CN114634370A - 高强度囊泡孔氧化铝材料及其制备方法 - Google Patents
高强度囊泡孔氧化铝材料及其制备方法 Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 30
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Abstract
本发明公开了一种高强度囊泡孔氧化铝材料及其制备方法。本发明的球形氧化铝中，囊泡孔体积含量为5%‑60%，压碎强度为10‑50N/颗，BET比表面积为100‑350m2/g。制备方法如下：（1）将氧化铝前体、碳酸钙粉末、水、表面活性剂及淀粉混合均匀，打浆成均匀；（2）将步骤（1）的混合物滴入到融化的凡士林中，形成液滴球并老化后，滤出、干燥、焙烧，然后采用酸液水热处理；（3）将步骤（2）得到的物料洗涤、干燥、焙烧，得到囊泡孔氧化铝球形颗粒。本发明的高强度囊泡孔氧化铝材料机械强度高，能够满足现有多相催化反应的强度要求，可作为多相催化剂载体、填料或作为保护剂使用。
Description
技术领域
本发明属于无机材料制备领域，涉及一种高强度囊泡孔氧化铝材料及其制备方法。
背景技术
多孔氧化铝被广泛应用于多相催化剂的载体材料。孔道结构是催化剂的重要物化性质，通常情况下，孔道的特性对于催化性能具有决定性的影响。对于大分子物料参与的催化反应，催化剂还需要具备大孔甚至超大孔（大于1000nm）结构以进一步提高大分子物料的传质能力。
物理化学学报, 2006, 22(7)：831-835提供了一种大孔氧化铝材料的制备方法，将聚苯乙烯颗粒与氧化铝前体混合并处理后得到囊泡状大孔氧化铝，所得材料物理强度较低，不能制备成为固定的形状，所用聚苯乙烯颗粒成本较高，环境污染严重。
CN 201010221297.6把铝源、聚乙二醇、低碳醇、水及环氧烷烃混合用于制备整体式大孔氧化铝，具有囊泡状大孔，其孔径可为0.05-10μm，该方法所用的环氧烷烃等原料较贵，制备成本较高，且该方法所得材料在外形上不具备固定的形状，不利于装填到反应器中以控制物料传质及床层压降。
发明内容
针对现有技术的不足，本发明提供了一种高强度囊泡孔氧化铝材料及其制备方法。本发明的高强度囊泡孔氧化铝材料机械强度高，能够满足现有多相催化反应的强度要求，可作为多相催化剂载体、填料或作为保护剂使用。
本发明的高强度囊泡孔氧化铝材料，具有球形颗粒形状，其直径为1-5mm，囊泡孔平均孔径大于500nm且小于5000nm，囊泡孔含量以体积计为5%-60%；球形颗粒的压碎强度为10-50N/颗，BET比表面积为100-350m2/g。
本发明的高强度囊泡孔氧化铝材料的制备方法，包括如下内容：
（1）将氧化铝前体、碳酸钙粉末、水、表面活性剂及淀粉混合均匀，打浆成均匀的溶胶状混合物；
（2）将步骤（1）的溶胶状混合物滴入到融化的凡士林中，形成液滴球并老化后，分离出凝胶球，凝胶球经干燥、焙烧和酸液水热处理；
（3）将步骤（2）产物经洗涤、干燥、焙烧，得到高强度囊泡孔氧化铝材料。
本发明方法中，步骤（1）所述的氧化铝前体为拟薄水铝石胶粉，或经硅、硼、磷、钛或锆等元素改性的拟薄水铝石胶粉，或经焙烧后可转化为氧化铝的铝氧化合物，以及经硅、硼、磷、钛或锆等元素改性的且经过焙烧后可转化为氧化物的铝氧化合物。
本发明方法中，步骤（1）所述的碳酸钙粉末，粒径为500-5000nm，形状为球形或近球形。
本发明方法中，步骤（1）所述的表面活性剂为磺酸盐类阴离子表面活性剂中一种或多种，包括但不限于十二烷基磺酸钠、十二烷基苯磺酸钠等中的一种或多种。
本发明方法中，步骤（1）所述的淀粉为玉米淀粉、藕粉淀粉、马铃薯淀粉或其任意比例的混合物。
本发明方法中，步骤（1）所述的打浆，通过机械搅拌（包括剪切搅拌），磁力搅拌等方式进行，打浆的程度满足浆液溶胶状，至少在室温下至少静置30分钟保持稳定，无明显的分层、沉淀现象。本步骤的混合物料打浆温度保持在80-100℃，打浆时间5-30分钟。
