CN112225536B - 一种硅铁矿热炉用无水炮泥 - Google Patents

一种硅铁矿热炉用无水炮泥 Download PDF

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CN112225536B
CN112225536B CN202011101351.3A CN202011101351A CN112225536B CN 112225536 B CN112225536 B CN 112225536B CN 202011101351 A CN202011101351 A CN 202011101351A CN 112225536 B CN112225536 B CN 112225536B
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CN112225536A (zh
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刘坤仑
李胜春
王勇
王东雄
徐小雷
宋永宏
华永才
邸俊明
牛强
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Inner Mongolia Erdos Electric Power Metallurgy Group Co Ltd
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Abstract

本发明属于耐火材料制备技术领域，具体涉及一种硅铁矿热炉用无水炮泥。其原料组成质量百分比为：所述的硅灰为15～20％，粉煤灰为15～25％，粘土为3～7％，无烟煤为4～7％，焦粉为15～20％，石墨为5～10％，废旧抹包料为5～11％，煤焦油为7～11％，酚醛树脂为0.3～0.7％，磷酸铝为0.3～0.8％，沥青粉为1.4～5％，铝粉为0.2～0.5％，硅铁渣为3～7％，羧甲基纤维素钠为0.5～1％，聚乙烯醇为0.3～0.5％。本发明在满足堵铁口功能的同时，高温条件下能够与炉眼砖牢固的结合为一体，自行修复逐渐扩大的炉眼尺寸，实现炉眼不需要每两周左右修复的目的，增加了炉眼砖的使用寿命。

