CN110590346A - 一种用于循环流化床锅炉的高导热耐磨材料 - Google Patents
一种用于循环流化床锅炉的高导热耐磨材料 Download PDFInfo
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Abstract
本发明公开一种用于循环流化床锅炉的高导热耐磨材料,由如下重量份的原料加工制备而成:锆刚玉细粉17‑25重量份、纳米氮化铝9‑13重量份、石墨烯3‑6重量份、碳化硅23‑26重量份、氧化锆细粉8‑16重量份、纯铝酸钙水泥5‑9重量份、氧化铝细粉3‑7重量份、分散剂0.2‑0.4重量份、硅溶胶4‑8重量份、防爆纤维0.1‑0.15重量份、氧化钙1‑3重量份、改性白黏土1‑2重量份;本发明所述高导热耐磨材料在制备过程中,通过高固含量的硅溶胶作为粘结剂,在添加硅溶胶时,将碳化硅、含有氧化铝的均化粉与未凝胶化的硅溶胶均匀混合,然后再通过烘干的方式除去硅溶胶中的水分,从而提升了高导热耐磨材料烧结形成锅炉内衬的致密性。
Description
技术领域
本发明属于耐火材料技术领域,具体的,涉及一种用于循环流化床的高导热耐磨材料。
背景技术
循环流化床是一种新型燃煤锅炉,它是通过将煤破碎成10mm以下后通入炉膛,通过炉膛底部配风,将煤与炉膛中的惰性高温物料充分混合并形成流化态燃烧,并在之后的工序中安装气固分离装置,将未完全燃烧的煤颗粒收集后继续进行燃烧;
循环流化床锅炉的优点在于能够使燃料充分的被利用,相较于煤粉炉,不需要对煤燃料进行高质量的粉碎就可以达到对煤的充分燃烧利用的目的,并且循环流化床锅炉对燃料的品质要求不高,劣质的燃料都能够在锅炉中充分的燃烧,但是由于循环流化床在工作过程中,固体燃料会在流化床内高速运动撞击流化床的内壁,因此为了提升流化床工作的安全性,会在流化床的内壁上浇筑一层耐磨耐火材料,以达到防护的作用,在实际生产过程中,锅炉的水冷壁等部位需要采用高导热材料进行浇筑,因此该部位的耐火材料除了需要具备耐火耐高温的效果之外,还需要具备良好的导热效果,为了解决这一问题,本发明提供了以下技术方案。
发明内容
本发明的目的在于提供一种用于循环流化床锅炉的高导热耐磨材料。
本发明需要解决的技术问题为:
1、现有技术中循环流化床锅炉的内层涂料均能够达到耐火要求,但是涂料形成的涂层由于具有较大的厚度,且涂层的导热效果较差,因此会影响炉膛与水冷管的热转换效率,从而影响循环流化床锅炉对燃料中能量的利用效率;
2、在现有技术中,循环流化床的耐火内衬层是通过耐火材料浇筑后固化形成,因此耐火材料需要具备良好的流动性,使浇筑形成的耐火内衬层具有良好的致密性,同时,还要保证浇筑成型后的内火材料能够快速定型,缩短成型时间;
3、在现有技术中,循环流化床内衬层在经过长时间的使用后会出现大量微观裂纹,从而导致内衬层的耐高温性能下降,耐久性下降。
本发明的目的可以通过以下技术方案实现:
一种用于循环流化床锅炉的高导热耐磨材料,由如下重量份的原料加工制备而成:
粒度为1-2.5mm的锆刚玉细粉17-25重量份、纳米氮化铝9-13重量份、石墨烯3-6重量份、粒度为0.1-0.3mm的碳化硅23-26重量份、粒度为0.072-0.093mm的氧化锆细粉8-16重量份、纯铝酸钙水泥5-9重量份、氧化铝细粉3-7重量份、分散剂0.2-0.4重量份、硅溶胶4-8重量份、防爆纤维0.1-0.15重量份、氧化钙1-3重量份、改性白黏土1-2重量份;
