强了耐磨性、抗侵蚀性能和抗冲刷性能;同时,高铝矾土和均化矾土中存在着的莫来石矿相,提高了炮泥材料的抗热震性能。
碳化硅具有导热率高、耐磨性好、高温强度高、热膨胀系数小、热震稳定性好的优点,作为炮泥的原料可改善其抗熔渣侵蚀和冲刷等性能,提高高温结构强度和热稳定性,抑制其它原料的氧化。
焦炭的导热性能好,与熔渣难润湿,抗渣侵蚀性和热震稳定性好。焦炭的疏松气孔有利于改善炮泥的透气性,便于挥发性成分的释放、逸出,防止耐火原料过烧结,有利于炮泥开口操作。
沥青具有不含水、不浸水和残炭率高的特点。沥青升温过程中软化熔化,增强了炮泥材料塑性。在烧结过程中,主要是帮助结合剂发挥强化效应,可以进一步起到改进泥料某些性能的作用。如在高温条件下沥青成分碳化析出石墨碳,使泥料具有较好的高温结构强度。
可塑粘土粉主要是利用其可塑性,提高炮泥的作业性能;此外,粘土具有很好的烧结性能,是炮泥中温强度的重要来源之一。
金属铝粉的熔点在698℃,它在此温度下熔化,形成局部液相,有利于促进炮泥材料的快速烧结,增强材料致密性,提高材料的中低温强度;而且铝粉在高温还原气氛下容易与C源材料、CO等反应生成Al2O3、Al4C3等,反应产生的微量体积膨胀堵塞气孔,导致材料密度的提高;同时,形成高熔点颗粒状物或纤维状物生成物,都构成材料的基质增强体,有利于提高高温强度。
金属硅粉在高温状态下能与C源反应生成β-SiC,这种形态的SiC通过“桥接”强化了材料间的中、高温粘结强度,利于炮泥的抗侵蚀和抗冲刷性能的提高。
高含碳量树脂粉残碳量非常高,其残碳量接近常使用的沥青粉含碳量的2倍。部分取代沥青粉,可以形成更多的碳结合,能够有效提高炮泥材料的力学强度;形成的碳化结构是一种石墨化的结构,材料韧性好、抗热震性能优良。
氧化铝超微粉和硅灰都属于超微粉,起着改善泥料塑性、强化基质的作用;两种高活性微粉在1000℃左右两者反应生成莫来石,使得炮泥材料的抗热震性大幅提高;造成的体积膨胀有利于增加材料致密度性,在一定程度上补偿烧结过程中产生的体积收缩,同时生成的莫来石充当材料基质增强基体,有利于提高材料的高温强度和抗冲蚀性能。
具体实施方式
以下结合实施例对本发明作进一步详细描述,需要指出的是,以下所述实施例仅用于举例说明本发明,而发明的范围不局限于此具体实施例中。
实施例1
按照重量份称量粉料,包括金属硅粉1份、金属铝粉0.3份、高碳树脂粉2份、氧化铝微粉5份以及硅灰1份、羧甲基纤维素钠0.1份、六偏磷酸钠0.2份,室温条件下搅拌5~10分钟混合均匀后,即得到所述的炮泥用微粉添加剂;
炮泥的制备按其组分及重量份为:高铝矾土骨料36.7份,棕刚玉细粉9份,碳化硅骨料及细粉共10份,焦炭15份,可塑粘土粉16份,沥青粉4份;采用实施例1中制备的高炉出铁口炮泥微粉添加剂9.3份;外加焦油13份。
炮泥制备中,依据炮泥方案配比,将高铝矾土骨料和细粉、90碳化硅骨料和细粉、焦炭、可塑粘土粉、沥青粉等原材料先进行干料搅拌拌2~3分钟预混合,再加入所需的微粉添加剂继续搅拌形成均匀的混合粉料,加入焦油结合剂;经搅拌、碾压、混炼工序30分钟,使得结合剂充分润湿干料,获得可塑性良好的泥料后,挤压、成型后即得无水炮泥。
上述无水炮泥在某钢铁厂2000cm3高炉上使用,效果很好。泥料塑性好,打泥容易;烧结速度快,压炮时间较短,无铁口浅、断漏铁口等现象;打开铁口容易,无任何喷溅现象;抗高温渣铁侵蚀和冲刷能力强,铁口深度合格率达90%以上;出铁过程中,铁口扩径稳定,变化率稳定在0.2%以内;出铁时间达100分钟以上。
实施例2
按照重量份称量粉料,包括金属硅粉2份、金属铝粉0.5份、高碳树脂粉4份、氧化铝微粉6份以及硅灰1.5份,室温条件下搅拌5~10分钟混合均匀后,即得到所述的炮泥用微粉添加剂。
炮泥的制备按其组分及重量份为:高铝矾土骨料15份,均化矾土骨料20份,刚玉细粉12份,碳化硅12份,焦炭12份,可塑粘土粉12份,沥青粉3份;采用实施例2中制备的高炉出铁口炮泥用微粉添加剂14份;焦油12份。
