CN107986765B - 高炉用抗开裂摆动流槽浇注料及其制备方法 - Google Patents
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 16
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 claims abstract description 7
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
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Abstract
本发明涉及一种高炉炼铁用抗开裂摆动流槽浇注料及其制备方法。所述摆动流槽浇注料，按重量份计，包含：含镁铝尖晶石刚玉50～75份，碳化硅10～20份，莫来石5～15份，铝酸盐水泥1～4份，蓝晶石1～3份，复合抗氧化剂1～2份，减水剂0.05～0.2份，以及添加剂15～30份。采用本发明的抗开裂摆动溜槽浇注料制备的摆动沟内衬，具有良好的结构韧性、抗热震性、抗冲刷性、抗氧化性、微膨胀性和施工性，能够很好地抑制摆动溜槽的开裂现象，提高了高炉炼铁生产的安全性，延长了摆动溜槽的使用寿命，减轻了炉前工人的劳动强度。
Description
技术领域
本发明涉及一种高炉炼铁用抗开裂摆动流槽浇注料及其制备方法，属于高炉炼铁用耐火材料技术领域。
背景技术
高炉炼铁时，铁水从出铁口流出，经过主沟、铁沟、摆动流槽，最后到达了铁水罐。摆动流槽是更换铁水罐时变换铁水流向的专用设备，其性能直接影响了高炉炼铁的安全生产。
大中型高炉通常设有2-4个摆动流槽，高炉炼铁时2-3个摆动流槽轮流出铁，摆动流槽的受铁间歇在2-4小时，受铁时要经受约1400℃高温铁水的冲击磨损，受铁间歇时直接接触空气，承受较大的温度波动，因此摆动溜槽承受着较大的热应力。目前制备摆动溜槽内衬多采用Al2O3-SiC-C质浇注料，该材料具有良好的耐磨性，抗侵蚀性，但此种材料脆性较大，该材料制备的内衬长期经受间歇铁水及热应力冲击，易在流嘴部位内衬出现裂纹，铁水沿着裂纹渗入到流槽内部并扩展，并且裂纹扩展迅速，若没有及时发现，将导致摆动流槽的烧穿漏铁，烧坏摆动流槽支撑梁及下方铁道、鱼雷罐车等，从而造成严重的安全生产事故。
因此，摆动流槽的易开裂问题亟待解决，以保证高炉炼铁的安全生产，提高炉衬的使用寿命，降低炉前工人的劳动强度。
发明内容
本发明的目的在于提供一种抗开裂的摆动溜槽浇注料，以解决现有摆动溜槽内衬易开裂问题，提高高炉炼铁的安全性，延长摆动溜槽内衬的使用寿命。
本发明的另一目的在于提供上述抗开裂的摆动溜槽浇注料的制备方法。
为了实现上述目的，本发明采用了如下技术方案：
根据本发明的一个方面，本发明提供的抗开裂的摆动溜槽浇注料，按重量份计，包含：
其中，所述添加剂按重量份计，组成如下：铁铝尖晶石5～9份，炭黑1～3份，二氧化硅微粉1～3份，氧化铝微粉3～6份，二氧化锆2～4份，氮化硅铁1～3份，镁砂1～2份。
下面，更具体地说明本发明的抗开裂的摆动溜槽浇注料。
在本发明优选的实施方案中，其中：
所述含镁铝尖晶石刚玉，是氧化铝基镁质复相材料，可以按照如下方法得到：以工业氧化铝粉为主料，氧化镁粉为添加剂，经细磨、成型、干燥，在1750～1950℃温度下烧结而成，在反应过程中生成的镁铝尖晶石相，嵌入在刚玉相中，形成的含镁铝尖晶石刚玉，应用在耐火材料中，相比普通烧结刚玉具有较好的强度、抗热震性、抗剥落性、抗渣性和骨料与基质结合性增强。在本发明的含镁铝尖晶石刚玉中，要求Al2O3含量≥96wt％，MgO含量≤4wt％，级配为：8mm～5mm 10～15份，5mm～3mm 10～15份，3mm～1mm10～15份，1mm～0.2mm10～15份，粒度≤0.074mm 10～15份。
