CN114591094B - 熔铸耐火制品制备方法及其制备的产品 - Google Patents

熔铸耐火制品制备方法及其制备的产品 Download PDF

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CN114591094B
CN114591094B CN202210111644.2A CN202210111644A CN114591094B CN 114591094 B CN114591094 B CN 114591094B CN 202210111644 A CN202210111644 A CN 202210111644A CN 114591094 B CN114591094 B CN 114591094B
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张红哲
闫建敏
张艺峰
侯银慧
李龙刚
张天英
卢喜亮
魏杰
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Henan Ruitaike Industrial Group Co ltd
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Abstract

本发明提供一种熔铸耐火制品的制备方法及其制备的产品,将熔化好的耐火制品的原料注入放置在保温箱的耐火制品模型型腔进行自然冷却,在保温箱中设有至少两个耐火制品模型,耐火制品模型距离保温箱中心均匀分布,保温箱中心固定在水平放置的离心转盘上;冷却到1750℃—1680℃时,开始对保温箱进行旋转,旋转速度为3‑8转/min,每3‑5min,停1‑2min,一直到温度降至1200℃,然后继续保温至室温或30℃以下,制得熔铸耐火制品;制备耐火制品的原料中至少一种原料的成分含有氧化钠。通过离心,能够使得耐火制品中玻璃相在远离离心转盘的地方分布,从而提高砌筑靠近玻璃窑炉一面的莫来石耐火制品的性能或者氧化锆耐火制品的性能。

Description

熔铸耐火制品制备方法及其制备的产品
技术领域
本发明涉及耐火材料领域,尤其涉及一种熔铸耐火制品制备方法及其制备的产品。高锆砖及其玻璃相与高纯度玻璃的生产有直接关系,疫苗瓶不过关就是因为玻璃熔窑壁渗出的玻璃体进入玻璃中形成杂质,导致生产的疫苗瓶不过关,高纯氧化锆耐火制品的质量直接关系到疫苗瓶的质量,提高高纯氧化锆耐火制品的质量甚为迫切。
背景技术
熔铸莫来石耐火制品由于耐火度高、耐磨主要用于耐磨、耐高温的部位,如冶金推钢式加热炉的滑轨砖或步进式加热炉的出钢平台(出钢槽)以及垃圾焚烧炉的内衬等,应用广泛,但是莫来石砖中由于玻璃相的生成,用于作为玻璃窑时,容易出现高温下玻璃相融化,容易造成玻璃相成分渗出到玻璃熔窑内,从而污染玻璃窑中的产品。
高锆砖及其玻璃相与高纯度玻璃的生产有直接关系,疫苗瓶不过关就是因为玻璃熔窑壁渗出的玻璃体进入玻璃中形成杂质,导致生产的疫苗瓶不过关,高纯氧化锆耐火制品的质量直接关系到疫苗瓶的质量,提高高纯氧化锆耐火制品的质量甚为迫切。
