偏高岭土合成4A沸石机理的研究

用XRD、FT IR、ICP、SEM、化学分析等方法研究了偏高岭土合成4A沸石的晶化反应机理。偏高岭土在NaOH溶液中部分溶解 ,且结构迅速转变为偏高岭土 * ,并伴有硅铝酸钠凝胶形成。偏高岭土 *也不断在碱液的作用下凝胶化 ,生成的凝胶进一步再转变为4A沸石 ,这两个过程在大部分反应时间里是同时进行的 ,直到晶化结束。液相参与凝胶、4A沸石前驱及晶核等的形成和4A沸石的成长。偏高岭土 *的凝胶化速度是整个晶化过程的决定步骤 ,该晶化过程极易形成大量聚晶。     

Hollow STW-Type Zeolite Single Crystals with Aluminum Gradient for Highly Selective Production of p-Xylene from Methanol-Toluene Alkylation

Zeolites with uniform micropores are important shape-selective catalysts. However, the external acid sites of zeolites have a negative impact on shape-selective catalysis, and the microporosity may lead to serious diffusion limitation. Herein, we report on the direct synthesis of hierarchical hollow STW-type zeolite single crystals with a siliceous exterior. In an alkalinous fluoride medium, the nucleation of highly siliceous STW zeolites takes place first, and the nanocrystals are preferentially aligned on the outer surface of the gel agglomerates to grow into single crystalline shells upon crystallization. The lagged crystallization of the internal Al-rich amorphous gels onto the inner surface of nanocrystalline zeolite shells leads to the formation of hollow cavities in the core of the zeolite crystals. The hollow zeolite single crystals possess a low-to-high aluminum gradient from the surface to the core, resulting in an intrinsic inert external surface, and exhibit superior catalytic performance in toluene methylation reactions.     

蒸汽相中含硼多孔玻璃自转变合成沸石——Ⅱ．自转变动力学

以XRD为表征手段详细研究了408—453K温度范围、多孔玻璃粉在乙胺和水的蒸 汽相中自转变为B-Al-MFI型沸石的自转变动力学。由动力学曲线计算得到的成核活 化能和晶体生长活化能分别是102．0kJ／mol和34．7kJ／mol。沸石的结晶速率显 著受温度影响，低温有利于晶体成核和形成小晶体，高温有利于晶体生长和形成大 晶体。不同反应温度下的结晶速率几乎在相同时间内(cα．132h)达到最大值(νm) 。     

Growth of ZSM-5 crystals within hollow β-zeolite

A zeolite composite composed of ZSM-5 andβ-zeolites has been synthesized by a procedure of the nucleation and crystallization of ZSM-5 zeolite in the hollowβ-zeolite.The property ofβ-zeolite crystals with aluminum-poor interior and aluminum-rich outer rim results in silicon extraction favorably in the aluminum-poor bulk rather than the aluminum-rich external surface.Subsequently,alkaline treatment ofβ-zeolite crystals during the second-step synthesis leads to a preferential dissolution of the aluminum-poor center and the formation of hollowβ-zeolite crystals.ZSM-5 zeolite crystals are therefore embedded and grown within the hollowβ-zeolite.The catalytic activities of Co-Hβ,Co-HZSM-5 and Co-HZSM-5/BEA are investigated during the reaction of methane catalytic reduction NO in the presence of O₂.     

3D Study of the Morphology and Dynamics of Zeolite Nucleation

The principle aspects and constraints of the dynamics and kinetics of zeolite nucleation in hydrogel systems are analyzed on the basis of a model Na‐rich aluminosilicate system. A detailed time‐series EMT‐type zeolite crystallization study in the model hydrogel system was performed to elucidate the topological and temporal aspects of zeolite nucleation. A comprehensive set of analytical tools and methods was employed to analyze the gel evolution and complement the primary methods of transmission electron microscopy (TEM) and nuclear magnetic resonance (NMR) spectroscopy. TEM tomography reveals that the initial gel particles exhibit a core–shell structure. Zeolite nucleation is topologically limited to this shell structure and the kinetics of nucleation is controlled by the shell integrity. The induction period extends to the moment when the shell is consumed and the bulk solution can react with the core of the gel particles. These new findings, in particular the importance of the gel particle shell in zeolite nucleation, can be used to control the growth process and properties of zeolites formed in hydrogels.     

