沸石分子筛的形貌控制与催化吸附功能的研究
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摘要
微孔分子筛具有丰富的孔道结构,大的比表面积,较窄的孔径分布,高的热与水热稳定性以及超强的吸附能力,这些优异的性能使微孔分子筛成为工业界最重要的一类催化剂。分子筛的应用性能与其形貌有着密切的关系,例如大尺寸分子筛晶体在研究分子在分子筛内吸附、扩散机理以及加工成光学器件等方面有着重要应用,而小尺寸分子筛晶体由于反应物与产物更易扩散从而表现出良好的催化活性与使用寿命,在分子筛膜的研究工作中则需要粒径均一的纳米级分子筛晶体,并且要求分子筛晶体有特定的空间排列方向。可见分子筛的形貌控制工作无论是在基础理论研究方面还是从实际应用角度来说都极具意义。
本论文试图通过选择不同的沸石分子筛合成体系与不同的添加剂,并经过优化合成条件,如添加剂用量、添加剂加入时间、晶化温度、晶化时间,从而得到具有不同形貌的沸石分子筛产品。同时本论文对所得到分子筛产品的合成机理与催化吸附性能进行了全面系统的研究。
微孔MFI结构钛硅分子筛TS-1自从1983年被意大利Enichem公司开发出来以后,就以其良好的催化活性与稳定性而受到人们的广泛重视。特别需要提到的是,TS-1分子筛在催化氧化反应中更是表现出极高的催化活性,这些氧化反应包括烯烃的环氧化反应,芳香烃的羟化反应,烷烃、胺、醇、硫化物以及醚的氧化反应,在这些氧化反应中均需要用到对环境友好的H202作为氧化剂。TS-1的催化活性强烈依赖于其晶体尺寸。如果TS-1晶体尺寸为纳米级别(小于0.3微米),那么其在氧化反应中如苯酚羟化反应就会有很好的活性,相反若TS-1晶体的尺寸较大(大于1.0微米),其活性就会非常低。这主要是因为纳米级别分子筛的孔道长度比大晶体的孔道长度要短,反应物和产物分子在纳米分子筛中的传输与扩散更加容易,另外纳米分子筛的活性位暴露的也要更多,这同样有利于纳米分子筛的高活性。但是纳米分子筛尺寸小,往往在分离时就必须采用高速离心技术,这种分离方法大大增加了生产成本,在工业大规模生产也很难实现。为了克服以上问题,Xiao F S等人利用钛硅前驱体与三嵌段共聚物进行自组装,进而得到有序介孔钛硅材料MTS-9。MTS-9尺寸较大可以通过抽滤方法实现有效分离,但是MTS-9中钛物种的热稳定性相对较低,这个缺点严重影响了MTS-9在一系列催化反应中的催化性能。近些年来研究人员通过大量的研究工作使钛物种的热稳定性得到显著的提高,但是得到的钛硅材料的催化活性与纳米TS-1比起来还是要低许多。由此可见,一种既具有纳米TS-1的高催化活性同时又能够通过简单的抽滤方法实现分离的催化材料对于工业生产来说极具意义。我们通过在纳米TS-1合成体系内加入无机添加剂H2O2成功得到一种由纳米TS-1晶体聚集的大块状TS-1颗粒(Bulky-TS-1),这种大块状颗粒产品的尺寸可达到几十微米,通过简单抽滤方法就能够实现有效分离。由于大块状颗粒由纳米晶体聚集而成,因而保持了纳米TS-1的高催化活性,在苯酚羟化反应中大块状产品表现出与纳米TS-1相似的高活性。
我们知道,MFI型分子筛骨架结构为各向异性,两种类型的十员环孔道相互交叉,它们分别是平行于b-轴方向的十员环直孔道(5.3×5.6(?)),平行于a-轴方向的之字型十员环孔道(5.1×5.5(?))。由于直孔道的孔径尺寸更大,因此动力学半径尺寸较大的分子在直孔道内的传输与扩散要更加容易,如环己酮肟与对二甲苯(动力学半径为5.8(?))。而对于之字型孔道来说,由于其尺寸相对较小,较大尺寸分子在其内部的扩散与传输就要更加的困难。对于MFI型分子筛,更短的b-轴长度就意味着分子在分子筛内部具有更高的吸附与扩散速率,因而通过控制MFI分子筛晶体形貌,控制b-轴长度就可以有效控制MFI型分子筛的吸附与催化等性能。通过控制MFI型分子筛如ZSM-5或TS-1的形貌生长进而控制其性能的工作之前有过一些报道。例如Hwang等人在微波辐射加热条件下,成功得到分子筛晶体沿着b-轴方向相互连接的纤维状形貌TS-1产品,他们所得到的纤维状TS-1具有更高的催化活性,而且在二甲苯选择性吸附实验中,纤维状TS-1同样表现出优异的择形吸附性能。Ryoo R等人利用一种特殊的表面活性剂C22H45-N1(CH3)2-C6H12-N1(CH3)2-C6H13成功得到b-轴方向非常薄的MFI型分子筛,他们得到的产品只有两个MFI晶胞的厚度,这种非常薄的结构对于化学反应中的反应物与产物在其内部的扩散非常有利,在大分子催化反应中其产品表现出明显高于传统MFI分子筛的催化活性与更长的使用寿命。到目前为止,分子筛的形貌控制工作虽然取得了很大进展,但是多数工作需要非常苛刻的合成条件与非常昂贵的有机模板剂,并且合成过程复杂,这些问题限制了它们在工业生产中的实际应用。