Ultrasonic‐Assistance and Aging Time Effects on the Zeolitation Process of BZSM‐5 Zeolite

The isomorphic substitution of boron into ZSM‐5 zeolite under static hydrothermal condition was investigated. Evaluation of hydrothermal synthesis of BZSM‐5 was performed by treating the synthesis mixture by different aging processes, namely, ultrasonic, static, stirring, and microwave‐assisted aging prior to the conventional hydrothermal treatment. The synthetic processes with different techniques of aging prior to the onset of conventional hydrothermal crystallization were compared with a process without any prior aging. The obtained results showed that the ultrasonic and microwave assisted aging shortened the crystallization time and altered the crystal size and the morphology of the obtained products. The characteristics of the synthesized products were obtained by FT‐IR spectroscopic, XRD and SEM techniques.     

Laser‐Induced Crystallization and Crystal Growth

Recent streams of laser studies on crystallization and crystal growth are summarized and reviewed. Femtosecond multiphoton excitation of solutions leads to their ablation at the focal point, inducing local bubble formation, shockwave propagation, and convection flow. This phenomenon, called “laser micro tsunami” makes it possible to trigger crystallization of molecules and proteins from their supersaturated solutions. Femtosecond laser ablation of a urea crystal in solution triggers the additional growth of a single daughter crystal. Intense continuous wave (CW) near infrared laser irradiation at the air/solution interface of heavy‐water amino acid solutions results in trapping of the clusters and evolves to crystallization. A single crystal is always prepared in a spatially and temporally controlled manner, and the crystal polymorph of glycine depends on laser power, polarization, and solution concentration. Upon irradiation at the glass/solution interface, a millimeter‐sized droplet is formed, and a single crystal is formed by shifting the irradiation position to the surface. Directional and selective crystal growth is also possible with laser trapping. Finally, characteristics of laser‐induced crystallization and crystal growth are summarized.     

纳米 ZSM-22分子筛的水热合成及在甲醇转化反应中的性能

分子筛结构的独特性和多样性使其在催化、吸附分离和离子交换等领域有着广泛应用.近年来,纳米分子筛制备和应用受到极大关注.与传统微米分子筛相比,纳米分子筛具有较小的晶粒尺寸、较大的外表面积和较高的表面活性,能显著提高其分离和催化性能.制备纳米晶体的常用方法有过量模板法、空间限定法、晶种法、离子热合成法及微反应器合成法等.目前,已合成出多种拓扑结构的纳米分子筛,包括 FAU, MFI, MEL和CHA等. ZSM-22是一种具有 TON拓扑结构的一维十元环直孔道分子筛(孔口尺寸为0.45 nm ×0.55 nm),在长链烷烃异构化和烯烃异构化等反应中表现出优异的催化活性.水热合成法是制备 ZSM-22分子筛最常用的方法,所得样品晶粒尺寸为2–15μm,但由于 ZSM-22分子筛是一种亚稳态结构,为了防止杂晶生成,合成通常是在剧烈搅拌(通常大于400 r/min)下进行.目前已有报道在较低转速下合成 ZSM-22分子筛,但产物仍为微米晶体;或在微波辅助水热合成条件下合成亚微米 ZSM-22分子筛,但晶体尺寸不可调且合成过程需要较高功率的微波反应器.因此,在水热条件下合成纯纳米 ZSM-22分子筛仍然是一个巨大挑战.本文在上述研究基础上采用改进的水热合成法成功合成出纳米 ZSM-22分子筛,考察了转速﹑硅铝比及乙醇共溶剂对晶粒尺寸的影响,比较了纳米和常规微米 ZSM-22分子筛的甲醇转化反应性能.结果表明,采用改进的水热合成法能够在较低转速下合成出纳米 ZSM-22分子筛,晶体尺寸在150–800 nm范围可调.通过考察转速对晶粒尺寸的影响,发现静态合成条件下无法形成 ZSM-22分子筛,表明 ZSM-22分子筛合成需要一定的转速.转速在10–50 r/min变化时,可以合成出不同晶体尺寸的 ZSM-22分子筛,且随转速提高, ZSM-22分子筛晶体尺寸先减小后增大,表明纳米 ZSM-22分子筛合成存在最佳转速.另外,配料硅铝比能显著影响 ZSM-22分子筛晶体尺寸,随配料硅铝比增加, ZSM-22分子筛晶体尺寸先减小后增大.通过在合成体系中添加乙醇作为共溶剂,考察了有机溶剂对 ZSM-22分子筛晶粒尺寸的影响,发现有机溶剂能显著增大 ZSM-22的晶体尺寸.将本文合成的纳米和常规微米 ZSM-22分子筛用于甲醇转化反应,考察了晶体尺寸对 ZSM-22分子筛甲醇转化反应性能的影响.发现与常规微米 ZSM-22分子筛相比,纳米 ZSM-22分子筛催化剂寿命显著提高,说明晶粒尺寸减小能有效减缓积碳导致的分子筛失活;同时,反应产物中乙烯和芳烃选择性有所提高,这是由于外表面积增大所致.此外,还考察了不同硅铝比 ZSM-22分子筛的甲醇转化反应性能.结果表明,分子筛硅铝比会影响催化剂寿命,但晶体尺寸对催化剂寿命影响更大. ZSM-22分子筛硅铝比增大有助于提高低碳烯烃选择性,减少芳烃生成.     

