CN113233906B - 适用于冶炼洁净钢的镁钙质喷补料及其制备方法和应用 - Google Patents

适用于冶炼洁净钢的镁钙质喷补料及其制备方法和应用 Download PDF

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CN113233906B
CN113233906B CN202110666430.7A CN202110666430A CN113233906B CN 113233906 B CN113233906 B CN 113233906B CN 202110666430 A CN202110666430 A CN 202110666430A CN 113233906 B CN113233906 B CN 113233906B
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刘光平
李媛媛
宋雅楠
王玉龙
程文雍
沈明科
尹明强
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Abstract

本发明公开了一种适用于冶炼洁净钢的镁钙质喷补料及其制备方法和在冶炼洁净钢中的应用。按质量份数计，镁钙质喷补料原料组成包括：镁钙砂10～40份，镁砂料40～90份，镁硅胶凝剂10～26份；按质量份数计，镁硅胶凝剂原料组成包括：镁质结合剂5～15份，磷酸盐结合剂2～5份，熟石灰微粉1～4份，增稠剂0.05～0.5份，防爆剂0.05～1.5份；镁质结合剂的粒度不大于5μm，其组成中MgO含量≥77.00wt％，SiO2含量≥13.00wt％，950℃灼减量≤6.0wt％；镁硅胶凝剂通过组成它的原料共磨得到，粒度不大于3μm。制备方法包括：将包括镁钙砂、镁砂料和镁硅胶凝剂在内的组成镁钙质喷补料的原料在混料机内搅拌均匀即得镁钙质喷补料。

Description

适用于冶炼洁净钢的镁钙质喷补料及其制备方法和应用
技术领域
本发明涉及耐火材料技术领域，具体涉及一种适用于冶炼洁净钢的镁钙质喷补料及其制备方法和应用。
背景技术
随着炼钢技术不断发展，推进高效节能、功能化、长寿命和安全化的高性能先进耐火材料，降低耐火材料的消耗和成本，提高转炉、钢包、RH炉、中间包工作衬使用寿命是必然的趋势，目前对炉衬材料进行喷补维护是延长使用寿命、降低耐材消耗的重要措施之一。
但随着高级特种钢品种的增多，特别是洁净钢、铝镇静钢和硅钢需求的剧增，即要求耐火材料具有高的使用寿命，又需要其不影响钢水的品质。但因LF处理钢水温度高、渣碱度大、RH处理时间长、喷补维护时间短等苛刻的操作条件，而一般的镁质喷补料不能满足品种钢的冶炼要求，达不到转炉耳轴、RH炉浸渍管、中间包工作衬耐材的喷补维护需求，影响钢水质量和工作衬耐火材料的使用寿命，同时喷补料的消耗大、成本高。
转炉耳轴部位、RH浸渍管、中间包工作衬一般采用半干法喷补料。中国专利CN200910061416.3涉及一种转炉或电炉用镁碳质喷补料，其组份重量百分比为：烧结镁砂75～90％，含有粘土1～5％，碳5～10％、改质沥青1～5％、复合添加剂0～5％。中国专利CN200910097752.2涉及一种转炉用喷补料配方，主原料为镁橄榄石、白云石、中档镁砂和结合剂，存在使用寿命偏低的问题。中国专利CN103626508A涉及一种RH浸渍管用碱性喷补料，主原料为重烧镁砂、羧甲基纤维素、92硅微粉、防爆纤维、六偏磷酸钠、泡花碱、消石灰、麻刀、膨润土、硼酸和铬绿。因基质中含有大量的粘土、膨润土或者泡花碱，在高温下形成大量的低熔相，且加水量高，不利于抗钢水侵蚀性和抗渣性，造成喷补料使用寿命不佳。
