CN103537313B - 苯羟基化制苯酚的催化剂及其制备方法 - Google Patents
苯羟基化制苯酚的催化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种苯羟基化制苯酚的催化剂及其制备方法，其特征在于所述催化剂以介孔材料为载体，首先采用氨基硅烷对载体表面进行改性，然后用金属的乙酰丙酮盐溶液浸渍，最后洗涤、烘干制得催化剂。此发明的优点在于将活性金属负载于硅烷改性的介孔材料上，形成均相-非均相复合型催化剂，其中，活性金属组分以均相形式存在于反应体系中，保证了催化组分高催化性能，同时通过氨基硅烷的架桥作用负载于载体上，提高了金属组分与载体间的作用力，增强了催化剂的稳定性，有利于催化剂与产品的分离。催化剂制备工艺简单，催化性能优异，可应用于苯羟基化制备苯酚反应体系。
Description
技术领域
本发明涉及一种均相-非均相复合型催化剂的制备方法，尤其涉及苯羟基化制备苯酚的催化剂及其制备方法，属于催化技术领域。
背景技术
苯酚是一种重要的有机化工原料，主要用于酚醛树脂、双酚A、环氧树脂、己内酰胺、苯胺的生产，在合成纤维、合成橡胶、塑料、医药、农药、香料、染料以及涂料等方面也具有广泛的应用。目前世界上苯酚的工业生产方法主要是异丙苯法。该过程能耗大、苯酚收率低、同时生成大量的联产物丙酮，而且反应中要添加多种有机试剂，造成资源浪费、操作不便及环境的严重污染。近年来，直接将苯羟基化一步合成苯酚成为研究热点。该方法具有工艺简单、环境污染小等特点，是一种环境友好型催化过程，工业开发和应用前景十分广阔。
直接催化氧化苯制备苯酚，采用的氧化剂一般有氧气、N2O、H2O2。氧气来源广泛、价格低廉，因此，以氧气为氧化剂直接氧化苯制苯酚是最具开发价值和应用前景的途径。目前，氧气氧化苯制备苯酚的方法主要有气相法和液相法。气相法是高温反应，反应过程中易出现催化剂失活和产物深度氧化等问题。液相法的反应温度较低，反应条件温和，引起广泛关注。液相法的关键是设计使氧分子活化的催化剂。催化剂的活性组分一般为金属，例如铜、钒、钯、铁等。在反应过程中，催化剂金属组份的流失是限制此类催化剂应用的瓶颈问题。因此，开发高性能的催化剂是苯羟基化制备苯酚工艺的研究重点。
目前，已有专利公开的催化剂主要为负载型催化剂，所用载体主要有SiO2、C或Al2O3等，活性组分主要采用钯、铂、铜、钒、铁或锌等，在专利CN1102452901A、CN102463124A中提到了负载型催化剂的制备，并用于苯羟基化制备苯酚。这些催化剂的制备一般都需煅烧，制备成本高。且在反应过程中，金属组分发生溶解然后流失到反应液中，导致催化剂流失、活性降低，同时也影响产品的纯度。
发明内容
本发明的目的是为了克服现有苯羟基化制备苯酚催化剂在反应体系中易流失、稳定性差的问题，而提出了一种苯羟基化制备苯酚的催化剂，本发明的另一目的是提供上述催化剂的制备方法，将催化剂活性组份通过氨基硅烷与载体连接，形成均相-非均相复合型催化剂，增强活性组份与载体之间的作用力，提高催化剂的催化性能。
本发明的技术方案为：以介孔材料为载体，采用氨基硅烷对其孔道表面进行接枝功能化，然后通过浸渍法将活性组份负载到氨基硅烷改性的介孔材料上，制备高性能的均相-非均相复合型催化剂。氨基硅烷（如γ-氨丙基三乙氧基硅烷KH550）具有两个功能团，一个功能团烷氧基能与介孔载体表面的羟基进行缩合反应，形成Si-O-Si或Al-O-Si等化学键，另外一个功能团-NH2具有一对孤对电子，能与金属离子等形成配位键，牢固地吸附金属活性组份。因而，采用氨基硅烷如KH550对载体表面进行功能化改性，再将金属活性组份担载到改性载体上，可实现均相催化活性组分与非均相载体的复合，其中，活性金属组分以均相形式存在于反应体系中，保证了催化组分高催化性能，同时通过氨基硅烷的架桥作用负载于载体上，有利于催化剂与产品的分离，且催化剂在多次使用后仍保持良好的催化性能。
