CN112028653A - 一种高导热耐侵蚀高炉自护炭砖及制备方法 - Google Patents

一种高导热耐侵蚀高炉自护炭砖及制备方法 Download PDF

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CN112028653A
CN112028653A CN202010952465.2A CN202010952465A CN112028653A CN 112028653 A CN112028653 A CN 112028653A CN 202010952465 A CN202010952465 A CN 202010952465A CN 112028653 A CN112028653 A CN 112028653A
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陈佳
王悦
戴路
王杰
邵静
陈雪艳
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Wuhan Iron and Steel Co Ltd
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Abstract

一种高导热耐侵蚀高炉自护炭砖，其原料组成及wt%含量：石墨化无烟煤70～79%，金属硅粉8～12%，Al2O3粉6～10%，含钛不低于35%的物料4～8%，碳化硅粉3～7%，外加8～14%热固性酚醛树脂；步骤：将石墨化无烟煤粉粹并筛分；将各级粒度石墨化无烟煤、金属硅粉、Al2O3粉、含钛不低于35wt%的物料、碳化硅粉按照粒度要求及含量要求混合均匀；加入热固性酚醛树脂并搅拌均匀；机械成型；焙烧；保温；机械加工。本发明高炉炭砖导热系数由16W/mK提高到不低于25W/mK，平均孔径<1μm；由于在炭砖中加入含钛物料，在原位形成了Ti(C,N)，起到高炉末期钒钛矿护炉作用，保护了高炉炭砖，延长高炉寿命，并且制备工艺简单。

