CN112194465B - 一种中间包干式料及其制备方法 - Google Patents

一种中间包干式料及其制备方法 Download PDF

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CN112194465B
CN112194465B CN202011083333.7A CN202011083333A CN112194465B CN 112194465 B CN112194465 B CN 112194465B CN 202011083333 A CN202011083333 A CN 202011083333A CN 112194465 B CN112194465 B CN 112194465B
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dry material
fiber
magnesia
tundish
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CN112194465A (zh
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于九利
颜浩
胡玲军
赵现华
王培勇
刘丽
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Qinhuangdao Shounai New Materials Co ltd
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Beijing Lier High Temperature Materials Co Ltd
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Abstract

本发明提出了一种中间包干式料及其制备方法，由下述重量份数的原料制成：粒径为0.1‑1mm镁钙砂24～42份，粒径为1‑3mm镁钙砂为30～40份，粒径≤0.075mm镁钙砂20‑25份，结合剂4‑6份，复合纤维0.5‑1.5份，烧结剂2.5‑3.5份，所述结合剂为酚醛树脂或糖类结合剂。本发明通过采用三种不同粒径规格的镁钙砂结合其他组分提高了干式料的透气性，同时还加入了一定量的复合纤维，进一步减少了干式料在烘烤过程中收缩、燃烧，在干式料内部形成稳定的微小气孔及通道，烘烤时能够让结合剂裂解产生的气体快速排出，缓解内部应力，防止工作衬坍塌。同时，复合纤维的引入还能显著地降低干式料的体积密度，降低连铸生产耐材成本，节约镁质材料资源，提高干式料的保温性能。

