CN106892647B - 一种复合型镁碳砖及其制备方法 - Google Patents
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 182
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 91
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 88
- 239000011449 brick Substances 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000005350 fused silica glass Substances 0.000 claims abstract description 16
- 239000010439 graphite Substances 0.000 claims abstract description 15
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052839 forsterite Inorganic materials 0.000 claims abstract description 11
- 239000004576 sand Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000010426 asphalt Substances 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 6
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007767 bonding agent Substances 0.000 claims description 5
- 239000011863 silicon-based powder Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052948 bornite Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 230000035939 shock Effects 0.000 abstract description 12
- 239000011819 refractory material Substances 0.000 abstract description 9
- 230000003628 erosive effect Effects 0.000 abstract description 5
- 229910000831 Steel Inorganic materials 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
本发明属于耐火材料领域,尤其涉及一种复合型镁碳砖及其制备方法。复合型镁碳砖,其原料按重量百分比配比如下:再生镁碳砖40%‑50%,电熔镁砂25%‑40%,博耐特细粉3%‑6%、金属铝纤维0.5%‑2%、镁‑镁橄榄石合成砂细粉2%‑5%,沥青粉0.5‑1%,抗氧化添加剂1%‑5%,石墨1%‑10%,熔融石英1%‑8%;外加结合剂为上述原料总重量的2.8%‑3%。该镁碳砖具有耐高温、抗侵蚀和较好的抗热震性能。
Description
技术领域
本发明属于耐火材料领域,尤其涉及一种复合型镁碳砖及其制备方法。
背景技术
随着钢铁行业大力发展炉外精炼工艺,纯净钢、不锈钢、低碳钢和超低碳钢的产量越来越高。生产洁净钢工艺要求严格控制耐火材料中碳的含量,减少含碳内衬向钢中增碳,要求内衬总含碳量不超过6%,可明显降低材料的热导率,减少热损失,满足二次精炼工艺要求。传统的镁碳砖已不再适用于发展的冶炼技术对耐火材料的新要求,如何开发出既具有优良抗热震性、抗渣性和寿命长,同时又具有热导率低、利于超纯净钢及二次精炼技术发展的镁碳砖,已成为目前镁碳砖的发展趋势。虽然,低碳、超低碳镁碳耐火材料成为镁碳耐火材料新的发展热点,但传统镁碳砖使用寿命的提高也不容忽视,两者应相辅共同发展。
