CN110563476A - 纤维增强耐火砖及其制备方法 - Google Patents

纤维增强耐火砖及其制备方法 Download PDF

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CN110563476A
CN110563476A CN201911037045.5A CN201911037045A CN110563476A CN 110563476 A CN110563476 A CN 110563476A CN 201911037045 A CN201911037045 A CN 201911037045A CN 110563476 A CN110563476 A CN 110563476A
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fiber
parts
powder
refractory brick
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李雄
林发驹
屈小科
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Chengdu Advanced Metal Materials Industry Technology Research Institute Co Ltd
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Abstract

本发明涉及纤维增强耐火砖及其制备方法，属于钢铁冶金用耐火材料技术领域。本发明提供了纤维增强耐火砖，含有如下重量配比的组分：氧化镁和/或氧化铝70～90份，碳化硅1～4份，石墨0.5～10份，铝0.3～1份，耐火纤维0.2～10份，粘结剂1～8份。本发明很好地解决了现有耐火砖强度、耐热度、抗剥落性、抗侵蚀不能同时兼顾的问题，而且成本适中，所提供的耐火砖尤其适用于冶金工业电炉、转炉和精炼炉的炉衬以及浇铸用流钢砖。

Description

纤维增强耐火砖及其制备方法
技术领域
本发明涉及纤维增强耐火砖及其制备方法，属于钢铁冶金用耐火材料技术领域。
背景技术
冶金行业所采用的耐火材料，要求较好的耐热度、强度、抗热震性和耐侵蚀性，以满足钢铁制造的需求。如钢包内衬所用耐火材料，其高温综合性能要求非常高，需具备长时间与1650-1720℃的钢水接触而不被破坏的承受能力。目前国内在电炉、转炉、精炼炉和中间包所用的内衬使用寿命不高，一般为65炉左右，主要原因在于热震导致的剥落和熔渣的渗透侵蚀。因此，提供一种高强度、耐高温、耐热震、耐侵蚀的耐火砖对钢铁冶金业具有重要意义。
CN 101628818A公开了莫来石纤维砖及其制法，该方法采用耐火材料为主要原料，经过包括混料、成型、干燥、烧成工序制成，所述主要原料中添加有莫来石晶体纤维，所述莫来石纤维砖化学成分是：Al2O335～72％；SiO227～64％，Fe2O31～1.2％。该发明的产品兼有轻质莫来石砖和陶瓷纤维材料的优异性能，并具有体积密度较小，比热容小，抗热震性能好，导热系数小等优点，但其耐火度最高在1400℃以下，不适合用作与钢液接触的面砖。
发明内容
本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明的目的在于提供纤维增强耐火砖。本发明的另一目的在于提供所述纤维增强耐火砖的制备方法。
本发明提供了纤维增强耐火砖，含有如下重量配比的组分：氧化镁和/或氧化铝70～90份，碳化硅1～4份，石墨0.5～10份，铝0.3～1份，耐火纤维0.2～10份，粘结剂1～8份；优选地，含有如下重量配比的组分：氧化镁和/或氧化铝88～89份，碳化硅1.5～2份，石墨1～2份，铝0.3～0.5份，耐火纤维2～3份，粘结剂5～6份。
进一步地，所述的耐火纤维选自莫来石纤维、氧化铬纤维、钢纤维、碳纤维中一种或两种以上。
优选地，所述的莫来石纤维为马福特克纤维。
优选地，所述的钢纤维中碳含量不高于0.3％。
进一步地，所述耐火纤维的纤维长度为3～50mm。
进一步地，所述的粘结剂选自纸浆、酚醛树脂、沥青中一种或两种以上。
优选地，所述的纸浆为废纸浆。
