CN101300207B - 表现出增强的抗热冲击性的烧结耐火产品 - Google Patents

表现出增强的抗热冲击性的烧结耐火产品 Download PDF

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CN101300207B
CN101300207B CN2006800407134A CN200680040713A CN101300207B CN 101300207 B CN101300207 B CN 101300207B CN 2006800407134 A CN2006800407134 A CN 2006800407134A CN 200680040713 A CN200680040713 A CN 200680040713A CN 101300207 B CN101300207 B CN 101300207B
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refractory products
oxide compound
weight percent
refractory
meter based
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CN101300207A (zh
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R·阿维蒂奇安
M·波波
T·尚皮翁
C·希斯
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Saint Gobain Centre de Recherche et dEtudes Europeen SAS
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Saint Gobain Centre de Recherche et dEtudes Europeen SAS
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Abstract

本发明涉及具有如下平均化学组成的烧结耐火产品，以基于氧化物的重量百分比计：20％＜Al2O3＜90％；6％≤SiO2＜30％；3％＜ZrO2＜50％；0％≤Cr2O3＜50％。本发明产品的特征在于其包含17-85重量％的莫来石-锆颗粒。

Description

表现出增强的抗热冲击性的烧结耐火产品
技术领域
本发明涉及表现出增强的抗热冲击性的新型烧结耐火产品。
发明背景
在耐火产品中，可区分出熔铸产品和烧结产品。
与烧结产品相反，熔铸产品最通常具有连接晶态颗粒的晶间玻璃态相。烧结产品和熔铸产品具有的问题以及解决它们的技术方案因此通常不相同。为制造熔铸产品所开发的混合物因此不是可先验地原样用于制造烧结产品，反之亦然。
烧结产品，根据它们的化学组成和制备模式，旨在用于广泛类别的工业应用。
烧结产品的例子具体包括：氧化铝-氧化锆-氧化硅产品(通常称为AZS)以及所谓的矾土产品，该矾土产品特别用于玻璃制造炉的某些区域。
诸如Emhary Industries的专利FR 2 552 756中描述的那些产品通常适用于这种用途。由Saint-Gobain SefPro制造并销售的产品如BPAL、ZA33或ZIRAL也特别适合并且目前广泛用于玻璃制造炉的某些区域中。
还由EP 0 404 610已知含单斜氧化锆的耐火混合物，由该耐火混合物可以获得表现出卓越抗热冲击性的产品。
然而，玻璃制造和发电工业需要表现出更大性能水平的耐火产品。
发明内容
因此本发明的目的是提供一种耐火产品，该产品表现出增强的抗热冲击性和热机械强度，与当前使用的耐火产品相似或更好的耐腐蚀性和孔隙率性能。
根据本发明，通过具有如下平均化学组成的烧结耐火产品实现了这个目的，以基于氧化物的重量百分比计：
20％＜Al2O3＜90％
2％＜SiO2＜30％
3％＜ZrO2＜50％
0％≤Cr2O3＜50％，
其特征在于该产品(以基于氧化物的重量百分比计)包含：17-85％的莫来石-氧化锆颗粒。
如下文所示，本发明的烧结耐火产品表现出令人惊讶的增强的抗热冲击性。
