CN116351407B - 一种花瓣状α-Al2O3载体、载银催化剂的制备方法及其应用 - Google Patents
一种花瓣状α-Al2O3载体、载银催化剂的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种花瓣状α‑Al2O3载体、载银催化剂的制备方法及其应用，该载体可将银催化剂颗粒分散在花瓣之间，实现颗粒间彼此隔离，达到高分散的目的。该催化剂的制备过程主要包括以下步骤：一是制备花瓣状α‑Al2O3载体，二是将银负载至氧化铝的花瓣氧化之间。通过该方法制备花瓣状α‑Al2O3载体可以将Ag合理分散和隔离，提升催化性能和稳定性。本发明制备负载量Ag为10％的样品的催化效果明显高于中国石化和shell的16‑18％Ag含量样品的催化效果。
Description
技术领域
本发明属于催化剂制备技术领域，具体涉及一种花瓣状α-Al2O3载体、载银催化剂的制备方法其应用。
背景技术
环氧乙烷在有机化工产业中作用突出，是一种重要的化工原料，在众多乙烯系列产品中，产量仅次于聚乙烯。在合成纤维工艺中，环氧乙烷是一种重要的中间体，主要用来制备乙二醇，进一步加工，还可以用来合成聚酯纤维及薄膜或合成乙醇胺、乙二醇醚等。也就导致了环氧乙烷的消耗量的日益增加。载银催化剂在乙烯环氧化制备环氧乙烷反应中影响很大，这对催化剂的研发与生产提出了更高的要求。氧化铝载体作为该催化剂的重要组成部分，其性能与催化剂的性能有着千丝万缕的关系。传统的载银催化剂使用的氧化铝载体，一般为片状或球状堆积结构。
中国专利CN103816941选用含Si的不同种类的氢氧化铝，制备出了含硅的α-Al2O3载体，提高了载银催化剂的强度，使载体的孔结构也有所改善，用于乙烯环氧化反应效果良好。该样品为片状结构，容易使活性组分在表面堆积，导致分散度降低。
中国专利CN1802206A设计了一种催化剂，用于将乙烯转化为环氧乙烷，所述催化剂由淀积在载体上的银、碱金属(如铯)、硼和硫的临界组合组成，但其分散程度较低。
中国专利CN104549544在载体中加入一定量的矿化剂，含硅化合物以及含钛助剂，并提拱了一种新的合成载银催化剂的方法，将银负载至上述的载体上，从而改善催化活性组分在载体表面的分散性，但是其分散程度仍需要提高，其催化活性与选择性也有待提高。
发明内容
本发明的目的在于克服现有技术的不足，提供一种花瓣状α-Al2O3载体分散银催化剂的制备方法及其应用，通过加入助剂硫酸钾与尿素改变了载体α-Al2O3表面的形貌，大大提升了银在载体表面的分散性，进一步提高催化剂的初期活性与选择性。
实现本发明目的的技术方案为：
本发明的第一方面是提供了一种α-Al2O3载体，具有花瓣状的形貌，直径2-4μm，且表面花瓣分布均匀，花瓣间的间距0.1-0.2μm。
该α-Al2O3载体的制备方法为：
按照质量比为4～5：1～2：0.8～1.2称取九水合硝酸铝，硫酸钾，尿素，加入水中使九水合硝酸铝的浓度为0.01～0.1mol/L，磁力搅拌10-60min，混合均匀后，转移到高压反应釜中，150-200℃反应1-6h，冷却至室温后离心得到产品，依次经过水洗、醇洗，60-80℃烘干8-24h，再900-1200℃w焙烧1-5h，得到微观结构为花瓣状的氧化铝载体。
进一步地，所述九水合硝酸铝可以替换为硫酸铝或醋酸铝。
优选地，高压反应釜中170-180℃，反应3-4h。
载体需要在900-1200℃范围内煅烧，才能得到花瓣状的载体，更优的煅烧温度为1000-1100℃。
本发明的第二方面是提供了一种根据α-Al2O3载体制备的载银催化剂Ag@Al2O3，活性中心为Ag，Ag的负载量为5-20wt％，优选的负载量为8-12wt％。
该催化剂的制备方法，步骤如下：
将载体与含Ag浸渍液混合，加入硝酸调节pH值为2-5，优选3-4，浸渍5-6h，浸渍完成后，过滤，用蒸馏水洗涤3-5次，然后放至烘箱里，60-80℃烘干后，300-600℃焙烧1-5小时，待冷却至室温后，得到Ag@Al2O3。
所述含Ag浸渍液为硝酸银或者醋酸银所对应的水溶液。优选使用的是AgNO3的水溶液。
本发明的第三方面是提供了上述催化剂在乙烯环氧化制备环氧乙烷反应中的应用。
本发明的优点和有益效果：
1.本发明通过在九水合硝酸铝粉料中加入硫酸钾和尿素，高温焙烧后得到了微观结构为花瓣状的α-Al2O3，然后在硝酸银溶液中浸渍制得Ag@Al2O3，通过加入上述两个物质获得的载体具有更佳的空间利用效率，能够改变载体表面积，从而提升分散度，另一方面还能提升载体强度。
2.本发明引入改性剂还能引起载体表面性能的改变，影响载体与该发明中活性组分Ag的相互作用，促使活性组分在载体表面分布的更加均匀，进而影响催化剂的性能。
3.本发明制得的Ag@Al2O3催化剂改善催化剂的初期活性与选择性，并且具有能耗低、操作简单易实现等优点。
