CN113332998B - 一种负载在水镁铁石上的高分散钌纳米颗粒催化剂及其催化乙醇液相氧化制乙酸的应用 - Google Patents
一种负载在水镁铁石上的高分散钌纳米颗粒催化剂及其催化乙醇液相氧化制乙酸的应用 Download PDFInfo
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Abstract
本发明公开了一种负载在水镁铁石上的高分散钌纳米颗粒催化剂及其催化乙醇液相氧化制乙酸的应用。本发明以双滴法合成的MgFeRu三元水滑石作为前驱体，在氢气气氛中采用程序升温还原制得负载在水镁铁石上的高分散钌纳米颗粒催化剂。本发明制备的负载在水镁铁石上的高分散钌纳米颗粒催化剂中的Ru和Mg、Fe的协同效应促进了对O2的活化和对乙醇的吸附能力，不仅提高了乙醇的转化率，而且大大提高了乙酸的选择性。并且该催化剂制备过程无需使用高锰酸钾，重铬酸钾等无机强氧化剂，制备方法简便，环境友好，可重复使用。
Description
技术领域
本发明属于催化剂制备技术领域，具体涉及一种负载在水镁铁石上的高分散钌纳米颗粒催化剂及其催化乙醇液相氧化制乙酸的应用。
背景技术
由于能源的需求增加，化石原料的持续消耗，替代能源和可再生能源引起了最近研究的兴趣。生物质具有低二氧化碳排放的可再生性且价格比化石燃料便宜，其中生物乙醇是最常见的生物燃料之一，已作为燃料和燃料添加剂使用多年，其产量增长迅速达到每年46×109升。因此，从生物质中生产已被深入研究。醇类氧化反应是催化中较为重要的反应。将生物乙醇转化为其他化学物质可以有效解决化石能源带来的环境问题，从而得到人们的关注，其中生物乙醇氧化到高附加值的乙酸有重要价值。目前75％工业乙酸通过甲醇的羰基化制得。以甲醇为原料合成醋酸，不但原料价格低廉，容易得到，而且对醋酸的选择性在99％以上。但反应有副反应发生，且对反应温度要求高(150℃-200℃)。因此，迫切需要开发高效的催化剂来促进生物乙醇的转化。常用浸渍等方法负载贵金属得到催化剂进行反应，但是制备过程中不容易控制贵金属的尺寸和形貌，活性位暴露的面积小，不利于催化反应的进行，所以制备多相且绿色的催化剂一直是人们研究的方向。
在多相催化剂的制备过程中，控制固体表面活性纳米颗粒的分散仍然是重要的挑战之一，这种催化剂具有制备简单和存在大量催化活性位点的优势。LDHs(也称为类水滑石材料)属于二维(2D)化合物，其通式为[M2+ 1-xM3+ x(OH)2]x+(An-)x/nmH2O。M2+和M3+分别为二价和三价金属阳离子，分别位于主体层板上；An-为层间阴离子；x是M2+/(M2++M3+)的摩尔比；m是层间水分子的数目。LDHs结构与水镁石Mg(OH)2相似，主要层板由MO6八面体的边缘形成。在各种固体载体中，层状双氢氧化物(LDHs)由于其表面碱度、吸附能力和阴阳离子交换能力成为纳米非均相催化剂的潜在候选材料，而备受关注。LDHs的这些独特特性将为纳米级非均相催化剂的设计提供一条有吸引力的思路，以实现环境友好型有机合成。
发明内容
本发明的目的是提供一种负载在水镁铁石上的高分散钌纳米颗粒催化剂及其催化乙醇液相氧化制乙酸的应用。
本发明以双滴法合成的MgFeRu三元水滑石作为前驱体，在氢气气氛中采用程序升温还原制得负载在水镁铁石上的高分散钌纳米颗粒催化剂。
所述的负载在水镁铁石上的高分散钌纳米颗粒催化剂的结构为：金属钌颗粒均匀分散在水镁铁石片层载体中，该催化剂为黑色粉末状物质，单个颗粒粒径在1-2nm。
所述的负载在水镁铁石上的高分散钌纳米颗粒催化剂的制备方法为：
