CN116199500B - 一种转炉耳轴、渣线部位用高性能镁碳砖及其生产工艺 - Google Patents
一种转炉耳轴、渣线部位用高性能镁碳砖及其生产工艺 Download PDFInfo
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Abstract
本发明涉及一种转炉耳轴、渣线部位用高性能镁碳砖及其生产工艺，是由如下重量份数的原料制备而成：电熔大结晶镁砂70‑90份、镁铝硅合金粉1‑2份、增强剂混合物0.2‑0.5份、氮化钛(TiN)和氮化硅(Si3N4)和氮化铬(CrN)混合粉0.5‑1.5份、炭黑0.3‑1份、高温沥青粉1‑2份、超细石墨14‑16份、结合剂2‑3份。本发明增加致密性，抗冲刷性，同时具备良好的抗热震稳定性，实现耳轴、渣线部位的高寿命，减少因为转炉炉衬中易损部位侵蚀严重造成的转炉综合寿命降低，提高转炉炉衬的综合炉龄和稳定性及安全性。
Description
技术领域
本发明涉及钢铁冶金领域中的转炉炉衬镁碳砖的生产工艺及技术，具体涉及一种转炉耳轴、渣线部位用高性能镁碳砖及其生产工艺。
背景技术
在钢铁冶金炉衬材料领域，由于镁碳砖具有的耐火度高、抗渣侵性能好、耐热震性强及高温下具有优良稳定性能、导热性好、耐磨损、耐剥落性好等优良特性，已在电炉、转炉及精炼炉上得到广泛应用。但镁碳砖也存在着易氧化、结构易疏松、高温结构强度低和抗热冲刷性能差等缺点。在目前钢厂普遍提高转炉炉龄、降低耐火材料消耗的环境下，对镁碳砖关键理化性能的改善和优化已成为必然趋势。
镁碳砖转炉炉衬根据不同的部位，基本分为炉底，耳轴、渣线，装料侧，熔池，炉帽等，根据其工作环境和侵蚀机理，选择不同材质的镁碳砖。在炉底，采用不加金属添加剂、碳含量为14％～16％的中档镁碳砖。对于易损部位，如耳轴、渣线，由于经常受到气流、钢渣侵蚀等因素的影响，损毁严重，因此采用碳含量为16％～18％，并添加金属抗氧化剂的高档镁碳砖砌筑，以增强其抗侵蚀性。在装料侧，由于经常受到钢渣的冲刷、机械应力等作用，选用碳含量为10％～14％，并添加金属抗氧化剂的高档镁碳砖砌筑，以增强其抗冲击能力和炉渣的涂层保护，延长炉体的寿命。熔池部位由于经常受到钢水的侵蚀、气流等作用的影响，因此采用碳含量为16％～18％，并添加金属抗氧化剂的高档镁碳砖砌筑。在炉帽部位，采用碳含量为14％～16％的中档镁碳砖，以利于减少碳的汽化消失，增加衬体的严密性，防止掉砖、漏钢等事故的发生。总之，由于镁碳砖在转炉上实行综合砌炉，因此易损部位如耳轴、渣线镁碳砖的理化指标更加关键，如何实现对氧枪及底吹气流，钢渣侵蚀的抗损毁能力的提升，已成为转炉能否延长并提高转炉综合炉龄的重中之重。
发明内容
本发明提供了一种转炉耳轴、渣线部位用高性能镁碳砖及其生产工艺，增加致密性，抗冲刷性，同时具备良好的抗热震稳定性，实现耳轴、渣线部位的高寿命，减少因为转炉炉衬中易损部位侵蚀严重造成的转炉综合寿命降低，提高转炉炉衬的综合炉龄和稳定性及安全性。
为了达到上述目的，本发明采用以下技术方案实现：
一种转炉耳轴、渣线部位用高性能镁碳砖，是由如下重量份数的原料制备而成：电熔大结晶镁砂70-90份、镁铝硅合金粉1-2份、增强剂混合物0.2-0.5份、氮化钛(TiN)和氮化硅(Si3N4)和氮化铬(CrN)混合粉0.5-1.5份、炭黑0.3-1份、高温沥青粉1-2份、超细石墨14-16份、结合剂2-3份。