Description

一种硅铁矿热炉用无水炮泥
技术领域
本发明属于耐火材料制备技术领域，具体涉及一种硅铁矿热炉用无水炮泥。
背景技术
冶炼硅铁的矿热炉一般设置2-4个出铁口，硅铁合金和少量渣液从出铁口排出，因此，出铁口是矿热炉非常重要的部位。随着硅铁生产用矿热炉的大型化和强化冶炼技术的进步，出铁次数的增多，该部位的工艺条件变得更加苛刻。矿热炉在出铁水完成后，出铁口用炮泥堵塞，在矿热炉运行过程中，高温铁水及高压煤气射流频繁冲刷、侵蚀出铁口，并且在开、堵出铁口操作时，机械的震动和撞击，导致炉眼砖损坏速度快、使用周期较短、维护频率高，修眼的周期为2周左右；炉眼砖重新砌筑频率高，炉眼砖的使用寿命为2～3年，更换炉眼砖的直接及间接成本均较高，经济技术指标差。
中国专利申请CN201110284694.2中公开了一种用于矿热电炉的出铁口的堵眼耐火材料及其制造方法，所述堵眼耐火材料至少包括：电极糊、粘土耐火粉、石墨粉以及液体状的煤焦油。根据本发明实施例的堵眼耐火材料，通过采用液体状的煤焦油作为堵眼耐火材料的粘结剂，减少了由于水与碳的氧化还原反应对出铁口碳砖的侵蚀。又由于堵眼耐火材料的性质与出铁口碳砖材质的接近，使用该堵眼耐火材料能对被侵蚀的出铁口碳砖进行修补。
中国专利申请中CN201711080223.3公开了一种矿热炉用无水炮泥及其制备方法。该矿热炉用无水炮泥包括以下重量份的各组分：耐火胶介质粉末20～30份，骨料15～25份，氮化硅8～16份，塑结剂15～20份，附着剂2～5份，粉煤灰2～5份，冶金固体废弃物40～50份。本发明所提供的矿热炉用无水炮泥，可大幅度提高单个炉眼使用周期，提高单个炉眼使用寿命。
中国专利申请CN201810141559.4中公开了功能性环保无水炮泥及其制备方法，该无水炮泥的具体成分组成如下:刚玉或者矾土2030质量份,刚玉或者矾土除尘粉5～10质量份,碳化硅5～10质量份,叶腊石5～10质量份,改性氧化铝粉5～10质量份,碳化物除尘粉5～8质量份,酚醛树脂粉1～3质量份,氮化硅铁0～20质量份,软质粘土5～15质量份,蓝晶石3～7质量份,干熄焦3～15质量份,绢云母0～5质量份,铝钛渣5～10质量份,改性树脂15～20质量份。本发明在兼顾传统炮泥的特性外,还新开发了一项维护修复铁口通道的作用,并采用了多种工业回收料,实现了对材料价值的高效利用,利于节能环保。
目前国内硅铁矿热炉用无水炮泥大多从“无水”方面进行研究，功能上仅仅满足堵铁口的需求，但是炉眼砖寿命较短，通常矿热炉的大修周期较短，增加了矿热炉的运行成本。因此，研制出一种不含水、堵铁口后与炉眼砖结合能力较强修复效果恰好，低成本、环保的无水炮泥就显得尤为重要。
发明内容
本发明的目的在于克服现有技术的不足，提供一种硅铁矿热炉用无水炮泥。本发明在满足堵铁口功能的同时，高温条件下能够与炉眼砖牢固的结合为一体，自行修复逐渐扩大的炉眼尺寸，实现炉眼不需要每两周左右修复的目的，大大的增加了炉眼砖的使用寿命。
本发明的目的是通过以下技术方案来实现的：
一种硅铁矿热炉用无水炮泥，其特征在于，其具体的原料组成质量百分比为粉料41～45％、骨料35～41.5％、结合剂11～14.5％、抗氧化剂3～7.5％和增塑剂0.9～1.4％；
所述的骨料由无烟煤、焦粉、石墨和废旧抹包料组成。
优选地，所述的粉料由硅灰、粉煤灰和粘土组成。
优选地，所述的结合剂由煤焦油、酚醛树脂、磷酸铝和沥青粉组成；所述抗氧化剂由铝粉和硅铁渣组成；所述增塑剂由羧甲基纤维素钠和聚乙烯醇组成。
优选地，所述的硅灰为15～20％，粉煤灰为15～25％，粘土为3～7％，无烟煤为4～7％，焦粉为15～20％，石墨为5～10％，废旧抹包料为5～11％，煤焦油为7～11％，酚醛树脂为0.3～0.7％，磷酸铝为0.3～0.8％，沥青粉为1.4～5％，铝粉为0.2～0.5％，硅铁渣为3～7％，羧甲基纤维素钠为0.5～1％，聚乙烯醇为0.3～0.5％。
优选地，所述的硅灰为15％，粉煤灰为24.5％，粘土为5％，无烟煤为5％，焦粉为20％，石墨为5％，废旧抹包料为5％，煤焦油为8.3％，酚醛树脂为0.5％，磷酸铝为0.5％，沥青粉为4.5％，铝粉为0.3％，硅铁渣为5.4％，羧甲基纤维素钠为0.5％，聚乙烯醇为0.5％。
优选地，所述的硅灰、粉煤灰、粘土粒度均≧60目。
优选地，所述的无烟煤、焦粉、石墨、废旧抹包料粒度范围为16～60目；所述的沥青粉、铝粉均≧400目；所述的硅铁渣≧200目。
优选地，所述的硅灰中SiO2含量≧85％，CaO+MgO含量≦4.5％，Fe2O3+C含量≦3.5％；所述的粉煤灰中SiO2+Al2O3含量≧85％，Fe2O3含量≦6％，CaO+MgO含量≦4.5％；所述的粘土中SiO2含量≧44％，Al2O3含量≧37％，Fe2O3含量≦2％，TiO2含量≦2％，CaO+MgO含量≦0.8％，K2O+Na2O含量≦0.8％；所述的硅铁渣中Si+Fe含量≧75％。
优选地，所述的废旧抹包料为中国申请专利CN201910961416.2“一种铁水包内衬用捣打料及其制备方法”中铁水包内衬用捣打料经使用后的废料。
优选地，所述的硅铁渣为矿热炉法生产75硅铁生产过程中产生的硅铁渣。
本发明的硅灰、粉煤灰和粘土作为粉料，起填充骨料空隙、改善泥球制作加工性能、提高无水炮泥高温下的强度、增强料性等作用。同时还具有良好的结合性能，填充于骨料所形成的间隙，达到最佳的堆积密度，便于获得堵眼结实、不易跑眼等最佳的使用性能。选用硅灰、粉煤灰和粘土作为粉料是充分利用其粒度较小以及主要成分为SiO2、Al2O3且具有耐火度高、热导率小的特性，能够缩短无水炮泥堵眼后的烧成时间，提高堵眼的牢固程度，减少跑眼等安全事故的发生，尤其是硅灰、粉煤灰属于工业固废，在减少资源消耗的同时，变废为宝，大大的降低了无水炮泥的原料成本。
本发明的无烟煤、焦粉、石墨和废旧抹包料作为骨料，在无水炮泥成型过程中起到骨架的作用，尤其是在高温条件下，具有良好的物理力学性能，具有较高的耐火度，能够堵眼结实，同时低成本骨料的大量引入，特别是废旧抹包料的添加，在满足使用性能的同时，大大的降低了无水炮泥的成本，且实现了属于工业固废的废旧抹包料再利用。