因此,根据特定的需要,利用价格低廉的原料并通过简单的合成过程实现对分子筛形貌的有效控制就成为一项极具意义的工作。我们通过在传统TS-1合成体系内添加价格低廉的有机添加剂并利用一步水热合成法,成功实现了对TS-1分子筛的形貌控制。我们利用尿素作为添加剂得到b-轴方向非常薄的片层状TS-1 (TS-1-S),而利用氟碳表面活性剂FC-4作为添加剂我们成功得到b-轴方向非常长的链状TS-1 (TS-1-C)。通过改变实验条件,我们可以在80纳米至5微米长度范围内对TS-1的b-轴方向长度进行有效控制。我们得到的不同b-轴长度TS-1产品在催化贝克曼重排反应以及二甲苯异构体的选择性吸附实验中表现出优异的性能。
Y型沸石具有三维畅通的骨架结构、非常高的热稳定性与水热稳定性,在石油炼制及化学工业生产中,尤其是在流动床催化裂化(FCC)反应中表现出不可替代的作用。作为吸附剂,Y沸石对挥发性有机物同样表现出优良的吸附性能。Y沸石的催化性能与吸附性能与其骨架的硅铝摩尔比有着非常密切的关系。例如,当提高Y沸石的骨架硅铝比值时,其热稳定性与水热稳定性会随之提高,这将有利于制备出性能优异的FCC反应催化剂。一般情况下,常规Y型沸石需要在100℃左右晶化制备,而得到产品的摩尔硅铝比值为5.0-5.3,为了得到具有更高骨架硅铝比值的Y沸石产品,人们做了大量研究工作。二次后处理法是目前制备高硅铝比Y沸石应用比较广泛的一种方法。例如有人在高温条件下利用水蒸气处理常规Y沸石,Y沸石骨架中的铝会被部分脱除,骨架结构则会得到较好的保持,得到的产品具有很高的硅铝比,水热稳定性非常高,催化活性可以得到大幅度提升。二次法合成高硅铝比Y沸石虽然能够得到具有较高骨架硅铝比的产品,但是合成过程过于复杂,生产成本也较高,因而采用一步法直接合成高硅铝比Y沸石,就成为一项具有重要实际意义的工作。人们发现,较高的晶化温度对于得到高硅铝比Y沸石是有利的,但是较高的晶化温度往往会导致Y沸石产品的转晶。当前,Y沸石的合成大多是在110℃以下采取水热合成。虽然有人报道能够在高温条件(110-150℃)合成出Y型沸石,但是在这些合成中必须要用到有机模板剂,有机模板剂的加入一方面大大提高了生产成本,另一方面会使合成过程变得复杂。我们则在不添加有机模板剂的条件下,仅仅通过在Y沸石合成体系内加入少量甲基三乙氧基硅烷,在高晶化温度140℃条件下,水热法一步合成出具有六方片层状形貌的Y型沸石产品。与传统Y沸石相比,我们得到的产品具有更高的骨架硅铝比以及更小的晶体尺寸,同时对有机挥发物表现出明显高于传统Y沸石的吸附性能。
Zeolites are regarded as the most important heterogeneous acid catalyst in industry due to their rich channel structure, large surface area, narrow pore size distribution, high thermal and hydrothermal stabilities and high adsorption capacity. The service performance of zeolites are closely related to their morphology, for example, large size zeolites have an important application in studying the adsorption and diffusion mechanism of organic molecules or designing optical devices. Small size zeolites show excellent catalytic performance owes to good adsorptive and diffusive property of reactants and products, while in the fields of zeolites film, small and uniform zeolite crystals are necessary and these crystals need to be arranged in preferred orientation. Thus, the morphology control of zeolites is very meaningful not only for basic research but also for practical application.