炮泥制备中,依据炮泥方案配比,将高铝矾土骨料、均化矾土骨料、刚玉细粉、碳化硅骨料和细粉、焦炭、可塑粘土粉、沥青粉等原材料先进行干料搅拌拌2~3分钟预混合,再加入所需的微粉添加剂继续搅拌形成均匀的混合粉料,加入焦油等结合剂;经搅拌、碾压、混练等工序30分钟,使得结合剂充分润湿干料,获得可塑性良好的泥料后,挤压、成型后即得无水炮泥。
该炮泥在某钢铁厂3200cm3高炉上使用,效果很好。泥料塑性好,打泥容易;无铁口浅、断漏铁口等现象,开口时间小于5min,铁口无喷溅现象;铁口深度合格率达92%以上;出铁过程中,铁口扩径稳定,变化率稳定在0.2%以内;出铁时间达120分钟以上。
实施例3
按照重量份称量粉料,室温条件下搅拌5~10分钟混合均匀后,即得到所述的炮泥用微粉添加剂;包括金属硅粉2.5份、金属铝粉1.5份、高碳树脂粉5份、氧化铝微粉7份以及硅灰2份。
泥的制备按其组分及重量份为:棕刚玉骨料32.5份,刚玉粉12份,碳化硅15份,焦炭12份,可塑黏土粉9份,沥青粉2份;采用实施例2中制备的高炉出铁口炮泥用微粉添加剂17.5份;外加焦油12份。
炮泥制备中,依据炮泥方案配比,将棕刚玉骨料、刚玉细粉、碳化硅骨料及细粉、焦炭、可塑粘土粉、沥青粉等原材料先进行干料搅拌2~3分钟预混合,再加入所需的微粉添加剂继续搅拌形成均匀的混合粉料,加入焦油等结合剂;经搅拌、碾压、混练等工序30分钟,使得结合剂充分润湿干料,获得可塑性良好的泥料后,挤压、成型后即得无水炮泥。
该炮泥在某钢铁厂4000cm3高炉上使用,效果很好。泥料塑性好,打泥容易;无铁口浅、断漏铁口等现象,开口时间小于5min,无任何喷溅现象;铁口深度合格率达90%以上,出铁过程中,铁口扩径稳定,变化率稳定在0.2%以内;出铁时间达140分钟以上。
将基于普通炮泥技术与本发明的炮泥的测试性能指标进行了对比,其结果如下表所示:
以上所述的实施例对本发明的技术方案进行了详细说明,仅为本发明的具体实施例,并不用于限制本发明,凡在本发明的原则范围内所做的任何修改、补充或等同替换等,均应包含在本发明的保护范围之内。
Claims (3)
1.一种大中型高炉出铁口用无水炮泥,其特征在于,
所述炮泥原料按重量百分比计,组成如下:高铝骨料及细粉30~60%、碳化硅骨料及细粉5~20%、焦炭10~20%、可塑粘土粉8~15%、沥青粉3~7%及微粉添加剂8~20%,其中,
所述的高铝骨料和细粉包括棕刚玉、高铝矾土或者均质矾土,骨料的粒度为3-1mm和1-0mm两种,细粉粒度小于0.088mm,高铝材料的Al2O3含量大于85%;所述的碳化硅骨料粒度为1-0mm,细粉粒度小于0.088mm,SiC含量大于90%;所述的焦炭粒度为2-0mm,残炭量大于80%;所述的沥青粉粒度小于0.1mm,软化点大于120℃,结焦值大于60%;所述的可塑粘土粉粒度小于0.088mm;
所述微粉添加剂按重量份计,组成为:金属硅粉1~4份、金属铝粉0~1份、高碳树脂粉1~5份、氧化铝微粉5~8份、硅灰1~3份、羧甲基纤维素钠0.1~0.3份及六偏磷酸钠0.2~0.5份,所述金属硅粉的粒径小于0.088mm,纯度大于95%;所述金属铝粉的粒径大于150μm,纯度大于98%;所述高碳树脂粉的粒径小于0.088mm,含碳量大于80%;所述氧化铝微粉的粒径小于5μm,纯度大于99%;所述硅灰的粒径小于0.15μm,纯度大于92%;所述无水炮泥生产过程中,先预混所述微粉添加剂,然后与预混合的原料搅拌混合,且搅拌过程中以焦油作为结合剂。
2.根据权利要求1所述的大中型高炉出铁口用无水炮泥,其特征在于,
所述的沥青粉粒度小于0.088mm。
3.如权利要求1所述的大中型高炉出铁口用无水炮泥的制备方法,其特征在于,包括以下步骤:
(1)将金属硅粉、金属铝粉、高碳树脂粉、氧化铝微粉、硅灰、羧甲基纤维素钠和六偏磷酸钠,按照确立的比例进行混合均匀,制备成微粉添加剂;
(2)依据高炉出铁口无水炮泥配比,将高铝骨料及细粉、碳化硅骨料及细粉、焦炭、可塑粘土粉、沥青粉原材料先进行搅拌预混合,再加入(1)制备成的微粉添加剂继续搅拌形成均匀的混合粉料,加入焦油结合剂;经碾压、混炼获得可塑性良好的泥料后,挤压、成型后即得大中型高炉出铁口用无水炮泥。
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