本发明的煤焦油、酚醛树脂、磷酸铝和沥青粉作为结合剂，是无水炮泥的重要组分，在混料过程中，结合剂可以促使各类原料的混合均匀，填充空隙，提高无水炮泥的粘结强度，使用过程中，煤焦油和沥青炭化，提高了残炭量，对炮泥的高温性能有利，同时煤焦油中的非碳元素挥发排出，剩余的碳原子形成类石墨微晶，这些微晶的层状晶格呈不规则排列，高度分散，填充和封闭无水泥球与炉眼砖之间的空隙，提高了堵眼的牢固程度。
本发明的铝粉、硅铁渣作为抗氧化剂，主要作用是提高无水炮泥的耐高温、耐磨性、常温强度和高温使用性能。铝粉在高温条件下与碳反应生成碳化铝和部分的氧化铝，具有耐高温、强度高的特性，可增强材料的强度，生成的新晶相可堵塞气孔，降低气孔率，提高材料的致密度，有利于材料的常温强度和中高温强度、烧结性能和高温使用性能。同时铝粉的熔点为660℃左右，堵眼后无水炮泥的温度可达900℃以上，铝粉变为液相，有效促进无水炮泥的烧结效果。同时利用硅铁渣中的单质硅和单质铁，提高无水炮泥的高温强度，促进其烧结效果，减少炮泥内部的气孔率，提高堵眼牢固程度。
本发明的羧甲基纤维素钠、聚乙烯醇作为增塑剂，其作用是增强无水炮泥混合料的可塑性，降低混料过程中物料颗粒之间的摩擦力，并提高无水炮泥的成型质量，在颗粒之间起着柔性侨联作用，避免产生较大的应变而发生破裂及裂纹，脱模后仍然可保持所需的形状。
与现有技术相比，本发明的积极效果是：
(1)堵眼效果好，堵眼后经过高温的烧结，无水炮泥和炉眼砖结合成为一体，避免生产中跑眼事故的发生，大大的提高了炉前作业的安全系数，防止人员和设备的意外损失。
(2)对炉眼的修复效果显著，使用无水炮泥后，炉眼不需要每两周修复一次，大大的降低了炉眼修复的费用，以及修炉作业员工的劳动强度。
(3)无水炮泥采用工厂化生产方式，制作加工后直接运输到硅铁炉前使用，炮泥质量稳定性好，且混料均匀。
(4)改变了传统硅铁生产炉前人工配置含水泥球的作业方式，降低炉前作业人员劳动强度，改善炉前作业环境。
(5)有效利用硅灰、粉煤灰、废旧抹包料等固废，变废为宝，切身践行循环经济的绿色理念，并大大的降低了无水炮泥的原料成本。
具体实施方式
以下提供本发明一种硅铁矿热炉用无水炮泥的具体实施方式，但本发明不限于所提供的实施例。
实施例1-6与对比例1-2中硅铁矿热炉用无水炮泥的制备方法为：将其中相应的各原料按照配比放入搅拌机中，搅拌均匀后进入成型机压制成型，成型后放置1h即为成品。
Figure BDA0002724863070000041
Figure BDA0002724863070000051
本实施例1～6中，硅灰为15～20％，此时无水炮泥的Al2O3≧7.5％，常温耐压强度≧8.0MPa，提高了无水泡泥的抗侵蚀、抗冲刷性，确保堵口后的牢度，避免了跑眼等事故；在对比例1中，硅灰为25％，大于本发明15～20％的范围，此时无水炮泥的Al2O3≤7％，常温耐压强度≤7.5MPa，此时无水泡泥抗侵蚀性、抗冲刷性不如实施例1-6好，堵口不牢，不在本发明使用性能的最佳范围内。在实施例1～6中，粘土为3～7％，焦粉为15～20％，此时无水炮泥的C≧24％，无水泡泥耐高温性、热震性良好，同时对硅铁产品无害，不会引入有害元素；在对比例2中，粘土为12％，大于本发明限定的3～7％的范围，焦粉为10％，小于本发明限定的15～20％的范围，此时无水炮泥的C≤24％，不在本发明使用性能的最佳范围内。
本实施例1～6中粉料总的重量百分比为41～45％，堵眼烧结后的无水炮泥强度较高，不易发生脱落现象，大大的提高了堵眼的安全系数。同时由于大量微小粉体小颗粒的存在，有利于硅铁炉的开眼，有利于顺畅生产，减少炉前工人开眼过程中的劳动强度。
本实施例中1～6中骨料总的重量百分比为35～41.5％，此时烧结后的无水炮泥对炉眼的修复效果恰好，且在高温情况下强度较高，不易于脱落。对比例3中骨料总的重量百分比大于41.5％，对炉眼的修复效果过强，正常生产过程中，不到一天时间炉眼直径就小于80mm，难以满足正常的出铁要求；对比例4中骨料总的重量百分比小于35％，对炉眼的修复效果过弱，正常生产过程中，八天时间炉眼直径就扩大到150mm，就需要对炉眼进行修复，增加了维修成本。
本实施例1～6中结合剂总的重量百分比为11～14.5％，具有最佳的使用性能，此时无水炮泥的体积密度、耐压强度比较高，内部的气孔率较小。在炮泥制作过程中不添加水，因此添加酚醛树脂、磷酸铝，提高常温下的成型能力。
本实施例1～6中增塑剂总的重量百分比为0.9～1.4％，具有最佳的使用性能，添加量过少时，其作用难以有效体现，添加量过多时，会增加不必要的成本，且对炮泥的高温性能不利。
本实施例1～6粉料组成中，硅灰为15～20％，粉煤灰为15～25％，粘土为3～7％，三者的比例组合能够实现粉料在无水炮泥中的最佳使用效果，在此比例范围之外对比例中，则不能够达到本发明达到的使用效果。
本实施例1～6骨料组成中，无烟煤为4～7％，焦粉为15～20％，石墨为5～10％，废旧抹包料为5～11％，四者的比例组合能够实现骨料在无水炮泥中的最佳使用效果，在此比例范围之外，则不能够达到本发明达到的使用效果。
本实施例1～6结合剂组成中，煤焦油为7～11％，酚醛树脂为0.3～0.7％，磷酸铝为0.3～0.8％，沥青粉为1.4～5％，四者的比例组合能够实现结合剂在无水炮泥中的最佳使用效果，在此比例范围之外对比例中，则不能够达到本发明达到的使用效果。
本实施例1～6抗氧化剂组成中，铝粉为0.2～0.5％，硅铁渣为3～7％，二者的比例组合能够实现抗氧化剂在无水炮泥中的最佳使用效果，在此比例范围之外，则不能够达到本发明达到的使用效果。
本实施例1～6增塑剂组成中，羧甲基纤维素钠为0.5～1％，聚乙烯醇为0.3～0.5％，二者的比例组合能够实现增塑剂在无水炮泥中的最佳使用效果，在此比例范围之外，则不能够达到本发明达到的使用效果。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明构思的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围内。

