CN113666734A - 一种转炉用绿色环保型镁尖晶石质喷补料及其制备和应用 - Google Patents

一种转炉用绿色环保型镁尖晶石质喷补料及其制备和应用 Download PDF

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CN113666734A
CN113666734A CN202110900093.3A CN202110900093A CN113666734A CN 113666734 A CN113666734 A CN 113666734A CN 202110900093 A CN202110900093 A CN 202110900093A CN 113666734 A CN113666734 A CN 113666734A
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spinel
magnesium
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刘光平
李媛媛
宋雅楠
尹明强
徐亮
柯极峰
熊元杰
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Zhejiang Zili High Temperature Technology Co ltd
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Abstract

本发明公开了一种转炉用绿色环保型镁尖晶石质喷补料及其制备方法和在转炉维护中的应用。按质量份计,镁尖晶石质喷补料的原料组成包括:镁尖晶石回收料45~80份,镁砂料5~35份,镁质结合剂4~14份,磷酸盐结合剂1~5份,熟石灰微粉2~5份,增稠剂0.05~0.5份,防爆剂0.05~0.5份。本发明不含有沥青和树脂,环境友好,引入镁尖晶石回收料,采用镁质结合剂,使喷补料具有优异的粘附性和抗钢水侵蚀性。本发明实现了废旧耐火材料回收再利用,符合绿色环保的发展要求,保证了喷补料的使用寿命,降低了炼钢成本,利于推广应用。

Description

一种转炉用绿色环保型镁尖晶石质喷补料及其制备和应用
技术领域
本发明涉及转炉用耐火材料技术领域,具体涉及一种转炉用绿色环保型镁尖晶石质喷补料及其制备和应用。
背景技术
转炉是转炉炼钢生产的主要设备,转炉由于长期在高温状态下受到机械力冲击和炉渣侵蚀,转炉的耐火材料极易受损。转炉炉衬修补广泛应用喷补料,其修补效果和频次直接影响转炉使用寿命和生产节奏。随着废钢比例的不断提高,冶炼工况日益严峻,要求转炉维护用耐火材料要求越来越高。通常修补料颗粒部分基本都是用电熔镁砂或烧结镁砂作为主要原料,随着镁砂资源减少,价格较高,增加了补炉成本。因此,补炉效果较好,成本低廉的转炉修补料更受用户青睐。
目前转炉喷补料按结合剂分类主要有两类:一类是以沥青和树脂为结合剂的热态喷补料,一类为以偏硅酸盐和磷酸盐或无机物等为结合剂的水系材料。前者烧结时间长、使用寿命高,但施工时冒浓烟、释放大量有毒有害气体,对环境污染严重。后者烧结时间短且环保,但这种修补料结构疏松,强度较小,使用寿命较短。而且许多钢厂对使用的耐火材料的环保性要求也越来越高,一些严重污染环境的转炉喷补料越来越受到钢厂的排斥。
