CN117362002B - 以固废为原料的高温相变蓄热陶瓷砖及其制备方法 - Google Patents
以固废为原料的高温相变蓄热陶瓷砖及其制备方法 Download PDFInfo
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- CN117362002B CN117362002B CN202311638413.8A CN202311638413A CN117362002B CN 117362002 B CN117362002 B CN 117362002B CN 202311638413 A CN202311638413 A CN 202311638413A CN 117362002 B CN117362002 B CN 117362002B
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Abstract
本发明属于储能陶瓷材料技术领域,具体涉及以固废为原料的高温相变蓄热陶瓷砖及其制备方法。所述制备方法包括以下步骤:将预处理后的铁尾矿粉、钠长石粉、石英砂粉、Cr2O3和/或铬铁矿粉进行干混,将Al(H2PO4)3溶液和氢氧化铝粉进行湿混,将上述混料和预处理后的工业杂盐混合,经模压成型、干燥、烧结,得到微胶囊素坯;将电熔镁砂粉、Al(H2PO4)3溶液、钠长石粉、石英砂粉、无机硅胶溶液、粘结剂混合均匀,得到料浆悬浮液,喷涂或浸渍在微胶囊素坯表面,然后干燥、烧结,得到高温相变蓄热陶瓷砖。本发明利用工业杂盐和废弃的铁尾矿粉为主要原料,实现了工业固废的综合利用,且陶瓷砖显热潜热量大,热传导性能好。
Description
技术领域
本发明属于储能陶瓷材料技术领域,具体涉及以固废为原料的高温相变蓄热陶瓷砖及其制备方法。
背景技术
储能(蓄热)技术是可再生能源利用、工业窑炉余热利用以及城市智慧供热***的关键技术之一,而蓄热性能的优劣往往决定于其采用的储能材料性能,开发具有较好结构性能和蓄热性能的储能材料,是储能(蓄热)技术发展及应用的核心问题。
储能技术是将非稳态热量整流成稳态热量的技术,即将非稳态热量用储能材料将其存储,等到需要热量时,再可控和稳定地利用非稳态余热,它克服了钢铁工业许多余热间隙性的难点,并有效地解决了热量供需不匹配的矛盾关系。因此,将储能技术应用于钢铁工业,对具有非稳态余热资源的高品质回收利用具有重大的理论和实践意义。
在金属冶炼过程中的高温服役环境温度控制领域,封装后的高温相变储能材料具有蓄热性能且在蓄热过程中可以保持温度基本不变。若将封装后的高温相变蓄热材料代替或者部分代替常规的普通耐火材料永久层,利用高温吸收的热量补充低温时所需的热量,则可以起到一定的温控作用,使得整个冶炼过程处于相对平稳的温度环境。如果再通过对炉衬结构进行一体化设计,则不仅可以提高永久层和保温层的服役寿命,而且可以达到近零热损的理想节能效果。因此,用高温相变蓄热材料对高温工业中金属冶炼过程进行温度控制具有非常重要的意义。
储能(蓄热)技术主要包括显热储能、相变(潜热)储能、热化学/吸附储能技术等。其中,热化学储能的储能密度最大,但距离工业应用尚有很多问题亟待解决,并具有一定的危险性;显热储能技术是目前市场中应用最为成熟的储能技术(如镁砖),但显热储能材料的蓄热密度偏低,容易导致储能***体积庞大、成本过高;相变(潜热)储能主要是依靠相变材料在相变过程中吸收和释放热量的特性来进行蓄热和放热,其在一定程度上综合了热化学储能密度高和显热储能工艺简单成熟的优点。