Claims (6)

1.一种硅铁矿热炉用无水炮泥，其特征在于，其具体的原料组成质量百分比为硅灰为15-20％，粉煤灰为15-25％，粘土为3-7％，无烟煤为4-7％，焦粉为15-20％，石墨为5-10％，废旧抹包料为5-11％，煤焦油为7-11％，酚醛树脂为0.3-0.7％，磷酸铝为0.3-0.8％，沥青粉为1.4-5％，铝粉为0.2-0.5％，硅铁渣为3-7％，羧甲基纤维素钠为0.5-1％，聚乙烯醇为0.3-0.5％。
2.根据权利要求1所述的一种硅铁矿热炉用无水炮泥，其特征在于，所述的硅灰为15％，粉煤灰为24.5％，粘土为5％，无烟煤为5％，焦粉为20％，石墨为5％，废旧抹包料为5％，煤焦油为8.3％，酚醛树脂为0.5％，磷酸铝为0.5％，沥青粉为4.5％，铝粉为0.3％，硅铁渣为5.4％，羧甲基纤维素钠为0.5％，聚乙烯醇为0.5％。
3.根据权利要求1-2任意一项所述的一种硅铁矿热炉用无水炮泥，其特征在于，所述的硅灰、粉煤灰、粘土粒度均≥ 60目。
4.根据权利要求3所述的一种硅铁矿热炉用无水炮泥，其特征在于，所述的无烟煤、焦粉、石墨、废旧抹包料粒度范围为16～60目；所述的沥青粉、铝粉均≥ 400目；所述的硅铁渣≥ 200目。
5.根据权利要求4所述的一种硅铁矿热炉用无水炮泥，其特征在于，所述的硅灰中SiO2含量≥ 85％，CaO+MgO含量≤ 4.5％，Fe2O3+C含量≤ 3.5％；所述的粉煤灰中SiO2+Al2O3含量≥ 85％，Fe2O3含量≤ 6％，CaO+MgO含量≤ 4.5％；所述的粘土中SiO2含量≥ 44％，Al2O3含量≥ 37％，Fe2O3含量≤ 2％，TiO2含量≤ 2％，CaO+MgO含量≤ 0.8％，K2O+Na2O含量≤0.8％；所述的硅铁渣中Si+Fe含量≥ 75％。
6.根据权利要求5所述的一种硅铁矿热炉用无水炮泥，其特征在于，所述的硅铁渣为矿热炉法生产75硅铁生产过程中产生的硅铁渣。
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