近年来,国内外镁碳砖生产企业在加强镁碳砖性能研究方面,取得了巨大的进步,现有的镁碳砖主要是利用纳米体系及添加剂改善制品的各种性能,如:添加纳米氧化锌、B4C-C复合粉体和纳米TiC粉体、纳米级非氧化物(括氮化物、塞隆或硼化物)等,这些方法虽然解决了一定问题,但其价格昂贵,制造成本高、传统工业化生产难度大。因此,开发出成本低,性能优越,能满足冶炼技术发展需要的镁碳砖,显得尤为重要。
发明内容
针对上述问题,本发明提供一种复合型镁碳砖及其制备方法。该镁碳砖具有耐高温、抗侵蚀和较好的抗热震性能。
为了实现上述目的,本发明提供的复合型镁碳砖,其原料按重量百分比配比如下:再生镁碳砖40%-50%,电熔镁砂25%-40%,博耐特细粉3%-6%、金属铝纤维0.5%-2%、镁-镁橄榄石合成砂细粉2%-5%,沥青粉0.5-1%,抗氧化添加剂1%-5%,石墨1%-10%,熔融石英1%-8%;外加结合剂为上述原料总重量的2.8%-3%。
所述的再生镁碳砖的成分含量要求:MgO含量78%-87%,其中A12O3含量≦4.85%;SiO2含量≦2.8%;C含量≦6%。
所述的电熔镁砂的成分含量要求:MgO含量不低于97%。
所述的博耐特细粉的成分含量要求:A12O3含量不低于90%,CaO含量不低于8.5%。
所述的金属铝纤维的成分含量要求:A12O3含量不低于98%。
所述的镁-镁橄榄石合成砂细粉的成分含量要求:MgO不低于75%,SiO2:15%-17%,Fe2O3:3%-4%。
所述的抗氧化添加剂为金属硅粉、碳化硅粉和铝镁合金粉中的一种或两种混合物。
所述的石墨,依镁碳砖中碳含量的不同,可以部分或全部替换为电极石墨;其中,所述的石墨中碳含量不低于96%,粒度为100目;所述的电极石墨中碳含量不低于97%,粒度为500目。
所述的外加结合剂为改性酚醛树脂。
为了实现上述目的,本发明提供该复合型镁碳砖的制备方法,具体包括以下步骤。
步骤1、准备骨料:将粒度为1-10mm再生镁碳砖40-50%,粒度为3-5mm电熔镁砂5%-10%,粒度为1-3mm电熔镁砂5%-10%,粒度为0.1-1mm电熔镁砂10%-15%,按所需比例混合,得骨料,备用。
步骤2、制备预混合粉:将粒度为0.1μm-88μm的电熔镁砂细粉5%-10%,复合添加剂细粉,沥青粉,抗氧化添加剂,按所需比例预混合,得预混合粉,备用;所述的复合添加剂由博耐特细粉、金属铝纤维和镁-镁橄榄石合成砂细粉组成。
步骤3、混炼:将步骤1和步骤2中的骨料和预混合粉,粒度为100目的石墨或500目电极石墨的一种或两种,依次加入到混炼机中进行低速混炼2-4分钟,再加入外加结合剂低速混炼10-15分钟,得到混合泥料;再向混炼机中的泥料中加入颗粒粒度为0.25-0.5mm的熔融石英(SiO2含量不低于99.8%),高速混炼15-25分钟,使熔融石英均匀分布在泥料中,出料,备用。
步骤4、成型:将步骤3中混炼后泥料进行困料和筛分,将其打击成型形成砖坯,成型砖坯的密度为 2.95-3.3g/cm3。
步骤5、干燥:将步骤4中的成型砖坯置于180-220℃的温度条件下,干燥24h后,即得镁碳砖。
本发明的显著效果。
本发明的再生镁砖为直接购买的废弃镁碳砖,进行表面处理后进行破碎再利用,合理利用资源实现废弃耐材变废为宝;本发明的镁碳砖利用所添加普通的耐火原料博耐特(Bonite)细粉(六铝酸钙(CA6))、自制的镁-镁橄榄石合成砂细粉、金属铝纤维的综合特性及熔融石英颗粒,在不改变原有传统生产工艺的情况下,研制出一种特别适用于AOD、VOD炉的渣线部位高性能的镁碳砖;博耐特(Bonite)细粉是基于六铝酸钙(CA6)矿物相的一种新型合成致密耐火原料,具有高纯致密、高耐火度、良好的抗热震性及低热导率的性能,在含铁熔渣中的溶解度低,在还原气氛中的稳定性高,在碱性环境中的化学稳定性好,对熔融金属和熔渣的润湿性低(钢铁和有色金属),可以优化本发明镁碳砖制品的基质组成,其在使用环境下能原位和电熔镁砂细粉形成板状式的镶嵌尖晶石结构,增强制品的高温强度,如碳含量在12%左右的普通镁碳砖中,单独加入博耐特(Bonite)细粉,制品的寿命可提高约15%;同时