Description

一种中间包干式料及其制备方法
技术领域
本发明涉及不定形耐火材料，主要涉及一种中间包干式料及其制备方法。
背景技术
中间包工作衬用干式料是一种碱性不定形耐火材料，其具有如下优点：
1)施工快捷简便
中间包干式料施工时不需加水，不需搅拌，施工简便，速度快，劳动强度低
2)可快速烘烤而不开裂或剥落
中间包干式料振动施工完以后，施工体不需养护，可直接点火烘烤，施工体不会出现裂或剥落现象
3)抗侵蚀性能优良
中间包干式料在使用过程中，耐钢水和熔渣的侵蚀，使用寿命长
4)便于翻包以及可净化钢液
镁质干式料具有较好的抗高铁和高碱性熔渣的侵蚀性能，具有使用寿命长、不污染钢液的特点，已逐渐在中间包工作衬中应用，具有良好的使用效果和应用前景。例如在中国专利CN201210553421.8中公开了一种环保无碳中间包干式料。该环保无碳中间包干式料包括如下重量百分含量的组分：镁砂87.4-95％，金属硅粉0.2-1.5％，膨润土0.2-1.5％，环保结合剂3-9％，酚醛树脂0-0.6％。由此可见该发明提供的环保无碳中间包干式料主要采用镁砂为主原料，采用新型的环保结合剂取代固体酚醛树脂，其在烘烤过程中不产生或产生微量刺激性气体，连铸时对钢水不增氢、不增碳，保证超低碳钢的冶炼，并不向钢水中带入其他杂质，不塌包，具有强度高、施工方便、易于解体、寿命长和绿色环保等优点。但是碱性材料，尤其是镁质材料的热膨胀系数大，并随温度升高而增加，产生的热应力不断积累可能会使工作衬离鼓。目前中间包干式料工作衬以酚醛树脂结合，烘烤过程中，随着中间包温度的升高，酚醛树脂逐渐固化，固化后的结合剂在200℃～800℃时分解，释放出CO2、CO、CH4、H2及H2O等气体，同时留下固定炭，即结合剂被碳化，形成碳网络结构，这种气体量虽没有涂料产生的水汽量大，但如果升温速度快导致结合剂分解过快，会造成大量气体聚集膨胀，再加上干式料工作衬体密大，振动比较密实，严重时会导致工作层烘烤塌包，导致生产不能顺行。目前常用的干式料体积密度大，保温性能差，增加了中间包单包用量，浪费了矿产资源，也增加了企业的耐材成本。
另外，CaO能够吸附钢中的夹杂物和S、P等有害元素，具有很好的净化钢水能力，同时，CaO的高温稳定性最好，对钢液污染少，并能吸收钢液中非金属夹杂物，对提高钢的质量，尤其对洁净钢的生产十分重要。
发明内容
基于上述问题，本发明的目的是提供一种中间包干式料，旨在克服现有干式料在烘烤过程糖类结合剂或酚醛树脂集中分解，产生大量气体，导致工作衬容易塌包的问题，并能缓解镁质工作衬高温产生的热应力，减少离鼓。同时，还能显著地降低连铸耐材生产成本，节约矿产资源，提高干式料的保温性能。
为了解决上述技术问题，本发明采用的技术解决方案是：
一种中间包干式料，由下述重量份数的原料制成：
粒径为0.1-1mm镁钙砂24～42份，
粒径为1-3mm镁钙砂为30～40份，
粒径≤0.075mm镁钙砂20-25份，
糖类结合剂或酚醛树脂4-6份，
复合纤维0.5-1.5份，
烧结剂2.5-3.5份。
具体而言，在一些实施例中，所述所述糖类结合剂为麦芽糖、葡萄糖、蔗糖中的一种。
具体而言，在一些实施例中，所述烧结剂为硼酸与高岭土或硅微粉中的至少一种构成的混合物。优选地，所述烧结剂为硼酸、高岭土、硅微粉按照重量比为1:1:2的比例混合而成。
具体而言，在一些实施例中，所述复合纤维为有机纤维、植物纤维、玻璃纤维中的至少两种。优选地，所述有机纤维为熔点为160℃～170℃的聚丙烯有机纤维(长度3mm，直径20～40μm)，所述植物纤维为纸纤维或黄麻纤维中的一种(长度约为2mm)，所述玻璃纤维为无碱硼硅酸盐玻璃，熔点约500℃～750℃(长度为3～5mm，直径30～50μm)。进一步优选地，所述有机纤维是由有机纤维、植物纤维和玻璃纤维按照重量比为3:2:1混合而成。
本发明的另一目的是提供了所述中间包干式料的制备方法，步骤如下：
(1)将所有原料按重量配比称重；
(2)将粒径为0.1-1mm、1-3mm以及≤0.075mm的镁钙砂先倒进混砂机内混合1～2min，然后加入复合纤维混合1～2min搅拌均匀，形成混合物；
(3)将烧结剂、结合剂加入到步骤(2)制备出的混合物中混合6～8min，并搅拌均匀，得到中间包干式料成品。
与现有技术相比，本发明具有以下有益效果：本发明的中间包干式料采用镁钙砂作为主要原料加工而成，镁钙砂中钙含量为40-65％，通过采用三种不同粒径规格的镁钙砂结合其他组分提高了干式料的透气性，同时还加入了一定量的复合纤维，进一步减少了干式料在烘烤过程中收缩、燃烧，在干式料内部形成稳定的微小气孔及通道，烘烤时能够让结合剂裂解产生的气体快速排出，缓解内部应力，防止工作衬坍塌。同时，复合纤维的引入还能显著地降低干式料的体积密度，降低连铸生产耐材成本，节约矿产资源，提高干式料的保温性能。同时，干式料中的游离CaO并能吸收钢液中非金属夹杂物，对提高钢的质量，尤其对洁净钢的生产十分重要。
具体实施方式
下面结合具体实施例对本发明作进一步说明，同时以下实施例采用的镁钙砂中钙的含量为50wt％。有机纤维为长度3mm，直径30μm且熔点为165℃的聚丙烯有机纤维，所述植物纤维为长度2mm的黄麻纤维，所述玻璃纤维为长度为5mm，直径50μm的无碱硼硅酸盐玻璃，其熔点为750℃。
