CN111548171B - 一种高温性能优良的硅质耐火泥浆 - Google Patents

一种高温性能优良的硅质耐火泥浆 Download PDF

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CN111548171B
CN111548171B CN202010361981.8A CN202010361981A CN111548171B CN 111548171 B CN111548171 B CN 111548171B CN 202010361981 A CN202010361981 A CN 202010361981A CN 111548171 B CN111548171 B CN 111548171B
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邵荣丹
何见林
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Wuhan Research Institute of Metallurgical Construction Co Ltd
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Abstract

本发明公开了一种高温性能优良的硅质耐火泥浆，其粉料组成按质量百分数计如下：废硅砖粉0.5‑0mm，20～50％；石英粉0.3‑0mm，15～35％；石英粉0.088‑0mm，25～45％；碳化硅抽尘粉1～3％；二氧化硅微粉1～3％；糊精1～1.5％；羧甲基纤维素0.1～0.5％；矿化剂0.05～0.2％；外加占粉料27～30wt％的水混合而成。本发明提供的硅质耐火泥浆二氧化硅含量大于等于94％，不添加生粘土，钠膨润土等，氧化铝含量低，低熔物含量低，荷重软化温度点高。同时，添加废硅砖粉，实现了资源二次利用，且废硅砖粉基本以磷石英相存在，体积稳定性好，与所砌硅砖材质匹配，高温使用环境中粘结好，不脱面。

