CN110002860A - 刚玉莫来石隔热砖 - Google Patents

刚玉莫来石隔热砖 Download PDF

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CN110002860A
CN110002860A CN201910149624.2A CN201910149624A CN110002860A CN 110002860 A CN110002860 A CN 110002860A CN 201910149624 A CN201910149624 A CN 201910149624A CN 110002860 A CN110002860 A CN 110002860A
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parts
corundum
insulating brick
zirconium oxide
microns
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CN201910149624.2A
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林伟
范新晖
吴则昌
林金宏
吴志坚
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Heyuan Dongyuan Yingpai Ceramics Co. Ltd
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EAGLE BRAND CERAMIC (HEYUAN) Co Ltd
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Abstract

本发明提供了一种刚玉莫来石隔热砖，属于材料领域。一种刚玉莫来石隔热砖，其原料以重量份数计，包括：刚玉20‑40份、莫来石30‑50份、氧化锆15‑25份、氧化钙3‑5份、氧化钇3‑5份、氧化镁1‑3份、聚苯乙烯球0.5‑1份、有机烧失物0.5‑1份、聚丙烯基离子交换纤维1‑3份、聚丙烯腈纤维1‑3份、碳纤维0.1‑0.5份。本申请提供的刚玉莫来石隔热砖，热震稳定性好，导热系数低；隔热性能优异，有利于降低能耗，节能环保。

