CN109072085A - 炼焦炉用预制块状耐火物 - Google Patents

炼焦炉用预制块状耐火物 Download PDF

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CN109072085A
CN109072085A CN201780021635.1A CN201780021635A CN109072085A CN 109072085 A CN109072085 A CN 109072085A CN 201780021635 A CN201780021635 A CN 201780021635A CN 109072085 A CN109072085 A CN 109072085A
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prefabricated
coke oven
refractory material
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CN109072085B (zh
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寺岛英俊
筒井康志
竹本宽直
松井泰次郎
松永隆志
北泽浩
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Nippon Steel Corp
Krosaki Harima Corp
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Abstract

本发明提供一种炼焦炉用预制块状耐火物，其在具有较高的高温强度的同时，高温时的负载下膨胀收缩挙动稳定。即，本发明的特征为，硅质炼焦炉用预制块状耐火物中，含有0.3质量％以上、2质量％以下的P2O5成分。

Description

炼焦炉用预制块状耐火物
技术领域
本发明涉及一种适于在炼焦炉中使用的预制块状耐火物。
背景技术
以往，炼焦炉中，作为衬料而使用了硅石砖。但是，当使用硅石砖时，由于需要对大量的砖进行施工，因此存在施工上费时间的问题。于是，近几年，尤其在高温修补施工中，较多地采用使用比硅石砖更容易实现大型化的硅石质的预制块状耐火物的施工。
对这样的预制块状耐火物，要求作为结构体的高温特性。尤其在炼焦炉中，在高温强度的基础上，要求高温时的负载下膨胀挙动及负载下收缩挙动(以下，总称为负载下膨胀收缩挙动)的稳定化。当高温时的负载下膨胀收缩挙动并不稳定时(当伴随高温时的负载下膨胀、负载下收缩的变形较大时)，压出焦炭时的阻力变大而有可能在妨碍作业的同时使预制块状耐火物自身发生破损。
专利文献1中记载有如下技术，将熔凝石英作为主原料，作为结合剂而使用硅酸盐水泥。但是，当炼焦炉用预制块状耐火物中作为结合剂而使用大量(例如，相对于主原料的2～10重量％)的硅酸盐水泥时，存在因硅酸盐水泥的水合反应而高温时的负载下会较大地发生收缩的问题。
另外，专利文献2中，作为结合剂(固化剂)而替代以往通常使用的高铝水泥而使用胶态二氧化硅及硅酸钠，从而想要抑制高温时的负载下收缩。但是，当使用胶态二氧化硅及硅酸钠时，存在高温强度降低的问题。
专利文献1：日本国特开昭56-78476号公报
专利文献2：日本国特开2013-189322号公报
发明内容
本发明所要解决的技术问题是提供一种炼焦炉用预制块状耐火物，其在具有较高的高温强度的同时，高温时的负载下膨胀收缩挙动稳定。
本发明者们为了解决所述问题而进行了锐意研究。例如，如专利文献1所记载，当作为结合剂而使用大量的水泥时，因水泥的水合反应而高温时的负载下收缩挙动并不趋于稳定化。另外，当作为结合剂而使用胶态二氧化硅及硅酸钠时，高温强度发生了降低。于是，本发明者发现了如下知识，在硅质的炼焦炉用预制块状耐火物中，作为结合剂而并不使用大量的水泥或者作为结合剂而使用胶态二氧化硅及硅酸钠，而是作为结合剂成分而使用P2O5成分，从而能够在维持较高的高温强度的同时稳定地控制高温时的负载下膨胀收缩挙动。