无机盐类相变储能材料,主要包括各类硝酸盐、碳酸盐、氟盐、盐酸盐及其混合物。工业生产中通常使用其混合物作为储能材料,通过选择混合盐中不同组分的配比来调整其熔点,以适应不同场景下的工作温度或寻求更高的相变潜热。常用无机盐混合物的熔点一般在150-900℃,甚至可达更高温度,主要应用于中高温储能领域。熔融盐类潜热(相变)储能材料是由多种酸根与碱性金属复合组成,其中常见的有氯化盐(盐酸盐)、氟化盐、硝酸盐、碳酸盐、硫酸盐等,常见的碱金属有锂、钠、钾、镁等。复合形成的熔融盐类相变储能材料种类广泛,且相较于有机类相变储能材料,其蓄热密度高,对温度变化响应速度更快。
氯化盐的相变潜热大、黏度小、热稳定性好,常见的单盐有氯化钠、氯化钾、氯化锂、氯化钙、氯化镁等,纯氯化钠(NaCl)的熔点为801℃,熔化潜热为491kJ/kg。硫酸钠盐是一种重要的化工原料,硫酸钠又称元明粉、无水芒硝、无水皮硝,纯无水硫酸钠(Na2SO4)的熔点884℃、熔化潜热为172kJ/kg。而工业杂盐主要成分是氯化钠和硫酸钠的混合物,将其利用的环保效益重大。
工业固废铁尾矿是铁矿石开采后,经选矿厂洗选以后的废弃物,是工业固体废弃物的主要组成部分。目前,我国的尾矿综合利用率只有7%,堆存的铁尾矿量高达十几亿吨,占全部尾矿堆存总量的近1/3。因此,进行尾矿资源的综合回收与利用,不仅可以充分利用矿产资源,扩大矿产资源利用范围,也是治理污染、保护生态的重要手段,从而实现资源效益、经济效益、社会效益和环境效益的有效统一,其节能与环保意义同样重大。
发明内容
针对现有技术的不足,本发明的目的是:提供一种以固废为原料的高温相变蓄热陶瓷砖,利用工业杂盐和废弃的铁尾矿粉为主要原料,实现了工业固废的综合利用,且显热潜热量大,热传导性能好,可以最大程度储能蓄热;本发明还提供其制备方法,原材料与制作成本低,制备工艺简单可行,适合大规模工业生产与应用。
本发明所述的以固废为原料的高温相变蓄热陶瓷砖的制备方法,包括以下步骤:
(1)素坯原料混合:将铁尾矿粉和工业杂盐分别球磨、过筛,再在380-400℃温度下保温2-4h,得到预处理后的铁尾矿粉和工业杂盐;
将预处理后的铁尾矿粉、钠长石粉、石英砂粉、Cr2O3和/或铬铁矿粉进行干混,得到混合干料;将Al(H2PO4)3溶液和氢氧化铝粉进行湿混,硬化,得到混合湿料;然后将上述混合干料、混合湿料混合,并加入预处理后的工业杂盐,混合均匀后得到素坯浆料;
(2)微胶囊素坯制备:将素坯浆料经模压成型,然后干燥、烧结、冷却,得到微胶囊素坯;
(3)素坯封装:将电熔镁砂粉、Al(H2PO4)3溶液、钠长石粉、石英砂粉、无机硅胶溶液、粘结剂混合均匀,得到料浆悬浮液,喷涂或浸渍在微胶囊素坯表面,然后干燥、烧结、冷却,得到高温相变蓄热陶瓷砖。
本发明所采用的粉料粒度均在200-400目之间,优选为300目。
步骤(1)中,以质量份数计,各原料的用量如下:
铁尾矿粉100份,
工业杂盐70-90份,
Al(H2PO4)3溶液20-30份,
氢氧化铝粉4-8份,
钠长石粉5-10份,
石英砂粉5-10份,
Cr2O3和/或铬铁矿粉15-20份。
其中,在对铁尾矿粉和工业原盐进行预处理时,经球磨机干磨0.5-2h,过200-400目筛后,在380-400℃干燥箱内保温2-4h,以便去除铁尾矿粉、工业杂盐内含的自由水、结晶水、一些有机物杂质。
工业杂盐满足以下要求:NaCl含量30-70wt.%,Na2SO4含量30-70wt.%,Ca2+、Mg2+、TFe、F-杂质总含量≤1wt.%,有机质含量≤20wt.%,水分含量≤20wt.%。
铁尾矿粉满足以下要求:压滤后铁尾矿细度小于300目的含量≥40wt.%,SiO2含量30-60wt.%,CaO含量5-10wt.%,MgO含量4-10wt.%,Al2O3含量10-20wt.%,TFe含量≤6wt.%,其它杂质总含量20-40wt.%,水分含量≤20wt.%。
