Selenium clusters in channels of the porous silica ZSM-11

The distribution and structure of selenium nanoclusters synthesized in crystals of the porous silica ZSM-11 are investigated using the maximum-entropy method and the Rietveld analysis. It is demonstrated that the intercalated selenium atoms are arranged in channels of the ZSM-11 zeolite in the form of scraps of infinite chains similar to those observed in massive selenium. The distances between the nearest neighbor selenium atoms vary in the range 2.53–2.70 Å.     

Organic template-free synthesis of ZSM-5/ZSM-11 co-crystalline zeolite

A series of ZSM-5/ZSM-11 co-crystalline zeolites with various compositions and morphologies were successfully synthesized via an organic template-free hydrothermal route and characterized by XRD, XRF, SEM, NMR and N₂ adsorption/desorption technologies. The effects of raw materials and batch composition were investigated systematically. Various silicon sources can be employed in the organic template-free synthesis of ZSM-5/ZSM-11 co-crystalline zeolite, however only a few types of aluminum sources are available. This organic template-free system is favorable to the aluminum-rich zeolite. With the increase of initial SiO₂/Al₂O₃ ratio, the ZSM-5 percentage in the ZSM-5/ZSM-11 co-crystalline zeolite increases as well as the crystal size, and especially the morphology of ZSM-5/ZSM-11 co-crystalline zeolite prepared from the colloidal silica-NaAlO₂ solution system changes gradually from nano-rod aggregation, micro-spindle to single hexagon and then to twinned hexagon crystals. Moreover, Na⁺ and OH⁻ in the initial materials can promote the nucleation of the ZSM-5/ZSM-11 co-crystalline zeolite significantly and are beneficial to the formation of crystals with relatively low length/width ratio, while K⁺ postpones the crystallization process seriously.     

协同导向法合成ZSM-5/ZSM-11共生分子筛

使用四丁基铵(TBA~+)模板剂和Beta分子筛作晶种协同导向合成ZSM-5/ZSM-11共生分子筛。Beta分子筛晶种的加入扩大了ZSM-5/ZSM-11分子筛的合成相区,抑制了丝光沸石杂相的生成。研究了合成条件对共生结构中ZSM-5、ZSM-11的含量及分子筛晶体形貌的影响,发现相同条件下晶种添加量越大、合成碱度越小、投料硅铝比越高,共生结构中ZSM-11的含量越高,分子筛的晶粒尺寸越小。用X射线衍射(XRD)、扫描电镜(SEM)、N_2物理吸附(BET)、~(27)Al魔角旋转固体核磁(MAS-NMR)、NH_3程序升温脱附(NH_3-TPD)等对样品进行表征,发现ZSM-5/ZSM-11共生分子筛具有高的结晶度、丰富的孔结构、优良的Al的配位状态和强酸性,是具有潜在应用价值的优良催化剂。     

Activated diffusion in relaxed porous clusters

We study diffusion through disordered porous structures, where the size of the diffusing particle is of the order of the pore diameter, and focus on the effect of particle-wall interactions. Such ‘configurational diffusion’ is important in catalysis, separation, and membrane technology, yet it is still poorly understood. We consider three types of cluster cluster aggregation (CCA) structures using simulations carried out on a cubic lattice. Namely, (1) next-neighbor (classic) CCA, where each site may have up to six nearest neighbors; (2) CCA where each site may have up to 26 nearest neighbor in its first coordination shell; and (3) a relaxed CCA solid formed by a process of energy minimization. We find that at low interaction strengths, diffusivity through the various types of CCA structure of similar porosity is independent of the mode of preparation and can be well predicted. However, at high interaction strengths which inhibit the diffusivity considerably, clusters characterized by lower surface-to-volume ratio display lower diffusivities. We suggest a simple model that accounts for the dependence of the diffusivity on the interaction parameter.     

Macromorphologies in electrochemically formed porous silica

Mesoporous silica is formed by high-potential anodisation of single-crystal silicon in dilute fluoride electrolyte of neutral pH and low buffer strength. A quantitative study of the morphologies obtained as a function of the preparation conditions on rotating-disk silicon electrodes has been performed, using optical and scanning electron microscopy, followed by image processing. For anodisation potentials below 15 V, the mesoporous material exhibits a homogeneous structure. At higher potentials, macrostructures consisting of micron-size depressions appear. Upon further potential increases, these depressions turn to self-organised circular “bowls”, then coalesce, forming labyrinth patterns, whose aspect ratio goes through a maximum at around 40-50 V anodisation potential. The morphology map is somewhat sensitive to fluoride concentration and electrode rotation rate. The macrostructures can be understood as a consequence of the local pH lowering associated with oxygen evolution.     

