CN103930385A - 可浇注耐火组合物 - Google Patents

可浇注耐火组合物 Download PDF

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CN103930385A
CN103930385A CN201280050970.1A CN201280050970A CN103930385A CN 103930385 A CN103930385 A CN 103930385A CN 201280050970 A CN201280050970 A CN 201280050970A CN 103930385 A CN103930385 A CN 103930385A
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weight
fire proofing
approximately
pourable
proofing composition
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CN103930385B (zh
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J·苏迪尔
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Calderys France SAS
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Calderys France SAS
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Abstract

本发明涉及可浇注耐火组合物、耐火内衬和由其形成的物品以及由所述可浇注耐火组合物安装耐火材料的方法。

Description

可浇注耐火组合物
技术领域
本发明涉及可浇注耐火组合物、耐火内衬和由其形成的物品以及由所述可浇注耐火组合物安装耐火材料的方法。
背景技术
耐火材料(refractory)是具有使其在高温应用中适合用作耐热性屏障的性质的材料。未经成型的耐火材料具有形成无结点内衬的能力，且通常称为单片型(monolithic)。这些材料可用作例如以下的衬底：包含或引导流体或者适于辅助液体金属和矿渣或者任何其它高温液体、固体或气体的工业处理的冲天炉炉底(cupolas hearth)和虹吸管、鼓风炉、主流道、次级流道和倾斜流道，且更一般而言，容器或容器喷嘴、钢包、中间包(tundish)、反应室和反应槽。未经成型的耐火材料通常制造为粉末形式，并在应用之前与水混合。通过应用诸如浇注、喷洒和喷补并继以凝固(setting)和干燥随后加热等技术，可将湿材料应用作为内衬。
任何耐火材料的一个重要方面在于其在凝固后安全快速干燥的能力。因此，湿材料应该具有在加热时的干燥过程中对气体尤其是水蒸气的高渗透性。因此，某些耐火材料、特别是专用于厚型高导热性内衬(例如，含单片的碳和/或SiC)或者要求在热条件(即，100℃至800℃)下的极快内衬试运行(commissioning)或安装的应用的那些耐热材料利用下述成分来制备：所述成分在润湿和凝固过程中放出可燃性氢气，后者产生孔、空洞和微裂隙，而这进而增加了对气体的渗透性，因此使得在加热期间水能快速干燥蒸发。通常，耐火材料被制备来包括反应性金属成分，所述反应性金属成分在水存在时且在特定pH下会水解而生成氢气。
然而，由于在燃烧源的存在下，存在着凝固期间排放出的氢气在与来自空气的氧气混合时的偶发性爆炸的风险，因而氢气的排放存在安全问题。因此，理想的是能制备在凝固时不散发氢气的耐火材料。
然而，由于氢气的不存在以及预期的随之引起的对气体渗透性的降低，存在任何在安全性方面的改进可能被以下因素抵消的风险：耐火内衬在短时间内被干燥和加热至作业温度(service temperature)的能力的降低，或者对在热条件下将耐火材料安装在热基质上的能力方面的有害影响。例如，随着水蒸气在干燥期间能借之逃逸的孔和空洞的减少，因干燥期间在内衬内部的水蒸气压力的产生所导致的爆炸的风险会提高。
因此，存在对进一步的可浇注耐火材料的需求，所述可浇注耐火材料在凝固时不会排放显著量的氢气，并且与常规的氢气排放性耐火材料相比，其具有至少同样优良甚至更为改善的化学、物理、矿物学、热性质、试运行和/或安装性质。例如，试运行应该容易且快速，且安装应该尽可能的直接且不需要增加的复杂性，诸如要求使用特定的液体(如胶体悬浮液)或其它化学品(如磷酸、磷酸盐溶液、硅酸钠)和适于聚合的有机化合物以用于湿式混合。
发明内容
根据第一方面，提供了一种可浇注耐火组合物，其包含：
5重量%至95重量%的氧化铝、铝硅酸盐或其混合物；
可选的至多70重量%的碳化硅，
可选的至多10重量%的碳，
0.1重量%至5重量%的碱土金属氧化物和/或氰化物，和
0.1重量%至5重量%的表面积至少为10m2/g的二氧化硅；
其中，所述耐火组合物包括不多于约0.5重量%的胶结性粘结剂；