Description

一种高导热耐侵蚀高炉自护炭砖及制备方法
技术领域
本发明涉及一种高炉炉衬耐火材料，具体说是一种高导热耐侵蚀高炉自护炭砖及其制备方法。
背景技术
随着高炉冶炼强度的不断提高，炉缸炉底炭砖的侵蚀加速，己成为影响高炉生产和寿命的关键因素。
从砖衬侵蚀原因分析，强化冷却，降低砖衬温度对多种侵蚀原因都有缓解作用。例如碱金属的富集温度是900～1200℃，如果将砖衬温度降低到900℃以下，碱金属就侵蚀不了砖衬。炉渣、铁水的侵蚀也都是随着温度降低侵蚀速度降低，提高导热系数是降低砖衬温度，减少砖衬侵蚀最有效的途径之一。
结果表明，炉缸、炉底炭砖侵蚀最严重的部位是铁口中心线以下的圆周侧墙和炉底炭砖，其侵蚀原因是铁水溶蚀、铁水渗透侵蚀及铁水流动的机械磨损，炉缸侧墙的炭砖还有炉缸上部延伸下来的环缝侵蚀带，其主要原因是碱金属、氧化和热应力。因此提高高炉炭砖耐侵蚀性，也是减少砖衬侵蚀最有效的途径之一。
在高炉炉役后期，高炉炉衬会产生严重侵蚀现象。人们为确保高炉安全操作，往往要采用钒钛矿对高炉进行护炉操作。这种方式的护炉，由于该护炉层中的Ti(C,N)很容易与渣铁粘附，并随铁滴下落而进入风口区，其中少部分Ti(C,N)会悬浮在渣铁界面与金属铁和炉渣等形成多相物质。这种多项物质由于结构致密，硬度大，熔点较高，其随着放渣出铁，液面下降而与炉衬接触并粘附在砖衬上。而铁水中固溶的Ti(C,N)在靠近炉墙的时候温度将下降，Ti(C,N)可以析出，也在砖衬上沉积，就这样逐渐形成了沉积物层。其虽然能起到保护炉缸炉底砖衬的作用，但导致高炉操作复杂，产量降低，成本增加等问题，是保护高炉炭砖不得已采取的措施。
众所周知，炭砖的使用寿命决定着高炉的炉役长短。为保证高炉长寿，通常将导热系数、＜1μm孔容积率、抗碱性、抗氧化性及铁水溶蚀指数等作为炭砖的关键性能指标。提高炭砖的导热能力，不仅可以缓解烘炉和投产初期温差应力对炉缸砌体的破坏，而且有利于在炭砖热面形成一层渣铁壳，阻止铁水和渣对炭砖的侵蚀。有研究表明，在铁水温度为1500℃和压力为0.66MPa的条件下，铁水能够渗入孔径1μm以上的微孔中，故减小炭砖气孔直径和提高炭砖的微孔化程度将有利于缓解铁水的渗透，避免炭砖出现脆化层，延长炭砖寿命。炭砖直接与铁水相接触，在铁水中的溶蚀指数越低越好。因此，高导热、抗侵蚀是高炉用炭砖的主要发展方向。
目前，高炉炭砖一般采用电锻无烟煤为主要原料，添加金属硅粉，Al2O3粉，以沥青为结合剂。由于电煅烧无烟煤是一种低石墨化碳且自身多孔，因此电煅煤基炭砖的导热系数差。为提高电锻煤基炭砖的导热系数，国内外大多数研究者都采用添加高导热石墨物质，在炭砖的制备过程中添加超过30wt％的石墨物质，在一定程度上虽提高了炭砖的导热系数，但在高炉的实际生产环境条件下，这些石墨物质极易向铁水中溶解，从而在炭砖中留下孔洞，为铁水的渗透提供了通道，进而导致炭砖形成脆化层，在铁水的冲刷作用下造成炭砖结构性剥落；再高炉炭砖结合剂目前一般为沥青，沥青加入量大，生产过程中(混捏、成型、焙烧)烟气大，对环境有污染。
发明内容
本发明的目的在于克服现有技术存在的不足，提供一种炭砖导热系数由16W/mK提高到不低于25W/mK，平均孔径<1μm，通过在原料中加入含Ti物料，生成Ti(C,N)，起到护炉的作用，且制备工艺简单的高导热耐侵蚀高炉自护炭砖及制备方法。
实现上述目的的措施：
一种高导热耐侵蚀高炉自护炭砖，其原料组成及重量百分比含量为：粒度<6mm的石墨化无烟煤70～79％，粒度≤0.074mm的金属硅粉8～12％，粒度≤0.074mm的Al2O3粉6～10％，粒度为≤0.074mm的含钛不低于35％的物料4～8％，粒度为≤0.074mm的碳化硅粉3～7％，按照上述原料总重量的8～14％外加热固性酚醛树脂。
其在于：石墨化无烟煤粒度组成及各粒级的所占百分比为：粒度在6mm至大于等于3mm的占23～30wt％；粒度在3mm至大于等于1mm占20～28wt％；粒度在1mm至大于等于0.1mm的占5～10wt％；粒度<0.1mm的占35～45wt％。
其在于：所述含钛不低于35％的物料系指：钛粉或TiO2粉或钛精矿粉或其中二种以上的以任意比例的混合。
制备一种高导热耐侵蚀高炉自护炭砖的方法，其步骤：
1)将石墨化无烟煤粉粹并筛分，筛分粒度按照：6mm至大于等于3mm，3mm至大于等于1mm，1mm至大于等于0.1mm，<0.1mm进行分级；
2)将筛分出的各级粒度的干料，即石墨化无烟煤、金属硅粉、Al2O3粉、含钛不低于35wt％的物料、碳化硅粉按照粒度要求及含量要求混合均匀；
3)在步骤2)混合干料中按照混合料总重量的8～14％加入热固性酚醛树脂并搅拌均匀；
4)进行机械成型；
5)进行焙烧，焙烧温度控制在1380～1430℃；
6)进行保温，保温时间控制在15～20h；
7)机械加工。
优选地：焙烧温度在1386～1423℃。
本发明中各原料及主要工艺的机理及作用
石墨化无烟煤：石墨化无烟煤处理温度达2300℃，比电煅无烟煤煅烧温度(约1700℃)高很多，用石墨化无烟煤制备的炭砖热导率电煅无烟煤更高、抗铁水侵蚀性能也比添加人造石墨原料更优异。
金属粉、碳化硅粉、Al2O3粉：其是微孔、超微孔炭砖生产中的添加剂，其能与碳材料反应生成碳化物(如β-sic)，填充堵塞气孔，具有微孔化的功能，同时具有提高炭砖抗氧化性、抗铁水溶蚀性，提高炭砖耐压强度作用。
含钛不低于35wt％的物料：指钛粉，TiO2粉、钛精矿粉。其在原料中加入的Ti能与原料中C，N在制品制造或使用过程中生成Ti(C,N)，能提高熔渣的粘度，凝固渣皮，起到护炉的作用。替代了一般高炉末期钒钛矿护炉操作，简化了高炉操作流程，降低了高炉操作成本。
热固性酚醛：采用热固性酚醛作结合剂，可以减少加入量，同时生产环境大大改善。
本发明之所以将各所组成石墨化无烟煤粉粹并筛分，筛分粒度按照：6mm至大于3mm、3mm至大于1mm、1mm至大于0.1mm、<0.1mm进行分级，该粒度组成成型性能较好，密度较高。
本发明之所以控制焙烧温度在1380～1430℃，并控制保温时间在15～20h，是为了保证结合剂热固性酚醛树脂炭化。
本发明与现有技术相比：
一是采用石墨化无烟煤为主要原料，大大提高了炭砖导热系数，一般采用电煅无烟煤超微孔炭砖室温导热系数为16W/mK，采用石墨化无烟煤超微孔炭砖室温导热系数达到25W/mK以上。导热性能提高后能与水冷却壁配合把热量传出去，把1150℃渣铁凝固等温线推到炉内，在炉衬表面形成渣皮保护，延长高炉炭砖使用寿命。
二是采用金属硅粉，Al2O3粉，碳化硅粉等微孔添加剂，能与碳材料反应生成碳化物(如ρ-sic)，填充堵塞气孔，减轻渣铁渗透侵蚀；同时具有提高炭砖抗氧化性、抗铁水溶蚀性，提高炭砖耐压强度作用。平均孔径<1μm，氧化率，铁水熔蚀指数等均有不同程度提高。
三是具有钛矿护炉的作用，用钛矿护炉是当今高炉炉缸、炉底长寿有效手段之一。有在烧结铁矿石里配加钛精矿补炉的，有在风口喷吹含钛精矿煤粉的，也有在风口喂氧化钛丝的。由于加有含钛物质，原位形成了Ti(C,N)，起到就地护炉的作用和“自身保护”的作用。简化了高炉操作流程，降低了高炉操作成本。
四是采用热固性酚醛作结合剂与采用煤沥青相比，大大改善了混捏、成型、焙烧生产环境。
具体实施方式
下面对本发明予以详细描述：
表1为本发明各实施例原料及含量的取值列表；
表2为本发明各实施例主要工艺参数取值列表；
表3为本发明各实施例及目前国内微孔炭砖、超微孔炭砖主要性能列表。
以下各实施例均按照以下步骤进行：
1)将石墨化无烟煤粉粹并筛分，筛分粒度按照：6mm至大于等于3mm，3mm至大于等于1mm，1mm至大于等于0.1mm，<0.1mm进行分级；
2)将筛分出的各级粒度的干料，即石墨化无烟煤、金属硅粉、Al2O3粉、含钛不低于35wt％的物料、碳化硅粉按照粒度要求及含量要求混合均匀；
3)在步骤2)混合干料中按照混合料总重量的8～14％加入热固性酚醛树脂并搅拌均匀；
4)进行机械成型；
5)进行焙烧，焙烧温度控制在1380～1430℃；
6)进行保温，保温时间控制在15～20h；
7)机械加工。
表1本发明各实施例原料取值列表(wt％))
Figure BDA0002677477880000051
Figure BDA0002677477880000061
表2本发明各实施例主要工艺参数取值列表
Figure BDA0002677477880000062
表3本发明各实施例炭砖及目前市场微孔炭砖、超微孔炭砖主要性能列表
Figure BDA0002677477880000063
从表3检测结果看出，本发明和现有微孔炭砖，超微孔炭砖相比，其砖导热系数大大提高，抗氧化性更好，抗铁水溶蚀性增强，因此抗侵蚀性更强，并且原料中添加有含钛物料，对炭砖有保护作用，有利于炭砖使用寿命，进而延长高炉寿命。
上述实施例仅为最佳例举，而并非是对本发明的实施方式的限定。