即，本发明的炼焦炉用预制块状耐火物为硅质，其特征为，含有0.3质量％以上、2质量％以下的P2O5成分。
根据本发明，得到一种炼焦炉用预制块状耐火物，其在发挥较高的高温强度的同时，高温时的负载下膨胀收缩挙动稳定。
附图说明
图1是表示实施例及比较例的负载下膨胀收缩挙动的曲线图。
具体实施方式
本发明的炼焦炉用预制块状耐火物是将硅质即SiO2成分作为主成分的炼焦炉用预制块状耐火物。虽然具体的SiO2成分的含有量位于技术常识的范围内，但是优选65质量％以上、99质量％以下，更优选80质量％以上、99质量％以下。
作为SiO2成分源虽然可使用熔凝硅石、硅石(烧成硅石、生硅石等)、热解硅石等各种硅质原料，但是在本发明中，原料配合中优选熔凝硅石的配合量为65质量％以上，更优选72质量％以上。另外，优选硅石的配合量为17质量％以下，热解硅石的配合量为0.5质量％以上、15质量％以下。即，从能够消除因干燥时的脱水而发生的收缩的观点考虑，优选熔凝硅石的配合量为65质量％以上，硅石的配合量为17质量％以下。此时，硅石的配合量还可以是0质量％。另外，从维持较高的高温强度的观点考虑，优选热解硅石的配合量为0.5质量％以上、15质量％以下。另外，考虑填充性及作业性，硅质原料的粒度优选从最大尺寸5mm的骨料到超微粒子为止组合使用。而且，为了使负载下热膨胀、收缩率(以下称为“负载下膨胀收缩率”)更加稳定，优选使1mm以上的粗粒为25质量％以上。
并且，作为主骨料，还可以作为硅质原料以外的原料而同时使用氧化铝质原料。作为氧化铝质原料可以使用电融氧化铝、烧结氧化铝等。但是，当SiO2成分小于65质量％时，由于高温强度降低，因此不应优选大量添加氧化铝质原料。
在本发明的炼焦炉用预制块状耐火物中的P2O5成分，虽然作为如上所述的结合剂成分而发挥功能，但是其含有量为0.3质量％以上、2质量％以下。当P2O5成分的含有量小于0.3质量％时，无法发挥作为结合剂成分的结合功能。当P2O5成分的含有量超过2质量％时，由于会过剩生成低熔点物质(SiO2-P2O5类)，因此在高温时的负载下，伴随收缩的变形变大。
虽然作为P2O5成分源可使用磷酸盐，但是此时从抑制生成低熔点物质的观点考虑，作为不纯物而包含于磷酸盐的Na2O成分及K2O成分，作为预制块状耐火物中的含有量而合量优选为0.5质量％以下。
另外，在本发明的炼焦炉用预制块状耐火物的原料配合中，从提高养护时的强度的观点考虑，优选固化促进剂的配合量为0.05质量％以上，而且，从维持较高的高温强度的观点考虑，优选1.9质量％以下。作为固化促进剂可例举氧化镁粉末、消石灰等
而且，优选本发明的炼焦炉用预制块状耐火物不包含水泥。当包含水泥时，虽然因水泥的水合反应而发生负载下收缩，但是当不包含水泥时，能够抑制负载下收缩。
可通过如下的通常的预制块状耐火物的制造方法来得到本发明的炼焦炉用预制块状耐火物，即配合作为主原料的上述的硅质原料(SiO2成分源)及作为结合剂的磷酸钠(P2O5成分源)，另外根据需要而配合作为其他添加剂的有机纤维、分散剂、固化促进剂、固化延迟剂、烧结補助剂等，在所得到的原料配合物中添加適量(例如5质量％～7质量％)的施工用水，在此基础上进行混炼、成形、养护、脱模、干燥。
实施例
按照表1的原料配合而配合各原料，添加6.5质量％的施工用水，在此基础上进行混炼、成形、养护、脱模、干燥而得到炼焦炉用预制块状耐火物的试样，使用这样的试样而测定了负载下膨胀收缩挙动及高温弯曲强度，进行了综合评价。并且分析了所得到的试样的化学成分。在此，使用了粒度分别为5-1mm及小于1mm的熔凝石英、烧成硅石、生硅石及电融氧化铝分别以6：4的比率混合的试样。另外，使用了热解硅石的粒度为平均粒径0.5μm的试样。并且，使用了原料的化学成分分别为如下所示的试样，即熔凝石英含有99.7质量％的SiO2成分，烧成硅石含有99.5质量％的SiO2成分，生硅石含有99.7质量％的SiO2成分，热解硅石含有96质量％的SiO2成分、0.2质量％的Na2O成分，电融氧化铝含有100质量％的Al2O3，磷酸钠含有65质量％的P2O5成分、23质量％的Na2O成分，硅酸钠含有64质量％的SiO2成分、22质量％的Na2O成分，胶态二氧化硅含有40质量％的SiO2成分，硅酸盐水泥含有24质量％的SiO2成分，氧化镁粉末含有100质量％的MgO成分，消石灰含有100质量％的CaO。
