CN112604702B - 一种微波驱动型催化剂的制备方法及应用 - Google Patents
一种微波驱动型催化剂的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种微波驱动型催化剂的制备方法及应用。所述微波驱动型催化剂为在碳化硅泡沫陶瓷外表面烧结一层金属氧化物。其制备是先通过有机泡沫浸渍法采用高温烧结制备碳化硅泡沫陶瓷；再在碳化硅外表面低温烧结一层金属氧化物。本发明微波驱动型催化剂具有致密的微波吸收层和疏松的催化活性层。本发明微波驱动型催化剂可用于生物质热解、有机合成反应中。本发明微波驱动型催化剂应用于微波体系中可实现催化剂“原位吸波生热”和“催化转化”的协同，充分发挥微波加热特性，减缓催化剂结焦、提高催化效率及催化剂使用寿命。同时，本发明微波驱动型催化剂具有压降低的特点，适合工业化生产应用，可避免因催化压降大而导致的高能耗和安全问题。
Description
技术领域
本发明涉及催化剂领域，特别涉及一种微波驱动型催化剂的制备方法及应用。
背景技术
生物质热解技术是生物质转化，发展可再生能源的重要技术之一。催化剂的应用可以有效缓解生物油含氧量高、热值低、粘度大等问题。催化体系的引入可以有效提升生物油品质、减少气体中焦油含量，常用的催化剂包括分子筛催化剂、金属氧化物催化剂、金属盐催化剂，催化温度通常在400-600℃。分子筛催化剂，如ZSM-5，表现出了优异的芳构化和脱氧能力；金属氧化物催化剂，如CaO、MgO，表现出了良好的脱氧能力。目前，催化剂易钝化失活、使用寿命短，经济效益差仍是限制生物质广泛替代石油的瓶颈问题之一。因此如何提高催化体系的催化性能和使用寿命，对生物质热解转化制油、产气十分重要。多环芳烃是催化剂结焦钝化的重要前驱物，减少多环芳烃的产生或提高多环芳烃的降解显得十分重要。
微波加热具有即时性、整体性、选择性和高效性等优点。前期研究表明，微波应用于催化体系可以提高催化剂的催化活性。以ZSM-5为例，在微波体系下催化剂的脱氧和芳构化能力均得到增强。传统分子筛催化、金属氧化物催化剂均不具有微波吸收能力，一定程度上限制了微波加热在催化体系的应用。
发明内容
本发明提供了一种微波驱动型催化剂的制备方法，制备工艺简单，具有微波耦合能力，可实现催化剂“原位吸波生热”和“催化转化”的协同，充分发挥微波加热特性，减缓催化剂结焦、提高催化效率及催化剂使用寿命。
本发明是通过以下技术方案实现的。
本发明所述的一种微波驱动型催化剂的制备方法，按如下步骤。
(1)“核”体陶瓷浆料配制：SiC与TiC按比例混合后，低速球磨混合0.5-2小时制备陶瓷骨料。陶瓷骨料与磷酸二氢铝按照1:1-4:1进行混合并添加高岭土和去离子水配置浆料。浆料搅拌混匀后室温困料12-48小时。
(2)将聚胺酯泡沫切割成需要的形状大小后用8％-20％的氢氧化钠溶液浸泡揉搓1-3小时，洗净后再用0.5％-3％的羧甲基纤维素钠溶液浸渍0.5-3小时后备用。
(3)处理过后的聚胺酯泡沫浸入浆料中，通过辊压工艺除去多余浆料得到预制体。
(4)预制体在室温下干燥12-48小时，转入烘箱中在65℃下干燥8-24小时，最后空气中煅烧制得微波耦合“核”体材料。煅烧过程采用程序升温，首先以2℃/min从室温到200℃，随后以1℃/min从200℃升温至500℃并保持1小时，最后以2℃/min升至终温并保持2小时。
(5)“壳”体催化剂浆料配制：选用原料氢氧化钙、氧化镁、氧化铝、氧化铈和氧化锆中的一种或多种按照比例进行复配后在球磨机中低速混合0.5-2小时，记为复配原料1。以复配原料1为100份计，按照聚乙烯醇0.1-0.5份、羧甲基纤维素0.5-4.0份、碱性硅溶胶0.2-1.0份称取溶于一定量去离子水中，混合均匀后记为复配原料2。复配原料1和复配原料2混合，搅拌0.5-1.5小时制备得到“壳”体催化剂浆料。
