CN110330314A - 一种炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料及其制备方法 - Google Patents

一种炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料及其制备方法 Download PDF

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CN110330314A
CN110330314A CN201910632149.4A CN201910632149A CN110330314A CN 110330314 A CN110330314 A CN 110330314A CN 201910632149 A CN201910632149 A CN 201910632149A CN 110330314 A CN110330314 A CN 110330314A
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黄军同
刘明强
闫明格
张梦
冯志军
陈智
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Nanchang Hangkong University
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Abstract

本发明公开了一种炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料及其制备方法，该耐火材料原料包括：镁钙砂和细粉、镁砂颗粒和细粉、无水酚醛树脂、0.1～4wt％的鳞片状碳质原料、硝酸盐、抗氧化剂、高温沥青粉；首先将配制好的硝酸盐酒精溶液和鳞片状碳质原料一起倒入酚醛树脂中搅拌混合，经三辊研磨循环剥离得到微纳米石墨薄片酚醛树脂基混合物，并将镁钙砂颗粒和镁砂颗粒干混后加入其中，最后加入镁钙砂和镁砂细粉、抗氧化剂和高温沥青组成的混合粉。经混炼、困料、压制成型、固化后，即得到所述的低碳超低碳镁钙碳耐火材料。该耐火材料具有较低的碳含量和热导率、优良的抗氧化性和抗酸性渣侵蚀性能，有利于洁净钢的冶炼。