以氧化锆(ZrO2)为主成分的耐火材料对熔融玻璃呈现出优异的耐腐蚀性,因此广泛用于与玻璃熔融窑的熔融玻璃接触的内壁部分。但是,其组织基本由ZrO2结晶(斜锆石)构成的高氧化锆质铸造耐火材料在1100℃附近发生ZrO2结晶中特有的从单斜晶向正方晶的结晶转变,伴随着该结晶转变而产生异常的体积膨胀和收缩,特别是实际使用的大尺寸耐火材料存在容易发生开裂的问题。制造含有90质量%左右或以上的ZrO2的耐火材料的方法,已知有以下方法:在以埋入ZrO2结晶之间的SiO2为主成分的玻璃相(以下称为基体玻璃)中加入使玻璃软化的成分后调整其粘性,在ZrO2结晶发生结晶转变的温度范围内,用较软的基体玻璃吸收因ZrO2结晶的膨胀和收缩而引起的变形。但是由于形成玻璃相,在作为玻璃熔融窑使用时,容易造成玻璃相成分渗出到玻璃熔融窑内,从而污染产品。
发明内容
为解决上述问题,本发明提供一种熔铸耐火制品的制备方法及其制备的产品,通过离心,能够使得耐火制品中玻璃相在远离离心转盘的地方分布,从而提高砌筑靠近玻璃窑炉一面的莫来石耐火制品的性能或者氧化锆耐火制品的性能。
本发明的目的是以下述方式实现的:一种熔铸耐火制品制备方法,包括以下步骤,将制备耐火制品的原料混匀,然后加入电熔炉或三相电炉进行加热至2100~2200℃进行熔融,熔融过程中进行搅拌,熔融完成后,将熔化好的料液注入放置在保温箱的耐火制品模型型腔中,注入完成后,上部覆盖保温材料进行保温,然后进行自然冷却,在保温箱中设有至少两个耐火制品模型,耐火制品模型距离保温箱中心均匀分布,保温箱中心固定在水平放置的离心转盘上;冷却到1750℃—1680℃时,开始对保温箱进行旋转,旋转速度为3-8转/min,每3-5min,停1-2min,一直到温度降至1200℃,然后继续保温至室温或30℃以下,制得熔铸耐火制品;制备耐火制品的原料中至少一种原料的成分含有氧化钠。
冷却到1710℃时,开始对保温箱进行旋转,旋转速度为5转/min,每3min,停1min。
将冷却完成的从保温箱中取出的产品进行切断、研磨、钻孔等冷加工处理,最终得到耐火制品成品。
耐火制品为氧化锆耐火制品;制备氧化锆耐火制品的原料中:氧化锆含量之和为87%-95%,氧化硅含量之和为3%-11%,Na2O+Al2O3+TiO2+Fe2O3+K2O≤2%。
上述方法制备的熔铸耐火制品。
所述熔铸耐火制品的应用,在砌筑玻璃窑炉尤其是内衬时,把熔铸耐火制品靠近离心转盘中心的一面朝向窑炉内部砌筑。
相对于现有技术,本发明提供的熔铸耐火制品的制备方法,制备的熔铸莫来石耐火制品,靠近离心转盘中心一半的莫来石成品,软化温度提高到1750℃以上,原因可能是在形成部分莫来石晶体时,此时要形成玻璃相的物质仍然为液体,通过离心,使得形成玻璃相的液体向外,靠近离心转盘中心一半的莫来石成品中的玻璃相大大减少,从而提高了软化温度,从而在砌筑玻璃窑炉尤其是内衬时,可以把莫来石成品靠近离心转盘中心的一面朝向窑炉内部砌筑。
制备的熔铸氧化锆耐火制品,靠近离心转盘中心一半的熔铸氧化锆耐火制品,大大通过离心大大减少了玻璃相的存在,从而提高耐火制品的软化温度,降低降低熔铸氧化锆产品中玻璃相的渗出,从而在砌筑玻璃窑炉尤其是内衬时,可以把熔铸氧化锆耐火制品靠近离心转盘中心的一面朝向窑炉内部砌筑。
附图说明
图1耐火制品型腔在保温箱a中的结构示意图。
具体实施方式
一种熔铸耐火制品制备方法,包括以下步骤,将制备耐火制品的原料混匀,然后加入电熔炉或三相电炉进行加热至2100~2200℃进行熔融,熔融过程中进行搅拌,熔融完成后,将熔化好的料液注入放置在保温箱的耐火制品模型型腔中,注入完成后,上部覆盖保温材料进行保温,然后进行自然冷却,在保温箱中设有至少两个耐火制品模型,耐火制品模型距离保温箱中心均匀分布,保温箱中心固定在水平放置的离心转盘上;冷却到1750℃—1680℃时,开始对保温箱进行旋转,旋转速度为3-8转/min,每3-5min,停1-2min,一直到温度降至1200℃,然后继续保温至室温或30℃以下,制得熔铸耐火制品;制备耐火制品的原料中至少一种原料的成分含有氧化钠。