所述碳化硅，其SiC含量≥97wt％，级配为：3mm～1mm 0～5份，1mm～0.2mm 5～7份，粒度≤0.074mm 5～8份。
所述莫来石为电熔莫来石，其Al2O3含量≥70wt％，级配为：5mm～3mm0～3份，3mm～1mm 1～2份，1mm～0.2mm 2～5份，粒度≤0.074mm 2～5份。
所述铝酸盐水泥，其Al2O3含量≥77wt％。
所述蓝晶石，其粒度≤0.5mm。
所述减水剂，例如可以为德国巴斯夫FS65型高效减水剂。
所述复合抗氧化剂，按重量份计，组成如下：金属硅粉0.5～1.5份，碳化硼0.5～1.5份，其中，所述金属硅粉，其Si含量≥95wt％，为粉料，要求粒度≤74μm；所述碳化硼，其B4C含量≥95wt％，为粉料，要求粒度≤74μm。
在所述添加剂中，所述铁铝尖晶石，其FeAl2O4含量≥95wt％，为粉料，要求粒度≤74μm；
所述炭黑，其碳含量≥99wt％；
所述二氧化硅微粉，其SiO2含量≥93wt％，平均粒径D50为0.1～0.3μm；
所述氧化铝微粉，其Al2O3含量≥99wt％，平均粒径D50为1～3μm；
所述二氧化锆，其ZrO2含量≥99wt％，为粉料，要求粒度≤74μm；
所述氮化硅铁，其总氮TN含量27wt％～32wt％，Fe含量11wt％～15wt％，为粉料，要求粒度为≤74μm；
所述镁砂，其MgO含量≥95wt％，为粉料，要求粒度≤74μm。
在本发明中，所述添加剂的制备方法是：将添加剂的各组分按其重量份称量，倒入倾斜式搅拌机中混合，转子转速控制在135～153r/min，混合时间控制在3～5分钟，混合后即可装入防水包装袋中密封保存。
根据本发明的另一方面，本发明提供的上述高炉用抗开裂摆动溜槽浇注料的制备方法，该方法包括：将浇注料的各组分按其重量份称量，倒入倾斜式搅拌机中混合，转子转速控制在117～135r/min，混合时间控制在3～5分钟，混合后即可装入防水包装袋中密封保存。
本发明与现有技术相比具有以下创新性和有益效果：
(1)本发明的浇注料骨料采用含镁铝尖晶石刚玉，可强化骨料与基质的结合性，提高浇注料的强度、抗热震性和抗剥落性。基质部分以高莫氏硬度的SiC和莫来石为主成分，可提高浇注料的抗冲刷性和抗热震性。从而增强了摆动溜槽抵抗不断的温度波动而变形的能力，提高了抗开裂性，最终延长摆动溜槽的使用寿命。
(2)本发明添加了抗开裂的摆动溜槽浇注料用添加剂，引入的铁铝尖晶石具有高温的结构柔韧性，在高温下与镁砂进行Fe2+和Mg2+离子互扩散，形成镁铝尖晶石，同时伴随着体积膨胀促进微裂纹的形成，微裂纹可以吸收主裂纹扩展的能量，可有效阻止裂纹的扩展；引入的二氧化锆，在温度变化时，会发生的马氏体相变，吸收了能量，提高了断裂能，从而提高了断裂韧性，抑制裂纹的扩展。所以，这三种物质的复配可有效降低浇注料的脆性，提高浇注料的结构韧性和抗剥落性。
(3)本发明添加了抗开裂的摆动溜槽浇注料用添加剂，引入的炭黑，碳含量高，灰分小，保证高温环境下的化学稳定性，有效地抵抗铁水的浸润，减小侵蚀，同时还与加入的金属硅反应生成SiC，这种原位形成的SiC结合强度高，更有利于抗铁水的冲刷。
(4)本发明添加了抗开裂的摆动溜槽浇注料用添加剂，引入的氧化铝微粉和二氧化硅微粉，可在高温下反应生成针棒状或晶须状的莫来石的网络结构，可有效提高结构强度，提高抗热震性和抗冲刷性。