实施例1
一种中间包干式料，由以下重量份数的原料构成：
粒径为0.1-1mm镁钙砂26份，粒径为1-3mm镁钙砂为40份，粒径≤0.075mm 镁钙砂25份，酚醛树脂4份(该酚醛树脂为我自产原料其市场销售型号为D012)，复合纤维1.5份，烧结剂3.5份。其中复合纤维具体是由有机纤维、植物纤维和玻璃纤维按照重量比为3:2:1混合而成，烧结剂为硼酸、高岭土、硅微粉按照重量比为1:1:2的比例混合而成。
本实施例提供了所述中间包干式料的制备方法，包括以下步骤：按比例取各原料；将粒径为0.1-1mm、1-3mm以及≤0.075mm的镁钙砂先倒进混砂机内混合2min，然后加入复合纤维混合1min，再加入烧结剂、结合剂，再将所述其余原料放进搅拌机中混合8min，搅拌均匀装袋即可。
经检测，本实施例所制备的中间包干式料的体积密度为2.16g/cm3。
实施例2
一种中间包干式料，由以下重量份数的原料按照实施例1的制备方法加工而成：
粒径为0.1-1mm镁钙砂32份，粒径为1-3mm镁钙砂为35份，粒径≤0.075mm 镁钙砂25份，麦芽糖结合剂5份，复合纤维0.5份，烧结剂2.5份。其中其中复合纤维具体是所述有机纤维是由有机纤维、植物纤维和玻璃纤维按照重量比为3:2:1混合而成，烧结剂为硼酸、高岭土、硅微粉按照重量比为1:1:2的比例混合而成。
经检测，本实施例所制备的中间包干式料的体积密度为2.28g/cm3。
实施例3
一种中间包干式料，由以下重量份数的原料按照实施例1的制备方法加工而成：
粒径为0.1-1mm镁钙砂40份，粒径为1-3mm镁钙砂为30份，粒径≤0.075mm 镁钙砂20份，葡萄糖6份，复合纤维1份，烧结剂3份。其中其中复合纤维具体是所述有机纤维是由有机纤维、植物纤维和玻璃纤维按照重量比为3:2:1混合而成，烧结剂为硼酸、高岭土、硅微粉按照重量比为1:1:2的比例混合而成。
经检测，本实施例所制备的中间包干式料的体积密度为2.20g/cm3。
实施例4
一种中间包干式料，由以下重量份数的原料按照实施例1的制备方法加工而成：
粒径为0.1-1mm镁钙砂33份，粒径为1-3mm镁钙砂为36份，粒径≤0.075mm 镁钙砂22份，蔗糖5份，复合纤维1份，烧结剂3份。其中其中复合纤维具体是所述有机纤维是由有机纤维、植物纤维和玻璃纤维按照重量比为3:2:1混合而成，烧结剂为硼酸、高岭土、硅微粉按照重量比为1:1:2的比例混合而成。
经检测，本实施例所制备的中间包干式料的体积密度为2.21g/cm3。
对比例1
一种中间包干式料，由以下重量份数的原料按照实施例1的制备方法加工而成：
粒径为0.1-1mm镁钙砂26份，粒径为1-3mm镁钙砂为40份，粒径≤0.075mm 镁钙砂25份，酚醛树脂4份(该酚醛树脂为我自产原料其市场销售型号为D012)，烧结剂3.5份。其中烧结剂为硼酸、高岭土、硅微粉按照重量比为1:1:2的比例混合而成
经检测，本对比例所制备的中间包干式料的体积密度为2.41g/cm3。
对比例2
一种中间包干式料，由以下重量份数的原料构成：
粒径为0.1-1mm镁钙砂26份，粒径为1-3mm镁钙砂为40份，粒径≤0.075mm 镁钙砂25份，酚醛树脂4份(该酚醛树脂为我自产原料其市场销售型号为D012)，有机纤维1.5份，烧结剂3.5份。其中烧结剂为硼酸、高岭土、硅微粉按照重量比为1:1:2的比例混合而成。
经检测，本对比例所制备的中间包干式料的体积密度为2.35g/cm3。
对比例3
根据实施例1的中间包干式料的原料组成，只采用粒径为0.1-1mm镁钙砂和粒径≤0.075mm镁钙砂作为原料制备而成，具体原料组成如下：
粒径为0.1-1mm镁钙砂67份，粒径≤0.075mm镁钙砂25份，酚醛树脂5 份，复合纤维0.5份，烧结剂2.5份。
经检测，本对比例所制备的中间包干式料的体积密度为2.33g/cm3。
对比例4
根据实施例1的中间包干式料的原料组成，只采用粒径为1-3mm镁钙砂和粒径≤0.075mm镁钙砂作为原料制备而成，具体原料组成如下：
粒径为1-3mm镁钙砂67份，粒径≤0.075mm镁钙砂25份，酚醛树脂5份，复合纤维0.5份，烧结剂2.5份。
经检测，本对比例所制备的中间包干式料的体积密度为2.35g/cm3。
将实施例1-4以及对比例1-4所制备的中间包干式料制备中间包工作衬，具体方法如下：
将干式料倒入中间包模胎外壁和中间包永久衬之间，振动5～10min，在200℃～350℃温度煤气烘烤2小时，冷却后吊出胎模，即可得到所述的干式工作衬。
实施例1-4所制备的中间包干式料在35吨连铸中间包上使用，打结100mm 厚，连续浇钢24小时，残厚约40mm，烘烤及浇钢过程无干式料塌落现象，抗钢渣侵蚀冲刷性能优良，自动解体容易。而对比例1-4所制备的中间包干式料则存在干式料塌落现象，抗钢渣侵蚀冲刷性能较差。
本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；同时，对于本领域的一般技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处。综上所述，本说明书内容不应理解为对本发明的限制。