冷却到1710℃时,开始对保温箱进行旋转,旋转速度为5转/min,每3min,停1min。
将冷却完成的从保温箱中取出的产品进行切断、研磨、钻孔等冷加工处理,最终得到耐火制品成品。
耐火制品为氧化锆耐火制品;制备氧化锆耐火制品的原料中:氧化锆含量之和为87%-95%,氧化硅含量之和为3%-11%,Na2O+Al2O3+TiO2+Fe2O3+K2O≤2%。
上述方法制备的熔铸耐火制品。
(一)熔铸莫来石耐火制品的生产工艺流程:设计,模型,配料,熔融,组型,浇铸,保温,取出,加工。
(1)设计:熔铸莫来石模型的设计。
(2)模型:熔铸莫来石模型的制作。
(3)配料:按重量份配比要求称取所需原料氧化铝、氧化硅、氧化钠、氧化铁;氧化铝、氧化硅、氧化钠、氧化铁原料为莫来石耐火制品的常规用料,精确称量,均匀搅拌;
(4)熔融:将上述原料充分搅拌混合,放入三相电炉进行加热至2100~2200℃进行熔融;
(5)组型:把制作好的莫来石模型放入保温箱中,四周填充保温氧化铝。
(6)浇铸:将熔化好的料液铸入组好的莫来石模型中,上部覆盖保温氧化铝。
(7)保温:将保温箱集中放置,自然冷却;
(8)取出:保温一定天数后,把浇铸好的莫来石从保温箱中取出,得到半成品,准备后续加工;
(9)加工:将冷却至室温的莫来石半成品进行切断、研磨、钻孔等冷加工处理,最终得到莫来石成品。
(二)熔铸氧化锆耐火制品的生产工艺流程
未浸渍溶液A前的熔铸氧化锆产品的生产工艺流程:设计,模型,配料,熔融,组型,浇铸,保温,取出,加工。未浸渍溶液A前的熔铸氧化锆产品可以为熔铸高锆砖。
(1)设计:熔铸高锆砖模型的设计。
(2)模型:熔铸高锆砖模型的制作。
(3)配料:按氧化锆+氧化铪、氧化硅、氧化钠重量份配比要求称取所需原料,精确称量,均匀搅拌;
上述原料来源可以为符合要求的一种、两种、三种、四种原料组成,原料可以为:
(a)脱硅锆
产地:安徽蚌埠中恒
专业从事氧化锆系列产品的研发和生产,选用澳大利亚高品质原矿锆英砂作为原料的。该产品具有品位高、质量优、化学组成及粒子分布稳定和均匀的特征,可满足陶瓷、电子、航天、钢铁、耐火材料等行业的各类工艺要求。其中按重量百分比计,氧化锆≥98.90%。
(b)锆英砂
产地:澳大利亚
澳大利亚的Iluka公司是世界上最大的锆英砂生产商,占据全球锆金属产量的32%,约35.2万吨。其中按重量百分比计,氧化硅≥32.64%,氧化锆≥66.48%。
(c)碱粉:湖北双环;按重量百分比计,氧化钠≥54%。
(d)高锆砖熟料:来自于河南省瑞泰科实业集团有限公司生产的废料;按重量百分比计,氧化硅≥7.11%,氧化锆≥91%,氧化钠≥0.85%。
(4)熔融:将上述原料充分搅拌混合,放入三相电炉进行加热至2700~2900℃进行熔融;
(5)组型:把制作好的高锆砖模型放入保温箱中,四周填充合适的保温材。
(6)浇铸:将熔化好的料液铸入组好的高锆砖模型中,上部覆盖保温材。
(7)保温:将保温箱集中放置,自然冷却;
(8)取出:保温一定天数后,把浇铸好的高锆砖从保温箱中取出,得到半成品,准备后续加工;
(9)加工:将冷却至室温的高锆砖半成品进行切断、研磨、钻孔等冷加工处理,最终得到高锆砖成品。