本发明的具体技术方案为：一种苯羟基化制备苯酚的催化剂，其特征在于：以采用氨基硅烷对其孔道表面进行功能化改性的介孔材料SBA-15、SBA-16或MCM-41为载体，以钯、铂、铜、钒、铁或锌为活性组分，通过浸渍法将活性组份负载到氨基硅烷改性的介孔材料上，制备的均相-非均相复合型催化剂，其中，活性金属组分通过氨基硅烷的架桥作用负载于载体上，提高了金属组分与载体间的作用力，增强了催化剂的稳定性，有利于催化剂与产品的分离；而且以均相形式存在于反应体系中，保证了催化组分高催化性能。优选活性组分为铜或钒。
本发明还提供了制备上述催化剂的方法，其具体步骤为：
A.载体表面改性过程：将载体浸入浓度为0.1～2g/L氨基硅烷溶液中，在20～40℃温度条件下进行表面改性，取出洗涤、晾干；
B.浸渍过程：将改性后的载体浸入含活性组份钯、铂、铜、钒、铁或锌的乙酰丙酮盐溶液中，在温度为20～40℃条件下浸渍6～36h；其中浸渍溶液浓度为0.1～0.25mol/L；
C.洗涤干燥过程：使用无水乙醇或二氯甲烷洗涤催化剂并干燥。
优选步骤A中氨基硅烷为γ-氨丙基三乙氧基硅烷（KH550）或N-(β-氨乙基)-γ-氨丙基三甲氧基硅（KH792）或N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷（硅烷偶联剂602）；溶剂为二氯甲烷、甲苯或无水乙醇；改性时间为1～32h。
本发明采用以下条件进行催化剂的活性评价。
反应在150ml的三口烧瓶中进行。将40ml冰醋酸、10ml蒸馏水、2g苯、4g抗坏血酸、0.5g催化剂依次加入反应烧瓶中，调节进料氧气流速为30ml/min，控制温度恒定为30℃，反应6h后取样，用高效液相色谱分析产物，根据标准曲线计算苯的转化率和苯酚选择性。
有益效果：
本发明通过浸渍法将活性组份负载到氨基硅烷改性的介孔材料上，形成均相-非均相复合型催化剂，其中，活性金属组分以均相形式存在于反应体系中，保证了催化组分高催化性能，同时通过氨基硅烷的架桥作用负载于载体上，有利于催化剂与产品的分离，且催化剂在多次使用后仍保持良好的活性。
附图说明
图1为SBA-15载体、V/NH2-SBA-15（实施例1）催化剂以及乙酰丙酮氧钒(VO(C5H7O2)2)前躯体的X射线衍射图。
图2为SBA-15、NH2-SBA-15（实施例1）、VO(C5H7O2)2以及V/NH2-SBA-15的红外表征图。
具体实施方式
下面通过实施例进一步说明本发明方法及催化剂的使用效果。
实施例1V/NH2-SBA-15催化剂的制备
将2gSBA-15分散于50ml二氯甲烷溶剂中，加入0.05g氨基硅烷KH550，25℃下搅拌，浸渍1h，无水乙醇洗涤，过滤后烘干，得到NH2-SBA-15粉末。将1.33gVO(C5H7O2)2（分子量为265.15）加入至50mlCH2Cl2，搅拌，待固体完全溶解后，加入1.5gNH2-SBA-15粉末，40℃下搅拌，浸渍12h后过滤，无水乙醇洗涤，于90℃下烘干，得到V/NH2-SBA-15催化剂。
图1显示了V/NH2-SBA-15催化剂的X射线衍射分析结果。SBA-15在22°处有一强峰，对应于无定型Si。V/NH2-SBA-15出现了VO(C5H7O2)2以及Si的特征峰，说明催化剂组分已负载于SBA-15载体上。
从图2可以看出：960cm-1对应Si-OH，V/NH2-SBA-15在960cm-1处的强度明显减弱，这是由于载体的硅烷官能化和VO(acac)2的负载。此外，比较c和a可以发现，在2930，2848cm-1处多出了两个峰，其对应C-H伸缩振动，而1557cm-1对应了N-H弯曲振动，说明硅烷通过化学键接枝到SBA-15的表面。
将催化剂用于苯羟基化制备苯酚体系中，反应6h后，苯酚收率为4.5%。催化剂经五次使用后，催化效果降低为新催化剂的70%。
实施例2V/NH2-MCM-41催化剂的制备
将2gSBA-15分散于50ml二氯甲烷溶剂中，加入0.1g氨基硅烷KH792，20℃下搅拌，浸渍8h，无水乙醇洗涤，过滤后烘干，得到NH2-MCM-41粉末。取3.31gVO(C5H7O2)2（分子量为265.15）加入至50mlCH2Cl2，搅拌，待固体完全溶解后，加入1.5gNH2-SBA-15粉末，20℃下搅拌，浸渍6h后过滤，无水乙醇洗涤，于90℃下烘干，得到V/NH2-MCM-41催化剂。