钠长石粉一种常见的长石矿物,钠长石的化学分子式为Na2O·Al2O3·6SiO2,其理论化学组成为:Na2O11.8%,Al2O319.4%,SiO268.8%。
石英砂粉的主要矿物成分是SiO2。
铬铁矿粉的主要成分为铁、镁和铬的氧化物。高温相变储能陶瓷材料在使用过程中,工业杂盐会频繁处于熔融状态,可能会分解产生氯气或氯化氢气体,加入的Cr2O3或铬铁矿粉起到酸性抑制剂的作用,防止产生过量的氯气或氯化氢气体。
Al(H2PO4)3溶液的浓度为40-60wt.%;无机硅胶溶液的浓度为30-40wt.%。
Al(H2PO4)3溶液的pH值≥2.0,浓度在40-60wt.%之间为宜,优选为50wt.%。本发明将Al(H2PO4)3溶液和氢氧化铝粉进行湿混时,可以加入适量水进行稀释,水的加入量优选为Al(H2PO4)3溶液质量的0.2-1倍。湿混后的得到混料pH值为中性,采用酸性的Al(H2PO4)3溶液(pH≥2.0)加入适量的氢氧化铝粉,可以加快微胶囊素坯的硬化时间,其中Al(H2PO4)3溶液pH≥2.0,过低的酸性会导致制成的微胶囊素坯强度过低。
步骤(1)中,将Al(H2PO4)3溶液和氢氧化铝粉进行湿混后,硬化4-6h。
步骤(2)中,模压成型时,将素坯浆料在4h之内压制成型;所采用的模具可以为标准试样模具、方形砖模具、孔型砖模具等;压力机操作时,加压次数3次,加压速度为“一轻、二重、慢提起”。
步骤(2)中,干燥时,在100-120℃保温3-4h,优选的,在0.5-1h时间内由室温匀速升至100-120℃。
步骤(2)中,烧结时,在740-760℃保温0.5-2h,优选的,在5-6h时间内匀速升至740-760℃。烧结时需要控制适宜的升温速率,若升温过快,素坯极易开裂。
步骤(2)中,冷却时,自然条件下冷却至室温。
步骤(3)中,以质量份数计,各原料的用量如下:
电熔镁砂粉100份,
Al(H2PO4)3溶液40-50份,
钠长石粉10-15份,
石英砂粉6-10份,
无机硅胶溶液10-16份,
粘结剂 10-16份。
其中,电熔镁砂粉为死烧细粉,选取电熔镁砂的目的,一是改善粘结性能;二是因为镁砂具有较高的导热系数,一般为40-60W·m-1·K-1,加入镁砂以后,能够明显增加成品陶瓷材料的导热性能。如果选择轻烧氧化镁(≤1350℃烧结),硬化速度过快,一般几秒内硬化,不易控制料浆和涂覆性能。
Al(H2PO4)3溶液的pH值≥2.0,浓度在40-60wt.%之间为宜,优选为50wt.%。
钠长石粉一种常见的长石矿物,钠长石的化学分子式为Na2O·Al2O3·6SiO2,其理论化学组成为:Na2O11.8%,Al2O319.4%,SiO268.8%。
石英砂粉的主要矿物成分是SiO2。
无机硅胶溶液的浓度为30-40wt.%,优选为35wt.%。无机硅胶平均孔径为2-3nm,比表面积为650-800m2/g,添加无机硅胶可以改善粘结性能。
粘结剂为羧甲基纤维素钠(CMC)、甲基纤维素、聚乙烯醇、聚丙烯酸中的一种或多种。粘结剂25℃粘度为10000-20000Pa·s。
步骤(3)中,当采用喷涂方式将料浆悬浮液喷涂在微胶囊素坯表面时,一般采用喷枪喷涂;当采用浸渍方式将料浆悬浮液浸渍在微胶囊素坯表面时,一般浸渍1-5s。
步骤(3)中,干燥时,在100-120℃保温3-4h,优选的,在0.5-1h时间内由室温匀速升至100-120℃。
步骤(3)中,烧结时,在820-850℃保温0.5-2h,优选的,在5-6h时间内匀速升至820-850℃。烧结时需要控制适宜的升温速率,要求不得高于120℃/h,若升温过快(大于200℃/h),封装层容易开裂。
步骤(3)中,冷却时,自然条件下冷却至室温。
