CN100564311C - 烧制的耐火陶瓷制品及用于其制备的配料 - Google Patents

烧制的耐火陶瓷制品及用于其制备的配料 Download PDF

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CN100564311C
CN100564311C CNB2005800047825A CN200580004782A CN100564311C CN 100564311 C CN100564311 C CN 100564311C CN B2005800047825 A CNB2005800047825 A CN B2005800047825A CN 200580004782 A CN200580004782 A CN 200580004782A CN 100564311 C CN100564311 C CN 100564311C
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B·布赫伯格
R·尼利卡
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Abstract

本发明涉及一种烧制的耐火陶瓷制品及一种可用于制备制品的配料。该配料(混合物)和制成的烧制制品是利用由MgO和Al2O3组成的尖晶石。

Description

烧制的耐火陶瓷制品及用于其制备的配料
本发明涉及一种烧制的耐火陶瓷制品及一种可用于制备该制品的配料。配料(混合物)和制成的烧制制品均是利用由MgO和Al2O3组成的尖晶石(下面称为MA尖晶石)。
大量的尖晶石适于制备耐火制品。这些尖晶石可作为烧结尖晶石(如通过在管式转炉或立式炉中烧结)或作为熔融尖晶石(如在电孤炉中)合成制备。
氧化镁尖晶石砖在矿物学上主要由方镁石(MgO)和MA尖晶石(MgO-Al2O3)组成并含至少40重量％的MgO。该MA尖晶石可经预合成加入或在“就地”煅烧期间由MgO添加物和Al2O3添加物形成(DE 3617904C2)。
含化学计量组成的MA尖晶石的烧制尖晶石制品与含非化学计量组成的尖晶石的制品相比，通常有较好的耐火特性，特别是改进的抗渣特性。以准确到两位小数点计算的MA尖晶石的化学计量组成为28.33重量％的MgO和71.67重量％的Al2O3。但在本发明范围内，考虑到工业规模的技术可能性，其每个组分与上述准确的化学计量组成的绝对偏差为±0.5重量％的所有组合物均归入“化学计量的MA尖晶石”中。即使使用这种惯例，在工业规模上仍特别难以再现地制备化学计量组成的MA尖晶石。
但在市场上越来越需求具有对浸蚀性渣的耐性的特别高质的产品。例如在来自造纸工业的碱液在所谓的黑液气化器中气化时，有机成分经煅烧，而强碱性盐的混合物保留在反应器中，并对反应器衬里的耐火材料产生影响。使用通常的基于α-β-刚玉的熔体浇注耐火制品时，会通过腐蚀和体胀导致快速磨损。渣强烈渗入已知的氧化镁砖中。
本发明的目的在于提供一种产品(制品)，该产品在工业上可再现地以优质制备，并具有对上述类浸蚀性渣的高耐性。
本发明在其最一般的实施方案中包括一种烧制的耐火陶瓷制品，其具有下列矿物学相：70-98重量％的化学计量的MgO-Al2O3尖晶石，1-15重量％的镁橄榄石，1-15重量％的方镁石，不超过10重量％的其它矿物学相，其总和为100重量％。
在优选的实施方案中，上述制品具有下列矿物学相：70-97重量％的化学计量的MgO-Al2O3尖晶石，1-10重量％的镁橄榄石，1-10重量％的方镁石，1-10重量％的ZrO2和/或至少一种Ca-Al氧化物相。
在优选的实施方案中，上述制品的密度大于3.35g/cm3。
本发明基于下面的考虑：
非化学计量组成的尖晶石，特别是MgO含量超过化学计量尖晶石的MgO含量的尖晶石，构成主要的配料组分。该MA尖晶石在制备耐火制品的烧制中应转变成基本上是化学计量组成的尖晶石。为此该混合物(配料)中要加入其它组分，这些组分在烧制中与MA尖晶石中的超化学计量的MgO含量反应，并由此使配料-尖晶石中的MgO含量下降到化学计量范围。
作为这种其它组分建议使用富铝红柱石(3Al2O3 x 2SiO2)。
在烧制中由这些组分(富含MgO的MA尖晶石和富铝红柱石)形成的耐火陶瓷制品的特性可按图1所示的三物质体系MgO-Al2O3-SiO2讨论。
由非化学计量的富含MgO的尖晶石和富铝红柱石组成的混合物的组成显示为虚线，其走向是在尖晶石组成之间即在MgO和MgO x Al2O3和富铝红柱石组成即3Al2O3 x 2SiO2之间。
在混合物烧制成耐火制品时的条件应如此控制，即使得在约1710℃可达到三元低共熔混合物。为此拟选择在共结三角方镁石(MgO)-MA尖晶石-镁橄榄石(2MgO x SiO2)内的混合物组成。
在上述低共熔混合物中，化学计量组成的尖晶石、镁橄榄石和方镁石彼此平衡。
以超化学计量存在的MgO以方镁石形式析出。
对在该混合物组分烧制和烧结时混合物的反应进程重要的是在烧结时中间出现的熔融相。借助于该熔融相得到密实的烧结制品，该制品可具有超过90％的该制品的理论纯物质密度。因此该熔融相对该烧制的制品的耐火性是重要的，因为在烧制中，特别是在烧结中该熔融相转变成高熔点的化合物。