进一步地，所述的纤维增强耐火砖各组分满足以下至少一项：
氧化镁以电熔镁砂颗粒料和/或粉体料的形式加入，MgO含量大于95％；
氧化铝以刚玉颗粒料和/或粉体料的形式加入，Al2O3含量大于95％；
碳化硅以粉体的形式加入；
石墨以鳞片石墨粉的形式加入；
铝以铝粉的形式加入；
所述颗粒料的粒径为0.3～5mm；
优选地，所述颗粒料的粒径为1～1.2mm；
所述粉体料的粒径不大于0.2mm；
优选地，所述粉体料的粒径不大于0.12mm；
颗粒料：粉体料的粒径比大于4：1；
电熔镁砂颗粒料：电熔镁砂粉体料的重量比小于1.5：1；
优选地，电熔镁砂颗粒料：电熔镁砂粉体料的重量比为(1～1.4)：1；
刚玉颗粒料：刚玉粉体料的重量比小于1.5：1；
优选地，刚玉颗粒料：刚玉粉体料的重量比为(1～1.4)：1。
本发明提供了所述纤维增强耐火砖的制备方法，包括如下步骤：取各重量百分比的组分，混合均匀，压制成型，干燥，烧结，即得。
进一步地，所述的混合均匀包括干混、湿混和终混三个步骤，其中，干混步骤将粉体料和耐火纤维混合，湿混步骤将颗粒料和粘结剂混合，终混步骤将干混和湿混所得物料再次混合均匀。
进一步地，所述的制备方法满足以下至少一项：
干混时间为10～30分钟；
湿混时间为10～30分钟；
终混时间为20～30分钟；
干混步骤中将耐火纤维分次均匀加入；
湿混步骤中将颗粒料和粘结剂用湿碾机混合均匀。
其中，干混步骤中将耐火纤维分次均匀加入，能够避免混搅成团。
其中，湿混步骤中将颗粒料和粘结剂用湿碾机混合均匀，以使粘结剂完全涂布在颗粒料表面。
进一步地，所述压制成型采用不少于三次压实或等静压成型方法。
进一步地，压制前还包括困料步骤：将混合均匀的原料放置在60～80℃的烘干室5～10小时，得到含水量≤5％的坯料。
进一步地，所述干燥的方法为：首先，在压制成砖坯后，在自然状态下晾晒15～20h后置于干燥窑内，在120～180℃下干燥20～40h；然后，热风温度150～250℃，干燥时间8～15h，得到含水率为0.2～0.8％的干燥态耐火砖坯。
进一步地，所述烧结的条件为：从常温以≤20℃/min的速度升温至150～185℃，保温2～5h，然后以≤80℃/min的速度升温至1550～1700℃，保温时间30～35h，最后在炉内以≤350℃/min的速度冷却至室温，出炉。
本发明提供了纤维增强耐火砖，采用中性或碱性耐火材料为主要原料，添加适量的耐高温纤维，经过包括配料、混合、成型、干燥、烧结等工序制成。所得耐火砖的物理性能指标如下：
本发明提供的耐火砖耐火度可达到1750℃，能够充分耐受钢铁冶炼过程中钢液的高温，更为重要的是，很好地解决了现有耐火砖强度、耐热度、抗剥落性、抗侵蚀不能同时兼顾的问题，而且成本适中。本发明耐火砖具有广阔的推广应用前景，尤其适用于冶金工业电炉、转炉和精炼炉的炉衬以及浇铸用流钢砖。
具体实施方式
下面将结合实施例对本发明的方案进行解释。本领域技术人员将会理解，下面的实施例仅用于说明本发明，而不应视为限定本发明的范围。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1本发明纤维增强耐火砖的制备
将电熔镁砂(MgO含量96％)、刚玉粉(Al2O3含量98％)、SiC粉、鳞片石墨粉、铝粉、马福特克纤维(纤维长度3-10mm)、氧化铬纤维(纤维长度3-10mm)、废纸浆和酚醛树脂按74：15：1.5：2：0.5：1：1：3：2重量比例分别备料，其中镁砂颗粒料：镁砂粉体料的重量比为1.4：1，镁砂颗粒料粒径1mm，除镁砂颗粒料、纤维和粘结剂(废纸浆和酚醛树脂)外，其它均为粉体料，粒径不大于0.2mm。
将镁砂颗粒料和粘结剂湿混10～30分钟，其它原料干混10～30分钟，然后将干混料和湿混料再次混合混练20～30分钟。混练好后将混合料放置在60～80℃的烘干室5～10小时，得到含水量≤5％的坯料。将坯料在压机压实成砖，在自然状态下晾晒15～20h后置于干燥窑内，在120～180℃下干燥20～40h。然后将砖体按如下干燥工艺进行干燥：热风温度150～250℃，干燥时间8～15h，得到含水率为0.2～0.8％的干燥态耐火砖坯。将干燥态耐火砖从常温以≤20℃/min的速度缓慢升温至150～185℃，保温2～5h，然后以≤80℃/min的速度升温至1550℃，保温时间30～35h，最后在炉内以≤350℃/min的速度缓慢冷却至室温，出炉。