所述电熔大结晶镁砂中MgO≥97.7％；电熔大结晶镁砂连续颗粒级配按重量份比例：≤6mm且≥3mm，20-25份；＜3mm且≥1mm，25-30份；＜1mm且≥0.212mm，15-20份；＜0.088mm，10-15份。
所述的镁铝硅合金中Al≥50％，Si含量2％～5％，其粒度要求为≤0.045mm。
所述增强剂混合物为硼化锆(ZrB2)和硼化锰(MnB2)的混合物，添加的质量比为硼化锆：硼化锰＝5：1～10：1，粒度要求为≤0.045mm。
所述的氮化钛、氮化硅、氮化铬混合粉的添加质量比为7:2:1～5:4:1；其粒度要求为≤0.088mm。
所述的炭黑粒度要求为≤100nm，碳含量≥99％；所述的高温沥青粉粒度要求为≤0.088mm，固定碳含量≥60％；所述超细石墨粒度要求为≤0.01mm，固定碳含量≥97％。
所述的结合剂为酚醛树脂，要求树脂残碳含量≥45％。
转炉耳轴、渣线部位用高性能镁碳砖的性能指标为：显气孔率1.5％-2.5％；体积密度2.98-3.02g/cm3；常温耐压强度45-55MPa，1400℃×0.5h(埋碳)高温抗折强度15-20Mpa；1000℃*2h重烧线变化率0.3％-0.5％；使用寿命为：≥180ton的转炉，9000-10000炉。
一种转炉耳轴、渣线部位用高性能镁碳砖的生产工艺，
1)首先按上述配比通过称量车进行称量，将粒度＜0.212mm的原料颗粒及微细粉通过锥式预混机预混20-40min，出预混料备用；
2)在采用高速混练机先加入粒度≤6mm且≥3mm、＜3mm且≥1mm、＜1mm且≥0.212mm的原料颗粒混练2-3min后加入酚醛树脂后混练1-2min，然后加入步骤1)得到的预混料继续混练10-15min即可出料；
3)混练好的泥料经困料0.5-3小时，采用摩擦压砖机或液压机进行成型；
4)成型后经拣选合格砖坯首先自然干燥2-6小时，后在200±10℃高温温度下干燥16-24小时，出窑后拣选即得成品。
下面就配方中各种材料的引入做具体说明：
转炉使用时的温差达到1620-1650℃，镁碳砖的损毁，首先是由于砖内的碳氧化，形成脱碳层，加之高温下氧化镁与石墨的热膨胀率相差悬殊(1000℃时，分别为1.4％和0.2％)，导致组织结构疏松，强度降低，再经熔渣的侵蚀、机械冲刷等作用，砖中的氧化镁颗粒逐渐被熔蚀，逐层脱落，从而造成镁碳砖的损毁。镁碳砖的损毁过程是：氧化→脱碳→疏松→侵蚀→冲刷→脱落→损毁。
在1600℃以上，如下反应是导致镁碳砖损毁的主要原因：
MgO(s)+C(s)→Mg(g)+CO(g)
镁碳砖的损毁，首先是工作衬热面中的碳氧化，形成一层薄的脱碳层，碳的氧化是由于不断被炉渣中铁的氧化物和空气中的O2以及CO2、SiO2等氧化物氧化的结果，其核心是溶解于钢液之中或砖中的MgO对碳的汽化作用；其次是高温液态熔渣渗入脱碳层的气孔或由于热应力的作用产生的裂纹之中，与砖中的氧化镁反应形成低熔点的化合物，致使砖的表面层发生质变并弱化。最终在强大的钢渣搅动、机械冲刷等应力作用下逐层脱落，导致镁碳砖的损毁，如此周而复始多次使用，炉衬逐层变薄。