The present project try to obtain zeolites with different morphology by choosing different zeolites synthesis system and different additives and the synthesis conditions such as amount of additives, adding order of additives, crystallization temperature, crystallization time also need to be optimized. The crystallization mechanism and the catalytic and adsorptive properties of the products are also studied systematically in present project.
Microporous titanosilicate zeolite with MFI structure (TS-1), discovered by Enichem Company in 1983, obtains great attention for its excellent catalytic activity and stability. Especially, TS-1 shows superior catalytic properties in a series of oxidations such as epoxidation of linear olefins, hydroxylation of aromatics, oxidations of linear alkanes, amines, alcohols, sulfur compounds and ethers in the presence of environmentally benign oxidant of H2O2. The catalytic activities of TS-1 zeolite is dramatically dependent on the crystal sizes. For example, TS-1 nanocrystals (less than 0.3μm) show good activity in the hydroxylation of phenol, while the crystals larger than 1μm are almost inactive. For TS-1 nanocrystals, the transmission and diffusion of reactants and products are much more easier and there are more active sites exposed. The preparation of TS-1 crystals with small sizes (<0.3μm) usually required a centrifugation route for the separation of TS-1 nanocrystals from a slurry system, which is not suitable for the production of TS-1 zeolite in a large scale for industrial process. To overcome these problems, the self-assembly of preformed titanosilicate precusors with triblock copolymers has been employed by Xiao F.-S., giving ordered mesoporous titanosilicates (MTS-9). In this case, MTS-9 was easily obtained from a normal industrial route of filtration. However, the thermal stability of titanium in MTS-9 is relatively low, which strongly influences its catalytic properties in a series of oxidations. Despite of encouraging progresses for the thermal stability of titanium species in recent years, the catalytic performances of the current titanosilicate materials are yet generally lower than those of TS-1 nanocrystals. Therefore, the preparation of TS-1 zeolite with good properties in catalytic oxidations by a simple filtration route is strongly desirable. We demonstrate here a facile filtration methodology for preparation of stable bulky-particles of TS-1 zeolite with good catalytic activities (Bulky-TS-1) in the presence of H2O2. Bulky-TS-1 exhibits comparable properties in catalytic phenol hydroxylation with TS-1 nanocrystals collected from a high-speed centrifugation.
MFI-type zeolite possesses an anisotropic framework with two intersecting 10-membered ring channels including straight channels (5.3x5.6 A) parallel to b-axis and zig-zag channels (5.1x5.5 A) parallel to a-axis. The straight channels are favorable for diffusion and formation of relatively large products such as cyclohexanone oxime and p-xylene (kinetic diameter ca.5.8 A), while the zig-zag channels are difficult for the adsorption of these molecules due to the shape selectivity. The MFI zeolites with shorter b-orientation mean higher diffusive and adsorptive rates for molecules. Therefore, by controlling crystalline length along b-axis, catalytic and adsorptive properties over MFI crystals could be significantly adjusted. There are successful examples for preferential growth of ZSM-5 (aluminosilicate MFI-type) and TS-1 crystals. Hwang et al. show microwave fabrication of MFI zeolite crystals with a fibrous morphology and the product they got shows excellent catalytic and adsorptive property. Ryoo R et al produced MFI zeolites with very short b-axis by empoying a kind of special surfactant C22H45-N1(CH3)2-C6H12-N1(CH3)2-C6H13. The thickness of the product is as thin as two crystal cell and the short b-oriented length is favorable for the catalytic reaction. Despite of encouraging progresses for the zeolite morphology control in recent years, most need complex procedure and expensive template and these are not suitable for industrial process. Thus, the morphology control of zeolite by employing cheap raw materials and simple synthesis process is a meaningful work. We report an one-pot growth of TS-1 crystals with various b-oriented length by introducing organic additives in the starting titanosilicate gels. After addition of urea in the starting gel, TS-1 crystals with sheet-like morphology designated as TS-1-S have been successfully synthesized. After addition of surfactant FC-4, TS-1 with chain-like morphology designated as TS-1-C have also been successfully obtained. By optimizing the synthesis conditions,b-oriented length of the TS-1 crystals can be varied from 80 nm to 5μm. The TS-1 products we obtained exhibit quite distinguishable catalytic activities in the Beckmann rearrangement of cyclohexanone oxime and good adsorptive properties for xylenes.
