CN110423100B - 一种添加镁碳超细粉的高纯镁碳砖及其制备方法 - Google Patents
一种添加镁碳超细粉的高纯镁碳砖及其制备方法 Download PDFInfo
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Abstract
本产品属于耐火材料定型含碳耐火制品领域,具体涉及一种镁碳超细粉结合的高纯镁碳砖及其制备方法,制品可用于钢包使用环境最恶劣的渣线部位;本发明特点在于以二钙电熔镁砂和鳞片石墨为主要原料构建高纯体系镁碳砖,具有在高温下的强度高、抗渣性能优良和抗热震性好的特性;还引入经特殊工艺处理的镁碳超细粉,其中位粒径小于10μm,具有较高的活性、分散性和填充性能,高温下有利于原位生成纳米晶须,提高制品体积密度和高温强度;本发明制备的镁碳砖在马钢长材事业部70t钢包渣线部位多次试用,可使该渣线砖的使用寿命由原来的50次提高至100余次,其平均使用寿命为103次,高于传统镁碳砖近一倍,达到国际先进水平。
Description
技术领域
本产品属于耐火材料定型含碳耐火制品领域,具体涉及一种镁碳超细粉结合的高纯镁碳砖及其制备方法,制品可用于钢包使用环境最恶劣的渣线部位。
背景技术
随着炉外精炼等冶炼技术的发展和进步,钢包用含碳耐火材料所面临的使用环境愈加苛刻,钢厂对钢包衬砖的使用寿命要求逐步增加。目前,国内耐火行业制造所面临的现状总结如下:1)随着国际耐火原料的价格持续上涨,导致耐火制品的生产成本逐渐增加,因此国内大部分耐火制造企业开始启动再生料、磨下料等大量回收再利用的降本增效方案,这些方案虽能为企业带来可观效益,但废料性能的不稳定性势必会导致耐火制品性能的下降和产品使用质量的波动;2)钢包渣线部位是衬砖使用环境最为恶劣之处,钢包渣线砖的使用寿命对钢包的使用周转频率和上线使用次数具有决定性影响,目前国内钢包渣线砖的平均使用寿命因冶炼工艺、钢包的不同而不同。因此开发研制出与钢包熔池砖使用次数相匹配的长寿渣线砖已成为国内耐火制造厂商迫切需解决的问题。
目前马钢长材事业部70t钢包渣线砖的平均使用寿命为50次左右,针对马钢精炼比例高、钢渣酸碱度及下渣量复杂等苛刻使用环境的钢包,研制开发出适应其恶劣使用环境的长寿渣线砖已成为本公司迫切需解决的难题。
发明内容
本发明技术人员在研究过程中预料不到的发现:以高纯98二钙电熔镁砂和98鳞片石墨为主要原料,添加镁碳超细粉,经混碾、困料、压制、烘烤,得到的镁碳砖具有高强度、抗渣性和抗热震性优良等特性,能适应精炼比例高、钢渣酸碱性复杂等恶劣使用环境要求的钢包渣线部位。
具体的,本发明公开了一种镁碳砖,包括质量百分比为如下含量的组分:60%~80%的二钙电熔镁砂颗粒为骨料,5%~10%的二钙电熔镁砂细粉,5%~10%的鳞片石墨,1%~2%的沥青,5%~15%的活性镁碳超细粉,1~4%的抗氧化剂,外加前述组分总量2~4%的热固性酚醛树脂,所述抗氧化剂为金属铝粉和金属硅粉。
优选的,所述活性镁碳超细粉由如下方法制备而成:将60~80%小于74μm二钙电熔镁砂细粉和20~40%小于13μm鳞片石墨通过添加0.05~1%,优选0.2~0.5%的金属纳米铁片经高速球磨而成,活性镁碳超细粉中位粒径小于10μm,MgO≥60%,C≤40%。
优选的,所述二钙电熔镁砂颗粒粒度分别为5~3mm、3~1mm、1~0mm,各粒径的质量百分比分别均为15%~30%,更优选分别为15%~25%、15%~30%、15%~25%。
优选的,所述二钙电熔镁砂细粉粒径小于88μm;所述鳞片石墨的粒径为小于149μm;所述沥青的粒径为小于149μm,质量百分比为1%~1.5%;所述抗氧化剂中金属铝粉和硅粉粒径均为小于44μm,所述金属铝粉与硅粉质量比为5:1~1:5,优选2:1~1:1。
本发明还涉及上述任一项所述的镁碳砖的制备方法,其特征在于,以二钙电熔镁砂颗粒为骨料、二钙电熔镁砂细粉及鳞片石墨为基质,沥青、镁碳超细粉和金属铝粉、金属硅粉为添加剂,外加热固性酚醛树脂作为结合剂,经过泥料混碾、养护、压制成型后再进行烘烤处理得到。