微介孔复合分子筛合成及其在汽车冷启动尾气控制中的应用

分别采用稀溶液和浓溶液双模板剂两步水热合成法,以二氧化硅微硅粉和铝酸钠为硅源和铝源,第一步获得β分子筛晶种,第二步以β分子筛晶种为结构单元组装形成兼具MCM-41分子筛和β分子筛结构特点的复合型分子筛β/M(其中β是指β分子筛,M是指MCM-41介孔分子筛).采用X射线衍射(XRD)、傅里叶变换红外(FT-IR)光谱、氮气吸附(BET)和高分辨透射电镜(HRTEM)对样品的物相结构和微观形貌进行了表征,并对复合分子筛的合成过程进行了分析.结果表明:复合分子筛β/M的形成是微孔β结构和介孔MCM-41结构的竞争生长过程,β分子筛晶种的晶化时间和晶粒度大小对β/M复合分子筛的结构有重要影响.此外,我们以甲苯为探针分子,比较研究了三类分子筛β/M、MCM-41和β的原样以及经高温水热处理后样品的吸附性能,结果表明:β/M复合分子筛的热稳定性优于介孔分子筛MCM-41,其甲苯吸附容量比MCM-41和β分子筛的高,其中以浓溶液法合成的复合分子筛吸附容量最高.     

Preparation and characterization of nanosized ZSM-5 zeolite using kaolin and investigation of kaolin content, crystallization time and temperature changes on the size and crystallinity of products

Nano sized ZSM-5 zeolite samples were synthesized successively from kaolin clay as alumina source having a large amount of quartz (39%) and silicic acid as silica source by hydrothermal treatment with NaOH in the presence of tetrapropylammonium hydroxide as a template. Then the effect of kaolin content, crystallization temperature and time on the size and crystallinity of the products were investigated. The prepared samples were characterized using XRD, SEM, EDS and FT-IR techniques. The results showed that the synthesized ZSM-5 zeolite samples were almost pure and their crystallization was almost complete. The average particle size, as determined by Debye-Scherrer equation, was in the range of 20-42 nm. Increasing kaolin content on crystal size was more effective than increase in crystallization temperature and time. Additional evidences for the nano sized ZSM-5 zeolite were the asymmetric stretch vibration band at 1225 cm^-1 in the FT-IR spectra and TEM images. The scanning electron micrographs of the synthesized zeolites showed that they are spherical shape crystals.     

有机空间位阻剂对NaP分子筛的调控作用

以粉煤灰中提取出的硅酸钠和铝酸钠为原料,通过水热合成法制备NaP型分子筛。通过正交实验优化了晶化时间、晶化温度和溶液硅水比等工艺参数,提出了通过空间位阻效应调控晶粒生长过程的方法,探索了结构空间位阻作用对NaP型分子筛生长过程晶型、粒径的调控规律。采用XRD、FI-IR、SEM、BET等手段对产物的晶型、粒径和形貌进行表征,并对不同条件下制备的NaP型分子筛的吸附性能进行了评价。结果表明,水热反应体系中引入空间位阻效应能有效调控Na P型分子筛的形貌和粒径;空间位阻效应的影响规律为环状结构链状结构,长链结构短链结构。吸附性能测试表明,Zn~(2+)有效吸附去除率可达99.8%。     

Zeolite LTA Nanoparticles Prepared by Laser-Induced Fracture of Zeolite Microcrystals