(6)将烧制成型的“核”体材料浸入“壳”体催化剂浆料中，甩去多余浆料后室温干燥12-24小时。干燥后的胚体采用浆料喷淋法二次挂浆，甩去多余浆料后室温干燥12-24小时。同二次挂浆，可进行多次挂浆，直到胚体均匀挂浆。最后一次挂浆后室温干燥12-24小时，转入烘箱中65℃干燥8-24小时得到催化剂胚体。
(7)催化剂胚体煅烧：催化剂胚体煅烧采用程序升温，首先以2℃/min从室温到300℃，随后以1℃/min从300℃升温至500℃并保持1小时，最后以2℃/min升至终温并保持2小时。最终制得微波驱动型催化剂。
进一步地，所述步骤(1)中去离子水按浆料固含率为60-80％进行添加。
进一步地，所述步骤(4)中终温设定在1000-1500℃。
进一步地，所述步骤(5)中去离子水按浆料固含率为40-60％进行添加。
进一步地，所述步骤(7)中终温设定在800-1200℃。
本发明所述的一种微波驱动型催化剂，以具有微波吸收性能的SiC和TiC为“核”体材料，以具有催化性能的金属氧化物为“壳”体材料。“核”体采用高温烧结制成致密结构的微波耦合材料，“壳”体采用低温烧结制成疏松结构的催化材料。将微波驱动型催化剂应用于生物质热解的微波催化体系中，“核”体吸收微波迅速升温，带动催化剂整体迅速升温，生物质热解蒸汽通过时，即可实现快速催化提质。催化剂在微波场中形成的热点可以实现消碳反应，减少焦的沉积，提高催化效率及催化剂使用寿命。泡沫陶瓷的多孔结构可以降低催化压减，减少副反应发生，同时降低能耗、提高安全性能。本发明对生物质热解制油、产气的产业化运营具有重要的现实意义。
具体实施方式
本发明将通过以下实施例进一步说明，其仅用作对本发明的解释而并非限制。
实施例1
(1)称取40g SiC与40g TiC按比例混合后，低速球磨混合1小时制备陶瓷骨料。称取磷酸二氢铝40g、高岭土4g和去离子水41.33g配置浆料。浆料搅拌混匀后室温困料24小时。
(2)将聚胺酯泡沫切割成直径3厘米、厚度0.5厘米的圆柱体后用15％的氢氧化钠溶液浸泡揉搓2小时，洗净后再用1％的羧甲基纤维素钠溶液浸渍1小时后备用。
(3)处理过后的聚胺酯泡沫浸入浆料中，通过辊压工艺除去多余浆料得到预制体。
(4)预制体在室温下干燥24小时，转入烘箱中在65℃下干燥12小时，最后空气中煅烧制得微波耦合“核”体材料。煅烧过程采用程序升温，首先以2℃/min从室温到200℃，随后以1℃/min从200℃升温至500℃并保持1小时，最后以2℃/min升至终温并保持2小时。终温设定为1000℃。
(5)“壳”体催化剂浆料配制：称取94g氢氧化钙和6g氧化锆，低速球磨混合1小时，记为复配原料1。称取聚乙烯醇0.4g、羧甲基纤维素2g、碱性硅溶胶0.5g溶于102.9g去离子水1小时制备得到“壳”体催化剂浆料。
(6)将烧制成型的“核”体材料浸入“壳”体催化剂浆料中，甩去多余浆料后室温干燥12小时。干燥后的胚体采用浆料喷淋法二次挂浆，甩去多余浆料后室温干燥12小时。二次挂浆干燥后的胚体采用浆料喷淋法三次挂浆，甩去多余浆料后室温干燥24小时后，转入烘箱中65℃干燥18小时得到催化剂胚体。
(7)催化剂胚体煅烧：催化剂胚体煅烧采用程序升温，首先以2℃/min从室温到300℃，随后以1℃/min从300℃升温至500℃并保持1小时，最后以2℃/min升至终温并保持2小时。终温设定在1100℃。最终制得微波驱动型催化剂。
本实施例中，称取50g微波驱动型催化剂装填在催化管中，采用微波加热，催化温度设置为400℃。以200g皂脚为原料，热解温度为550℃，热解蒸汽经催化管催化后冷凝收集生物油。取生物油样分析，生物油中烃含量89.23％，单环芳烃含量为60.24％。
实施例2
(1)称取60g SiC与20g TiC按比例混合后，低速球磨混合1小时制备陶瓷骨料。称取磷酸二氢铝40g、高岭土4g和去离子水41.33g配置浆料。浆料搅拌混匀后室温困料24小时。
(2)将聚胺酯泡沫切割成直径3厘米、厚度0.5厘米的圆柱体后用15％的氢氧化钠溶液浸泡揉搓2小时，洗净后再用1％的羧甲基纤维素钠溶液浸渍1小时后备用。
(3)处理过后的聚胺酯泡沫浸入浆料中，通过辊压工艺除去多余浆料得到预制体。