Zeolite Y possesses a three dimensional channel structure and high thermal and hydrothermal stability, in chemical industry especially for FCC reaction, zeolite Y shows excellent catalytic property. As a adsorbent, zeolite Y also shows good adsorptive property towards volatile organic compounds. The Si/Al ratio of framework is very important for zeolite Y. As increasing the Si/Al ratio, the stability of Y can be improved, this is favorable for FCC reaction. Generally, the crystallization temperature of Y is 100℃and the Si/Al ratio of the framework is about 5.0-5.3. So far, researchers have made lots of efforts to increase the Si/Al ratio of zeolite Y. Post treatment is a popular method for preparing zeolite Y with higher Si/Al ratio. For example, high temperature steam can be employed to dealuminize zeolite Y and the framework can be maintained, thus high Si/Al ratio Y can be obtained. Although post treatment method is effective to prepare high Si/Al ratio Y, the synthesis procedure is complex and the cost is high. If high Si/Al ratio Y can be synthesized by one-pot method, it will be a very meaningful work for industry. We know high crystallization temperature is favorable for synthesizing high Si/Al ratio Y, but high crystallization temperature sometimes leads to the phase transition of zeolite crystals. Up to now, crystallization temperature of Y zeolite is mainly lower than 110℃, although some reached 110-150℃, the expensive organic templates must be employed and the addition of template will make the synthesizing process more complex. Here, without using organic template, just by adding a little methyltriethoxysilane (MTS), we have successfully obtained sheet-like zeolite Y crystals in high crystallization temperature (140℃) through one-pot hydrothermal synthesis. Compared with conventional Y zeolite, Y product we got own higher Si/Al ratio of the framework, smaller crystal size and better adsorptive property towards organic volatile compounds.
本论文试图通过选择不同的沸石分子筛合成体系与不同的添加剂,并经过优化合成条件,如添加剂用量、添加剂加入时间、晶化温度、晶化时间,从而得到具有不同形貌的沸石分子筛产品。同时本论文对所得到分子筛产品的合成机理与催化吸附性能进行了全面系统的研究。
微孔MFI结构钛硅分子筛TS-1自从1983年被意大利Enichem公司开发出来以后,就以其良好的催化活性与稳定性而受到人们的广泛重视。特别需要提到的是,TS-1分子筛在催化氧化反应中更是表现出极高的催化活性,这些氧化反应包括烯烃的环氧化反应,芳香烃的羟化反应,烷烃、胺、醇、硫化物以及醚的氧化反应,在这些氧化反应中均需要用到对环境友好的H202作为氧化剂。TS-1的催化活性强烈依赖于其晶体尺寸。如果TS-1晶体尺寸为纳米级别(小于0.3微米),那么其在氧化反应中如苯酚羟化反应就会有很好的活性,相反若TS-1晶体的尺寸较大(大于1.0微米),其活性就会非常低。这主要是因为纳米级别分子筛的孔道长度比大晶体的孔道长度要短,反应物和产物分子在纳米分子筛中的传输与扩散更加容易,另外纳米分子筛的活性位暴露的也要更多,这同样有利于纳米分子筛的高活性。但是纳米分子筛尺寸小,往往在分离时就必须采用高速离心技术,这种分离方法大大增加了生产成本,在工业大规模生产也很难实现。为了克服以上问题,Xiao F S等人利用钛硅前驱体与三嵌段共聚物进行自组装,进而得到有序介孔钛硅材料MTS-9。MTS-9尺寸较大可以通过抽滤方法实现有效分离,但是MTS-9中钛物种的热稳定性相对较低,这个缺点严重影响了MTS-9在一系列催化反应中的催化性能。近些年来研究人员通过大量的研究工作使钛物种的热稳定性得到显著的提高,但是得到的钛硅材料的催化活性与纳米TS-1比起来还是要低许多。由此可见,一种既具有纳米TS-1的高催化活性同时又能够通过简单的抽滤方法实现分离的催化材料对于工业生产来说极具意义。我们通过在纳米TS-1合成体系内加入无机添加剂H2O2成功得到一种由纳米TS-1晶体聚集的大块状TS-1颗粒(Bulky-TS-1),这种大块状颗粒产品的尺寸可达到几十微米,通过简单抽滤方法就能够实现有效分离。由于大块状颗粒由纳米晶体聚集而成,因而保持了纳米TS-1的高催化活性,在苯酚羟化反应中大块状产品表现出与纳米TS-1相似的高活性。