由于热应力的变化对镁碳砖的热震产生非常大的影响，易引发热震裂纹的发生，抗侵蚀性变差。为提高镁碳砖的热震稳定性及保持良好的抗侵蚀能力及抗冲刷性能，引入电熔大结晶镁砂。其用量大于上限值(＞90份)时，因其本身的热震稳定性差，易引发镁碳砖热震裂纹产生，加速镁碳砖的脱碳氧化，在强大的钢渣搅动、机械冲刷下逐层脱落，导致镁碳砖的损毁。当用量小于其下限值(＜70份)时，对钢水的侵蚀和钢渣中非金属夹杂物的侵蚀抵抗能力差，引起耳轴和渣线部位镁碳砖的抗侵蚀能力及抗冲刷性能变差，因此在上述用量范围内最佳。
金属镁铝硅合金比金属铝具有更加优良的承受热冲击能力，金属镁铝硅合金粉的引入，可以提高镁碳砖制品的中高温抗折强度、耐侵蚀性、热震稳定性。当金属镁铝硅合金粉用量大于其上限值(＞2份)时，抗热熔损性差；用量小于其下限值(＜1份)时，砖体的强度、热震稳定性差。最佳使用量为上述范围值1-2份。
为了改善镁碳砖在高温的性能，防止钢液、钢渣对镁碳砖的氧化侵蚀，本发明中添加硼化锆(ZrB2)和硼化锰(MnB2)的混合物，作为C的防氧化剂和镁铝硅合金的增强剂。
为了改善镁碳砖耐高温氧化、耐磨损、耐侵蚀的性能，本发明中添加氮化钛(TiN)、氮化硅(Si3N4)、氮化铬(CrN)混合粉，即可提高抗氧化性能又能改善镁碳砖的高温抗折强度和抗热冲击性。
纳米炭黑的引入，可使制品更加致密，抗钢渣和气体渗透能力增强，并具有高的热态强度，良好的抗冲刷、抗化学侵蚀性强等优点，减少和抑制热裂纹的产生和扩大。
高温沥青粉，可以实现堵塞气孔，提高抗氧化性，增加中高温强度等作用，进一步提高耳轴、渣线部位镁碳砖的抗侵蚀能力。
超细石墨的引入可以提高制品的抗渣性和热震稳定性，考虑到耳轴、渣线部位的使用特点，本发明中超细石墨的引入量控制在14-16份。
与现有技术相比，本发明的有益效果是：
1)本发明通过引入大结晶镁砂，超细石墨，镁铝硅合金微粉，氮化钛(TiN)、氮化硅(Si3N4)、氮化铬(CrN)混合粉，高温沥青粉，炭黑为主要原料，ZrB2和MnB2复合作为抗氧化剂及镁铝硅合金微粉的增强剂；通过材质优化降低耳轴和渣线部位镁碳砖的热膨胀率，1000℃*2h的重烧线变化由原该部位普通镁碳砖的0.7-0.9％降低为0.3-0.5％；进一步提高镁碳砖的热震稳定性；同时高温抗折指标由10-13MPa提高至15-20Mpa。实现耳轴、渣线部位镁碳砖的高寿命，由5000-7000炉，提升至9000-10000炉，降低吨钢耐材消耗。采用ZrB2和MnB2复合作为防氧化剂和增强剂，大大改善了镁碳砖的抗氧化性能和抗冲刷、抗侵蚀能力。引入氮化钛(TiN)、氮化硅(Si3N4)、氮化铬(CrN)混合粉，即可提高抗氧化性能又能改善镁碳砖的高温抗折强度和抗热冲击性。减少因为转炉炉衬中耳轴、渣线易损部位侵蚀严重造成的转炉综合寿命降低，提高转炉炉衬的综合炉龄，并进一步改善了使用的安全性。
2)优化和改善后的耳轴、渣线部位镁碳砖，既保持了优良的抗热震性和抗侵蚀性，又提高了高温强度和抗氧化性；无论从材质设计理念特点，还是使用性能均有突出优点，已成为转炉新型镁碳砖技术发展的重要趋势，因此市场前景看好。
3)本发明提高转炉炉衬的综合炉龄，并进一步改善了使用的安全性。
具体实施方式
下面结合实施例对本发明进一步说明：
以下实施例对本发明进行详细描述。这些实施例仅是对本发明的最佳实施方案进行描述，并不对本发明的范围进行限制。
本发明实施例组分配比及性能指标见表1；
表1：实施例配方
上述实施例的生产工艺：
1)首先按上述配比通过称量车进行称量(精度1％以内)，将粒度＜0.212mm的原料颗粒及微细粉通过锥式预混机预混20-40min，出预混料；
