CN111606725A - 一种适合高温炼铁工艺用环保型碱性炮泥 - Google Patents

一种适合高温炼铁工艺用环保型碱性炮泥 Download PDF

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CN111606725A
CN111606725A CN202010702153.6A CN202010702153A CN111606725A CN 111606725 A CN111606725 A CN 111606725A CN 202010702153 A CN202010702153 A CN 202010702153A CN 111606725 A CN111606725 A CN 111606725A
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柳军
冯海霞
唐碧辉
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Sinosteel Luoyang Institute of Refractories Research Co Ltd
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Sinosteel Nanjing Environmental Engineering Technology Research Institute Co ltd
Sinosteel Luoyang Institute of Refractories Research Co Ltd
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Abstract

本发明涉及一种环保型的碱性炮泥。提出的炮泥原料及质量百分比为：镁橄榄石颗粒20%‑30%，镁橄榄石细粉20%‑30%，废镁碳砖颗粒0%‑10%，焦炭颗粒5%‑15%，铬铁矿颗粒10%‑15%，铬铁矿细粉0%‑5%，广西白泥10%‑15%，改性炭0%‑5%，外加结合剂；本发明是以镁橄榄石‑铬铁矿‑碳为主体系的耐火可塑料，具有高耐火度，良好的抗渣性能和抗热震性能等特点，更能适应出铁温度更高、炉渣比高和熔渣量更大的较为苛刻的炼铁工况；改性炭特殊的碳组织结构有利于改善材料的高温使用性能，其具有的粘塑性配合材料中添加的广西白泥和结合剂，更加有利于调整炮泥的可塑性和烧结性能。