Zeolite LTA nanoparticles are prepared by laser-induced fragmentation of zeolite LTA microparticles using a pulsed laser. Zeolite nanoparticle formation is attributed to absorption of the laser at impurities or defects within the zeolite microcrystal generating thermoelastic stress that mechanically fractures the microparticle into smaller nanoparticle fragments. Experimentally, it is found that nanoparticles have a wide size and morphology distribution. Large nanoparticles (>200 nm) are typically irregularly shaped crystals of zeolite LTA, whereas small nanoparticles (<50 nm) tend to be spherical, dense, and amorphous, indicative of destruction of the original LTA crystal structure. Results of the fragmentation versus laser parameters show that shorter laser wavelengths are more efficient at producing zeolite nanoparticles, which is explained based on a larger cross section for optical absorption in the zeolite crystal. Increasing the laser energy density irradiating the sample was found to be a trade-off between increasing the amount of fragmentation and increasing the amount of structural damage to the zeolite crystal. It is suggested that in the presence of strongly absorbing defects, plasma formation is induced resulting in dramatically higher temperatures. On the basis of these results it is suggested the optimal laser processing conditions are 355 nm and 10 mJ/pulse laser energy for our LTA samples.     

新型高硅Y(NHSY)沸石的研究:Ⅰ.NHSY沸石的制备

新型高硅Ｙ（ＮＨＳＹ）沸石的研究　Ⅰ．ＮＨＳＹ沸石的制备刘兴云，裴站芬，佘励勤，李宣文（北京大学化学系，北京１００８７１）关键词ＮａＹ沸石，骨架改性，化学脱铝，ＮＨＳＹ沸石，草酸为了提高用于制备裂化催化剂的Ｙ沸石的稳定性，必须对其骨架进行改性．实用的...     

Synthesis and Properties of Zeolites from Autoclaved Aerated Concrete (AAC) Waste

Syntheses routes for the conversion of autoclaved aerated concrete (AAC) waste into aluminosilicate zeolites like LTA and related phases were developed. The procedures always started with leaching steps of the pure AAC waste by combinations of strong alkaline (NaOH) and mild acid (citric acid) treatments, before the real crystallization process was performed separately under addition of sodium aluminate. All products were characterized by X‐ray powder diffraction (XRD), scanning electron microscopy (SEM) combined with energy dispersive X‐ray analysis (EDX‐analysis) and Fourier‐transform infrared spectroscopy (FTIR). Zeolites LTA and related phases basic sodalite (SOD), hydrosodalite (SOD), cancrinite (CAN) and an intermediate phase between SOD and CAN were observed. Depending on the preparation route tailor made synthesis of pure phase zeolite LTA with crystal sizes up to 5 μm was worked out. In addition to syntheses procedures important properties of the zeolites were discussed with respect to the treatment procedure of AAC. It is shown, that the special synthesis pathway is not only responsible for the product composition and formation of a certain structure type but also exhibits a strong influence on the crystallinity, crystal size, and morphology. The water sorption capacity and the hydrothermal stability of the products were selected for those further investigations. Whereas adequate water sorption capacity up to 272 mg · g^–1 were measured for zeolites LTA obtained from two different reaction routes, limited hydrothermal stabilities were revealed for other products. Under the conditions of strong hydrothermal treatment at a temperature of 473 K for 72 h, a more or less extended phase transformation into ANA‐Type zeolites occurred. This process was least extensive for pure phase zeolite LTA obtained from the alkaline solution of AAC leaching.     

ZSM‐5 Zeolite Nanosheets with Improved Catalytic Activity Synthesized Using a New Class of Structure‐Directing Agents

A new series of multiquaternary ammonium structure‐directing agents, based on 1,4‐diazabicyclo[2.2.2]octane, was prepared. ZSM‐5 zeolites with nanosheet morphology (10 nm crystal thickness) were synthesized under hydrothermal conditions using multiquaternary ammonium surfactants as the zeolite structure‐generating agents. Both wide‐angle and small‐angle diffraction patterns were obtained using only a suitable structure‐directing agent under a specific zeolite synthesis composition. A mechanism of zeolite formation is proposed based on the results obtained from various physicochemical characterizations. ZSM‐5 materials were investigated in catalytic reactions requiring medium to strong acidity, which are important for the synthesis of a wide range of industrially important fine and specialty chemicals. The catalytic activity of ZSM‐5 materials was compared with that of the conventional ZSM‐5 and amorphous mesoporous aluminosilicate Al‐MCM‐41. The synthesis strategy of the present investigation using the new series of structure‐directing agents could be extended for the synthesis of other related zeolites or other porous materials in the future. Zeolite with a structural feature as small as the size of a unit cell (5–10 nm) with hierarchically ordered porous structure would be very promising for catalysis.     

