CN113149669A - 一种以用后耐火材料为原料的镁质结合剂及其应用 - Google Patents
一种以用后耐火材料为原料的镁质结合剂及其应用 Download PDFInfo
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- CN113149669A CN113149669A CN202110302915.8A CN202110302915A CN113149669A CN 113149669 A CN113149669 A CN 113149669A CN 202110302915 A CN202110302915 A CN 202110302915A CN 113149669 A CN113149669 A CN 113149669A
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 46
- 239000011777 magnesium Substances 0.000 title claims abstract description 46
- 239000011230 binding agent Substances 0.000 title claims abstract description 38
- 239000002994 raw material Substances 0.000 title claims abstract description 28
- 239000011819 refractory material Substances 0.000 title claims abstract description 28
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000007524 organic acids Chemical class 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000012216 screening Methods 0.000 claims abstract description 4
- 239000007767 bonding agent Substances 0.000 claims description 17
- 239000011449 brick Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical compound [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 claims description 3
- NACUKFIFISCLOQ-UHFFFAOYSA-N [Mg].[Cr] Chemical compound [Mg].[Cr] NACUKFIFISCLOQ-UHFFFAOYSA-N 0.000 claims description 3
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004568 cement Substances 0.000 abstract description 8
- 230000036571 hydration Effects 0.000 abstract description 2
- 238000006703 hydration reaction Methods 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 description 24
- 239000010431 corundum Substances 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
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Abstract
本发明公开了一种以用后耐火材料为原料的镁质结合剂及其应用，镁质结合剂是由镁质粉体和有机酸组成，镁质粉体与有机酸的质量比为0.1:1‑10:1，镁质粉体是以用后的镁质耐火材料为原料经筛选、破碎和细磨得到的，要求粉体的粒径小于75μm和氧化镁的含量大于40％，有机酸为柠檬酸、丙烯酸、草酸等中的任一种或一种以上的组合，该镁质结合剂可用于制备无水泥耐火浇注料。本发明的镁质结合剂不仅可制备出高温性能优异的耐火浇注料，且可提高用后耐火材料的利用率和附加值；镁质结合剂中有机酸抑制氧化镁水化带来的膨胀，可制备具有良好强度的浇注料柸体；采用本发明的镁质结合剂制备的耐火浇注料的常温强度可到达传统铝酸钙水泥结合浇注料的强度。
Description
技术领域
本发明属于耐火浇注料技术领域，具体涉及一种以用后耐火材料为原料的镁质结合剂及其应用。
背景技术
随着我国钢铁行业的迅速发展，耐火材料的需求逐年增加，伴随着也产生了大量的废弃耐火材料。在传统耐火材料服役模式中，使用后的耐火材料常被作为废弃物由钢厂进行堆积或填埋处理，大多没有被回收利用，这造成了资源的极大浪费和严重的环境污染。系统性开发耐火材料循环再利用技术，是耐火材料生产服务行业与高温工业共赢的迫切需求。
镁质耐火浇注料因具有耐火度高，抗渣性能优异和抗热震性能优异等优点，广泛应用于钢铁、建材高温窑炉。目前制备镁质耐火浇注料常用的结合剂为铝酸钙水泥、硅微粉和硅溶胶。其中，铝酸钙水泥可以赋予镁质耐火浇注料优异的常温力学性能，但是在高温，铝酸钙水泥中的氧化钙会与氧化镁反应生成钙镁橄榄石低熔点相(CaO·MgO·SiO2)，这些低熔点相会降低浇注料高温力学性能和抗渣侵蚀性能，进而影响浇注料的使用寿命；而且铝酸钙水泥结合浇注料初次烘烤易出现剥落甚至爆裂现象，需要格外注意养护和脱水过程。在含氧化镁的镁质耐火浇注料中加入硅微粉易发生反应生成水合硅酸镁(M-S-H)，该化合物是一种在加热过程中具有良好粘结强度的胶凝材料，但是，在室温环境下，水合硅酸镁(M-S-H)的形成速率过慢限制了硅微粉结合剂的应用；而且，此结合体系中的二氧化硅在高温会形成液相，会对浇注料的抗渣性和高温力学性能产生负面影响。硅溶胶结合的镁质耐火浇注料因脱模强度低造成脱膜困难，且浇注料中添加硅溶胶会在体系中引入二氧化硅，从而影响浇注料的高温使用性能。
发明内容
针对以上技术需求，本发明提出了一种以用后的镁质耐火材料为原料制备镁质结合剂及其应用，解决用后耐火材料对环境的造成污染和现有的结合剂在制备耐火浇注料时易对浇注料的使用寿命低、抗渣性和高温性能产生负面影响的问题。
为了实现上述目的，本发明采用如下技术方案予以实现：
一种以用后耐火材料为原料的镁质结合剂，包括镁质粉体和有机酸，所述镁质粉体与有机酸的质量比为0.1:1-10:1。
优选的，有机酸为柠檬酸、丙烯酸、草酸中的任一种或一种以上的组合。
优选的，所述镁质粉体粒径小于75μm；镁质粉体中氧化镁的含量大于 40％。
优选的，所述镁质粉体是以用后的镁质耐火材料为原料经筛选、破碎和细磨得到的。
优选的，所述用后镁质耐火材料为镁碳耐火砖、镁铬耐火砖、镁钙耐火砖中的一种或一种以上混合。
本发明还公开了所述的镁质结合剂用于制备无水泥耐火浇注料的应用。
具体的，将镁质结合剂与耐火浇注料原料混合，得到无水泥耐火浇注料；所述镁质结合剂质量占耐火浇注料质量的1％～25％。
可选的，将镁质粉体与有机酸粉体预混均匀得到镁质结合剂，根据镁质结合剂在耐火浇注料的添加量混合镁质结合剂与耐火浇注料原料，然后加入水搅拌，得到无水泥耐火浇注料。
可选的，根据镁质粉体在耐火浇注料的添加量混合镁质粉体与耐火浇注料原料，然后加入有机酸的水溶液搅拌，得到无水泥耐火浇注料。