(5)本发明添加了抗开裂的摆动溜槽浇注料用添加剂，引入的氮化硅铁，含有氮化硅，硬度高，熔点高，导热性好，含有少量的Fe，可以与炭黑反应生成SiC和N2，N2可与配料中的金属硅反应生成Si3N4，提高浇注料的导热性，抗金属铁液的侵蚀。
(6)本发明添加了蓝晶石，能够很好抑制物料烧后收缩，浇注料呈现微膨胀，此种膨胀作用使得浇注料与摆动钢壳内的衬砖结合得更为紧密，防止结构的松动，浇注料和基体结构融为一体，以降低衬体开裂的可能性。
(7)本发明添加以金属硅和碳化硼复配的抗氧化剂，这两种物质都能起到抗氧化作用，互为补充，以减少SiC的氧化。金属硅起到抗氧化作用的同时可与炭黑高温下原位形成SiC，提高抗冲刷性。碳化硼在被氧化后生成的B2O3可以与基质中Al2O3高温下形成9Al2O3·2B2O3的柱状晶体，分布在耐火材料的基质和间隙里，从而降低气孔率，提高中温强度。
(8)本发明采用的减水剂为德国巴斯夫FS65高效减水剂，能够大幅降低浇注料的用水量，降低润湿时间，提高施工效率，显著提高浇注料的流动性，提高施工质量。
在高炉炼铁生产过程中，采用本发明的抗开裂摆动溜槽浇注料制备的摆动沟内衬，具有良好的结构韧性、抗热震性、抗冲刷性、抗氧化性、微膨胀性和施工性，能够很好地抑制摆动溜槽的开裂现象，提高了高炉炼铁生产的安全性，延长了摆动溜槽的使用寿命，减轻了炉前工人的劳动强度。使用传统的摆动溜槽浇注料与按照本发明的摆动沟浇注料用于高炉摆动溜槽的使用情况对比见表1，其中传统的摆动溜槽浇注料主要组分包括：矾土；棕刚玉；碳化硅；沥青粉；铝酸盐水泥；硅微粉；金属铝粉；三聚磷酸钠等。
表1传统的摆动溜槽浇注料与本发明的抗开裂摆动溜槽浇注料的性能对比
由表1可见，本发明的摆动溜槽浇注料相比传统的摆动溜槽浇注料，有较高的结合强度，抗冲刷耐磨性好；体积稳定性好，抗剥落抗开裂性好；使用寿命大幅提高。
具体实施方式
下面结合具体实施例对本发明作进一步的描述，下述各实施例仅用于说明本发明，而本发明的范围并不局限于这些具体实施例中。
含镁铝尖晶石刚玉的制备：
以工业氧化铝粉为主料，氧化镁粉为添加剂，经细磨、成型、干燥，在1750～1950℃温度下烧结而成，在反应过程中生成的镁铝尖晶石相，嵌入在刚玉相中，冷却，破碎得到各粒度的含镁铝尖晶石刚玉，其中Al2O3含量约97.5wt％，MgO含量约2.5wt％。
一、抗开裂摆动溜槽浇注料用添加剂的制备
实施例1-实施例3
在实施例1-3中，将添加剂的各组分按表2所示的重量份准确称量，倒入倾斜式搅拌机中混合，转子转速控制在135-153r/min，混合时间控制在3-5分钟，混合后所得添加剂即可装入防水包装袋中密封保存。
表2实施例1-实施例3的添加剂的组成
| 项目 | 实施例1 | 实施例2 | 实施例3 |
| 铁铝尖晶石 | 5 | 7 | 9 |
| 炭黑 | 2 | 2 | 2 |
| 二氧化硅微粉 | 2 | 2 | 2 |
| 氧化铝微粉 | 4 | 4 | 4 |
| 二氧化锆 | 3 | 3 | 3 |
| 氮化硅铁 | 1 | 2 | 3 |
| 镁砂 | 2 | 2 | 2 |
二、采用抗开裂摆动溜槽浇注料用添加剂制备的浇注料
浇注料制备例1
其组分及重量份为：含镁铝尖晶石刚玉57份；碳化硅15份；莫来石5份；铝酸盐水泥1.9份；蓝晶石1份；复合抗氧化剂1份(金属硅粉0.5份；碳化硼0.5份)；减水剂0.1份；以及采用上述实施例1制备的抗开裂摆动溜槽浇注料用添加剂19份。
其中，含镁铝尖晶石刚玉级配为：8mm～5mm 10份，5mm～3mm 12份，3mm～1mm 12份，1mm～0.2mm 10份，粒度≤0.074mm 13份；