加入的金属铝纤维与基质中的碳、氧化物高温反应,形成碳化物、尖晶石等针状或柱状纤维结构,进一步增强制品的高温强度,两者的共同强化作用,使制品具有更好的高温使用性能;利用添加剂博耐特(Bonite)细粉(六铝酸钙(CA6))和金属铝纤维,可以发挥材料各自的优异特性,即强化了制品的基质本身性能,又增强了制品的整体高温使用性能和抗侵蚀性;复合添加剂中还加入公司自制的镁-镁橄榄石合成砂细粉(采用201210149376.X的配方),可以降低MgO和博耐特(Bonite)细粉生成的MA尖晶石的温度,抑制MgO的异常膨胀,提高制品韧性和抗渗透性;熔融石英熔化温度约1713℃,导热系数低,热膨胀系数几乎是所有耐火材料中最小的,它具有极高的热震稳定性,本发明的镁碳砖原料中辅以0.5-0.25mm颗粒形式的熔融石英,熔融石英大约在1200℃高温下会转变为方石英,当温度下降至300℃左右,方石英又由高温型转变为低温型,这种高、低温晶型转变会在制品内部产生微裂纹,增韧制品,当温度变化时,这些微裂纹会吸收异常膨胀,从而使制品的抗热震性能大大提高。
本发明的镁碳砖明显改善了耐火材料的热震稳定性和提高了热态抗折强度和热态抗侵蚀性,即使制品的含碳量在2-15%波动下,仍能满足现有技术中冶炼不同钢种的使用需求。本发明采用以上几种原料,其复合作用显著,即使制品碳含量在2-15%大幅度改变的情况下,其高温强度,热震稳定性、抗渣性、抗渗透性也会有很大的提高,达到比传统高碳镁碳砖更高的使用寿命;本发明方法制备的镁碳砖在优化制品基质的同时,可使制品在使用过程中形成片状或针状、柱状纤维式镶嵌结构的结合相,增强镁碳砖结构;在不同温度下晶型转变产生的微裂纹吸收异常膨胀增韧制品,生产出碳含量在2-15%,具有耐高温、抗侵蚀、抗热震性能好的镁碳砖,适合工业化生产。
具体实施方式
下面结合具体实施例对本发明做详细的说明。
实施例1。
利用复合添加剂增强镁碳砖制备的方法如下。
步骤1、准备骨料:粒度为1-10mm再生镁碳砖45%,粒度为3-5mm电熔镁砂5%,粒度为1-3mm电熔镁砂10%,粒度为0.1-1mm电熔镁砂15%,按所需比例混合,备用。
步骤2、制备预混合粉:将粒度为0.1μm-88μm的电熔镁砂细粉,重量百分比为10%;博耐特(Bonite)细粉(六铝酸钙(CA6))4%,金属铝纤维0.5%,镁-镁橄榄石合成砂细粉合成砂细粉2%;沥青粉0.5%,金属硅粉1.5%,金属铝镁合金粉1.5%,按比例预混合备用。
步骤3、混炼:将步骤1和步骤2中的骨料和预混合粉,粒度为500目的电极石墨2%,依次加入到混炼机中进行低速混炼2分钟,再加3%的外加液体酚醛树脂结合剂低速混炼15分钟,再向混炼机中的泥料中加入粒度为0.25-0.5mm颗粒形式熔融石英3%,高速混炼25分钟,使熔融石英均匀分布在泥料中,出料备用。
步骤4、混炼结束后从高速混炼机中放出泥料,困料1小时,再在在1000T摩擦压砖机中打击成型形成砖坯,打击过程中每个砖坯打击次数3轻8重,成型后砖坯。
步骤5、成型的砖坯经过200-220℃温度的隧道式干燥器中烘拷24小时,即可制成低碳镁碳砖。
本实施例制备的低碳镁碳砖和本公司生产的低碳镁碳砖对比(专利号l201410822205.8)成品的主要物理性能如下。
进行显气孔率、体积密度(GB/T2997-2000)、常温耐压强度(GB/T5072-2008)、热震稳定性(YB/T376.1-1995)、高温抗折(GB/T3002)常规性能指标检测的数据,见表1。
表1 性能检测结果。
从表1中数据对比:本发明的制品与原低碳镁碳砖相比(碳含量均在3%左右),其耐压强度、高温抗折强度和热震稳定性均有所提高,其它变化不大。
本发明的制品与原低碳镁碳砖(制造工艺一样,碳含量均在3%左右,只是添加剂不同,如博耐特、熔融石英等)在中冶石钢京城钢厂100吨特钢精炼钢包使用包龄从原来的60多次,提高到平均85次,质量提升明显。
实施例2。
利用复合添加剂增强镁碳砖制备的方法。
步骤1、准备骨料:粒度为1-10mm再生镁碳砖50%,粒度为3-5mm电熔镁砂5%,粒度为1-3mm电熔镁砂5%,粒度为0.1-1mm电熔镁砂10%,按所需比例混合,备用。
步骤2、制备预混合粉:将粒度为0.1μm-88μm的电熔镁砂细粉,重量百分比为9%;博耐特(Bonite)细粉(六铝酸钙(CA6))3%,金属铝纤维0.5%,镁-镁橄榄石合成砂细粉合成砂细粉2%;沥青粉1%,金属硅粉1%,金属铝镁合金粉1.5%,按比例预混合,备用。
步骤3、混炼:将步骤1和步骤2中的骨料和混合粉,粒度为100目的石墨8%,粒度为500目的电极石墨2%,依次加入到混炼机中进行低速混炼2-4分钟,再加3%的外加液体酚醛树脂结合剂低速混炼10-15分钟,再向混炼机中的泥料中加入粒度为0.5-0.25mm颗粒形式熔融石英2%,高速混炼15-25分钟,使熔融石英均匀分布在泥料中,出料,备用。
步骤4、混炼结束后从高速混炼机中放出泥料,困料1小时,再在在1000T摩擦压砖机中打击成型形成砖坯,打击过程中每个砖坯打击次数3轻8重,成型后砖坯。
步骤5、成型的砖坯经过200-220℃温度的隧道式干燥器中烘拷24小时,即可制成镁碳砖。
本实例2制备的复合型镁碳砖和本公司生产的普通镁碳砖对比成品的主要物理性能如下。
进行显气孔率、体积密度(GB/T2997-2000)、常温耐压强度(GB/T5072-2008)、热震稳定性(YB/T376.1-1995)、高温抗折(GB/T3002)常规性能指标检测的数据,见表2。
表2 性能检测结果。
从表中数据对比:本发明的制品与普通镁碳砖相比(碳含量均在3%左右),其耐压强度、高温抗折强度、热震稳定性均有所提高,其它变化不大。
本发明的制品与低碳镁碳砖(制造工艺一样,碳含量均在11%左右,只添加剂不同,如博耐特、熔融石英等)在通化钢厂120吨钢包使用包龄从原来的100多次,提高到120次以上,质量提升明显。
Claims (4)
1.一种复合型镁碳砖,其特征在于,其原料按重量百分比配比如下:再生镁碳砖40%-50%、电熔镁砂25%-40%、博耐特细粉3%-6%、金属铝纤维0.5%-2%、镁-镁橄榄石合成砂细粉2%-5%、沥青粉0.5-1%、抗氧化添加剂1%-5%、石墨1%-10%、熔融石英1%-8%和外加结合剂,外加结合剂为上述原料总重量的2.8%-3%;
所述的镁-镁橄榄石合成砂细粉的成分含量:MgO不低于75%,SiO 2:15%-17%,Fe 2O 3:3%-4%;
所述的再生镁碳砖的成分含量要求:MgO含量78%-87%, A12O3含量≤4.85%;SiO2含量≤2.8%;C含量≤6%;
所述的电熔镁砂的成分含量要求:MgO含量不低于97%;
所述的博耐特细粉的成分含量要求:A12O3含量不低于90%,CaO含量小于8.5%;
所述的石墨为电极石墨,所述的电极石墨中碳含量不低于97%,粒度为500目。
2.如权利要求1所述的复合型镁碳砖,其特征在于,所述的抗氧化添加剂为金属硅粉、碳化硅粉和铝镁合金粉中的一种或两种混合物。
3.如权利要求1所述的复合型镁碳砖,其特征在于,所述的外加结合剂为改性酚醛树脂。
4.如有权利要求1-3任一所述的复合型镁碳砖的制备方法,其特征在于,具体包括以下步骤:
步骤1、准备骨料:粒度为1-10mm再生镁碳砖45%,粒度为3-5mm电熔镁砂5%,粒度为1-3mm电熔镁砂10%,粒度为0.1-1mm电熔镁砂15%,按所需比例混合,备用;
步骤2、制备预混合粉:将粒度为0.1μm-88μm的电熔镁砂细粉,重量百分比为10%;博耐特细粉4%,金属铝纤维0.5%,镁-镁橄榄石合成砂细粉2%;沥青粉0.5%,金属硅粉1.5%,金属铝镁合金粉1.5%,按比例预混合备用;
步骤3、混炼:将步骤1和步骤2中的骨料和预混合粉,粒度为500目的电极石墨2%,依次加入到混炼机中进行低速混炼2分钟,再加3%的外加液体酚醛树脂结合剂低速混炼15分钟,再向混炼机中的泥料中加入粒度为0.25-0.5mm颗粒形式熔融石英3%,高速混炼25分钟,使熔融石英均匀分布在泥料中,出料备用;
步骤4、混炼结束后从高速混炼机中放出泥料,困料1小时,再在1000T摩擦压砖机中打击成型形成砖坯,打击过程中每个砖坯打击次数3轻8重,成型后砖坯;
步骤5、成型的砖坯经过200-220℃温度的隧道式干燥器中烘拷24小时,即可制成低碳镁碳砖。
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