优选地，根据本发明的产品还具有一种或多种可选的下列特性：
-Al2O3、SiO2、ZrO2和Cr2O3含量的总和(以基于氧化物的重量百分比计)是94％或更大，优选98％或更大。据认为在这些条件下，其它氧化物的存在不会显著改变得到的结果。
-根据本发明的产品包含(以基于氧化物的重量百分比计)大于19％、优选大于24％、更优选大于30％和/或小于60％、且优选小于50％的莫来石-氧化锆颗粒。
-根据本发明的产品包含(以基于氧化物的重量百分比计)至少10％和/或至多33％的ZrO2。
-根据本发明的产品包含(以基于氧化物的重量百分比计)至少6％和/或至多18％的SiO2。
-根据本发明的产品包含(以基于氧化物的重量百分比计)至少50％和/或至多80％的Al2O3。
-根据本发明的产品包括大于99重量％，优选基本100重量％的氧化物。为此目的，优选起始进料中使用的所有原料均为氧化物，成形相所需的添加物除外。
-在一个实施方案中，根据本发明的产品包含少于0.5％的Cr2O3，且优选不包含或仅包含痕量的Cr2O3。这是因为这种氧化物在某些应用中是不希望的杂质，特别是当根据本发明的砌块(bloc)与某些熔融玻璃接触时。具体而言，其可能导致因起泡或着色现象引起熔融玻璃品质的降低。
-根据本发明的起始进料和产品都不包含金属硅，至少在根据本发明的产品意图用于玻璃制造应用中的情况下，因为金属硅与这样的应用不相容。出于相同的原因，根据本发明的产品优选不包含金属纤维。
-莫来石-氧化锆的颗粒尺寸处在0-3mm的范围内。
-根据本发明的产品优选包含(以基于氧化物的重量百分比计)至少3％、优选至少4％且更优选少于22％、优选少于10％、且优选少于6％的尺寸为0.7mm或更小的莫来石-氧化锆颗粒。
-根据本发明的产品优选包含(以基于氧化物的重量百分比计)至少1％、优选至少1.5％的尺寸为0.3mm或更小的莫来石-氧化锆颗粒。这导致抗热冲击性的显著改善。
-根据本发明的产品包含(基于氧化物)小于1重量％的MgO，且优选不包含MgO，除非以杂质形式，即其量小于0.5％且优选小于0.2％。
-根据本发明的产品在被放入其工作位置或安装之前已经被烧结，即并非原位烧结。
本发明还涉及根据本发明的耐火产品的用途，例如有待用作可消耗层或耐火衬里的用于成形熔融玻璃的成形耐火部件，特别是用于工业生产设备的燃烧室。
具体实施方式
“莫来石-氧化锆颗粒”意指通过烧结或熔融生产的耐火颗粒，该颗粒具有包含如下的化学组成(作为其主要组分)：氧化铝(Al2O3)、氧化硅(SiO2)和氧化锆(ZrO2)，其中氧化硅和氧化铝以2SiO2-3Al2O3(莫来石)的形式存在。因此(Al2O3)、氧化硅(SiO2)和氧化锆(ZrO2)是莫来石-氧化锆颗粒的三种主要组分(基于重量)。
“颗粒尺寸”是指其最大的尺寸。根据定义认为“颗粒”具有小于4mm的尺寸。
为了制造根据本发明的烧结砌块形式的耐火产品，即在放入其工作位置之前为成形的烧结部件，可以进行包含如下连续步骤的制造工艺：
a)制备起始进料；
b)将所述进料注入模具或通过在模具内振动和/或压制和/或夯实所述进料对其进行成型以形成预制件(preforme)；
c)将所述预制件从模具中取出；
d)干燥所述预制件，优选在空气或者水分受控制的气氛中使得预制件中的残余水分保持在0-0.5％；
e)在氧化性气氛中于1300-1800℃的温度下烧制所述预制件，以便形成根据本发明的烧结耐火砌块。
步骤a)至e)是为制造烧结产品而常规进行的步骤。
在步骤a)中，起始进料由多种原料制成，其化学组成和粒度分布可以变化。根据本发明，其包含(以基于耐火氧化物的重量百分比计)17-85％的莫来石-氧化锆颗粒，以及容许实现所需总组成的任何耐火材料，例如片状氧化铝，电熔融刚玉，锆石，氧化铬，特别是以粘土熟料形式烧结的氧化铬，电熔融材料，例如基于Al2O3-ZrO2-SiO2的电熔融材料，氧化铝，气相法白炭黑，单斜和/或稳定的氧化锆，氧化铬颜料等。
对起始进料进行确定使得在步骤e)之后得到的产品符合于本发明并进一步表现出根据本发明产品的优选特征中的一种或者优选几种。
起始进料优选包含(以基于氧化物的重量百分比计)至少1％、优选至少1.5％的尺寸为0.3mm或更小的莫来石-氧化锆颗粒。可以按任何适宜粒度的玻璃添加这些颗粒，例如但不限制于0-0.7mm、0-0.3mm或0-0.15mm。