(1)双滴法制备MgFeRu三元水滑石前体：室温下，将可溶镁盐、可溶铁盐、可溶钌盐配制成混合盐溶液与碱溶液一起滴加至四口烧瓶中，维持四口烧瓶中混合液的pH值为9-10，滴加完成后将混合液转入高压水热釜中，100-150℃下水热晶化12-48h，冷却至室温，用去离子水洗涤至中性，干燥后获得MgFeRu三元水滑石前体；
(2)将步骤(1)制备的MgFeRu三元水滑石前体在氢气气氛中还原，还原温度为180-220℃，还原时间为2-5h，还原完成后降至室温，最后在氮气氛中钝化0.5-1h。
所述的可溶镁盐、可溶铁盐、可溶钌盐分别为硝酸镁、硝酸铁、氯化钌。
所述的碱溶液为氢氧化钠溶液、或氢氧化钠和碳酸钠的混合碱溶液。
所述的混合盐溶液中Mg和Fe的摩尔比为2-4:1，Mg和Ru的摩尔比为30-70:1。
将上述制备得到的负载在水镁铁石上的高分散钌纳米颗粒催化剂应用于催化醇氧化反应中。
所述的醇为苯环醇、长链醇中的一种或几种。
所述的醇为乙醇时，催化乙醇液相氧化制乙酸的催化反应条件为：将负载在水镁铁石上的高分散钌纳米颗粒催化剂和乙醇溶液混合置于高压反应釜中，反应温度为100-150℃，空气压力为0.5-2MPa，反应时间3-5h，搅拌速度为300-1000r/min。
本发明制备的负载在水镁铁石上的高分散钌纳米颗粒催化剂中，水镁铁石是一种良好的载体，对金属钌颗粒进行固定，使得贵金属Ru的分散更均匀，贵金属与载体之间相互作用更强，防止了贵金属的聚集，并且为反应物提供了反应的活性位点，增加了底物与活性位点的有效接触。该催化剂中的Ru和Mg，Fe的协同效应促进了对O2的活化和对乙醇的吸附能力，不仅提高了乙醇的转化率，而且大大提高了乙酸的选择性，其在120℃、1MPa空气压力、反应物/催化剂为10:1的条件下，乙醇液相氧化到乙酸的转化率为95.62％，乙酸产率为91.23％。并且该催化剂制备过程无需使用高锰酸钾，重铬酸钾等无机强氧化剂，制备方法简便，环境友好，可重复使用。
附图说明
图1是实施例1制得的MgFeRu-LDHs前驱体的XRD(a)和SEM(b)图。
图2是实施例1制得的MgFeRu-LDHs前驱体以及在氢气气氛中不同温度下还原后得到的催化剂样品的XRD图。
图3是实施例1制得的MgFeRu-LDHs的H2-TPR曲线。
图4是实施例1中200℃还原制得的催化剂样品的高分辨透射电镜的照片以及相应的颗粒尺寸分布图。
图5是实施例1制得的Ru/sjoegrenite催化剂的CO2-TPD曲线。
具体实施方式
实施例1
A.采用双滴法制备了Mg/Fe摩尔比3.0、Mg/Ru摩尔比50.0的MgFeRu-LDHs前体：首先，将6.35g Mg(NO3)2·6H2O、3.33g Fe(NO3)3·9H2O和0.129g RuCl3·3H2O溶于50mL去离子水中得到混合盐溶液，总金属离子浓度为0.66mol/L。再将2.96g NaOH和2.45g Na2CO3溶于70mL去离子得到混合碱溶液。将两个溶液超声，使药品充分溶解。然后利用双通道注射器将盐溶液和碱性溶液加入四口烧瓶中，通过调节两种溶液的流速，将浆液的pH控制在10.0±0.1。滴加完毕后，将浆液倒入内衬为聚四氟乙烯的高压釜中，在120℃干燥箱中老化24h。之后取出冷却至室温，用低速离心机离心，去离子水洗至中性，80℃烘干得到结晶良好的MgFeRu-LDHs，前体的XRD、SEM见图1。
B.将步骤A制备的MgFeRu-LDHs放置于气氛管式炉中，常压下通入高纯氢气进行还原，氢气流速为20mL/min，还原温度为200℃，还原时间为3h，升温速率为5℃·min-1。样品还原后待温度降至室温后换成N2钝化1h后取出，得到200℃下还原的催化剂样品Ru/sjoegrenite。