Description

一种高温性能优良的硅质耐火泥浆
技术领域
本发明属于材料技术领域，具体涉及一种高温性能优良的硅质耐火泥浆。
背景技术
现有技术中，硅质耐火泥浆主要用在各种焦炉、热风炉等高温窑炉中，砌筑硅质耐火砖。例如在现代焦炉中，硅砖的使用量达到整个耐火制品的60-70％，由此，硅质耐火泥浆的使用量在砌筑硅砖过程中使用量也达到了硅砖总量的3-5％左右。用于焦炉的硅质耐火泥浆需要具有较高的荷重软化温度点，较高的热导率，抗热震性好，高温体积稳定等特性。在长期高温使用的过程中，高温下质量较差的硅质泥浆和硅砖没有烧结成一个整体，硅砖砌体的砖缝容易脱开，造成砌体出现裂缝，掉砖，甚至垮塌的现象。传统的硅质耐火泥浆，为了保证良好的和易性和施工性能，需要加入一定量的生粘土。国内的生粘土主要矿物相属于高岭石类，主要化学成分为氧化铝，二氧化硅以及较多的低熔物杂质。在硅质耐火泥浆中氧化铝是一种有害物质，在高温下会与二氧化硅反应产生大量液相，造成硅质耐火泥浆的荷重软化温度点低，烧后收缩大，在窑炉长期高温运行的过程中，容易造成炉衬出现裂缝，垮塌。所以在硅质制品中，应该尽量减少氧化铝的含量。
CN201811033620.X公开了一种废硅砖生产的硅质耐火泥浆，采用不同的粒度级配配置硅质耐火泥浆使其具备较好的性能；虽然大量使用废硅砖粉，节约了资源，但是泥浆作为粉体，大量使用了体积稳定性和化学性质稳定的废硅砖粉有可能造成烧后收缩，降低泥浆粘结强度，二氧化硅含量较低。采用粘土引进了氧化铝杂质等低熔物。
CN200710062483.8公开了一种硅质耐火泥浆粉，采用废硅砖粉，硅石，粘土，搭配各原料不同粒度制备出与硅砖材质匹配的硅质耐火泥浆；虽然解决了硅质耐火泥浆和硅砖材质不匹配的问题，但是添加了生粘土，引入了氧化铝杂质，及其它低熔物，对荷软有影响。
发明内容
针对现有技术问题，本发明目的在于提供一种高荷软，高温性能良好的硅质耐火泥浆，不添加粘土，杂质含量低，荷重软化开始温度高，高温粘结性能好，满足工业窑炉的长期使用。
为达到上述目的，采用技术方案如下：
一种高温性能优良的硅质耐火泥浆，其粉料组成按质量百分数计如下：
Figure BDA0002475419630000011
Figure BDA0002475419630000021
外加占粉料27～30wt％的水混合而成。
按上述方案，所述的废硅砖粉主要物相为磷石英相，来源于硅砖烧后的形状缺损或者裂纹而化学成分合格的残次品，以及从焦炉，热风炉等工业窑炉上拆除的硅砖，经拣选后将其破碎成粒度为0.5-0mm的颗粒，其中SiO2含量大于94wt％。
按上述方案，所述的石英粉为未经煅烧的高纯度石英砂，其SiO2含量≥98.5wt％。
按上述方案，所述的碳化硅抽尘粉是碳化硅生产过程中收集的烟尘废料，粒度≤20um，碳化硅含量≥95wt％。
按上述方案，二氧化硅微粉是二氧化硅含量≥99wt％，粒度d50约为0.15um左右的高纯度超细微粉。
按上述方案，所述的糊精为一种黄糊精，其粘结力大于1.8kg/cm2，在15-17℃水中溶解度大于96％。
按上述方案，所述的羧甲基纤维素中纤维素含量大于等于97.5wt％。
按上述方案，所述的矿化剂为铁鳞粉和硼砂的组合；铁鳞粉来源于钢材加热和轧制过程中，由于表面受到氧化而脱落形成的鱼鳞状物，粒度范围为0.044-0mm，铁鳞粉与硼砂质量比为1:(1～3)。
本发明所用废硅砖由于经过严格控温的高温煅烧，晶型转变完全，主要晶相为磷石英相，体积稳定性好，高温性能好。
本发明所用的石英粉价格低廉，耐火度高，二氧化硅含量高，杂质少，是制备硅质耐火泥浆的必要原料，而且因为泥浆属于大量细粉组成，高温烧结后容易收缩，加入石英粉可降低烧成时的收缩。
本发明所用碳化硅抽尘粉属于工业废料，但是碳化硅含量高，粒度超细，呈现出一种疏松灰尘状堆积，改善了硅质耐火泥浆的和易性。且碳化硅导热系数高，有利于改善硅质耐火泥浆的导热性。
本发明所用二氧化硅微粉由于粒度超细，分散性好，在硅质耐火泥浆中起到悬浮耐火泥浆，使耐火泥浆和易性较好，不沉淀，并且由于二氧化硅含量超高，可以提高硅质耐火泥浆中二氧化硅的含量。在中高温阶段还可以促进烧结，提高泥浆粘结强度。
糊精起到了增加耐火泥浆和易性，并且增加烘后粘结强度的作用。
羧甲基纤维素在耐火泥浆中起到保水，增加耐火泥浆悬浮性，使泥浆具有一定可塑性，保证灰缝饱满的作用。
本发明所用铁鳞粉是一种来源于轧钢过程中，产生的氧化铁皮，主要成分为Fe2O3、FeO等，粒度为0.044-0mm，TFe含量大于等于90wt％；硼砂即硼酸钠，是一种易溶于水，熔点较低的化学试剂。铁鳞粉和硼酸组合作为矿化剂在硅质耐火泥浆中起到促进烧结，促使生石英粉在较低温度的烧结过程中即可开始大量转化为磷石英，有利于提高硅质泥浆的体积稳定性，且形成的磷石英呈现矛头状双晶，互相交错，有利于提高泥浆强度。
相对于现有技术，本发明的有益效果为：
本发明提供的硅质耐火泥浆二氧化硅含量大于等于94％，不添加生粘土，钠膨润土等，氧化铝含量低，低熔物含量低，荷重软化温度点高。
添加了碳化硅废料，有利于节约资源，且有利于提高硅质耐火泥浆的温度传导性。
添加废硅砖粉，实现了资源二次利用，且废硅砖粉基本以磷石英相存在，体积稳定性好，与所砌硅砖材质匹配，高温使用环境中粘结好，不脱面。
一定量的矿化剂复合添加，促使硅质泥浆中的石英粉(基本物相为β-石英)在加热过程中较低温度即可开始大量转化为鳞石英相，而不直接生成体积膨胀较大的方石英相，有利于耐火泥浆在高温使用过程中不产生过大膨胀。
具体实施方式
以下实施例进一步阐释本发明的技术方案，但不作为对本发明保护范围的限制。
以下各实施例中，所用原料指标为：
废硅砖粉粒度为0-0.5mm,其SiO2含量为94.5wt％；
石英粉粒度为0-0.3mm,及0.088-0mm,其SiO2含量为99wt％；
碳化硅抽尘粉粒度≤20um，碳化硅含量为95.2wt％；
二氧化硅微粉平均粒度为0.15um左右，二氧化硅含量99.3wt％；
糊精为一种黄糊精，其粘结力大于1.8kg/cm2，在15-17℃水中溶解度大于96％，酸度小于35％。
矿化剂由铁鳞粉和硼砂复合或者单独添加组成。其中铁鳞粉中，TFe含量为93.5％。
实施例1
所述硅质耐火泥浆由以下组分及重量百分数组成：
Figure BDA0002475419630000041
本实施例提供的硅质耐火泥浆的性能指标测试结果参见表1
实施例2
所述硅质耐火泥浆由以下组分及重量百分数组成：
Figure BDA0002475419630000042
本实施例提供的硅质耐火泥浆的性能指标测试结果参见表1
实施例3
所述硅质耐火泥浆由以下组分及重量百分数组成：
Figure BDA0002475419630000043
Figure BDA0002475419630000051
本实施例提供的硅质耐火泥浆的性能指标测试结果参见表1
实施例4
所述硅质耐火泥浆由以下组分及重量百分数组成：
Figure BDA0002475419630000052
本实施例提供的硅质耐火泥浆的性能指标测试结果参见表1
实施例5
所述硅质耐火泥浆由以下组分及重量百分数组成：
Figure BDA0002475419630000053
Figure BDA0002475419630000061
本实施例提供的硅质耐火泥浆的性能指标测试结果参见表1。
表1 实施例1-5中的硅质耐火泥浆的性能指标测试
Figure BDA0002475419630000062
表1显示，本发明实施例1-3提供的硅质耐火泥浆，不添加生粘土，采用高纯硅微粉和超细的碳化硅抽尘粉来改善材料的和易性，二氧化硅含量高，杂质含量低，高温粘结强度高，荷重软化温度开始点高，有效改善了硅质耐火泥浆的高温使用性能。
采用一定量矿化剂复合加入，经1300℃×5h烧后，泥浆真密度降低，说明残余石英少，矿化剂有利于石英相大量转变为高温体积稳定性好的磷石英相。

