CN106478134A - 耐高温低温合成块状尖晶石气凝胶材料的制备方法 - Google Patents
耐高温低温合成块状尖晶石气凝胶材料的制备方法 Download PDFInfo
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- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
本发明涉及一种耐高温低温合成块状尖晶石气凝胶材料的制备方法。通过将镁源和铝源进行混合，经水解反应后，引入促凝剂环氧化物，经溶胶‑凝胶、老化和超临界干燥得到尖晶石气凝胶前驱体，然后在马弗炉下进行空气热煅烧，从而最终制备出一种耐高温低温合成块状尖晶石气凝胶材料。本发明具有用料简单和工艺简捷的优点，同时能耗低，工艺过程操作简单，容易实现规模生产。
Description
技术领域
本发明属于气凝胶材料的制备工艺领域，具体涉及一种耐高温低温合成块状尖晶石气凝胶材料的制备方法。
背景技术
镁铝尖晶石(MgAl2O4)是一种具备特殊性能的氧化物材料，具有良好的抗侵蚀，腐蚀、剥落能力强，抗渣性能好，抗磨蚀能力，热震稳定性好，同时又具备耐高温、光催化性能优异、光学性能优异等特点，可以广泛应用于光催化、电化学、耐火材料、钢铁冶炼、水泥回转窑、流变及化学工业等领域。其中，制备高纯度、高化学均匀性、粒度均、孔径分布一致的尖晶石纳米材料已经引起了科研人员的极大兴趣。当前制备尖晶石材料主要有固相法和湿化学方法，其中传统的固相法需要更高的热处理温度、更长的反应时间，能耗较高，并且晶粒尺寸很容易长大。而湿化学方法主要包括共沉淀法、喷涂法、冷冻干燥法、水热法、乳液法、溶胶-凝胶法等等。其中溶胶-凝胶法由于反应温度低、制备的材料纯度高，比表面积大，孔径分布集中，因此被广泛使用。
气凝胶作为一种具备三维纳米多孔结构的轻质多孔材料，具有低密度、高比表面积、高孔隙率等特点，在吸附、催化、隔热和阻抗耦合等方面具备广阔的应用前景。如能将尖晶石材料制备成多孔气凝胶结构，将会进一步提高尖晶石材料的相关性能，诸如耐温性能、比表面积、孔径分布及光催化性能。当前有关于尖晶石介孔材料和纳米晶的研究报道，但是并没有关于合成尖晶石气凝胶材料的相关文献，因此本专利中采用溶胶凝胶法结合超临界干燥工艺和热处理低温合成尖晶石气凝胶材料将为该材料在光催化、电化学、耐火材料、钢铁冶炼、高温气体过滤器、膜分离、流变化学工业等领域的应用提供强大的物质基础。
发明内容
本发明的目的是为了改进现有技术存在的不足而提供一种耐高温低温合成块状尖晶石气凝胶材料的制备方法，该方法用料和工艺简单，结构可控，能耗低，制备出的气凝胶材料具备低密度、高比表、抗氧化、耐高温等特性，对实现气凝胶材料在光催化、电化学、耐火材料、钢铁冶炼、水泥回转窑、流变及化学工业等领域的应用具备积极的生产意义。
本发明的技术方案为：耐高温高比表块状尖晶石气凝胶材料的制备方法，其具体步骤如下：
(1)将镁源、铝源、水、乙醇均匀混合后，在20～50℃的温度下均匀搅拌后，得到水解的镁铝二元溶胶体系；
(2)将环氧化物加入到步骤(1)中得到的二元溶胶体系中，在20～40℃的温度下均匀搅拌倒入模具中反应至凝胶，放置15～30h；
(3)将步骤(2)中加入老化液，在30～60℃的烘箱内进行置换3～6次，每次12～24h；
(4)将步骤(3)中得到的湿凝胶进行超临界干燥处理，得到镁铝尖晶石气凝胶前驱体；