羟基自由基在沸石分子筛合成中的作用

沸石分子筛由于具有独特的形选催化作用及可调的酸性, 已成为化学工业中最重要的固体催化材料. 沸石分子筛的合成主要基于碱性条件下的水热晶化, OH^?被认为起到催化硅铝物种的解聚及聚合作用. 近年来, 研究者发现了羟基自由基加速分子筛的水热晶化机制. 通过利用紫外光照射或芬顿反应等物理或化学方法向分子筛合成体系引入羟基自由基, 可以实现沸石分子筛的加速晶化及高硅沸石分子筛的合成. 理论计算结果表明, 羟基自由基可以促进Si—O—Si 键的断裂和重新生成, 从而显著加快分子筛成核并促进硅原子进入骨架. 本综述介绍了羟基自由基在沸石分子筛晶化方面的最新研究进展, 探讨了羟基自由基的主要作用和优势, 并对沸石分子筛合成的羟基自由基路线发展前景进行了展望.     

Factors that control zeolite L crystal size

Time-series hydrothermal syntheses from two organic-cation-free gels with different compositions were employed to study the factors that control the final size of zeolite L crystals. The first gel had a starting K/Al ratio of 10, whereas in the second one it was three times lower. The relatively simple chemical composition of the starting gels and the combination of complementary characterization methods allowed us to track down the different stages of transformation of the initial amorphous gels into zeolite crystals and the factors that control the nucleation and growth processes. The role of the starting mixture components in the formation of the primary amorphous particles was explored. It was found that the profoundly different reaction kinetics in the two systems are caused by the difference in diffusion rates, which in turn are controlled by the extent of the polymerization reactions at room temperature during mixing of the starting components prior to hydrothermal treatment. As a consequence, nucleation is fast and ubiquitous in the first system with higher water content and K/Al ratio, whereas it is slow and sporadic in the second system with lower water content and K/Al ratio. Ultimately, these differences in the kinetics lead to the formation of two distinctly different patterns of crystal-size distribution, with a large number of small nanocrystals in the first sample and fewer large crystals in the second sample. The new findings put zeolite crystal growth on a rational basis that would enable the control of zeolite crystal size in similar organic-template-free systems.     

Crystal nucleation in an electric field

Nucleation of polar and apolar crystals in an electrostatic field has been analyzed. The analysis is based on the extended nucleation theory which takes into account orientation of amorphous kinetic elements and the resulting crystals. In an electric field free energy of transformation is orientation-dependent which leads to orientation and field effects in thermodynamic (critical crystallization temperature) and kinetic crystallization characteristics (thermal and athermal nucleation rates).     

Synthesis of zeolite nanocrystals at room temperature

Zeolite A nanoparticles were synthesized under room-temperature conditions from a very reactive organic-template-free gel system. The optimization of the syntheses parameters, namely, the composition of the initial system and the careful choice of the reactants, allowed the crystallization to be accomplished within 3 days. At this stage the individual zeolite crystals were in the range of 100-300 nm without well-developed crystal faces. The prolongation of the synthesis time up to 10 days led to formation of larger well-faceted cubic crystals averaging about 400-500 nm in size. The high-resolution transmission electron microscopy (HRTEM) study revealed that a thin layer of amorphous material covers the zeolite particles acting as a binder between individual zeolite crystals. The postsynthesis treatment of the product in NH(3) media under ultrasonic radiation disintegrated the loosely attached zeolite particles and decreased the fraction of zeolite A particles with low colloidal stability. The employed approach, however, did not result in complete disintegration of aggregated crystals. The zeolite crystals obtained under ambient conditions were characterized by XRD, SEM, dynamic light scattering, and N(2) adsorption measurements.     

Effect of Sodium Concentration on the Synthesis of Faujasite by Two-step Synthesis Procedure

The relationship between the concentration of sodium cations and the properties of faujasite(FAU) zeolite was investigated using a two-step synthesis procedure including (1) formation of amorphous aluminosilicate precursors and separation of amorphous nanoparticles, and (2) transformation of these amorphous particles into zeolite crystals by treatment with alkali solutions(NaOH). Three representative samples including two nano-sized zeolites and one micron-sized zeolite were prepared using different concentrations of sodium hydroxide. The crystallization process of these zeolites was studied in detail by Fourier transform infrared(FTIR) spectrometry, nuclear magnetic resonance spectroscopy(NMR), X-ray diffraction(XRD), scanning electron microscopy (SEM), transmission electron microscopy(TEM), and N₂ adsorption. The results indicated that minor changes in the concertation of inorganic cations can significantly shorten the induction period and crystallization time and thus affect the morphology, size and chemical composition of the zeolite crystals.     