此外，半干法喷补料基质中的微粉、结合剂和外加剂分散加入，因搅拌设备的差异，造成基质中的成分分布不均匀，喷补施工时，一般在喷枪口处加水，混合时间短，易造成枪口阻塞、水料不均匀，造成喷补料掉落和垮塌，从而影响喷补效果。
综上所述，为了满足洁净钢等特种钢冶炼需要，提高喷补料的使用寿命，有必要对现有技术中碱性喷补料进行改进，需要碱性喷补料不影响钢水质量，具有优异的喷补效果、烧结时间短、强度高、粘附性、抗爆裂性和抗侵蚀性优等特性。
发明内容
针对上述技术问题以及本领域存在的不足之处，本发明提供了一种适用于冶炼洁净钢的镁钙质喷补料，采用特定粒径、特定组成的镁质结合剂，与磷酸盐结合剂、熟石灰微粉、增稠剂、防爆剂等组分预先共磨形成特定粒径的镁硅胶凝剂，然后再与镁钙砂、镁砂料等原料一起组成镁钙质喷补料，所得镁钙质喷补料可吸附钢水中的杂质，降低夹杂物含量和粒径，具有优异的高温性能以及高纯度、粘附性好、烧结时间短、强度高、抗爆裂性和抗侵蚀性优等特性，能够满足洁净钢冶炼，适用于转炉耳轴、RH浸渍管和中间包工作衬耐材的喷补维护，提高其使用寿命，降低喷补料使用消耗。
一种适用于冶炼洁净钢的镁钙质喷补料，按质量份数计，原料组成包括：
镁钙砂 10～40份，
镁砂料 40～90份，
镁硅胶凝剂 10～26份；
按质量份数计，所述镁硅胶凝剂的原料组成包括：
Figure BDA0003117615990000021
所述镁质结合剂的粒度不大于5μm，其组成中MgO含量≥77.00wt％，SiO2含量≥13.00wt％，950℃灼减量≤6.0wt％，以降低低熔点相杂质对镁钙质喷补料性能的影响；
所述镁硅胶凝剂通过组成它的原料共磨得到，粒度不大于3μm。
所述镁钙质喷补料以镁钙砂和镁砂料为主料，采用镁硅胶凝剂作为结合剂，各组分之间具有协同作用、增效作用。在喷补施工过程中，镁硅胶凝剂在喷枪口能够与水快速均匀混合，只需少量水即可达到优异的喷补效果和粘附性，而且由于用水量少，喷补形成的材料更为致密，强度更高；另一方面，本发明共磨特制的镁硅胶凝剂能够在较低温度下原位形成微米级镁橄榄石相，产生体积微膨胀，且封闭的基质气孔，使喷补料具有优异的抗渣侵蚀和渗透性。其中，所述镁硅胶凝剂中特定的镁质结合剂能够促进喷补料基质烧结，提升喷补料的耐高温性和抗钢水冲刷性。本发明的镁质结合剂能够在喷补过程中与水快速反应形成MgO-SiO2-H2O结合相，改善喷补料的喷补强度、粘附性和抗爆裂性。
镁硅胶凝剂原料中镁质结合剂、熟石灰微粉、磷酸盐结合剂、增稠剂、防爆剂进行共磨，一方面，使基质组分更加均匀，提升喷补效果，防止因物料不均匀造成喷补料喷补效果异常，增加其使用寿命，降低喷补料消耗，并且可明显减少喷补施工过程中的加水量，节约成本的同时提高材料的致密性和强度；另一方面，在共磨过程中，镁质结合剂粉体表面会反应生成微纳米级镁橄榄石相晶核，从而可以大幅度降低镁橄榄石相生成的温度(可降低50～100℃)，促进喷补料的烧结，降低喷补料的气孔率。
本发明的镁钙质喷补料的原料中不含有粘土、膨润土或者泡花碱，不会在材料内部形成大量的低熔相，因此，制得的镁钙质喷补料的耐高温强度、抗渣侵蚀和渗透性能好。
作为优选，所述的镁钙质喷补料，所述镁钙砂的粒度不大于3mm，其组成中MgO和CaO的总含量不低于92wt％。
作为优选，所述的镁钙质喷补料，所述镁砂料为烧结镁砂、电熔镁砂中的一种或两种。
作为优选，所述的镁钙质喷补料，所述镁砂料中MgO含量≥95wt％。
作为优选，所述的镁钙质喷补料，所述镁砂料的粒度不大于3mm。
作为优选，所述的镁钙质喷补料，按质量份数计，所述镁砂料具体粒度级配为：
3～1mm 0～30份；
1～0.045mm(不含1mm) 20～35份；
＜0.045mm 10～25份。
所述粒度级配中的粒径均为数均粒径。
作为优选，所述的镁钙质喷补料，所述熟石灰微粉的粒度为5～10μm。
作为优选，所述的镁钙质喷补料，所述磷酸盐结合剂为六偏磷酸钠、三聚磷酸钠、磷酸二氢铝中的一种或多种复合而成。
作为优选，所述的镁钙质喷补料，所述增稠剂为羧甲基纤维素、羧甲基淀粉醚、木质素磺酸钙中的一种或多种复合而成。
作为优选，所述的镁钙质喷补料，所述防爆剂为有机纤维、纸纤维或铝粉中的一种或多种复合而成。
作为优选，所述共磨为球磨，球磨转速为150～250rpm，球磨时间为2.5～3.5h。
本发明还提供了所述的镁钙质喷补料的制备方法，包括：将包括镁钙砂、镁砂料和镁硅胶凝剂在内的组成所述镁钙质喷补料的原料在混料机内搅拌均匀即得所述镁钙质喷补料。
本发明还提供了所述的镁钙质喷补料在冶炼洁净钢中的应用。所述镁钙质喷补料特别适用于转炉耳轴、RH浸渍管、中间包工作衬耐材的喷补维护，加水量仅为镁钙质喷补料的11wt％～13wt％。
本发明与现有技术相比，主要优点包括：
1)本发明采用特定粒径、特定组成的镁质结合剂，与磷酸盐结合剂、熟石灰微粉、增稠剂、防爆剂等组分预先共磨形成特定粒径的镁硅胶凝剂，然后再与镁钙砂、镁砂料等原料一起组成镁钙质喷补料，所得镁钙质喷补料可吸附钢水中的杂质，降低夹杂物含量和粒径，具有优异的高温性能以及高纯度、粘附性好、烧结时间短、强度高、抗爆裂性和抗侵蚀性优等特性，能够满足洁净钢冶炼，适用于转炉耳轴、RH浸渍管和中间包工作衬耐材的喷补维护，提高其使用寿命，降低喷补料使用消耗。
2)镁硅胶凝剂原料中Al2O3、Fe2O3等低熔点相杂质很少，能够提升喷补料的高温性能、抗渣侵蚀和渗透性。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法，通常按照常规条件，或按照制造厂商所建议的条件。
实施例1～5
按质量份计，将10份镁质结合剂(宜兴自立微粉材料科技有限公司，LIMAGEL-75高强度镁质结合剂，粒度不大于5μm，其组成中MgO含量≥77.00wt％，SiO2含量≥13.00wt％，950℃灼减量≤6.0wt％)，2.0份六偏磷酸钠，1份三聚磷酸钠，2份熟石灰微粉(粒度为5～10μm)、0.2份羧甲基纤维素和0.2份有机纤维在高能球磨机中进行共磨3h，球磨机的转速为200r/min，制得镁硅胶凝剂，其粒度不大于3μm。
按质量份计，镁钙质喷补料的原料组成如表1所示，将镁钙砂(MgO和CaO的总含量不低于92wt％)、镁砂料(MgO含量≥95wt％)与上述制备的镁硅胶凝剂在混料机中进行搅拌均匀，制得镁钙质喷补料。测试镁钙质喷补料的线变化率、体积密度、抗折强度、耐压强度、高温抗折强度和渣侵指数，测试结果见表3。
表1
Figure BDA0003117615990000051
实施例1～5的镁钙质喷补料用于转炉耳轴、RH浸渍管、中间包工作衬耐材的喷补维护时，加水量仅为镁钙质喷补料的11wt％～13wt％。
对比例1
按质量份计，镁质喷补料的原料组分如表2所示，先按2.5份膨润土、3份泡花碱、3份92级氧化硅微粉(SiO2含量≥92wt％)、3份六偏磷酸钠、1份三聚磷酸钠以及3份熟石灰微粉，进行配料然后在混料设备中搅拌20min混匀，得到预混合粉；再将镁砂料与预混合粉在混料机进行搅拌20min混匀，制得镁质喷补料。测试镁质喷补料的线变化率、体积密度、抗折强度、耐压强度、高温抗折强度和渣侵指数，测试结果见表3。
表2
Figure BDA0003117615990000061
对比例2参照实施例5的配方，区别仅在于不预先共磨制备镁硅凝胶剂而是直接将各原料组分在混料机中搅拌均匀，制得镁钙质喷补料，其余步骤、条件均相同。
对比例1和对比例2的镁钙质喷补料用于转炉耳轴、RH浸渍管、中间包工作衬耐材的喷补维护时，对比例1中加水量为镁钙质喷补料的15wt％～18wt％，对比例2中加水量为镁钙质喷补料的14wt％～16wt％。
表3
Figure BDA0003117615990000071
可见，本发明的镁钙质喷补料，加水量低、致密度高，具有良好的体积稳定性、高的高温强度、优异的抗渣侵蚀和渗透性能，能够满足洁净钢冶炼，适用于转炉耳轴、RH浸渍管和中间包工作衬耐材的喷补维护，提高其使用寿命，降低喷补料使用消耗。
此外应理解，在阅读了本发明的上述描述内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (10)

1.一种适用于冶炼洁净钢的镁钙质喷补料，其特征在于，按质量份数计，原料组成包括：
镁钙砂 10～40份，
镁砂料 40～90份，
镁硅胶凝剂 10～26份；
按质量份数计，所述镁硅胶凝剂的原料组成包括：
Figure FDA0003117615980000011
所述镁质结合剂的粒度不大于5μm，其组成中MgO含量≥77.00wt％，SiO2含量≥13.00wt％，950℃灼减量≤6.0wt％；
所述镁硅胶凝剂通过组成它的原料共磨得到，粒度不大于3μm。
2.根据权利要求1所述的镁钙质喷补料，其特征在于，所述镁钙砂的粒度不大于3mm，其组成中MgO和CaO的总含量不低于92wt％。
3.根据权利要求1所述的镁钙质喷补料，其特征在于，所述镁砂料为烧结镁砂、电熔镁砂中的一种或两种；
所述镁砂料中MgO含量≥95wt％。
4.根据权利要求1或3所述的镁钙质喷补料，其特征在于，所述镁砂料的粒度不大于3mm，按质量份数计，具体粒度级配为：
3～1mm 0～30份；
1～0.045mm，不含1mm 20～35份；
＜0.045mm 10～25份。
5.根据权利要求1所述的镁钙质喷补料，其特征在于，所述熟石灰微粉的粒度为5～10μm。
6.根据权利要求1所述的镁钙质喷补料，其特征在于，所述磷酸盐结合剂为六偏磷酸钠、三聚磷酸钠、磷酸二氢铝中的一种或多种复合而成；
所述增稠剂为羧甲基纤维素、羧甲基淀粉醚、木质素磺酸钙中的一种或多种复合而成；
所述防爆剂为有机纤维、纸纤维或铝粉中的一种或多种复合而成。
7.根据权利要求1所述的镁钙质喷补料，其特征在于，所述共磨为球磨，球磨转速为150～250rpm，球磨时间为2.5～3.5h。
8.根据权利要求1～7任一权利要求所述的镁钙质喷补料的制备方法，其特征在于，包括：将包括镁钙砂、镁砂料和镁硅胶凝剂在内的组成所述镁钙质喷补料的原料在混料机内搅拌均匀即得所述镁钙质喷补料。
9.根据权利要求1～7任一权利要求所述的镁钙质喷补料在冶炼洁净钢中的应用。
10.根据权利要求9所述的应用，其特征在于，所述镁钙质喷补料用于转炉耳轴、RH浸渍管、中间包工作衬耐材的喷补维护，加水量为所述镁钙质喷补料的11wt％～13wt％。
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