我们知道,MFI型分子筛骨架结构为各向异性,两种类型的十员环孔道相互交叉,它们分别是平行于b-轴方向的十员环直孔道(5.3×5.6(?)),平行于a-轴方向的之字型十员环孔道(5.1×5.5(?))。由于直孔道的孔径尺寸更大,因此动力学半径尺寸较大的分子在直孔道内的传输与扩散要更加容易,如环己酮肟与对二甲苯(动力学半径为5.8(?))。而对于之字型孔道来说,由于其尺寸相对较小,较大尺寸分子在其内部的扩散与传输就要更加的困难。对于MFI型分子筛,更短的b-轴长度就意味着分子在分子筛内部具有更高的吸附与扩散速率,因而通过控制MFI分子筛晶体形貌,控制b-轴长度就可以有效控制MFI型分子筛的吸附与催化等性能。通过控制MFI型分子筛如ZSM-5或TS-1的形貌生长进而控制其性能的工作之前有过一些报道。例如Hwang等人在微波辐射加热条件下,成功得到分子筛晶体沿着b-轴方向相互连接的纤维状形貌TS-1产品,他们所得到的纤维状TS-1具有更高的催化活性,而且在二甲苯选择性吸附实验中,纤维状TS-1同样表现出优异的择形吸附性能。Ryoo R等人利用一种特殊的表面活性剂C22H45-N1(CH3)2-C6H12-N1(CH3)2-C6H13成功得到b-轴方向非常薄的MFI型分子筛,他们得到的产品只有两个MFI晶胞的厚度,这种非常薄的结构对于化学反应中的反应物与产物在其内部的扩散非常有利,在大分子催化反应中其产品表现出明显高于传统MFI分子筛的催化活性与更长的使用寿命。到目前为止,分子筛的形貌控制工作虽然取得了很大进展,但是多数工作需要非常苛刻的合成条件与非常昂贵的有机模板剂,并且合成过程复杂,这些问题限制了它们在工业生产中的实际应用。因此,根据特定的需要,利用价格低廉的原料并通过简单的合成过程实现对分子筛形貌的有效控制就成为一项极具意义的工作。我们通过在传统TS-1合成体系内添加价格低廉的有机添加剂并利用一步水热合成法,成功实现了对TS-1分子筛的形貌控制。我们利用尿素作为添加剂得到b-轴方向非常薄的片层状TS-1 (TS-1-S),而利用氟碳表面活性剂FC-4作为添加剂我们成功得到b-轴方向非常长的链状TS-1 (TS-1-C)。通过改变实验条件,我们可以在80纳米至5微米长度范围内对TS-1的b-轴方向长度进行有效控制。我们得到的不同b-轴长度TS-1产品在催化贝克曼重排反应以及二甲苯异构体的选择性吸附实验中表现出优异的性能。
Y型沸石具有三维畅通的骨架结构、非常高的热稳定性与水热稳定性,在石油炼制及化学工业生产中,尤其是在流动床催化裂化(FCC)反应中表现出不可替代的作用。作为吸附剂,Y沸石对挥发性有机物同样表现出优良的吸附性能。Y沸石的催化性能与吸附性能与其骨架的硅铝摩尔比有着非常密切的关系。例如,当提高Y沸石的骨架硅铝比值时,其热稳定性与水热稳定性会随之提高,这将有利于制备出性能优异的FCC反应催化剂。一般情况下,常规Y型沸石需要在100℃左右晶化制备,而得到产品的摩尔硅铝比值为5.0-5.3,为了得到具有更高骨架硅铝比值的Y沸石产品,人们做了大量研究工作。二次后处理法是目前制备高硅铝比Y沸石应用比较广泛的一种方法。例如有人在高温条件下利用水蒸气处理常规Y沸石,Y沸石骨架中的铝会被部分脱除,骨架结构则会得到较好的保持,得到的产品具有很高的硅铝比,水热稳定性非常高,催化活性可以得到大幅度提升。二次法合成高硅铝比Y沸石虽然能够得到具有较高骨架硅铝比的产品,但是合成过程过于复杂,生产成本也较高,因而采用一步法直接合成高硅铝比Y沸石,就成为一项具有重要实际意义的工作。人们发现,较高的晶化温度对于得到高硅铝比Y沸石是有利的,但是较高的晶化温度往往会导致Y沸石产品的转晶。当前,Y沸石的合成大多是在110℃以下采取水热合成。虽然有人报道能够在高温条件(110-150℃)合成出Y型沸石,但是在这些合成中必须要用到有机模板剂,有机模板剂的加入一方面大大提高了生产成本,另一方面会使合成过程变得复杂。我们则在不添加有机模板剂的条件下,仅仅通过在Y沸石合成体系内加入少量甲基三乙氧基硅烷,在高晶化温度140℃条件下,水热法一步合成出具有六方片层状形貌的Y型沸石产品。与传统Y沸石相比,我们得到的产品具有更高的骨架硅铝比以及更小的晶体尺寸,同时对有机挥发物表现出明显高于传统Y沸石的吸附性能。
Zeolites are regarded as the most important heterogeneous acid catalyst in industry due to their rich channel structure, large surface area, narrow pore size distribution, high thermal and hydrothermal stabilities and high adsorption capacity. The service performance of zeolites are closely related to their morphology, for example, large size zeolites have an important application in studying the adsorption and diffusion mechanism of organic molecules or designing optical devices. Small size zeolites show excellent catalytic performance owes to good adsorptive and diffusive property of reactants and products, while in the fields of zeolites film, small and uniform zeolite crystals are necessary and these crystals need to be arranged in preferred orientation. Thus, the morphology control of zeolites is very meaningful not only for basic research but also for practical application.