用后耐火材料的分级处理和回收利用,可减少资源的浪费和环境的污染,用后耐火材料资源化对降低企业生产成本、环境保护和节约资源具有十分重要的意义。中国专利申请CN109650914A涉及一种回用废镁碳砖的环保型转炉修补料及其制备方法,利用回收的废镁碳砖作为制备原料来制备转炉修补料,节省了成本,实现了废物回收利用。中国专利申请CN109320266A涉及一种采用废旧镁钙砖生产环保型速干转炉喷补料的方法,利用回收的镁钙砖作为制备原料来制备转炉修补料,实现了废弃物的回收、及高效利用,符合绿色环保的发展要求。中国专利申请CN110563449A涉及一种RH炉用环境友好型镁碳质喷补料及其制备方法,利用用后MgO-C砖生产的镁碳质喷补料,达到降本增效,废料循环利用的目的。
本发明所使用的废旧镁尖晶石砖主要为回收RH内衬用后的废旧镁尖晶石砖,材质主要为氧化镁、镁铝尖晶石。现有钢厂产生的废旧镁尖晶石砖全部作为工业垃圾处理,造成资源浪费和环境污染。
综上所述,为了达到绿色环保要求,满足转炉冶炼维护需要,提高转炉喷补料的使用寿命,降低资源消耗和成本,本发明介绍一种通过以镁尖晶石回收料为主要原料,添加自产镁质结合剂、磷酸盐结合剂、熟石灰微粉、合适增稠剂、防爆剂等经搅拌混合而制备的转炉用绿色环保型镁尖晶石质喷补料。
发明内容
针对本领域存在的不足之处,本发明提供了一种转炉用绿色环保型镁尖晶石质喷补料,回收RH内衬用后的废旧镁尖晶石砖并进行特定处理得到适用于转炉的、符合特定指标条件的镁尖晶石回收料,变废为宝,并以镁尖晶石回收料为主料,与少量的镁砂料、镁质结合剂、磷酸盐结合剂、熟石灰微粉、增稠剂、防爆剂等组分搅拌均匀得到镁尖晶石质喷补料,其喷补使用时,具有强度和纯度高、粘附性好、烧结时间短、抗爆裂性和抗侵蚀性优等特性,适用于转炉内衬的喷补维护,提高其使用寿命,降低喷补料使用消耗,具有环境友好型、资源节约型的特点。
一种转炉用绿色环保型镁尖晶石质喷补料,按质量份计,原料组成包括:
所述镁质结合剂的粒度不大于5μm,其组成中MgO含量≥77.00wt%,SiO2含量≥13.00wt%,950℃灼减量≤6.0wt%,以降低低熔点相杂质对镁尖晶石质喷补料性能的影响;
所述镁尖晶石回收料中MgO和Al2O3的总含量不低于95wt%,粒度不大于5mm,具体粒度级配为:
5~3mm 10~20质量份,
3~1mm,不含3mm 20~35质量份,
1~0.045mm,不含1mm 15~25质量份;
所述镁尖晶石回收料通过以下方法得到:
1)回收RH内衬用后的废旧镁尖晶石砖,剔除表面杂物,烘干后经颚式破碎机、圆锥破碎,破碎过程中利用磁铁除铁,再经过筛分得到粒度为5~3mm、<3~1mm和<1~0.045mm的骨料;
2)5~3mm和<3~1mm的骨料通过轮碾机消除表面附着的假颗粒,提高颗粒圆度,再通过二级筛网筛分,得到5~3mm和<3~1mm的高质量镁尖晶石回收颗粒料。
不同于现有技术通常是在高温过程中形成尖晶石相,本发明的镁尖晶石质喷补料首创以镁尖晶石回收料为主料,以镁砂料为辅料,采用镁质结合剂作为结合剂,各组分之间具有协同作用、增效作用。在喷补施工过程中,镁质结合剂在喷枪口能够与水快速均匀混合,具有优异的喷补效果和粘附性,因加水量少,喷补衬更为致密,强度更高。另一方面,微纳米级的镁质结合剂能够在较低温度下原位形成微米级镁橄榄石相,产生体积微膨胀,且封闭的基质气孔,使喷补料具有优异的抗渣侵蚀和渗透性。进一步,骨料为高纯度和高致密度的镁尖晶石回收料,提升喷补料的耐高温性和抗钢水冲刷性。本发明的镁质结合剂能够在喷补过程中与水快速反应形成MgO-SiO2-H2O结合相,改善喷补料的喷补强度、粘附性和抗爆裂性。
本发明的镁尖晶石质喷补料的原料中不含沥青和树脂,使用过程中不污染环境;基质中不含有粘土、膨润土或者泡花碱,不会在材料内部形成大量的低熔相,因此,制得的镁尖晶石质喷补料的耐高温强度、抗渣侵蚀和渗透性能好。
作为优选,所述镁砂料为烧结镁砂、电熔镁砂中的一种或两种。
作为优选,所述镁砂料中MgO含量≥95wt%。