与现有技术相比，本发明的有益效果是：
(1)本发明的镁质结合剂采用用后镁质耐火材料，提高了用后镁质耐火材料的利用率和附加值，减少用后耐火材料对环境负面影响；
(2)本发明制备的镁质结合剂在高温不生成低熔点相，提高了浇注料的耐火度和高温力学性能；
(3)本发明制备的镁质结合剂中有机酸抑制氧化镁水化带来的膨胀，可制备具有良好强度的浇注料胚体；采用本发明的镁质结合剂制备的耐火浇注料的常温强度可到达传统铝酸钙水泥结合浇注料的强度；
(4)本发明制备的镁质结合剂提高耐火材料的纯度，利于耐火材料二次开发利用。
(5)本发明镁质结合剂适用范围广，适用于高铝质、刚玉质、碳化硅质等无水泥耐火浇注料，也适用于耐火捣打料、喷补料、可塑料等形式的不定形耐火材料。
附图说明
图1是本发明制备的耐火浇注料与对比例1制备的耐火浇注料的抗渣侵蚀指数图。
图2是本发明制备的耐火浇注料与对比例1制备的耐火浇注料在热振前后的抗折强度图。
具体实施方式
本发明以镁质粉体和有机酸为原料按照质量比为0.1:1～10:1混合制备得到镁质结合剂。本发明优选的，镁质粉体是以用后的镁质耐火材料为原料经筛选、破碎和细磨得到的，要求粉体的粒径小于75μm和氧化镁的含量大于 40％。用后镁质耐火材料优选镁碳耐火砖、镁铬耐火砖、镁钙耐火砖中的一种，也可将多种砖混合使用。
有机酸优选柠檬酸、丙烯酸、草酸等中的一种，也可将一种或者多种酸混合使用，本发明实施例中仅给出了单独使用的情况。
将本发明的镁质结合剂用于制备无水泥耐火浇注料，具体使用方法为：
方式一：将镁质粉体与有机酸粉体预混均匀得到镁质结合剂，将镁质结合剂与耐火浇注料原料混合，然后加入水搅拌，得到无水泥耐火浇注料。其中，镁质结合剂质量占耐火浇注料质量的1％～25％。
方式二：根据镁质粉体在耐火浇注料的添加量混合镁质粉体与耐火浇注料，然后加入有机酸的水溶液搅拌，得到无水泥耐火浇注料。
本发明的耐火浇注料原料如实施例中所示例，包括板状刚玉骨料、板状刚玉细粉(Al2O3＞95wt％)、α-氧化铝微粉(Al2O3＞95wt％)、硅微粉等。
以下给出本发明的具体实施例，需要说明的是本发明并不局限于以下具体实施例中，凡在本申请技术方案基础上做的等同变换均落入本发明的保护范围。
实施例1
本实施例公开了一种镁质结合剂，由镁质粉体和柠檬酸按照质量比为 1:3混合而成，其中，柠檬酸为分析纯；镁质粉体为用后的镁碳耐火砖经粉碎球磨至粒径小于75μm的粉体，镁质粉体是由66.23％的MgO、25.96％的 C、4.01％的Al2O3、0.76％的Fe2O3、1.18％的CaO和1.86％的SiO2组成。
实施例2
本实施例公开了一种镁质结合剂，由镁质粉体和丙烯酸按照质量比为 1:1混合而成，其中，丙烯酸为分析纯；镁质粉体为用后的镁铬耐火砖经粉碎球磨至粒径小于75μm的粉体，镁质粉体是由70.92％的MgO、20.51％的 Cr2O3、2.51％的Al2O3、3.80％的Fe2O3、0.43％的CaO和1.83％的SiO2组成。
实施例3
本实施例公开了一种镁质结合剂，由镁质粉体和草酸按照质量比为1:3 混合而成，其中，草酸为分析纯；镁质粉体为用后的镁钙耐火砖经粉碎球磨至粒径小于75μm的粉体。镁质粉体是由72.18％的MgO、25.94％的CaO和 1.88％的SiO2组成。
实施例4
本实施例公开了一种无水泥耐火浇注料的制备，本实施例的无水泥耐火浇注料原料由不同粒径的板状刚玉颗粒、硅微粉、活性氧化铝微粉(即α- 氧化铝微粉)和镁质结合剂，其中镁质结合剂采用实施例1的镁质结合剂。各原料质量分数为：35％的粒径为3.0mm～5.0mm的板状刚玉颗粒，17％的粒径为1.0mm～3.0mm的板状刚玉颗粒，20％的粒径为0mm～1.0mm的板状刚玉颗粒，14％的粒径为0μm～45μm的板状刚玉细粉，1％的硅微粉，9％的d50≦5μm的活性氧化铝，1％的粒径小于75μm的用后镁质粉体，3％的柠檬酸，原料质量分数之和为100％。
制备方法为：将镁质粉体与柠檬酸粉体预混均匀得到镁质结合剂，再将镁质结合剂与耐火浇注料原料(即不同粒径的板状刚玉颗粒、硅微粉、活性氧化铝微粉)混合，然后加入水搅拌，震动成型浇注料试样。
本实施例的浇注料试样的性能见表1所示。
实施例5
本实施例公开了一种无水泥耐火浇注料的制备，与实施例4的区别在于：镁质结合剂采用实施例2的镁质结合剂；
各原料质量分数分别为：35％的粒径为3.0mm～5.0mm的板状刚玉颗粒，17％的粒径为1.0mm～3.0mm的板状刚玉颗粒，20％的粒径为 0mm～1.0mm的板状刚玉颗粒，14％的粒径为0μm～45μm的板状刚玉细粉， 1％的硅微粉，9％的d50≦5μm的活性氧化铝，2％的粒径小于75μm的用后镁质粉体，2％的丙烯酸，原料质量分数之和为100％。
本实施例的浇注料试样的制备方法同实施例1。
本实施例的浇注料试样的性能见表1所示。
实施例6
本实施例公开了一种无水泥耐火浇注料的制备，与实施例4的区别在于：镁质结合剂采用实施例3的镁质结合剂；
各原料质量分数分别为：35％的粒径为3.0mm～5.0mm的板状刚玉颗粒，17％的粒径为1.0mm～3.0mm的板状刚玉颗粒，20％的粒径为 0mm～1.0mm的板状刚玉颗粒，14％的粒径为0μm～45μm的板状刚玉细粉，1％的硅微粉，9％的d50≦5μm的活性氧化铝，1％的粒径小于75μm的用后镁质粉体，3％的草酸，原料质量分数之和为100％。
制备方法为：将镁质粉体与耐火浇注料(即不同粒径的板状刚玉颗粒、硅微粉、活性氧化铝微粉)混合，然后加入有机酸的水溶液搅拌，震动成型浇注料试样。
本实施例的浇注料试样的性能见表1所示。
表1实施案1～3性能指标
对比例1
本对比例的镁质结合剂为铝酸钙水泥；
本对比例的耐火浇注料中各原料的质量分数为：35％的粒径为 3.0mm～5.0mm的板状刚玉颗粒，17％的粒径为1.0mm～3.0mm的板状刚玉颗粒，20％的粒径为0mm～1.0mm的板状刚玉颗粒，14％的粒径为0μm～45μm 的板状刚玉细粉，1％的硅微粉，10％的d50≦5μm的活性氧化铝，3％的铝酸钙水泥，原料质量分数之和为100％。制备方法同实施例1。
本对比例制备耐火浇注料与本发明制备的耐火浇注料的抗热震性能和抗渣性能如图1和图2所示，从图中可以看出，采用本发明的镁质结合剂制备的耐火浇注料具有良好的抗渣侵蚀性能和抗热震性能。
Claims (9)
1.一种以用后耐火材料为原料的镁质结合剂，其特征在于，包括镁质粉体和有机酸，所述镁质粉体与有机酸的质量比为0.1:1～10:1。
2.如权利要求1所述的镁质结合剂，所述有机酸为柠檬酸、丙烯酸、草酸中的一种或一种以上的组合。
3.如权利要求1所述的镁质结合剂，其特征在于，所述镁质粉体是以用后的镁质耐火材料为原料经筛选、破碎和细磨得到的。
4.如权利要求1所述的镁质结合剂，其特征在于，所述镁质粉体粒径小于75μm，镁质粉体中氧化镁的含量大于40％。
5.如权利要求1所述的镁质结合剂，其特征在于，所述用后镁质耐火材料为镁碳耐火砖、镁铬耐火砖、镁钙耐火砖中的一种或一种以上混合。
6.权利要求1～5任一项所述的镁质结合剂用于制备无水泥耐火浇注料。
7.如权利要求6所述的应用，其特征在于，将镁质结合剂与耐火浇注料混合，得到无水泥耐火浇注料；所述镁质结合剂质量占耐火浇注料质量的1％～25％。
8.如权利要求7所述的应用，其特征在于，将镁质粉体与有机酸粉体预混均匀得到镁质结合剂，根据镁质结合剂在耐火浇注料的添加量混合镁质结合剂与耐火浇注料原料，然后加入水搅拌，得到无水泥耐火浇注料。
9.如权利要求7所述的应用，其特征在于，根据镁质粉体在耐火浇注料的添加量混合镁质粉体与耐火浇注料原料，然后加入有机酸的水溶液搅拌，得到无水泥耐火浇注料。
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