Electron Microscopy Reveals the Nucleation Mechanism of Zeolite Y from Precursor Colloids

The growth of nanoscale crystals of zeolite Y from colloidal aluminosilicate gel particles has been investigated with high-resolution electron microscopy. Each amorphous gel particle nucleates only a single zeolite crystal, with nucleation beginning at the gel-solution interface (see scheme). Further growth of these nanocrystals is possible through the solution-mediated transport of framework building blocks.     

TEM investigation of formation mechanism of monocrystal-thick b-oriented pure silica zeolite MFI film

The first direct transmission electron microscopic (TEM) observation has been carried out on the continuous monocrystal-thick b-oriented pure silica zeolite MFI films produced by in situ crystallization. The self-supporting film samples for TEM study were fabricated by dissolving the steel substrate with acid. This TEM study is free of those artifacts that are typically associated with TEM sample preparations, and allows us to investigate the "true" structure and texture of a very large area of the film and at the same time to focus at will on each individual zeolite crystal in the film. Abundant TEM information including crystallographic orientation relationships among crystals in the film (both out-of-plane and in-plane), grain boundaries, and each crystal grain was obtained. This TEM investigation provides direct unambiguous new evidence to support the homogeneous nucleation mechanism, by which the films form through homogeneous nucleation and crystal growth in the bulk to form equal-sized disk-shape crystals, followed by self-assembly of these crystals onto the substrate to produce a two-dimensional close-packed structure. The last stage of the film formation involves simultaneous space-limited growth and rotation of the individual crystals to realize the in-plane crystallographic control within the film.     

纳米富铝β沸石的合成与表征

以低硅铝比焙烧后的硅铝胶固体为初始原料,在含F-近中性与低含水量体系下晶化合成出相对高结晶度的纳米富铝β沸石。实验考察了合成条件、硅铝胶焙烧对晶化产物的影响和晶化过程中Al配位状况变化,并采用XRD、XRF、SEM/TEM2、7AlMAS NMR物化方法对晶化产物进行表征。结果表明,含F-离子、H2O/SiO2摩尔比为2.4～6.0以及高温焙烧硅铝胶有利于合成高结晶度的纳米富铝β沸石;硅铝胶固体焙烧后能产生易于转化为β沸石晶核的Al四配位结构,而部分六配位Al在晶化过程中缓慢溶入β沸石晶核中而最终生成纳米富铝β沸石。     

沸石转晶的研究(Ⅲ)——NaY型沸石的稳定性及NaPc型沸石的结构

研究了原始凝胶3、3Na₂O·Al₂O₃·10SiO₂·200H₂O在100℃NaY型沸石向NaPc型沸石转晶的晶化过程,应用电子显微镜、X-射线衍射、TMS-GC和固体高分辨Si²⁹-NMR方法研究了沸石晶核的形成、晶体粒度和外貌的变化及液、固相中硅酸根离子存在状况及转晶中沸石结构的变化,并提出了转晶的液相传质机理。     

干胶法合成分子筛

相对于传统的水热合成法,干胶法(dry gel conversion,DGC)合成分子筛具有产量高、废液量少等优势。本文综述了近十年来DGC合成分子筛的研究进展。以水为线索,总结了外加水和固有水(指原料干胶所含的水)在DGC中对分子筛的生长、晶相的转换与物化性质的影响,论述了在DGC条件下分子筛的生长过程和晶化机理,介绍了DGC在介孔-微孔复合分子筛、分子筛膜、单块材料等新型分子筛材料合成中的一些实例。     

The phase morphology and crystal growth habits of DNA fractions. Optical microscopy and light scattering