(5)将步骤(4)中得到的复合气凝胶在马弗炉的空气氛围下进行空气热处理，最终得到尖晶石气凝胶；
其中：步骤(1)中的镁源、铝源、水、乙醇按照1：(1～4)：(70～120)：(15～45)的摩尔比均匀混合；步骤(2)中的环氧化物与镁源按照摩尔比(8～16)：1进行混合。
优选步骤(1)中所述的铝源为六水合氯化铝、九水合硝酸铝、仲丁醇铝或异丙醇铝中的一种或几种。优选步骤(1)中所述的镁源为六水合氯化镁、九水合硝酸镁、二水合硝酸镁、七水合硫酸镁或一水合硫酸镁中的一种或几种。
优选步骤(2)中所述的环氧化物为环氧丙烷、顺式-2,3环氧丁烷、氧杂环丁烷或环氧丙醇中的一种或几种。
优选步骤(1)中的搅拌速度为400～600rpm，搅拌时间为0.5～4h；步骤(2)中的搅拌速度为400～600rpm，搅拌时间为0.1～1h；步骤(2)中的置换次数为3～6次，每次置换时间为12～24h。
优选步骤(3)中所述的老化液为乙醇、甲醇、丙酮、乙醚、正戊醇或异丙醇中的一种或几种。
优选步骤(5)中所述的干燥方法为乙醇或二氧化碳超临界干燥法：乙醇超临界干燥时，反应温度为250～270℃，高压反应釜内压强为8～17MPa，干燥时间为1～8h；二氧化碳超临界干燥时，反应温度为50～70℃，高压反应釜内压强为8～12MPa，放气速率为5～10L/min，干燥时间为8～15h。
优选步骤(5)中所述的空气热处理温度在400～1200℃之间；升温速度为2-8℃/min，热处理保温时间为2～5h。
有益效果：
(1)工艺简单，低温合成，能耗低。采用一步溶胶-凝胶法，同时引入铝源和镁源，并通过后续的超临界干燥和热处理过程，使铝源和镁源在400℃的温度下即可反应生成尖晶石相。
(2)制备的材料耐温性能优越，孔隙率高，比表面积大，颗粒均匀，尺寸小，1200℃处理两小时后尺寸仅为10nm左右。
(3)本方法中制备的尖晶石气凝胶材料为完整块状，客服了传统氧化镁气凝胶成块性弱的问题，这对于实现气凝胶材料在催化剂载体、高温气体过滤器、膜分离、传感器等领域的应用具备积极的意义。
附图说明
图1是实例1制得的耐高温低温合成块状尖晶石气凝胶材料的实物照片；
图2是实例2中尖晶石气凝胶在不同热处理温度下的XRD衍射图；其中图中◆、●和▼分别代表的是镁铝尖晶石相、勃姆石相和镁铝羟基水合物相。
具体实施方式
实例1
将六水合氯化镁、六水合氯化铝、水、乙醇按照摩尔比1:2:80:30均匀混合后，在20℃的温度、转速400rpm下均匀搅拌4h，得到部分水解的镁铝二元溶胶体系。然后将环氧丙烷按与六水合氯化镁摩尔比为10:1加入到上述得到的二元溶胶体系中，在20℃的温度、转速400rpm下均匀搅拌0.1h后倒入模具中反应至凝胶，放置15h后加入乙醇老化液，在30℃的烘箱内进行置换3次，每次24h。然后将该湿凝胶进行乙醇超临界干燥，其中反应温度为260℃，高压反应釜内压强为8MPa，干燥时间为8h，从而得到尖晶石气凝胶前驱体。最后将该前驱体气凝胶在马弗炉的空气氛围下进行热处理，其中煅烧温度为400℃，升温速度为2℃/min，热处理时间为5h，从而得到最终的尖晶石气凝胶材料。经过表征发现，该块状尖晶石气凝胶材料的密度为0.08g/cm3，800℃热处理2小时后比表面积为150m2/g，晶粒尺寸为8nm。制得的耐高温低温合成块状尖晶石气凝胶材料的实物照片如图1所示，从图1可以看出，制得的尖晶石气凝胶呈现乳白色，虽然强度较差，但是质轻，孔隙率高，比表面积大。