其中，在添加水时，所述耐火组合物不释放显著量的氢气；
其中，在添加水时，所述耐火组合物凝固。
根据第二方面，提供了可安装的耐火内衬，所述耐火内衬通过将第一方面的可浇注耐火组合物与2重量%至40重量%的水混合。
根据第三方面，提供了利用选自浇注、自流、湿锚喷(shotcreeting)、棒捣(rodding)、浇注-振动、喷洒、常规干式喷补或高密度喷补的技术随后进行凝固和干燥来安装本发明的第二方面的可安装耐火内衬的方法。
根据第四方面，提供了可通过第三方面的方法获得的安装的耐火内衬。所述内衬可以为用于以下的内衬：包含或引导流体或者适于辅助液体金属和矿渣或者任何其它高温液体、固体或气体的工业处理的冲天炉炉底和虹吸管、鼓风炉、主流道、次级流道和倾斜流道、容器或容器喷嘴、钢包、中间包、反应室和反应槽。
根据第五方面，提供了安装耐火材料的方法，该方法包括：将本发明的第一方面所述的可浇注耐火组合物与水混合，将混合物成形为物品(article)，使得所述物品凝固，并使所述物品干燥以除去过量的水。
根据第六方面，提供了可通过本发明的第五方面的方法获得的耐火物品。
本发明涉及适合用作耐火材料的混合物，例如，作为用于以下的内衬：包含或引导流体或者适于辅助液体金属和矿渣或者任何其它高温液体、固体或气体的工业处理的冲天炉炉底和虹吸管、鼓风炉、主流道、次级流道和倾斜流道，更一般而言，容器或容器喷嘴、钢包、中间包、反应室和反应槽。所述混合物还可以用于整体或部分地制造预成型物品，例如耐火砖和耐火坩埚。所述混合物的部分特征在于在其制备、与水混合、安装和凝固的过程中不存在显著的气体排放，特别是可燃性氢气，这使得其特别适于改善安装和使用了该耐火材料的工业硬件的安全性。特别地，通过适当选择或省略金属或矿物添加剂，本发明的可浇注耐火组合物抑制或防止了如铝等金属物品的反应。虽然不存在气体(特别是氢气)的排放，所得到的耐火材料仍可安装于热基质上并进行快速安全的干燥和加热。耐火材料的部分特征在于干燥期间对气体和水蒸气的高渗透性、游离水的高比例和凝固后保留的水合的水的低比例、以及凝固后的高机械强度。这些性质的组合抑制或防止了在干燥和加热至工作温度的过程中裂隙的形成、散裂(spalling)或内衬爆炸。因此，由所述可浇注耐火组合物形成的内衬能被成功地用在下述的安装中：所述安装通常要求使用氢气排放性耐火材料或者在与胶体悬浮液或其它化学物质(如磷酸或磷酸盐溶液)混合后安装的耐火材料，以便与要求短的试运行时间和安全干燥的安装相匹配。
附图说明
图1是用于测定来自润湿的可浇注耐火组合物的氢气排放的测定步骤的示意图。
图2是用于测定浇注样品的气体渗透性的组装体的截面示意图。
具体实施方式
根据上文所述的第一方面，提供了一种可浇注耐火组合物。可浇注是指耐火组合物可以在添加水、凝固和干燥而除去过量水后被形成为无接缝或未定型的产品。
基于可浇注耐火组合物的总干重，可浇注耐火组合物包含约5重量%至95重量%的氧化铝、铝硅酸盐或其混合物。在一个实施方式中，可浇注耐火组合物包含约30重量%至95重量%、例如约、例如约30重量%至80重量%、例如约30重量%至70重量%、例如约40重量%至70重量%、例如约50重量%至70重量%、例如约60重量%至70重量%的氧化铝，或者例如约50重量%至60重量%的氧化铝、铝硅酸盐或其混合物。
氧化铝、铝硅酸盐或其混合物包含选自以下的材料：棕刚玉、烧结氧化铝、白刚玉、煅烧氧化铝、反应性或半反应性氧化铝、铝土矿、熔铸或烧结莫来石、红柱石和具有30重量%至75重量%的氧化铝含量的煅烧熟料
氧化铝、铝硅酸盐或其混合物可以包含尺寸至多为约30mm的颗粒、基本由所述颗粒组成或由所述颗粒组成，所述颗粒的尺寸通过适当尺寸的分子筛来确定。在实施方式中，氧化铝、铝硅酸盐或其混合物包含尺寸至多为约10mm、至多为约6mm、至多为约4mm、至多为约2mm或至多为约1mm的颗粒、基本由所述颗粒组成或由所述颗粒组成。
在其中可浇注耐火组合物包含的煅烧氧化铝为基于该可浇注耐火组合物的总干重的至多15重量%的实施方式中，所述煅烧氧化铝可以包含d50为至多约100μm、例如至多约50μm或例如约1μm至约10μm的颗粒。可以包含煅烧氧化铝作为成分，以调节或增强可浇注体一旦与水混合后的流动特性。包含其也可以是为了控制和调节整个混合物的粒径分布。
除非另外声明，平均(均)等同粒径(d50值)在本文中是指，利用由MicromeriticsInstruments Corporation(Norcross,Georgia，美国(电话：+17706623620；网址：www.micromeritics.com))所供应的Sedigraph5100机(本文称作“MicromeriticsSedigraph5100单元”)通过在水性介质中完全分散的条件下对颗粒材料的沉降而以公知方式测得。此类机器提供了具有某粒径(在本领域中称作“等同球直径”(esd))、小于给定的esd值的颗粒的累计重量百分比的测定值和图。平均粒径d50是以该方式确定的颗粒esd的值，该值是存在50重量%的其等同球直径小于该d50值的颗粒时的值。