Polydisperse DNA of reasonable molecular weights was prepared from a mammalian source via sonication and fractionation. A method for characterizing the molecular weight using gel electrophoresis is described. Quiescent crystallization was studied in thin films of one of the fractions induced by rapidly changing the hydration state isothermally. We report the occurrence of the semicrystalline nature of DNA. The crystal growth occurring via aggregates is best described as sheaves and spherulites from DNA gels in the relative humidity range (RH) corresponding to A-DNA. These habits exhibit primary nucleation and secondary growth, which closely resemble those of melt-crystallized, synthetic macromolecules and, in a follow-up report, will be shown to be lamellar in nature. Small, needle-like crystals are observed for B-DNA hydration levels, and are unstable at lower hydration levels. A transformation from needle to lamellar crystals can occur, even when the primary nucleation of lamellar forms is otherwise absent at that hydration level, through a cylindrical phase exhibiting selective reflection of colored bands. The hydration level plays, in part, the role of the supercooling in this system and the long-known hysteresis in the formation and dissolution of the A-DNA (crystals) can now be viewed in light of those factors known to operate in semicrystalline systems. A morphological phase diagram is developed and is in accord with the known physical evidence. Because this preparation and these morphological observations are without precedence, substantial detail into methodology is included for this first article in the series. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1843–1854, 1997     

超微NaY分子筛的合成(Ⅰ)──添加轻稀土离子的影响

导向剂的陈化时间和反应胶的晶化温度可以影响NaY分子筛的晶化行为.随导向剂陈化时间的增加,NaY分子筛的晶化速度加快,晶粒尺寸减小;随晶化温度的升高,NaY分子筛的晶化速度加快,但晶粒尺寸增加.而向合成体系中添加轻稀土离子(Ln³⁺)对NaY分子筛的晶化行为影响更为明显.与未添加稀土离子时相比较,在一定的稀土离子添加量范围内[n(Ln³⁺)/n(Al³⁺)<0.2],NaY分子筛的晶化速度明显加快而晶粒尺寸显著减小,同时所合成出的NaY分子筛的n(SiO₂)/n(Al₂O₃)比也有较大的提高.添加稀土离子使合成体系中形成异晶晶种的Ln(OH)₃微晶,从而进一步引发NaY分子筛的成核.     

A hybrid rheological model for particulate suspension in zeolite crystal growth

A hybrid constitutive model is developed to represent the thixotropic behavior of particulate suspension during zeolite crystallization from solution. This model is valid over the complete solid fraction range typical for such a process. It employs two internal variables, agglomeration and contiguity, to describe the degree to which the gel particles form short- and long-range networks. The contiguity is used to weigh the effects of hydrodynamic to chain-like network deformation on the suspension viscosity. Heterogeneous nucleation and surface reaction-controlled crystal growth are assumed to describe the evolution of microstructure and solid fraction of gel and crystals. Such a model successfully captures the thixotropic behavior of zeolite particulate suspension by comparison of the predictions with a set of experimental data.     

Investigating the kinetics of liquid-free,OSDA-free ZSM-5 zeolite synthesis from iron ore tailings

In this study, ZSM-5, which is a Mobil-type five-type zeolite with well-defined crystal morphology, is successfully synthesized via a seed-assisted, liquid-free method that uses iron ore tailings as a silica source. The ZSM-5 crystallization kinetics at 423, 433, and 443 K and different synthesis times are investigated to identify the nucleation and crystallization mechanisms of the synthesized ZSM-5 zeolites, and results suggest that the crystallization kinetics follow a Kolmogorov-Johnson-Mehl-Avrami-type behavior. The activation energies for the induction and transition periods are 112.38 and 58.35 kJ mol⁻¹, respectively. Furthermore, the Avrami exponent indicates three-dimensional crystal growth from both sporadic and instantaneous nucleation mechanisms. A comparison of our results with previous reports of the ZSM-5 crystallization mechanism demonstrates that the seed crystals play a significant role in nucleation and crystal growth. Finally, seed surface crystallization and new nuclei crystallization dual mechanism has been proposed to describe the crystallization process of ZSM-5.     

过饱和铝酸钠溶液中氢氧化铝自发成核动力学规律的研究

用电导法和吸光光度法首次对苛性比相同的不同浓度过饱和铝酸钠溶液自发分解过程进行了实时跟踪研究,获得铝酸钠溶解氢氧化铝自发成核动力学方程,探索了H₂O和Na⁺对氢氧化铝自发成核过程的影响.结果表明,过饱和铝酸钠溶液分解为氢氧化铝属化学反应控制过程;H₂O参与了溶液分解过程控制步骤的反应;K⁺和Na⁺等阳离子参与了溶液的重构,但对溶液分解的控制步骤影响不大.