优选的,所述混碾方法为:首先将二钙电熔镁砂细粉、活性镁碳超细粉、沥青、金属硅粉和金属铝粉预混合,得到预混粉;混碾加料顺序如下,先加二钙电熔镁砂颗粒,混碾后,加入部分液体酚醛树脂润湿颗粒,再风送鳞片石墨混碾,再加预混粉混碾,最后加剩余液体酚醛树脂混碾,得到泥料。
更优选的,所述混碾时间为10~25min,优选15~20min。
优选的,所述养护为将混好的泥料置于温度为18~22℃,湿度为43~47%的恒温恒湿房进行16h~24h的困料。
优选的,所述成型为按照工艺图纸和工艺规程要求的压机类型和成型参数进行生产,控制好砖坯尺寸、飞边、缺损、麻皮、层裂等外观质量,成型。
优选的,所述烘烤处理温度从低到高逐步升高,在180~250℃热处理12~24h后冷却出辊道窑。
本发明生产的镁碳砖,各项检测指标均高于传统镁碳砖,2019年3~5月本发明制备的镁碳砖在马钢长材事业部70t钢包渣线部位多次试用,可使该渣线砖的使用寿命由原来的50次提高至100余次,其平均使用寿命为103次,高于传统镁碳砖近一倍,达到国际先进水平,具备良好的国际市场竞争力。
马钢长材事业部月平均产钢量40万吨,如果按照吨钢消耗耐材22kg计,则每月钢包消耗耐材量约为3000t,若全部使用本发明的镁碳砖,则长材事业部每月可节省约1500t耐材的消耗,能为公司及钢厂带来巨大的经济效益。
与现有技术相比,本发明还具有如下优点:(1)本发明以二钙电熔镁砂和鳞片石墨为主要原料构建高纯体系镁碳砖,具有在高温下的强度高、抗渣性能优良和抗热震性好的特性;
(2)本发明引入经特殊工艺处理的镁碳超细粉,其中位粒径小于10μm,具有较高的活性、分散性和填充性能,高温下有利于原位生成纳米晶须,提高制品体积密度和高温强度。
具体实施方式
下面结合实施例对本发明作进一步的描述。所描述的实施例及其结果仅用于说明本发明,而不应当也不会限制权利要求书中所详细描述的本发明。
为了避免重复,先将具体实施方式中所涉及实验过程及参数统一描述如下,实施例中不再赘述:
本实施例中二钙电熔镁砂细粉的粒径≤0.088mm、化学组分MgO≥98%,鳞片石墨的粒径≤0.149mm、C≥98%,沥青的粒径≤0.149mm,抗氧化剂的粒径≤0.045mm,结合剂为5326液体酚醛树脂。
镁碳超细粉的制备方法是:将60~80%的粒径≤0.074mm二钙电熔镁砂细粉和20~40%粒径≤0.013mm鳞片石墨通过添加0.05~1%,优选0.05%~0.2%金属纳米铁片,经行星式球磨机高速球磨4~8h即得中位粒径小于10μm的镁碳超细粉,总量为200kg。
此外,本发明还提供了制备上述渣线镁碳砖的方法。
具体的,首先是制备预混粉,其方法为:将二钙电熔镁砂细粉、镁碳超细粉、沥青和抗氧化剂置于V型混合机中均匀混合20~30min即得预混粉待用。
其次以5-3mm、3-1mm和1-0mm的二钙电熔镁砂颗粒、预混粉和鳞片石墨为原料,混合均匀,每次配料总重量为1吨,再外加所述原料的酚醛树脂进行混练,然后经养护、压制成型、干燥,即得渣线镁碳砖。
实施例1
一种渣线镁碳砖及其制备方法:
(1)将所有原料按配比称重:粒径5~3mm的二钙电熔镁砂颗粒25%、粒径3-1mm的二钙电熔镁砂颗粒30%、粒径1-0mm的二钙电熔镁砂颗粒25%;粒径≤0.088mm二钙电熔镁砂细粉5%、粒径≤0.149mm的98鳞片石墨5%、粒径≤0.149mm的沥青2%、粒径≤10μm的镁碳超细粉5%、粒径≤0.045mm的抗氧化剂(金属铝粉和金属硅粉质量比2:1)3%;外加上述原料总重量的酚醛树脂3.6%;
(2)混练步骤:首先依次加粒径为5~3mm、3~1mm和1~0mm的二钙电熔镁砂颗粒,混碾1~2分钟后外加1.8%的液体树脂润湿颗粒1~2分钟,再风送粒径≤0.149mm的鳞片石墨混碾1~2分钟后,加预混粉混碾1~2分钟,最后外加1.8%的液体树脂,再混碾12~20min即得渣线镁碳砖泥料。
(3)养护:将渣线镁碳砖泥料置于温度为20℃、湿度为45%的恒温恒湿房进行24h的困料;
(4)成型:按照工艺图纸和工艺规程要求的压机类型和成型参数进行生产,控制好砖坯尺寸、飞边、缺损、麻皮、层裂等外观质量,成型后砖坯做好工号标记,码放整齐;
(5)烘烤处理:经200℃热处理24h后冷却出辊道窑即得渣线镁碳砖成品。
将本发明在马钢长材事业部使用验证,经过实际检测,实施例渣线镁碳砖性能数据见下表:
项目 | 渣线镁碳砖 | MT-10A(规定值) |
W(MgO)/% | 84.75 | ≥80 |
W(C)/% | 10.58 | ≥10 |
显气孔率/% | 2.4 | ≤4.0 |
体积密度/(g/cm<sup>3</sup>) | 3.08 | 3.10±0.08 |
常温耐压强度/MPa | 54 | ≥40 |
高温抗折强度(1400℃,0.5h)/MPa | 15.2 | ≥6 |
钢厂使用炉数/次 | 101 | / |
平均熔损速率(mm/炉) | 1.24 | / |
实施例2
一种渣线镁碳砖及其制备方法。
(1)将所有原料按配比称重:粒径5~3mm的二钙电熔镁砂颗粒15%、粒径3-1mm的二钙电熔镁砂颗粒30%、粒径1-0mm的二钙电熔镁砂颗粒15%;粒径≤0.088mm二钙电熔镁砂细粉10%、粒径≤0.149mm的98鳞片石墨10%、粒径≤0.149mm的沥青2%、粒径≤10μm的镁碳超细粉15%、粒径≤0.045mm的抗氧化剂(金属铝粉和金属硅粉质量比1:1)3%;外加上述原料总重量的酚醛树脂3.6%;
(2)其他均与实施例1相同。
经过实际检测,实施例渣线镁碳砖性能数据见下表:
实施例3
一种渣线镁碳砖及其制备方法。
(1)将所有原料按配比称重:粒径5~3mm的二钙电熔镁砂颗粒25%、粒径3-1mm的二钙电熔镁砂颗粒15%、粒径1-0mm的二钙电熔镁砂颗粒25%;粒径≤0.088mm二钙电熔镁砂细粉10%、粒径≤0.149mm的98鳞片石墨10%、粒径≤0.149mm的沥青2%、粒径≤10μm的镁碳超细粉10%、粒径≤0.045mm的抗氧化剂(金属铝粉和金属硅粉质量比5:1)3%;外加上述原料总重量的酚醛树脂3.6%;
(2)其他均与实施例1相同。
经过实际检测,实施例渣线镁碳砖性能数据见下表:
项目 | 渣线镁碳砖 | MT-10A |
W(MgO)/% | 83.45 | ≥80 |
W(C)/% | 11.23 | ≥10 |
显气孔率/% | 2.1 | ≤4.0 |
体积密度/(g/cm<sup>3</sup>) | 3.09 | 3.10±0.08 |
常温耐压强度/MPa | 57 | ≥40 |
高温抗折强度(1400℃,0.5h)/MPa | 15.5 | ≥6 |
钢厂使用炉数/次 | 103 | / |
平均熔损速率(mm/炉) | 1.21 | / |
实施例4
选择实施例2作对比,其他条件不变,将二钙电熔镁砂改变为97电熔镁砂和98鳞片石墨改变为96鳞片石墨,97电熔镁砂颗粒粒径分别为5~3mm、3-1mm和1~0mm,97电熔镁砂细粉粒径≤0.088mm,MgO%≥97%,96鳞片石墨粒径≤0.149mm,C%≥96%。
一种渣线镁碳砖及其制备方法。
(1)将所有原料按配比称重:粒径5~3mm的97电熔镁砂颗粒15%、粒径3-1mm的97电熔镁砂颗粒30%、粒径1-0mm的97电熔镁砂颗粒15%;粒径≤0.088mm二钙电熔镁砂细粉10%、粒径≤0.149mm的96鳞片石墨10%、粒径≤0.149mm的沥青2%、粒径≤10μm的镁碳超细粉15%、粒径≤0.045mm的抗氧化剂(金属铝粉和金属硅粉质量比1:1)3%;外加上述原料总重量的酚醛树脂3.6%;
(2)其他均与实施例2相同。
实施例4和实施例2中的渣线镁碳砖性能数据对比见下表:
从表中数据对比,两制品在相同生产工艺、MgO和C含量相近的条件下,本发明制品使用二钙电熔镁砂和98鳞片石墨的性能指标与使用97电熔镁砂和96鳞片石墨的性能指标对比,显气孔率、体积密度及常温耐压强度均有改善,且高温抗折强度有较大提升,钢厂使用效果改善显著。