在其中可浇注耐火组合物包含的反应性或半反应性氧化铝为基于该可浇注耐火组合物的总干重的至多15重量%的实施方式中，所述反应性或半反应性可包括最大粒径为至多约50μm、例如至多约25μm或d50为约0.5μm至5μm的颗粒。可以包含反应性或半反应性氧化铝作为成分，以调节或增强可浇注体一旦与水混合后的流动特性。包含其也可以是为了控制和调节整个混合物的粒径分布。
有利的是，基于可浇注耐火组合物的总干重，可浇注耐火组合物可以包含至多约70重量%的碳化硅、例如约5重量%至70重量%的碳化硅。在一个实施方式中，可浇注耐火组合物包含约10重量%至50重量%、例如约10重量%至40重量%、例如约15重量%至40重量%、例如约20%至40%、例如约20重量%至30重量%的碳化硅。
碳化硅可以包含尺寸至多为约30mm的颗粒、基本由所述颗粒组成或由所述颗粒组成，所述颗粒的尺寸通过适当尺寸的分子筛来确定。在实施方式中，碳化硅包含尺寸至多为约10mm、至多为约8mm、至多为约6mm、至多为约4mm、至多为约2mm、至多为约1mm的颗粒、至多为约0.5mm的颗粒或至多为约0.2mm的颗粒、基本由所述颗粒组成或由所述颗粒组成。在其它实施方式中，碳化硅包含d50为至多约300μm的颗粒、基本由所述颗粒构成或由所述颗粒构成。碳化硅可以包含d50为至多约200μm、例如至多约100μm、例如d50为至多约60μm的颗粒、基本由所述颗粒构成或由所述颗粒构成。
有利的是，基于可浇注耐火组合物的总干重，可浇注耐火组合物可以包含至多约10重量%、例如约1重量%至10重量%的碳。在一个实施方式中，可浇注耐火组合物包含约1重量%至5重量%、例如约1重量%至4重量%、例如约2重量%至3重量%的碳。所述碳可以包括选自以下的材料：炭黑、石墨、焦炭、在焦化后具有至少约5重量%的碳残留物的固体烃或者它们的组合。在一个实施方式中，碳包括石墨和炭黑的混合物。
石墨可以是单晶或多晶石墨(也称作“无定型石墨”)，并且可以包括由适当尺寸的分子筛确定的尺寸至多为约1mm的颗粒。
炭黑可以包括d50为至多约100μm、例如至多约75μm、例如至多约50μm的颗粒。炭黑的颗粒可以具有约50m2/g的最大比表面积(利用BET比表面积测定法通过氮气吸附而确定)，并且在1000℃的燃烧损失(LOI)为至少90重量%。
焦炭可以包括由适当尺寸的分子筛确定的尺寸至多为约2mm的颗粒，且在1000℃的LOI至少为80重量%。
固体烃可以在焦化后具有至少约10重量%的碳残留物。固体烃可以处于粉末形式，该粉末形式包括由适当尺寸的分子筛确定的尺寸至多为约2mm的颗粒，或者所述固体烃可以处于0.5mm以上的聚集体(aggregates)的涂层的形式。固体烃的实例有地沥青(bitumens)、石油沥青(asphalts)、苯酚类树脂以及合成聚合物或低聚物。
在一个实施方式中，可浇注耐火组合物包含约5重量%至70重量%的碳化硅和约1重量%至约10重量%的碳。在另一个实施方式中，可浇注耐火组合物包含约5重量%至70重量%的碳化硅并且基本不含碳。在再一个实施方式中，可浇注耐火组合物包含约1重量%至约10重量%的碳并且基本不含碳化硅。
基于可浇注耐火组合物的总干重，可浇注耐火组合物包含约0.1重量%至5重量%的碱土金属氧化物和/或氢氧化物。碱土金属氧化物和/或氢氧化物是在添加水时和凝固过程中的粘结剂的成分。在一个实施方式中，可浇注耐火组合物包含约0.1重量%至4重量%的碱土金属氧化物和/或氢氧化物、例如约0.1重量%至3重量%的碱土金属氧化物和/或氢氧化物、例如约0.1重量%至2重量%的碱土金属氧化物和/或氢氧化物、例如约0.1重量%至1.5重量%或者例如约0.5重量%至1.5重量%的碱土金属氧化物和/或氢氧化物。在一个实施方式中，碱土金属氧化物和/或氢氧化物是镁、钙或钡的氧化物和/或氢氧化物或者它们的混合物。在一个实施方式中，碱土金属氧化物和/或氢氧化物是氧化镁和/或氢氧化镁。在一个实施方式中，氧化物包含部分水合的氧化镁、基本由其组成或由其组成。在另一个实施方式中，碱土金属氧化物和/或氢氧化物是氢氧化钙和/或氧化钙。在另一个实施方式中，碱土金属氧化物和/或氢氧化物是氧化钡和/或氢氧化钡。碱土金属氧化物和/或氢氧化物可以包括d50小于约100μm、例如d50小于约75μm或者d50小于约50μm的颗粒、由其组成或基本由其组成。
可浇注耐火组合物包含0.1重量%至5重量%的表面积为至少约10m2/g的二氧化硅，所述表面积为利用BET比表面积测定法通过氮气吸附而测定。在一个实施方式中，可浇注耐火组合物包含0.1重量%至4重量%的二氧化硅、例如约0.1重量%至3重量%的二氧化硅、例如约0.5重量%至3重量%的二氧化硅或例如约1重量%至3重量%的二氧化硅。二氧化硅的表面积可以为至少约20m2/g、例如至少约50m2/g、例如至少约100m2/g或例如至少约200m2/g。在一个实施方式中，二氧化硅的表面积不超过500m2/g。在一个实施方式中，二氧化硅选自由气相二氧化硅(也称为热解二氧化硅)、硅灰(也称作氧化硅蒸气)、微细二氧化硅、微研磨二氧化硅和沉淀二氧化硅组成的组。表面积为至少约10m2/g的二氧化硅与碱土金属氧化物或氢氧化物和水同是粘结剂的成分。
