CN105967703A - 一种MgO-Si2N2O-C质耐火材料及其制备方法 - Google Patents
一种MgO-Si2N2O-C质耐火材料及其制备方法 Download PDFInfo
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- 239000011819 refractory material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000009970 fire resistant effect Effects 0.000 claims 11
- 239000001095 magnesium carbonate Substances 0.000 claims 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims 3
- 235000014380 magnesium carbonate Nutrition 0.000 claims 3
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 2
- 235000013312 flour Nutrition 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 2
- 239000000843 powder Substances 0.000 claims 2
- 229910002790 Si2N2O Inorganic materials 0.000 claims 1
- 229920001807 Urea-formaldehyde Polymers 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 28
- 238000007254 oxidation reaction Methods 0.000 abstract description 19
- 230000003647 oxidation Effects 0.000 abstract description 18
- 229910000831 Steel Inorganic materials 0.000 abstract description 15
- 239000010959 steel Substances 0.000 abstract description 15
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005011 phenolic resin Substances 0.000 abstract description 10
- 229920001568 phenolic resin Polymers 0.000 abstract description 10
- 239000011863 silicon-based powder Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000007670 refining Methods 0.000 abstract description 4
- 230000003628 erosive effect Effects 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 239000002893 slag Substances 0.000 description 11
- 230000003064 anti-oxidating effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal 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
- 238000003723 Smelting Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- -1 ferrous metals Chemical class 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
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Abstract