实施例5
选择实施例2作对比,其他条件不变,将镁碳超细粉按照MgO与C含量为4:1的配比量分别加到二钙电熔镁砂细粉和98鳞片石墨中。
一种渣线镁碳砖及其制备方法。
(1)将所有原料按配比称重:粒径5~3mm的二钙电熔镁砂颗粒15%、粒径3-1mm的二钙电熔镁砂颗粒30%、粒径1-0mm的二钙电熔镁砂颗粒15%;粒径≤0.088mm二钙电熔镁砂细粉22%、粒径≤0.149mm的98鳞片石墨13%、粒径≤0.149mm的沥青2%、粒径≤0.045mm的抗氧化剂(金属铝粉和金属硅粉质量比1:1)3%;外加上述原料总重量的酚醛树脂3.6%;
(2)其他均与实施例2相同。
实施例5和实施例2中的渣线镁碳砖性能数据对比见下表:
从表中数据对比,两制品在相同生产工艺、MgO和C含量相近的条件下,本发明制品使用镁碳超细粉的性能指标与未添加的性能对比,显气孔率、体积密度和常温耐压强度均有较大提升,且高温抗折强度和钢厂使用效果均改善显著。
Claims (10)
1.一种镁碳砖, 其特征在于:包括如下质量百分比的组分:60%~80%的二钙电熔镁砂颗粒为骨料,5%~10%的二钙电熔镁砂细粉,5%~10%的鳞片石墨,1%~2%的沥青,5%~15%的活性镁碳超细粉,1%~4%的抗氧化剂,外加前述组分总量2%~4%的热固性酚醛树脂,所述抗氧化剂为金属铝粉和金属硅粉;
所述金属铝粉与硅粉质量比为5:1~1:5;
所述二钙电熔镁砂细粉粒径小于88μm;所述鳞片石墨的粒径为小于149μm;所述沥青的粒径为小于149μm;所述抗氧化剂中金属铝粉和硅粉粒径均为小于44μm;
所述二钙电熔镁砂颗粒粒度分别为5~3mm、3~1mm、1~0mm,各粒径的质量百分比分别均为15%~30%;
所述活性镁碳超细粉由如下方法制备而成:将60%~80%小于74μm二钙电熔镁砂细粉和20%~40%小于13μm鳞片石墨通过添加0.05~1%的金属纳米铁片经高速球磨而成,活性镁碳超细粉中位粒径小于10μm,MgO≥60%,C≤40%。
2.根据权利要求1所述的镁碳砖,其特征在于:所述二钙电熔镁砂颗粒粒度分别为5~3mm、3~1mm、1~0mm,各粒径的质量百分比分别为15%~25%、15%~30%、15%~25%。
3.根据权利要求1所述的镁碳砖,其特征在于:所述沥青质量百分比为1%~1.5%。
4.根据权利要求1所述的镁碳砖,其特征在于:所述金属铝粉与硅粉质量比为2:1~1:1。
5.一种权利要求1-4任一项所述的镁碳砖的制备方法,其特征在于,以二钙电熔镁砂颗粒为骨料、二钙电熔镁砂细粉及鳞片石墨为基质,沥青、镁碳超细粉和金属铝粉、金属硅粉为添加剂,外加热固性酚醛树脂作为结合剂,经过泥料混碾、养护、压制成型后再进行烘烤处理得到;
混碾方法为:首先将二钙电熔镁砂细粉、活性镁碳超细粉、沥青、金属硅粉和金属铝粉预混合,得到预混粉;混碾加料顺序如下,先加二钙电熔镁砂颗粒,混碾后,加入部分液体酚醛树脂润湿颗粒,再风送鳞片石墨混碾,再加预混粉混碾,最后加剩余液体酚醛树脂混碾,得到泥料。
6.根据权利要求5所述的制备方法,其特征在于混碾时间为10~25min。
7.根据权利要求5所述的制备方法,其特征在于混碾时间为15~20min。
8.根据权利要求5所述的制备方法,其特征在于所述养护为将混好的泥料置于温度为18~22℃,湿度为43~47%的恒温恒湿房进行16h~24h的困料。
9.根据权利要求5所述的制备方法,其特征在于所述成型为按照工艺图纸和工艺规程要求的压机类型和成型参数进行生产,控制好砖坯尺寸、飞边、缺损、麻皮、层裂的外观质量,成型。
10.根据权利要求5所述的制备方法,其特征在于,所述烘烤处理的温度从低到高逐步升高,在180~250℃热处理12~24h后冷却出辊道窑。
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