本发明在微胶囊素坯烧结过程中,会有少量有机物或结晶水以气体的方式溢出,这是为了排除有机物和陶瓷胶囊内残存的结晶水,而最终制备的高温相变储能陶瓷材料,在今后的使用中,因为进行了封装,一些残存或工业杂盐融化产生的一些气体,因毛细管的作用,会依附在微胶囊内壁,并不会有气体溢出成品陶瓷砖外。
本发明还提供上述制备方法所制备的高温相变蓄热陶瓷砖,体积密度为2.0-2.2g/cm3(GB/T2997-2015),常温耐压强度≥7MPa(GB/T5072-2008),800℃×0.5h条件下高温抗折强度≥0.83MPa(GB/T3002-2017),导热系数≥40W·m-1·K-1。
盐酸盐的相变潜热大,发生相变时的温度变化小且易于控制,但在盐酸盐发生相变过程时会有大量的熔融盐产生,其流出会对容器和设备造成很强的腐蚀。氧化铝陶瓷材料本身具有高抗压强度和良好的致密度,且其耐高温和化学稳定性良好,其性质正好可以弥补熔融盐作为相变材料存在的缺陷。高温相变蓄热陶瓷砖由氧化铝陶瓷基体材料和盐酸盐相变材料复合而成,在进行高温烧结的过程中陶瓷材料表面会形成致密的微观网络结构,其产生的毛细作用力可以将在高温熔融盐吸附在氧化铝陶瓷基体内。
此外,在金属冶炼过程中的高温服役环境温度控制领域,封装后的高温相变储能材料具有蓄热性能且在蓄热过程中可以保持温度基本不变。将封装后的高温相变蓄热材料代替或者部分代替常规的普通耐火材料永久层,利用高温吸收的热量补充低温时所需的热量,可以起到一定的温控作用,使得整个冶炼过程处于相对平稳的温度环境。
与现有技术相比,本发明的有益效果如下:
(1)本发明利用工业杂盐和废弃的铁尾矿粉为主要原料制备陶瓷砖,原材料与制作成本低,实现了工业固废的综合利用,制得的陶瓷砖由氧化铝陶瓷基体材料和盐酸盐相变材料复合而成,其中盐酸盐的相变潜热大,发生相变时的温度变化小,从而使陶瓷砖可以以最大程度储能蓄热;
(2)本发明在陶瓷砖表面进行封装,外表面的陶瓷膜层封装材料耐强碱酸腐蚀性好,冷热循环过程中不开裂,延长了陶瓷砖的使用寿命;
(3)本发明制得的高温相变蓄热陶瓷砖,体积密度为2.0-2.2g/cm3,常温耐压强度≥5MPa,800℃×0.5h条件下高温抗折强度≥0.7MPa,导热系数≥40W·m-1·K-1,具有较高的常温耐压强度和优异的储能蓄热功能。
附图说明
图1为本发明实施例1所制备的高温相变蓄热陶瓷砖的微观形貌图;
图2为本发明实施例1所制备的高温相变蓄热陶瓷砖的差示扫描量热仪DSC测试图。
具体实施方式
下面结合实施例对本发明作进一步说明,实施例中所使用的原料,如无特别说明,均为市售常规原料;实施例中所使用的工艺方法,如无特别说明,均为本领域常规方法。
实施例中,所采用的工业杂盐满足以下要求:NaCl含量30-70wt.%,Na2SO4含量30-70wt.%,Ca2+、Mg2+、TFe、F-杂质总含量≤1wt.%,有机质含量≤20wt.%,水分含量≤20wt.%。
实施例中,所采用的铁尾矿粉满足以下要求:压滤后铁尾矿细度小于300目的含量≥40wt.%,SiO2含量30-60wt.%,CaO含量5-10wt.%,MgO含量4-10wt.%,Al2O3含量10-20wt.%,TFe含量≤6wt.%,其它杂质总含量20-40wt.%,水分含量≤20wt.%。
实施例中,所采用的粉料粒度均在200-400目之间。
实施例中,高温相变储能陶瓷材料的起始融化温度、起始凝固温度、融化相变焓、凝固相变焓采用差示扫描量热仪DSC测试,温度范围30-900℃,升温速率10℃/min;体积密度依据标准GB/T2997-2015进行测试,常温耐压强度依据标准GB/T5072-2008进行测试,800℃×0.5h条件下高温抗折强度依据标准GB/T3002-2017进行测试。
实施例1
一种高温相变蓄热陶瓷砖,制备方法如下:
(1)素坯原料混合:
将铁尾矿粉和工业杂盐分别经球磨机干磨1h,过300目筛,再在390℃温度下保温2h,得到预处理后的铁尾矿粉和工业杂盐;
称取以下质量份数的原料:预处理后的铁尾矿粉100份,预处理后的工业杂盐80份,Al(H2PO4)3溶液(浓度50wt.%)25份,氢氧化铝粉6份,钠长石粉8份,石英砂粉7份,Cr2O3粉18份;
将称取的预处理后的铁尾矿粉、钠长石粉、石英砂粉、Cr2O3粉进行干混,得到混合干料;
将称取的Al(H2PO4)3溶液加入其质量0.5倍的水稀释,并加入氢氧化铝粉混合,置于通风良好处,硬化5h,得到混合湿料;
将上述混合干料、混合湿料进行混合,再加入预处理后的工业杂盐,混合均匀后得到素坯浆料。
(2)微胶囊素坯制备:
采用标准试样模具(直径50mm,高50mm,依据GB/T5072-2008),将素坯浆料在压力机上半干压制成型,0.5h由室温匀速升至120℃,然后保温3h,进行干燥;6h由室温匀速升至750℃,然后保温1h,进行烧结;之后自然匀速冷却到室温,制得到微胶囊素坯。
(3)素坯封装:
称取以下质量份数的原料:电熔镁砂粉100份,Al(H2PO4)3溶液(浓度50wt.%)50份,钠长石粉12份,石英砂粉8份,无机硅胶溶液(浓度35wt.%)15份,羧甲基纤维素钠12份;
将上述原料混合均匀,得到料浆悬浮液,喷涂在微胶囊素坯表面,将喷涂料浆悬浮液后的微胶囊素坯0.5h由室温匀速升至120℃,然后保温3h,进行干燥;6h由室温匀速升至830℃,然后保温1h,进行烧结,之后自然匀速冷却到室温,制得高温相变蓄热陶瓷砖。
所制备的高温相变蓄热陶瓷砖的微观形貌图如图1所示,差示扫描量热仪DSC测试结果如图2所示。经测试,高温相变蓄热陶瓷砖的起始融化温度为624.3℃,融化相变焓为129.7J/g,起始凝固温度为617.0℃,凝固相变焓为127.1J/g,体积密度为2.02g/cm3,常温耐压强度7.0MPa,800℃×0.5h条件下高温抗折强度0.83MPa,导热系数41.5W·m-1·K-1。
实施例2
一种高温相变蓄热陶瓷砖,制备方法如下:
(1)素坯原料混合:
将铁尾矿粉和工业杂盐分别经球磨机干磨2h,过400目筛,再在380℃温度下保温4h,得到预处理后的铁尾矿粉和工业杂盐;
称取以下质量份数的原料:预处理后的铁尾矿粉100份,预处理后的工业杂盐70份,Al(H2PO4)3溶液(浓度40wt.%)30份,氢氧化铝粉8份,钠长石粉10份,石英砂粉5份,Cr2O3粉15份;
将称取的预处理后的铁尾矿粉、钠长石粉、石英砂粉、Cr2O3粉进行干混,得到混合干料;
将称取的Al(H2PO4)3溶液加入其质量0.5倍的水稀释,并加入氢氧化铝粉混合,置于通风良好处,硬化6h,得到混合湿料;
将上述混合干料、混合湿料进行混合,再加入预处理后的工业杂盐,混合均匀后得到素坯浆料。
(2)微胶囊素坯制备:
采用标准试样模具(200mm×53mm×35mm),将素坯浆料在160吨压力机上半干压制成型,1h由室温匀速升至100℃,然后保温4h,进行干燥;5h由室温匀速升至740℃,然后保温2h,进行烧结;之后自然匀速冷却到室温,制得到微胶囊素坯。
(3)素坯封装:
称取以下质量份数的原料:电熔镁砂粉100份,Al(H2PO4)3溶液(浓度40wt.%)50份,钠长石粉10份,石英砂粉10份,无机硅胶溶液(浓度40wt.%)10份,甲基纤维素16份;
将上述原料混合均匀,得到料浆悬浮液,喷涂在微胶囊素坯表面,将喷涂料浆悬浮液后的微胶囊素坯1h由室温匀速升至100℃,然后保温4h,进行干燥;5h由室温匀速升至820℃,然后保温2h,进行烧结,之后自然匀速冷却到室温,制得高温相变蓄热陶瓷砖。