本发明方法中，以步骤（1）所得的混合物的重量为基准，水的加入量为30wt%-70wt%，氧化铝前体的加入量为10wt%-50wt%，碳酸钙粉末加入量为5wt%-25wt%，表面活性剂加入量为0.5wt%-10wt%，淀粉的加入量为1wt%-15wt%。
本发明方法中，步骤（2）所述凡士林为液态，温度为50-80℃
本发明方法中，步骤（2）所述的老化条件为：50-80℃下老化0.5-6小时。
本发明方法中，步骤（2）中所述的干燥，干燥温度不大于150℃，优选为40-120℃，12-48小时。
本发明方法中，步骤（2）中所述的酸液为盐酸、硝酸或醋酸中的一种或多种，优选为醋酸；酸液浓度0.1-3mol/L，优选为0.5-2mol/L。所述酸液的用量满足能够在容器中完全淹没固体物料即可。
本发明方法中，步骤（2）中所述的焙烧条件：温度为300-550℃，焙烧时间0.5-12小时。
本发明方法中，步骤（2）中所述的酸液水热回流处理条件：水热处理温度50-100℃，水热处理时间为0.5-6小时。一般在常压容器中进行即可。
本发明方法中，步骤（3）中所述洗涤采用的介质为水，洗涤程度直至洗涤液pH值为中性或接近中性。
本发明方法中，步骤（3）中所述的干燥，干燥温度不大于200℃，优选为100-150℃干燥，干燥时间12-24小时。
本发明方法中，步骤（3）中所述的焙烧条件：温度为450-750℃，焙烧时间1-12小时。
本发明的囊泡孔氧化铝材料具有较高的压碎强度，内部含有含量及孔径可控的囊泡孔，可以作为多相催化剂的载体，应用于各类大分子催化反应，如渣油、蜡油加氢反应中的特定反应流程。
附图说明
图1为实施例1制备的高强度囊泡孔氧化铝球形颗粒的光学相机照片。
图2为实施例1制备的高强度囊泡孔氧化铝球形颗粒的扫描电镜图像。
具体实施方式
下面结合实施例对本发明作进一步详细说明。本发明中，以游标卡尺随机测量100个颗粒的直径，计算平均直径。以扫描电镜观察囊泡孔形态，并测量孔道尺寸。比表面积采用BET法测试，载体的机械强度采用DL3型强度仪进行测试。囊泡大孔的体积含量的计算：采用扫描电镜观察样品剖面，寻找最大的囊泡孔及最小的囊泡孔，计算其直径平均值，以该直径平均值作为剖面的厚度，得出剖面的体积，再计算剖面所能观察到的所有的囊泡孔的总体积，并将其与剖面体积相比乘以100%得到囊泡孔体积含量。
实施例1
室温下将水、SB粉、碳酸钙粉末（平均粒径1100nm），十二烷基苯磺酸钠，玉米淀粉混合均匀，再使用剪切搅拌器使混合物成为稳定的溶胶状物，使最终体系温度达到95℃。混合物各组分以重量计含量分别为：水60%，SB粉30%，碳酸钙粉3%，十二烷基苯磺酸钠1%，淀粉6%。把溶胶状物用分散液头滴入到70℃的液态凡士林中，形成液滴后，继续老化5小时，过滤出凝胶球，在90℃下烘干12小时，500℃下焙烧5小时后，浸泡于2.0mol/L的醋酸溶液中，于60℃下水热回流处理3小时，用蒸馏水过滤洗涤直至洗涤液接近中性，120℃干燥后，550℃焙烧3小时得到最终样品。
所得产品为尺寸均匀的球形颗粒，平均直径1.7mm。产品经扫描电镜观察颗粒剖面，具有直径约0.8μm的囊泡孔，囊泡大孔体积含量为11%，材料的压碎强度12N/颗，BET比表面积为256m2/g。
实施例2
室温下将水、SB粉、碳酸钙粉末（平均粒径2500nm），十二烷基磺酸钠，马铃薯淀粉混合均匀，再使用剪切搅拌器使混合物成为稳定的溶胶状物，使最终体系温度达到80℃。混合物各组分以重量计含量分别为：水50%，SB粉30%，碳酸钙粉10%，十二烷基磺酸钠4%，淀粉6%。把溶胶状物用分散液头滴入到60℃的液态凡士林中，形成液滴后，继续老化5小时，过滤出凝胶球，在120℃下烘干12小时，500℃下焙烧5小时后，浸泡于0.5mol/L的醋酸溶液中，于70℃下水热回流处理3小时，用蒸馏水过滤洗涤直至洗涤液接近中性，120℃干燥后，650℃焙烧5小时得到最终样品。
所得产品为尺寸均匀的球形颗粒，平均直径2mm。产品经扫描电镜观察颗粒剖面，具有直径约2.3μm的囊泡孔，囊泡大孔体积含量为18%，材料的压碎强度13N/颗，BET比表面积为277m2/g。
实施例3
