CN112608134B - 一种多孔陶瓷球催化剂的制备方法及应用 - Google Patents

一种多孔陶瓷球催化剂的制备方法及应用 Download PDF

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CN112608134B
CN112608134B CN202011434602.XA CN202011434602A CN112608134B CN 112608134 B CN112608134 B CN 112608134B CN 202011434602 A CN202011434602 A CN 202011434602A CN 112608134 B CN112608134 B CN 112608134B
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porous ceramic
temperature
ceramic ball
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catalyst
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CN112608134A (zh
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吴秋浩
王允圃
彭渝洁
杨琦
徐佳敏
刘玉环
李薇
李志�
柯林垚
马晨露
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Nanchang University
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Abstract

本发明公开了一种多孔陶瓷球催化剂的制备方法及应用。所述多孔陶瓷球催化剂为以金属氧化物为骨架材料，表面可负载包括金属氧化物和贵金属在内的多种具有催化活性的物质。其制备是先通过发泡法采用高温烧结制备多孔陶瓷球基体；再采用浸渍法在多孔陶瓷球基体表面负载具有催化活性的物质。本发明多孔陶瓷球催化剂具有强度高、孔隙结构丰富、比表面积大的基体，拥有高性能的催化活性位点。本发明的多孔陶瓷球催化剂可用于生物质热解、有机合成反应中。本发明多孔陶瓷球催化剂具有耐高温、机械强度高、催化压降低的特点，适合工业化生产应用，可避免因机械强度低导致催化剂破碎污染产物及催化压降大而导致的高能耗和安全问题。

