CN115716753A - 一种高炉环保碳质结合剂、制备方法及高炉炮泥 - Google Patents
一种高炉环保碳质结合剂、制备方法及高炉炮泥 Download PDFInfo
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Abstract
本发明公开一种高炉环保碳质结合剂，各组分按如下质量份组成：环保沥青2‑25份，页岩焦油32‑63份，环保沥青粉3‑20份，增塑剂8‑25份，增碳剂5‑29份，其中增塑剂采用氢化三联苯、树脂类物质与高芳碳类的环保油通过特定工艺混合配制而成，增碳剂为选取石油焦与半焦通过研磨设备将其研磨至≤2000目在150℃‑280℃下通过剪切搅拌与环保油、环保沥青进行共熔从而制备得到。本发明的高炉环保碳质结合剂能够增强炮泥的可塑性，并且热稳定性强，高温产生的苯并芘含量极低，能够极大地改善炮泥的施工性能和现场工作环境。
Description
技术领域
本发明涉及高炉炼铁用耐火材料技术领域，更具体地说是涉及一种高炉无水炮泥结合剂。本发明还涉及该高炉无水炮泥结合剂的制备方法，以及含有该高炉无水炮泥结合剂的高炉炮泥。
背景技术
高炉炮泥在高炉生产过程中起着非常重要的作用，其质量的好坏直接影响着高炉的稳定运行和正常生产。目前，国内外的高炉炮泥分为两大类：有水炮泥和无水炮泥。前者只适用于小型高炉，而后者则可以满足现代大中型高炉炼铁的生产需要。随着我国钢铁工业的快速发展，钢铁工业生产中大都采用大中型炼铁高炉，而大中型高炉朝着大型化、长寿化、强化冶炼的方向发展，对高炉出铁口所用炮泥的要求越来越高，同时人们对环境保护方面也越来越重视，要求炮泥要对环境友好，有利于环境保护。因此，研究开发环保型高性能高炉无水炮泥是保障我国钢铁工业健康发展的现实需要。
目前，国内环保型高性能高炉无水炮泥的研究思路主要包括从开发新型无水炮泥和改进或开发新型无水炮泥结合剂两种方式。如中国专利CN 110272264 A公开的用于高炉的无水炮泥及制备方法、中国专利CN 110981447 A公开的大型高炉用碳复合无水炮泥及其制备方法、中国专利CN 112374870 A公开的一种环保型无水炮泥即属于第一种研究思路。但是，现代高炉发明于19世纪50年代中期，经过两百多年的运行，目前已经相当成熟，包括用于高炉出铁口的炮泥材料。因此，相对而言，开发新型无水炮泥结合剂成本更低、实用性也更强。
目前，无水炮泥结合剂主要以煤焦油系、煤沥青系、树脂系以及多种添加剂复合使用为主。以煤焦油系和煤沥青系为主的结合剂固定碳含量高、热稳定性好、流动性好有着广泛的应用，但其产品中含有大量对人体有致癌作用的苯并芘，在实际的生产过程中对作业环境造成极大的污染，严重危害人体健康且无法满足目前新形势下的环保发展需求；以树脂系为主的高炉炮泥结合剂虽然在环保性能方面能达到环保要求标准，但在实际生产过程中对现场的适应性差，容易出现打不动，硬炮现象，应用效果较差。
目前无水炮泥结合剂技术改进主要是围绕以下两个方面：
(1)对现有结合剂进行改性减少苯并芘含量来降低其危害性。如中国专利CN113149665B提供了一种炮泥结合剂，由常压条件下煤焦油的低温馏分油和高温馏程沥青组成，其中低温馏分油的馏程温度为400℃以下，高温馏程沥青为煤焦油经过500℃以上温度蒸馏后的残渣。虽然采用这种方法在一定程度上的确能改善无水炮泥的使用性能，也在一定程度上能增加环保性，但是由于改性的焦油或者其替代品仍属于大分子的有机结合剂，就必然会产生苯并芘或醛类等致癌物质或污染物，对环境和炉前工人产生的污染和伤害不能从根本上得到解决。