该高导热耐磨材料的制备方法为:
步骤一、将防爆纤维与改性白黏土加入纯铝酸钙水泥中,高速搅拌混合,使防爆纤维与改性白黏土均匀分散在纯铝酸钙水泥中,得到混合物料A;
步骤二、调节硅溶胶的pH值为8.5-9.5,硅溶胶的固含量为20%-30%,由于硅溶胶中含有大量水分,在以硅凝胶作为粘结剂时,容易导致成型的内衬层内含有大量气泡结构,导致内衬层的导热性能下降,因此提升硅溶胶的固含量能够有效改善这一状况,但是由于硅溶胶的凝胶化速度会受到硅溶胶中固含量的影响,胶凝速度会随着固含量的提升而提升,导致硅溶胶无法保存而迅速凝胶化,因此调节pH值为8.5-9.5,引入大量氢氧根离子,提升硅溶胶颗粒之间的排斥力,使其不易凝胶化;将分散剂与氧化铝细粉在振动磨中共磨30min,使得分散剂和氧化铝细粉充分均化,制成均化粉;
步骤三、将碳化硅与均化粉加入步骤二得到的硅溶胶中,搅拌混合后加入球磨机中,在转速250-400r/min的条件下,球磨15-28min,使碳化硅、均化粉与硅溶胶均匀混合,然后向球磨机中加入乙醇,乙醇与硅溶胶的体积比为0.3-1:1,继续在转速250-400r/min的条件下,球磨至硅溶胶完全凝胶化,得到凝胶中间体,从而在碳化硅颗粒与氧化铝细粉颗粒的表面均匀覆盖有一层硅凝胶;
在这一过程中,无水乙醇虽然降低了硅溶胶的固含量,但是由于乙醇为非极性物质,不导电,因而缩短了硅溶胶中氢氧根离子的移动距离,起到了明显降低pH值的效果,从而促进硅溶胶的凝胶化;
作为本发明的进一步方案,步骤三在向球磨机中加入的乙醇中混合添加有有机酸,具体的,该有机酸为乙酸,添加有机酸能够调节硅溶胶的pH值,当硅溶胶的pH值降低时,硅溶胶的凝胶化速度提升;
步骤四、将步骤三中得到的凝胶中间体加入烘箱中,在90-96℃的温度条件下烘干干燥,除去凝胶中的水、乙醇,然后加入球磨机中,以250-400r/min转速球磨30-40min,得到混合物料B;
步骤五、按照重量份称取锆刚玉细粉、纳米氮化铝、石墨烯、氧化锆细粉与氧化钙,并将各物料与混合物料A以及混合物料B均匀混合后得到高导热耐磨材料。
所述氧化铝细粉粒度小于0.044mm,Al2O3含量大于等于 99.5wt%,体积密度大于等于3.50g/cm3;
所述纯铝酸钙水泥的颗粒直径小于200目,Al2O3含量大于75wt%;
所述分散剂由17wt%-28wt%柠檬酸钠、25wt%-30wt%六偏磷酸钠与45wt%-53wt%聚丙烯酸铵均匀混合而成;
所述改性白黏土的制备方法为
S1、配制饱和硝酸钙水溶液,将白黏土完全浸没在饱和硝酸钙水溶液中,超声处理10-20min后过滤得到湿润的白黏土;
S2、向球磨机中加入硅酸钠与步骤S1中处理得到的白黏土,其中白黏土与硅酸钠的重量比为20:0.5-1,球磨机以转速300-600r/min球磨1-2h后得到以白黏土为载体的CSH凝胶聚合体,球磨过程中可根据实际情况添加少量清水;
S3、配制硅酸钠饱和水溶液,将上一步骤得到的以白黏土为载体的CSH凝胶聚合体加入硅酸钠饱和水溶液中,搅拌混合反应1.5-2h,其中硅酸钠与硝酸钙反应生成CSH凝胶;
S4、将上一步骤中反应得到的混合物过滤得到滤饼,用去离子水清洗滤饼后再次过滤,重复3-7次后将滤饼烘干干燥后粉碎,得到改性白黏土,该步骤能够除去滤饼中未反应的硅酸钠与硝酸钙。
以白黏土作为载体,形成被CSH凝胶填充并在表面形成凹凸不平的CSH凝胶结构的白黏土,在将改性的白黏土与其它CSH凝胶均匀分散在混凝土中时,以CSH凝胶与改性的白黏土作为媒介,加快纤维状CSH凝胶网状结构的形成,加速水泥浆的凝结,其中以白黏土作为载体能够提升CSH凝胶的分散效果。
本发明的有益效果:
1、本发明所述高导热耐磨材料在制备过程中添加有纳米氮化铝、碳化硅等具有高导热效果的材料,因此保证其具有良好的导热效果,同时,本发明在制备过程中,通过高固含量的硅溶胶作为粘结剂,但是在添加硅溶胶时,是将碳化硅、含有氧化铝的均化粉与未凝胶化的硅溶胶均匀混合,然后通过乙醇稀释以及添加酸调节pH的方式,促进硅溶胶的的凝胶化,从而使硅凝胶能够均匀的分布在碳化硅与氧化铝的表面,然后再通过烘干的方式除去硅溶胶中的水分,从而提升了高导热耐磨材料烧结形成锅炉内衬的致密性质,同时在高温焙烧过程中,硅溶胶中的硅煅烧形成二氧化硅微粒,二氧化硅微粒在煅烧过程中起到粘结碳化硅的效果,提升了成型后锅炉内衬的强度。
2、采用复合分散剂,并且通过将硅溶胶与碳化硅、含有氧化铝的均化粉均匀混合后再除去硅溶胶中的水的方式,避免硅溶胶加入时,致局部位置的物料聚集成团,提升了材料的自流性。
3、本发明在制备过程中,添加有改性白黏土与防爆纤维,其中改性白黏土均匀分散在纯铝酸钙水泥中时,以CSH凝胶与改性的白黏土作为媒介,加快纤维状CSH凝胶网状结构的形成,加速水泥的凝结,从而提升内衬浇筑初期的强度,避免初期脱水产生内部气泡与表面裂纹。
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作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
一种用于循环流化床锅炉的高导热耐磨材料,由如下重量份的原料加工制备而成:
粒度为1-1.5mm的锆刚玉细粉22重量份、纳米氮化铝12重量份、石墨烯3重量份、粒度为0.1-0.13mm的碳化硅26重量份、粒度为0.072-0.093mm的氧化锆细粉12重量份、纯铝酸钙水泥6重量份、氧化铝细粉5.5重量份、分散剂0.3重量份、硅溶胶5重量份、防爆纤维0.12重量份、氧化钙1.5重量份、改性白黏土2重量份;
该高导热耐磨材料的制备方法为:
步骤一、将防爆纤维与改性白黏土加入纯铝酸钙水泥中,高速搅拌混合,使防爆纤维与改性白黏土均匀分散在纯铝酸钙水泥中,得到混合物料A;
步骤二、调节硅溶胶的pH值为9,硅溶胶的固含量为25%;将分散剂与氧化铝细粉在振动磨中共磨30min,使得分散剂和氧化铝细粉充分均化,制成均化粉;
步骤三、将碳化硅与均化粉加入步骤二得到的硅溶胶中,搅拌混合后加入球磨机中,在转速350r/min的条件下,球磨17min,使碳化硅、均化粉与硅溶胶均匀混合,然后向球磨机中加入乙醇,乙醇与硅溶胶的体积比为0.4:1,继续在转速350r/min的条件下,球磨至硅溶胶完全凝胶化,得到凝胶中间体,从而在碳化硅颗粒与氧化铝细粉颗粒的表面均匀覆盖有一层硅凝胶;
