CN113200755B - 环境友好型连铸中间包干式料及其制备方法 - Google Patents
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Abstract
本发明公开了一种环境友好型连铸中间包干式料及其制备方法，该干式料按质量份数计包括如下组分：镁橄榄石生料10～25份、镁碳复合料20～50份、烧结镁砂20～60份、改性固体树脂粉0.5～2份、磷酸镁胶结剂2～4份、促烧剂0.3～0.8份、增强剂0.3～0.8份。本发明的环境友好型连铸中间包干式料具有良好的节能与环保性能，使用过程中强度高、整体性能好，抗渣侵蚀性能优良，使用寿命长且能自动解体。
Description
技术领域
本发明涉及中间包干式料的技术领域，具体涉及一种环境友好型连铸中间包干式料及其制备方法。
背景技术
目前，连铸中间包干式料使用的结合剂主要包括固体树脂粉、无机盐、多羟基糖等，添加剂包括硼酸、硫酸盐、粘土等促烧剂。采用固体树脂粉作结合剂时，在中间包干式料烘烤和使用过程中会释放出甲醛、甲酚、二甲醛等气体，污染环境，有损职工健康；采用无机盐作结合剂时，带模烘烤后强度较低，脱模过程操作不当会造成局部干式料垮塌和较大裂纹的产生，使用过程中干式料的抗渣性较差，使干式料在服役过程中发生过烧结而与中间包永久衬发生粘连，难以自动翻包；而以多羟基糖作为结合剂的干式料烘包温度低，环境友好，但使用寿命短。
发明内容
本发明的目的在于克服上述背景技术的不足，提供一种环境友好型连铸中间包干式料及其制备方法，该干式料具有良好的节能与环保性能，使用过程中强度高、整体性能好，抗渣侵蚀性能优良，使用寿命长且能自动解体，具有显著的社会效益和经济效益。
为实现上述目的，本发明提供的一种环境友好型连铸中间包干式料，它按质量份数计包括如下组分：
进一步地，所述的环境友好型连铸中间包干式料，它按质量份数计包括如下组分：
进一步地，所述镁橄榄石生料中MgO质量百分含量≥42％；其中，3mm＜粒度≤5mm的镁橄榄石生料占镁橄榄石生料总质量的40～80％，1mm≤粒度≤3mm的天然烧结莫来石占天然烧结莫来石总质量的20～60％。镁橄榄石生料的粒度＞5mm时会影响施工质量变差，上述镁橄榄石生料的粒度级配为最佳范围，各个粒度镁橄榄石生料的重量百分比超出上述范围会直接影响干式料的粒度级配，进而影响产品的施工性能和使用性能。
进一步地，所述镁碳复合料中MgO质量百分含量≥60％；其中，3mm＜粒度≤5mm的镁碳复合料占镁碳复合料总质量的20～50％，1mm＜粒度≤3mm的镁碳复合料占镁碳复合料总质量的30～60％，0.088mm≤粒度≤1mm的镁碳复合料占镁碳复合料总质量的10～30％。由于复合料中假颗粒的存在会影响干式料的整体粒度级配和强度，加入粒度＜0.088mm的镁碳复合料会导致干式料烧结性能和中高温强度变差。上述镁碳复合料的粒度级配为最佳范围，各个粒度镁碳复合料的重量百分比超出上述范围会直接影响干式料的粒度级配，进而影响产品的施工性能和使用性能。镁碳复合料的使用不仅能够节约资源，保护环境，还能够增加干式料在使用过程中的抗渣侵蚀性能和下线后的自动解体性能。
进一步地，所述烧结镁砂中MgO质量百分含量≥93％，其中，0.088mm＜粒度≤1mm的烧结镁砂占烧结镁砂总质量的20～40％，粒度≤0.088mm的烧结镁砂占烧结镁砂总质量的60～80％。烧结镁砂粒度为0.088mm＜粒度≤1mm，粒度≤0.088mm，考虑到节约资源、能耗以及环保因素，粒度＞1mm的原料选用原生矿石和再生资源(复合料)。
进一步地，所述改性固体树脂粉的软化点90～110℃，固含量≥96％，残碳量≥50％，游离酚≤4％，粒度≤0.088mm。控制改性固体树脂粉的软化点能够更好满足现场施工与烘烤要求，控制固含量、残碳量、游离酚能保证干式料在带模烘烤后产生足够的强度，不至于因强度和操作不当导致脱模后垮塌、产生较大裂纹；同时可以控制干式料在烘烤过程中产生的挥发份浓度，减少对环境的污染和职工身体健康危害。
进一步地，所述磷酸镁胶结剂选自磷酸二氢镁的溶液，其中，MgO质量百分含量为11％，磷酸质量百分含量为89％。在加热过程中发生脱水和转化反应，最后生成偏磷酸镁，能够增强干式料在烘烤过程中以及使用过程中的整体强度。
再进一步地，所述促烧剂为金属铝粉、碳化硅粉、碳化硼粉中的一种或多种，有助于减少干式料中镁碳复合料的氧化，生成的氧化物能与干式料中MgO反应生成尖晶石、硅酸镁等物质，促进干式料在使用过程中的烧结，保证良好的整体强度。
更进一步地，所述增强剂为金属铝粉、单质硅粉中一种或两种，添加到含碳的耐火材料中可在使用过程中发生碳化、氮化等反应，原位生成大量的非氧化物增强相，使材料的结构转化为以非氧化物结合为主，极大地提高材料的高温性能。
本发明还提供一种上述环境友好型连铸中间包干式料的制备方法，包括如下步骤：
1)按照组分配方进行配料，粒度≤0.088mm的烧结镁砂、改性固体树脂粉和促烧剂、增强剂进行2～3分钟均混，再将均混后的物料加入镁橄榄石生料、镁碳复合料、0.088mm＜粒度≤1mm的烧结镁砂、磷酸镁胶结剂中，搅拌3～5分钟，混合均匀，得到混合料；
2)将步骤1)的混合料倒入中间包包底，均匀平铺；然后放入干式料工作衬胎模，按照设计方案将胎模居中对齐，最后将混合料沿胎模四周倒入并捣实，待混合料与中间包包沿平齐后，开启胎模震动开关，并同时沿胎模四周补充混合料至与包沿平齐；
3)待中间包干式料工作衬静置0.5～1小时后点火加热进行烘烤处理，停火后自然冷却8～12小时，待温度降至50℃以下时脱模，制得环境友好型连铸中间包干式料。
更进一步地，所述步骤3)中，烘烤处理包括第一阶段由常温升温至120℃，升温速度为40～50℃/h；第二阶段由120℃升温至270～290℃，升温速度为40～50℃/h，保温时间为0.5～1h。
与现有技术相比，本发明具有如下优点：
其一，本发明的干式料由于加入镁橄榄石生料和镁碳复合料，有利于合理利用和保护镁砂资源，缓解不可再生矿产资源逐渐匮乏的趋势，同时减轻菱镁矿开采带来的能源环保问题；镁橄榄石生料与熟料相比，使用生料不仅能节约能源，还有助于减少对大气的污染和降低碳排放，具有较好的社会效益和经济效益。
其二，本发明的干式料由于采用改性固体树脂粉和磷酸镁胶结剂作复合结合剂，具有良好的低温烘烤性能和脱模强度，抗渣侵蚀性能和高温性能优良，使用寿命长，有效降低中间包工作衬耐材的吨钢耐材消耗；同时，能有效减少对环境污染和职工身体健康危害。
其三，本发明的干式料由于加入促烧剂与增强剂，在使用过程中产生的氧化与化学反应能促进干式料在使用过程中的烧结，保证良好的整体强度；由于发生碳化和氮化反应而原位生成的非氧化物增强相能使材料的结构转化为以非氧化物结合为主，极大地提高材料的高温性能。