The present project try to obtain zeolites with different morphology by choosing different zeolites synthesis system and different additives and the synthesis conditions such as amount of additives, adding order of additives, crystallization temperature, crystallization time also need to be optimized. The crystallization mechanism and the catalytic and adsorptive properties of the products are also studied systematically in present project.
Microporous titanosilicate zeolite with MFI structure (TS-1), discovered by Enichem Company in 1983, obtains great attention for its excellent catalytic activity and stability. Especially, TS-1 shows superior catalytic properties in a series of oxidations such as epoxidation of linear olefins, hydroxylation of aromatics, oxidations of linear alkanes, amines, alcohols, sulfur compounds and ethers in the presence of environmentally benign oxidant of H2O2. The catalytic activities of TS-1 zeolite is dramatically dependent on the crystal sizes. For example, TS-1 nanocrystals (less than 0.3μm) show good activity in the hydroxylation of phenol, while the crystals larger than 1μm are almost inactive. For TS-1 nanocrystals, the transmission and diffusion of reactants and products are much more easier and there are more active sites exposed. The preparation of TS-1 crystals with small sizes (<0.3μm) usually required a centrifugation route for the separation of TS-1 nanocrystals from a slurry system, which is not suitable for the production of TS-1 zeolite in a large scale for industrial process. To overcome these problems, the self-assembly of preformed titanosilicate precusors with triblock copolymers has been employed by Xiao F.-S., giving ordered mesoporous titanosilicates (MTS-9). In this case, MTS-9 was easily obtained from a normal industrial route of filtration. However, the thermal stability of titanium in MTS-9 is relatively low, which strongly influences its catalytic properties in a series of oxidations. Despite of encouraging progresses for the thermal stability of titanium species in recent years, the catalytic performances of the current titanosilicate materials are yet generally lower than those of TS-1 nanocrystals. Therefore, the preparation of TS-1 zeolite with good properties in catalytic oxidations by a simple filtration route is strongly desirable. We demonstrate here a facile filtration methodology for preparation of stable bulky-particles of TS-1 zeolite with good catalytic activities (Bulky-TS-1) in the presence of H2O2. Bulky-TS-1 exhibits comparable properties in catalytic phenol hydroxylation with TS-1 nanocrystals collected from a high-speed centrifugation.