(2)通过制备混合结合剂来提高结合剂的应用效果。如中国专利CN 106145966 B公开的一种高炉炮泥用结合剂中，所述结合剂包括煤焦油蒸馏釜底物40-70份、酚醛清漆树脂30-60份、表面活性剂2-5份。再如中国专利CN102875178B提供的一种大型高炉炮泥用结合剂，采用有机硅树脂、呋喃树脂、三聚氰胺甲醛树脂复配作为固化成分使用，采用氢化三联苯作为增效剂，塑性高且具有较低的固化速率，结合剂的固化速率的降低有利于提高炮泥高温下的流动性，克服泥炮易结块的不足，但是原料中采用有机硅树脂、呋喃树脂、三聚氰胺甲醛树脂三种树脂进行复配，存在产品保质期短、实用性差的问题。
发明内容
本发明所要解决的技术问题是，现有技术中改性焦油或者其替代品制得的煤焦油系无水炮泥结合剂苯并芘等致癌物质含量高、以及树脂系无水炮泥结合剂存在产品保质期短、实用性差的问题，提供一种大型高炉环保碳质结合剂，采用本发明的结合剂所配制的炮泥，环保性能和使用性能更好。
为达到上述目的，本发明提供的技术方案为：
一种大型高炉环保碳质结合剂，各组分按如下质量份组成：
环保沥青2-25份、页岩焦油32-63份、环保沥青粉3-20份、增塑剂8-25份、增碳剂5-29份。
优选地，所述的环保沥青采用石油沥青，该石油沥青中的沥青质为15％以上
优选地，所述的环保沥青粉采用石油沥青粉，该石油沥青粉的固定碳含量为50％以上优选地，所述的增塑剂采用氢化三联苯、树脂类物质与高芳碳类的环保油混合配置而成。
优选地，所述的增碳剂为选取石油焦与半焦通过研磨设备将其研磨至≤2000目在150℃-280℃下通过剪切搅拌与环保油、环保沥青进行共熔从而制备出增碳剂。
优选地，其各组分按质量份组成如下：
环保沥青9份、页岩焦油55份、环保沥青粉14份、增塑剂10份、增碳剂12份。
所述的高炉环保碳质结合剂的制备方法，包括如下步骤：
(1)按一定比例称取一定量的石油焦与半焦放入研磨设备将其研磨至小于2000目，将研磨好的粉末放入剪切搅拌的容器中在150-280℃下熔融后加入一定量的环保油与环保沥青进行剪切搅拌，搅拌20-30分钟后即得增碳剂；
(2)按一定比例称取一定量的氢化三联苯、树脂类物质与高芳碳类的环保油，放入剪切搅拌的容器中在110-130℃下进行剪切搅拌互溶，搅拌20-30分钟后即得增塑剂；
(3)按质量份数称取环保沥青和增碳剂，依次加入反应釜在90-120℃的温度下进行混合搅拌20-30分钟，然后按照1.5-5℃/min的升温速率使反应釜内温度达到110-130℃，加入一定质量份数的环保沥青粉，继续搅拌混合20-30分钟后，在保持反应釜内温度不变的情况下，按质量份数向反应釜内依次加入一定质量份数的增塑剂和页岩焦油，继续搅拌混合20-30分钟，即得高炉环保碳质结合剂。
本发明还涉及一种高炉炮泥，其特征在于，含有上述技术方案所述的高炉环保碳质结合剂。
优选地，所述高炉用炮泥包括以下重量份的组分：棕刚玉10-20份、高铝矾土10-25份、碳化硅15-25份、蓝晶石2-7份、氮化硅铁粉3-10份、绢云母5-8份、球粘土10-20份和所述高炉环保碳质结合剂15-20份。
优选地，所述的高炉用炮泥中，棕刚玉中粒度大于70μm的粒状材料质量占比为10％～15％。
优选地，所述的高炉用炮泥中，高铝矾土中粒度为40μm～60μm。
优选地，所述的高炉用炮泥中，氮化硅铁粉粒度为30μm-70μm。
优选地，所述的高炉用炮泥中，绢云母粒度为70μm-1mm。
优选地，所述的高炉用炮泥中，所述碳化硅由质量占比为15％～20％的粒度大于70μm的粒状材料和余量的粉状材料组成。