Claims (5)

1.一种高导热耐侵蚀高炉自护炭砖，其原料组成及重量百分比含量为：粒度<6mm的石墨化无烟煤70～79%，粒度≤0.074mm的金属硅粉8～12%，粒度≤0.074mm的Al2O3粉6～10%，粒度为≤0.074mm的含钛不低于35%的物料4～8%，粒度为≤0.074mm的碳化硅粉3～7%，按照上述原料总重量的8～14%外加热固性酚醛树脂。
2.如权利要求1所述的一种高导热耐侵蚀高炉自护炭砖，其特征在于：石墨化无烟煤粒度组成及各粒级的所占百分比为：粒度在6mm至大于等于3mm的占23～30wt%；粒度在3mm至大于等于1mm占20～28 wt%；粒度在1mm至大于等于0.1mm的占5～10wt%；粒度<0.1mm的占35～45wt%。
3.如权利要求1所述的一种高导热耐侵蚀高炉自护炭砖，其特征在于：所述含钛不低于35%的物料系指：钛粉或TiO2粉 或钛精矿粉或其中二种以上的以任意比例的混合。
4.制备如权利要求1所述的一种高导热耐侵蚀高炉自护炭砖的方法，其步骤：
1）将石墨化无烟煤粉粹并筛分，筛分粒度按照：6mm至大于等于3mm，3mm至大于等于1mm，1mm至大于等于0.1mm，<0.1mm进行分级；
2）将筛分出的各级粒度的干料，即石墨化无烟煤、金属硅粉、Al2O3粉、含钛不低于35wt%的物料、碳化硅粉按照粒度要求及含量要求混合均匀；
3） 在步骤2）混合干料中按照混合料总重量的8～14%加入热固性酚醛树脂并搅拌均匀；
4）进行机械成型；
5）进行焙烧，焙烧温度控制在1380～1430℃；
6）进行保温，保温时间控制在15～20h；
7) 机械加工。
5.如权利要求4所述的制备一种高导热耐侵蚀高炉自护炭砖的方法，其特征在于：焙烧温度在1386～1423℃。
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