Incorporation of CoS nanoparticles into ZSM-5 zeolite by hydrothermal and ion exchange methods

Cobalt sulfide nanoparticles were introduced into the medium-pore zeolite ZSM-5 (Zeolite Scony Mobil Five) by ion exchange in aqueous suspension and also by the addition of cobalt sulfate to the synthesis gel in hydrothermal zeolite synthesis. The latter method was systematically studied in the presence of tetraethylammonium ions as organic agents. The materials were characterized by chemical analysis, x-ray diffraction (XRD), scanning electron microscopy (SEM), Transmission electron microscopy (TEM), energy dispersion x-ray (EDX), IR, BET and diffuse reflectance spectroscopy (DRS). SEM picture and BET were used to discriminate between CoS nanoparticles in the zeolite pores and on the outer crystal surface. Their crystalline structure and morphology were studied by XRD and scanning electron microscopy. The results showed that in hydrothermal method zeolite acts as a template. CoS nanoparticles with an approximate size of 22 nm grow on the surface of zeolite. In ion exchange method, however, the majority of CoS nanoparticles are about 6 nm in diameter, located on the surface of the MFI (type materials ZSM-5) structure. Exciton absorption peaks at higher energy than the fundamental absorption edge of bulk CoS indicate quantum confinement effect in nanoparticles as a consequence of their small size. The absorption spectra show that the optical band gap for CoS nanoparticles produced by hydrothermal and ion exchange methods is 3.68 and 4.1 eV, respectively.     

烃类在β沸石上的吸附与扩散：粒度效应

β沸石首次为美国Mobil公司所合成,其骨架结构具有三维12元环孔道(两维线性,一维非线性)。与Y型分子筛相比,β沸石具有更高的热稳定性和耐酸性,对加氢裂化,加氢异构化,裂解,芳构化等反应有良好的催化性能。人们过去着重研究沸石的表面酸性质,本文报道粒度对沸石吸附与扩散的影响。     

多产低碳烯烃及柴油用分子筛的设计

目前,催化裂化的原料大多是蜡油和减压渣油的混合油,或全部的常压渣油 .其相对分子量范围很宽,组成十分复杂 .为了分别对待大小不同的分子和不同碳氢比化合物的裂化性能,现代催化裂化催化剂应具有梯度孔结构与梯度酸中心的优化结构配置 .而目前催化裂化的主导分子筛 USY二次孔含量还不能满足原料油日趋变重的需求,并且滞留在分子筛孔 /笼内的非骨架铝限制了其选择性的进一步提高,因此有必要对其结构进一步修饰 .　　本研究在 USY基础上合成新的催化裂化多产低碳烯烃和柴油用分子筛催化剂 .新型 USY基分子筛从晶体结构、孔容及孔…     

不同粒径ZSM-5分子筛在苯与甲醇烷基化反应中催化性能及反应条件优化

采用水热合成法合成了不同粒径的ZSM-5分子筛催化剂,系统考察了分子筛粒径变化对苯与甲醇烷基化反应的影响。研究结果表明,随着ZSM-5分子筛粒径增大,不但苯的转化率和二甲苯选择性降低,而且催化剂稳定性明显下降。其中,粒径为0.25 μm的ZSM-5分子筛在苯烷基化反应中的催化性能最佳,且催化剂稳定性最好。另外,采用拉曼光谱和热重等方法对催化剂积碳物种和失活机理进行了深入研究,发现催化剂失活主要是由于反应过程中生成的大分子稠环芳烃堵塞了分子筛孔道并覆盖活性位点造成的。最后,考察了反应温度、原料组成及空速对苯烷基化反应的影响并优化出最佳的苯烷基化反应条件。     

微波场中T型分子筛的合成及晶化研究

研究了微波场中T型分子筛的结晶过程。考察了微波加热体系中合成参数如合成时间、溶胶组成、反应压力和模板剂用量对分子筛晶化的影响。微波加热的主要优点是减少合成时间,无模板剂的溶胶在普通加热条件下的晶化时间需要120 h,而在微波场中则仅需要20～25 h。另一方面,由于微波的快速加热特性促进了稳定相钙十字沸石的生成,从而减小了次稳定相T型分子筛的结晶区间。在未添加模板剂条件时,100 ℃下微波水热合成T型分子筛的结晶区间为：20≤n_SiO2/n_Al2O3≤22和0.31≤ n_M2O/n_SiO2≤0.33(其中M₂O=Na₂O+K₂O, n_Na/n_K=3和n_M2O/n_SiO2=11.70)。在普通加热和微波加热合成体系中,添加模板剂均能扩大结晶区间,同时还可以进一步减少合成时间。     