作为本发明的进一步方案,步骤三在向球磨机中加入的乙醇中混合添加有乙酸;
步骤四、将步骤三中得到的凝胶中间体加入烘箱中,在90℃的温度条件下烘干干燥,除去凝胶中的水、乙醇,然后加入球磨机中,以350r/min转速球磨40min,得到混合物料B;
步骤五、按照重量份称取锆刚玉细粉、纳米氮化铝、石墨烯、氧化锆细粉与氧化钙,并将各物料与混合物料A以及混合物料B均匀混合后得到高导热耐磨材料。
所述氧化铝细粉粒度小于0.044mm,Al2O3含量大于等于 99.5wt%,体积密度大于等于3.50g/cm3;
所述纯铝酸钙水泥的颗粒直径小于200目,Al2O3含量大于75wt%;
所述分散剂由23wt%柠檬酸钠、26wt%六偏磷酸钠与51wt%聚丙烯酸铵均匀混合而成;
所述改性白黏土的制备方法为
S1、配制饱和硝酸钙水溶液,将白黏土完全浸没在饱和硝酸钙水溶液中,超声处理16min后过滤得到湿润的白黏土;
S2、向球磨机中加入硅酸钠与步骤S1中处理得到的白黏土,其中白黏土与硅酸钠的重量比为20:0.7,球磨机以转速450r/min球磨2h后得到以白黏土为载体的CSH凝胶聚合体;
S3、配制硅酸钠饱和水溶液,将上一步骤得到的以白黏土为载体的CSH凝胶聚合体加入硅酸钠饱和水溶液中,搅拌混合反应2h,其中硅酸钠与硝酸钙反应生成CSH凝胶;
S4、将上一步骤中反应得到的混合物过滤得到滤饼,用去离子水清洗滤饼后再次过滤,重复7次后将滤饼烘干干燥后粉碎,得到改性白黏土,该步骤能够除去滤饼中未反应的硅酸钠与硝酸钙。
实施例2
一种用于循环流化床锅炉的高导热耐磨材料,由如下重量份的原料加工制备而成:
粒度为1-1.5mm的锆刚玉细粉21重量份、纳米氮化铝11重量份、石墨烯3重量份、粒度为0.1-0.3mm的碳化硅25重量份、粒度为0.072-0.093mm的氧化锆细粉13重量份、纯铝酸钙水泥7重量份、氧化铝细粉7重量份、分散剂0.4重量份、硅溶胶5重量份、防爆纤维0.16重量份、氧化钙1重量份、改性白黏土2重量份;
该高导热耐磨材料的制备方法为:
步骤一、将防爆纤维与改性白黏土加入纯铝酸钙水泥中,高速搅拌混合,使防爆纤维与改性白黏土均匀分散在纯铝酸钙水泥中,得到混合物料A;
步骤二、调节硅溶胶的pH值为8.7,硅溶胶的固含量为20%;将分散剂与氧化铝细粉在振动磨中共磨30min,使得分散剂和氧化铝细粉充分均化,制成均化粉;
步骤三、将碳化硅与均化粉加入步骤二得到的硅溶胶中,搅拌混合后加入球磨机中,在转速300r/min的条件下,球磨24min,使碳化硅、均化粉与硅溶胶均匀混合,然后向球磨机中加入乙醇,乙醇与硅溶胶的体积比为0.3:1,继续在转速300r/min的条件下,球磨至硅溶胶完全凝胶化,得到凝胶中间体,从而在碳化硅颗粒与氧化铝细粉颗粒的表面均匀覆盖有一层硅凝胶;
作为本发明的进一步方案,步骤三在向球磨机中加入的乙醇中混合添加有有机酸,具体的,该有机酸为乙酸,添加有机酸能够调节硅溶胶的pH值,当硅溶胶的pH值降低时,硅溶胶的凝胶化速度提升;
步骤四、将步骤三中得到的凝胶中间体加入烘箱中,在90℃的温度条件下烘干干燥,除去凝胶中的水、乙醇,然后加入球磨机中,以300r/min转速球磨35min,得到混合物料B;