Description

一种炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料及其制备 方法
技术领域
本发明涉及耐火材料的技术领域，特别是涉及一种炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料及其制备方法。
背景技术
由于钢中杂质对其各方面性能有着极大负面影响，且洁净钢的用途广泛，国内对其需求量也在不断增加，电子器件、汽车器件、食品包装、大型工程等领域均有洁净钢的身影。有些要求钢的碳含量越低越好，同时就会要求冶炼低碳钢、超低碳钢精炼炉内衬的碳含量越低越好。天然鳞片石墨和膨胀石墨应用于炼钢精炼炉内衬耐火材料中，能够显著提高其抗渣侵蚀和抗热震性能。而传统炼钢精炼炉内衬耐火材料由于含有较高的碳含量(一般10～20wt％的碳含量) 导致其抗氧化性差、脆性大、热导率高等性能问题。炼钢精炼炉内衬耐火材料中的碳在与钢水直接接触中会溶于钢水，进而影响洁净钢的冶炼。且碳含量的降低也能减少耐火材料的制造成本。
低碳镁钙碳耐火材料的使用取代了含碳量过高的镁碳耐火材料以及造价贵、污染环境的镁铬耐火材料，达到了冶炼洁净钢的技术要求和降低了耐火材料的成本。低碳镁钙碳耐火材料中CaO的存在使其与低碳镁碳耐火材料相比，抗酸性渣性能更好，且低碳镁钙碳耐火砖无需高温烧成，节能环保，使用寿命长，此技术有利于节能减排和低碳钢、超低碳钢等洁净钢生产与二次精炼技术的发展。寻找新型的碳源，降低在镁钙碳耐火材料中的含碳量的同时又保证其高温性能是镁钙碳耐火材料的研究中的重大课题之一。
发明内容
本发明旨在克服现有技术存在的不足，目的是提供一种生产成本低和性能优异的炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料的制备方法；其中所制备的低碳超低碳镁钙碳耐火材料，降低了含碳耐火材料的碳含量和导热率。镁钙砂中CaO的存在使其与低碳镁碳砖相比，抗酸性渣性能更好，且低碳超低碳镁钙碳砖无需高温烧成，节能环保，使用寿命长，此技术有利于节能减排和低碳钢、超低碳钢等洁净钢生产与二次精炼技术的发展。
本发明采用如下技术方案：一种炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料，组分按重量百分数计为：镁钙砂颗粒50～75wt％、镁钙砂细粉5～20wt％、镁砂颗粒0.1～18wt％、镁砂细粉0.1～8wt％、2～5wt％的无水树脂结合剂、0.1～4wt％的碳质原料、0～0.5wt％的硝酸盐化合物、0.1～3.5wt％的复合抗氧化剂，0～1wt％高温沥青粉；所述的碳质原料为鳞片石墨、膨胀石墨的一种或两种混合物；所述的硝酸盐化合物为无水硝酸镍、无水硝酸铁、无水硝酸钴的一种或者两种以上。
优选地，所述镁钙砂为烧结镁钙砂或电熔镁钙砂，其主要成分为MgO和 CaO，其中MgO含量为66～84wt％，CaO的含量为16～34wt％，镁钙砂颗粒占总配料的50～75wt％，其中粒度5～3mm的占总配料的15～25wt％，粒度3～1mm的占总配料的25～35wt％，粒度≤1mm的占总配料的10～20wt％；镁钙砂细粉的粒度≤0.074mm，占总配料的5～20wt％。
优选地，所述镁砂为烧结镁砂或电熔镁砂，其MgO含量为≥96wt％；镁砂颗粒占总配料0.1～18wt％、其中颗粒粒度5～3mm的占总配料的0.1～6wt％，粒度 3～1mm的占总配料的0.1～12wt％，粒度≤1mm的占总配料的0.1～6wt％；镁砂细粉的粒度≤0.074mm，占总配料的0.1～8wt％。
优选地，所述抗氧化剂为金属Al粉、Si粉、SiC粉、硼化物(B4C或BN 或ZrB2或CaB6)的一种或者几种，粒径≤0.074mm。
一种炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料制备方法，包括以下步骤：
(1)、先将0～0.5wt％的硝酸盐化合物配制成质量百分数浓度为5～30wt％的无水酒精溶液；
(2)、再将配制好的硝酸盐酒精溶液、0.1～4wt％的碳质原料一起倒入 2～5wt％的无水树脂中搅拌混合2～18min；
(3)、然后将步骤(2)中的混合物从进料辊加入到三辊研磨机进行三辊差速剥离，循环剥离1～20次后，从出料辊收集得到石墨剥离形成的微纳米石墨薄片均匀分散在含硝酸盐的树脂中的混合物；三辊研磨机中的三辊速率的转速比为N3(进料辊):N2(中心辊):N1(出料辊)在1:1.5:3～1:3:9以内，每个辊轴之间的间隙为0.01～0.2mm；
(4)、为降低步骤(3)中收集得到的树脂基混合物的粘度以增加流动性，将其在40℃～90℃水浴中进行5～30min的加热；
(5)、将镁钙砂细粉5～20wt％、镁砂细粉0.1～8wt％、0.1～3.5wt％的复合抗氧化剂、0.01～1wt％高温沥青粉混合均匀，得到混合细粉；
(6)、将占总配料50～75wt％的镁钙砂颗粒和0.1～18wt％镁砂颗粒放入混料机中干混1～15min，然后加入步骤(4)中加热后的树脂基混合物继续混炼 3～15min，最后加入步骤(5)中的镁钙砂细粉和镁砂细粉、复合抗氧化剂和高温沥青形成的混合粉继续混炼4～15min制成泥料，然后困料1～24h；
(7)、将困好的泥料加入模具中采用复合式摩擦压砖机进行压制成型制成砖坯；
(8)、将成型的砖坯置于隧道式干燥窑中烘烤固化(烘烤温度160～280℃，烘烤时间为8～20h)，即得到本发明所述的低碳超低碳镁钙碳耐火材料。
优选地，所述碳质原料的粒度为0.045mm～5mm，所述树脂为热塑型液体酚醛树脂、热固性液体酚醛树脂中的一种。
与现有技术相比，本发明具有的优点：以天然石墨片作为起始原料，通过三辊差速研磨剥离获得结晶效果好且比表面积大、均匀分散在无水树脂中的微纳米石墨薄片，将其应用到高性能低碳超低碳镁钙碳耐火材料中，可以有效降低生产成本；数次剥离后的微纳米石墨薄片均匀分散在砖基质中，能在保持超低碳含量的同时充分发挥石墨的优异性能。因此，本发明所制备的低碳超低碳镁钙碳耐火材料性能优异、成本较低，能在保持或提高含碳耐火材料的综合性能的基础上，大幅度降低含碳耐火材料的碳含量和导热率，对节能减排具有显著的效果。而镁钙砂中CaO的存在使其与低碳镁碳砖相比，抗酸性渣性能更好，且低碳超低碳镁钙碳砖无需高温烧成，节能环保，使用寿命长，对我国洁净钢精炼技术和高温行业的发展具有重要推动作用和实际应用价值。