优选地，所述的高炉用炮泥中，球粘土粒度为48μm-70μm。
采用本发明提供的技术方案，与已有的公知技术相比，具有如下显著效果：
(1)本发明的一种大型高炉环保碳质结合剂，其中采用石油系沥青和页岩焦油为基料，且采用氢化三联苯、树脂类物质与高芳碳类的环保油通过特定工艺混合配置而成的混合溶液为增塑剂及选取石油焦与半焦通过研磨设备将其研磨至≤2000目在150℃-280℃下通过剪切搅拌与环保油、环保沥青进行共熔从而制备出增碳剂，使炮泥粘合剂的可塑性更好，热稳定性更好。
(2)加入本发明的结合剂配置炮泥，炮泥的施工性能更好，苯并芘的含量低于300ppm，更低且符合环保标准，现场的工作环境更好。
具体实施方式
为进一步了解本发明的内容，下面结合实施例对本发明作进一步的描述。
实施例1
本实施例的一种高炉环保碳质结合剂，各组分按如下质量份组成：环保沥青4份，页岩焦油60份，环保沥青粉13份，增塑剂9份，增碳剂14份；制备方法如下：
(1)按一定比例称取一定量的石油焦与半焦放入研磨设备将其研磨至小于2000目，将研磨好的粉末放入剪切搅拌的容器中在200℃下熔融后加入一定量的环保油与环保沥青进行剪切搅拌，搅拌30分钟后即得增碳剂。
(2)按一定比例称取一定量的氢化三联苯、树脂类与高芳碳类的环保油，放入剪切搅拌的容器中在120℃下进行剪切搅拌互溶，搅拌20分钟后即得增塑剂。
(3)按质量份数称取环保沥青和增碳剂，依次加入反应釜在100℃的温度下进行混合搅拌30分钟，然后按照2℃/min的升温速率使反应釜内温度达到116℃，加入一定质量份数的环保沥青粉，继续搅拌混合20分钟后，在保持反应釜内温度不变的情况下，按质量份数向反应釜内依次加入一定质量份数的增塑剂和页岩焦油，继续搅拌混合25分钟，即得一定粘度的高炉环保碳质结合剂。
(4)炮泥原料：棕刚玉18份、高铝矾土20份、碳化硅15份、蓝晶石5份、氮化硅铁粉6份、绢云母8份、球粘土13份以及结合剂15份。通过特定的炮泥加工工艺按照上述配方制备出一种大型高炉环保型无水炮泥。
实施例2
本实施例的一种高炉环保碳质结合剂，各组分按如下质量份组成：环保沥青6份，页岩焦油58份，环保沥青粉5份，增塑剂11份，增碳剂10份；制备方法如下：
(1)按一定比例称取一定量的石油焦与半焦放入研磨设备将其研磨至小于2000目，将研磨好的粉末放入剪切搅拌的容器中在208℃下熔融后加入一定量的环保油与环保沥青进行剪切搅拌，搅拌28分钟后即得增碳剂。
(2)按一定比例称取一定量的氢化三联苯、树脂类与高芳碳类的环保油，放入剪切搅拌的容器中在116℃下进行剪切搅拌互溶，搅拌25分钟后即得增塑剂。
(3)按质量份数称取环保沥青和增碳剂，依次加入反应釜在105℃的温度下进行混合搅拌30分钟，然后按照2.5℃/min的升温速率使反应釜内温度达到118℃，加入一定质量份数的环保沥青粉，继续搅拌混合20分钟后，在保持反应釜内温度不变的情况下，按质量份数向反应釜内依次加入一定质量份数的增塑剂和页岩焦油，继续搅拌混合25分钟，即得一定粘度的高炉环保碳质结合剂。
(4)备用炮泥原料：棕刚玉13份、高铝矾土24份、碳化硅18份、蓝晶石6份、氮化硅铁粉4份、绢云母6份、球粘土12份以及结合剂17份。通过特定的炮泥加工工艺按照上述配方制备出一种大型高炉环保型无水炮泥。
实施例3
本实施例的一种高炉环保碳质结合剂，各组分按如下质量份组成：环保沥青9份，页岩焦油55份，环保沥青粉14份，增塑剂10份，增碳剂12份；制备方法如下：