本发明涉及一种MgO‑Si2N2O‑C质耐火材料及其制备方法。其技术方案是:以65~85wt%的电熔镁砂、5~25wt%的氧氮化硅、2~10wt%的鳞片石墨、0.2~1.0wt%的铝粉和1~6wt%的硅粉为原料,在混碾机中混合1~3min,再外加所述原料2~7wt%的热固性酚醛树脂,混合3~7min,压制成型,然后在150~250℃条件下烘烤20~25h,即得MgO‑Si2N2O‑C质耐火材料。本发明具有工艺简单和生产成本低的特点;所制备的MgO‑Si2N2O‑C质耐火材料常温强度大、抗氧化性能优良和对钢水的增碳小,适用于洁净钢的钢包内衬与精炼炉炉衬。
Description
技术领域
本发明属于MgO-C质耐火材料技术领域。具体涉及一种MgO-Si2N2O-C质耐火材料及其制备方法。
背景技术
镁碳质耐火材料由于其优异的使用性能如抗热震稳定性好、抗渣侵蚀能力强,广泛应用于钢铁冶炼设备。但这种材料在实际应用时出现的对钢水增碳行为和使用过程中强度不高等问题,影响了洁净钢的质量和炉衬材料的使用寿命,寻求新型替代的氧化物-非氧化物耐火材料是耐火材料及冶金行业关注的焦点。
由于SiC具有对熔融金属不润湿性、高温氧化后能促进材料反应烧结等特点,故选择将其加入到镁碳质耐火材料中使其成为MgO-SiC-C质复合耐火材料来改善上述问题。但是,MgO-SiC-C质复合耐火材料中含有的SiC和C等成分在氧化气氛下易发生氧化反应,降低了MgO-SiC-C质复合耐火材料的强度和抗渣性,导致MgO-SiC-C质复合耐火材料在使用过程中发生损毁,并且MgO-SiC-C质复合耐火材料对钢水的增碳行为也会影响低碳钢和超低碳钢等洁净钢的冶炼。“一种方镁石-碳化硅-碳复合材料及其制备方法”(CN200610019553.7)专利技术,用镁砂和工业SiC为主要原料,以酚醛树脂为结合剂,采用机械混合后再经压力机械压制成型而产生的,其中工业SiC的市场价格较高,使MgO-SiC-C质耐火材料的生产成本也不断提高。
发明内容
本发明旨在克服现有技术缺陷,目的在于提供一种工艺简单和生产成本低的MgO-Si2N2O-C质耐火材料的制备方法;用该方法制备的MgO-Si2N2O-C质耐火材料常温强度大、抗氧化性能优良和对钢水的增碳小,适用于洁净钢的钢包内衬与精炼炉炉衬。
为实现上述目的,本发明采用的技术方案是:以65~85wt%的电熔镁砂、5~25wt%的氧氮化硅、2~10wt%的鳞片石墨、0.2~1.0wt%的铝粉和1~6wt%的硅粉为原料,在混碾机中混合1~3min,再外加所述原料2~7wt%的热固性酚醛树脂,混合3~7min,压制成型,然后在150~250℃条件下烘烤20~25h,即得MgO-Si2N2O-C质耐火材料。
所述电熔镁砂的MgO含量≥97%;所述电熔镁砂的颗粒级配是:粒度小于5mm且大于等于3mm占17~27wt%,粒度小于3mm且大于等于1mm占30~40wt%,粒度小于1mm且大于等于0.044mm占33~50wt%。
所述氧氮化硅的Si2N2O含量≥96%,粒度为0.044~0.088mm。
所述鳞片石墨的C含量≥97wt%,粒度为0.3~0.5mm。
所述铝粉的Al含量≥99wt%,粒度为0.02~0.074mm。
所述硅粉的Si含量≥98wt%,粒度为0.02~0.074mm。
所述热固性酚醛树脂的固含量为75~80%。
所述压制成型的压力为120~150MPa。
由于采用上述技术方案,本发明与现有技术相比具有如下积极效果:
本发明将Si2N2O作为主要成分引入到材料中,由于Si2N2O中不含碳,所以MgO-Si2N2O-C质耐火材料对熔钢的增碳行为比MgO-SiC-C质耐火材料要小得多。同时,Si2N2O具有很好的抗氧化性能和抗熔融有色金属和盐的侵蚀性。在高温下Si2N2O可以与MgO-Si2N2O-C质耐火材料中产生的CO发生反应,抑制MgO-Si2N2O-C质耐火材料中石墨的氧化,并且减弱渣对耐火材料的侵蚀与渗透。Si2N2O在高温下还能分解成一些晶须状或颗粒状的碳化物和氮化物,使所制备的MgO-Si2N2O-C质耐火材料的强度、抗氧化性均有所提高。并且所需原料中的氧氮化硅可通过Si和SiO2在N2气氛下合成,成本较低。
本发明所制备的MgO-Si2N2O-C质耐火材料,在200℃×24h和1450℃×3h条件下热处理后体积密度相应地为2.80~2.90g/cm3和2.95~3.05g/cm3,常温耐压强度相应地为75~100MPa和55~75MPa;在1450℃×3h条件下进行抗氧化实验后质量损失率为0.1~0.87%,氧化因子为8~20%,在1450℃×3h条件下抗渣侵蚀经检测为无明显侵蚀。
因此,本发明具有工艺简单和生产成本低的特点;所制备的MgO-Si2N2O-C质耐火材料常温强度大、抗氧化性能优良和对钢水的增碳小,适用于洁净钢的钢包内衬与精炼炉炉衬。