将催化剂用于苯羟基化制备苯酚体系中，反应6h后，苯酚收率为3.9%。催化剂经五次使用后，催化效果降低为新催化剂的62%。
实施例3Pd/NH2-SBA-15催化剂的制备
将2gSBA-15分散于50ml二氯甲烷溶剂中，加入0.05g氨基硅烷KH550，40℃下搅拌，浸渍24h，无水乙醇洗涤，过滤后烘干，得到NH2-SBA-15粉末。取3.05gPd(C5H7O2)2（分子量为304.64）加入至50mlCH2Cl2，搅拌，待固体完全溶解后，加入1.5gNH2-SBA-15粉末，40℃下搅拌，浸渍36h后过滤，无水乙醇洗涤，于90℃下烘干，得到Pd/NH2-SBA-15催化剂。
将催化剂用于苯羟基化制备苯酚体系中，反应6h后，苯酚收率为2.5%。催化剂经五次使用后，催化效果降低为新催化剂的60%。
实施例4Cu/NH2-SBA-16催化剂的制备
将2gSBA-16分散于50ml二氯甲烷溶剂中，加入0.005g硅烷偶联剂602，30℃下搅拌，浸渍32h，无水乙醇洗涤，过滤后烘干，得到NH2-SBA-16粉末。取1.96gCu(C5H7O2)2（分子量为261.76）加入至50mlCH2Cl2，搅拌，待固体完全溶解后，加入1.5gNH2-SBA-16粉末，25℃下搅拌，浸渍12h后过滤，无水乙醇洗涤，于90℃下烘干，得到Cu/NH2-SBA-16催化剂。
将催化剂用于苯羟基化制备苯酚体系中，反应6h后，苯酚收率为3.1%。催化剂经五次使用后，催化效果降低为新催化剂的65%。
Claims (2)
1.一种催化剂在苯羟基化制备苯酚中的应用，其特征在于由以下方法制得：将40ml冰醋酸、10ml蒸馏水、2g苯、4g抗坏血酸、0.5g催化剂依次加入反应烧瓶中，调节进料氧气流速为30ml/min，控制温度恒定为30℃，反应6h；其中所述的催化剂以采用氨基硅烷对其孔道表面进行功能化改性的介孔材料SBA-15、SBA-16或MCM-41为载体，以钯、铂、铜、钒、铁或锌的乙酰丙酮盐为活性组分，通过浸渍法将活性组分负载到氨基硅烷改性的介孔材料上，制备的均相-非均相复合型催化剂，其中，活性金属组分通过氨基硅烷的架桥作用负载于载体上；其具体步骤为：
A．载体表面改性过程：将载体浸入浓度为0.1～2g/L氨基硅烷溶液中，在20～40℃温度条件下进行表面改性，取出洗涤、晾干；其中氨基硅烷为γ-氨丙基三乙氧基硅烷或N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷或N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷；溶剂为二氯甲烷、甲苯或无水乙醇；改性时间为1～32h；
B．浸渍过程：将改性后的载体浸入含活性组分为钯、铂、铜、钒、铁或锌的乙酰丙酮盐溶液中，在温度为20～40℃条件下浸渍6～36h；其中浸渍溶液浓度为0.1～0.25mol/L；
C．洗涤干燥过程：使用无水乙醇或二氯甲烷洗涤催化剂并干燥。
2.根据权利要求1所述的应用，其特征在于活性组分为铜或钒的乙酰丙酮盐。
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Citations (1)
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|---|---|---|---|---|
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| Title |
|---|
| Synthesis, characterization, and catalytic activity of vanadium-incorporated, -grafted, and -immobilized mesoporous MCM-41 in the oxidation of aromatics;S. Shylesh, et al.;《Journal of Catalysis》;20041022;第228卷;第333-346页 * |
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