硼和氟掺杂ZSM-5分子筛的制备及其甲醇制丙烯反应性能

采用两步水热晶化法,通过在合成体系中加入硼酸、氟化铵、氟硼酸铵,合成出了硼和氟改性的ZSM-5分子筛。利用X射线衍射、氮气吸附-脱附、29Si固体核磁共振波谱、傅里叶变换红外光谱、扫描电子显微镜以及NH₃程序升温脱附等测试手段对样品进行了表征。结果表明：硼和氟掺杂条件下可以合成具有较高结晶度的ZSM-5分子筛,杂原子掺杂提高了分子筛的硅铝比;硼和氟掺杂可以显著降低ZSM-5分子筛的Lewis酸量,但提高了Brønsted酸量;硼和氟共同作用可以降低ZSM-5分子筛的颗粒尺寸。甲醇制丙烯评价结果显示：较低的Lewis酸量和适宜的Brønsted酸性有利于提高丙烯选择性和催化剂寿命;NH₄BF₄改性的ZSM-5分子筛（Z5-BF2）表现出较高的丙烯选择性和较长的催化剂寿命。     

Comparative study on pore structures of mesoporous ZSM-5 from resorcinol-formaldehyde aerogel and carbon aerogel templating

Resorcinol-formaldehyde aerogels and carbon aerogels of different mesoporosities have been used as templates for preparing bimodal zeolites of mesopores. Samples were thoroughly characterized with X-ray diffraction, field emission scanning electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, N(2) adsorption at 77 K, as well as FT-IR spectroscopy and (29)Si nuclear magnetic resonance spectroscopy. The mesoporous ZSM-5 zeolites have additional mesopores of 9-25 nm in widths and 0.07-0.2 cm(3)/g in volumes, besides their perfect inherent micropores. Experimental results show the mesoporous systems of the finally obtained zeolites can be influenced by proper preparation of resorcinol-formaldehyde aerogels and carbon aerogels through solution chemistry. Consequently, zeolites of tunable mesoporosities can be prepared with this unique methodology.     

混合胺体系中 MCM-49/ZSM-35 复合分子筛的晶化过程

 采用 X 射线衍射、N2 吸附-脱附、扫描电镜和傅里叶变换红外光谱等技术, 研究了 MCM-49/ZSM-35 复合分子筛在 Na2O-SiO2-Al2O3-CHA (环己胺)-HMI (六亚甲基亚胺)-H2O 合成体系中, 先在低温 80 ?C 老化 4 h, 再经 160 ?C 晶化不同时间的演变过程. 结果表明, 在该混合胺体系中, 首先生成 MCM-49 分子筛, 随着晶化时间的延长, 形成 ZSM-35 含量逐渐增加的 MCM-49/ZSM-35 复合分子筛, 最后生成纯 ZSM-35 分子筛; ZSM-35 的生成是以 MCM-49 分子筛的消耗为代价的.     

晶种导向干凝胶法制备成型ZSM-5分子筛

在干凝胶法制备ZSM-5 分子筛的体系中添加晶种导向剂, 控制分子筛的生长, 制备了纳米沸石组装的无粘结剂成型多级孔ZSM-5 分子筛, 一步完成纳米分子筛的制备及组装成型, 即克服了传统纳米粒子难以过滤分离的问题, 同时组装所形成的多级孔有助于改善分子在催化剂内的扩散, 从而提高催化反应效率. 以硅胶、薄水铝石为原料, 四丙基氢氧化铵(TPAOH)和ZSM-5 晶种导向胶作为粘结剂, 通过混捏、挤条得到直径2 mm的条状前驱物, 随后通过干凝胶转换法制备成型分子筛. 所用晶种导向剂组成为0.35TPAOH:1SiO₂:20H₂O:4C₂H₅OH. 通过X射线衍射(XRD), 热重(TG)分析和傅里叶变换红外(FTIR)光谱等方法对分子筛晶化过程进行了表征, 结果表明晶种导向剂加入量对分子筛生长速度及多级孔结构均有影响. 当所加晶种导向剂中TPAOH与SiO₂的摩尔比为0.025时, 经过3 h晶化, 分子筛相对结晶度达到100%. 扫描电镜(SEM)结果表明, 合成的分子筛尺寸约为200 nm, 组装形成的多级孔分子筛的介孔体积为0.28 cm³·g^-1. 通过NH₃ 程序升温脱附(NH₃-TPD)考察了所得成型分子筛的酸性, 发现该分子筛酸性与市售的粉末H-ZSM-5分子筛类似.     

