CN116063089B - 一种超薄型炉墙用可塑料及其制备方法 - Google Patents
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Abstract
本发明涉及耐火材料技术领域,特别涉及一种超薄型炉墙用可塑料及其制备方法,所述可塑料包括以下原料:50‑60重量份的棕刚玉、10‑20重量份的碳化硅、10‑15重量份的纳米氧化镁、5‑10重量份的α‑氧化铝微粉、5‑10重量份的促凝剂、2‑5重量份的保存剂与10‑20重量份的磷酸。本发明通过将上述组分混合,制得的超薄型炉墙用可塑料具有耐热震性能强、适应快速升降温、热膨胀系数低、气孔率低、便于施工等优点,适用于各种锅炉的炉墙、炉顶等易磨损处的修补或防磨处理。
Description
技术领域
本发明涉及可塑料制备技术领域,特别涉及一种超薄型炉墙用可塑料及其制备方法。
背景技术
随着国内环保要求日益严格,燃煤与环保的矛盾日益突出,流化床锅炉因其燃料适应性广、燃烧效率高、高效脱硫、氮氧化物(NOX)排放低等诸多优点,已成首选的节能、高效、低污染锅炉,在循环流化床锅炉运行过程中,将物质流化后循环在炉膛中燃烧,并加入石灰石、石灰等脱硫物质,在循环过程中反复脱硫。但正是由于多次的循环过程,颗粒物质不断冲刷、撞击锅炉内壁,使循环流化床锅炉出现严重的磨损,甚至龟裂现象。
可塑料是一种不定形耐火材料,呈硬泥膏状,材质多为黏土质和高铝质,也有硅质、镁质、铬质、锆英石质和碳化硅质等,一般由耐火骨料、粉料、生黏土、外加剂和化学复合结合剂构成,经配制混炼、挤压成砖坯状,并在较长时间内保持较高可塑性,含有较多的可塑黏土组分,水分也较捣打料多。可塑料中某些结合剂或其他成分也可在施工时加入,使用时将混合物压实或捣打,经烘烤后即可构成密实的内衬及构筑物,适用于各种锅炉,尤其是循环流化床锅炉炉墙、炉顶、旋风分离器等易磨损处的修补或防磨处理。
但现有可塑料的抗剥落、耐热震等性能一般,气孔率高,热膨胀系数大对可塑料的使用寿命造成不利影响,并且若长时间持续运作的循环流化床锅炉因可塑料损坏不得不检修时,现有可塑料又存在投入使用前需要较长时间硬化与施工不便等问题,使维修成本增加。
发明内容
有鉴于此,本发明提供了一种超薄型炉墙用可塑料及其制备方法,以解决现有可塑料抗剥落、耐热震性能一般、气孔率高、硬化时间长等的技术问题。
为了解决上述技术问题,本发明提供了一种超薄型炉墙用可塑料及其制备方法,所述可塑料包括以下重量份的原料:
优选的,在上述超薄型炉墙用可塑料中,所述棕刚玉的粒径≤5mm,且粒径≤1mm的所述棕刚玉质量占所述棕刚玉总质量的83-100%。
本发明以棕刚玉作为耐火骨料,在可塑料中起骨架与填充作用,并且可以很好的传递牛顿力,以提高强度与坚固性,本发明选取粒径小于1mm的棕刚玉作为主要原料,合理对骨料级配,可以使堆积空隙率小,颗粒总比表面积减小,以减少粉体填补空隙时的用量,使可塑料的气孔率降低,抗折强度与使用寿命增加,同时棕刚玉自身线膨胀系数低,耐腐蚀,因此以棕刚玉为骨料,进一步增强了可塑料的机械性能。
优选的,在上述超薄型炉墙用可塑料中,所述碳化硅为黑碳化硅。
本发明的化学助剂为黑碳化硅烧结助剂,少量的烧结助剂可以对可塑料的烧结效果带来提升明显,其作用在于:阻止晶型转变,在烧结时发生晶型转变并伴有较大体积效应,这就会使烧结致密化发生困难,并容易引起坯体开裂,这时若能选用适宜的烧结助剂加以抑制,即可促进烧结;抑制晶粒长大,由于烧结后期晶粒长大,对烧结致密化有重要作用。但若二次再结晶或间断性晶粒长大过快,又会因晶粒变粗、晶界变宽而出现反致密化现象并影响制品的显微织构,这时可通过加入能抑制晶粒异常长大的烧结助剂,来促进致密化进程,在氧化铝中加入少量氧化镁就有这种作用,本发明的氧化镁与氧化铝形成的镁铝尖晶石分布于氧化铝颗粒之间,抑制了晶粒长大,并促使气孔的排除,因而获得充分致密的透明氧化铝多晶体。
优选的,在上述超薄型炉墙用可塑料中所述促凝剂为磷酸钙水泥、烧结镁砂粉、氟化铵中的一种或几种,进一步优选为磷酸钙水泥。
本发明的可塑料原料中,促凝剂可加快结合剂的结合速度,缩短施工时间,在制备过程中可以将促凝剂或结合剂中的任一种与可塑料其他原料分开存放,有助于原料的保质期,待需要使用时再将其加入并混合,使可塑料迅速凝结、硬化后投入使用。
优选的,在上述超薄型炉墙用可塑料中,所述保存剂为乙二酸、2-羟基丙烷-1,2,3-三羧酸、2,3-二羟基琥珀酸中的一种或几种。