(1)按一定比例称取一定量的石油焦与半焦放入研磨设备将其研磨至小于2000目，将研磨好的粉末放入剪切搅拌的容器中在203℃下熔融后加入一定量的环保油与环保沥青进行剪切搅拌，搅拌22分钟后即得增碳剂。
(2)按一定比例称取一定量的氢化三联苯、树脂类与高芳碳类的环保油，放入剪切搅拌的容器中在122℃下进行剪切搅拌互溶，搅拌20分钟后即得增塑剂。
(3)按质量份数称取环保沥青和增碳剂，依次加入反应釜在110℃的温度下进行混合搅拌30分钟，然后按照3℃/min的升温速率使反应釜内温度达到120℃，加入一定质量份数的环保沥青粉，继续搅拌混合20分钟后，在保持反应釜内温度不变的情况下，按质量份数向反应釜内依次加入一定质量份数的增塑剂和页岩焦油，继续搅拌混合25分钟，即得一定粘度的高炉环保碳质结合剂。
(4)备用炮泥原料：棕刚玉20份、高铝矾土15份、碳化硅23份、蓝晶石3份、氮化硅铁粉5份、绢云母6份、球粘土10份以及结合剂18份。通过特定的炮泥加工工艺按照上述配方制备出一种大型高炉环保型无水炮泥。
实施例4
本实施例的一种高炉环保碳质结合剂，各组分按如下质量份组成：环保沥青12份，页岩焦油49份，环保沥青粉10份，增塑剂14份，增碳剂15份；制备方法如下：
(1)按一定比例称取一定量的石油焦与半焦放入研磨设备将其研磨至小于2000目，将研磨好的粉末放入剪切搅拌的容器中在195℃下熔融后加入一定量的环保油与环保沥青进行剪切搅拌，搅拌30分钟后即得增碳剂。
(2)按一定比例称取一定量的氢化三联苯、树脂类与高芳碳类的环保油，放入剪切搅拌的容器中在118℃下进行剪切搅拌互溶，搅拌26分钟后即得增塑剂。
(3)按质量份数称取环保沥青和增碳剂，依次加入反应釜在108℃的温度下进行混合搅拌30分钟，然后按照3.5℃/min的升温速率使反应釜内温度达到118℃，加入一定质量份数的环保沥青粉，继续搅拌混合20分钟后，在保持反应釜内温度不变的情况下，按质量份数向反应釜内依次加入一定质量份数的增塑剂和页岩焦油，继续搅拌混合25分钟，即得一定粘度的高炉环保碳质结合剂。
(4)备用炮泥原料：棕刚玉10份、高铝矾土13份、碳化硅20份、蓝晶石4份、氮化硅铁粉8份、绢云母7份、球粘土18份以及结合剂20份。通过特定的炮泥加工工艺按照上述配方制备出一种大型高炉环保型无水炮泥。
实施例5
本实施例的一种高炉环保碳质结合剂，各组分按如下质量份组成：环保沥青15份，页岩焦油50份，环保沥青粉7份，增塑剂12份，增碳剂16份；制备方法如下：
(1)按一定比例称取一定量的石油焦与半焦放入研磨设备将其研磨至小于2000目，将研磨好的粉末放入剪切搅拌的容器中在210℃下熔融后加入一定量的环保油与环保沥青进行剪切搅拌，搅拌20分钟后即得增碳剂。
(2)按一定比例称取一定量的氢化三联苯、树脂类与高芳碳类的环保油，放入剪切搅拌的容器中在115℃下进行剪切搅拌互溶，搅拌30分钟后即得增塑剂。
(3)按质量份数称取环保沥青和增碳剂，依次加入反应釜在108℃的温度下进行混合搅拌30分钟，然后按照4℃/min的升温速率使反应釜内温度达到122℃，加入一定质量份数的环保沥青粉，继续搅拌混合20分钟后，在保持反应釜内温度不变的情况下，按质量份数向反应釜内依次加入一定质量份数的增塑剂和页岩焦油，继续搅拌混合25分钟，即得一定粘度的高炉环保碳质结合剂。
(4)备用炮泥原料：棕刚玉15份、高铝矾土17份、碳化硅20份、蓝晶石2份、氮化硅铁粉10份、绢云母5份、球粘土15份以及结合剂16份。通过特定的炮泥加工工艺按照上述配方制备出一种大型高炉环保型无水炮泥。
实施例1至实施例5制得的高炉环保碳质结合剂的性能指标见下表1。
表1
