【作者】 庄壮；

【导师】 辛峰；

【作者基本信息】 天津大学 ， 化学工程， 2013， 博士

【摘要】 钛硅分子筛（TS-1）具有独特的孔道结构，在以过氧化氢为氧化剂的一系列有机物的选择性催化氧化反应中具有优异的择形催化功能，若将TS-1分子筛以分子筛膜的形式负载于载体上用于催化反应具有潜在的应用前景。本论文以蒸汽辅助结晶法、水热合成法、二次生长法制备b取向的TS-1分子筛膜，并讨论一维窄尺寸的板式微反应器在环己酮氨肟化反应中的应用。主要研究内容和结果如下：一、利用蒸汽辅助结晶法在晶体硅表面上生长TS-1分子筛膜，研究晶化方法与晶化釜内水的用量对TS-1分子筛膜形成的影响。结果表明：分步蒸汽辅助结晶法有利于制备b轴取向的TS-1分子筛膜，且避免了凝胶形成过程中干燥温度对膜的取向性的影响，减少了成膜所需模板剂的使用量；相对一步蒸汽辅助结晶法，结晶时间缩短；另外，增加水热晶化釜内水的用量，有利于制备b取向的TS-1分子筛膜，且所得TS-1分子筛晶体尺寸增大。二、利用溶胶-凝胶法将TS-1前驱物涂覆于玻璃表面，然后采用水热合成法在修饰过的玻璃表面上制备b取向的单层TS-1分子筛膜。实验考察了浸涂时间、水热晶化釜放置方式及结晶时间对取向TS-1分子筛膜的影响。结果表明：浸涂时间延长易于形成b取向TS-1分子筛膜，且浸涂时间为12h时，所得分子筛膜为单层；晶化釜旋转速度为10转/分，且结晶时间为24h时，在玻璃表面形成b取向的单层TS-1分子筛膜。三、以聚丙烯酰胺修饰玻璃表面，采用蒸发-沉积法将不同尺寸的TS-1分子筛排列在玻璃表面，形成TS-1分子筛晶种层，考察二次水热合成时间对取向TS-1分子筛膜的影响。研究表明：聚丙烯酰胺的修饰有利于实现TS-1分子筛微晶的b取向排布；二次水热合成时间为12h时，所得TS-1分子筛以b取向生长在玻璃表面，随着合成时间延长，非b取向TS-1分子筛膜逐渐增厚。四、通过构建具有一维窄尺寸的板式微反应器，研究取向和随机取向TS-1分子筛膜催化环己酮氨肟化反应活性，进而以取向TS-1分子筛膜为研究对象，分别考察TS-1分子筛用量、反应温度、WHSV对环己酮转化率和环己酮肟选择性的影响，以及取向TS-1分子筛膜的催化寿命。结果表明：取向TS-1分子筛膜使得环己酮转化率和环己酮肟的选择性分别达到0.96和0.98，而随机取向TS-1分子筛膜的转化率和选择性为0.81和0.82；当反应温度为343K、TS-1用量为0.16g，WHSV为5h-1或10h-1时，反应条件为最优，环己酮转化率和环己酮肟的选择性分别达到0.97和0.98，其催化寿命分别维持在144h或94h左右。更多还原

【Abstract】 Titanium Silicalite-1(TS-1) molecular sieve possesses an outstandingshape-selective catalysis in a series of organic catalytic-oxidation reactions with H2O2as oxidant due to its unique pore structure, and TS-1molecular sieve films supportedon substrate have potential applications in the oxidation reactions. In this paper,b-oriented TS-1molecular sieve films were fabricated by stepwise steaming-assistedcrystallization, hydrothermal synthesis and secondary growth, respectively. Moreover,a narrow-sized plated micro reactor was constructed and used to evaluate the reactionof cyclohexanone ammoximation. The main researchs and results are as follows:1. TS-1molecular sieve films grew on the surface of silicon wafers bysteaming-assisted crystallization, and the effects of the volume ratios of H2O inautoclave and crystallization methods on TS-1films were also investigated. Theresults showed that b-oriented TS-1film could be prepared over the silicon wafer bystepwise steaming-assisted crystallization, and such a method avoided the formationof the dried gel over the Si wafer before crystallization, and allowed the limitedconsumption of template required for growing TS-1crystals. In contrast to one-stepsteaming-assisted crystallization, the stepwise crystallization reduced crystallizationtime for the formation of the oriented TS-1film. In addition, the increased volumeratio of water was in favor for the preparation of the b-oriented TS-1film.2. The surface of glasses was modified with TS-1precursors by sol-gel method,and b-oriented TS-1monolayer grew on the modified glass by hydrothermal synthesis.The effects of immersion time, rotation of autoclave and crystallization on TS-1filmswere investigated. The results showed that the oriented TS-1monolayer could beprepared with the immersion time of12h. A b-oriented TS-1monolayer could befabricated on the glass with the rotation speed of10rad/min and the crystallizationtime of24h.3. TS-1seed layers with the different sizes of TS-1crystals were prepared onPAM-modified glasses by evaporation-deposition method. The effects ofcrystallization time of secondary growth on TS-1films were also investigated. Theresult showed that the PAM-modified glasses were in favor for the oriented alignmentof TS-1crystals. The oriented TS-1film could be formed on the glass while the crystallization time of secondary growth was12h, and non-b oriented TS-1filmthickness increased with the increasing crystallization time.4. The narrow-sized micro reactor was constructed to evaluate the catalyticperformance of oriented and random TS-1films in the reaction of cyclohexanoneammoximation. The effects of different reaction conditions on the cyclohexanoneconversion and the oxime selectivity and the catalyst lifetime of the oriented TS-1films were investigated. In the reaction of cyclohexanone ammoximation, thecyclohexanone conversion and the oxime selectivity of the oriented TS-1films were0.96and0.98, but the conversion and the selectivity of random ones were merely0.81and0.82; the optimized condition of reaction was WHSV of5h-1or10h-1, theamount of TS-1of0.16g, reaction temperature of343K, and the cyclohexanoneconversion and the oxime selectivity were0.97and0.98, respectively, meanwhile, thelifetimes of the reaction were144h or94h.更多还原