不同温度处理的水滑石样品的XRD见图2。由图2可以看出，当温度从室温升高到200℃时，MgFeRu-LDHs的特征峰消失，出现了几个新的峰，表明LDHs结构发生了转变，水镁铁石是由于温度升高LDHs脱水得到的。图3为水滑石前体的H2-TPR曲线，可以看出Ru的加入促进了金属Fe的还原，降低了铁的还原温度。图4为还原样品的HRTEM图，可以看到金属钌颗粒均匀分散在水镁铁石上，钌颗粒平均粒径不大。图5是200℃还原样品的CO2-TPD曲线，催化剂有很强的中等碱性位，中等强度的碱性位有利于醇在有氧氧化中O-H键的断裂。
应用例1
利用50mL高压反应釜进行实验。反应釜中加入5wt％的乙醇溶液10mL，0.15g实施例1制得的催化剂和磁子。然后将高压反应釜密封并充入空气至压力为1MPa(室温下)，插入热电偶并开加热电流。温度设置为120℃，搅拌速度为500r/min。反应结束后将反应釜置于冰水浴中冷却，再将釜中气体放空，开釜取样。氧化反应产物定量分析使用岛津气相色谱分析，色谱柱采用InertCap FFAP型，检测器为离子火焰检测器(反应结果见表1)。表1为MgFeRu-LDHs前驱体和实施例1还原制备的催化剂样品对催化乙醇氧化制乙酸的转化率，选择性与产率的数据表。
表1
Claims (9)
1.一种催化醇氧化反应的方法，其特征在于，所述反应采用的催化剂为负载在水镁铁石上的高分散钌纳米颗粒催化剂。
2.根据权利要求1所述的方法，其特征在于，所述催化剂的结构为：金属钌颗粒均匀分散在水镁铁石片层载体中，该催化剂为黑色粉末状物质，单个颗粒粒径在1-2 nm。
3.根据权利要求1所述的方法，其特征在于，所述负载在水镁铁石上的高分散钌纳米颗粒催化剂的制备方法为：以双滴法合成的MgFeRu三元水滑石作为前驱体，在氢气气氛中采用程序升温还原制得负载在水镁铁石上的高分散钌纳米颗粒催化剂。
4.根据权利要求3所述的方法，其特征在于，所述制备方法的具体步骤为：
（1）双滴法制备MgFeRu三元水滑石前体：室温下，将可溶镁盐、可溶铁盐、可溶钌盐配制成混合盐溶液与碱溶液一起滴加至四口烧瓶中，维持四口烧瓶中混合液的pH值为9-10，滴加完成后将混合液转入高压水热釜中，100-150 ℃下水热晶化12-48h，冷却至室温，用去离子水洗涤至中性，干燥后获得MgFeRu三元水滑石前体；
（2）将步骤（1）制备的MgFeRu三元水滑石前体在氢气气氛中还原，还原温度为180-220℃，还原时间为2-5h，还原完成后降至室温，最后在氮气氛中钝化0.5-1h。
5.根据权利要求4所述的方法，其特征在于，所述的可溶镁盐、可溶铁盐、可溶钌盐分别为硝酸镁、硝酸铁、氯化钌。
6.根据权利要求4所述的方法，其特征在于，所述的碱溶液为氢氧化钠溶液、或氢氧化钠和碳酸钠的混合碱溶液。
7.根据权利要求4所述的方法，其特征在于，所述的混合盐溶液中Mg和Fe的摩尔比为2-4:1，Mg和Ru的摩尔比为30-70:1。
8.根据权利要求1所述的方法，其特征在于，所述的醇为苯环醇、长链醇中的一种或几种。
9.根据权利要求1所述的方法，其特征在于，所述的醇为乙醇时，即为负载在水镁铁石上的高分散钌纳米颗粒催化剂催化乙醇液相氧化制乙酸的催化反应，该催化反应的条件为：将负载在水镁铁石上的高分散钌纳米颗粒催化剂和乙醇溶液混合置于高压反应釜中，反应温度为100-150 °C，空气压力为0.5-2MPa，反应时间3-5 h，搅拌速度为300 -1000r/min。
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