室温下将水、氧化铝粉体、碳酸钙粉末（平均粒径5000nm），十二烷基磺酸钠，藕粉淀粉混合均匀，再使用剪切搅拌器使混合物成为稳定的溶胶状物，使最终体系温度达到100℃。混合物各组分以重量计含量分别为：水40%，SB粉25%，碳酸钙粉20%，十二烷基磺酸钠5%，淀粉10%。把溶胶状物用分散液头滴入到80℃的液态凡士林中，形成液滴后，继续老化5小时，过滤出凝胶球，在120℃下烘干12小时，500℃下焙烧5小时后，浸泡于0.5mol/L的醋酸溶液中，于80℃下水热回流处理3小时，用蒸馏水过滤洗涤直至洗涤液接近中性，120℃干燥后，750℃焙烧5小时得到最终样品。
所得产品为尺寸均匀的球形颗粒，平均直径2.5mm。产品经扫描电镜观察颗粒剖面，具有直径约4.7μm的囊泡孔，囊泡大孔体积含量为39%，材料的压碎强度17N/颗，BET比表面积为212m2/g。
实施例4
将碳酸钙粉末替换为等量的水，其它条件同实施例3一致。所得样品剖面致密，无明显的囊泡孔。
对比例1
按照CN 201010221297.6的实施例1的方法制备材料，所得样品含有囊泡状大孔，所得产物的形态是不具有固定形状及确定尺寸的碎粒。
Claims (13)
1.一种高强度囊泡孔氧化铝材料，其特征在于：具有球形颗粒形状，直径为1-5mm，囊泡孔平均孔径大于500nm且小于5000nm，囊泡孔含量以体积计为5%-60%；压碎强度为10-50N/颗。
2.一种高强度囊泡孔氧化铝材料的制备方法，其特征在于包括如下内容：（1）将氧化铝前体、碳酸钙粉末、水、表面活性剂及淀粉混合均匀，打浆成均匀的溶胶状混合物；（2）将步骤（1）的溶胶状混合物滴入到融化的凡士林中，形成液滴球并老化后，分离出凝胶球，凝胶球经干燥、焙烧和酸液水热回流处理；（3）将步骤（2）产物经洗涤、干燥、焙烧，得到高强度囊泡孔氧化铝材料。
3.根据权利要求2所述的方法，其特征在于：步骤（1）所述的氧化铝前体为拟薄水铝石胶粉，或经硅、硼、磷、钛或锆元素改性的拟薄水铝石胶粉，或经焙烧后转化为氧化铝的铝氧化合物，以及经硅、硼、磷、钛或锆元素改性的且经过焙烧后可转化为氧化物的铝氧化合物中的一种或多种。
4.根据权利要求2所述的方法，其特征在于：步骤（1）所述的碳酸钙粉末，粒径为500-5000nm。
5.根据权利要求2所述的方法，其特征在于：步骤（1）所述的表面活性剂为磺酸盐类阴离子表面活性剂中一种或多种；优选十二烷基磺酸钠、十二烷基苯磺酸钠中的一种或多种。
6.根据权利要求2所述的方法，其特征在于：步骤（1）所述的淀粉为玉米淀粉、藕粉淀粉、马铃薯淀粉或其任意比例的混合物。
7.根据权利要求2所述的方法，其特征在于：步骤（1）所述的溶胶状混合物至少在室温下静置30分钟保持稳定，无明显的分层、沉淀现象；打浆温度为80-100℃，时间5-30分钟。
8.根据权利要求2所述的方法，其特征在于：以步骤（1）所得的混合物的重量为基准，水的加入量为30wt%-70wt%，氧化铝前体的加入量为10wt%-50wt%，碳酸钙粉末加入量为5wt%-25wt%，表面活性剂加入量为0.5wt%-10wt%，淀粉的加入量为1wt%-15wt%。
9.根据权利要求2所述的方法，其特征在于：步骤（2）所述融化的凡士林温度为50-80℃。
10.根据权利要求2所述的方法，其特征在于：步骤（2）所述的老化条件为：50-80℃下老化0.5-6小时。
11.根据权利要求2所述的方法，其特征在于：步骤（2）中所述的酸液为盐酸、硝酸或醋酸中的一种或多种，优选为醋酸；酸液浓度0.1-3mol/L；所述酸液的用量满足能够在容器中完全淹没固体物料即可。
12.根据权利要求2所述的方法，其特征在于：步骤（2）中所述的酸液回流水热处理条件：水热处理温度50-100℃，水热处理时间为0.5-6小时。
13.一种权利要求1所述的囊泡孔氧化铝材料在大分子催化反应中的应用。
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Effective date of registration: 20231214 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |