CN101903305B - 混合物和由此制备的具有高抗水化性的耐火产品 - Google Patents

混合物和由此制备的具有高抗水化性的耐火产品 Download PDF

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CN101903305B
CN101903305B CN200880121108.9A CN200880121108A CN101903305B CN 101903305 B CN101903305 B CN 101903305B CN 200880121108 A CN200880121108 A CN 200880121108A CN 101903305 B CN101903305 B CN 101903305B
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mixture
powder
quality
carbon
shaped body
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CN101903305A (zh
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C·G·阿内其瑞斯
U·克利佩尔
C·托恩特拉普
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Tech Univ Ber Frei Inst Fuer K.
Evonik Operations GmbH
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TECH UNIV BER FREI INST fur K
Evonik Degussa GmbH
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Abstract

本发明公开了混合物，其包含a)一种或多种非常微细的平均粒径为2到100nm，BET表面积至少为30m2/g的二氧化硅粉末，b)一种或多种选自氧化物、碳化物和氮化物的颗粒组分，每一种的平均粒径为＞0.5μm到30mm，c)一种或多种作为粘合剂的合成树脂，和d)一种或多种平均粒径为＞0.5μm到250μm的金属抗氧化剂。本发明还公开了制备成形体的方法，其中将所述混合物引入塑模中，如果合适加压该塑模并将该塑模加热至所述合成树脂热交联的温度。本发明还公开了可由此获得的成形体。本发明还公开了制备耐火成形体的方法，其中将所述成形体碳化。本发明还公开了可由此获得的耐火成形体。

Description

混合物和由此制备的具有高抗水化性的耐火产品
本发明涉及混合物，由该混合物制备成形体的方法，以及成形体本身。
碳结合(carbon-bonded)的耐火产品在冶金容器中广泛用作衬里(例如作为转换器中的碳结合的氧化镁砖)，或作为关键组分(例如浸没式排出口(immersed discharge outlet)或滑块板或塞子或连续铸造中的浇道(pouringchannel))。
碳结合的耐火产品也用于高炉区、运输容器(例如铸勺)中，或在化学工业或废物焚化工业中作为耐热管，或在水泥工业中作为衬里材料。
陶瓷的碳结合膜或陶瓷的碳结合的挡热板是这种组分的其他实例。
加入抗氧化剂(例如金属粉末、硼化物粉末或氮化物粉末)可以改进耐火产品的氧化和热冲击性。这可通过抗氧化剂与粘合剂、炭黑或石墨反应形成纤维性金属碳化物来解释。
然而，现有技术没有公开如何使用金属抗氧化剂改进制成的含碳耐火产品的抗水化性。在碳化过程期间这些抗氧化剂和碳反应形成金属碳化物。这些碳化物可以在储存期间吸收水分，这可能导致耐火产品的体积膨胀和破坏。
本发明的目的在于提供使这些缺点最小化或完全避免这些缺点的碳结合的耐火产品。
此外，本发明的目的在于制备混合物，由该混合物可以制备耐火产品。
本发明提供混合物，其包含：
a)一种或多种非常微细的平均粒径为2到100nm，优选为7到60nm，BET表面积至少为30m2/g，优选BET表面积为30到100m2/g，尤其优选为30到500m2/g之间，最优选为40到400m2/g之间，
b)一种或多种选自氧化物、碳化物和氮化物的颗粒组分，每一种的平均粒径为＞0.5μm到30mm，
c)一种或多种作为粘合剂的合成树脂，和
d)一种或多种平均粒径为＞0.5μm到250μm的金属抗氧化剂。
在本发明的一个特别的实施方案中，混合物由具有特征a)到d)的组分组成。
在本发明的混合物中存在的非常微细的二氧化硅粉末可以聚集体和/或孤立的单个颗粒的形式存在。聚集体的单个颗粒称作初级颗粒。平均粒径基于单个的孤立颗粒或聚集体内的初级颗粒。二氧化硅粉末的来源不是关键性的。因此，本发明的混合物中可以存在通过溶胶凝胶法、沉淀法或火焰法获得的二氧化硅粉末。已发现混合物中存在通过火焰法制备的粉末(称作热解二氧化硅粉末)是有利的。热解二氧化硅粉末的初级颗粒特别没有孔且纯度高。
合适的热解二氧化硅粉末是
Figure BPA00001160068300021
Figure BPA00001160068300022
和
Figure BPA00001160068300023
均产自Evonik Degussa。另外，可以使用结构减小的改性二氧化硅粉末，如BET表面积在90和200m2/g之间的和
Figure BPA00001160068300025
或类似的类型。
二氧化硅粉末也可以是具有不同来源、不同BET表面积和/或不同粒径的粉末的混合物。
所述非常微细的二氧化硅粉末也可以表面改性的形式存在。因此，可通过卤化有机硅烷、烷氧基硅烷、硅氮烷、硅氧烷或聚硅氧烷改性表面。硅烷化剂可优选为三甲氧基辛基硅烷[(CH3O)3-Si-C8H17]、八甲基环四硅氧烷或六甲基二硅氮烷。
所述非常微细的二氧化硅优选用作粉末。然而，也可以使用有机分散液。此处有机物包括例如醇和二醇。所述分散液的二氧化硅含量应很高。基于所述分散液，二氧化硅含量优选为至少15重量％。理想地，就在长时间内的凝胶化和沉淀而言，所述分散液应当是稳定的。这可通过例如加入添加剂来实现。
所述非常微细的二氧化硅粉末在本发明的混合物中的比例尤其取决于颗粒组分、含碳粘合剂和抗氧化剂的类型及它们的比例。通常，基于所述混合物的颗粒组分，所述非常微细的二氧化硅粉末的比例为0.01～5质量％，优选为0.1～1质量％。
所述混合物的颗粒氧化物组分可优选自：氧化镁、氧化钙、白云石、氧化铝、氧化钇、二氧化锆、锆莫来石(zirconium mullite)、镁-铝尖晶石、矾土、上述材料的物理混合物和上述材料的化学混合物。特别优选的颗粒氧化物组分是氧化镁。
所述颗粒组分也可选自：碳化硅、氮化硅、氮化硼和上述材料的混合物。
所述混合物的另一重要成分是合成树脂。这可优选为酚醛树脂、酚醛清漆(novolak)、或甲阶酚醛树脂(resol)。
此外，根据本发明的混合物可包含石墨或炭黑形式的碳、合成沥青、沥青(pitch)、柏油(bitumen)和它们的混合物。
基于所述混合物的颗粒组分，合成树脂(如果合适，包括碳、合成沥青、沥青和柏油)的比例优选为0.5到20质量％。基于所述混合物的颗粒组分，特别优选1到5质量％的比例。
此外，本发明的混合物含有一种或多种金属抗氧化剂。这些优选选自铝、铁、镁、硅和钛的粉末。基于所述混合物的颗粒组分，所述抗氧化剂在本发明的混合物中的比例可优选为0.5～5质量％。
另外，本发明的混合物可另外含有至少一种其他成分，所述其他组分选自二氧化钛、钛铁矿、FeTiO3、CaTiO3、MgTiO3和BaTiO3。基于所述混合物的颗粒组分，这些成分的总比例优选为0.01～5质量％，尤其优选为0.1～1质量％。这些成分的粒径优选为2nm到5μm。
特别优选下面的混合物，其包含：
-0.1～2质量％的平均粒径为7到50nm，BET表面积为40到400m2/g的热解二氧化硅粉末作为非常微细的组分，和
-平均粒径为1μm到10mm的氧化镁作为颗粒组分，
-1～5质量％的酚醛树脂、酚醛清漆或甲阶酚醛树脂作为合成树脂，和
-平均粒径为1～100μm的铝粉作为抗氧化剂，
-各个百分数均基于所述混合物的颗粒组分。
本发明还提供制备耐火成形体的方法，其中如果合适，向本发明的混合物中加入至少一种硬化剂，将混合物引入塑模中，如果合适加压该塑模并将该塑模加热至所述合成树脂热交联的温度。
优选使用酚醛树脂，酚醛树脂随后借助硬化剂固化，作为含碳粘合剂。在甲醛或释放甲醛的化合物(例如六亚甲基四胺)的存在下，也可适当使用酚醛清漆。
本发明还提供可通过本发明方法获得的耐火成形体。
按这种方法获得的成形体的特征在于它在使用期间在很大程度上抗水化。众所周知，在含有金属抗氧化剂的成形体的碳化中形成碳化物相。在成形体在原位碳化后显著冷却并因此吸水的应用中，例如在生产中断的情况中，在碳化期间形成的碳化物分解，体积减小，因此成形体破坏，现有技术中已知的这一情况不再发生。所述非常微细的二氧化硅的作用尚未阐明。
本发明还提供制备耐火成形体的方法，其中在750～1500℃的温度下碳化本发明的成形体。
本发明还提供可通过本发明的方法获得的耐火成形体。对于本发明，耐火指软化点超过1500℃。
可按这种方法获得的成形体的特征在于它具有高抗水化性。这意味着即使在储存数周后(储存期间它可以吸收水分)，它不因碳化期间金属抗氧化剂与合成树脂反应形成的碳化物相的分解引起的体积增大而破坏。这可以省去耐火成形体(例如滑块板(slider plate)、浸没式排出口、塞子、冲刷漏斗(flushing cone)、黑影管(shadow tube)、出口喷嘴)的精心包装。
本发明还提供本发明的成形体的用途，该成形体用于制备滑块板、浸没式排出口、塞子、冲刷漏斗、黑影管、出口喷嘴、膜、隔热材料、挡热板(heat shield)和石墨电极，和用作耐火砖。
实施例
MgO-C转化器块(converter bricks)
使用颗粒体积密度为3.52g/cm3，纯度为97质量％，分成四个粒径级分，设计成最佳堆积密度的市售高纯度电熔镁(fused magnesia)(Possehl，Germany)作为颗粒组分。
使用天然石墨(来自Kropfmühl，Germany的石墨)作为碳。该石墨含有94质量％的碳，比表面积为1m2/g，d50值为0.2mm。
酚醛清漆树脂(Hexion Specialty Chemicals，Germany)和源于煤焦油沥青的
Figure BPA00001160068300051
(Rütgers，Germany)一起作为含碳粘合剂。六亚甲基四胺用作酚醛清漆树脂的硬化剂。
使用d90＜75μm的粗铝粉(TLS Technik，Germany)作为抗氧化剂。
使用Evonik Degussa GmbH的产品作为非常微细的金属氧化物。
此外，也使用Evonik Degussa GmbH的这是基于乙二醇，二氧化硅的比例为20重量％的分散液。
作为比较，使用相对粗糙的微粒硅-RW Füller。
表1显示基础混合物，粘合剂含量基于氧化镁颗粒和石墨的总量。
表2给出试验的混合物的概况。在Eirich实验室混合器中进行均化。
借助于具有浮沉模(floating die)的单轴压力机进行成形。将150MPa的最大冲压压力和约80MPa的两次预压和释放阶段相结合。在还原气氛下(碳床)在1000℃下进行碳化。加热速率为1.5K/分钟，保持时间为300分钟。
碳化后，全部混合物显示相似的机械和热性质，即对D约40MPa，45MPa的冷抗压强度，和在1400℃下约10MPa的热抗弯强度。
约24小时后，因体积百分数增大，“参比”样品显示碎裂并形成大裂缝。
约48小时后，样品B和C出现相同的现象，而根据本发明的混合物A和D即使在六个月后也未显示显著的体积增大或裂缝形成。
表1：基础混合物
Figure BPA00001160068300054
表2：混合物
$：参比；& 根据本发明；# 基于固体X

Claims (4)

1.混合物，其特征在于其包含
a)基于所述混合物的颗粒组分，0.01～5质量%的一种或多种非常微细的、聚集的、热解二氧化硅粉末，所述二氧化硅粉末的平均粒径为2到100nm，BET表面积至少为30m2/g，其中，所述微细的二氧化硅粉末以具有二氧化硅含量至少为15重量%的有机分散液的形式使用，所述有机分散液的分散剂选自醇，
b)氧化镁颗粒组分，其平均粒径为＞0.5μm到30mm，
c)基于所述混合物的颗粒组分，0.5～20质量%的一种或多种作为粘合剂的合成树脂，和
d)基于所述混合物的颗粒组分，0.5～5质量%的一种或多种金属抗氧化剂，所述金属抗氧化剂是选自铝、铁、镁、硅和钛的粉末，并且平均粒径为＞0.5μm到250μm。
2.根据权利要求1所述的混合物，其特征在于所述有机分散液的分散剂选自二醇。
3.根据权利要求1所述的混合物，其特征在于其包含石墨或炭黑形式的碳、合成沥青、沥青、柏油和它们的混合物。
4.制备成形体的方法，其特征在于，任选地，向根据权利要求1-3任一项所述的混合物中加入至少一种硬化剂，将混合物引入塑模中，任选地加压该塑模并将该塑模加热至所述合成树脂热交联的温度。
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