由表1可以看出，本发明采用环保沥青、页岩焦油、环保沥青粉、增塑剂与增碳剂所配置的环保型结合剂与本发明中的骨料相结合制备高炉炮泥有助于提高高炉炮泥的可塑性、抗折强度、耐压强度以及抗渣铁侵蚀冲刷的能力，填充效果更加密实。与现有的煤焦油系、煤沥青系的结合剂相比，本发明中的结合剂在环保性能方面更加突出，现场作业环境得到了极大的改善，对现场作业人员的身体健康危害度也极大的降低。与现有的树脂系结合剂相比，本发明中的结合剂更加方便储存，不易固化且成本较低。因此，本发明中的增碳剂在与结合剂中其他成分物质进行混合后均匀性较好；与骨料中的棕刚玉、碳化硅、高铝矾土等原料结合时黏结性能较好且易于成型，施工性能较好。同时，本发明中的结合剂与现有的煤焦油系、煤沥青系类的结合剂相比，苯并芘含量明显降低，在实施例提供的高炉环保碳质结合剂产品中，苯并芘最高含量为432ppm，而最佳的实施例中则可降至269ppm，因此，能够使炉前作业环境得到很大的改善。
Claims (10)
1.一种高炉环保碳质结合剂，其特征在于：由如下质量份的组分组成：
2.根据权利要求1所述的一种高炉环保碳质结合剂，其特征在于：所述的环保沥青为石油沥青，所述的石油沥青中沥青质含量15％以上。
3.根据权利要求2所述的一种高炉环保碳质结合剂，其特征在于：所述的石油沥青采用石油沥青粉，该石油沥青粉的固定碳含量为50％以上。
4.根据权利要求1所述的一种高炉环保碳质结合剂，其特征在于：所述的增塑剂由氢化三联苯、树脂类物质与高芳碳类的环保油混合配制而成。
5.根据权利要求1所述的一种高炉环保碳质结合剂，其特征在于：所述的增碳剂为选取石油焦与半焦通过研磨设备将其研磨至≤2000目在150℃-280℃下通过剪切搅拌与环保油、环保沥青进行共熔而制得的产物。
6.一种权利要求1所述的高炉环保碳质结合剂的制备方法，其步骤为：
(1)按一定比例称取一定量的石油焦与半焦放入研磨设备将其研磨至小于2000目，将研磨好的粉末放入剪切搅拌的容器中在150-280℃下熔融后加入一定量的环保油与环保沥青进行剪切搅拌，搅拌20-30分钟后即得增碳剂；
(2)按一定比例称取一定量的氢化三联苯、树脂类物质与高芳碳类的环保油，放入剪切搅拌的容器中在110-130℃下进行剪切搅拌互溶，搅拌20-30分钟后得到增塑剂；
(3)按质量份数称取环保沥青和步骤(1)中得到的增碳剂，依次加入反应釜在90-120℃的温度下进行混合搅拌20-30分钟，然后按照1.5-5℃/min的升温速率使反应釜内温度达到110-130℃，加入一定质量份数的环保沥青粉，继续搅拌混合20-30分钟后，在保持反应釜内温度不变的情况下，按质量份数向反应釜内依次加入一定质量份数的步骤(2)中得到的增塑剂和页岩焦油，继续搅拌混合20-30分钟，制得高炉环保碳质结合剂。
7.一种高炉炮泥，其特征在于含有权利要求1至5中任一项所述的高炉环保碳质结合剂。
8.根据权利要求7所述的高炉炮泥，其特征在于，所述高炉用炮泥包括以下重量份的组分：棕刚玉10-20份、高铝矾土10-25份、碳化硅15-25份、蓝晶石2-7份、氮化硅铁粉3-10份、绢云母5-8份、球粘土10-20份和高炉环保碳质结合剂15-20份。
9.根据权利要求8所述的高炉炮泥，其特征在于，所述棕刚玉中粒度大于70μm的粒状材料质量占比为10％～15％。
10.根据权利要求8所述的高炉炮泥，其特征在于，所述碳化硅由质量占比为15％～20％的粒度大于70μm的粒状材料和余量的粉状材料组成。
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