实际在熔铸莫来石或者氧化锆耐火制品的生产工艺流程中在配料之前还包括设计,模型的步骤,但是一旦模型设计好,或者沿用以前的模型时,就不需要这两个步骤。
下面结合具体实施例对本发明进行具体描述,有必要在此指出的是本实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,该领域的技术熟练人员可以根据上述本发明的内容做出一些非本质的改进和调整。
实施例1
按照上述相应工艺流程处理得到的同一配方,同一原料的同一批莫来石原料熔融液,按下述方法进行保温处理:
其中不自然冷却过程中的保温箱为常规保温箱,为保温箱b。其中自然冷却过程中的保温箱为保温箱a。
保温箱a设置为正六边形,莫来石砖模型为长方体型,如图1所示,在横截面上,莫来石砖模型型腔的宽边的中心a距离正六边形中心o的距离为正六边形中心o到正六边形角b的距离的1/2,且点a位于线段ob的中心,莫来石砖模型型腔的的长边与正六边形的边平行,莫来石砖模型型腔的长边长度为610mm,宽边为400mm,高度为210mm。每一个保温箱中均匀分布有三个莫来石砖模型。除此之外,保温箱a与莫来石砖的设置为常规的,与保温箱b相同。
熔融完成后,将熔化好的原料熔融液分别注入6个分别放置于保温箱b中的莫来石砖模型型腔中和分别放置于2个保温箱a中的6个莫来石砖模型型腔中,莫来石砖模型四周填充保温氧化铝,注入料液完成后,上部覆盖保温氧化铝,然后进行自然冷却。
其中2个保温箱a中心固定在水平放置的离心转盘上,冷却到1750℃时,开始对保温箱进行离心,旋转速度为3-8转/min,每3-5min,停1-2min,一直到温度降至1200℃,然后继续保温至室温或30℃以下,将冷却完成的从保温箱a中取出的产品分别按常规处理:如进行研磨等处理,最终得到用于玻璃窑的莫来石成品A。
另外6个保温箱b正常自然冷却;将冷却完成的从保温箱b中取出的产品分别按常规处理:如进行研磨等处理,最终得到玻璃窑的莫来石成品B。
温度检测设备可以为如德国进口Tpye C型热电偶,品牌:Buffalo,型号TC,测温0-2300℃,最高测试温度达到2300℃(国内目前没有能做到分度号C的热电偶,采用反应原件为钨铼合金,探针护鞘材质为钼、钽或钨等昂贵的耐高温金属。
对莫来石成品进行检测:
对于莫来石成品A:从靠近离心转盘中心一半的莫来石成品C中进行取样,按重量百分比计,所有莫来石成品A的平均值为:SiO2 16.2 %(检测依据或说明GB/T 6900-2016),Al2O3 75.7%(检测依据或说明GB/T 6900-2016),ZrO2 +HfO2为5.2%(检测依据或说明GB/T4984-2007),Fe2O3 2.2%(检测依据或说明ISO 21587-2007),TiO2+CaO+MgO+Na2O+K2O≤0.7%,所有莫来石成品A的性能平均值:体积密度(致密部分)3.25g/cm3(检测依据或说明GB/T 2997-2015),常温抗折强度162MPa,抗折强度(1350℃)113Mpa,热线膨胀率(1300℃)0.87%;荷重软化开始温度(0.2MPa)为≥1750℃。