本发明添加保存剂的作用是能够保持可塑料储存一定的时间后施工,且可塑料性能不变或变化很小。
优选的,在上述超薄型炉墙用可塑料中,所述α-氧化铝微粉的目数160-350目。
本发明中的粉料为α-氧化铝,α-氧化铝既可以填充粒径相对较大的耐火骨料堆积所形成的间隙并增加凝聚作用,从而减小气孔率,增加致密度;又与纳米氧化镁反应,在高温下α-氧化铝与纳米氧化镁可以生成镁铝尖晶石,而尖晶石型矿物耐高温、热膨胀系数小、热稳定性好、抗渣性强,对可塑料的耐火性、抗压强度与抗折强度有极大的提升。
另外,本发明还提供了一种上述超薄型炉墙用可塑料的制备方法,包括以下步骤:
(1)将棕刚玉、碳化硅、α-氧化铝微粉、保存剂、三分之一磷酸与二分之一纳米氧化镁进行混炼5-10min,得到组分A;
(2)将所述促凝剂、剩余所述磷酸与剩余所述纳米氧化镁混合并搅拌3-5min,得到组分B;
(3)将所述组分A与所述组分B进行混炼10-20min,即得到可塑料。
优选的,上述步骤(3)至少与步骤(2)间隔10h。
优选的,上述超薄型炉墙用可塑料的制备方法中,所述步骤(1)中混炼机工作参数:温度为20-45℃,混炼时间为10-30min,进一步优选为30℃下混炼20min。
以及本发明还公开了一种上述超薄型炉墙用可塑料在循环流化床锅炉与废物焚烧炉中应用。
本发明公开了一种超薄型炉墙用可塑料及其制备方法,与现有技术相比,其有益效果在于:
本发明所有原料均采用小粒径原料,制备出的可塑料厚度薄;对于混炼过程中各原料的流动性强,因此得到的可塑料混合均匀度高;本发明的可塑料施工方便,锅炉短时间内就可以投入使用,可用于紧急抢修;相较于现有的可塑料,具有更强的机械性能;抗热震性能强,当产生较快的温度变化时,不会因为剧烈的热胀冷缩现象使可塑料出现脱落或龟裂导致使用寿命短。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
下面将列举本发明下的部分实施例和测定数据以阐述本发明的显著的进步:
实施例1
本实施例提供了一种超薄型炉墙用可塑料,原料组成如下:
(1)将上述配比的棕刚玉、碳化硅、α-氧化铝微粉、2-羟基丙烷-1,2,3-三羧酸、磷酸总重量份数的1/3与纳米氧化镁总重量份数的1/2进行混炼5-10min,得到组分A;
(2)将磷酸钙水泥、剩余所述磷酸与剩余纳米氧化镁混合并搅拌3-5min,得到组分B;
(3)将组分A与组分B进行混炼10-20min,即得到超薄型锅炉用可塑料。
实施例2
本实施例提供了一种超薄型炉墙用可塑料,原料组成如下:
(1)将上述配比的棕刚玉、碳化硅、α-氧化铝微粉、2,3-二羟基琥珀酸、磷酸总重量份数的1/3与纳米氧化镁总重量份数的1/2进行混炼5-10min,得到组分A;
(2)将烧结镁砂粉、剩余所述磷酸与剩余纳米氧化镁混合并搅拌3-5min,得到组分B;
(3)将组分A与组分B进行混炼10-20min,即得到超薄型锅炉用可塑料。
实施例3
本实施例提供了一种超薄型炉墙用可塑料,原料组成如下:
(1)将上述配比的棕刚玉、碳化硅、α-氧化铝微粉、2,3-二羟基琥珀酸、磷酸总重量份数的1/3与纳米氧化镁总重量份数的1/2进行混炼5-10min,得到组分A;
(2)将氟化铵、剩余所述磷酸与剩余纳米氧化镁混合并搅拌3-5min,得到组分B;
(3)将组分A与组分B进行混炼10-20min,即得到超薄型锅炉用可塑料。
实施例4
本实施例与实施例3的区别之处在于,棕刚玉级配不同,棕刚玉配比如下:
棕刚玉(粒径<1mm) 55份
棕刚玉(粒径为3-5mm) 5份。
实施例5
本实施例与实施例3的区别之处在于,棕刚玉级配不同,棕刚玉配比如下:
棕刚玉(粒径<1mm) 55份
棕刚玉(粒径为1-3mm) 5份。
实施例6
本实施例提供了一种超薄型炉墙用可塑料,原料组成如下:
对比例1
本对比例与实施例1的区别之处在于,棕刚玉粒径不同,本对比例采用:棕刚玉(粒径为1-3mm)60份。
对比例2
本对比例与实施例1的区别之处在于,棕刚玉粒径不同,本对比例采用:棕刚玉(粒径为3-5mm)60份。
对比例3
本对比例与实施例1的区别之处在于,本对比例没有添加纳米氧化镁。
对比例4
本对比例与实施例1的区别之处在于,本对比例没有添加化学助剂碳化硅。
对比例5
本对比例与实施例1的区别之处在于,所选取化学助剂为绿碳化硅,用量为:绿碳化硅10份。
