CN1836053B - 建造还原铁矿的流化床还原炉内结构的耐火组合物 - Google Patents

建造还原铁矿的流化床还原炉内结构的耐火组合物 Download PDF

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CN1836053B
CN1836053B CN2004800232287A CN200480023228A CN1836053B CN 1836053 B CN1836053 B CN 1836053B CN 2004800232287 A CN2004800232287 A CN 2004800232287A CN 200480023228 A CN200480023228 A CN 200480023228A CN 1836053 B CN1836053 B CN 1836053B
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fire proofing
proofing composition
fluidized bed
reduction furnace
bed reduction
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CN1836053A (zh
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崔导文
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CHOSUN REFRACTORIES Co Ltd
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Abstract

一种耐火组合物，其用于建造FINEX法中还原铁矿粉的流化床还原炉内的某一结构，该耐火组合物包括9-17wt％煅烧氧化铝，3-6wt％特级脱水二氧化硅SiO2，5-10wt％高铝水泥，以及余量的烧结或熔融氧化铝，而制成100wt％耐火组合物，由此建造的结构具有对还原性气体的耐化学品性，并具有高耐热冲击性、高强度以及高耐磨性。

Description

建造还原铁矿的流化床还原炉内结构的耐火组合物
技术领域
本发明涉及一种耐火材料，其用于建造通过流化反应还原铁矿粉的流化床还原炉内的某一结构，更具体地，本发明涉及一种耐火组合物，其用于建造一种新的炼铁方法，即FINEX法中采用的流化床还原炉内的某一结构。
背景技术
在现代钢制造业中，采用对首先制成的熔融铁进行脱碳处理来制造钢的间接方法。熔融铁是采用高炉法制造的，其中采用焦炭作为燃料。
图1是采用高炉法制造铁的方法的示意图，其中当采用由火焰煤制得的焦炭作为燃料时，铁矿石经过预处理工艺，对铁矿石进行粉碎、精选、将铁矿粉压制成块、烧结而成硬球状，该硬球是具有可装入高炉中的预定尺寸的团块。将该硬球和焦炭装入高炉中，进行焙烧以获得熔融铁。
尽管高炉法是目前大规模制造铁的最好炼铁方法，但高炉法由于工艺复杂以及要求额外的单独大规模设备用于烧结和制造焦炭而具有成本高的特点，而且也导致了从烧结钢和焦炭制造工艺中释放出硫的氧化物SOx，氮化物NOx，二氧化碳CO2等环境污染物的问题。
韩国炼钢公司POSCO开发了一种设备，其中高炉法这一制造方法被转变为直接通过流化反应还原天然状态的铁矿粉而无需对铁矿石和焦炭进行预处理，其专利的韩国专利申请号为10-1995-41931，韩国专利登记号为10-236160，该方法被称为FINEX法，该设备已建成并于近期投入了测试操作。
图2是将本发明应用其中的炼铁方法FINEX法的示意图，而图3则是对图2中流化床还原炉的关键部分的截面的详细图示。FINEX法是用于经济地制造熔融铁的一种新型的铁生产方法，其中粒径分布较宽的铁矿粉通过流化床还原炉1的多个分段逐步被还原，并与粒径为8-50mm的煤块一起装入到熔炉2中以形成熔融铁，其中粒径为约8mm的铁矿粉经过流化床还原炉1的多个分段而转变为被还原的铁矿，形成了颗粒(HCI；HotCompact Iron)，然后被装入熔炉中。