该起始进料还可以包含一种或多种微粒或非微粒形式的添加剂，以便在成形步骤b)期间向起始进料提供足够的塑性并且用以向步骤d)结束时得到的预制件提供足够的机械强度。添加剂的量是非限制性的。特别地，常规用于已知烧结工艺的量是合适的。
可以通过添加剂引入某些氧化物。
可用添加剂的非限制性实例包括：
-暂时性的有机粘结剂(即在干燥和烧制步骤期间完全或部分消除的)例如树脂、纤维素或木纤维质衍生物，例如羧甲基纤维素、糊精、聚乙烯醇等。优选地，暂时性粘结剂的量相对于起始进料中的微粒氧化物混合物为0.1重量％至6重量％；
-化学粘结剂，例如磷酸、单磷酸铝等；
-水硬性粘结剂，例如矾土水泥，例如SECAR 71或CaO铝酸盐型的矾土水泥；
-抗絮凝剂，例如碱金属多磷酸盐或甲基丙烯酸酯衍生物；
-烧结促进剂，例如二氧化钛(以不超过组合物重量的约2％的比例)或氢氧化镁；
-成形助剂，例如镁或钙的硬脂酸盐；
-粘土基添加物，用以促进利用和辅助烧结。
根据粘土的类型，这些添加物引入氧化铝和氧化硅以及少量碱金属或碱土金属氧化物，或甚至氧化铁。
在该耐火混合物包含化学或水硬性粘结剂的情形中，这时其是一种在实际中可通过振动浇注使用的混凝土。
优选地，起始进料包含(基于氧化物的重量)少于1％的MgO，且更优选不包含MgO，除杂质形式以外，即少于0.5％、优选少于0.2％的量。由此使该工艺更简单。
为了在步骤e)结束时获得根据本发明的耐火产品，起始进料表现出如下平均化学组成，以基于耐火氧化物的重量百分比计：
20％＜Al2O3＜90％
2％＜SiO2＜30％
3％＜ZrO2＜50％
0％≤Cr2O3＜50％
并且包含17-85％的莫来石-氧化锆颗粒，这些百分比是按重量基于耐火氧化物。
通常还向起始进料中加入水。
持续进行各种起始进料组分的混合，直到获得基本均匀的起始进料。
在步骤b)中，对进料成形并放入模具中。
当通过压制进行成形时，400-800Kg/cm2的特定压力对于非塑性的糊料是适宜的。优选单轴或等静压地进行压制，例如使用液压。在其之前可有利进行手动或气动和/或振动夯实操作。
可以在适当高的温度下进行步骤d)中的干燥。优选地，在室温至200℃范围的温度下进行。该干燥通常持续10小时至一星期，取决于预制件的形式，直到预制件的残余水分含量小于0.5％。
然后烧制干燥的预制件(步骤e))以便将其烧结。该烧结操作对于本领域的技术人员是公知的。烧结对应于材料的热固结。其通常伴随着孔隙率的降低和尺寸收缩。
烧结温度取决于起始混合物的组成，但是在大多数情形中1300-1800℃的温度是适宜的。优选在氧化性气氛中且更优选在空气中进行烧结，优选在大气压力下。烧制持续时间(冷态到冷态约为1至15天)取决于材料并且还取决于要制造的耐火产品的尺寸和形状。
步骤e)将预制件转变成根据本发明的耐火产品，其特别适合作为用于成形熔融玻璃的成形耐火部件或者作为工业制造设备的燃烧室中的耐火砖。
通常，在烧制炉中烧制该预制件。
不同于原位烧结的产品，即被放在它们的工作位置之后(例如置于要保护的壁上之后)被烧结的产品，根据本发明的砌块由烧结炉内的烧结产生，因此在放置到工作位置之前，其每个侧面是以基本相同的方式被加热。因此，这防止了砌块外表面上的指定点位置上的任何温度梯度相关性。与原位烧结的产品相反，根据本发明的产品因此各处表现出均匀的密度和显微组织，因此导致对热冲击、水蒸气引起的腐蚀和对熔融玻璃引起的腐蚀的改良抵抗性。
然后可以直接使用根据本发明的耐火产品，或者根据本领域技术人员众所周知的技术在通过适当的膨胀连接组装之后进行使用。
确定耐火产品中成分的量的方式是本领域技术人员所熟知的。具体地，本领域的技术人员清楚，也可以在烧结耐火产品中发现莫来石-氧化锆颗粒以及存在于起始进料中的氧化物Al2O3、SiO2、ZrO2和Cr2O3。对于烧结耐火产品中相同量的成分，然而起始进料的组成可以根据这些量以及存在于所述进料中的添加剂的性质而改变。
为了进一步说明本发明，给出下面的非限制性实施例。
在这些实施例中，使用的原料选自：
-熔融莫来石-氧化锆颗粒，其包含大于99％的ZrO2+Al2O3+SiO2和35％的主要为单斜形式的氧化锆，所述颗粒具有0-3mm的尺寸。