(4)预制体在室温下干燥24小时，转入烘箱中在65℃下干燥12小时，最后空气中煅烧制得微波耦合“核”体材料。煅烧过程采用程序升温，首先以2℃/min从室温到200℃，随后以1℃/min从200℃升温至500℃并保持1小时，最后以2℃/min升至终温并保持2小时。终温设定为1200℃。
(5)“壳”体催化剂浆料配制：称取90g氢氧化钙和10g氧化锆，低速球磨混合1小时，记为复配原料1。称取聚乙烯醇0.4g、羧甲基纤维素2g、碱性硅溶胶0.5g溶于102.9g去离子水1小时制备得到“壳”体催化剂浆料。
(6)将烧制成型的“核”体材料浸入“壳”体催化剂浆料中，甩去多余浆料后室温干燥12小时。干燥后的胚体采用浆料喷淋法二次挂浆，甩去多余浆料后室温干燥12小时。二次挂浆干燥后的胚体采用浆料喷淋法三次挂浆，甩去多余浆料后室温干燥24小时后，转入烘箱中65℃干燥18小时得到催化剂胚体。
(7)催化剂胚体煅烧：催化剂胚体煅烧采用程序升温，首先以2℃/min从室温到300℃，随后以1℃/min从300℃升温至500℃并保持1小时，最后以2℃/min升至终温并保持2小时。终温设定在1000℃。最终制得微波驱动型催化剂。
本实施例中，称取50g微波驱动型催化剂装填在催化管中，采用微波加热，催化温度设置为400℃。以200g皂脚为原料，热解温度为550℃，热解蒸汽经催化管催化后冷凝收集生物油。取生物油样分析，生物油中烃含量90.47％，单环芳烃含量为61.37％。
实施例3
(1)称取60g SiC与20g TiC按比例混合后，低速球磨混合1小时制备陶瓷骨料。称取磷酸二氢铝40g、高岭土4g和去离子水41.33g配置浆料。浆料搅拌混匀后室温困料24小时。
(2)将聚胺酯泡沫切割成直径3厘米、厚度0.5厘米的圆柱体后用15％的氢氧化钠溶液浸泡揉搓2小时，洗净后再用1％的羧甲基纤维素钠溶液浸渍1小时后备用。
(3)处理过后的聚胺酯泡沫浸入浆料中，通过辊压工艺除去多余浆料得到预制体。
(4)预制体在室温下干燥24小时，转入烘箱中在65℃下干燥12小时，最后空气中煅烧制得微波耦合“核”体材料。煅烧过程采用程序升温，首先以2℃/min从室温到200℃，随后以1℃/min从200℃升温至500℃并保持1小时，最后以2℃/min升至终温并保持2小时。终温设定为1200℃。
(5)“壳”体催化剂浆料配制：称取80g氢氧化钙、10g氧化镁和10g氧化锆，低速球磨混合1小时，记为复配原料1。称取聚乙烯醇0.4g、羧甲基纤维素2g、碱性硅溶胶0.5g溶于102.9g去离子水1小时制备得到“壳”体催化剂浆料。
(6)将烧制成型的“核”体材料浸入“壳”体催化剂浆料中，甩去多余浆料后室温干燥12小时。干燥后的胚体采用浆料喷淋法二次挂浆，甩去多余浆料后室温干燥12小时。二次挂浆干燥后的胚体采用浆料喷淋法三次挂浆，甩去多余浆料后室温干燥24小时后，转入烘箱中65℃干燥18小时得到催化剂胚体。
(7)催化剂胚体煅烧：催化剂胚体煅烧采用程序升温，首先以2℃/min从室温到300℃，随后以1℃/min从300℃升温至500℃并保持1小时，最后以2℃/min升至终温并保持2小时。终温设定在1000℃。最终制得微波驱动型催化剂。
本实施例中，称取50g微波驱动型催化剂装填在催化管中，采用微波加热，催化温度设置为400℃。以200g皂脚为原料，热解温度为550℃，热解蒸汽经催化管催化后冷凝收集生物油。催化管冷却后，再次称取200g皂脚为原料，热解温度为550℃，热解蒸汽经催化管催化后冷凝收集生物油，共进行10次热解。对十次生物油分别取样分析，生物油中烃含量从第一次到第十次依次为88.93％、88.29％、87.69％、86.47％、87.26％、87.64％、86.31％、86.46％、87.06％、85.43％，单环芳烃含量从第一次到第十次依次为60.87％、59.36％、58.37％、58.96％、57.41％、58.19％、57.32％、58.51％、57.94％、57.34％。