Particulate clusters and permeability in porous media

The permeability of particulate colloidal titanium dioxide, P25, was investigated during sedimentation, permeation and filtration when suspended in water at a consistent ionic strength similar to tap water. Happel's cell model of permeability was used to determine the apparent particle size during these processes, and compared with the size of particle clusters measured using laser diffraction under identical ionic conditions and varying degree of shear. The primary particle size of the P25 was determined to be 28 nm, from consideration of the surface area and density of the particles, and the cluster size during permeation and filtration was close to 100 nm. During sedimentation the cluster size was determined to be close to 10 μm, which is the same size obtained by laser diffraction when measuring under conditions of low shear. Using the above two sizes (28 nm and 10 μm) as limits in Happel's permeability model it was possible to determine an ‘operating envelope’ of permeability that matched the experimentally measured values for the sedimentation, permeation and filtration processes.     

Differences between ZSM-5 and ZSM-11 zeolite catalysts in 1-hexene aromatization and isomerization

ZSM-5 and ZSM-11 zeolites with high crystallinity are synthesized and tested in the aromatization and isomerization reactions of 1-hexene at 370 °C in a continuous flow fixed bed. The results indicate that ZSM-5 and ZSM-11 zeolites possess similar acid site amount and strength, and most of the acid sites belong to Brønsted acid. When the ZSM-5 and ZSM-11 zeolites were used as catalysts, the aromatics selectivity over ZSM-11 catalyst was higher than that over ZSM-5 catalyst in contrast to i-paraffins selectivity, maybe attributed to that the C₇ and C₈ aromatics have an easier exit from the ZSM-11 zeolite. Moreover, the decrease of particle size can present superior aromatics selectivity and less i-paraffins selectivity in the aromatization and isomerization of 1-hexene over the ZSM-11 catalyst.     

Near-limiting detonation in channels with porous walls

The propagation of detonation is studied in channels with walls whose acoustic resistance varies over a factor of 4000. Noticeable weakening of detonation waves is observed in near-critical regions. Optimum dimensions for coatings of porous materials to quench near-limiting detonation are determined.M. A. Lavrentev Institute of Hydrodynamics, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk. Translated from Fizika Goreniya i Vzryva, Vol. 30, No. 1, pp. 101–106, January–February, 1994.     

Electrochemical detection of large channels in porous rocks

An electrochemical method for studying channels in porous rocks and similar insulators, has been developed. In principle, the method consists of displacing a nonconducting liquid from the pores by an inflow of an ionically conducting solution. The conductance is monitored continually as the rate of flow through the rock is gradually increased. The rate of conductance increase is interpreted in terms of a simple model, based on Poiseuille flow through a capillary network, to provide information about the sizes and numbers of large pores in the rock. Three rock samples have been analysed.     

Crystal growth of high silica ZSM-5 at low temperature synthesis conditions

At the temperature of 90°C and under atmospheric pressure, growth kinetics of high silica ZSM-5 was investigated through a long induction, nucleation and crystal growth periods. It was found the entire crystallization mechanism of ZSM-5 seems to be the combined process of the nucleation via solid-solid transformation, intergrowth among seed crystals and the normal growth in the reaction mixture. Nuclei were initially formed on the Si-rich surface of the amorphous intermediates, indicating that the reaction of TPA with Si species was prior to that with Al species. As the reaction time proceeded, various types of intergrowth among the seed crystals were observed along with the crystals growing independently. The intergrowth seems to play a role for forming typical ZSM-5 crystal shapes. And then ZSM-5 crystals further grew in the reaction mixture, so that the bulk Si/Al₂ ratio of crystals approached that of the initial reaction mixture.     