具体实施方式
下面对本发明的优选实施例进行详细阐述，以使本发明的优点和特征能更易于被本领域技术人员理解，从而对本发明的保护范围做出更为清楚明确的界定。
实施例1
一种炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料的制备方法。将2.5wt％的鳞片石墨倒入4wt％的无水树脂中搅拌混合15min；然后将上述混合物从进料辊加入到三辊研磨机进行三辊差速剥离，三辊研磨机中的三辊速率的转速比为 N3(进料辊):N2(中心辊):N1(出料辊)为1:3:6，进料辊与中心辊之间的间隙为0.07mm，中心辊与出料辊之间的间隙为0.02mm，循环剥离20次后，从出料辊收集得到石墨剥离形成的微纳米石墨薄片均匀分散在树脂中的混合物；将树脂基混合物在40℃水浴中进行25min的加热；同时，将13wt％的镁钙砂细粉、 3.5wt％的镁砂细粉和2wt％的金属Al粉混合均匀，得到混合细粉；再将占总配料70wt％的镁钙砂颗粒(粒度5～3mm：18wt％，3～1mm：32wt％，≤1mm： 20wt％)和5wt％镁砂颗粒(粒度5～3mm：1wt％，3～1mm：2.5wt％，≤1mm： 1.5wt％)放入混料机中干混15min，然后加入加热后的树脂基混合物继续混料 15min，最后加入镁钙砂细粉和镁砂细粉和复合抗氧化剂形成的混合粉继续混料 15min制成泥料，然后困料20h；将困好的泥料加入模具中采用复合式摩擦压砖机进行压制成型制成砖坯；将成型的砖坯置于隧道式干燥窑中烘烤固化(烘烤温度240℃，烘烤时间为12h)，即得到本发明所述的低碳镁钙碳耐火材料。
所制备得到的一种低碳镁钙碳耐火材料制品的技术指标如下：碳含量为 4.8％，体积密度2.94g/cm3，显气孔率3.7％，常温耐压强度72.5MPa，高温抗折强度(1400℃*3h)8.2MPa。
实施例2
一种炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料的制备方法。先将 0.05wt％的无水硝酸镍配制成质量百分数浓度为5wt％的无水酒精溶液；再将配制好的硝酸盐酒精溶液和1.5wt％的膨胀石墨一起倒入3wt％的无水树脂中搅拌混合15min；然后将上述混合物从进料辊加入到三辊研磨机进行三辊差速剥离，三辊研磨机中的三辊速率的转速比为N3(进料辊):N2(中心辊):N1(出料辊)为 1:3:6，进料辊与中心辊之间的间隙为0.12mm，中心辊与出料辊之间的间隙为 0.01mm，循环剥离15次后，从出料辊收集得到石墨剥离形成的微纳米石墨薄片均匀分散在含硝酸盐的树脂中的混合物；将树脂基混合物在60℃水浴中进行20min的加热；同时，将20wt％镁钙砂细粉、5wt％镁砂细粉、1.5wt％的金属Si 粉、0.45wt％的Al粉和0.5wt％高温沥青粉混合均匀，得到混合细粉；再将占总配料50wt％的镁钙砂颗粒(粒度5～3mm：15wt％，3～1mm：25wt％，≤1mm： 10wt％)和18wt％镁砂颗粒(粒度5～3mm：6wt％，3～1mm：6wt％，≤1mm： 6wt％)放入混料机中干混15min，然后加入加热后的树脂基混合物继续混料15 min，最后加入镁钙砂细粉和镁砂细粉、复合抗氧化剂和高温沥青形成的混合粉继续混料15min制成泥料，然后困料22h；将困好的泥料加入模具中采用复合式摩擦压砖机进行压制成型制成砖坯；将成型的砖坯置于隧道式干燥窑中烘烤固化(烘烤温度240℃，烘烤时间为12h后)，即得到本发明所述的超低碳镁钙碳耐火材料。
所制备得到的一种超低碳镁钙碳耐火材料制品的技术指标如下：碳含量为3.6％，体积密度3.08g/cm3，显气孔率3.4％，常温耐压强度78.3MPa，高温抗折强度(1400℃*3h)9.6MPa。
实施例3
一种炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料的制备方法。先将 0.2wt％的无水硝酸铁配制成质量百分数浓度为15wt％的无水酒精溶液；再将配制好的硝酸盐酒精溶液和1wt％的鳞片石墨、1wt％的膨胀石墨一起倒入5wt％的无水树脂中搅拌混合15min；然后将上述混合物从进料辊加入到三辊研磨机进行三辊差速剥离，三辊研磨机中的三辊速率的转速比为N3(进料辊):N2(中心辊):N1(出料辊)为1:3:6，进料辊与中心辊之间的间隙为0.1mm，中心辊与出料辊之间的间隙为0.03mm，循环剥离20次后，从出料辊收集得到石墨剥离形成的微纳米石墨薄片均匀分散在含硝酸盐的树脂中的混合物；将树脂基混合物在 75℃水浴中进行10min的加热；同时，将8.8wt％镁钙砂细粉、7wt％镁砂细粉、 1.5wt％的Si粉、2wt％的BN复合抗氧化剂与1wt％高温沥青粉混合均匀混合均匀，得到混合细粉；再将占总配料68wt％的镁钙砂颗粒(粒度5～3mm：18wt％，3～1mm：33wt％，≤1mm：18wt％)和4.5wt％镁砂颗粒(粒度5～3mm：1.5wt％， 3～1mm：1.5wt％，≤1mm：1.5wt％)放入混料机中干混15min，然后加入加热后的树脂基混合物继续混料15min，最后加入镁钙砂细粉和镁砂细粉、复合抗氧化剂和高温沥青形成的混合粉继续混料15min制成泥料，然后困料24h；将困好的泥料加入模具中采用复合式摩擦压砖机进行压制成型制成砖坯；将成型的砖坯置于隧道式干燥窑中烘烤固化(烘烤温度240℃，烘烤时间为12h)，即得到本发明所述的低碳镁钙碳耐火材料。
所制备得到的一种低碳镁钙碳耐火材料制品的技术指标如下：碳含量为 5.5％，体积密度2.90g/cm3，显气孔率4.05％，常温耐压强度68.3MPa，高温抗折强度(1400℃*3h)7.9MPa。
不局限于此，任何不经过创造性劳动想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求书所限定的保护范围为准。