可浇注耐火组合物包含不多于0.5重量%的胶结性粘结剂，例如，不多于约0.5重量%的铝酸钙胶结剂和/或硅酸钙胶结剂。在一个实施方式中，可浇注耐火组合物包含不多于0.25重量%的胶结性粘结剂、不多于0.25重量%的铝酸钙胶结剂和/或硅酸钙胶结剂。在另一个实施方式中，可浇注耐火组合物包含不多于0.1重量%的胶结性粘结剂、例如不多于0.1重量%的铝酸钙胶结剂和/或硅酸钙胶结剂。在再一个实施方式中，可浇注耐火组合物基本不含胶结性粘结剂、例如基本不含铝酸钙胶结剂和/或硅酸钙胶结剂。
根据第一方面，耐火组合物在添加水时不会释放出显著量的氢气。“添加水时不会释放出显著量的氢气”是指，根据以下测定程序，可浇注耐火组合物在与水混合后即刻产生少于25cm3氢气/千克润湿的可浇注耐火组合物，即氢气排放量小于约25cm3H2/kg润湿的可浇注耐火组合物，例如小于约15cm3H2/kg，或例如小于约10cm3H2/kg润湿的可浇注耐火组合物。在一个实施方式中，在根据参考图1描述的以下程序进行测定时，无法检测到氢气排放。
在将可浇注耐火组合物与水混合后，立即根据EN1402，准确称取约300g的所得湿产物(2)并置于可密封的接受体(4)内。用合适的密封装置(例如，橡胶塞)将接受体(4)密封，并经管(8)连接至容器(10)和装有水(14)的柱体(12)。通过合适的称重装置对水柱(12,14)连续称重。温度为20℃且压力为1atm，且在该程序期间保持恒定。如果释放氢气(18)，气体(18)将从柱体(12)中排出水(14)。将水柱(12,14)的重量损失用来计算在72小时的时段内的累积氢气排放量，其以cm3氢气/kg润湿的可浇注耐火组合物表达。
在添加合适量的浇注用水后，可浇注耐火组合物凝固。合适量的水将根据可浇注耐火组合物的确切组成、其规定用途以及耐火材料的安装方法而变化。
在一个实施方式中，基于可浇注耐火组合物的总干重，添加约2%至40%的水。例如，当将使用常规干式喷补技术来安装耐火材料时，向可浇注耐火组合物添加约10重量%至40重量%的水。例如，当将使用浇注或喷雾浇注技术来安装耐火材料时，向可浇注耐火组合物添加约2重量%至8重量%的水。例如，当将使用高密度喷补技术(如FR2798092和FR2798091所述)来安装耐火材料时，向可浇注耐火组合物添加约5重量%至20重量%的水。
在实施方式中，基于可浇注耐火组合物的总干重，可浇注耐火组合物与约2重量%至30重量%的水、例如约2重量%至20重量%的水、例如约12重量%至10重量%的水、例如约5重量%至30重量%的水、例如约10重量%至30重量%的水、例如约2重量%至20重量%的水、例如约5重量%至20重量%的水、例如约10重量%至20重量%的水、例如约2重量%至10重量%的水或例如约3重量%至7重量%的水混合。
可浇注耐火组合物还可以包含约0.01重量%至约3重量%的固体粉末有机添加剂、例如约0.05重量%至约3重量%或例如约0.05重量%至约2重量%的固体粉末有机添加剂。这些添加剂可以用作分散剂(例如，用来将微细或高比表面积的疏水性成分分散在水中，并由此使得能够在添加最少的水时调节可浇注体的流动)或用于调节与水混合的可浇注体的凝固时间和作用时间。固体粉末添加剂可以选自聚丙烯酸酯、聚二醇、聚二醇醚、羧酸醚、聚蜜胺、聚萘、醚、柠檬酸、水合柠檬酸、柠檬酸盐及其混合物。
可浇注耐火组合物还可以包含约0.01重量%至约3重量%的固体可溶性矿物添加剂，例如约0.05重量%至约3重量%或例如约0.05重量%至约2重量%的的固体可溶性添加剂。这些添加剂可以用作分散剂(例如，用来将微细或高比表面积的疏水性成分分散在水中，并由此使得能够在添加最少的水时调节可浇注体的流动)或用于调节与水混合的可浇注体的凝固时间和作用时间。固体粉末添加剂可以选自磷酸钠、铝酸钠、硼酸、硅酸钙、铝酸钙及其混合物。
基于可浇注耐火组合物的总干重，可浇注耐火组合物还可以包含至多约5重量%的金属添加剂。金属添加剂包括铝、硅、镁、铁、铬、锆、其合金以及它们的混合物。金属添加剂可以为粉末形式。在一个实施方式中，可浇注耐火组合物包含小于约4重量%、例如小于约3重量%、例如小于约2重量%、例如小于约1重量%、例如小于约0.75重量%、例如小于约0.5重量%、例如小于约0.25重量%的金属添加剂。如下文所注明，在一个实施方式中，可浇注耐火组合物基本不含金属添加剂。
添加剂可以被包含在可浇注耐火组合物中以便抑制或防止碳氧化。因此，在一个实施方式中，基于可浇注耐火组合物的总干重，可浇注耐火组合物可以包含至多约5重量%的一种或多种抑制或防止碳氧化的添加剂。在一个实施方式中，所述添加剂选自由氮化铝、氧氮化铝、碳化硼、碳化锆、碳化钙、包括铝、硅、镁、铁、铬、锆、其合金以及它们的混合物在内的金属组成的组。在一个实施方式中，一种或多种抑制或防止碳氧化的添加剂不是金属性的。在另一个实施方式中，可浇注耐火组合物包含不多于约4重量%的所述一种或多种添加剂、例如不多于约3重量%的所述一种或多种添加剂、例如不多于约2重量%的所述一种或多种添加剂或者例如不多于约1重量%的所述一种或多种添加剂。
如果所包含的金属添加剂具有在添加水时足以产生水解反应的反应性，则可以通过避免水与金属颗粒物的直接接触来抑制或防止氢气的生发。直接接触可以通过用防渗非反应性材料涂布金属颗粒物来避免。涂层可以在将金属添加至可浇注耐火组合物之前施涂，或者在制备可浇注耐火组合物过程中原位进行。
基于可浇注耐火组合物的总干重，可浇注耐火组合物还可以包含至多约1.0重量%的有机纤维。有机纤维可以改善在凝固和干燥期间的组合物强度以及抑制或消除干燥时裂纹的出现。有机纤维在耐火材料的烧制期间被消除，这导致创建了小毛细管网络，小毛细管网络可提高水的排出。在一个实施方式中，耐火可浇注组合物包含至多约0.8重量%的有机纤维、例如至多约0.5重量%、例如至多约0.3重量%、例如至多约0.2重量%或例如至多约0.1重量%的有机纤维。在其它实施方式中，可浇注耐火组合物包含少于约0.1重量%的有机纤维，例如少于约0.05重量%的有机纤维。有机纤维包括聚丙烯、聚丙烯腈或聚乙烯醇纤维、源自任何合适的来源(诸如椰子、木材、草本(例如，甘蔗、竹)、织物废料、棉花、大麻、亚麻或亚麻布)的天然纤维及其组合。如下文所述，在一个实施方式中，可浇注耐火组合物基本不含有机纤维。
如本文所用，术语“基本不含”是指完全不存在或者近于完全不存在特定的化合物或组合物。例如，当说组合物基本不含氧化锆时，或者在组合物中不存在氧化锆，或者在组合物中仅有痕量的氧化锆。本领域技术人员可以理解，痕量是可以被检测到但无法定量的量，而且，当存在时，不会对可浇注耐火组合物或由此形成的物品的性质产生负面影响。
因此，在其它实施方式中，耐火组合物基本不含一种或多种的以下物质：
(a)氧化锆；
(b)锆砂(硅酸锆)；
(c)沥青(pitch)；
(d)焦油；
(e)基本不含氧化钙的水力凝固化反应性氧化铝，称作“水合性氧化铝”或ρ-氧化铝；
(f)尖晶石，在将耐火材料浇注前；
(g)红柱石；
(h)金属添加剂，其在水存在时能够水解而形成氢气；例如，铝、硅、镁和镁合金；和
(i)有机纤维(如上所述)。
在其它实施方式中，本发明不会利用、依赖于或涉及以下粘结体系中的一种或多种：
(j)胶体氧化铝悬浮液和/或胶体二氧化硅悬浮液，其用作制备可安装产品的液体添加物，从而允许在通过胶体分散体的去稳定化和凝胶化进行安装后可浇注混合物的硬化和凝固；
(k)如磷酸等酸，其与如氧化镁和氧化铝等氧化物或氢氧化物或者其它杂质反应从而导致交叉网络化(cross reticulation)；
(l)硅酸钠，其与酸(通过羟基硅酸盐的凝胶化而导致凝固)、盐(增加硅酸盐溶液的粘度和凝胶形成)或碱土金属氢氧化物(导致聚结)反应；
(m)磷酸铝，其在大于100℃时硬化或通过创建Mg和/或P水合物网络而在较低温度与如氧化镁等氧化物反应而形成键；
(n)多糖类水溶性聚合物；
(o)会导致有机成分的网络化、聚合或共聚的物质，所述有机成分在存在时会在所述物质的存在下网络化、聚合或共聚；和
(p)基本不含氧化钙的反应性氧化铝(称作水合性氧化铝或ρ-氧化铝)的水合。
根据上文所述的第二方面，本发明涉及通过将根据第一方面的上述可浇注耐火组合物与2重量%至40重量%的水混合而获得的可安装耐火内衬。“可安装(installable)”是指耐火内衬具有能够通过任何下文所述的方法来安装的形式。
根据上文所述的第三方面，本发明涉及利用选自浇注、自流、锚喷、棒捣、浇注-振动、喷洒、常规干式喷补或高密度喷补的技术并随后凝固和干燥来安装本发明的第二方面的可安装耐火内衬的方法。这些技术是本领域普通技术人员所公知的。
根据本发明的第二和第三方面，与可浇注耐火组合物混合的浇注水的量会根据可浇注耐火组合物的确切组成、其规定用途以及安装耐火材料的方法而变化。
例如，当利用常规干式喷补技术来安装耐火材料时，向可浇注耐火组合物添加约10重量%至约40重量%的水。
例如，当利用浇注或喷雾浇注技术来安装耐火材料时，向可浇注耐火组合物添加约2重量%至约8重量%的水。
例如，当利用高密度喷补技术来安装耐火材料时，向可浇注耐火组合物添加约5重量%至约20重量%的水。
在实施方式中，基于可浇注耐火组合物的总干重，将可浇注耐火组合物与约2重量%至30重量%的水、例如约2重量%至20重量%的水、例如约2重量%至10重量%的水、例如约5重量%至30重量%的水、例如约10重量%至30重量%的水、例如约2重量%至20重量%的水、例如约5重量%至20重量%的水、例如约10重量%至20重量%的水、例如约2重量%至10重量%的水或例如约3重量%至7重量%的水混合。
为了实现用于通过浇注、棒捣、浇注-振动、自流或锚喷而安装的干燥的可浇注耐火组合物的适当润湿，混合时间为约30秒至约10分钟，例如约30秒至约5分钟或者例如约30秒至约2分钟。合适的混合装置是本领域普通技术人员所公知的。
在一个实施方式中，凝固步骤(期间混合物硬化)包括在无需烧制的情况下使碱土金属氧化物和/或氢氧化物、表面积为至少10m2/g的二氧化硅(例如，硅灰)与水反应。
凝固时间为约1小时至约10小时，例如约2小时至约8小时，例如约3小时至约7小时，例如约4小时至约6小时，或者例如约4小时至约5小时。
