CN103819301B - 一种光催化降冰片二烯异构化制备四环庚烷的复合催化剂及其制备方法 - Google Patents

一种光催化降冰片二烯异构化制备四环庚烷的复合催化剂及其制备方法 Download PDF

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CN103819301B
CN103819301B CN201410052298.0A CN201410052298A CN103819301B CN 103819301 B CN103819301 B CN 103819301B CN 201410052298 A CN201410052298 A CN 201410052298A CN 103819301 B CN103819301 B CN 103819301B
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photosensitive agent
organic photosensitive
solid photocatalysts
composite catalyst
quadricyclane
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CN103819301A (zh
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邹吉军
张香文
王莅
王庆法
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Tianjin University
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Abstract

本发明公开了一种光催化降冰片二烯异构化制备四环庚烷的复合催化剂，其包括：固体光催化剂；其选自TiO2、Ti-MCM-41、Ti-SBA-15、ZnO、WO3、Ta2O5或SrTiO3；负载在所述固体光催化剂表面或孔道上的有机光敏剂，该有机光敏剂选自二苯甲酮、苯乙酮、米氏酮、四乙基米氏酮、二乙基米氏酮；其中，有机光敏剂占所述固体光催化剂的0.5%～20%，重量百分比。本发明的催化剂，能够在不使用溶剂的条件下催化目标反应，且目标产物四环庚烷收率高，且本发明的催化剂活性稳定，能反复使用。本发明还公开了该复合催化剂的制备方法。