附图说明
图1为负载银前、后的XRD对比图(Ag的负载量为10％)，其中★是α-Al2O3，代表的是θ-Al2O3，经过1100℃煅烧后，α-Al2O3为主要晶型。
图2为1100℃煅烧后的Al2O3 SEM图。
图3为Ag@Al2O3 SEM图。
具体实施方案
通过以下实施例来进一步说明本发明的技术方案，但本发明的保护范围并不局限于以下实施例。
实施例1
a)花瓣状载体的制备
称取九水合硝酸铝100g,改性剂硫酸钾46.5g,尿素33g。加入5.3L水后，磁力搅拌20min，混合均匀后，转移到高压反应釜中，180℃反应3h，冷却至室温后通过离心得到产品，依次经过水洗、醇洗各3-5次，80℃烘干12h，烘干后在转入马弗炉中1100℃焙烧2h，得到微观结构花瓣状的氧化铝载体，SEM图如图2所示。
b)载银催化剂的制备
测定氧化铝的吸水率，然后配置在一定量的硝酸银水溶液，使最终的负载比例为Ag:Al2O3＝10:100。将步骤a)制得载体与前驱体溶液混合，加硝酸将pH调节到4，浸渍5小时，以达到均匀负载的目的。浸渍完成后，过滤，用蒸馏水洗涤3-5次，用滤纸擦净表面的水分，然后放至烘箱里烘干，温度为80℃，烘干后，转入马弗炉中焙烧。焙烧温度为400℃，焙烧2小时，待冷却至室温后，得到Ag@Al2O3，SEM图如图3所示。
c)催化剂性能评价
在微型反应器评价装置上进行上述载银催化剂在乙烯环氧化反应中的初期活性和选择性。催化剂的装填体积为1ml，反应器的进口气体组成为：乙烯(C2H2)29±1mol％,氧气(O2),7.5±0.1mol％，二氧化碳(CO2)≤9mol％，空速5000/h，出口EO浓度2.5％，时空产率为245kgEO/1m3Cat./h。孔的结构性质通过压汞法测定。测定结果进行体积收缩校正后按以下公式计算选择性：
其中ΔEO是出口气与进口气的浓度差，取6组实验结果的平均值。测试结果列于表1。
实施例2
同实施例1，不同之处在于步骤b)中Ag的负载量改为5％，测试结果列于表1。
实施例3
同实施例1，不同之处在于步骤b)中Ag的负载量改为15％，测试结果列于表1。
实施例4
同实施例1，不同之处在于步骤b)中Ag的负载量改为18％。测试结果列于表1。
对比例1
同实施例4，不同之处在于步骤b)中载体换为由三水铝石煅烧的得到的片状氧化铝。测试结果列于表1。
对比例2
同实施例4，不同之处在于催化剂换为中石化生产的型号为YS-8520的催化剂，测试结果列于表1。
对比例3
同实施例4，不同之处在于催化剂换为shell公司生产的型号为S-875的催化剂，测试结果列于表1。
表1
从表1数据中可以看出，通过本发明中提供的方法，制得了一种花瓣状氧化铝载体，会影响载银催化剂的各项指标。载银催化剂的初期活性和选择性均随Ag的负载量的增加而增加。并且我们发现负载量为10％花瓣状Ag@Al2O3的选择性与初期活性与负载量为18％片状Ag@Al2O3上得到结果相当。Ag在载体表面的分散度增加，暴露了更多的活性位点，从而提高了催化剂的性能。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (4)
1.一种用于乙烯环氧化制备环氧乙烷反应的α-Al2O3载银催化剂，其特征在于，α-Al2O3载体具有花瓣状的形貌，直径2-4μm，且表面花瓣分布均匀，花瓣间的间距0.1-0.2μm，Ag的负载量为5-20wt％；
所述的α-Al2O3载体的制备方法，按照质量比为4～5：1～2：0.8～1.2称取九水合硝酸铝，硫酸钾，尿素，加入水中使九水合硝酸铝的浓度为0.01～0.1mol/L，磁力搅拌10-60min，混合均匀后，转移到高压反应釜中，150-200℃反应1-6h，冷却至室温后离心得到产品，依次经过水洗、醇洗，60-80℃烘干8-24h，再900-1200℃焙烧1-5h，得到微观结构为花瓣状的氧化铝载体。
2.根据权利要求1所述的用于乙烯环氧化制备环氧乙烷反应的α-Al2O3载银催化剂，其特征在于，所述九水合硝酸铝替换为硫酸铝或醋酸铝。
3.根据权利要求1所述的用于乙烯环氧化制备环氧乙烷反应的α-Al2O3载银催化剂，其特征在于，α-Al2O3载银催化剂的制备方法如下：
将α-Al2O3载体与含Ag浸渍液混合，加入硝酸调节pH值为2-5，浸渍5-6h，浸渍完成后，过滤，用蒸馏水洗涤3-5次，然后放至烘箱里，60-80℃烘干后，300-600℃焙烧1-5小时，待冷却至室温后，得到Ag@Al2O3。
4.根据权利要求3所述的用于乙烯环氧化制备环氧乙烷反应的α-Al2O3载银催化剂，其特征在于，所述含Ag浸渍液为硝酸银或者醋酸银所对应的水溶液。
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