CN112851380A - 一种镁钙质冶金炉盖浇注料及其制备方法 - Google Patents
一种镁钙质冶金炉盖浇注料及其制备方法 Download PDFInfo
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- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 96
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 79
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 239000000292 calcium oxide Substances 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 43
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 235000019738 Limestone Nutrition 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 16
- 239000006028 limestone Substances 0.000 claims abstract description 16
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004576 sand Substances 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 239000001095 magnesium carbonate Substances 0.000 claims description 9
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 9
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 9
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 abstract description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 4
- 239000000920 calcium hydroxide Substances 0.000 abstract description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 4
- 230000036571 hydration Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 239000011819 refractory material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000004321 preservation Methods 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 235000019830 sodium polyphosphate Nutrition 0.000 description 4
- 229910001208 Crucible steel Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000009847 ladle furnace Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000912 Bell metal Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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Abstract
本发明公开了一种镁钙质冶金炉盖浇注料及其制备方法。其组成按质量百分数计如下：石灰石颗粒20～35wt％；镁钙砂颗粒20～40wt％；生石灰颗粒5～15wt％；镁砂细粉10～18wt％；氧化镁微粉2～8wt％；金属钼粉0.5～3wt％；金属铝粉1～6wt％；醇类混合物2～6wt％；以上成分总量为100wt％；外加减水剂0.1～0.2wt％。本发明利用氧化钙的水化膨胀以及金属铝粉的水化、钼粉催化、醇类分解气体反应形成紧密逐层气孔结构；伴随烘烤温度的升高，生石灰中氧化钙和水蒸气反应更强烈，形成氢氧化钙，同时生石灰和金属铝粉共同逐步水化反应，结构逐层烧结致密度且不开裂。
Description
技术领域
本发明属于耐火材料技术领域，具体涉及一种镁钙质冶金炉盖浇注料及其制备方法。
背景技术
近年来，随着钢包、中间包等炼钢系统用冶金炉的冶金功能增强以及环保节能降耗的需求，冶金炉盖的作用极为凸显，各品种钢产量和质量直接受其使用状况好坏的影响。冶金炉盖的主要作用为：为钢包冶金炉烘烤和浇注过程提供隔热保温作用，提高烘烤效率、减少钢水热量损失，同时保护现场测温与取样人员安全。
冶金炉盖主要有两种形式：
(1)全铸钢或全铸铁冶金炉盖形式。采用全铸钢件制造冶金炉盖，一般浇钢使用几次后，盖板整体产生严重变形、翘曲，盖板表面剧烈氧化、粘钢，冶金炉盖的保温效果减弱，塞棒上下操作运动受阻。采用全铸钢件的冶金炉盖影响其浇钢正常操作，备件消耗大、使用寿命短且备件消耗量大。
(2)金属-耐火浇注料复合结构的冶金炉盖形式。金属-耐火浇注料复合结构的冶金炉盖有3种损毁形式：①烧蚀冶金炉盖金属边框；②冶金炉盖中部区域弯曲变形；③冶金炉盖用耐火浇注料覆盖层剥落。其中，普遍主要出现烧蚀冶金炉盖金属边框和冶金炉盖边框弯曲的破损形式，多伴生出现。冶金炉盖耐火浇注料覆盖层的剥落先是以边框局部剥落为起点而不断延伸扩展，最终发展成大面积的冶金炉盖剥落。冶金炉盖耐火浇注料的覆盖层的大面积剥落会导致冶金炉盖保温性能下降、保温防护功能逐步丧失，同时连铸坯的开浇也因耐火材料掉块导致堵塞浇铸水口而受影响。
目前，国内外冶金炉多使用钢结构加耐火材料的结构形式的冶金炉盖，其主要失效形式为钢结构烧损、整体尺寸变大、耐火材料剥落等。例如：对于大型的槽形中间包，中间包冶金炉盖因中间包尺寸较大而采用多段组合的方式。塞棒孔和烧嘴孔布置在中间包冶金炉盖上，冶金炉盖中部极易下陷损坏、冶金炉盖耐火浇注料覆盖层严重剥落、以及严重烧蚀金属结构边框等，大大减少了中间包冶金炉盖使用寿命，一般平均使用寿命最多仅3-5个浇次。通过大量冶金炉盖材料损失分析：温度剧烈变化会使整体焊接的钢结构产生较大变形，导致耐火材料与钢结构因其自身膨胀系数的差异而无法长时间紧密接触，耐火材料很容易形成开裂而剥落，烧损钢结构，最终冶金炉盖全部失去功效。因此，中间包冶金炉盖损坏的主要原因为冶金炉盖耐火材料的热震性差，而前期发明的一种中间包冶金炉盖浇注料及其制备方法(ZL201410242492.5)较好的解决热震稳定性，但碳的引入导致导热性较高、污染钢水，亟待解决。
发明内容
本发明目的在于提供一种拥有良好的抗热震性和保温性且能不污染钢水、长寿有效的冶金炉盖浇注料及其制备方法。
为达到上述目的，采用技术方案如下：
一种镁钙质冶金炉盖浇注料，其组成按质量百分数计如下：
石灰石颗粒20～35wt％；
镁钙砂颗粒20～40wt％；
生石灰颗粒5～15wt％；
镁砂细粉10～18wt％；
氧化镁微粉2～8wt％；
金属钼粉0.5～3wt％；
金属铝粉1～6wt％；
醇类混合物2～6wt％；
以上成分总量为100wt％；外加减水剂0.1～0.2wt％。
按上述方案，所述石灰石颗粒CaO的含量大于52wt％，粒径为0.1～10mm。
按上述方案，所述镁钙砂颗粒CaO的含量大于等于20wt％，粒径为0.1～10mm。
按上述方案，所述生石灰颗粒CaO的含量大于95wt％，粒径为0.1～8mm。
按上述方案，所述镁砂细粉MgO的含量大于99wt％，粒径为小于0.088mm。
按上述方案，所述金属钼粉钼含量大于98wt％，粒径小于0.088mm。
按上述方案，所述金属铝粉铝含量大于98wt％，粒径小于0.088mm。
按上述方案，所述醇类混合物为乙醇和甲醇含量大于95wt％的醇类混合物。
按上述方案，所述氧化镁微粉MgO含量大于99wt％，粒径小于0.01mm。