为了更好的与本发明的镁尖晶石回收料相配合,更好地应用于转炉维护,作为优选,所述镁砂料的粒度小于1mm。
进一步优选,按质量份数计,所述镁砂料具体粒度级配为:
1~0.045mm,不含1mm 0~20份,
<0.045mm 5~15份。
本发明涉及的粒度级配中的粒径均为数均粒径。
作为优选,所述磷酸盐结合剂为六偏磷酸钠、三聚磷酸钠中的一种或多种复合而成。
作为优选,所述熟石灰微粉的粒度为5~10μm。
作为优选,所述增稠剂为羧甲基纤维素、羧甲基淀粉醚、木质素磺酸钙中的一种或多种复合而成。
作为优选,所述防爆剂为有机纤维、纸纤维或铝粉中的一种或多种复合而成。
本发明还提供了所述的转炉用绿色环保型镁尖晶石质喷补料的制备方法,包括:将镁尖晶石回收料和镁砂料加入搅拌机预混1-2min,然后加入其他原料,搅拌3-5min后,出料得到所述转炉用绿色环保型镁尖晶石质喷补料。
本发明还提供了所述的转炉用绿色环保型镁尖晶石质喷补料在转炉维护中的应用。本发明的镁尖晶石质喷补料特别适用于转炉耳轴的喷补维护,加水量为所述转炉用绿色环保型镁尖晶石质喷补料的12wt%~15.2wt%。
本发明不含有沥青和树脂,环境友好,引入镁尖晶石回收料,采用镁质结合剂,使喷补料具有优异的粘附性和抗钢水侵蚀性。本发明实现了废旧耐火材料回收再利用,符合绿色环保的发展要求,保证了喷补料的使用寿命,降低了炼钢成本,利于推广应用。
本发明与现有技术相比,主要优点包括:
1)本发明回收RH内衬用后的废旧镁尖晶石砖,经特定处理得到适用于转炉的、符合特定指标条件的镁尖晶石回收料,并以之为主要骨料,本发明的特定来源的镁尖晶石回收料具有高的纯度和致密度,提高转炉喷补料的耐高温、耐冲刷性能和抗侵蚀性,节约了资源消耗,降低了喷补料的成本。
2)喷补料采用镁质结合剂,喷补施工性改善,加水量降低,粘附性优、强度高;较低温度下原位形成镁橄榄石相,促进基质烧结,提高中温强度;基质中Al2O3、Fe2O3等杂质含量少,能够提升喷补料的高温性能、抗渣侵蚀和渗透性。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法,通常按照常规条件,或按照制造厂商所建议的条件。
镁尖晶石回收料通过以下方法得到:
1)回收RH内衬用后的废旧镁尖晶石砖,剔除表面杂物,烘干后经颚式破碎机、圆锥破碎,破碎过程中利用磁铁除铁,再经过筛分得到粒度为5~3mm、<3~1mm和<1~0.045mm的骨料;
2)5~3mm和<3~1mm的骨料通过轮碾机消除表面附着的假颗粒,提高颗粒圆度,再通过二级筛网筛分,得到5~3mm和<3~1mm的高质量镁尖晶石回收颗粒料。
实施例1~5、对比例1
按质量份计,实施例1~5的镁尖晶石质喷补料和对比例1的板状刚玉喷补料的原料组成如表1所示,将镁尖晶石回收料(MgO和Al2O3的总含量不低于95wt%)、镁砂料(MgO含量≥95wt%),或者镁砂料(MgO含量≥95wt%)、板状刚玉按比例加入搅拌机预混1-2min,然后按比例加入防爆剂、镁质结合剂(宜兴自立微粉材料科技有限公司,LIMAGEL-75高强度镁质结合剂,粒度不大于5μm,其组成中MgO含量≥77.00wt%,SiO2含量≥13.00wt%,950℃灼减量≤6.0wt%)、磷酸盐结合剂、熟石灰微粉、增稠剂,在混料机中进行搅拌均匀3-5min,制得相应的镁尖晶石质喷补料或板状刚玉喷补料。测试镁尖晶石质喷补料、板状刚玉喷补料喷补使用时加水量,以及线变化率、体积密度、抗折强度、耐压强度和渣侵指数,测试结果见表3。
表1
对比例2