-通过研磨电熔融耐火产品得到的具有0-20mm尺寸的颗粒，所述电熔融耐火产品是例如由SociétéEuropéenne des ProduitsRéfractaires生产并销售的ER-1681或ER-1711。这些产品包含(以基于氧化物的重量百分比计)：32-54％的ZrO2、36-51％的Al2O3、2-16％的SiO2和0.2-1.5％的Na2O；
-片状氧化铝颗粒，其包含大于99％的氧化铝并且具有40μm至3.5mm的尺寸；
-熔融或烧结的莫来石颗粒，例如包含76.5％的Al2O3和22.5％的SiO2并且颗粒尺寸为0.7-3mm的粉末；
-具有高氧化锆含量的产品，例如由SociétéEuropéenne desProduits Réfractaires生产并销售的CS10或CC10。这些产品包含超过99％的ZrO2并且氧化锆颗粒的中值直径(D50)为3.5μm；
-活性氧化铝或者多种活性氧化铝的混合物，其包含超过99％的Al2O3，活性氧化铝颗粒的中值直径为0.5-3μm；
-电熔融氧化铝，其具有0.04-0.5mm的颗粒尺寸；
-由SociétéEuropéenne des Produits Réfractaires销售的气相法白碳黑。这种玻璃态氧化硅包含超过93％的氧化硅(SiO2)并且可以按颗粒中值直径最高为1μm的粉末形式得到；
-水硬性水泥或多种水泥的混合物；优选使用具有高氧化铝含量的水泥，例如由Almatys销售的CA25。CA25包含78％的Al2O3和18％的CaO；
-锆石，其为砂形式或完全微粉化形式并且包含33％的氧化硅；
-碳酸钙Na2CO3；
-颜料形式的氧化铬，Cr2O3，其包含超过99％的铬(3)氧化物并且能够以中值直径为2μm的粉末形式得到。
根据上述方法制造烧结耐火砌块。
在步骤a)中，计量原料使得起始进料具有期望的平均矿物化学组成(按重量计)，然后在水和至少一种分散剂如磷酸钠的存在下进行混合。
然后将起始进料注入模具中以便形成具有足够机械强度可供操纵的生预制件。然后将其在110℃下干燥12小时。在1350℃或1630℃的温度下对预制件进行最终烧结以便形成耐火砌块。
从不同的砌块实施例取得样品以便制备125×25×25mm杆件形式的试样。
为了测量抗热冲击性能，采用被称为PRE III.26/PRE/R.5.1/78的标准化测试。该测试允许使用在一个或多个循环后抗弯强度的相对损失(ΔMOR)来评价热冲击行为，每个所述循环是将试样从室温(20℃)加热到1200℃的最大温度T，将试样保持在该温度T下持续30分钟然后将试样投入冷水中。
MOR是断裂模量。
在下面的表中，MOR20对应于在任何热冲击循环之前样品在20℃下的MOR值，而MORx循环对应于在“x”个热冲击循环之后的MOR值。
所测产品的组成以及它们的特性如表1所示。
表1
Figure S2006800407134D00091
*：本发明范围之外的实施例
这些结果示出在起始进料耐火混合物中需要超过17％量的莫来石-氧化锆颗粒以便获得抗热冲击性的显著改善。
这是因为，超出该限度，可注意到MOR的损失受到限制和/或MOR值在20℃下较大。
此外，进行测试以便评价在水蒸气腐蚀后的抗热冲击性。
因此，事先将样品保持在处于恒定水蒸气流速的炉中。在该处理之后，它们进行前面提到的抗热冲击性测试。结果列于表2中，其中MORcve是样品在水蒸气腐蚀之后、任何热冲击循环之前的MOR值。
表2
Figure S2006800407134D00101
注意到，即使根据本发明的产品经历水蒸气腐蚀之后，它们也导致抗热冲击性的提高。
此外，实施例11至17的产品表现出至少与对比产品相当的抗熔融玻璃腐蚀性。
下面的表3说明了尺寸小于0.7的颗粒存在的益处。
表3
Figure S2006800407134D00102
*：所指示的百分比是按重量基于总的组合物重量。
实施例A、B、C和D的比较证实了细粒度范围(0-0.7mm)对热冲击后的断裂模量以及对(特别是淬火之后的)ΔMOR的积极影响。实施例E和F证实了这种观察结果，并且优选所述粒度范围的含量为5％。
所使用的0-0.7mm范围内的莫来石-氧化锆颗粒混合物通常包含30-50重量％的小于0.3mm的颗粒。因此，实施例F包含1.5-2.5重量％的尺寸小于0.3mm的莫来石-氧化锆颗粒，相对于总的组合物重量。优选地，根据本发明的产品还包含至少1％、优选至少1.5％的尺寸为0.3mm或更小的莫来石-氧化锆颗粒，以基于氧化物的重量百分比计。