从结构来看，流化床还原炉1设置有体11(体11具有位于下部并供给还原性气体的供气口11a)，位于体11内部空间中的多个垂直柱(verticalcolumns)12，以及垂直柱上支撑的分配板13，以使分配板(distributionplate)13的多个部分同时得到平衡和支撑。
柱12只是支撑分配板13，而分配板13则分配通过供气口11a供给体11内部空间的高温高压还原性气体，从而流化和还原铁矿，其中，由于柱12和分配板13不能，但却被曝于体11内部空间的高温高压还原性气体中，因而，柱12和分配板13应由具有良好耐化学品、良好耐热冲击性、良好机械性能、良好耐磨性等的耐火材料构成。
同时，柱12和分配板13分别具有多个通孔12a和13a，以使气体平稳地流动和穿过而流化和还原铁矿粉。
由于柱12和分配板13是反应炉中的结构，而反应炉并不是小尺寸的实验设备，而是全尺寸的商业化制造设备，因此要求柱12和分配板13的材料在柱12和分配板13工作期间的主要工作温度，即600-1000℃附近时不与还原性气体和铁矿中的各种成分发生反应，在铁矿粉的高温和高速流化条件下具有良好的耐磨性，以及具有良好的耐热冲击性足以耐受由于裂纹出现而以间歇操作方式而非连续操作方式重新操作设备之后发生的快速升温和快速降温。
而且，由于要求柱12和分配板13依据设备的设计而成各种结构形状，因此要求柱12和分配板13的材料不具有固定的形状，从而能形成各种形状；以及，由于多数设备是大尺寸结构，因此要求柱12和分配板13的材料在成形之后的固化和干燥期间不变形，或在成形期间不膨胀。
为形成所述流化床还原炉1的柱12和分配板13，在制备形成柱12和分配板13的耐火组合物之后，分别形成柱12和分配板13，其中尽管可通过形成耐火组合物的单元块，并将这些单元块以实施方式附图所示的一般砌砖方式安装在体11内部空间中而形成柱12和分配板13，但与该方法不同的方法是，在体11内部空间中建造模具后，将耐火组合物与粘合剂等按照混合普通混凝土的方法混合，然后填充到模具中进行固化，以形成柱12和分配板13。
显而易见的是，用制成的耐火材料制备柱12和分配板13的同时要设置多个通孔12a和13a，用于使还原性气体平稳地流动和穿过，如上所述。
因此，为形成流化床还原炉的体11内的柱12和分配板13，耐火组合物是必要的。由于可预见柱12和分配板13的工作条件是严格的，因此要求耐火组合物满足下列产品设计标准：结构体密度为3.2或更高，在工作条件下的抗压强度为1500kg/cm2或更高，具有良好的耐热冲击性，耐磨性满足ASTM C704磨损率为3.0cm3或更低，等等。
然而，考虑到用于FINEX法的设备是世界上的首台设备，没有相关技术的耐火组合物来形成应用到商业规模FINEX法中的柱和分配板。尽管在实验设备中采用含有大于90％的氧化铝，抗压强度约为1000kg/cm2，且无高强度二氧化硅组分的耐火材料(比较实施例1)，但该耐火材料在工作期间由于耐热冲击性低而导致很大程度的收缩和许多裂纹，尽管该耐火材料具有对CO气体的良好抵抗性质。
发明内容
本发明的目的之一是提供用于建造用于还原铁矿粉的流化床还原炉内某一结构的耐火组合物，该耐火组合物不同于相关领域的实验性耐火组合物，流化床还原炉内的某一结构为柱和分配板，从而当具有宽范围颗粒分布的铁矿粉在其中具有柱和分配板的流化床还原炉的多个分段中逐步被还原时，使柱和分配板具有对还原性气体的良好耐化学品性，在高温高速度流化床条件下具有良好的耐磨性，以及具有良好的耐热冲击性足以耐受以间歇操作方式进行重操作之后的快速升温和降温。
本发明的目的可通过提供用于建造用于还原铁矿粉的流化床还原炉内某一结构的耐火组合物而实现，该耐火组合物包括9-17wt％煅烧氧化铝，3-6wt％特级脱水二氧化硅SiO2，5-10wt％高铝水泥，以及余量的烧结或熔融氧化铝，而制成100wt％耐火组合物。
优选地，该耐火组合物还包括0.03-0.3wt％含有缓凝剂的分散剂。该分散剂选自一种或多种无机盐：六偏磷酸钠，三聚磷酸钠，四聚磷酸钠，酸式六偏磷酸钠，以及碳酸钠，柠檬酸钠，酒石酸盐，聚丙烯酸盐(poly-acrylate-salts)，磺酸钠和萘-磺酸钠，而该缓凝剂则为柠檬酸，葡糖酸或硼酸。