Description

一种多孔陶瓷球催化剂的制备方法及应用
技术领域
本发明涉及多孔陶瓷球领域，特别涉及多孔陶瓷球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。现有研究表明金属氧化物在生物质热解中表现出良好的脱氧效果，但存在易失活、机械强度低、易破碎等问题。
陶瓷具有机械强度高、耐高温等优点。已有的多孔陶瓷包括闭孔陶瓷用于隔热、隔音和轻质结构部件，开孔陶瓷用于催化剂、过滤器、生物反应器和骨替代物的载体等。应用于催化剂载体的主要包括除氮硫化合物，如空气净化、尾气处理等，应用于有机反应的陶瓷催化剂还较少。
发明内容
本发明提供了一种多孔陶瓷球催化剂的制备方法，制备工艺简单，机械强度高、孔隙结构丰富、催化压降低，适合工业化生产应用。
本发明是通过以下技术方案实现的。
本发明所述的一种多孔陶瓷球催化剂的制备方法，按如下步骤。
(1)多孔陶瓷球载体浆料配制：选用氢氧化钙、碳酸钙、碳酸镁、氧化锆、氧化铝、氧化铈中的一种或多种按比例混合后，低速球磨混合0.5-2小时制备陶瓷骨料。将生物质颗粒和聚氨酯泡沫按比例混合后进行破碎筛分制得发泡剂。以陶瓷骨料为100份计，加入发泡剂6-12份、助溶剂3-6份、高温粘结剂2-6份、低温粘结剂0.5-2份制备浆料。
(2)将制备好的浆料进行造粒成球，室温风干12-36小时，随后采用烘箱105℃烘干12-36小时。
(3)烘干处理后的胚体进行高温煅烧。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，随炉冷却后即可得到多孔陶瓷球基体。
(4)选用氢氧化钙、氢氧化锆、氢氧化镁、硫酸铝中的一种配制悬浊液或溶液，浓度设置在0.1-1mol/L。
(5)将多孔陶瓷球浸渍在悬浊液或溶液中，在磁力搅拌器下低速搅拌6-24小时，浸渍后的陶瓷球室温干燥6-12小时后转入烘箱以105℃继续干燥6-12小时。
(6)干燥后的陶瓷球放入马弗炉中煅烧。煅烧过程采用程序升温，以2℃/min从室温升至终温并保持2-4小时，随炉冷却后即可得到多孔陶瓷球催化剂。
进一步地，所述步骤(1)中的助溶剂为硼酸锌、高温粘结剂为30％硅溶胶、低温粘结剂为羧甲基纤维素。
进一步地，所述步骤(1)中的生物质颗粒和聚氨酯泡沫质量比为10:1。
进一步地，所述步骤(3)的煅烧终温设定在1000-1500℃。
进一步地，所述步骤(6)的煅烧终温设定在500-800℃。
本发明所述的一种多孔陶瓷球催化剂，以金属氧化物为骨架材料，表面可负载包括金属氧化物和贵金属在内的多种具有催化活性的物质。本发明多孔陶瓷球催化剂具有强度高、孔隙结构丰富、比表面积大的基体，拥有高性能的催化活性位点。应用于生物质热解、有机合成反应中，可避免因机械强度低导致催化剂破碎污染产物及催化压降大而导致的高能耗和安全问题，适合工业化生产应用。
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)多孔陶瓷球载体浆料配制：氢氧化钙、碳酸钙、碳酸镁、氧化锆、氧化铝、氧化铈按2:0:10:0:0:1的比例混合后，低速球磨混合0.5小时制备陶瓷骨料。将生物质颗粒和聚氨酯泡沫按10:1比例混合后进行破碎筛分制得发泡剂。以陶瓷骨料为100份计，加入发泡剂6份、助溶剂3份、高温粘结剂3份、低温粘结剂1份制备浆料。其中助溶剂为硼酸锌、高温粘结剂为30％硅溶胶、低温粘结剂为羧甲基纤维素。
(2)将制备好的浆料进行造粒成球，室温风干24小时，随后采用烘箱105℃烘干24小时。
(3)烘干处理后的胚体进行高温煅烧。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1000℃并保持2小时，随炉冷却后即可得到多孔陶瓷球基体。
(4)配制硫酸铝溶液，浓度为0.2mol/L。
(5)将多孔陶瓷球浸渍在溶液中，在磁力搅拌器下低速搅拌8小时，浸渍后的陶瓷球室温干燥6小时后转入烘箱以105℃继续干燥6小时。
(6)干燥后的陶瓷球放入马弗炉中煅烧。煅烧过程采用程序升温，以2℃/min从室温升至800℃并保持4小时，随炉冷却后即可得到多孔陶瓷球催化剂。
本实施例中，称取50g多孔陶瓷球催化剂装填在催化管中，催化温度设置为500℃。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。生物油产率为52.16wt.％，取生物油样分析，生物油中烃含量87.23％，单环芳烃含量为39.51％。
实施例2
(1)多孔陶瓷球载体浆料配制：氢氧化钙、碳酸钙、碳酸镁、氧化锆、氧化铝、氧化铈按0:1:0:0:2:0的比例混合后，低速球磨混合0.5小时制备陶瓷骨料。将生物质颗粒和聚氨酯泡沫按10:1比例混合后进行破碎筛分制得发泡剂。以陶瓷骨料为100份计，加入发泡剂6份、助溶剂3份、高温粘结剂2份、低温粘结剂1份制备浆料。其中助溶剂为硼酸锌、高温粘结剂为30％硅溶胶、低温粘结剂为羧甲基纤维素。
(2)将制备好的浆料进行造粒成球，室温风干24小时，随后采用烘箱105℃烘干24小时。
(3)烘干处理后的胚体进行高温煅烧。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1200℃并保持2小时，随炉冷却后即可得到多孔陶瓷球基体。
(4)配制氢氧化钙悬浊液，氢氧化钙含量为0.4mol/L。
(5)将多孔陶瓷球浸渍在悬浊液中，在磁力搅拌器下低速搅拌24小时，浸渍后的陶瓷球室温干燥6小时后转入烘箱以105℃继续干燥6小时。
(6)干燥后的陶瓷球放入马弗炉中煅烧。煅烧过程采用程序升温，以2℃/min从室温升至650℃并保持4小时，随炉冷却后即可得到多孔陶瓷球催化剂。
本实施例中，称取50g多孔陶瓷球催化剂装填在催化管中，催化温度设置为500℃。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。生物油产率为53.59wt.％，取生物油样分析，生物油中烃含量88.61％，单环芳烃含量为44.05％。
实施例3
(1)多孔陶瓷球载体浆料配制：氢氧化钙、碳酸钙、碳酸镁、氧化锆、氧化铝、氧化铈按0:1:0:10:0:0的比例混合后，低速球磨混合0.5小时制备陶瓷骨料。将生物质颗粒和聚氨酯泡沫按10:1比例混合后进行破碎筛分制得发泡剂。以陶瓷骨料为100份计，加入发泡剂6份、助溶剂3份、高温粘结剂2份、低温粘结剂1份制备浆料。其中助溶剂为硼酸锌、高温粘结剂为30％硅溶胶、低温粘结剂为羧甲基纤维素。
(2)将制备好的浆料进行造粒成球，室温风干24小时，随后采用烘箱105℃烘干24小时。
(3)烘干处理后的胚体进行高温煅烧。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1400℃并保持2小时，随炉冷却后即可得到多孔陶瓷球基体。
(4)配制氢氧化镁悬浊液，氢氧化镁含量为0.4mol/L。
(5)将多孔陶瓷球浸渍在悬浊液中，在磁力搅拌器下低速搅拌24小时，浸渍后的陶瓷球室温干燥6小时后转入烘箱以105℃继续干燥6小时。
(6)干燥后的陶瓷球放入马弗炉中煅烧。煅烧过程采用程序升温，以2℃/min从室温升至500℃并保持4小时，随炉冷却后即可得到多孔陶瓷球催化剂。
本实施例中，称取50g多孔陶瓷球催化剂装填在催化管中，催化温度设置为500℃。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。生物油产率为51.06wt.％，取生物油样分析，生物油中烃含量86.32％，单环芳烃含量为43.93％。
实施例4
(1)多孔陶瓷球载体浆料配制：氢氧化钙、碳酸钙、碳酸镁、氧化锆、氧化铝、氧化铈按0:0:10:0:1:0的比例混合后，低速球磨混合0.5小时制备陶瓷骨料。将生物质颗粒和聚氨酯泡沫按10:1比例混合后进行破碎筛分制得发泡剂。以陶瓷骨料为100份计，加入发泡剂6份、助溶剂3份、高温粘结剂4份、低温粘结剂1.5份制备浆料。其中助溶剂为硼酸锌、高温粘结剂为30％硅溶胶、低温粘结剂为羧甲基纤维素。
(2)将制备好的浆料进行造粒成球，室温风干24小时，随后采用烘箱105℃烘干24小时。
(3)烘干处理后的胚体进行高温煅烧。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1500℃并保持2小时，随炉冷却后即可得到多孔陶瓷球基体。
(4)配制氢氧化锆悬浊液，氢氧化锆含量为0.4mol/L。
(5)将多孔陶瓷球浸渍在悬浊液中，在磁力搅拌器下低速搅拌24小时，浸渍后的陶瓷球室温干燥6小时后转入烘箱以105℃继续干燥6小时。
(6)干燥后的陶瓷球放入马弗炉中煅烧。煅烧过程采用程序升温，以2℃/min从室温升至600℃并保持4小时，随炉冷却后即可得到多孔陶瓷球催化剂。
本实施例中，称取50g多孔陶瓷球催化剂装填在催化管中，催化温度设置为500℃。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。生物油产率为56.29wt.％，取生物油样分析，生物油中烃含量85.42％，单环芳烃含量为39.13％。
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 (1)