具体实施方式
下面结合具体实施方式对本发明作进一步的描述,并非对其保护范围的限制。
为避免重复,先将本具体实施方式中所涉及的原料统一描述如下,实施例中不再赘述:
所述电熔镁砂的MgO含量≥97%;所述电熔镁砂的颗粒级配是:粒度小于5mm且大于等于3mm占17~27wt%,粒度小于3mm且大于等于1mm占30~40wt%,粒度小于1mm且大于等于0.044mm占33~50wt%。
所述氧氮化硅的Si2N2O含量≥96%,粒度为0.044~0.088mm。
所述鳞片石墨的C含量≥97wt%,粒度为0.3~0.5mm。
所述铝粉的Al含量≥99wt%,粒度为0.02~0.074mm。
所述硅粉的Si含量≥98wt%,粒度为0.02~0.074mm。
所述热固性酚醛树脂的固含量为75~80%。
实施例1
一种MgO-Si2N2O-C质耐火材料及其制备方法。以65~69wt%的电熔镁砂、21~25wt%的氧氮化硅、8~10wt%的鳞片石墨、0.2~0.4wt%的铝粉和1~2wt%的硅粉为原料,在混碾机中混合1~3min,再外加所述原料5~6wt%的热固性酚醛树脂,混合3~7min,压制成型,然后在150~250℃条件下烘烤20~25h,即得MgO-Si2N2O-C质耐火材料。
本实施例所述压制成型的压力为120~135MPa。
本实施例所制备的MgO-Si2N2O-C质耐火材料,在200℃×24h和1450℃×3h条件下热处理后体积密度相应地为2.80~2.84g/cm3和2.95~2.99g/cm3,常温耐压强度相应地为75~82MPa和55~63MPa;在1450℃×3h条件下进行抗氧化实验后质量损失率为0.42~0.87%,氧化因子为12~20%,在1450℃×3h条件下抗渣侵蚀经检测为无明显侵蚀。
实施例2
一种MgO-Si2N2O-C质耐火材料及其制备方法。以69~73wt%的电熔镁砂、17~21wt%的氧氮化硅、7~8wt%的鳞片石墨、0.4~0.5wt%的铝粉和2~3wt%的硅粉为原料,在混碾机中混合1~3min,再外加所述原料4~5wt%的热固性酚醛树脂,混合3~7min,压制成型,然后在150~250℃条件下烘烤20~25h,即得MgO-Si2N2O-C质耐火材料。
本实施例所述压制成型的压力为125~140MPa。
本实施例所制备的MgO-Si2N2O-C质耐火材料,在200℃×24h和1450℃×3h条件下热处理后体积密度相应地为2.82~2.86g/cm3和2.96~3.01g/cm3,常温耐压强度相应地为78~86MPa和59~68MPa;在1450℃×3h条件下进行抗氧化实验后质量损失率为0.1~0.43%,氧化因子为8~14%,在1450℃×3h条件下抗渣侵蚀经检测为无明显侵蚀。
实施例3
一种MgO-Si2N2O-C质耐火材料及其制备方法。以73~77wt%的电熔镁砂、13~17wt%的氧氮化硅、2~4wt%的鳞片石墨、0.8~1.0wt%的铝粉和4~5wt%的硅粉为原料,在混碾机中混合1~3min,再外加所述原料2~3wt%的热固性酚醛树脂,混合3~7min,压制成型,然后在150~250℃条件下烘烤20~25h,即得MgO-Si2N2O-C质耐火材料。
本实施例所述压制成型的压力为130~145MPa。
本实施例所制备的MgO-Si2N2O-C质耐火材料,在200℃×24h和1450℃×3h条件下热处理后体积密度相应地为2.85~2.88g/cm3和2.97~3.02g/cm3,常温耐压强度相应地为80~88MPa和63~70MPa;在1450℃×3h条件下进行抗氧化实验后质量损失率为0.35~0.78%,氧化因子为10~18%,在1450℃×3h条件下抗渣侵蚀经检测为无明显侵蚀。
实施例4
一种MgO-Si2N2O-C质耐火材料及其制备方法。以77~81wt%的电熔镁砂、9~13wt%的氧氮化硅、5~7wt%的鳞片石墨、0.5~0.6wt%的铝粉和3~4wt%的硅粉为原料,在混碾机中混合1~3min,再外加所述原料3~4wt%的热固性酚醛树脂,混合3~7min,压制成型,然后在150~250℃条件下烘烤20~25h,即得MgO-Si2N2O-C质耐火材料。
本实施例所述压制成型的压力为135~150MPa。
本实施例所制备的MgO-Si2N2O-C质耐火材料,在200℃×24h和1450℃×3h条件下热处理后体积密度相应地为2.84~2.87g/cm3和2.99~3.04g/cm3,常温耐压强度相应地为85~95MPa和65~72MPa;在1450℃×3h条件下进行抗氧化实验后质量损失率为0.25~0.68%,氧化因子为14~20%,在1450℃×3h条件下抗渣侵蚀经检测为无明显侵蚀。