碳化硅级配为：3mm～1mm 5份，1mm～0.2mm 5份，粒度≤0.074mm 5份；
莫来石为电熔莫来石，级配为：3mm～1mm 1份，1mm～0.2mm 2份，粒度≤0.074mm 2份。
将浇注料的各组分按其重量份称量，倒入倾斜式搅拌机中混合，转子转速控制在117-135r/min，混合时间控制在3-5分钟，混合后所得浇注料即可装入防水包装袋中密封保存。
浇注料制备例2
其组分及重量份为：含镁铝尖晶石刚玉54份；碳化硅15份；莫来石5份；铝酸盐水泥1.9份；蓝晶石1份；复合抗氧化剂1份(金属硅粉0.5份；碳化硼0.5份)；减水剂0.1份；以及采用上述实施例2制备的抗开裂的摆动溜槽浇注料用添加剂22份。
其中，含镁铝尖晶石刚玉级配为：8mm～5mm 10份，5mm～3mm 12份，3mm～1mm12份，1mm～0.2mm 10份，粒度≤0.074mm 10份；
碳化硅级配为：3mm～1mm 5份，1mm～0.2mm 5份，粒度≤0.074mm 5份；
莫来石为电熔莫来石级配为：3mm～1mm 1份，1mm～0.2mm 2份，粒度≤0.074mm 2份。
将浇注料的各组分按其重量份称量，倒入倾斜式搅拌机中混合，转子转速控制在117-135r/min，混合时间控制在3-5分钟，混合后所得浇注料即可装入防水包装袋中密封保存。
浇注料制备例3
其组分及重量份为：含镁铝尖晶石刚玉51份；碳化硅15份；莫来石5份；铝酸盐水泥1.9份；蓝晶石1份；复合抗氧化剂1份(金属硅粉0.5份；碳化硼0.5份)；减水剂0.1份；以及采用上述实施例3制备的抗开裂的摆动溜槽浇注料用添加剂25份。
其中，含镁铝尖晶石刚玉级配为：8mm～5mm 10份，5mm～3mm 10份，3mm～1mm 11份，1mm～0.2mm 10份，粒度≤0.074mm 10份；
碳化硅级配为：3mm～1mm 5份，1mm～0.2mm 5份，粒度≤0.074mm 5份；
莫来石为电熔莫来石，级配为：3mm～1mm 1份，1mm～0.2mm 2份，粒度≤0.074mm 2份。
将浇注料的各组分按其重量份称量，倒入倾斜式搅拌机中混合，转子转速控制在117-135r/min，混合时间控制在3-5分钟，混合后所得浇注料即可装入防水包装袋中密封保存。
将浇注料制备例1-3制备的浇注料，加入适量水搅拌均匀后浇注到40×40×160mm三联模具中，脱模后于110℃烘烤24小时，1450℃埋炭保温3小时。分别按照标准YB/T5200、GB/T3001、GB/T 5072、GB/T 5988检测试样体积密度、抗折强度、耐压强度、线变化率，检测结果见表3：
表3本发明制备的摆动溜槽浇注料性能检测结果
由表3可见，本发明的抗开裂的摆动溜槽浇注料具有良好结合强度，烧结性好，结构柔韧性好，抗开裂效果好，在实际应用过程中，通铁量达到了15～18万吨，使用寿命相比传统浇注料提高约1倍。
Claims (8)
1.一种高炉用抗开裂摆动流槽浇注料，按重量份计，组成如下：
其中，所述添加剂按重量份计，组成如下：铁铝尖晶石5～9份，炭黑1～3份，二氧化硅微粉1～3份，氧化铝微粉3～6份，二氧化锆2～4份，氮化硅铁1～3份，镁砂1～2份；在所述添加剂中，所述铁铝尖晶石，其FeAl2O4含量≥95wt％，为粉料，粒度≤74μm；所述炭黑，其碳含量≥99wt％；所述二氧化硅微粉，其SiO2含量≥93wt％，平均粒径D50为0.1～0.3μm；所述氧化铝微粉，其Al2O3含量≥99wt％，平均粒径D50为1～3μm；所述二氧化锆，其ZrO2含量≥99wt％，为粉料，粒度≤74μm；所述氮化硅铁，其总氮TN含量27wt％～32wt％，Fe含量11wt％～15wt％，为粉料，粒度为≤74μm；所述镁砂，其MgO含量≥95wt％，为粉料，粒度≤74μm；