如上文所述，可浇注耐火组合物与水的混合物可以释放少于25cm3氢气/千克混合物，例如少于15cm3H2/kg混合物，或例如少于10cm3H2/kg混合物。在一个实施方式中，通过本文所述的测定程序无法检测到氢气排放。
为减少或消除残留水而进行的干燥是根据对于本领域技术人员显而易见的常规程序进行的。通常，在安装期间，在大约环境温度(例如，约20℃)至800℃的温度在空气中进行干燥。
烧制(firing)(即将混合物在升高的温度加热以产生陶瓷/氧化物键)可以在大于约800℃、例如大于或等于约900℃、例如大于或等于约1000℃、例如大于或等于约1100℃、例如大于或等于约1200℃、例如大于或等于约1300℃、例如大于或等于约1400℃、例如大于或等于约1500℃或者例如大于或等于约1600℃的温度进行。
通过使用上文所述的可溶性粉末有机添加剂或可溶性矿物添加剂，可以调节可浇注耐火组合物与水的混合物的粘度。此类添加剂称作分散剂，通过直接吸附于颗粒表面上或使水悬浮性离子组合物改性而起到改变颗粒表面性质的作用。
如果混合物旨在通过浇注、浇注-振动、棍捣、自流或锚喷而安置，则该混合物在混合后可以具有根据EN1402测定为约50%至200%的流动性。在一个实施方式中，混合物的流动性为约100%至200%，例如约100%至150%。因此，在另一个实施方式中，可以利用上述可溶性粉末有机添加剂或可溶性矿物添加剂来调节混合后的混合物的流动性。
本发明还涉及可通过本发明的第三方面的方法而获得的安装的工厂内衬。所述内衬可以为用于以下的内衬：包含或引导流体或者适于辅助液体金属和矿渣或者任何其它高温液体、固体或气体的工业处理的冲天炉炉底和虹吸管、鼓风炉、主流道、次级流道和倾斜流道、容器或容器喷嘴、钢包、中间包、反应室和反应槽。
根据上述第四方面，本发明涉及安装耐火材料的方法，所述方法如上所述，包括：将根据本发明的第一方面的可浇注耐火组合物与水混合，将混合物形成为物品，使得所述物品可以凝固，干燥所述物品以除去过量的水，和可选地在升高的温度烧制所述物品。
如上所述，凝固步骤包括在无需烧制的情况下使碱土金属氧化物和/或氢氧化物、表面积为至少10m2/g的二氧化硅(例如，硅灰)与水反应。
根据上述第六方面，本发明涉及可通过本发明的第五方面的方法获得的耐火物品。由可浇注耐火组合物形成的耐火物品有很多且各式各样，包括例如整体或部分的预成型的物品，如耐火砖和耐火坩埚。
为避免疑问，本发明是涉及以下编号的段落中所描述的主题内容：
1.可浇注耐火组合物，其包含：
5重量%至95重量的氧化铝、铝硅酸盐或其混合物，
可选的至多70重量%的碳化硅，
可选的至多10重量%的碳，
0.1重量%至5重量%的碱土金属氧化物和/或氢氧化物，和
0.1重量%至5重量%的表面积为至少10m2/g的二氧化硅；
其中，所述耐火组合物包含不多于0.5重量%的胶结性粘结剂；
其中，所述耐火组合物在添加水时不释放显著量的氢气；且
其中，所述耐火组合物在添加水时凝固。
2.如段落1所述的可浇注耐火组合物，其还包含0.01重量%至3重量%的固体粉末有机添加剂。
3.如段落1或段落2所述的可浇注耐火组合物，其还包含0.01重量%至3重量%的可溶性矿物添加剂。
4.如前述编号的段落中任一项所述的可浇注耐火组合物，其还包含至多约1重量%的金属添加剂。
5.如前述编号的段落中任一项所述的可浇注耐火组合物，其还包含至多约5重量%的抑制或防止碳氧化的添加剂或添加剂组合。
6.如前述编号的段落中任一项所述的可浇注耐火组合物，其还包含至多0.5重量%的有机纤维。
7.如前述编号的段落中任一项所述的可浇注耐火组合物，其中所述氧化铝、铝硅酸盐或其混合物包含选自由以下组成的组的材料：棕刚玉(brown fused alumina)、烧结氧化铝、白刚玉(white fused alumina)、煅烧氧化铝、反应性或半反应性氧化铝、铝土矿、熔铸莫来石(fused mullite)或烧结莫来石、红柱石和具有30重量%至75重量%的氧化铝含量的煅烧熟料(calcined chamotte)。
8.如前述编号的段落中任一项所述的可浇注耐火组合物，其包含5重量%至70重量%的碳化硅和/或1%至10%的碳。
9.如前述编号的段落中任一项所述的可浇注耐火组合物，其中所述碳化硅包含尺寸至多为约30mm的颗粒。
10.如前述编号的段落中任一项所述的可浇注耐火组合物，其中所述碳包含选自炭黑、石墨、焦炭、在焦化后具有至少约5重量%的碳残留物的固体烃或其组合的材料。
11.如前述编号的段落中任一项所述的可浇注耐火组合物，其中表面积为至少约10m2/g的二氧化硅选自由气相二氧化硅、硅灰、微细二氧化硅、微研磨二氧化硅和沉淀二氧化硅组成的组。
12.如前述编号的段落中任一项所述的可浇注耐火组合物，其中所述碱土金属氧化物和/或氢氧化物是镁、钙、钡的氧化物和/或氢氧化物或其混合物。
13.如前述编号的段落中任一项所述的可浇注耐火组合物，其中所述组合物包含小于约0.5重量%的铝酸钙胶结剂和/或硅酸钙胶结剂。
14.如前述编号的段落中任一项所述的可浇注耐火组合物，其中所述耐火组合物基本不含氧化锆。
15.如前述编号的段落中任一项所述的可浇注耐火组合物，其中所述组合物在将耐火材料浇注前基本不含尖晶石。