Claims (5)

1.一种中间包干式料，其特征在于，由下述重量份数的原料制成：
粒径为0.1-1mm镁钙砂24~42份，
粒径为1-3mm镁钙砂为30~40份，
粒径≤0.075mm镁钙砂20-25份，
糖类结合剂或酚醛树脂4-6份，
复合纤维0.5-1.5份，
烧结剂2.5-3.5份；
所述复合纤维是由有机纤维、植物纤维和玻璃纤维按照重量比为3:2:1混合而成；
所述有机纤维为长度3mm，直径20~40μm且熔点为160℃~170℃的聚丙烯有机纤维，所述植物纤维为长度2mm的纸纤维或黄麻纤维中的一种，所述玻璃纤维为长度为3-5mm，直径30~50μm的无碱硼硅酸盐玻璃，其熔点为500℃~750℃。
2.根据权利要求1所述的中间包干式料，其特征在于，所述糖类结合剂为麦芽糖、葡萄糖、蔗糖中的至少一种。
3.根据权利要求1所述的中间包干式料，其特征在于，所述烧结剂为硼酸与高岭土或硅微粉中的至少一种构成的混合物。
4.根据权利要求3所述的中间包干式料，其特征在于，所述烧结剂为硼酸、高岭土、硅微粉按照重量比为1:1:2的比例混合而成。
5.根据权利要求1-4任意一项所述的中间包干式料的制备方法，其特征在于，其方法步骤如下：
（1）将所有原料按重量配比称重；
（2）将粒径为0.1-1mm、1-3mm以及≤0.075mm的镁钙砂先倒进混砂机内混合1~2min，然后加入复合纤维混合1~2min搅拌均匀，形成混合物；
（3）将烧结剂、结合剂加入到步骤（2）制备出的混合物中混合6~8min，并搅拌均匀，得到中间包干式料成品。
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