实例2
将九水合硝酸镁、九水合硝酸铝、水、乙醇按照摩尔比1:1.5:100:40均匀混合后，在40℃的温度、转速500rpm下均匀搅拌1h，得到部分水解的镁铝二元溶胶体系。然后将顺式-2,3环氧丁烷按与六水合氯化镁摩尔比为8:1加入到上述得到的二元溶胶体系中，在40℃的温度、转速500rpm下均匀继续搅拌0.5h后倒入模具中反应至凝胶，放置20h后加入丙酮老化液，在50℃的烘箱内进行置换4次，每次12h。然后将该湿凝胶进行乙醇超临界干燥，其中反应温度为250℃，高压反应釜内压强为10MPa，干燥时间为2h，从而得到尖晶石气凝胶前驱体。最后将该前驱体气凝胶在马弗炉的空气氛围下进行不同温度热处理，升温速度为5℃/min，热处理时间为2h，从而得到最终的尖晶石气凝胶材料。经过表征发现，该块状尖晶石气凝胶材料的密度为0.12g/cm3，700℃热处理2小时后比表面积为163m2/g，晶粒尺寸为8.5nm。所制得的尖晶石气凝胶在不同热处理温度下的XRD衍射图如图2所示，从图中可以看出，对于超临界干燥之后的样品，只含有镁铝羟基水合物和勃姆石两种晶相，并且勃姆石呈现非晶态，而镁铝羟基水合物的结晶度较高。当热处理温度增加到400℃时，结构中慢慢产生了尖晶石相，而当热处理温度到达600℃时，尖晶石相已经较为明显，当热处理温度为1200℃时，晶型完整，晶粒尺度经谢乐公式计算为10nm左右。
实例3
将九水合硝酸镁、六水合氯化铝、水、乙醇按照摩尔比1:3:100:20均匀混合后，在35℃的温度、转速400rpm下均匀搅拌4h，得到部分水解的镁铝二元溶胶体系。然后将环氧丙烷按与九水合硝酸镁摩尔比为12:1加入到上述得到的二元溶胶体系中，在35℃的温度、转速400rpm下均匀搅拌1h后倒入模具中反应至凝胶，放置30h后加入乙醇老化液，在40℃的烘箱内进行置换5次，每次24h。然后将该湿凝胶进行二氧化碳超临界干燥，其中反应温度为50℃，高压反应釜内压强为8MPa，放气速率为5L/min，干燥时间为8h，从而得到尖晶石气凝胶前驱体。最后将该前驱体气凝胶在马弗炉的空气氛围下进行热处理，其中煅烧温度为900℃，升温速度为3℃/min，热处理时间为3h，从而得到最终的尖晶石气凝胶材料。经过表征发现，该块状尖晶石气凝胶材料的密度为0.08g/cm3，800℃热处理2小时后比表面积为134m2/g，晶粒尺寸为9.3nm。
实例4
将二水合硝酸镁、六水合氯化铝、水、乙醇按照摩尔比1:2:110:45均匀混合后，在35℃的温度、转速600rpm下均匀搅拌2h，得到部分水解的镁铝二元溶胶体系。然后将环氧丙醇按与二水合硝酸镁摩尔比为10:1加入到上述得到的二元溶胶体系中，在20℃的温度、转速600rpm下均匀搅拌0.1h后倒入模具中反应至凝胶，放置15h后加入乙醚老化液，在30℃的烘箱内进行置换6次，每次24h。然后将该湿凝胶进行乙醇超临界干燥，其中反应温度为270℃，高压反应釜内压强为15MPa，干燥时间为5h，从而得到尖晶石气凝胶前驱体。最后将该前驱体气凝胶在马弗炉的空气氛围下进行热处理，其中煅烧温度为1000℃，升温速度为5℃/min，热处理时间为2h，从而得到最终的尖晶石气凝胶材料。经过表征发现，该块状尖晶石气凝胶材料的密度为0.13g/cm3，1000℃热处理2小时后比表面积为100m2/g，晶粒尺寸为9.6nm。
实例5