1.一种多孔陶瓷球催化剂的应用，其特征是：称取50g多孔陶瓷球催化剂装填在催化管中，催化温度设置为500℃；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；生物油产率为53.59 wt.%，取生物油样分析，生物油中烃含量88.61%，单环芳烃含量为44.05%；
所述的多孔陶瓷球催化剂制备步骤如下：（1）多孔陶瓷球载体浆料配制：氢氧化钙、碳酸钙、碳酸镁、氧化锆、氧化铝、氧化铈按0:1:0:0:2:0的比例混合后，低速球磨混合0.5小时制备陶瓷骨料；将生物质颗粒和聚氨酯泡沫按10:1比例混合后进行破碎筛分制得发泡剂；以陶瓷骨料为100份计，加入发泡剂6份、助溶剂3份、高温粘结剂2份、低温粘结剂1份制备浆料；其中助溶剂为硼酸锌、高温粘结剂为30%硅溶胶、低温粘结剂为羧甲基纤维素；（2）将制备好的浆料进行造粒成球，室温风干24小时，随后采用烘箱105℃烘干24小时；（3）烘干处理后的胚体进行高温煅烧；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1200℃并保持2小时，随炉冷却后即可得到多孔陶瓷球基体；（4）配制氢氧化钙悬浊液，氢氧化钙含量为0.4 mol/L；（5）将多孔陶瓷球浸渍在悬浊液中，在磁力搅拌器下低速搅拌24小时，浸渍后的陶瓷球室温干燥6小时后转入烘箱以105℃继续干燥6小时；（6）干燥后的陶瓷球放入马弗炉中煅烧；煅烧过程采用程序升温，以2℃/min从室温升至650℃并保持4小时，随炉冷却后即可得到多孔陶瓷球催化剂。
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