2)在高速混练机先加入粒度≤6mm且≥3mm、＜3mm且≥1mm、＜1mm且≥0.212mm的原料颗粒混练2-3min后加入酚醛树脂后混练1-2min，然后加入预混料继续混练10-15min即可出料；
3)混练好的泥料经困料0.5-3小时，采用摩擦压砖机或液压机进行成型；
4)成型后经拣选合格砖坯首先自然干燥2-6小时，后在200±10℃高温温度下干燥16-24小时，出窑后拣选即得成品。
本发明实施例与常规转炉耳轴、渣线镁碳砖材质的性能指标比较见表2；
表2：
由表1和表2中数据说明实施例1-3比常规耳轴渣线镁碳砖产品的体密、显气孔率、常温耐压强度、重烧线变化、高温抗折、热震稳定性等性能指标都有了明显的提高和改善。
Claims (4)
1.一种转炉耳轴、渣线部位用高性能镁碳砖，其特征在于，是由如下重量份数的原料制备而成：电熔大结晶镁砂70-90份、镁铝硅合金粉1-2份、增强剂混合物0.2-0.5份、氮化钛和氮化硅和氮化铬混合粉0.5-1.5份、炭黑0.3-1份、高温沥青粉1-2份、超细石墨14-16份、结合剂2-3份；
所述增强剂混合物为硼化锆和硼化锰的混合物，添加的质量比为硼化锆：硼化锰=5：1～10：1，粒度要求为≤0.045mm；
所述的氮化钛、氮化硅、氮化铬混合粉的添加质量比为7:2:1～5:4:1；其粒度要求为≤0.088mm；
所述电熔大结晶镁砂中MgO≥97.7%；电熔大结晶镁砂连续颗粒级配按重量份比例：≤6mm且≥3mm，20-25份；＜3mm且≥1mm，25-30份；＜1mm且≥0.212mm，15-20份；＜0.088mm，10-15份；
所述的镁铝硅合金中Al≥50%，Si含量2%～5%，其粒度要求为≤0.045mm；
转炉耳轴、渣线部位用高性能镁碳砖的性能指标为：显气孔率1.5%-2.5%；体积密度2.98-3.02g/cm3；常温耐压强度 45-55MPa，1400℃×0.5h埋碳处理后高温抗折强度 15-20Mpa；1000℃×2h重烧线变化率 0.3%-0.5%；使用寿命为：≥180ton的转炉，9000-10000炉。
2.根据权利要求1所述的一种转炉耳轴、渣线部位用高性能镁碳砖，其特征在于，所述的炭黑粒度要求为≤100nm，碳含量≥99%；所述的高温沥青粉粒度要求为≤0.088mm，固定碳含量≥60%；所述超细石墨粒度要求为≤0.01mm，固定碳含量≥97%。
3.根据权利要求1所述的一种转炉耳轴、渣线部位用高性能镁碳砖，其特征在于，所述的结合剂为酚醛树脂，要求树脂残碳含量≥45%。
4.一种如权利要求1-3其中任意一项所述的转炉耳轴、渣线部位用高性能镁碳砖的生产工艺，其特征在于，
1）将粒度＜0.212mm的原料颗粒及微细粉通过锥式预混机预混20-40min，出预混料备用；
2）在混练机中先加入粒度≤6mm且≥3mm、＜3mm且≥1mm、＜1mm且≥0.212mm的原料颗粒混练2-3min后加入酚醛树脂后混练1-2min，然后加入步骤1）得到的预混料继续混练10-15min；
3）混练好的泥料经困料0.5-3小时，采用摩擦压砖机或液压机进行成型；
4）成型后首先自然干燥2-6小时，后在200±10℃高温温度下干燥16-24 小时，出窑后拣选即得成品。
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