负载下膨胀收缩挙动则在从室温到1300℃为止的温度域中根据JIS R 2207-2施加0.2MPa的负载而进行了测定。将负载下膨胀收缩率位于-0.1％以上、小于0.5％的范围的情况作为优(◎)，将位于-0.3％以上、小于-0.1％的范围的情况或位于+0.5％以上、小于+0.7％的范围的情况作为良(○)，将位于-0.5％以上、小于-0.3％的范围的情况或位于0.7％以上、小于+0.8％的范围的情况作为可(△)，将小于-0.5％或+0.8％以上的情况作为不可(×)，将可(△)以上的情况作为合格。并且，-(负)表示负载下收缩，+(正)表示负载下膨胀。
高温弯曲强度则在1000℃下根据JIS R 2213进行了测定。并且，为了做成测定温度而将试样在炉内保持了1个小时，测定了高温弯曲强度。将高温弯曲强度为10MPa以上作为优(◎)，将5MPa以上、小于10MPa作为良(○)，将3MPa以上、小于5MPa作为可(△)，将小于3MPa作为不可(×)，将可(△)以上作为合格。
而且，综合评价则将在所述2个评价中存在2个优(◎)的情况作为优(◎)，将优(◎)与良(○)的组合情况作为良(○)，将优(◎)或良(○)与可(△)的组合情况作为可(△)，将存在不可(×)的情况作为不可(×)，将可(△)以上作为合格。
将这些评价结果同时表示于表1。
表1
表1中，实施例1～15都是位于范围内的炼焦炉用预制块状耐火物。综合评价为可(△)以上，负载下膨胀收缩挙动及高温弯曲强度都是合格水准。
比较例1是P2O5成分的含有量较低的例子。无法得到充分的结合功能，高温弯曲强度未能满足合格水准。另一方面，比较例2是P2O5成分的含有量较高的例子。由于过剩生成低熔点物质(SiO2-P2O5)，因此负载下膨胀收缩挙动未能满足合格水准。
比较例3是在将Al2O3成分作为主成分的炼焦炉用预制块状耐火物中作为结合剂成分而使用P2O5成分的例子。负载下膨胀收缩挙动未能满足合格水准。
比较例4是相当于所述专利文献1的例子，是作为结合剂为使用胶态二氧化硅及硅酸钠的例子。高温弯曲强度未能满足合格水准。
比较例5是作为结合剂而仅使用硅酸盐水泥的例子。负载下膨胀收缩挙动未能满足合格水准。
另外，图1是表示实施例1及比较例5的从室温到1300℃为止的负载下膨胀收缩挙动的曲线图。作为结合剂而配合有磷酸盐(P2O5成分源)的满足本发明的范围的实施例1的负载下膨胀收缩挙动稳定，作为结合剂而大量(5质量％)配合有硅酸盐水泥的比较例5则在1000℃附近开始显著发生了负载下收缩。

Claims (7)

1.一种炼焦炉用预制块状耐火物，其为硅质，其特征为，含有0.3质量％以上、2质量％以下的P2O5成分。
2.根据权利要求1所述的炼焦炉用预制块状耐火物，其特征为，含有65质量％以上、99质量％以下的SiO2成分。
3.根据权利要求1所述的炼焦炉用预制块状耐火物，其特征为，含有80质量％以上、99质量％以下的SiO2成分。
4.根据权利要求1至3中任意一项所述的炼焦炉用预制块状耐火物，其特征为，原料配合中，熔凝硅石的配合量为65质量％以上。
5.根据权利要求1至4中任意一项所述的炼焦炉用预制块状耐火物，其特征为，原料配合中，硅石的配合量为17质量％以下，热解硅石的配合量为0.5质量％以上、15质量％以下。
6.根据权利要求1至5中任意一项所述的炼焦炉用预制块状耐火物，其特征为，原料配合中，固化促进剂的配合量为0.05质量％以上、1.9质量％以下。
7.根据权利要求1至6中任意一项所述的炼焦炉用预制块状耐火物，其特征为，作为结合剂并不包括水泥。
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