经测试,高温相变蓄热陶瓷砖的起始融化温度为618.5℃,融化相变焓为125.4J/g,起始凝固温度为616.2℃,凝固相变焓为124.8J/g,体积密度为2.04g/cm3,常温耐压强度7.3MPa,800℃×0.5h条件下高温抗折强度0.84MPa,导热系数41.0W·m-1·K-1。
实施例3
一种高温相变蓄热陶瓷砖,制备方法如下:
(1)素坯原料混合:
将铁尾矿粉和工业杂盐分别经球磨机干磨0.5h,过200目筛,再在400℃温度下保温3h,得到预处理后的铁尾矿粉和工业杂盐;
称取以下质量份数的原料:预处理后的铁尾矿粉100份,预处理后的工业杂盐90份,Al(H2PO4)3溶液(浓度60wt.%)20份,氢氧化铝粉4份,钠长石粉5份,石英砂粉10份,铬铁矿粉18份;
将称取的预处理后的铁尾矿粉、钠长石粉、石英砂粉、铬铁矿粉进行干混,得到混合干料;
将称取的Al(H2PO4)3溶液加入其质量0.2倍的水稀释,并加入氢氧化铝粉混合,置于通风良好处,硬化4h,得到混合湿料;
将上述混合干料、混合湿料进行混合,再加入预处理后的工业杂盐,混合均匀后得到素坯浆料。
(2)微胶囊素坯制备:
采用标准试样模具(220mm×80mm×65mm),将素坯浆料在400吨压力机上半干压制成型,0.5h由室温匀速升至120℃,然后保温3h,进行干燥;6h由室温匀速升至760℃,然后保温0.5h,进行烧结;之后自然匀速冷却到室温,制得到微胶囊素坯。
(3)素坯封装:
称取以下质量份数的原料:电熔镁砂粉100份,Al(H2PO4)3溶液(浓度60wt.%)45份,钠长石粉12份,石英砂粉8份,无机硅胶溶液(浓度30wt.%)14份,聚丙烯酸13份;
将上述原料混合均匀,得到料浆悬浮液,喷涂在微胶囊素坯表面,将喷涂料浆悬浮液后的微胶囊素坯0.5h由室温匀速升至120℃,然后保温3h,进行干燥;6h由室温匀速升至850℃,然后保温0.5h,进行烧结,之后自然匀速冷却到室温,制得高温相变蓄热陶瓷砖。
经测试,高温相变蓄热陶瓷砖的起始融化温度为628.0℃,融化相变焓为130.2J/g,起始凝固温度为618.5℃,凝固相变焓为129.3J/g,体积密度为2.12g/cm3,常温耐压强度7.7MPa,800℃×0.5h条件下高温抗折强度0.86MPa,导热系数41.6W·m-1·K-1。
实施例4
一种高温相变蓄热陶瓷砖制备方法如下:
(1)素坯原料混合:
将铁尾矿粉和工业杂盐分别经球磨机干磨1h,过300目筛,再在390℃温度下保温2h,得到预处理后的铁尾矿粉和工业杂盐;
称取以下质量份数的原料:预处理后的100份,预处理后的工业杂盐85份,Al(H2PO4)3溶液(浓度50wt.%)25份,氢氧化铝粉5份,钠长石粉8份,石英砂粉8份,铬铁矿粉20份;
将称取的铁尾矿粉、钠长石粉、石英砂粉、铬铁矿粉进行干混,得到混合干料;
将称取的Al(H2PO4)3溶液加入其质量1倍的水稀释,并加入氢氧化铝粉混合,置于通风良好处,硬化5h,得到混合湿料;
将上述混合干料、混合湿料进行混合,再加入预处理后的工业杂盐,混合均匀后得到素坯浆料。
(2)微胶囊素坯制备:
采用标准试样模具(220mm×200mm×76mm,20孔型砖),将素坯浆料在400吨压力机上半干压制成型,0.5h由室温匀速升至120℃,然后保温3h,进行干燥;6h由室温匀速升至750℃,然后保温1h,进行烧结;之后自然匀速冷却到室温,制得到微胶囊素坯。
(3)素坯封装:
称取以下质量份数的原料:电熔镁砂粉100份,Al(H2PO4)3溶液(浓度50wt.%)40份,钠长石粉15份,石英砂粉6份,无机硅胶溶液(浓度35wt.%)16份,聚乙烯醇10份;
将上述原料混合均匀,得到料浆悬浮液,喷涂在微胶囊素坯表面,将喷涂料浆悬浮液后的微胶囊素坯0.5h由室温匀速升至120℃,然后保温3h,进行干燥;6h由室温匀速升至830℃,然后保温1h,进行烧结,之后自然匀速冷却到室温,制得高温相变蓄热陶瓷砖。