对以上实施例与对比例制备出的各可塑料进行性能测试,测试结果如下表,其中:
显气孔率的测定方法:(1)采用体积为125cm3的试样,并称量该干试样质量m1;
(2)将试样抽真空后加入液体充分饱和试样,称量饱和试样在空气中的质量m3;
(3)饱和试样的表观质量m2,即饱和试样完全淹没在浸液中时,饱和试样的质量减去被排开液体的质量。
计算:显气孔率=(m3-m1)÷(m3-m2)
热膨胀系数的测定方法:以一个激光束扫描试样,而不断测定试样在加热过程中长度的变化,其由计算机组成的全自动控制、记录,测量精度高。
导热系数的测定方法:将可塑料用模具制备成30cm*30cm*5cm的块状物,并放入防护热板导热仪测定其导热系数。
抗折强度的测定方法:抗折强度是指材料单位面积承受弯矩时的极限折断应力,试验在通用万能材料试验机上进行,可塑料试件为高(10-16)毫米*120毫米的圆柱体。
表1超薄型炉墙用可塑料物理性能表
由表1可知:当采用孔径较大的耐火骨料时,不仅可塑料显气孔率明显高于小孔径耐火骨料;对比例可塑料的热膨胀系数也略高于本发明实施例的可塑料;而导热系数的主要影响因素是材料本身,因此没有较大差异。
加热线变化是指不定形耐火材料经加热后所产生的长度不可逆变化量,分为干燥线变化及烧后线变化。由于不定形耐火材料一般不经过成型、烧成,而是加入结合剂直接用来砌筑热工设备使用的,加入结合剂的性质和数量都十分重要。在加热过程中,由于发生物理化学反应,必然会产生收缩或膨胀,因此加热线变化是衡量可塑料性能的一个重要参数。本发明可塑料加热线变化率的测定方法为:将可塑料加水制成160mm*40mm*40mm的长方体试样,升温至110±5℃,干燥至恒量,测量干燥前后长度的不变化,计算干燥线变化,再升温至一定温度下,保温3小时,冷却后根据伸长或缩短的长度变化率确定可塑料的烧后线变化。
表2超薄型炉墙用可塑料加热线变化率(%)
序号 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 |
110℃ | -0.15 | -0.27 | -0.24 | -0.21 | -0.19 | -0.24 |
1350℃ | 0.14 | 0.16 | 0.27 | 0.24 | 0.17 | 0.25 |
序号 | 对比例1 | 对比例2 | 对比例3 | 对比例4 | 对比例5 | |
110℃ | -0.51 | -0.46 | -0.32 | -0.37 | -0.43 | |
1350℃ | 0.46 | 0.65 | 0.44 | 0.51 | 0.59 |
由表2可知:本发明实施例的可塑料加热线变化率低于对比例,较小的加热线变化率对可塑料使用寿命影响较大。本实施例可塑料对快速升降温的耐受能力强,因此当锅炉由于工作需要频繁变温,不易开裂或收缩,从而使炉壁产生裂缝。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (5)
1.一种超薄型炉墙用可塑料,其特征在于,所述可塑料包括以下重量份的原料:
所述棕刚玉的粒径≤5mm,且粒径≤1mm的所述棕刚玉质量占所述棕刚玉总质量的83-100%;
所述促凝剂为磷酸钙水泥、烧结镁砂粉、氟化铵中的一种或几种;
所述碳化硅为黑碳化硅;
所述α-氧化铝微粉的目数为160-350目。
2.根据权利要求1所述的超薄型炉墙用可塑料,其特征在于,所述保存剂为乙二酸、2-羟基丙烷-1,2,3-三羧酸、2,3-二羟基琥珀酸中的一种或几种。
3.一种权利要求1-2任一项所述的超薄型炉墙用可塑料的制备方法,其特征在于,包括以下步骤:
(1)将棕刚玉、碳化硅、α-氧化铝微粉、保存剂、三分之一磷酸与二分之一纳米氧化镁进行混炼5-10min,得到组分A;
(2)将所述促凝剂、剩余所述磷酸与剩余所述纳米氧化镁混合并搅拌3-5min,得到组分B;
(3)将所述组分A与所述组分B进行混炼10-20min,即得到可塑料;
所述步骤(1)中混炼机工作参数:温度为20-40℃,混炼时间为10-30min。
4.根据权利要求3所述的超薄型炉墙用可塑料的制备方法,其特征在于,所述步骤(3)至少与步骤(2)间隔10h。
5.一种权利要求1-2任一项所述的超薄型炉墙用可塑料在循环流化床锅炉与废物焚烧炉中应用。
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