烧制好后的耐火砖比重3.35g/cm3，耐火度1750℃，1500℃抗压强度和抗折强度分别为110MPa和41MPa；钢包使用寿命由现有镁铝砖的65炉提升至92炉。镁铝砖主要由含钙少的煅烧镁砂(MgO＞90％，CaO＜2.2％)做原料，加入约8％的工业氧化铝粉，以亚硫酸纸浆废液做结合剂，在1580℃的高温下烧成的制品。
实施例2本发明纤维增强耐火砖的制备
将镁砂粉(MgO含量97％)、刚玉颗粒和刚玉粉(Al2O3含量98％)、SiC粉、鳞片石墨粉、铝粉、马福特克纤维(纤维长度10-20mm)、氧化铬纤维(纤维长度10-20mm)、钢纤维(碳含量不高于0.3％的低碳钢纤维，纤维长度3-10mm)、废纸浆和酚醛树脂按65：24：1.5：1：0.3：1：1：1：2.5：2.7重量比例分别备料，其中刚玉颗粒料：刚玉粉体料的重量比为1：1，刚玉颗粒料粒径1.2mm，除刚玉颗粒料、纤维和粘结剂(废纸浆和酚醛树脂)外，其它均为粉体料，粒径不大于0.2mm。
将刚玉颗粒料和粘结剂湿混10～30分钟，其它原料干混10～30分钟，然后将干混料和湿混料再次混合混练20～30分钟。混练好后将混合料放置在60～80℃的烘干室5～10小时，得到含水量≤5％的坯料。将坯料在压机压实成砖，在自然状态下晾晒15～20h后置于干燥窑内，在120～180℃下干燥20～40h。然后将砖体按如下干燥工艺进行干燥：热风温度150～250℃，干燥时间8～15h，得到含水率为0.2～0.8％的干燥态耐火砖坯。将干燥态耐火砖从常温以≤20℃/min的速度缓慢升温至150～185℃，保温2～5h，然后以≤80℃/min的速度升温至1450℃，保温时间30～35h，最后在炉内以≤350℃/min的速度缓慢冷却至室温，出炉。
烧制好后的耐火砖比重3.4g/cm3，耐火度1700℃，1500℃抗压强度和抗折强度分别为105MPa和39MPa；大大改善了现有氧化铝砖的侵蚀和剥落问题。氧化铝砖以氧化铝(电熔刚玉及莫来石料)为主要原料，加入碳素原料(如鳞片石墨、炭黑和硬质沥青)，并添加较少量的其他原料(如金属硅粉、SiC粉、铝粉)，以酚醛树脂或沥青为结合剂，经过压制、热处理成型。
实施例3本发明纤维增强耐火砖的制备
将镁砂颗粒和镁砂粉(MgO含量97.5％)、刚玉颗粒和刚玉粉(Al2O3含量99％)、SiC粉、鳞片石墨粉、铝粉、马福特克纤维(纤维长度20-30mm)、氧化铬纤维(纤维长度30-50mm)、废纸浆和酚醛树脂按44：44：2：1.2：0.3：1.5：1：3：3重量比例分别备料，其中镁砂颗粒料：镁砂粉体料的重量比为1：1，刚玉颗粒料：刚玉粉体料的重量比为1：1，颗粒料粒径1mm，除刚玉和镁砂颗粒料、纤维和粘结剂(废纸浆和酚醛树脂)外，其它均为粉体料，粒径不大于0.2mm。
将刚玉与镁砂颗粒料和粘结剂湿混10～30分钟，其它原料干混10～30分钟，然后将干混料和湿混料再次混合混练20～30分钟。混练好后将混合料放置在60～80℃的烘干室5～10小时，得到含水量≤5％的坯料。将坯料在压机压实成砖，在自然状态下晾晒15～20h后置于干燥窑内，在120～180℃下干燥20～40h。然后将砖体按如下干燥工艺进行干燥：热风温度150～250℃，干燥时间8～15h，得到含水率为0.2～0.8％的干燥态耐火砖坯。将干燥态耐火砖从常温以≤20℃/min的速度缓慢升温至150～185℃，保温2～5h，然后以≤80℃/min的速度升温至1550℃，保温时间30～35h，最后在炉内以≤350℃/min的速度缓慢冷却至室温，出炉。
烧制好后的耐火砖比重3.38g/cm3，耐火度1750℃，1500℃抗压强度和抗折强度分别为112MPa和40.5MPa；大大改善了现有镁碳砖的耐侵蚀性和抗剥落性。镁碳砖主要采用优质镁砂，高纯石墨和金属硅、碳化硅等添加物，用酚醛树脂作结合剂压制而成。
需要说明的是，本说明书中描述的具体特征、结构、材料或者特点可以在任一个或多个实施例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例以及不同实施例的特征进行结合和组合。