Characteristics of ammonia permeation through porous silica membranes

A sol–gel method was applied for the preparation of silica membranes with different average pore sizes. Ammonia (NH₃) permeation/separation characteristics of the silica membranes were examined in a wide temperature range (50–400°C) by measurement of both single and binary component separation. The order of gas permeance through the silica membranes, which was independent of membrane average pore size, was as follows: He > H₂ > NH₃ > N₂. These results suggest that, for permeation through silica membranes, the molecular size of NH₃ is larger than that of H₂, despite previous reports that the kinetic diameter of NH₃ is smaller than that of H₂. At high temperatures, there was no effect of NH₃ adsorption on H₂ permeation characteristics, and silica membranes were highly stable in NH₃ at 400°C (i.e., gas permeance remained unchanged). On the other hand, at 50°C NH₃ molecules adsorbed on the silica improved NH₃‐permselectivity by blocking permeation of H₂ molecules without decreasing NH₃ permeance. The maximal NH₃/H₂ permeance ratio obtained during binary component separation was ～30 with an NH₃ permeance of ～10^?7 mol m^?2 s^?1 Pa^?1 at an H₂ permeation activation energy of ～6 kJ mol^?1. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Amorphous silica wastes for reusing in highly porous ceramics

The paper analyzes a solution in green manufacturing of foamed or cellular ceramics. The objective of this study was to determine the technical solution for rice husk ash and “tales” of mixed glass cullet reusing based on the specific properties of these materials for creation of spherical holes inside ceramic using the process of coalescence of cellular glass. The paper reports on experimental results obtained from the production of lightweight cellular glass granules produced using glass cullet and rice husk ash. Lightweight cellular glass granules were mixed with clay, pressed and fired in air at 920°C. Clay sintering and the formation of ceramic were followed with the coalescence of cellular structure of glass granules and with the formation of spherical hollows inside the matrix. Density and strength of the fired ceramic bodies were determined. It is observed that the lightweight ceramics with density 900 ÷ 920 kg/m³ possess a compressive strength of about 5 MPa that is acceptable for bricks or tiles manufacture. The utilization of amorphous silica waste for lightweight ceramics manufacture helps in reducing waste disposal concerns and costs associated, and also transforms the waste into an alternative raw material with added value, moreover making the final product cheap.     

3-氨丙基三乙氧基硅烷作用下合成多级孔道ZSM-5分子筛

多级孔道ZSM-5分子筛因同时具有微孔和介孔结构,在催化领域显示出较好的应用前景。对高硅铝比下以3-氨丙基三乙氧基硅烷作为硅烷化试剂合成具有多级孔道的ZSM-5分子筛进行研究,并采用X射线衍射、N₂吸附-脱附和扫描电镜等进行表征。结果表明,合成的多级孔道ZSM-5分子筛是由小晶粒聚集而成的椭球状团簇体,晶粒间会形成介孔;硅烷化试剂的添加量可以在一定程度上调控微介孔比例,介孔孔容随着3-氨丙基三乙氧基硅烷添加量的增加而增大,3-氨丙基三乙氧基硅烷添加量较高时,预晶化与否对多级孔道ZSM-5分子筛的孔结构、形貌和产率产生较大的影响;3-氨丙基三乙氧基硅烷与SiO₂物质的量比为0.05∶1时,预晶化条件下合成的样品介孔孔容为0.154 cm³·g^-1,明显高于未预晶化条件下合成的样品（0.084 cm³·g^-1）,产率为91.8%,高于未预晶化条件下合成的样品（65.3%）。     

Coke burning behavior of a catalyst of ZSM-5/ZSM-11 co-crystallized zeolite in the alkylation of benzene with FCC off-gas to ethylbenzene

Since the commercialization of ethylbenzene production via alkylation of benzene with the dilute ethene in FCC off-gas over a ZSM-5/ZSM-11 co-crystallized zeolite catalyst in China, the catalyst has been regenerated several times and showed good regeneration performance. During the alkylation process, the catalytic activity decreases, some of the catalyst pores are blocked and the acid centers are partly covered by coke deposition. Influence of the factors such as catalyst particle size, temperature, etc. on the burning rate of the coke was investigated by the TG technique, and a rate equation for coke burning on the ZSM-5/ZSM-11 co-crystallized catalyst was established.     