对于莫来石成品B:按重量百分比计,所有莫来石成品B的平均值为:SiO2 16.1 %(检测依据或说明GB/T 6900-2016),Al2O3 75.1%(检测依据或说明GB/T 6900-2016),ZrO2+HfO2为4.8%(检测依据或说明GB/T 4984-2007),Fe2O3 1.9%(检测依据或说明ISO 21587-2007),TiO2+CaO+MgO+Na2O+K2O≤2.1%,所有莫来石成品B的性能平均值:体积密度(致密部分)3.22g/cm3(检测依据或说明GB/T 2997-2015),常温抗折强度143MPa,抗折强度(1350℃)98Mpa,热线膨胀率(1300℃)0.89%;荷重软化开始温度(0.2MPa)为≥1650℃。
另外横切各莫来石成品,对于莫来石成品A,横切方向与莫来石成品A靠近离心转盘中心的一面平行,间隔距离为1cm,横切后观察切面:随着距离离心转盘中心越来越远,莫来石成品A的切面上从几乎不能观察到玻璃相的存在,到渐渐观察到玻璃相的存在,然后切面上的玻璃相逐渐增多;莫来石成品B切面方向玻璃相成网状进行分布,网状玻璃相分割连续的莫来石相。
实施例2
按照上述相应工艺流程处理得到的同一配方,同一原料的同一批莫来石原料熔融液,按下述方法进行保温处理:
其中不自然冷却过程中的保温箱为常规保温箱,为保温箱b。其中自然冷却过程中的保温箱为保温箱a。
保温箱a设置为正六边形,莫来石砖模型为长方体型,如图1所示,在横截面上,莫来石砖模型型腔的宽边的中心a距离正六边形中心o的距离为正六边形中心o到正六边形角b的距离的1/2,且点a位于线段ob的中心,莫来石砖模型型腔的的长边与正六边形的边平行,莫来石砖模型型腔的长边长度为610mm,宽边为400mm,高度为210mm。每一个保温箱中均匀分布有三个莫来石砖模型。除此之外,保温箱a与莫来石砖的设置为常规的,与保温箱b相同。
熔融完成后,将熔化好的原料熔融液分别注入6个分别放置于保温箱b中的莫来石砖模型型腔中和分别放置于2个保温箱a中的6个莫来石砖模型型腔中,莫来石砖模型四周填充保温氧化铝,注入料液完成后,上部覆盖保温氧化铝,然后进行自然冷却。
其中2个保温箱a中心固定在水平放置的离心转盘上,冷却到1650℃时,开始对保温箱进行离心,旋转速度为5转/min,每3min,停1min,一直到温度降至1200℃,然后继续保温至室温或30℃以下,将冷却完成的从保温箱a中取出的产品分别按常规处理:如进行研磨等处理,最终得到用于玻璃窑的莫来石成品C。
另外6个保温箱b正常自然冷却;将冷却完成的从保温箱b中取出的产品分别按常规处理:如进行研磨等处理,最终得到玻璃窑的莫来石成品D。
温度测量设备与实施例1相同。
对莫来石成品进行检测:
对于莫来石成品C:从靠近离心转盘中心一半的莫来石成品C中进行取样,按重量百分比计,所有莫来石成品C的平均值为:SiO2 17.4%,(检测依据或说明GB/T 6900-2016),Al2O3 77.9%(检测依据或说明GB/T 6900-2016),ZrO2+HfO2为1.3%(检测依据或说明GB/T4984-2007),Fe2O3为2.0%(检测依据或说明ISO 21587-2007),TiO2+CaO+MgO+Na2O+K2O≤1.4%,所有莫来石成品C的性能平均值:体积密度(致密部分)3.19g/cm3(检测依据或说明GB/T 2997-2015),常温抗折强度123MPa,抗折强度(1350℃)79Mpa,热线膨胀率(1150℃)0.55%;荷重软化开始温度(0.2MPa)为≥1750℃。