实施例5
一种MgO-Si2N2O-C质耐火材料及其制备方法。以81~85wt%的电熔镁砂、5~9wt%的氧氮化硅、4~5wt%的鳞片石墨、0.6~0.8wt%的铝粉和5~6wt%的硅粉为原料,在混碾机中混合1~3min,再外加所述原料6~7wt%的热固性酚醛树脂,混合3~7min,压制成型,然后在150~250℃条件下烘烤20~25h,即得MgO-Si2N2O-C质耐火材料。
本实施例所述压制成型的压力为127~142MPa。
本实施例所制备的MgO-Si2N2O-C质耐火材料,在200℃×24h和1450℃×3h条件下热处理后体积密度相应地为2.86~2.90g/cm3和3.00~3.05g/cm3,常温耐压强度相应地为91~100MPa和68~75MPa;在1450℃×3h条件下进行抗氧化实验后质量损失率为0.30~0.73%,氧化因子为9~16%,在1450℃×3h条件下抗渣侵蚀经检测为无明显侵蚀。
本具体实施方式与现有技术相比具有如下积极效果:
本具体实施方式将Si2N2O作为主要成分引入到材料中,由于Si2N2O中不含碳,所以MgO-Si2N2O-C质耐火材料对熔钢的增碳行为比MgO-SiC-C质耐火材料要小得多。同时,Si2N2O具有很好的抗氧化性能和抗熔融有色金属和盐的侵蚀性。在高温下Si2N2O可以与MgO-Si2N2O-C质耐火材料中产生的CO发生反应,抑制MgO-Si2N2O-C质耐火材料中石墨的氧化,并且减弱渣对耐火材料的侵蚀与渗透。Si2N2O在高温下还能分解成一些晶须状或颗粒状的碳化物和氮化物,使所制备的MgO-Si2N2O-C质耐火材料的强度、抗氧化性均有所提高。并且所需原料中的氧氮化硅可通过Si和SiO2在N2气氛下合成,成本较低。
本具体实施方式所制备的MgO-Si2N2O-C质耐火材料,在200℃×24h和1450℃×3h条件下热处理后体积密度相应地为2.80~2.90g/cm3和2.95~3.05g/cm3,常温耐压强度相应地为75~100MPa和55~75MPa;在1450℃×3h条件下进行抗氧化实验后质量损失率为0.1~0.87%,氧化因子为8~20%,在1450℃×3h条件下抗渣侵蚀经检测为无明显侵蚀。
因此,本具体实施方式具有工艺简单和生产成本低的特点;所制备的MgO-Si2N2O-C质耐火材料常温强度大、抗氧化性能优良和对钢水的增碳小,适用于洁净钢的钢包内衬与精炼炉炉衬。
Claims (9)
1.一种MgO-Si2N2O-C质耐火材料的制备方法,其特征在于所述制备方法是:以65~85wt%的电熔镁砂、5~25wt%的氧氮化硅、2~10wt%的鳞片石墨、0.2~1.0wt%的铝粉和1~6wt%的硅粉为原料,在混碾机中混合1~3min,再外加所述原料2~7wt%的热固性酚醛树脂,混合3~7min,压制成型,然后在150~250℃条件下烘烤20~25h,即得MgO-Si2N2O-C质耐火材料。
2.根据权利要求1所述MgO-Si2N2O-C质耐火材料的制备方法,其特征在于所述电熔镁砂的MgO含量≥97%;所述电熔镁砂的颗粒级配是:粒度小于5mm且大于等于3mm占17~27wt%,粒度小于3mm且大于等于1mm占30~40wt%,粒度小于1mm且大于等于0.044mm占33~50wt%。
3.根据权利要求1所述MgO-Si2N2O-C质耐火材料的制备方法,其特征在于所述氧氮化硅的Si2N2O含量≥96%,粒度为0.044~0.088mm。
4.根据权利要求1所述MgO-Si2N2O-C质耐火材料的制备方法,其特征在于所述鳞片石墨的C含量≥97wt%,粒度为0.3~0.5mm。
5.根据权利要求1所述MgO-Si2N2O-C质耐火材料的制备方法,其特征在于所述铝粉的Al含量≥99wt%,粒度为0.02~0.074mm。
6.根据权利要求1所述MgO-Si2N2O-C质耐火材料的制备方法,其特征在于所述硅粉的Si含量≥98wt%,粒度为0.02~0.074mm。
7.根据权利要求1所述MgO-Si2N2O-C质耐火材料的制备方法,其特征在于所述热固性酚醛树脂的固含量为75~80%。
8.根据权利要求1所述MgO-Si2N2O-C质耐火材料的制备方法,其特征在于所述压制成型的压力为120~150MPa。
9.一种MgO-Si2N2O-C质耐火材料,其特征在于所述MgO-Si2N2O-C质耐火材料是根据权利要求1~8项中任一项所述的MgO-Si2N2O-C质耐火材料的制备方法所制备的MgO-Si2N2O-C质耐火材料。
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