Description

刚玉莫来石隔热砖
技术领域
本发明涉及材料领域，具体而言，涉及一种刚玉莫来石隔热砖。
背景技术
在传统能源日益枯竭，而新能源发展缓慢的今天，工业窑炉的节能问题 是全球冶金、建材、石化等能耗大户的一个重要课题。因此，节能降耗是我 国当前很紧迫的一个现实需要。传统的隔热材料已不能满足需要，高强、高 效、高热震稳定性的隔热保温炉衬材料的研发和应用就显得极为重要。
在耐火材料行业，国内几个主要耐火材料生产基地约有隧道窑1127条， 梭式窑649座，特种陶瓷以及石化等行业也有许多高温工业窑炉。这些窑炉 炉衬一般采用重质致密砖或氧化铝空心球砖砌筑。但是重质致密砖体积密度 大、蓄热多、热导率大，不节能；氧化铝空心球砖体积密度大，隔热效果不 明显。因此，解决体积密度大、导热率大、隔热效果差等问题所带来的高能 耗困局，显得尤为重要。
有鉴于此，特提出本发明。
发明内容
本发明的目的在于提供一种刚玉莫来石隔热砖，所述刚玉莫来石隔热砖 密度和导热系数小、隔热效果好，节能环保。
为了实现本发明的上述目的，特采用以下技术方案：
一种刚玉莫来石隔热砖，其原料以重量份数计，包括：刚玉20-40份、莫 来石30-50份、氧化锆15-25份、氧化钙3-5份、氧化钇3-5份、氧化镁1-3份、聚 苯乙烯球0.5-1份、有机烧失物0.5-1份、聚丙烯基离子交换纤维1-3份、聚丙烯 腈纤维1-3份、碳纤维0.1-0.5份。
刚玉和莫来石作为砖体的主体和主晶相，可以提供良好的隔热基础和较 高的强度；添加氧化锆的目的是：高温条件下，氧化锆单斜与四方相之间的 可逆转变并伴随有体积效应，这种可逆转变和体积效应是有益于形成隔热需 要的气相-固相通道的。此外，适量的CaO、Y2O3、MgO等阳离子半径与锆 离子半径相差12％以内的氧化物，经高温稳定后可以形成固溶体，形成了部分 稳定的氧化锆，降低四方相到单斜相的转变温度。固溶体不分解，而且具有 很好的力学性能和较低的热膨胀系数，利用应力诱导相变使四方相氧化锆转 变为单斜相氧化锆，起到相变增韧的作用。从实际的增韧效果看，四方相氧 化锆只有一部分可以产生相变，所以实际的增韧效果与可相变的氧化锆成正 比，对氧化锆相变机制的研究表明，相变往往从晶界开始，相邻晶粒间的结 构紧密程度也影响相变的完全性。因此，氧化锆的使用，与氧化钙、氧化钇、 氧化镁协同，合适的使用量使得氧化锆晶相转变处于一个较佳的范畴，隔热 砖整体从而获得较佳的导热系数和热震性能；氧化钙、氧化钇、氧化镁除了保障隔热砖在制备过程中的可塑性和物理稳定性外，还会改变隔热砖的固相 导热性能，从固相角度入手，进一步降低导热系数；聚苯乙烯球和有机烧失 物，可以为使得砖体内部获得优异的、有利于降低导热系数的气孔结构分布 和气体氛围。聚丙烯基离子交换纤维、聚丙烯腈纤维、碳纤维的添加，除了 增强隔热砖的强度外，碳纤维改善了固相传热通道，聚丙烯基离子交换纤维、 聚丙烯腈纤维除了改善部分固相通道外，还能够改变气相通道，从而进一步 降低导热系数，优化隔热性能。
为了进一步的达到节能环保、废物利用的目的，氧化锆、氧化钙、氧化 钇、氧化镁等组分，可以用废旧的含锆陶瓷辊棒进行替代。
优选地，所述聚苯乙烯球的粒径为0.5-1.5mm。
聚苯乙烯球的粒径决定了其在砖体内部所能形成的空穴的尺寸，同时， 优选地粒径也可以改善其与其他组分混合之后的分布，进而优化气相空穴在 固相中的分布，形成有益于隔热的固相-气相传热通道。粒径过小，不利于形 成合适的气相通道，粒径过大则容易造成显微裂纹，经过高温受热之后容易 发生断裂。
优选地，所述有机烧失物选自木屑、稻谷壳、草木灰和焦炭粉中的一种 或多种。
有机烧失物的选择，是形成合适的气相导热通道的影响因素之一。除了 气相通道的位置分布、数量分布之外，通道内的气体类型也是尤为重要的。 上述有机烧失物在高温条件下可以在砖体密闭的气孔内生成导热系数小于空 气的气体，因此，气相通道的导热系数进一步下降。
优选地，所述氧化锆的粒径为10-105微米。
更加优选地，所述氧化锆的粒径分布为：粒径大于等于10微米、小于50 微米的，占所述氧化锆总质量的45-69％，粒径大于等于50微米、小于90微米 的，占所述氧化锆总质量的5-40％，粒径大于等于90微米、小于等于105微米 的，占所述氧化锆总质量的1-30％。
氧化锆的粒径的选择，是为了获得高温条件下氧化锆晶体相转变的适当 分布，优化单斜相和四方相之间的位置布局，与氧化钙、氧化钇和氧化镁配 合，完成稳定氧化锆和半稳定氧化锆的布局，从而获得较佳的内应力作用结 果，进而降低导热系数，提高隔热性能。
优选地，所述聚丙烯基离子交换纤维、所述聚丙烯腈纤维、所述碳纤维 的长度均为1-3mm。
纤维长度的选择，一方面是为了更好的在固相中获得适当的位置，另一 方面，是为了在烧制过程中获得大小合适的空穴，建立起有利于降低导热系 数的气相传热通道。
进一步优选地，所述聚丙烯基离子交换纤维是指聚丙烯纤维经过苯乙烯 接枝反应、氯甲基化和胺化反应得到的强碱性阴离子交换纤维。
使用强碱性阴离子交换纤维，有利于进一步优化气相传热通道。
更加优选地，所述聚丙烯腈纤维的直径为15-45微米。
更为优选地，所述碳纤维的纤度为19-22D。
聚丙烯腈纤维直径和碳纤维纤度的选择，均是为了达到与其他组分配合， 获得最有利于提升隔热性能的气相-固相传热通道的目的。
可选地，砖坯烧制前含水量为1-2wt％。
含水量的控制，一方面是为了控制水蒸气产生的孔洞参与气相传热通道 的建立，另一方面是为了保证隔热砖的强度和成品率。
与现有技术相比，本发明的有益效果为：
(1)热震稳定性好；
(2)密度小、导热系数低；