优选地，该耐火组合物还包括0.03-0.15wt％的一种或多种金属铝粉或有机纤维。在包括金属铝粉的情况下，该耐火组合物进一步包括0.01-0.05wt％的反应阻滞剂以调节铝金属粉末的反应速度。优选地，该反应阻滞剂是抑制剂。
优选地，该耐火组合物中8mm-1mm的粒径占45-59wt％，1mm-75μm的粒径占14-20wt％，而75μm及以下的粒径占27-33wt％。优选地，煅烧氧化铝中3-5μm的平均粒径占6-10wt％，而2-0.5μm的平均粒径占3-7wt％。优选地，高铝水泥包括26-30wt％的CaO。
附图说明
用于进一步理解本发明的附图对实施方式进行了阐释。图中：
图1是示出采用高炉法制造铁的方法的示意图；
图2是示出应用了本发明的FINEX法的示意图；
图3是对图2中流化床还原炉的关键部分的截面的详细图示；
图4是对图3中沿I-I线的截面图示；
图5是图3流化床还原炉内柱的透视图；以及
图6是图3流化床还原炉内分配板的透视图。
最佳实施方式
优选地，本发明的最终耐火组合物具有45-59wt％(重量百分比)的8-1mm颗粒，14-20wt％的1mm-75μm颗粒，以及27-33wt％的75μm及以下的颗粒，该组合物是考虑结构和材料的特性而进行重复实验获得的结果。如果该耐火组合物中59wt％以上的颗粒的粒径等于或大于8mm，这种情况下很难搅拌与其他材料相混合的耐火组合物来制备形成柱12和分配板13的材料，并且将与其它材料混合的耐火组合物倒入模具中时也很难形成紧密且不带孔的柱12和分配板13的层。
已经确定耐火材料中含有45-59wt％的8-1mm颗粒，理由是在耐火组合物中8-1mm颗粒的含量低于45wt％时，即使流动性由于细粉尘的相对增加而增加，但抗散裂性仍由于在主要工作温度1000℃时发生很大程度的收缩而变弱，而如果耐火组合物中8-1mm的颗粒含量超过59wt％，则柱和分配板成形的状态由于缺乏细粉尘而变差，这使得柱和分配板的成形性变差。
对于作为主要原材料的氧化铝，优选采用纯度为95％或更高的烧结氧化铝块，熔融的白色氧化铝块，或熔融的棕色氧化铝块，考虑到反应炉的设计而采用密度高于3.2的原材料，尤其优选孔隙率低于10％的熔融氧化铝。或者，块可以是耐火的诸如高密度锆石，氧化锆，氧化镁的块，除了耐热冲击性，耐化学品性质，可加工性等特性要求外，它们满足密度要求。
因此，所形成的密度接近理论密度的烧结或熔融氧化铝是合适的，优选地，熔融氧化铝具有致密结构，孔隙率低，杂质含量低。
考虑到柱12和分配板13中许多管的设置是用于高速传送高温还原性气体，因此要求流化床还原炉1内的柱12和分配板13的材料能确保平稳形成柱12和分配板13的最低流动性。
将形成的材料在固化和干燥后的抗压强度设计为高于1500kg/cm2，为满足抗压强度要求，采用9-17wt％的煅烧氧化铝(该煅烧氧化铝由6-10wt％平均粒径为3-5μm的煅烧氧化铝，3-7wt％平均粒径为0.5-2μm的煅烧氧化铝构成)以及3-6wt％的特级脱水二氧化硅。
因此，各种粒径的氧化铝一起被采用，以确保获得要求的流动性和致密结构，而上述范围之外的组合物则不能提供令人满意的性质。
在纯度分别为94％和97％的两种特级脱水二氧化硅中，优选采用纯度为97％的那一种，原因是其中存在的杂质Fe和Si组分导致了破坏结构的还原反应。在分散剂的辅助作用下，对脱水二氧化硅进行抗絮凝处理，使其含水量低，从而获得结构。特级脱水二氧化硅在高于800℃的温度下开始反应并转变成莫来石(mullite)而形成更稳定的结构，从而能补偿由水泥在高温下脱水导致的强度下降，因而在实际上保持了高强度而并未发生强度下降。
为了确保本发明结构(柱和分配板)的设计强度为1500kg/cm2或更高，采用5-9wt％的高铝水泥，该高铝水泥中CaO的含量为26-30％。如果采用5wt％以下的高铝水泥，则不能得到要求的强度，而如果采用超过9wt％的高铝水泥，则也不能获得要求的强度，或者即使获得了要求的强度，也会由于液相材料的增加以及莫来石的形成量减少而导致抗散裂性变差。