Claims (6)

1.一种高温性能优良的硅质耐火泥浆，其特征在于粉料组成按质量百分数计如下：
Figure FDA0003489343060000011
外加占粉料27～30wt％的水混合而成；
所述的矿化剂为铁鳞粉和硼砂的组合；铁鳞粉来源于钢材加热和轧制过程中，由于表面受到氧化而脱落形成的鱼鳞状物，粒度范围为0.044-0mm，铁鳞粉与硼砂质量比为1:(1～3)；
所述的碳化硅抽尘粉是碳化硅生产过程中收集的烟尘废料，粒度≤20um，碳化硅含量≥95wt％。
2.如权利要求1所述高温性能优良的硅质耐火泥浆，其特征在于所述的废硅砖粉主要物相为磷石英相，来源于硅砖烧后的形状缺损或者裂纹而化学成分合格的残次品，以及从焦炉，热风炉上拆除的硅砖，经拣选后将其破碎成粒度为0.5-0mm的颗粒，其中SiO2含量大于94wt％。
3.如权利要求1所述高温性能优良的硅质耐火泥浆，其特征在于所述的石英粉为未经煅烧的高纯度石英砂，其SiO2含量≥98.5wt％。
4.如权利要求1所述高温性能优良的硅质耐火泥浆，其特征在于二氧化硅微粉是二氧化硅含量≥99wt％，粒度d50为0.15um的高纯度超细微粉。
5.如权利要求1所述高温性能优良的硅质耐火泥浆，其特征在于所述的糊精为一种黄糊精，其粘结力大于1.8kg/cm2，在15-17℃水中溶解度大于96％。
6.如权利要求1所述高温性能优良的硅质耐火泥浆，其特征在于所述的羧甲基纤维素中纤维素含量大于等于97.5wt％。
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