其四，本发明通过控制镁橄榄石生料、镁碳复合料、烧结镁砂、改性固体树脂粉、磷酸镁胶结剂的粒度和加入量，外加促烧剂与增强剂，以及均混时间、混匀时间和烘烤制度等工艺参数，可以制备出一种节能环保，强度高、整体性能好，抗渣侵蚀性能优良，使用寿命长且能自动解体，具有显著经济效益和社会效益的环境友好型连铸中间包干式料。
具体实施方式
下面结合实施案例详细说明本发明的实施情况，但它们并不构成对本发明的限定，仅作举例而已。同时通过说明本发明的优点将变得更加清楚和容易理解。
本发明实施例1～5的环境友好型连铸中间包干式料和对比例1～2的干式料，按质量份数计的配方如表1所示。
表1
本发明实施例1～5的环境友好型连铸中间包干式料和对比例1～2的干式料的制备方法，包括如下步骤：按照所述原料的成分及其含量进行配料，先将基质料(粒度≤0.088mm的烧结镁砂、改性固体树脂粉)和促烧剂、增强剂进行均混，再将均混后的基质料加入骨料(镁橄榄石生料、镁碳复合料、0.088mm＜粒度≤1mm的烧结镁砂、磷酸镁胶结剂)中，混合均匀，得到混合料。均混这个工艺过程能够有效降低干式料中的重要原料混合不均匀的现象，避免工艺缺陷造成对产品施工性能和使用性能的不良影响。先取用适量混合料倒入中间包包底，均匀平铺；然后放入干式料工作衬胎模，按照设计方案将胎模居中对齐，四周距离永久衬适当，最后将混合料沿胎模四周倒入并用钢钎等工具捣实，待混合料与中间包包沿平齐后，开启胎模震动开关，并同时沿胎模四周补充混合料至与包沿平齐，振动时间以表面干式料密实为宜，一般在5～10分钟。待中间包干式料工作衬静置0.5～1小时后，接通燃气管道，点火加热，按照以下烘烤制度对干式料进行烘烤，停火后自然冷却8～12小时，待温度降至50℃以下时脱模，制得环境友好型连铸中间包干式料。各实施例1～5和对比例1～2的主要工艺参数如下表2所示：
表2
| 项目 | 均混时间，分钟 | 混匀时间，分钟 | 升温速度，℃/h | 最高烘烤温度，℃ |
| 实施例1 | 3 | 4 | 40 | 270 |
| 实施例2 | 2 | 3 | 50 | 290 |
| 实施例3 | 2.5 | 3.5 | 45 | 280 |
| 实施例4 | 3 | 4.5 | 48 | 275 |
| 实施例5 | 2 | 5 | 43 | 285 |
| 对比例1 | 0 | 6 | 70 | 350 |
| 对比例2 | 4 | 1 | 20 | 200 |
本发明实施例1～5的环境友好型连铸中间包干式料和对比例1～2的干式料的理化测试结果，如下表3所示：
表3
如上表实施例1～5所示，在本发明限定的原料加入量及粒度，干式料中加入适量的镁橄榄石生料、镁碳复合料、烧结镁砂、改性固体树脂粉、磷酸镁胶结剂、促烧剂、增强剂，同时控制好均混时间、混匀时间与烘烤制度这些工艺参数，就能制备出一种节能环保，强度高、整体性能好，抗渣侵蚀性能优良，使用寿命长且能自动解体，具有显著经济效益和社会效益的环境友好型连铸中间包干式料。
相对地，对于未控制原料加入量、生产工艺及烘烤制度的对比例1～2中，干式料不能同时具备良好的节能环保性，强度与整体性能，抗渣侵蚀性能，使用寿命与自动解体性能，无法满足产品的施工、烘烤和使用性能。
以上，仅为本发明的具体实施方式，应当指出，任何熟悉本领域的技术人员在本发明所揭示的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内，其余未详细说明的为现有技术。
Claims (3)
1.一种环境友好型连铸中间包干式料，其特征在于：它按质量份数计包括如下组分：
所述镁橄榄石生料中MgO质量百分含量≥42％；其中，3mm＜粒度≤5mm的镁橄榄石生料占镁橄榄石生料总质量的40～80％；
所述镁碳复合料中MgO质量百分含量≥60％；其中，3mm＜粒度≤5mm的镁碳复合料占镁碳复合料总质量的20～50％，1mm＜粒度≤3mm的镁碳复合料占镁碳复合料总质量的30～60％，0.088mm≤粒度≤1mm的镁碳复合料占镁碳复合料总质量的10～30％；
所述烧结镁砂中MgO质量百分含量≥93％；其中，0.088mm＜粒度≤1mm的烧结镁砂占烧结镁砂总质量的20～40％，粒度≤0.088mm的烧结镁砂占烧结镁砂总质量的60～80％；
所述改性固体树脂粉的软化点90～110℃，固含量≥96％，残碳量≥50％，游离酚≤4％，粒度≤0.088mm；
所述磷酸镁胶结剂选自磷酸二氢镁的溶液，其中，MgO质量百分含量为11％，磷酸质量百分含量为89％；
所述促烧剂为金属铝粉、碳化硅粉、碳化硼粉中的一种或多种；所述增强剂为金属铝粉、单质硅粉中一种或两种；
所述环境友好型连铸中间包干式料由如下方法制备而成：
1)按照组分配方进行配料，将粒度≤0.088mm的烧结镁砂、改性固体树脂粉和促烧剂、增强剂进行2～3分钟均混，再将均混后的物料加入镁橄榄石生料、镁碳复合料、0.088mm＜粒度≤1mm的烧结镁砂、磷酸镁胶结剂中，搅拌3～5分钟，混合均匀，得到混合料；
2)将步骤1)的混合料倒入中间包包底，均匀平铺；然后放入干式料工作衬胎模，按照设计方案将胎模居中对齐，最后将混合料沿胎模四周倒入并捣实，待混合料与中间包包沿平齐后，开启胎模震动开关，并同时沿胎模四周补充混合料至与包沿平齐；
3)待中间包干式料工作衬静置0.5～1小时后点火加热进行烘烤处理，停火后自然冷却8～12小时，待温度降至50℃以下时脱模，制得环境友好型连铸中间包干式料；
其中，烘烤处理包括第一阶段由常温升温至120℃，升温速度为40～50℃/h；第二阶段由120℃升温至270～290℃，升温速度为40～50℃/h，保温时间为0.5～1h。
2.一种权利要求1所述环境友好型连铸中间包干式料的制备方法，其特征在于：包括如下步骤：
1)按照组分配方进行配料，将粒度≤0.088mm的烧结镁砂、改性固体树脂粉和促烧剂、增强剂进行2～3分钟均混，再将均混后的物料加入镁橄榄石生料、镁碳复合料、0.088mm＜粒度≤1mm的烧结镁砂、磷酸镁胶结剂中，搅拌3～5分钟，混合均匀，得到混合料；
2)将步骤1)的混合料倒入中间包包底，均匀平铺；然后放入干式料工作衬胎模，按照设计方案将胎模居中对齐，最后将混合料沿胎模四周倒入并捣实，待混合料与中间包包沿平齐后，开启胎模震动开关，并同时沿胎模四周补充混合料至与包沿平齐；
3)待中间包干式料工作衬静置0.5～1小时后点火加热进行烘烤处理，停火后自然冷却8～12小时，待温度降至50℃以下时脱模，制得环境友好型连铸中间包干式料。
3.根据权利要求2所述的环境友好型连铸中间包干式料的制备方法，其特征在于：所述步骤3)中，烘烤处理包括第一阶段由常温升温至120℃，升温速度为40～50℃/h；第二阶段由120℃升温至270～290℃，升温速度为40～50℃/h，保温时间为0.5～1h。
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