此外，其它测试显示添加莫来石-氧化锆颗粒的有益效果不受至少50％Cr2O3存在的影响(参见实施例20和21)。虽然不优选，但根据本发明的产品因此有利地且令人惊讶地容许高的Cr2O3含量。此外，添加Cr2O3可有利地改善对熔融玻璃腐蚀的抵抗性。
当然，前述实施方案只是实例，可以对这些实例进行修改特别是替换技术等同物，然而仍保持在本发明的范围内。

Claims (24)

1.砌块形式的耐火烧结产品，其具有下面的平均化学组成，以基于氧化物的重量百分比计：
20％＜Al2O3＜90％
2％＜SiO2＜30％
3％＜ZrO2＜50％
0％≤Cr2O3＜0.5％，
该产品包含17-85％的莫来石-氧化锆颗粒，至少1％的尺寸为0.3mm或更小的莫来石-氧化锆颗粒。
2.根据权利要求1的耐火产品，以基于氧化物的重量百分比计，该产品包含大于19％且小于60％的莫来石-氧化锆颗粒。
3.根据权利要求1的耐火产品，以基于氧化物的重量百分比计，该产品包含大于24％且小于50％的莫来石-氧化锆颗粒。
4.根据权利要求1的耐火产品，以基于氧化物的重量百分比计，该产品包含至少10％且至多33％的ZrO2。
5.根据权利要求1的耐火产品，以基于氧化物的重量百分比计，该产品包含至多18％的SiO2。
6.根据权利要求1的耐火产品，以基于氧化物的重量百分比计，该产品包含至少50％且至多80％的Al2O3。
7.根据权利要求1的耐火产品，其中以基于氧化物的重量百分比计，Al2O3、SiO2、ZrO2和Cr2O3含量的总和是94％或更大。
8.根据权利要求1的耐火产品，以基于氧化物的重量百分比计，该耐火产品包含大于19％且小于50％的莫来石-氧化锆颗粒，至少10％的ZrO2和小于0.5％的MgO。
9.根据权利要求1的耐火产品，以基于氧化物的重量百分比计，该耐火产品包含小于0.5％的MgO。
10.根据权利要求1的耐火产品，根据包含如下连续步骤的制造工艺制造该耐火产品：
a)制备适宜的起始进料，
b)将所述进料注入模具或通过在模具内振动和/或压制和/或夯实所述进料对其进行成型以形成预制件，
c)将所述预制件从模具中取出，
d)干燥所述预制件，
e)在氧化性气氛中于1300-1800℃范围的温度下烧制所述预制件。
11.根据权利要求1的耐火产品，该耐火产品在被放入其工作位置之前进行烧结。
12.根据权利要求1的耐火产品，该耐火产品包括大于99重量％的氧化物。
13.根据权利要求1的耐火产品，该耐火产品不包含金属硅和/或不包含金属纤维。
14.根据权利要求1的耐火产品，其中莫来石-氧化锆的颗粒尺寸处在0-3mm的范围内。
15.根据权利要求1的耐火产品，该耐火产品以基于氧化物的重量百分比计包含至少3％且小于22％的尺寸为0.7mm或更小的莫来石-氧化锆颗粒，和/或以基于氧化物的重量百分比计包含至少1％的尺寸为0.3mm或更小的莫来石-氧化锆颗粒。
16.根据权利要求1的耐火产品，以基于氧化物的重量百分比计，该耐火产品包含小于1重量％的MgO。
17.根据权利要求3的耐火产品，以基于氧化物的重量百分比计，该耐火产品包含至少10％且至多33％的ZrO2。
18.根据权利要求3的耐火产品，以基于氧化物的重量百分比计，该耐火产品包含至多18％的SiO2。
19.根据权利要求3的耐火产品，以基于氧化物的重量百分比计，该耐火产品包含至少50％且至多80％的Al2O3。
20.根据权利要求17的耐火产品，以基于氧化物的重量百分比计，该耐火产品包含至多18％的SiO2。
21.根据权利要求17的耐火产品，以基于氧化物的重量百分比计，该耐火产品包含至少50％且至多80％的Al2O3。
22.根据权利要求20的耐火产品，以基于氧化物的重量百分比计，该耐火产品包含至少50％且至多80％的Al2O3。
23.根据权利要求20的耐火产品，该耐火产品包含小于0.5％的Cr2O3。
24.根据权利要求1-23任一项的耐火产品作为用于成形熔融玻璃的成形耐火部件或者作为耐火砖或者作为耐火衬里的用途。
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