Claims (6)

1.一种炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料，其特征在于，组分按重量百分数计为：镁钙砂颗粒50～75wt％、镁钙砂细粉5～20wt％、镁砂颗粒0.1～18wt％、镁砂细粉0.1～8wt％、2～5wt％的无水树脂结合剂、0.1～4wt％的碳质原料、0～0.5wt％的硝酸盐化合物、0.1～3.5wt％的复合抗氧化剂，0～1wt％高温沥青粉；所述的碳质原料为鳞片石墨、膨胀石墨的一种或两种混合物；所述的硝酸盐化合物为无水硝酸镍、无水硝酸铁、无水硝酸钴的一种或者两种以上。
2.根据权利要求1所述的炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料，其特征在于，所述镁钙砂为烧结镁钙砂或电熔镁钙砂，其主要成分为MgO和CaO，其中MgO含量为66～84wt％，CaO的含量为16～34wt％，镁钙砂颗粒占总配料的50～75wt％，其中粒度5～3mm的占总配料的15～25wt％，粒度3～1mm的占总配料的25～35wt％，粒度≤1mm的占总配料的10～20wt％；镁钙砂细粉的粒度≤0.074mm，占总配料的5～20wt％。
3.根据权利要求1所述的炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料，其特征在于，所述镁砂为烧结镁砂或电熔镁砂，其MgO含量为≥96wt％；镁砂颗粒占总配料0.1～18wt％、其中颗粒粒度5～3mm的占总配料的0.1～6wt％，粒度3～1mm的占总配料的0.1～12wt％，粒度≤1mm的占总配料的0.1～6wt％；镁砂细粉的粒度≤0.074mm，占总配料的0.1～8wt％。
4.根据权利要求1所述的炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料，其特征在于，所述抗氧化剂为金属Al粉、Si粉、SiC粉、硼化物(B4C或BN或ZrB2或CaB6)的一种或者几种，粒径≤0.074mm。
5.一种炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料制备方法，其特征在于，包括以下步骤：
(1)、先将0～0.5wt％的硝酸盐化合物配制成质量百分数浓度为5～30wt％的无水酒精溶液；
(2)、再将配制好的硝酸盐酒精溶液、0.1～4wt％的碳质原料一起倒入2～5wt％的无水树脂中搅拌混合2～18min；
(3)、然后将步骤(2)中的混合物从进料辊加入到三辊研磨机进行三辊差速剥离，循环剥离1～20次后，从出料辊收集得到石墨剥离形成的微纳米石墨薄片均匀分散在含硝酸盐的树脂中的混合物；三辊研磨机中的三辊速率的转速比为N3(进料辊):N2(中心辊):N1(出料辊)在1:1.5:3～1:3:9以内，每个辊轴之间的间隙为0.01～0.2mm；
(4)、为降低步骤(3)中收集得到的树脂基混合物的粘度以增加流动性，将其在40℃～90℃水浴中进行5～30min的加热；
(5)、将镁钙砂细粉5～20wt％、镁砂细粉0.1～8wt％、0.1～3.5wt％的复合抗氧化剂、0.01～1wt％高温沥青粉混合均匀，得到混合细粉；
(6)、将占总配料50～75wt％的镁钙砂颗粒和0.1～18wt％镁砂颗粒放入混料机中干混1～15min，然后加入步骤(4)中加热后的树脂基混合物继续混炼3～15min，最后加入步骤(5)中的镁钙砂细粉和镁砂细粉、复合抗氧化剂和高温沥青形成的混合粉继续混炼4～15min制成泥料，然后困料1～24h；
(7)、将困好的泥料加入模具中采用复合式摩擦压砖机进行压制成型制成砖坯；
(8)、将成型的砖坯置于隧道式干燥窑中烘烤固化(烘烤温度160～280℃，烘烤时间为8～20h)，即得到本发明所述的低碳超低碳镁钙碳耐火材料。
6.根据权利要求5所述的炼钢精炼炉内衬用低碳超低碳镁钙碳耐火材料制备方法，其特征在于，所述碳质原料的粒度为0.045mm～5mm，所述树脂为热塑型液体酚醛树脂、热固性液体酚醛树脂中的一种。
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