Description

一种光催化降冰片二烯异构化制备四环庚烷的复合催化剂及其制备方法
技术领域
本发明属于催化剂制备领域。
背景技术
四环庚烷是重要的高能航天燃料，密度达到0.98g·cm-3、冰点低于-40℃，可应用于火箭、导弹、卫星和飞船等航天航空推进系统，与煤油燃料相比，具有高能量的优势，与肼类燃料相比，具有高安全性的优势。
四环庚烷采用光化学方法合成，以降冰片二烯为原料、紫外光照射、有机光敏剂或固体光催化剂作为反应的催化剂，通过降冰片二烯的分子内加成反应生成四环庚烷。催化剂是决定反应速率的关键因素。
光催化降冰片二烯异构合成四环庚烷采用两类催化剂，一是有机光敏剂，一是固体光催化剂。
有机光敏剂可以溶解在反应溶液中，也叫均相光敏剂。常用有机酮类光敏剂，例如二苯甲酮、苯乙酮、米氏酮、四乙基米氏酮、二乙基米氏酮等。
美国专利US5076813采用150W高压汞灯照射含有110g降冰片二烯和0.1g米氏酮的溶液，反应37小时后，转化率99%，四环庚烷选择性99%。
美国专利US2004/0054244A1采用400W高压汞灯照射分别含有5ml降冰片二烯和0.32%米氏酮或0.75%乙基米氏酮的溶液，16小时后转化率分别为53.7%和65.8%。
固体光催化剂不溶于反应物，因此也叫非均相光催化剂。本专利的申请人此前报道了V-Ti-MCM-41固体光催化剂（Applied Catalysis B(2010)439-445），采用400W高压汞灯照射含有5ml降冰片二烯、0.1g催化剂和500ml二甲苯的溶液，4小时后转化率90%。
但现有催化剂存在各种缺点，有机光敏剂因能溶解于反应溶液中，其与反应产物以及未反应充分的反应物的分离和回收利用将成为问题。有机光敏剂活性较低，在不添加溶剂的情况下，反应时间需要20h小时以上，添加稀释溶剂的情况下反应时间可以降到10小时以内，但因溶剂稀释作用，单位时间内的反应物处理量较小。难以满足大规模制备的需要。
而固体光催化剂虽然能解决催化剂与反应体系的分离回收问题，但需要在大量溶剂存在的条件下反应，单位时间内的反应物处理量有限，制约了其使用。
因此，人们希望能有更新型的、活性更高的光催化降冰片烯异构化制备四环庚烷的催化剂，其最好能够在不添加溶剂的情况下，在10小时的反应时间以内，实现高于90%的四环庚烷的收率，且催化剂活性稳定，能够容易地分离回收。
本发明则旨在解决上述问题。
发明内容
第一方面，本发明涉及一种光催化降冰片二烯异构化制备四环庚烷的复合催化剂，其包括：
固体光催化剂；其选自TiO2、Ti-MCM-41、Ti-SBA-15、ZnO、WO3、Ta2O5或SrTiO3；
负载在所述固体光催化剂表面或孔道上的有机光敏剂，该有机光敏剂选自二苯甲酮、苯乙酮、米氏酮、四乙基米氏酮、二乙基米氏酮；
其中，有机光敏剂占所述固体光催化剂的0.5%～20%，重量百分比。
该第一方面的优选实施方案中，所述有机光敏剂与所述固体光催化剂的表面羟基相结合。
第二方面，本发明涉及一种光催化降冰片二烯异构化制备四环庚烷的复合催化剂的制备方法，包括以下步骤：
a.将有机光敏剂溶于有机溶剂中所得到的溶液与经干燥处理后的固体光催化剂按照有机光敏剂：固体光催化剂为0.5%～20%的重量比例混合并充分搅拌，以使有机光敏剂被吸附到固体光催化剂表面；其中所述固体光催化剂选自TiO2、Ti-MCM-41、Ti-SBA-15、ZnO、WO3、Ta2O5或SrTiO3；其中所述有机光敏剂选自二苯甲酮、苯乙酮、米氏酮、四乙基米氏酮、二乙基米氏酮；
b.过滤掉多余溶液，并将该吸附有有机光敏剂的固体光催化剂真空干燥。
本发明涉及的催化剂为复合型催化剂，即有机光敏剂与固体光催化剂相结合，发明人惊讶地发现，将有机光敏剂负载到所述固体光催化剂之上之后，二者之间产生了某种协同效应，能大幅度提高光催化异构化反应的效率。
附图说明
图1是本发明的催化剂作用下的四环庚烷收率随时间变化的图。
图2是本发明的催化剂重复使用下的四环庚烷收率随时间变化的图。
图3是对比催化剂重复使用下的四环庚烷收率随时间变化的图。
实施例
通过以下实施例来进一步说明本发明。实施例仅仅是示例性的，而非限制性的。
1.复合催化剂的制备
具体的有机光敏剂和固体光催化剂的选择和搭配如下表1中所示。具体制备过程如下：将有机光敏剂溶解于有机溶剂（例如乙醇）中配置成质量浓度20%的溶液，在100℃下干燥固体光催化剂；将含有有机光敏剂的溶液和干燥后的固体光催化剂按照有机光敏剂与固体光催化剂质量比为0.5%～20%的比例混合，搅拌24h，使有机光敏剂充分吸附在固体光催化剂上并与固体光催化剂表面或孔道内表面羟基基团发生充分的相互作用；然后，将多余溶液过滤、并在100℃下真空干燥5h（对真空度没有特殊要求），则得到本发明所述的复合催化剂。其中，由本发明的方法制备的催化剂被归入实施例中。
2.催化剂的催化活性实验
将上述各催化剂颗粒按照与降冰片二烯的重量比为2%～10%的比例加入到150ml降冰片二烯中，在氮气保护和磁力搅拌的条件下，在10～70℃下，采用400W高压汞灯照射8小时，来发生反应，定期采用色谱分析法来分析溶液组成，并计算目标产物四环庚烷的收率。不同时间下的收率如图1所示，各催化剂所对应的四环庚烷收率如表1所示。
此外，还在相同实验条件下测试了单独的有机光敏剂和单独的固体光催化剂以及有机光敏剂与固体光催化剂的简单的物理混合物的活性，这些并非由本发明的方法制备的催化剂被归入对比例中。
表1
3.结果分析
从图1可见，采用本发明的复合催化剂，四环庚烷的收率随时间呈线性增长的趋势，并能够在8小时以内就达到95%之高。
从表1中的实施例1与对比例1至对比例3之间的对比可见，在相同条件下，本发明的复合催化剂所实现的四环庚烷收率要远远高于单独的有机光敏剂、单独的固体光催化剂以及有机光敏剂与固体光催化剂的简单的物理混合物。这表明，经过本发明的方法制备的复合催化剂，在将有机光敏剂负载到固体光催化剂表面或孔道内部上的过程中，二者绝非简单的一种物质均匀地物理分散在另一种物质表面上那样的简单过程，而是二者之间发生了某种相互作用，产生了巨大的1+1>2的协同效果。对此现象，可能原因是有机光敏剂与固体光催化剂之间存在光生电荷的迁移，促进了电荷的分离并提高光生电荷用于异构反应的效率，但不排除存在其他原因，有待于今后做更多的探索。
表1中示出的本发明的实施例2至实施例11的实验结果也表明，本发明的复合催化剂，在与降冰片二烯的质量比为2%-8%的较低比例范围内，在10-70℃之间，都能实现大于90%的四环庚烷收率。这说明本发明的复合催化剂活性非常高，故可以减少催化剂的用量。
从催化活性实验条件来看，直接以反应物降冰片二烯作为介质，反应中没有使用任何溶剂，即便在这样的条件下，本发明的复合催化剂活性仍然很高，而对比例中的各催化剂则活性很差。这说明本发明的复合催化剂能够摆脱反应中对稀释溶剂的依赖，有利于提高单位体积催化剂所能处理的反应物的量。且本发明的复合催化剂为固体形式，便于分离回收并反复使用。
从图2可见，本发明的复合催化剂在重复使用五六次后，四环庚烷的收率仍较高，这说明本发明的复合催化剂活性非常稳定。这可能是因为本发明中将有机光敏剂负载在固体光催化剂上的过程中，二者通过化学作用牢固结合，致使有机光敏剂不容易流失到反应介质中所导致，当然，不排除还有发明人尚未知晓的其他原因导致了本发明的催化剂的稳定性。本发明的催化剂活性稳定性非常有利于其在工业上使用。
从图3可见，单独的有机光敏剂由于溶解在反应溶液中，无法重复利用，单独的固体光催化剂虽然能够重复利用，但活性呈不断下降的趋势，有机光敏剂与固体光催化剂的简单的物理混合物在第一次反应后的四环庚烷的收率迅速下降到与固体光催化剂相当的水平，说明其中的有机光敏剂已经流失，这说明对比例的催化剂的活性损失较大，不适合工业上反复使用。