只有在为获得要求的流动性而采用分散剂的情况下才可制备得到可加工的耐火组合物。分散剂可以选自下列无机盐中的一种：六偏磷酸钠，三聚磷酸钠，四聚磷酸钠，酸式六偏磷酸钠，以及碳酸钠，柠檬酸钠，酒石酸盐，聚丙烯酸盐，磺酸钠和萘-磺酸钠。
除了分散剂之外，可向耐火组合物中加入缓凝剂，优选的缓凝剂例如有柠檬酸，葡糖酸或硼酸，以确保延迟凝固。
根据结构的性质，对100wt％的耐火粉末，可采用与缓凝剂一起添加一种或多种分散剂，它们的总含量为0.03-0.3wt％。
另外，为了确保建造后的干燥，可采用0.03-0.15wt％的金属铝粉末，或一种或多种有机纤维。0.03wt％以下的金属铝粉末或有机纤维在干燥过程中不能提供防止散裂的作用，而超过0.15wt％的金属铝粉末或有机纤维会由于孔隙率过大而使结构的性质变差。
在采用铝粉防止干燥期间发生散裂时，要求调节金属铝粉的反应速率，其中采用0.01-0.05wt％的抑制剂作为金属组分的反应阻滞剂。如果不采用反应阻滞剂，反应速率会随温度而变化，导致结构表面和内部在固化期间的凝固速率有所不同，不能获得均匀的结构。含量低于0.01wt％的抑制剂不起作用，而含量超过0.05wt％的抑制剂则使强度变差。
通过向本发明的耐火组合物中加入水，可研磨耐火组合物并进行建造，在必要的情况下可加入钢纤维。
以下将描述本发明的实施方式。
表1
Figure G04823228720060222D000071
分散剂1*：氧化铝ADS(Alcoa)
分散剂2*：六偏磷酸钠
分散剂3*：焦磷酸钠
为了在流化床还原炉内形成柱12和分配板13，要求确保耐火组合物的流动性足以填充柱12和分配板13除通孔12a和13a之外的其余部分，采用台式流动测试法测定流动性，评价的流动性要求在台式流动测试中15个接头之后的最低值为110mm。上述的表1表明本发明的耐火组合物在台式流动测试中15个接头之后的流动性高于110mm，因此流动性良好。
表2
*散裂发生的测试：采用直径为100mm，高度为200mm的固化了24个小时的柱形测试片，通过非接触火焰加热法，在500℃下测试5个小时。
表3
Figure G04823228720060222D000091
**比较实施例
*膨胀：在35℃的固化温度下测定尺寸为350×350×500(宽×长×高)mm的结构的表面高度增长。
工业应用性
如上所述，采用本发明的耐火组合物形成流化床还原炉1内的柱12和分配板13的过程中，本发明提供了高强度、结构致密的耐火结构，该耐火结构能确保可加工性，体积比重大于3.2，可向其中加入建筑金属纤维，抗压强度高于1500kg/cm2，ASTM C 708磨损率为3或更低，这些基本设计标准在设备操作过程中，使柱12和分配板13具有对还原性气体的耐化学品性质，在高速流化条件下具有良好的耐磨性，具有良好的耐热冲击性而足以耐受快速升温和降温，因而能进行长时间的稳定操作，改进了铁的品质，使得工业应用性非常高。
对本领域技术人员显而易见的是，可对本发明进行各种润饰和改变而不偏离本发明的精神或范围。因此，本发明意欲覆盖本发明的各种润湿和改变，条件是这些润湿和改变落入后附的权利要求和其等价物的范围内。

Claims (3)

1.一种耐火材料，其用于建造还原铁矿粉的流化床还原炉内的某一结构，该耐火组合物包括12.5wt％的煅烧氧化铝，4.5wt％的特级脱水二氧化硅97％，7wt％的70％高铝水泥，以及余量熔融氧化铝，而构成100wt％的耐火组合物，其中所述熔融氧化铝8mm-1mm的粒径占57wt％，1mm以下的粒径占19wt％，所述煅烧氧化铝中4μm的平均粒径占8wt％，2μm的平均粒径占4.5wt％，所述耐火组合物还进一步包括0.07wt％的六偏磷酸钠、0.03wt％焦磷酸钠和0.03wt％的金属铝粉。
2.如权利要求1所述的耐火组合物，其中可由所述耐火组合物建造所述流化床还原炉内的柱。
3.如权利要求1所述的耐火组合物，其中可由所述耐火组合物建造所述流化床还原炉内的分配板。
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