步骤五、按照重量份称取锆刚玉细粉、纳米氮化铝、石墨烯、氧化锆细粉与氧化钙,并将各物料与混合物料A以及混合物料B均匀混合后得到高导热耐磨材料。
所述氧化铝细粉粒度小于0.044mm,Al2O3含量大于等于 99.5wt%,体积密度大于等于3.50g/cm3;
所述纯铝酸钙水泥的颗粒直径小于200目,Al2O3含量大于75wt%;
所述分散剂由25wt%柠檬酸钠、28wt%六偏磷酸钠与47wt%聚丙烯酸铵均匀混合而成;
所述改性白黏土的制备方法为
S1、配制饱和硝酸钙水溶液,将白黏土完全浸没在饱和硝酸钙水溶液中,超声处理20min后过滤得到湿润的白黏土;
S2、向球磨机中加入硅酸钠与步骤S1中处理得到的白黏土,其中白黏土与硅酸钠的重量比为20:0.7,球磨机以转速500r/min球磨2h后得到以白黏土为载体的CSH凝胶聚合体;
S3、配制硅酸钠饱和水溶液,将上一步骤得到的以白黏土为载体的CSH凝胶聚合体加入硅酸钠饱和水溶液中,搅拌混合反应2h,其中硅酸钠与硝酸钙反应生成CSH凝胶;
S4、将上一步骤中反应得到的混合物过滤得到滤饼,用去离子水清洗滤饼后再次过滤,重复7次后将滤饼烘干干燥后粉碎,得到改性白黏土,该步骤能够除去滤饼中未反应的硅酸钠与硝酸钙。
对比例1
对比实施例1,对比例1在步骤二至步骤四中,直接将硅溶胶、碳化硅以及均化粉均匀混合后,再与混合物料A与混合物料B均匀混合,其它条件与实施例1相同。
对比例2
对比实施例1,对比例2的组分中不包括改性白粘土,其它条件与实施例1相同。
对比例3
对比实施例1,对比例3中直接采用未经改性处理的白黏土替换改性白黏土,其它条件与实施例1相同。
实验数据与结果分析
对各实施例与对比例中加工形成的高导热耐磨材料的导热系数、长期使用最高温度、最高使用温度以及抗折强度进行检测,各项数据均为在对高导热耐磨材料在900℃温度下处理5h后的检测结果,具体结果见表1:
表1
检测项目 | 导热系数(W/(m·K)) | 体积密度(g/cm<sup>3</sup>) | 抗折强度(MPa) | 抗压强度(MPa) |
实施例1 | 21 | 3.54 | 46.3 | 192.7 |
实施例2 | 20 | 3.56 | 43.8 | 194.3 |
对比例1 | 19 | 3.47 | 42.6 | 191.2 |
对比例2 | 18 | 3.49 | 38.6 | 188.5 |
对比例3 | 19 | 3.46 | 39.1 | 190.6 |
由表1所述结果可知,本发明所述高导热耐磨材料在经过900℃温度处理5h后,具有不低于15的导热系数,同时致密的结构减少了内部孔隙数量,不仅提升了其导热能力,还提升了结构强度,使其具有更长的使用寿命。
以上内容仅仅是对本发明结构所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的结构或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (8)
1.一种用于循环流化床锅炉的高导热耐磨材料,其特征在于,由如下重量份的原料加工制备而成:
锆刚玉细粉17-25重量份、纳米氮化铝9-13重量份、石墨烯3-6重量份、碳化硅23-26重量份、氧化锆细粉8-16重量份、纯铝酸钙水泥5-9重量份、氧化铝细粉3-7重量份、分散剂0.2-0.4重量份、硅溶胶4-8重量份、防爆纤维0.1-0.15重量份、氧化钙1-3重量份、改性白黏土1-2重量份;