(3)隔热性能优异，有利于降低能耗，节能环保。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术 人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范 围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。 所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
首先对聚丙烯基离子交换纤维的制备方法进行简述：
先将聚丙烯纤维在有机溶剂中溶胀，然后放入苯乙烯的正辛醇和甲醇溶 液中浸渍，加入引发剂和交联剂进行接枝反应；将接枝后的纤维放入氯甲醚 中，加入催化剂氯化锌，反应得到氯甲基化纤维；再将氯甲基化后的纤维放 入三甲胺水溶液中反应，反应结束后加入盐酸中和，过滤后将纤维用去离子 水洗至中性即可。
实施例1
备料：完成原料检测后，取刚玉20份、莫来石50份、氧化锆15份、氧化 钙5份、氧化钇3份、氧化镁3份、聚苯乙烯球0.5份、木屑1份、聚丙烯基离子 交换纤维1份、聚丙烯腈纤维3份、碳纤维0.1份和适量水加入搅拌机搅拌。其 中，聚苯乙烯球的粒径为0.5mm；氧化锆的粒径为10微米；聚丙烯基离子交换 纤维、聚丙烯腈纤维、碳纤维的长度均为1mm；聚丙烯腈纤维的直径为15微 米；碳纤维的纤度为19D。
制坯：将搅拌好的泥料堆积在一起，陈腐24小时后加入到练泥机内挤压 成型符合要求的砖坯；将成型后的砖坯放进干燥房干燥，干燥结束时砖坯的 含水量为2wt％。
烧制：将干燥后的砖坯码在窑炉中进行烧制，控制烧成温度1600℃，然 后切磨、检验、包装得到成品刚玉莫来石隔热砖。
实施例2
备料：完成原料检测后，取刚玉40份、莫来石30份、氧化锆25份、氧化 钙3份、氧化钇5份、氧化镁1份、聚苯乙烯球1份、稻谷壳0.5份、聚丙烯基离 子交换纤维3份、聚丙烯腈纤维1份、碳纤维0.5份和适量水加入搅拌机搅拌。 其中，聚苯乙烯球的粒径为1.5mm；氧化锆的粒径分布为：粒径大于等于10 微米、小于50微米的，占氧化锆总质量的45％，粒径大于等于50微米、小于90 微米的，占氧化锆总质量的40％，粒径大于等于90微米、小于等于105微米的， 占氧化锆总质量的15％；聚丙烯基离子交换纤维、聚丙烯腈纤维、碳纤维的长 度均为3mm；聚丙烯腈纤维的直径为45微米；碳纤维的纤度为22D。
制坯：将搅拌好的泥料堆积在一起，陈腐48小时后加入到练泥机内挤压 成型符合要求的砖坯；将成型后的砖坯放进干燥房干燥，干燥结束时砖坯的 含水量为1wt％。
烧制：将干燥后的砖坯码在窑炉中进行烧制，控制烧成温度1620℃，然 后切磨、检验、包装得到成品刚玉莫来石隔热砖。
实施例3
备料：完成原料检测后，取刚玉30份、莫来石40份、氧化锆20份、氧化 钙4份、氧化钇4份、氧化镁2份、聚苯乙烯球0.8份、草木灰0.8份、聚丙烯基 离子交换纤维2份、聚丙烯腈纤维2份、碳纤维0.3份和适量水加入搅拌机搅拌。 其中，聚苯乙烯球的粒径为1mm；氧化锆的粒径分布为：粒径大于等于10微 米、小于50微米的，占氧化锆总质量的69％，粒径大于等于50微米、小于90 微米的，占氧化锆总质量的30％，粒径大于等于90微米、小于等于105微米的， 占氧化锆总质量的1％；聚丙烯基离子交换纤维、聚丙烯腈纤维、碳纤维的长 度均为2mm；聚丙烯腈纤维的直径为30微米；碳纤维的纤度为21D。
制坯：将搅拌好的泥料堆积在一起，陈腐48小时后加入到练泥机内挤压 成型符合要求的砖坯；将成型后的砖坯放进干燥房干燥，干燥结束时砖坯的 含水量为1.5wt％。
烧制：将干燥后的砖坯码在窑炉中进行烧制，控制烧成温度1610℃，然 后切磨、检验、包装得到成品刚玉莫来石隔热砖。
实施例4
备料：完成原料检测后，取刚玉25份、莫来石35份、氧化锆22份、氧化 钙3.5份、氧化钇4.5份、氧化镁1.5份、聚苯乙烯球0.9份、焦炭粉0.6份、聚丙 烯基离子交换纤维1.5份、聚丙烯腈纤维2.5份、碳纤维0.2份和适量水加入搅拌 机搅拌。其中，聚苯乙烯球的粒径为0.8mm；氧化锆的粒径分布为：粒径大于 等于10微米、小于50微米的，占氧化锆总质量的65％，粒径大于等于50微米、 小于90微米的，占氧化锆总质量的5％，粒径大于等于90微米、小于等于105 微米的，占氧化锆总质量的30％；聚丙烯基离子交换纤维、聚丙烯腈纤维、碳纤维的长度均为1.5mm；聚丙烯腈纤维的直径为20微米；碳纤维的纤度为21D。
制坯：将搅拌好的泥料堆积在一起，陈腐36小时后加入到练泥机内挤压 成型符合要求的砖坯；将成型后的砖坯放进干燥房干燥，干燥结束时砖坯的 含水量为1wt％。
烧制：将干燥后的砖坯码在窑炉中进行烧制，控制烧成温度1615℃，然 后切磨、检验、包装得到成品刚玉莫来石隔热砖。
比较例1
与实施例1相比，原料中不含聚苯乙烯球。
比较例2
与实施例2相比，原料中不含有机烧失物。
比较例3
与实施例3相比，原料中不含氧化钙、氧化钇和氧化镁。
比较例4
与实施例4相比，氧化锆的粒径均为5mm。
比较例5
与实施例3相比，原料中不含聚丙烯基离子交换纤维和聚丙烯腈纤维。
比较例6
与实施例4相比，原料中不含碳纤维。
对实施例1-4和比较例1-6得到的产品各500组进行性能测试。具体测试结 果如下表1所示：
表1测试结果
上述测试数据表明，本申请提供的刚玉莫来石隔热砖，成品率高、密度 小、导热系数小、热震稳定性强、耐压强度大。
尽管已用具体实施例来说明和描述了本发明，然而应意识到，在不背离 本发明的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意 味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。

Claims (10)

1.一种刚玉莫来石隔热砖，其特征在于，其原料以重量份数计，包括：刚玉20-40份、莫来石30-50份、氧化锆15-25份、氧化钙3-5份、氧化钇3-5份、氧化镁1-3份、聚苯乙烯球0.5-1份、有机烧失物0.5-1份、聚丙烯基离子交换纤维1-3份、聚丙烯腈纤维1-3份、碳纤维0.1-0.5份。
2.根据权利要求1所述的刚玉莫来石隔热砖，其特征在于，所述聚苯乙烯球的粒径为0.5-1.5mm。
3.根据权利要求1所述的刚玉莫来石隔热砖，其特征在于，所述有机烧失物选自木屑、稻谷壳、草木灰和焦炭粉中的一种或多种。
4.根据权利要求1所述的刚玉莫来石隔热砖，其特征在于，所述氧化锆的粒径为10-105微米。
5.根据权利要求4所述的刚玉莫来石隔热砖，其特征在于，所述氧化锆的粒径分布为：粒径大于等于10微米、小于50微米的，占所述氧化锆总质量的45-69％，粒径大于等于50微米、小于90微米的，占所述氧化锆总质量的5-40％，粒径大于等于90微米、小于等于105微米的，占所述氧化锆总质量的1-30％。
6.根据权利要求1所述的刚玉莫来石隔热砖，其特征在于，所述聚丙烯基离子交换纤维、所述聚丙烯腈纤维、所述碳纤维的长度均为1-3mm。
7.根据权利要求6所述的刚玉莫来石隔热砖，其特征在于，所述聚丙烯基离子交换纤维是指聚丙烯纤维经过苯乙烯接枝反应、氯甲基化和胺化反应得到的强碱性阴离子交换纤维。
8.根据权利要求7所述的刚玉莫来石隔热砖，其特征在于，所述聚丙烯腈纤维的直径为15-45微米。
9.根据权利要求6所述的刚玉莫来石隔热砖，其特征在于，所述碳纤维的纤度为19-22D。
10.根据权利要求1所述的刚玉莫来石隔热砖，其特征在于，砖坯烧制前含水量为1-2wt％。
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