以上所述仅表达了本发明的优选实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形、改进及替代，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。
Claims (5)
1.一种微波驱动型催化剂的制备方法，其特征在于先采用有机泡沫浸渍法通过高温烧结制备微波耦合“核”体材料，再采用浸渍法通过低温烧结制备具有催化活性的“壳”体材料，“核”体材料为具有微波吸收性能的SiC和TiC；
具体包括以下步骤：
（1）“核”体陶瓷浆料配制：SiC与TiC按比例混合后，低速球磨混合0.5-2小时制备陶瓷骨料；陶瓷骨料与磷酸二氢铝按照1:1-4:1进行混合并添加高岭土和去离子水配置浆料；浆料搅拌混匀后室温困料12-48小时；
（2）将聚氨酯泡沫切割成需要的形状大小后用8%-20%的氢氧化钠溶液浸泡揉搓1-3小时，洗净后再用0.5%-3%的羧甲基纤维素钠溶液浸渍0.5-3小时后备用；
（3）处理过后的聚氨 酯泡沫浸入浆料中，通过辊压工艺除去多余浆料得到预制体；
（4）预制体在室温下干燥12-48小时，转入烘箱中在65℃下干燥8-24小时，最后空气中煅烧制得微波耦合“核”体材料；煅烧过程采用程序升温，首先以2℃/min从室温到200℃，随后以1℃/min从200℃升温至500℃并保持1小时，最后以2℃/min升至终温1000-1500℃并保持2小时；
（5）“壳”体催化剂浆料配制：选用原料氢氧化钙、氧化镁、氧化铝、氧化铈和氧化锆中的一种或多种按照比例进行复配后在球磨机中低速混合0.5-2小时，记为复配原料1；以复配原料1为100份计，按照聚乙烯醇0.1-0.5份、羧甲基纤维素0.5-4.0份、碱性硅溶胶0.2-1.0份称取溶于一定量去离子水中，混合均匀后记为复配原料2；复配原料1和复配原料2混合，搅拌0.5-1.5小时制备得到“壳”体催化剂浆料；
（6）将烧制成型的“核”体材料浸入“壳”体催化剂浆料中，甩去多余浆料后室温干燥12-24小时；干燥后的胚体采用浆料喷淋法二次挂浆，甩去多余浆料后室温干燥12-24小时；同二次挂浆，可进行多次挂浆，直到胚体均匀挂浆；最后一次挂浆后室温干燥12-24小时，转入烘箱中65℃干燥8-24小时得到催化剂胚体；
（7）催化剂胚体煅烧：催化剂胚体煅烧采用程序升温，首先以2℃/min从室温到300℃，随后以1℃/min从300℃升温至500℃并保持1小时，最后以2℃/min升至终温800-1200℃并保持2小时；最终制得微波驱动型催化剂。
2.根据权利要求1所述的一种微波驱动型催化剂的制备方法，其特征在于，所述步骤（1）中去离子水按浆料固含率为60-80%进行添加。
3.根据权利要求1所述的一种微波驱动型催化剂的制备方法，其特征在于，所述步骤（5）中去离子水按浆料固含率为40-60%进行添加。
4.如权利要求1-3任一所述的制备方法得到的微波驱动型催化剂。
5.如权利要求1-3任一所述的制备方法得到的微波驱动型催化剂于生物质热解中的应用。
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| CN102872892A (zh) * | 2012-10-24 | 2013-01-16 | 浙江大学苏州工业技术研究院 | 一种泡沫陶瓷基光催化组件及其制备方法 |
| CN106635110A (zh) * | 2016-10-27 | 2017-05-10 | 陕西科技大学 | 一种农林废弃物微波催化热裂解制备富含酚类、醇类液体产物的方法 |
| CN109665821A (zh) * | 2019-01-02 | 2019-04-23 | 广东工业大学 | 一种用于催化剂载体的泡沫陶瓷及其制备方法和应用 |
| CN109796999A (zh) * | 2019-01-31 | 2019-05-24 | 盐城工学院 | 一种生物质催化热解方法 |
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