按上述方案，所述减水剂为聚羧酸、聚磷酸钠和聚丙烯酸的一种或任意混合。
上述镁钙质冶金炉盖浇注料的制备方法，包括以下步骤：
(1)将金属钼粉、金属铝粉、醇类混合物、氧化镁微粉以及减水剂混合均匀成微粉混合物；将石灰石颗粒、镁钙砂颗粒、生石灰颗粒和镁砂细粉混合均匀成颗粒混合物；
(2)将所得微粉混合物与颗粒混合物混合，外加4～8wt％的水，搅拌1～4分钟后浇注振动成型得到坯体；
(3)将所得坯体在室温下养护6～25小时，然后在110～200℃条件下保温10～38小时，即得镁钙质冶金炉盖浇注料。
相对于现有技术，本发明有益效果如下：
本发明利用氧化钙的水化膨胀以及金属铝粉的水化、钼粉催化、醇类分解气体反应形成紧密逐层气孔结构；
伴随烘烤温度的升高，生石灰中氧化钙和水蒸气反应更强烈，形成氢氧化钙，同时生石灰和金属铝粉共同逐步水化反应，结构逐层烧结致密度且不开裂；
其后，有残留具有较大活性的钙和镁消耗掉材料气孔中的水蒸气，形成氢氧化钙微晶进一步使材料致密化和前期形成的氢氧化钙构成交错的网络，并提高材料的中温强度；然后水化氧化钙逐步分解，材料内部形成大量微纳米闭口气孔；
同时，钼粉和醇催化反应产生的氢气和二氧化碳气体不断相互包裹，形成多层密闭孔状结构，能够容纳温度剧变带来的热应力，提高耐火材料的热震稳定性，还能有效降低热量散失，保证了材料良好的保温性能和抗热震性；
本发明运用于高品质钢连铸中间包上，能使冶金炉盖外壳温度平均降低10％以上，平均使用寿命达30次以上。
具体实施方式
以下实施例进一步阐释本发明的技术方案，但不作为对本发明保护范围的限制。
实施例1
一种镁钙质冶金炉盖浇注料，包括以重量百分比计的下列组分：
石灰石颗粒31wt％，粒径为0.1～10mm；镁钙砂颗粒35wt％，粒径为0.1～10mm；生石灰颗粒9wt％，粒径为0.1～8mm；镁砂细粉16wt％，粒径为小于0.088mm；金属钼粉1wt％，粒径小于0.088mm；金属铝粉2wt％，粒径小于0.088mm；醇类混合物3wt％；氧化镁微粉3wt％，粒径小于0.01mm以及减水剂0.1wt％(减水剂为外加)。
其中，所述石灰石颗粒中CaO含量大于52wt％。所述镁钙砂颗粒的CaO≥20wt％。所述生石灰颗粒的CaO含量大于95wt％。所述镁砂细粉的MgO含量大于99wt％。所述金属钼粉为钼含量大于98wt％的钼粉。所述醇类混合物为乙醇和甲醇含量大于95wt％的醇类混合物。所述金属铝粉为铝含量大于98wt％的金属铝粉。所述氧化镁微粉的MgO含量大于99wt％。所述减水剂为聚羧酸、聚磷酸钠和聚丙烯酸的一种或两种以上的混合物。
上述实施例1的镁钙质冶金炉盖浇注料的制备方法为：
(1)将金属钼粉、金属铝粉、醇类混合物、氧化镁微粉以及减水剂混合均匀成微粉混合物；将石灰石颗粒、镁钙砂颗粒、生石灰颗粒和镁砂细粉混合均匀成颗粒混合物；
(2)将所得微粉混合物与颗粒混合物混合，外加5wt％的水，搅拌1.5分钟后浇注振动成型得到坯体；
(3)将所得坯体在室温下养护8小时，然后在110℃条件下保温13小时，即得镁钙质冶金炉盖浇注料。
使用上述产品效果良好，钢包炉壳温度由220℃降低至180℃，使用寿命>38次。
实施例2
一种镁钙质冶金炉盖浇注料，包括以重量百分比计的下列组分：
石灰石颗粒30wt％，粒径为0.1～10mm；镁钙砂颗粒30wt％，粒径为0.1～10mm；生石灰颗粒10wt％，粒径为0.1～8mm；镁砂细粉15wt％，粒径为小于0.088mm；金属钼粉2wt％，粒径小于0.088mm；金属铝粉4wt％，粒径小于0.088mm；醇类混合物4wt％；氧化镁微粉5wt％，粒径小于0.01mm以及减水剂0.15wt％(减水剂为外加)。
其中，所述石灰石颗粒中CaO含量大于52wt％。所述镁钙砂颗粒的CaO≥20wt％。所述生石灰颗粒的CaO含量大于95wt％。所述镁砂细粉的MgO含量大于99wt％。所述金属钼粉为钼含量大于98wt％的钼粉。所述醇类混合物为乙醇和甲醇含量大于95wt％的醇类混合物。所述金属铝粉为铝含量大于98wt％的金属铝粉。所述氧化镁微粉的MgO含量大于99wt％。所述减水剂为聚羧酸、聚磷酸钠和聚丙烯酸的一种或两种以上的混合物。
上述实施例2的镁钙质冶金炉盖浇注料的制备方法为：