Synthesis of ZSM-5 with the silica source from industrial hexafluorosilicic acid as transalkylation catalyst

A new effective process to improve the utilization of industrial fluorosilicic acid of phosphate fertilizer by-product has been investigated to comprehensive application of the silicon and fluorine source.Two-step ammoniation was applied to recover high-quality silica.The recovered silica can be used to hydrothermal synthesize ZSM-5 zeolite without impurity phase contamination,which was confirmed by XRD,TG,SEM,BET and EDS characteristic techniques.It was found that with the increase of SiO2/Al2O3 ratio and the extension of reaction time,the crystal type transform from the orthorhombic to the monoclinic phase.The impurity fluorine content of the recovered SiO2 from H2SiF6 has great influence on the hydrothermal process for ZSM-5 crystal structure formation.zMoreover,the increase of fluorine ions content in the hydrothermal process can control the crystal morphology and size of synthesized ZSM-5.Catalytic properties of synthesized HZSM-5 with different SiO2/Al2O3 ratio in transalkylation of toluene and 1,2,4-trimethylbenzene show good and stable catalytic performance.The ZSM-5 synthesized with recovered silica source exhibits similar catalyst life as the performance of small particle size HZSM-5,because the ZSM-5 synthesized with the silica source from industrial hexafluorosilicic acid prefers a thin disk crystal along the b axis direction,which shortens the diffusion distance of generated products.     

ZSM-5改性酚醛树脂基多孔炭膜的微观结构研究

以ZSM-5掺杂改性酚醛树脂为前驱体,经成型和900℃热解制备了多孔炭膜。采用热失重分析、扫描电镜、X射线衍射、红外光谱与泡压法等表征手段分别对前驱体热稳定性、炭膜表观形貌、晶体结构、表面官能团与孔隙结构进行了表征。考察了ZSM-5用量对前驱体热稳定性、炭膜孔径、孔隙率的影响。结果表明,经ZSM-5改性后前驱体膜残炭量显著提高;热解后ZSM-5结构保留完好,其会促进酚醛树脂的热分解同时阻碍炭结构的热缩聚重排,有利于形成更多小孔径孔隙结构的乱层炭结构。     

ZSM-5改性酚醛树脂基多孔炭膜的微观结构研究

以ZSM-5掺杂改性酚醛树脂为前驱体,经成型和900℃热解制备了多孔炭膜。采用热失重分析、扫描电镜、X射线衍射、红外光谱与泡压法等表征手段分别对前驱体热稳定性、炭膜表观形貌、晶体结构、表面官能团与孔隙结构进行了表征。考察了ZSM-5用量对前驱体热稳定性、炭膜孔径、孔隙率的影响。结果表明,经ZSM-5改性后前驱体膜残炭量显著提高;热解后ZSM-5结构保留完好,其会促进酚醛树脂的热分解同时阻碍炭结构的热缩聚重排,有利于形成更多小孔径孔隙结构的乱层炭结构。     

Co-conversion of methanol and n-hexane into aromatics using intergrown ZSM-5/ZSM-11 as a catalyst

The conversion of n-hexane and methanol into value-added aromatic compounds is a promising method for their industrially relevant utilization. In this study, intergrown ZSM-5/ZSM-11 crystals were synthesized and their resulting catalytic performance was investigated and compared to those of the isolated ZSM-5 and ZSM-11 zeolites. The physicochemical properties of ZSM-5/ZSM-11 intergrown zeolite were analyzed using X-ray diffraction, N₂ isothermal adsorption-desorption, the temperature-programmed desorption of ammonium, scanning electron microscopy, Fourier transform infrared spectra of adsorbed pyridine, and nuclear magnetic resonance of ²⁷Al , and compared with those of the ZSM-5 and ZSM-11 zeolites. The catalytic performances of the materials were evaluated during the co-feeding reaction of methanol and n-hexane under the fixed bed conditions of 400°C, 0.5 MPa (N₂), methanol:꞉n-hexane=7꞉:3 (mass ratio), and weight hourly space velocity=1 h^–1 (methanol). Compared to the ZSM-5 and ZSM-11 zeolites, the ZSM-5/ZSM-11 zeolite exhibited the largest specific surface area, a unique crystal structure, moderate acidity, and suitable Brønsted/Lewis acid ratio. The evaluation results showed that ZSM-5/ZSM-11 catalyst exhibited better catalytic reactivity than the ZSM-5 and ZSM-11 catalysts in terms of methanol conversion rate, n-hexane conversion rate, and aromatic selectivity. The outstanding catalytic property of the intergrown ZSM-5/ZSM-11 was attributed to the enhanced diffusion associated with its unique crystal structure. The benefit of using zeolite intergrowth in the co-conversion of methanol and alkanes offers a novel route for future catalyst development.