该高导热耐磨材料的制备方法为:
步骤一、将防爆纤维与改性白黏土加入纯铝酸钙水泥中,搅拌混合,使防爆纤维与改性白黏土均匀分散在纯铝酸钙水泥中,得到混合物料A;
步骤二、调节硅溶胶的pH值为8.5-9.5,硅溶胶的固含量为20%-30%,将分散剂与氧化铝细粉在振动磨中共磨30min,使得分散剂和氧化铝细粉充分均化,制成均化粉;
步骤三、将碳化硅与均化粉加入硅溶胶中,搅拌混合后加入球磨机中,在转速250-400r/min的条件下,球磨15-28min,使碳化硅、均化粉与硅溶胶均匀混合,然后向球磨机中加入乙醇,乙醇与硅溶胶的体积比为0.3-1:1,继续在转速250-400r/min的条件下,球磨至硅溶胶完全凝胶化,得到凝胶中间体;
步骤四、将步骤三中得到的凝胶中间体加入烘箱中,在90-96℃的温度条件下烘干干燥,然后加入球磨机中,以250-400r/min转速球磨30-40min,得到混合物料B;
步骤五、按照重量份称取锆刚玉细粉、纳米氮化铝、石墨烯、氧化锆细粉与氧化钙,并将各物料与混合物料A以及混合物料B均匀混合后得到高导热耐磨材料。
2.根据权利要求1所述的一种用于循环流化床锅炉的高导热耐磨材料,其特征在于,所述锆刚玉细粉的粒度为1-2.5mm,所述碳化硅的粒度为0.1-0.3mm,所述氧化锆细粉的粒度为0.072-0.093mm。
3.根据权利要求1所述的一种用于循环流化床锅炉的高导热耐磨材料,其特征在于,所述氧化铝细粉粒度小于0.044mm,Al2O3含量大于等于 99.5wt%。
4.根据权利要求1所述的一种用于循环流化床锅炉的高导热耐磨材料,其特征在于,所述纯铝酸钙水泥的颗粒直径小于200目,Al2O3含量大于75wt%。
5.根据权利要求1所述的一种用于循环流化床锅炉的高导热耐磨材料,其特征在于,所述分散剂由17wt%-28wt%柠檬酸钠、25wt%-30wt%六偏磷酸钠与45wt%-53wt%聚丙烯酸铵均匀混合而成。
6.根据权利要求1所述的一种用于循环流化床锅炉的高导热耐磨材料,其特征在于,步骤三向球磨机中加入的乙醇中混合添加有有机酸。
7.根据权利要求6所述的一种用于循环流化床锅炉的高导热耐磨材料,其特征在于,所述有机酸为乙酸。
8.根据权利要求1所述的一种用于循环流化床锅炉的高导热耐磨材料,其特征在于,所述改性白黏土的制备方法为:
S1、配制饱和硝酸钙水溶液,将白黏土完全浸没在饱和硝酸钙水溶液中,超声处理10-20min后过滤得到湿润的白黏土;
S2、向球磨机中加入硅酸钠与步骤S1中处理得到的白黏土,其中白黏土与硅酸钠的重量比为20:0.5-1,球磨机以转速300-600r/min球磨1-2h后得到以白黏土为载体的CSH凝胶聚合体;
S3、配制硅酸钠饱和水溶液,将上一步骤得到的以白黏土为载体的CSH凝胶聚合体加入硅酸钠饱和水溶液中,搅拌混合反应1.5-2h;
S4、将上一步骤中反应得到的混合物过滤得到滤饼,用去离子水清洗滤饼后再次过滤,重复3-7次后将滤饼烘干干燥,粉碎,得到改性白黏土。
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