(1)将金属钼粉、金属铝粉、醇类混合物、氧化镁微粉以及减水剂混合均匀成微粉混合物；将石灰石颗粒、镁钙砂颗粒、生石灰颗粒和镁砂细粉混合均匀成颗粒混合物；
(2)将所得微粉混合物与颗粒混合物混合，外加6wt％的水，搅拌2分钟后浇注振动成型得到坯体；
(3)将所得坯体在室温下养护16小时，然后在160℃条件下保温24小时，即得镁钙质冶金炉盖浇注料。
使用上述产品效果良好，钢包炉壳温度由220℃降低至177℃，使用寿命>40次。
实施例3
一种镁钙质冶金炉盖浇注料，包括以重量百分比计的下列组分：
石灰石颗粒24wt％，粒径为0.1～10mm；镁钙砂颗粒32wt％，粒径为0.1～10mm；生石灰颗粒12wt％，粒径为0.1～8mm；镁砂细粉13wt％，粒径为小于0.088mm；金属钼粉3wt％，粒径小于0.088mm；金属铝粉5wt％，粒径小于0.088mm；醇类混合物5wt％，粒径小于0.045m；氧化镁微粉6wt％，粒径小于0.01mm以及减水剂0.2wt％(减水剂为外加)。
其中，所述石灰石颗粒中CaO含量大于52wt％。所述镁钙砂颗粒的CaO≥20wt％。所述生石灰颗粒的CaO含量大于95wt％。所述镁砂细粉的MgO含量大于99wt％。所述金属钼粉为钼含量大于98wt％的钼粉。所述醇类混合物为乙醇和甲醇含量大于95wt％的醇类混合物。所述金属铝粉为铝含量大于98wt％的金属铝粉。所述氧化镁微粉的MgO含量大于99wt％。所述减水剂为聚羧酸、聚磷酸钠和聚丙烯酸的一种或两种以上的混合物。
上述实施例3的镁钙质冶金炉盖浇注料的制备方法为：
(1)将金属钼粉、金属铝粉、醇类混合物、氧化镁微粉以及减水剂混合均匀成微粉混合物；将石灰石颗粒、镁钙砂颗粒、生石灰颗粒和镁砂细粉混合均匀成颗粒混合物；
(2)将所得微粉混合物与颗粒混合物混合，外加7wt％的水，搅拌3分钟后浇注振动成型得到坯体；
(3)将所得坯体在室温下养护24小时，然后在200℃条件下保温36小时，即得镁钙质冶金炉盖浇注料。
使用上述产品效果良好，钢包炉壳温度由220℃降低至170℃，使用寿命>45次。
Claims (10)
1.一种镁钙质冶金炉盖浇注料，其特征在于组成按质量百分数计如下：
石灰石颗粒20～35wt％；
镁钙砂颗粒20～40wt％；
生石灰颗粒5～15wt％；
镁砂细粉10～18wt％；
氧化镁微粉2～8wt％；
金属钼粉0.5～3wt％；
金属铝粉1～6wt％；
醇类混合物2～6wt％；
以上成分总量为100wt％；外加减水剂0.1～0.2wt％。
2.如权利要求1所述镁钙质冶金炉盖浇注料，其特征在于所述石灰石颗粒CaO的含量大于52wt％，粒径为0.1～10mm。
3.如权利要求1所述镁钙质冶金炉盖浇注料，其特征在于所述镁钙砂颗粒CaO的含量大于等于20wt％，粒径为0.1～10mm。
4.如权利要求1所述镁钙质冶金炉盖浇注料，其特征在于所述生石灰颗粒CaO的含量大于95wt％，粒径为0.1～8mm。
5.如权利要求1所述镁钙质冶金炉盖浇注料，其特征在于所述镁砂细粉MgO的含量大于99wt％，粒径为小于0.088mm。
6.如权利要求1所述镁钙质冶金炉盖浇注料，其特征在于所述金属钼粉钼含量大于98wt％，粒径小于0.088mm。
7.如权利要求1所述镁钙质冶金炉盖浇注料，其特征在于所述金属铝粉铝含量大于98wt％，粒径小于0.088mm。
8.如权利要求1所述镁钙质冶金炉盖浇注料，其特征在于所述醇类混合物为乙醇和甲醇含量大于95wt％的醇类混合物。
9.如权利要求1所述镁钙质冶金炉盖浇注料，其特征在于所述氧化镁微粉MgO含量大于99wt％，粒径小于0.01mm。
10.权利要求1-9任一项所述镁钙质冶金炉盖浇注料的制备方法，其特征在于包括以下步骤：
(1)将金属钼粉、金属铝粉、醇类混合物、氧化镁微粉以及减水剂混合均匀成微粉混合物；将石灰石颗粒、镁钙砂颗粒、生石灰颗粒和镁砂细粉混合均匀成颗粒混合物；
(2)将所得微粉混合物与颗粒混合物混合，外加4～8wt％的水，搅拌1～4分钟后浇注振动成型得到坯体；
(3)将所得坯体在室温下养护6～25小时，然后在110～200℃条件下保温10～38小时，即得镁钙质冶金炉盖浇注料。
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