经测试,高温相变蓄热陶瓷砖的起始融化温度为624.7℃,融化相变焓为130.9J/g,起始凝固温度为617.4℃,凝固相变焓为128.8J/g,体积密度为2.14g/cm3,常温耐压强度7.8MPa,800℃×0.5h条件下高温抗折强度0.88MPa,导热系数40.8W·m-1·K-1。
Claims (4)
1.一种以固废为原料的高温相变蓄热陶瓷砖的制备方法,其特征在于:包括以下步骤:
(1)素坯原料混合:将铁尾矿粉和工业杂盐分别球磨、过筛,再在380-400℃温度下保温2-4h,得到预处理后的铁尾矿粉和工业杂盐;
将预处理后的铁尾矿粉、钠长石粉、石英砂粉、Cr2O3和/或铬铁矿粉进行干混,得到混合干料;将Al(H2PO4)3溶液和氢氧化铝粉进行湿混,硬化,得到混合湿料;然后将上述混合干料、混合湿料混合,并加入预处理后的工业杂盐,混合均匀后得到素坯浆料;
(2)微胶囊素坯制备:将素坯浆料经模压成型,然后干燥、烧结、冷却,得到微胶囊素坯;
(3)素坯封装:将电熔镁砂粉、Al(H2PO4)3溶液、钠长石粉、石英砂粉、无机硅胶溶液、粘结剂混合均匀,得到料浆悬浮液,喷涂或浸渍在微胶囊素坯表面,然后干燥、烧结、冷却,得到高温相变蓄热陶瓷砖;
步骤(1)中,以质量份数计,各原料的用量如下:铁尾矿粉100份,工业杂盐70-90份,Al(H2PO4)3溶液20-30份,氢氧化铝粉4-8份,钠长石粉5-10份,石英砂粉5-10份,Cr2O3和/或铬铁矿粉15-20份;
工业杂盐满足以下要求:NaCl含量30-70wt.%,Na2SO4含量30-70wt.%,Ca2+、Mg2+、TFe、F-杂质总含量≤1wt.%,有机质含量≤20wt.%,水分含量≤20wt.%,以上含量合计为100wt.%;
铁尾矿粉满足以下要求:SiO2含量30-60wt.%,CaO含量5-10wt.%,MgO含量4-10wt.%,Al2O3含量10-20wt.%,TFe含量≤6wt.%,其它杂质总含量20-40wt.%,水分含量≤20wt.%,以上含量合计为100wt.%;其中压滤后铁尾矿细度小于300目的含量≥40wt.%;
步骤(2)中,干燥时,在100-120℃保温3-4h,在0.5-1h时间内由室温匀速升至100-120℃;烧结时,在740-760℃保温0.5-2h,在5-6h时间内匀速升至740-760℃;
步骤(3)中,干燥时,在100-120℃保温3-4h,在0.5-1h时间内由室温匀速升至100-120℃;烧结时,在820-850℃保温0.5-2h,在5-6h时间内匀速升至820-850℃;
步骤(3)中,以质量份数计,各原料的用量如下:电熔镁砂粉100份,Al(H2PO4)3溶液40-50份,钠长石粉10-15份,石英砂粉6-10份,无机硅胶溶液10-16份,粘结剂10-16份。
2.根据权利要求1所述的以固废为原料的高温相变蓄热陶瓷砖的制备方法,其特征在于:Al(H2PO4)3溶液的浓度为40-60wt.%;无机硅胶溶液的浓度为30-40wt.%。
3.根据权利要求1所述的以固废为原料的高温相变蓄热陶瓷砖的制备方法,其特征在于:步骤(1)中,将Al(H2PO4)3溶液和氢氧化铝粉进行湿混后,硬化4-6h。
4.一种由权利要求1-3任一项所述的制备方法制备得到的高温相变蓄热陶瓷砖,其特征在于:体积密度为2.0-2.2g/cm3,常温耐压强度≥7MPa,800℃×0.5h条件下高温抗折强度≥0.83MPa,导热系数≥40W·m-1·K-1。
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