按质量份计,对比例2的含碳镁质喷补料的原料组分如表2所示,其中92级氧化硅微粉即SiO2含量≥92wt%,各原料在混料机进行搅拌3-5min混匀,制得相应的含碳镁质喷补料。测试对比例2含碳镁质喷补料喷补使用时加水量,以及线变化率、体积密度、抗折强度、耐压强度和渣侵指数,测试结果见表3。
表2
表3
可见,本发明回收RH内衬用后的废旧镁尖晶石砖并进行特定处理得到适用于转炉的、符合特定指标条件的镁尖晶石回收料,变废为宝,并以镁尖晶石回收料为主料,与少量的特定粒度级配的镁砂料,以及镁质结合剂、磷酸盐结合剂、熟石灰微粉、增稠剂、防爆剂等组分搅拌均匀得到的镁尖晶石质喷补料,各组分协同作用,喷补使用时加水量低、致密度高,具有良好的体积稳定性、高的强度、优异的抗渣侵蚀和渗透性能,适用于转炉工作衬耐材的喷补维护,提高其使用寿命,降低喷补料使用消耗,其效果明显优于以含碳镁质喷补料和以镁砂料为主的、高温反应形成镁尖晶石的板状刚玉喷补料。
此外应理解,在阅读了本发明的上述描述内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (10)

1.一种转炉用绿色环保型镁尖晶石质喷补料,其特征在于,按质量份计,原料组成包括:
所述镁质结合剂的粒度不大于5μm,其组成中MgO含量≥77.00wt%,SiO2含量≥13.00wt%,950℃灼减量≤6.0wt%;
所述镁尖晶石回收料中MgO和Al2O3的总含量不低于95wt%,粒度不大于5mm,具体粒度级配为:
5~3mm 10~20质量份,
3~1mm,不含3mm 20~35质量份,
1~0.045mm,不含1mm 15~25质量份;
所述镁尖晶石回收料通过以下方法得到:
1)回收RH内衬用后的废旧镁尖晶石砖,剔除表面杂物,烘干后经颚式破碎机、圆锥破碎,破碎过程中利用磁铁除铁,再经过筛分得到粒度为5~3mm、<3~1mm和<1~0.045mm的骨料;
2)5~3mm和<3~1mm的骨料通过轮碾机消除表面附着的假颗粒,提高颗粒圆度,再通过二级筛网筛分,得到5~3mm和<3~1mm的高质量镁尖晶石回收颗粒料。
2.根据权利要求1所述的转炉用绿色环保型镁尖晶石质喷补料,其特征在于,所述镁砂料为烧结镁砂、电熔镁砂中的一种或两种。
3.根据权利要求1所述的转炉用绿色环保型镁尖晶石质喷补料,其特征在于,所述镁砂料中MgO含量≥95wt%。
4.根据权利要求1所述的转炉用绿色环保型镁尖晶石质喷补料,其特征在于,所述镁砂料的粒度小于1mm,按质量份数计,具体粒度级配为:
1~0.045mm,不含1mm 0~20份,
<0.045mm 5~15份。
5.根据权利要求1所述的转炉用绿色环保型镁尖晶石质喷补料,其特征在于,所述磷酸盐结合剂为六偏磷酸钠、三聚磷酸钠中的一种或多种复合而成。
6.根据权利要求1所述的转炉用绿色环保型镁尖晶石质喷补料,其特征在于,所述熟石灰微粉的粒度为5~10μm。
7.根据权利要求1所述的转炉用绿色环保型镁尖晶石质喷补料,其特征在于,所述增稠剂为羧甲基纤维素、羧甲基淀粉醚、木质素磺酸钙中的一种或多种复合而成。
8.根据权利要求1所述的转炉用绿色环保型镁尖晶石质喷补料,其特征在于,所述防爆剂为有机纤维、纸纤维或铝粉中的一种或多种复合而成。
9.根据权利要求1~8任一权利要求所述的转炉用绿色环保型镁尖晶石质喷补料的制备方法,其特征在于,包括:将镁尖晶石回收料和镁砂料加入搅拌机预混1-2min,然后加入其他原料,搅拌3-5min后,出料得到所述转炉用绿色环保型镁尖晶石质喷补料。
10.根据权利要求1~8任一权利要求所述的转炉用绿色环保型镁尖晶石质喷补料在转炉维护中的应用,其特征在于,加水量为所述转炉用绿色环保型镁尖晶石质喷补料的12wt%~15.2wt%。
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