在该混合物的富铝红柱石颗粒的邻近处可出现偏离该体系平均组成的组成。由此可出现熔融温度低于1710℃的局部组成，例如在1365℃的低共熔混合物范围内。高于此温度在此区域内可出现熔融相。该不同的组成通过扩散过程达平衡。局部偏离该体系平均组成的组成在非化学计量的富含MgO的原始尖晶石和富铝红柱石之间的虚线上向该体系平均组成方向变化。通过出现液相便于该平衡反应进行。
例如，富铝红柱石可作为烧结富铝红柱石或熔融富铝红柱石应用。重要的是将富铝红柱石至少部分现成地加到混合物中，并在该混合物烧制中最多是部分(就地)形成耐火制品。该混合物中的富铝红柱石含量为2-30重量％，例如下限为2或3或4重量％，上限为6或7或10重量％。
含过量MgO的MA尖晶石的含量为混合物的70-98重量％，例如80-98重量％，85-98重量％或92-96重量％。在非化学计量的尖晶石中的MgO含量例如可达40重量％，如下限为29、30、31或32重量％，上限为33-36重量％。下列示例性给出工业生产的非化学计量的尖晶石的组成：
MgO：          31.9重量％
Al2O3：        67.5重量％
CaO：          0.25重量％
Fe2O3：        0.20重量％
Na2O：         0.15重量％
               -------------------
               100.00重量％
该混合物可含次要成分如Fe2O3、CaO、SiO2、Na2O或K2O，可以是以杂质的形式。这些成分均不应超过2重量％。次要成分，特别是氧化物的总量＜5重量％。
该配料中除尖晶石和富铝红柱石外还可包括ZrO2或含ZrO2的组分。加到混合物中的二氧化锆几乎不受前述三物质体系中进行的反应的影响。但通过引入和微裂纹形成可改进该烧制制品(含ZrO2添加物)的结构弹性。由合成得到的或天然存在的ZrO2(斜锆石)均可用作二氧化锆组分。总混合物的含量可为1-10重量％，例如下限为1、2或3重量％，上限为5、6或7重量％。
下面示例性给出制备本发明混合物的方法：
首先研磨富含MgO的MA尖晶石，例如在振动磨中研磨。经研磨后该尖晶石可以下面的粒度存在：
d10：          0.9μm
d50：        4.6μm
d90：        14.1μm。
优选在任何情况下粒度＜50μm，优选＜30μm。
接着在尖晶石中混入烧结富铝红柱石，并在球磨机中一起研磨。在混合物中的各组分含量调节如下：
·非化学计量的富含MgO的MA尖晶石：93-97重量％
·烧结富铝红柱石：3-7重量％
·其它：达4重量％
之后在混合物中混入粘合剂，例如每100重量份的上述混合物中混入0.2-3重量份的聚乙烯醇，并在流化床造粒器中粒化。该颗粒(平均直径约1-5mm)的湿含量按总混合物计为1-2重量％。
然后将颗粒压制成所需形状，并干燥所形成的模制件。最后在约1700℃下烧制(烧结)该压制体，期间发生上述反应。
在应用上述实施例混合物时，该烧制的制品有下列组成：
  组分   重量％
  化学计量的MA尖晶石方镁石镁橄榄石   94.53.02.5
该产品密度为3.37g/cm3，其为理论密度3.58g/cm3的94％以上。
通常该烧制的制品中的化学计量的尖晶石的含量为70-98重量％，典型下限为70-85重量％，典型上限为90-98重量％或90-96重量％。
在烧制制品中镁橄榄石的含量示例性为1-15重量％，例如为1-7重量％，1.5-4重量％或1-5重量％。
在烧制制品中方镁石的含量可为1-15重量％，例如为1-8重量％，3-7重量％或2-5重量％。
在烧制制品中可能的ZrO2含量(来自配料或制造过程中的杂质)可为1-10重量％，例如1-7重量％或2-5重量％。
CaO杂质(如来自所用的原料尖晶石)在烧制的产品中可导致Ca-Al氧化物(如CaAl2O4，缩写为“CA”)。其它Ca-Al氧化物可能是：“C2A”、“CA2”、“C3A”、“C12A7”和/或“CA6”。
与已知产品相比，本发明的产品的优点列于图2-4。
用来自黑-液气化装置的相同量的渣充满各同样结构的坩埚，并在同样条件下于1100℃经48小时热负荷处理。
坩埚A(图2)由本发明的材料制成。其基本上无裂纹。渗入最少。未发生变形。
坩埚B(图3)为通常的刚玉-富铝红柱石质地。可看出渣完全渗入坩埚结构中。
坩埚C(图4)的材料由MgO+尖晶石组成。实验中通过形成β-刚玉使该坩埚假性“膨胀”。渣完全渗入坩埚中。

Claims (3)

1.一种烧制的耐火陶瓷制品，其具有下列矿物学相：
70-98重量％的化学计量的MgO-Al2O3尖晶石，
1-15重量％的镁橄榄石，
1-15重量％的方镁石，
不超过10重量％的其它矿物学相，
其中总和为100重量％。
2.权利要求1的制品，其具有下列矿物学相：
70-97重量％的化学计量的MgO-Al2O3尖晶石，
1-10重量％的镁橄榄石，
1-10重量％的方镁石，
1-10重量％的ZrO2和/或至少一种Ca-Al氧化物相。
3.权利要求1的制品，其密度大于3.35g/cm3。
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