Synthesis of ferrierite-type zeolite by microwave method using ethylenediamine as an organic structure-directing agent

A new method for the synthesis of ferrierite-type zeolite has been developed using microwave irradiation in the presence of structure-directing agents (templates). The physicochemical characteristics of the synthesized zeolites were investigated by X-ray diffraction analysis, low-temperature nitrogen adsorption–desorption and SEM-EDX. When comparing the synthesis products, it was found that microwave irradiation significantly reduces the crystallization time of the synthesized zeolites compared to traditional hydrothermal treatment     

Fabrication of Zeolite A Rods with Irregular Macropores by Self-assembly of Zeolite A Microcrystals Using Microwave-assisted Hydrothermal Synthesis

Zeolite A rods by self-assembly of zeolite A microcrystal were successfully synthesized by microwave-assisted hydrotherrnal synthesis. The average size of zeolite crystals consisting of self-assembling materials was about 300 nm and the length of zeolite rods was in the range of 15--30μm.     

Ultrasound promoted direct synthesis of nano Cu-Zn-Al-ZSM-5 in acid medium

Nano Cu-Zn-Al-ZSM-5 was directly synthesized in HCl solutions with the promotion of ultrasound. XRD results show that the appropriate concentrations of HCl in the synthetic process were between 0.25 M and 1 M, and the optimal crystallization time and temperature were 28 h and 200°C, respectively. The ultrasound irradiation can significantly increase the crystallization of Cu-Zn-Al-ZSM-5 within 0.5 h. SEM photographs of Cu-Zn-Al-ZSM-5 zeolite showed the crystal size is about 50–60 nm. Results of ICP/AES show that the weight% of Cu in 101(Cu-Zn-Al-SOD) and 202(Cu-Zn-Al-ZSM-5) were 4.42% and 2.30%, respectively.     

Supramolecular Interactions and Morphology Control in Microwave Synthesis of Nanoporous Materials

Application of a microwave technique to the conventional hydrothermal process is gaining importance, especially, in the synthesis of nanoporous materials. This microwave technique is regarded as a novel synthesis tool because it gives several beneficial advantages such as homogeneous nucleation, rapid synthesis, formation of uniform crystals, and small crystallites, facile morphology control, energy efficiency and so on. Recently, it was found that it offers an efficient way to control the crystal morphology, size and orientation, and even crystalline phase which are required for many emerging applications of nanoporous materials. This review summarizes recent work on the microwave effect, supramolecular interactions and control of crystal morphology upon microwave synthesis of nanoporous materials performed by the present authors. Synthesis and morphology control of nanoporous materials such as ZSM-5, zeolite beta, metallosilicates, AlPO, MCM-41, SBA-15, SBA-16, etc. have been accomplished with microwave irradiation. In particular, the rapid nucleation and crystallization of ZSM-5 zeolite under microwave irradiation made it possible to enable the continuous microwave synthesis, implying a great industrial and technological importance. The formation of nanoporous materials, especially, silicate or aluminosilicate molecular sieves was described on the basis of supramolecular interactions between organic template molecules and silicate species under microwave irradiation. Besides decreasing synthesis time, it was duly demonstrated that the microwave technique provides an effective way to control particle size distribution and macroscopic morphology in the synthesis. Moreover, for the application of these porous materials, microwave-induced nanofabrication of microporous and mesoporous materials is more important than that of simple porous materials.     

Synthesis of Colloidal Suspensions of Zeolite ZSM-2

Discrete colloidal particles of zeolite ZSM-2 with crystal sizes less than 100 nm, in the form of aqueous suspensions, have been synthesized in tetramethylammonium (TMA)-aluminosilicate solutions in the presence of either lithium or a combination of lithium and sodium hydroxide. The well-crystallized ZSM-2 has a specific surface area of 781 m²/g after purification and removal of the organic base by calcination. Synthesis times (t) are as short as 3 < t < 12 h and in certain cases, less than 3 h, less than those previously reported in the literature. Prolonged hydrothermal treatment of sols in the presence of sodium cations (>12 h) results in the phase transformation of ZSM-2 to the nitrogeneous edingtonite zeolite (Li,Na)-E. The synthesis of nitrogeneous (Li,Na)-E is also favored by a high TMA content in conjunction with sodium, whereas synthesis of zeolite N-A is favored by a high sodium content. Furthermore, it is shown that colloidal suspensions of TMA sodalite with crystal sizes less than 40 nm are synthesized in the absence of alkali cations.