Synthesis of mesoporous zeolite single crystals with cheap porogens

Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals have been successfully synthesized by adding soluble starch or sodium carboxymethyl cellulose (CMC) to a conventional zeolite synthesis system. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption analysis, ²⁷Al magic angle spinning nuclear magnetic resonance (²⁷Al MAS NMR), temperature-programmed desorption of ammonia (NH₃-TPD) and ultraviolet-visible spectroscopy (UV-vis). The SEM images clearly show that all zeolite crystals possess the similar morphology with particle size of about 300 nm, the TEM images reveal that irregular intracrystal pores are randomly distributed in the whole crystal. ²⁷Al MAS NMR spectra indicate that nearly all of the Al atoms are in tetrahedral co-ordination in ZSM-5, UV-vis spectra confirm that nearly all of titanium atoms are incorporated into the framework of TS-1. The catalytic activity of meso-ZSM-5 in acetalization of cyclohexanone and meso-TS-1 in hydroxylation of phenol was also studied. The synthesis method reported in this paper is cost-effective and environmental friendly, can be easily expended to prepare other hierarchical structured zeolites.     

核壳MFI/CHA分子筛的合成及催化性能

采用二次生长法(外延法)在ZSM-5(MFI型)晶体颗粒表面外延生长SAPO-34(CHA型)磷酸硅铝分子筛壳层,合成了MFI/CHA型核壳分子筛材料。并利用X射线衍射(XRD)、扫描电镜(SEM)、能量色散射线光谱(EDS)和傅里叶变换红外(FTIR)光谱对其进行了表征。结果表明,核相ZSM-5的预处理步骤对于成功合成此核壳型分子筛材料十分关键。通过研究晶化温度和晶化时间对MFI/CHA核壳型沸石分子筛合成的影响推测出MFI/CHA壳层生长的晶化机理,并考察在甲醇芳构化中的择形催化作用。     

Availability and interconnectivity of pores in mesostructured ZSM-5 zeolites by the adsorption and diffusion of mesitylene

Probing the mesopore architecture in mesoporous zeolites is of importance for large scale applications of the materials. In this work, the adsorption and diffusion of mesitylene with larger molecule size in mesoporous ZSM-5 zeolites were carried out, in order to acquaint the availability and interconnectivity of mesopores in zeolite crystals. The comparisons of the shape of adsorption isotherms and the mesopore volume calculated from mesitylene and N₂ adsorption in mesoporous ZSM-5 zeolites with different mesoporosities can be used to discriminate two cases of mesopores: accessible mesopores connected to external surface of the zeolite crystals and non-accessible meso-voids that are occluded in the microporous matrix. Furthermore, the effective diffusivity and activation energy of mesitylene in mesoporous ZSM-5 extracted from ZLC desorption curves as a function of mesopore volume calculated from mesitylene adsorption reveal the enhancement of mesopore interconnectivity to molecule diffusion in zeolite crystals.     

热处理对HZSM-5结构、酸性及催化乙醇脱水反应性能的影响

对商用HZSM-5分子筛进行高温热处理,利用X射线衍射(XRD)、核磁共振波谱法(²⁷Al-MAS NMR)低温氮吸附、电感耦和等离子体放射光谱(ICP-AES)、氨-程序升温脱附(NH₃-TPD)和吡啶吸附傅里叶变换红外(FT-IR)光谱等技术对高温热处理改性前后样品进行了表征,并考察了高温热处理对分子筛的结构、酸性及催化乙醇脱水制乙烯反应性能的影响。结果表明,热处理改性后的HZSM-5分子筛发生骨架脱铝,B酸减少,L酸增多,孔容增大,出现新的介孔;适中的酸性位和复合型的介-微双孔道结构使其减少了反应中的副反应,乙烯的选择性得到提高,催化剂寿命显著提高。     

Controllable synthesis of composites of ZSM-5 and KIT-1 using an ionic liquid as template

ZSM-5/KIT-1 composites were synthesized using an ionic liquid as a template. The structures and morphologies of as-obtained products were characterized using an infrared spectroscopy, X-ray diffractometer, N₂ adsorption/desorption, scanning electron microscopy and transmission electron microscopy. The resultant zeolites show a fully crystalline microporous MFI zeolite framework and a three-dimensional network of short worm-like channels. Mesopores and microspores of 4.2 and 0.8 nm in diameter coexist in the zeolite composites. Moreover, the ratio of ZSM-5 and KIT-1 could be simply adjusted by controlling the pre-crystalline time. We believe that the strategy for fabricating ZSM-5/KIT-1 through a simple method could potentially promote the large-scale production of zeolite composites.     

气相转移法合成ZSM-5/SAPO-5复合分子筛

以磷酸、拟薄水铝石和硅溶胶为原料, 三乙胺为模板剂, 采用气相转移法合成了一系列ZSM-5/SAPO-5复合分子筛. 产物经X射线衍射、扫描电镜、X射线能量散射谱、红外光谱及N2 静态吸附法等手段对其进行了表征, 证明合成材料是以ZSM-5为核、SAPO-5为壳的双结构分子筛. 实验结果表明, 干胶制备条件及液相组成都影响复合分子筛的结晶. 晶化温度的提高和晶化时间的延长有利于分子筛结晶度的提高. VPT法可以减小SAPO-5和复合分子筛颗粒的直径, 改善SAPO-5在ZSM-5分子筛表面的分布. 重油裂化结果表明, 核壳结构复合分子筛对生成低碳烯烃的性能优于机械混合的样品.