Description

一种适合高温炼铁工艺用环保型碱性炮泥
技术领域
本发明涉及的是一种耐火可塑料，具体涉及到一种适合高温炼铁工艺用环保型碱性炮泥。
背景技术
炼铁工艺用炮泥大多属于Al2O3-SiC-C体系，主要功能是排出1450~1500℃的(渣)铁水后堵塞出铁口。常以焦油或者酚醛树脂作为结合剂，需具备良好的施工性能、适宜的烧结性能、一定的抗渣/铁水侵蚀性能、抗冲刷性能和抗热震性能等。然而，随着冶炼工况的变化如炉内压力增大、出铁温度增加、铁流速度变大、渣量变大等，对炮泥的使用也变得更加苛刻，传统Al2O3-SiC-C质材料使用性能变差如易氧化、耐冲刷性变差、抗侵蚀性降低等，出现了铁口浅、难开口等技术问题。以矿热炉为例，其出铁温度高(1500~1550℃)、炉渣比高(80%以上) 、炉渣氧化性强(FeO含量比高炉大一个数量级)等，更适宜采用偏碱性的炮泥材料。当前较为常见的是MgO-C质炮泥，常以烧结镁砂或电熔镁砂为主原料，掺入部分镁碳砖用后废料降低生产成本，结合体系仍以改性的树脂或沥青(焦油)为主。这些结合体系生产或使用中均会产生影响操作人员和周围环境的有害物质，已逐渐被淘汰或限制其使用。如焦油中的苯并芘是一种具有强烈致癌作用的多环芳香烃，对环境和工作人员身体极为有害，现在正逐渐被淘汰使用。同样得，酚醛树脂因含有苯酚和甲醛等危险物质，也已开始被限制使用。欧盟等国家对相关行业制定了严苛标准，限定耐火材料中的苯并芘(BaP)含量小于50 mg/kg；我国对炮泥的BaP含量限定在500mg/kg以内，但距离欧盟标准及零污染排放仍有一定的距离；除了会形成污染外，传统炮泥结合剂常温下粘度高，放置时间长也容易增粘，因此需要加热后方可挤压制备，造成了能源的消耗和生产成本的增加。因此开发适应更苛刻的炼铁工艺(如高出铁温度、高炉渣比等)用环保型碱性炮泥材料成为了行业中一个热点研究领域。
发明内容
为解决上述问题，本发明的目的是提出一种适合高温炼铁工艺用环保型碱性炮泥。
本发明为完成上述目的采用如下技术方案：
一种适合高温炼铁工艺用环保型碱性炮泥，环保型碱性炮泥炮泥的原料及质量百分比为：
镁橄榄石颗粒 3mm≥粒径＞0.1mm 20%-30%；
镁橄榄石细粉 74μm≥粒径＞44μm 20%-30%；
废镁碳砖颗粒 1mm≥粒径＞0.1mm 0%-10%；
焦炭颗粒 1mm≥粒径＞0.5mm 5%-15%；
铬铁矿颗粒 1mm≥粒径＞0.1mm 10%-15%；
铬铁矿细粉 74μm≥粒径＞44μm 0%-5%；
广西白泥 74μm≥粒径＞44μm 10%-15% ；
改性炭 0%-5% ；
原料的总质量为100%；
环保型碱性炮泥炮泥中外加有结合剂，结合剂的加入量为原料重量的10%-20%。
所述镁橄榄石颗粒和细粉均为低铁含量的矿物原料，其中MgO>45%，Fe2O3<6%。
所述废镁碳砖颗粒为用后清除挂渣、筛检后的镁碳质或镁铝碳质材料，其中MgO>80%，C>5%。
所述焦炭颗粒为炭含量大于80%的冶金焦的任何一种。
所述铬铁矿颗粒或细粉为Cr2O3含量大于50%铬铁矿中的任何一种。
所述改性碳为一种具有粘塑性的改性树脂粉。
所述结合剂为水溶性聚丙烯酰胺树脂的任何一种，其粘度值在1000~10000。mPa·S，固含量>30%。
本发明提出了一种适合高温炼铁工艺用环保型碱性炮泥，以镁橄榄石为主原料，保障材料具有较高的耐火度和抗渣侵蚀性能；添加用后的废镁碳砖或镁铝碳砖的目的有两方面，一是充分利用该材料良好的抗高温熔渣侵蚀性能，但要避免过量加入带来杂质影响到材料的使用；二是可降低材料的生产成本；加入焦炭的作用一是提高的材料的抗渣侵蚀性能；二是防止材料过分烧结。铬铁矿引入的复合尖晶石固溶体(AB2O4)如镁铬尖晶石/镁铝尖晶石/铁铝尖晶石/铁铬尖晶石等均有助于提高炮泥的抗热冲刷性能、抗热震性能和抗渣侵蚀性能，更适合高温铁水冶炼的工况条件；广西白泥则起到调整材料的粘性和可塑性的作用，改善炮泥的施工性能和烧结性能。
本发明中添加的改性炭的残碳量高(超过80%)，有助于改善材料的抗热震性能和抗渣/铁水侵蚀性能，碳化后还能形成各向异性的组织结构，能够提高材料的中高温结合强度和抗热冲刷性能。此外，该改性炭具有一定的粘塑性，可实现干压成型，配合材料中添加的广西白泥和结合剂，更加有利于调整炮泥的可塑性和烧结性能。
本发明中的结合剂为水溶性氨基树脂，易溶于水，但不溶于其它有机溶剂，无气味、无毒性，制造和使用过程中不会产生对环境和操作人员任何有危害的气体挥发物等。该物质与专利中的其它成分在常温冷态混合后即可获得较好的可塑性，赋予材料足够的施工性能；该树脂属于螯合型聚合物，长期密封保存不会变质，对其粘度和性能几乎没有影响，保证了炮泥材料具有足够长的存放周期。同时，该树脂属于热固类，随着温度的提高在失去塑性后可获得一定的强度，有利于维持材料在出铁口中的形状，保障炮泥的使用效果。
综上所述，本发明具有如下特点：
(1) 本发明属于一种碱性炮泥，制备成镁橄榄石-铬铁矿-碳体系的耐火材料，具有高耐火度，良好的抗渣性能和抗热震性能等特点，更能适应比较苛刻的炼铁工况条件。
(2) 本发明中加入的改性炭碳化后形成各向异性结构能进一步优化炮泥的使用性能。该改性炭具有一定的粘塑性，有利于调整炮泥的可塑性和烧结性能。
(3) 本发明中添加了部分废镁碳砖，可进一步降低材料的成本。
(4) 本发明采用的原料和结合剂均属于环保型材料，生产和使用过程中几乎不会形成污染性的气体，符合国家环保政策和行业规定。
(5) 本发明为常温冷态下压制成型，工艺简单，生产成本低。
具体实施方式
结合具体实施例对本发明加以详细说明。
根据下述3个实施例中的方案进行原料称量。先将骨料放进轮碾机内混碾5 min，沿一定的方向缓慢加入约1/5的结合剂再混碾2~3 min；然后将用强力搅拌机预混后的基质全部加入轮碾机混碾8~10min，最后将剩余的结合剂缓慢加入继续混碾约20 min后出料；将挤出料在压机上给予一定压力压制成一定厚度的实体状，然后切割进行包装。
实施例1：
配比方案：
镁橄榄石颗粒 3mm≥粒径＞0.1mm 20%；
镁橄榄石细粉 74μm≥粒径＞44μm 20%；
废镁碳砖颗粒 1mm≥粒径＞0.1mm 10%；
焦炭颗粒 1mm≥粒径＞0.5mm 15%；
铬铁矿颗粒 1mm≥粒径＞0.1mm 15%；
铬铁矿细粉 74μm≥粒径＞44μm 2%；
广西白泥 74μm≥粒径＞44μm 13%；
改性炭 5% ；
水溶性树脂 粘度6000±500 mPa·S +16%；
改性炭为德国瑞嘉集团生产的CARBORESP-15。
实施例2：
配比方案：
镁橄榄石颗粒 3mm≥粒径＞0.1mm 30%；
镁橄榄石细粉 74μm≥粒径＞44μm 25%；
废镁碳砖颗粒 1mm≥粒径＞0.1mm 7%；
焦炭颗粒 1mm≥粒径＞0.5mm 10%；
铬铁矿颗粒 1mm≥粒径＞0.1mm 10%；
铬铁矿细粉 74μm≥粒径＞44μm 5%；
广西白泥 74μm≥粒径＞44μm 10%；
改性炭 3%；
水溶性树脂 粘度2000±500 mPa·S +12%；
改性炭为德国瑞嘉集团生产的CARBORESP-15。
实施例3：
配比方案：
镁橄榄石颗粒 3mm≥粒径＞0.1mm 26%；
镁橄榄石细粉 74μm≥粒径＞44μm 29%；
废镁碳砖颗粒 1mm≥粒径＞0.1mm 3%；
焦炭颗粒 1mm≥粒径＞0.5mm 8%；
铬铁矿颗粒 1mm≥粒径＞0.1mm 13%；
铬铁矿细粉 74μm≥粒径＞44μm 4%；
广西白泥 74μm≥粒径＞44μm 15%；
改性炭 2%；
水溶性树脂 粘度8000±500 mPa·S +18%；
改性炭为德国瑞嘉集团生产CARBORESP-15
附表说明：
表 不同炮泥标准的BaP含量
项目 欧盟标准 中国冶金标准 本发明产品
BaP含量（mg/kg） 50 500 <20

Claims (5)

1.一种环保型碱性炮泥的制备，其特征在于：所述原料及质量百分比为：
镁橄榄石颗粒 3mm≥粒径＞0.1mm 20%-30%
镁橄榄石细粉 74μm≥粒径＞44μm 20%-30%
废镁碳砖颗粒 1mm≥粒径＞0.1mm 0%-10%
焦炭颗粒 1mm≥粒径＞0.5mm 5%-15%
铬铁矿颗粒 1mm≥粒径＞0.1mm 10%-15%
铬铁矿细粉 74μm≥粒径＞44μm 0%-5%
广西白泥 74μm≥粒径＞44μm 10%-15%
改性炭 0%-5%
原料的总质量为100%；碱性炮泥的原料中还外加有结合剂，结合剂的加入量为原料重量的10%-20%，所述结合剂为水溶性聚丙烯酰胺树脂的任何一种，其粘度值在1000~10000mPa·S，固含量>30%。
2.如权利要求1所述的一种环保型碱性炮泥，其特征在于：所述镁橄榄石颗粒和细粉均为低铁含量的矿物原料，其中MgO>45%，Fe2O3<6%。
3.如权利要求1所述的一种环保型碱性炮泥，其特征在于：所述废镁碳砖颗粒为用后清除挂渣、筛检后的镁碳质或镁铝碳质材料，其中MgO>80%，C>5%。
4.如权利要求1所述的一种环保型碱性炮泥，其特征在于：所述铬铁矿颗粒或细粉为Cr2O3含量大于50%铬铁矿中的任何一种。
5.如权利要求1所述的一种环保型碱性炮泥，其特征在于：所述改性碳为一种具有粘塑性的改性树脂粉。
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