对于莫来石成品D:按重量百分比计,所有莫来石成品D的平均值为:SiO2 17.2 %(检测依据或说明GB/T 6900-2016),Al2O3 % 77.5%(检测依据或说明GB/T 6900-2016),ZrO2+HfO2为1.0%(检测依据或说明GB/T 4984-2007),Fe2O3 1.9%(检测依据或说明ISO21587-2007),TiO2+CaO+MgO+Na2O+K2O≤2.4%,所有莫来石成品D的性能平均值:体积密度(致密部分)3.20g/cm3(检测依据或说明GB/T 2997-2015),常温抗折强度105MPa,抗折强度(1350℃)66Mpa,热线膨胀率(1150℃)0.58%;荷重软化开始温度(0.2MPa)为≥1650℃
另外横切各莫来石成品,对于莫来石成品C,横切方向与莫来石成品C靠近离心转盘中心的一面平行,间隔距离为2cm,横切后观察切面:随着距离离心转盘中心越来越远,莫来石成品C的切面上从几乎不能观察到玻璃相的存在,到渐渐观察到玻璃相的存在,然后切面上的玻璃相逐渐增多;莫来石成品D切面方向玻璃相成网状进行分布,网状玻璃相分割连续的莫来石相。
另外生产熔铸高纯氧化铝耐火制品的保温也可以使用本申请的保温工艺进行。
以上所述的仅是本发明的优选实施方式,但本发明的保护范围并不局限于此,应当指出,对于本领域的及任何熟悉本技术领域的技术人员来说,在不脱离本发明整体构思前提下,根据本发明的技术方案及其发明构思加以等同替换或改变,及作出的若干改变和改进,这些也应该视为本发明的保护范围。

Claims (6)

1.一种熔铸耐火制品制备方法,其特征在于:包括以下步骤,将制备耐火制品的原料混匀,然后加入电熔炉或三相电炉进行加热至2100~2200℃进行熔融,熔融过程中进行搅拌,熔融完成后,将熔化好的料液注入放置在保温箱的耐火制品模型型腔中,注入完成后,上部覆盖保温材料进行保温,然后进行自然冷却,在保温箱中设有至少两个耐火制品模型,耐火制品模型距离保温箱中心均匀分布,保温箱中心固定在水平放置的离心转盘上;冷却到1750℃—1680℃时,开始对保温箱进行旋转,旋转速度为3-8转/min,每3-5min,停1-2min,一直到温度降至1200℃,然后继续保温至室温或30℃以下,制得熔铸耐火制品;熔铸耐火制品为莫来石耐火制品或氧化锆耐火制品,制备耐火制品的原料中至少一种原料的成分含有氧化钠;形成部分莫来石晶体或者氧化锆晶体时,此时要形成玻璃相的物质仍然为液体,通过离心,使得形成玻璃相的液体向外,靠近离心转盘中心一半的莫来石成品或氧化锆耐火制品中的玻璃相大大减少,从而提高了靠近离心转盘中心一半的莫来石成品或氧化锆耐火制品的软化温度。
2.根据权利要求1所述的熔铸耐火制品制备方法,其特征在于:冷却到1710℃时,开始对保温箱进行旋转,旋转速度为5转/min,每3min,停1min。
3.根据权利要求1所述的熔铸耐火制品制备方法,其特征在于:将冷却完成的从保温箱中取出的产品进行切断、研磨、钻孔冷加工处理,最终得到耐火制品成品。
4.根据权利要求1所述的熔铸耐火制品制备方法,其特征在于:制备氧化锆耐火制品的原料中:氧化锆含量之和为87%-95%,氧化硅含量之和为3%-11%,Na2O+Al2O3+TiO2+Fe2O3+K2O≤2%。
5.根据权利要求1-4任一方法制备的熔铸耐火制品。
6.根据权利要求1-4任一方法制备的熔铸耐火制品的应用,其特征在于:在砌筑玻璃窑炉的内衬时,把熔铸耐火制品靠近离心转盘中心的一面朝向窑炉内部砌筑。
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