16.如前述编号的段落中任一项所述的可浇注耐火组合物，其中所述组合物基本不含金属添加剂。
17.如前述编号的段落中任一项所述的可浇注耐火组合物，其中所述组合物基本不含有机纤维。
18.一种可安装耐火内衬，其通过将前述编号的段落中任一项所述的可浇注耐火组合物与2重量%至40重量%的水混合而获得。
19.一种安装段落18所述的可安装耐火内衬的方法，该方法利用选自浇注、自流、湿锚喷、棒捣、浇注-振动、喷洒、常规干式喷补或高密度喷补的技术并随后进行凝固和干燥。
20.如段落19所述的方法，其中所述凝固步骤包括在无需烧制的情况下使碱土金属氧化物和/或氢氧化物、表面积为至少10m2/g的二氧化硅与水反应。
21.如段落20所述的方法，其中所述混合物释放少于10cm3氢气/kg湿的可浇注耐火材料。
22.一种能够通过段落19-21中任一项所述的方法获得的安装的工厂内衬。
23.一种耐火材料安装方法，该方法包括：将段落1-17中任一项所述的可浇注耐火组合物与水混合，将混合物形成为物品，使所述物品凝固，将所述物品干燥以除去过量的水，和可选地将所述物品烧制。
24.一种能够通过段落23的方法获得的耐火物品。
现将参考以下非限制性实例对本发明进行说明。
实施例
实施例1
配制了4种可浇注体(A、B、C和D)并与水混合。组成数据总结在表1中。这些混合物适合用作以下应用的耐火内衬：引导液体金属和矿渣的流动的冲天炉炉底和虹吸管、鼓风炉、主流道、次级流道和倾斜流道、容器或容器喷嘴、槽的耐火内衬，或用于需要厚耐火内衬和/或热安装内衬和/或安全快速的干透和加热。
第一混合物(A)是典型的含有铝和硅金属粉末的超低胶结剂可浇注体，且因此在与水混合时产生氢。第二混合物(B)与混合物A相同，不同之处在于移除了铝和硅，并添加聚丙烯纤维。这是基于胶结剂的不释放氢的可浇注体的实例。第三和第四混合物(C和D)是根据本发明制备的无胶结剂且不释放氢的可浇注体。
调节固体粉末有机添加物和可溶性矿物添加物的分散和凝固时间变化，以对于所用的两种粘结体系提供类似的流动性和凝固时间，如表2所给出。
表1
对从较大的浇注件取中心部分得到的样品测定气体渗透性，所述浇注件预先在相对于浇注方向平行和垂直的方向上在表2中给定的温度进行了初步处理。对于耐火可浇注体的渗透性的测定，欧洲标准(EN993-4)中所描述的程序和美国标准(ASTM C577)中所述程序均不适用，除非将所述可浇注体烧制并且使其具有高于0.05×10-13m2的渗透性。因此，采用以下程序。组装体衍生自用于城市工程混凝土的组装体。所开发的设定(图2)相当类似。图2是穿过组装体的截面。组装体(1)包括由合适的固定装置(5)(例如，一对螺栓)保持在一起样品支撑构件(3)。以10N.m压在圆柱形样品(9)的底表面的轴向扁平橡胶环(7)留出直径为45mm的流动部分。样品在测试前以聚酯树脂(11)进行涂布。组装体还包括橡胶O型环(13)。使用4支毛细管流量计(未示出)来测定穿过可浇注样品(9)的极小流量，其测定范围为0.1cm3/分钟至100cm3/分钟。转子流量计(未示出)用于较高的流速。
对于不同的压降(输入压力为0.25MPa至0.6MPa，输出压力0.1MPa，样品厚度30mm)测定了处于稳态的氮气和氧气(80%N2–20%O2)的混合物的流速，以检测流动模式(滑流、粘性流或粘惯性流)。气体混合物穿过组装体和可浇注样品的方向由图2中的虚线箭头所指示。首先检验压降和测得的流速之间的关系以验证是否可以认为其为线性(即粘性流模式)。由此可以根据达西定律由斜率计算出渗透率值。这些达西渗透率值是表2中给出的值。
根据上文所述的方法测定氢气发生。
基于超低胶结键的两个配方(A和B)以及说明本发明的配方C和D展示出类似的润湿时间、流动和凝固时间。这说明了本发明的组合物可利用与超低胶结键配方相同的设备、相同的程序并以相同的容易程度通过浇注-振动法来混合和安装。
配方A由于因铝酸钙胶结剂的溶解所致的pH增加而展示出因金属粉末与水的水解反应所致的氢气排放。不含金属粉末的配方B、C和D没有释放可检测量的氢气。
在配方A中，凝固期间的氢气释放产生了孔、空洞和微裂隙。如上文所解释，这一公知机制起到增加对气体的渗透性的作用，并由此促进在加热期或在热基板上的安全安装过程中水的快速干燥。
配方B例示说明了一种其中渗透性通过由聚丙烯纤维烧尽所致的渗滤毛细管网络而得到提高的超低胶结剂可浇注体，在该配方B中，可以看出：(1)在110℃处理后的渗透性显著低于可浇注体A，和(2)渗透性仅在纤维熔融后增加。即使配方B的渗透性可通过使纤维熔融而增加，所造成的渗透性的增加也在这样的温度(>160℃)发生：在该温度可浇注体中所含的水大部分已转变为蒸气，因而太晚，以致于不允许容易且安全的水干燥。
表2
在配方C和D中，粘结体系令人惊讶地即使在110℃处理后仍导致特别高的气体渗透性，这表明了可浇注耐火组合物能快速安全干燥的能力。配方C和D还展示出比配方A和B更高的机械强度。该特定性质与高气体渗透性的结合将使得本发明的内衬能以更低的蒸汽散裂或内衬爆炸的风险而更快地干燥。此外，尤其是就爆炸风险的降低而言，氢气排放的不存在使得本发明的组合物与常规的超低类可浇注体相比可更安全的使用，所述爆炸风险产生自(1)干燥期间内衬内部的水蒸汽压的产生或(2)凝固期间释放的氢气在与空气中的氧气混合并呈递至意外燃烧源时的引爆。