Claims (4)

1.一种光催化降冰片二烯异构化制备四环庚烷的复合催化剂，其包括：
固体光催化剂；其选自TiO2、Ti-MCM-41、Ti-SBA-15、ZnO、WO3、Ta2O5或SrTiO3；
负载在所述固体光催化剂表面或孔道上的有机光敏剂，该有机光敏剂选自二苯甲酮、苯乙酮、米氏酮、四乙基米氏酮、二乙基米氏酮；
其中，有机光敏剂占所述固体光催化剂的0.5％～20％，重量百分比；
其中所述复合催化剂的制备方法包括以下步骤：
a.将有机光敏剂溶于有机溶剂中所得到的溶液与经干燥处理后的固体光催化剂按照有机光敏剂：固体光催化剂为0.5％～20％的重量比例混合并充分搅拌，以使有机光敏剂被吸附到固体光催化剂表面；
b.过滤掉多余溶液，并将该吸附有有机光敏剂的固体光催化剂真空干燥。
2.权利要求1的复合催化剂，其中所述有机光敏剂与所述固体光催化剂的表面或孔道内的羟基相结合。
3.一种光催化降冰片二烯异构化制备四环庚烷的复合催化剂的制备方法，包括以下步骤：
a.将有机光敏剂溶于有机溶剂中所得到的溶液与经干燥处理后的固体光催化剂按照有机光敏剂：固体光催化剂为0.5％～20％的重量比例混合并充分搅拌，以使有机光敏剂被吸附到固体光催化剂表面；其中所述固体光催化剂选自TiO2、Ti-MCM-41、Ti-SBA-15、ZnO、WO3、Ta2O5或SrTiO3；其中所述有机光敏剂选自二苯甲酮、苯乙酮、米氏酮、四乙基米氏酮、二乙基米氏酮；
b.过滤掉多余溶液，并将该吸附有有机光敏剂的固体光催化剂真空干燥。
4.权利要求3的方法，其中步骤a中，有机光敏剂在所述溶液中的质量浓度为20％，所述固体光催化剂在100℃下干燥，所述搅拌持续24h；其中步骤b中，所述真空干燥在100℃下进行5h。
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