所述含镁铝尖晶石刚玉，其Al2O3含量≥96wt％，MgO含量≤4wt％；
所述复合抗氧化剂，按重量份计，组成如下：金属硅粉0.5～1.5份，碳化硼0.5～1.5份，其中，所述金属硅粉，其Si含量≥95wt％，为粉料，粒度≤74μm；所述碳化硼，其B4C含量≥95wt％，为粉料，粒度≤74μm。
2.根据权利要求1所述的高炉用抗开裂摆动流槽浇注料，其特征是，所述含镁铝尖晶石刚玉按照如下方法得到：以工业氧化铝粉为主料，氧化镁粉为添加剂，在1750～1950℃温度下烧结而成。
3.根据权利要求1或2所述的高炉用抗开裂摆动流槽浇注料，其特征是，所述含镁铝尖晶石刚玉，级配为：8mm～5mm 10～15份，5mm～3mm 10～15份，3～1mm 10～15份，1mm～0.2mm 10～15份，粒度≤0.074mm 10～15份。
4.根据权利要求1所述的高炉用抗开裂摆动流槽浇注料，其特征是，所述碳化硅，其SiC含量≥97wt％，级配为：3mm～1mm 0～5份，1mm～0.2mm5～7份，粒度≤0.074mm 5～8份。
5.根据权利要求1所述的高炉用抗开裂摆动流槽浇注料，其特征是，所述莫来石为电熔莫来石，其Al2O3含量≥70wt％，级配为：5mm～3mm 0～3份，3mm～1mm 1～2份，1mm～0.2mm 2～5份，粒度≤0.074mm 2～5。
6.根据权利要求1所述的高炉用抗开裂摆动流槽浇注料，其特征是，所述铝酸盐水泥，其Al2O3含量≥77wt％；所述蓝晶石，其粒度≤0.5mm；所述减水剂为德国巴斯夫FS65型高效减水剂。
7.根据权利要求1所述的高炉用抗开裂摆动流槽浇注料，其特征是，所述摆动流槽浇注料形成的内衬110℃×24h处理，耐压强度为30～40MPa；1450℃×3h埋炭处理，耐压强度为50～80MPa。
8.一种权利要求1所述的高炉用抗开裂摆动流槽浇注料的制备方法，该制备方法包括：将浇注料的各组分按其重量份称量，倒入倾斜式搅拌机中混合，转子转速控制在117～135r/min，混合时间控制在3～5分钟，混合后即可装入防水包装袋中密封保存。
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| CN109851333B (zh) * | 2018-12-25 | 2021-12-07 | 中国京冶工程技术有限公司 | 高炉主铁沟用纳米溶胶结合耐磨板及其制备方法与应用 |
| CN111484346B (zh) * | 2020-05-27 | 2022-08-12 | 孙志红 | 用于高炉撇渣器的氮化硅结合浇注料及高炉撇渣器 |
| CN112062549B (zh) * | 2020-08-05 | 2022-05-17 | 山东金三河新材料科技有限公司 | 电熔锆刚玉砖及其制备方法 |
| CN116716041A (zh) * | 2023-07-08 | 2023-09-08 | 北京希柯节能环保科技有限公司 | 一种炼油加热炉炉管使用的复合结晶膜浆料 |
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| JP2012518589A (ja) * | 2009-02-19 | 2012-08-16 | コーニング インコーポレイテッド | 大型耐火性物品およびその製造方法 |
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