将六水合氯化镁、九水合硝酸铝、水、乙醇按照摩尔比1:4:120:30均匀混合后，在40℃的温度、转速550rpm下均匀搅拌2h，得到部分水解的镁铝二元溶胶体系。然后将环氧丙烷按与六水合氯化镁摩尔比为16:1加入到上述得到的二元溶胶体系中，在40℃的温度、转速550rpm下均匀搅拌0.2h后倒入模具中反应至凝胶，放置20h后加入正戊醇老化液，在45℃的烘箱内进行置换5次，每次24h。然后将该湿凝胶进行二氧化碳超临界干燥，其中反应温度为70℃，高压反应釜内压强为12MPa，放气速率为10L/min，干燥时间为15h，从而得到尖晶石气凝胶前驱体。最后将该前驱体气凝胶在马弗炉的空气氛围下进行热处理，其中煅烧温度为1200℃，升温速度为8℃/min，热处理时间为5h，从而得到最终的尖晶石气凝胶材料。经过表征发现，该块状尖晶石气凝胶材料的密度为0.25g/cm3，1200℃热处理2小时后比表面积为81m2/g，晶粒尺寸为12nm。
Claims (8)
1.耐高温低温合成块状尖晶石气凝胶材料的制备方法，其具体步骤如下：
(1)将镁源、铝源、水、乙醇均匀混合后，在20～50℃的温度下均匀搅拌后，得到水解的镁铝二元溶胶体系；
(2)将环氧化物加入到步骤(1)中得到的二元溶胶体系中，在20～40℃的温度下均匀搅拌倒入模具中反应至凝胶，放置15～30h；
(3)将步骤(2)中加入老化液，在30～60℃的烘箱内进行置换3～6次，每次12～24h；
(4)将步骤(3)中得到的湿凝胶进行超临界干燥处理，得到镁铝尖晶石气凝胶前驱体；
(5)将步骤(4)中得到的复合气凝胶在马弗炉的空气氛围下进行空气热处理，最终得到尖晶石气凝胶；
其中：步骤(1)中的镁源、铝源、水、乙醇按照1：(1～4)：(70～120)：(15～45)的摩尔比均匀混合；步骤(2)中的环氧化物与镁源按照摩尔比(8～16)：1进行混合。
2.根据权利要求1所述的制备方法，其特征在于步骤(1)中所述的铝源为六水合氯化铝、九水合硝酸铝、仲丁醇铝或异丙醇铝中的一种或几种。
3.根据权利要求1所述的制备方法，其特征在于步骤(1)中所述的镁源为六水合氯化镁、九水合硝酸镁、二水合硝酸镁、七水合硫酸镁或一水合硫酸镁中的一种或几种。
4.根据权利要求1所述的制备方法，其特征在于步骤(2)中所述的环氧化物为环氧丙烷、顺式-2,3环氧丁烷、氧杂环丁烷或环氧丙醇中的一种或几种。
5.根据权利要求1所述的制备方法，其特征在于步骤(1)中的搅拌速度为400～600rpm，搅拌时间为0.5～4h；步骤(2)中的搅拌速度为400～600rpm，搅拌时间为0.1～1h；步骤(2)中的置换次数为3～6次，每次置换时间为12～24h。
6.根据权利要求1所述的制备方法，其特征在于步骤(3)中所述的老化液为乙醇、甲醇、丙酮、乙醚、正戊醇或异丙醇中的一种或几种。
7.根据权利要求1所述的制备方法，其特征在于步骤(5)中所述的干燥方法为乙醇或二氧化碳超临界干燥法：乙醇超临界干燥时，反应温度为250～270℃，高压反应釜内压强为8～17MPa，干燥时间为1～8h；二氧化碳超临界干燥时，反应温度为50～70℃，高压反应釜内压强为8～12MPa，放气速率为5～10L/min，干燥时间为8～15h。
8.根据权利要求1所述的制备方法，其特征在于步骤(5)中所述的空气热处理温度在400～1200℃之间；升温速度为2-8℃/min，热处理保温时间为2～5h。
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