MFI-type zeolite possesses an anisotropic framework with two intersecting 10-membered ring channels including straight channels (5.3x5.6 A) parallel to b-axis and zig-zag channels (5.1x5.5 A) parallel to a-axis. The straight channels are favorable for diffusion and formation of relatively large products such as cyclohexanone oxime and p-xylene (kinetic diameter ca.5.8 A), while the zig-zag channels are difficult for the adsorption of these molecules due to the shape selectivity. The MFI zeolites with shorter b-orientation mean higher diffusive and adsorptive rates for molecules. Therefore, by controlling crystalline length along b-axis, catalytic and adsorptive properties over MFI crystals could be significantly adjusted. There are successful examples for preferential growth of ZSM-5 (aluminosilicate MFI-type) and TS-1 crystals. Hwang et al. show microwave fabrication of MFI zeolite crystals with a fibrous morphology and the product they got shows excellent catalytic and adsorptive property. Ryoo R et al produced MFI zeolites with very short b-axis by empoying a kind of special surfactant C22H45-N1(CH3)2-C6H12-N1(CH3)2-C6H13. The thickness of the product is as thin as two crystal cell and the short b-oriented length is favorable for the catalytic reaction. Despite of encouraging progresses for the zeolite morphology control in recent years, most need complex procedure and expensive template and these are not suitable for industrial process. Thus, the morphology control of zeolite by employing cheap raw materials and simple synthesis process is a meaningful work. We report an one-pot growth of TS-1 crystals with various b-oriented length by introducing organic additives in the starting titanosilicate gels. After addition of urea in the starting gel, TS-1 crystals with sheet-like morphology designated as TS-1-S have been successfully synthesized. After addition of surfactant FC-4, TS-1 with chain-like morphology designated as TS-1-C have also been successfully obtained. By optimizing the synthesis conditions,b-oriented length of the TS-1 crystals can be varied from 80 nm to 5μm. The TS-1 products we obtained exhibit quite distinguishable catalytic activities in the Beckmann rearrangement of cyclohexanone oxime and good adsorptive properties for xylenes.
Zeolite Y possesses a three dimensional channel structure and high thermal and hydrothermal stability, in chemical industry especially for FCC reaction, zeolite Y shows excellent catalytic property. As a adsorbent, zeolite Y also shows good adsorptive property towards volatile organic compounds. The Si/Al ratio of framework is very important for zeolite Y. As increasing the Si/Al ratio, the stability of Y can be improved, this is favorable for FCC reaction. Generally, the crystallization temperature of Y is 100℃and the Si/Al ratio of the framework is about 5.0-5.3. So far, researchers have made lots of efforts to increase the Si/Al ratio of zeolite Y. Post treatment is a popular method for preparing zeolite Y with higher Si/Al ratio. For example, high temperature steam can be employed to dealuminize zeolite Y and the framework can be maintained, thus high Si/Al ratio Y can be obtained. Although post treatment method is effective to prepare high Si/Al ratio Y, the synthesis procedure is complex and the cost is high. If high Si/Al ratio Y can be synthesized by one-pot method, it will be a very meaningful work for industry. We know high crystallization temperature is favorable for synthesizing high Si/Al ratio Y, but high crystallization temperature sometimes leads to the phase transition of zeolite crystals. Up to now, crystallization temperature of Y zeolite is mainly lower than 110℃, although some reached 110-150℃, the expensive organic templates must be employed and the addition of template will make the synthesizing process more complex. Here, without using organic template, just by adding a little methyltriethoxysilane (MTS), we have successfully obtained sheet-like zeolite Y crystals in high crystallization temperature (140℃) through one-pot hydrothermal synthesis. Compared with conventional Y zeolite, Y product we got own higher Si/Al ratio of the framework, smaller crystal size and better adsorptive property towards organic volatile compounds.
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