Claims (10)

1.纤维增强耐火砖，其特征是：含有如下重量配比的组分：氧化镁和/或氧化铝70～90份，碳化硅1～4份，石墨0.5～10份，铝0.3～1份，耐火纤维0.2～10份，粘结剂1～8份；优选地，含有如下重量配比的组分：氧化镁和/或氧化铝88～89份，碳化硅1.5～2份，石墨1～2份，铝0.3～0.5份，耐火纤维2～3份，粘结剂5～6份。
2.如权利要求1所述的纤维增强耐火砖，其特征是：所述的耐火纤维选自莫来石纤维、氧化铬纤维、钢纤维、碳纤维中一种或两种以上；优选地，所述的莫来石纤维为马福特克纤维；优选地，所述的钢纤维中碳含量不高于0.3％。
3.如权利要求1或2所述的纤维增强耐火砖，其特征是：所述耐火纤维的纤维长度为3～50mm。
4.如权利要求1所述的纤维增强耐火砖，其特征是：所述的粘结剂选自纸浆、酚醛树脂、沥青中一种或两种以上；优选地，所述的纸浆为废纸浆。
5.如权利要求1所述的纤维增强耐火砖，其特征是：各组分满足以下至少一项：
氧化镁以电熔镁砂颗粒料和/或粉体料的形式加入，MgO含量大于95％；
氧化铝以刚玉颗粒料和/或粉体料的形式加入，Al2O3含量大于95％；
碳化硅以粉体的形式加入；
石墨以鳞片石墨粉的形式加入；
铝以铝粉的形式加入；
所述颗粒料的粒径为0.3～5mm；
优选地，所述颗粒料的粒径为1～1.2mm；
所述粉体料的粒径不大于0.2mm；
优选地，所述粉体料的粒径不大于0.12mm；
颗粒料：粉体料的粒径比大于4：1；
电熔镁砂颗粒料：电熔镁砂粉体料的重量比小于1.5：1；
优选地，电熔镁砂颗粒料：电熔镁砂粉体料的重量比为(1～1.4)：1；
刚玉颗粒料：刚玉粉体料的重量比小于1.5：1；
优选地，刚玉颗粒料：刚玉粉体料的重量比为(1～1.4)：1。
6.权利要求1～5任意一项所述纤维增强耐火砖的制备方法，其特征是：包括如下步骤：取各重量百分比的组分，混合均匀，压制成型，干燥，烧结，即得。
7.如权利要求6所述的制备方法，其特征是：所述的混合均匀包括干混、湿混和终混三个步骤，其中，干混步骤将粉体料和耐火纤维混合，湿混步骤将颗粒料和粘结剂混合，终混步骤将干混和湿混所得物料再次混合均匀。
8.如权利要求7所述的制备方法，其特征是：满足以下至少一项：
干混时间为10～30分钟；
湿混时间为10～30分钟；
终混时间为20～30分钟；
干混步骤中将耐火纤维分次均匀加入；
湿混步骤中将颗粒料和粘结剂用湿碾机混合均匀。
9.如权利要求6所述的制备方法，其特征是：压制前还包括困料步骤：将混合均匀的原料放置在60～80℃的烘干室5～10小时，得到含水量≤5％的坯料。
10.如权利要求6所述的制备方法，其特征是：所述烧结的条件为：从常温以≤20℃/min的速度升温至150～185℃，保温2～5h，然后以≤80℃/min的速度升温至1550～1700℃，保温时间30～35h，最后在炉内以≤350℃/min的速度冷却至室温，出炉。
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CN112624774A (zh) * 2020-12-21 2021-04-09 马鞍山利尔开元新材料有限公司 一种金属陶瓷转炉挡渣滑板砖材料及制备方法
CN115259865A (zh) * 2021-04-29 2022-11-01 宝山钢铁股份有限公司 一种电炉炉底热修补用导电耐火材料
CN113754449B (zh) * 2021-08-23 2022-11-15 广东邦普循环科技有限公司 一种耐烧结材料及其制备方法和应用
CN113754449A (zh) * 2021-08-23 2021-12-07 广东邦普循环科技有限公司 一种耐烧结材料及其制备方法和应用
CN114057473A (zh) * 2021-11-30 2022-02-18 海城利尔麦格西塔材料有限公司 一种连铸中间包工作衬的干式料
CN115433017A (zh) * 2022-10-11 2022-12-06 中冶赛迪工程技术股份有限公司 一种耐火砖材料及其制备方法与应用

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