实施例2
配制了10种可浇注体并与水混合。组成数据总结于表3中。调节有机添加物和可溶性矿物添加物的分散和凝固时间变化，以对于所用的两种粘结体系提供类似的流动性和凝固时间，如表4所给出。
在含有胶结剂和金属铝的配方2、3、6和8中，发生了水解反应并导致氢气的产生。可浇注体的凝固步骤期间的这种氢气释放导致对气体的渗透性的增加，而后者是可浇注体快速安全地干燥和加热的能力的控制性因素。在两个受测胶结剂粘结体(低胶结剂和超低胶结剂)中现象相同。释放氢气的胶结剂粘结样品(混合物第2和6号)中聚丙烯纤维的存在不影响在110℃处理后测定的气体渗透性。同样的纤维在不释放氢气的胶结剂粘结的可浇注体(混合物第1和5号)中的存在不将渗透性增加至与释放氢气的类型相当的水平，这是因为110℃的温度太低而无法实现纤维的熔融以及相互连接的毛细管网络的创建(这据预期会导致渗透性增加)。在受测的两种胶结剂类粘结体(低胶结剂含量和超低胶结剂含量)中，纤维的存在不因此而增加可浇注体安全快速地干燥的能力。
说明本发明的混合物9和10可利用与其它胶结剂类组合物相同的设备、相同的程序并以相同的容易程度通过浇注-振动法来混合和安装。混合物9和10不含纤维也不在凝固期间释放任何气体，但仍然显示出与释放氢气的混合物同样数量级的渗透性。这一性质使得基于本发明的内衬能够以更低的蒸气散裂或内衬爆炸的风险而更快地干燥。这种能力与氢气排放的不存在相结合使得本发明的可浇注体能比常规低或超低胶结剂类可浇注体更安全地使用。

Claims (18)

1.一种可浇注耐火组合物，其包含：
5重量%至95重量%的氧化铝、铝硅酸盐或其混合物，
可选的至多70重量%的碳化硅，
可选的至多10重量%的碳，
0.1重量%至5重量%的碱土金属氧化物和/或氢氧化物，和
0.1重量%至5重量%的表面积为至少约10m2/g的二氧化硅；
其中，所述耐火组合物包含不多于0.5重量%的胶结性粘结剂；
其中，所述耐火组合物在添加水时不释放显著量的氢气；且
其中，所述耐火组合物在添加水后凝固。
2.如权利要求1所述的可浇注耐火组合物，其还包含至多约1重量%的金属添加剂。
3.如任何前述权利要求所述的可浇注耐火组合物，其还包含至多约5重量%的抑制或防止碳氧化的添加剂或添加剂的组合。
4.如任何前述权利要求所述的可浇注耐火组合物，其还包含至多0.5重量%的有机纤维。
5.如任何前述权利要求所述的可浇注耐火组合物，其中所述氧化铝、铝硅酸盐或其混合物包含选自由以下物质组成的组中的材料：棕刚玉、烧结氧化铝、白刚玉、煅烧氧化铝、反应性或半反应性氧化铝、铝土矿、熔铸或烧结莫来石、红柱石和具有30重量%至75重量%的氧化铝含量的煅烧熟料。
6.如任何前述权利要求所述的可浇注耐火组合物，其包含5重量%至70重量%的碳化硅和/或1%至10%的碳。
7.如任何前述权利要求所述的可浇注耐火组合物，其中所述碳化硅包含尺寸至多为约30mm的颗粒。
8.如任何前述权利要求所述的可浇注耐火组合物，其中所述碳包含选自炭黑、石墨、焦炭、在焦化后具有至少约5重量%的碳残留物的固体烃或其组合的材料。
9.如任何前述权利要求所述的可浇注耐火组合物，其中表面积为至少约10m2/g的二氧化硅选自由气相二氧化硅、硅灰、微细二氧化硅、微研磨二氧化硅和沉淀二氧化硅组成的组。
10.如任何前述权利要求所述的可浇注耐火组合物，其中所述碱土金属氧化物和/或氢氧化物是镁、钙、钡的氧化物和/或氢氧化物或其混合物。
11.如任何前述权利要求所述的可浇注耐火组合物，其中所述组合物包含小于约0.5重量%的铝酸钙胶结剂和/或硅酸钙胶结剂。
12.一种可安装耐火内衬，其通过将任何前述权利要求所述的可浇注耐火组合物与2重量%至40重量%的水混合而获得。
13.一种安装权利要求12所述的可安装耐火内衬的方法，该方法利用选自浇注、自流、湿锚喷、棒捣、浇注-振动、喷洒、常规干式喷补或高密度喷补的技术并随后进行凝固和干燥。
14.如权利要求13所述的方法，其中所述凝固步骤包括在无需烧制的情况下使碱土金属氧化物和/或氢氧化物、表面积为至少10m2/g的二氧化硅与水反应。
15.如权利要求14所述的方法，其中所述混合物释放少于10cm3氢气/kg湿的可浇注耐火材料。
16.一种通过权利要求13-15中任一项所述的方法获得的安装的工厂内衬。
17.一种耐火材料的安装方法，该方法包括：将权利要求1-11中任一项所述的可浇注耐火组合物与水混合，将混合物形成为物品，使所述物品凝固，将所述物品干燥以除去过量的水，和可选地将所述物品烧制。
18.一种能够通过权利要求17的方法获得的耐火物品。
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CN112341222A (zh) * 2020-11-11 2021-02-09 湖南湘钢瑞泰科技有限公司 一种铁水罐浇注料及其制作方法
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