The Conversion of 1-Propanamine on Copper-Containing MFI and BEA Zeolites Prepared by Aqueous and Vapor Ion-Exchange

A process has been developed for exchanging one Cu atom per ion exchange site in an MFI zeolite. The material is synthesized by reaction of the acidic zeolite with CuCl vapor, followed by oxidation with oxygen, and conversion of the Cu²⁺species to copper hydroxyl ions and copper hydroxyl dimers by reaction of the oxidized material with water upon exposure to humid air. This material, a similarly prepared BEA material, and copper-containing MFI and BEA zeolites prepared by conventional aqueous ion-exchange have been comparatively investigated for the conversion of 1-propanamine. Reaction products include C₆products such as dipropanamine and 1-propanamine, N-(1-propylidene). A bifunctional acid/metal reaction pathway is proposed to account for the observed products.     

Water and water vapor sorption studies in polypropylene–zeolite composites

Water and water vapor sorption to porous polypropylene–zeolite composites prepared by hot pressing have been studied as a function of zeolite loading. This work presents the first report on the effect of the zeolite as a filler on the water‐sorption properties of PP composites. Water swelling experiments were conducted at 25°C using pure PP and PP–zeolite films samples having different zeolite loadings (6–40 wt %). Because PP is a hydrophobic polymer, it does not sorp any water, but the composites having 10, 20, 30, and 40% zeolites have sorbed 0.63, 1.00, 1.72 and 3.74% water, respectively. The zeolite itself at the same conditions sorbed 24.5% water. As the filler loading in the composites increased, equilibrium uptake values increased also. On the other hand, water vapor sorption and kinetics has been studied using a Cahn 2000 gravimetric sorption system. Within in the range of 0.35–0.95% water vapor was adsorbed by the composites containing 10–40 wt % zeolites. Experimental effective water vapor diffusivities of the composite films was about one order of magnitude higher (10‐fold) than the experimental water diffusion coefficient in composites. The transport of water in composites was slower than that in the liquid water due to the longer diffusion pathway and adsorption on the surface of the composites. Although the liquid water may fill all the voids in the composite, water vapor is adsorbed on the surface of the zeolite only. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3069–3075, 2003     

Multiple paths to nanocrystalline high silica beta zeolite

Several principles from nanozeolite synthesis lore were investigated in order to prepare discrete pure silica nanocrystalline BEA zeolite. It was discovered that lowering reaction temperature to 100 °C results in a significant reduction in nano-BEA crystal size, that lowering synthesis mixture water content to the lowest possible level for a ‘pourable’ gel provides nano-BEA crystals, that tetraethylorthosilicate (TEOS) more consistently provides smaller crystals than fumed silica as a raw material, that increasing the level of structure-directing agent resulted in more discrete and smaller crystals (25–30 nm), and that ‘surfactant’ addition could generate even smaller nano-BEA crystals or nanocrystalline domains, but mild to severe aggregation was still a problem. Nearly pure silica nanocrystalline BEA zeolites were prepared from Al-containing products by a calcination followed by acid extraction procedure. The calcination step is critical for more complete Al removal. Defects generated by acid extraction could be healed by treatment of resultant powder with a hexamethyldisilazane (HMDS). Another key finding was that Al-containing synthesis mixtures could provide nanocrystalline BEA zeolite with 4,4′-trimethylenebis(N-methyl, N-benzyl-piperidinium) dihydroxide (TMP(OH)₂) as organic structure-directing agent. Interestingly, adjusting synthesis parameters in TMP and Al-containing synthesis mixtures provided some differences to pure Si BEA products. For example, stirring or lowering reaction temperature did not decrease crystal size, but did shorten crystallization time. The smallest crystals from TMP-based, Al-containing reaction mixtures were prepared when a freeze–dried colloidal silica was utilized as silica source.     

Transient adsorption studies of automotive hydrocarbon traps

A chromatographic adsorption unit was designed and built to study the adsorption of alkanes in zeolites for the hydrocarbon trap systems in three‐way catalysts, to assist in the selection of optimal materials for this application. The experimental apparatus used a zeolite bed in place of the column in an ordinary gas chromatograph and could be accurately modeled to determine the adsorption equilibrium constants for simple alkanes in MFI zeolites. The adsorption of iso‐pentane was studied in BEA zeolites with varying Si/Al₂ ratios, before and after ex situ zeolite aging simulating engine exhaust, and in the presence of water vapor. The elution times were shown to depend directly on the zeolite adsorption capacity. The primary effect of water was to decrease the iso‐pentane adsorption capacity by partial filling of the zeolite pores through adsorption of water at acid sites. Some implications of this work for choosing the best materials for hydrocarbon trapping are discussed. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2875–2881, 2014     

Conversion of dry gel to microporous crystals in gas phase

Recently the dry gel conversion (DGC) technique, where a hydrogel is dried and the resultant dry gel is converted into microporous crystals in steam or in a mixed vapor of steam and organic structure-directing agents (SDAs), has been developed. It has been shown that a wide variety of microporous crystals, pure silica microporous crystals, aluminosilicates, metallosilicates, and aluminophosphates, can be synthesized using the DGC method. Remarkable results have been reported in the synthesis of BEA types zeolites, namely aluminosilicate, titaniumsilicate, zincosilicate, and borosilicate with BEA topology, using tetraethylammonium hydroxide, a commercially available SDA. It has also been found that zeolite OU-1, probably analogous to SSZ-31 and NCL-1, is formed via phase transformation from BEA. Dense zeolite coatings like membranes are possible using this method. Characteristics of the DGC method are discussed in detail. This revised version was published online in August 2006 with corrections to the Cover Date.     

Fe-BEA Zeolite Catalysts for NH3-SCR of NOx

Iron-containing zeolites are known to be promising catalysts for the NH₃-SCR reaction. Here, we will investigate the catalytic activity of iron-based BEA catalysts, which was found to exhibit improved activities compared to previously described iron-containing zeolite catalysts, such as ZSM-5 and ZSM-12. Series of Fe-BEA zeolite catalysts were prepared using a range of different preparation methods. Furthermore, we found that an iron concentration around 3 wt% on BEA showed a small optimum in SCR activity compared to the other iron loadings studied.     

Influence of the exchanged cation in Pd/BEA and Pd/FAU zeolites for catalytic oxidation of VOCs

0.5 wt% palladium supported on exchanged BEA and FAU zeolites were prepared, characterized and tested in the total oxidation of volatile organic compounds (VOCs). The BEA and FAU zeolites were exchanged with different cations to study the influence of alkali metal cations (Na⁺, Cs⁺) and H⁺ in Pd-based catalysts on propene and toluene total oxidation. The exchange with different cations (Na⁺, Cs⁺) and H⁺ led to a decrease of the surface area and the micropore volume. All Pd/BEA and Pd/FAU zeolites were found to be powerful catalysts for the total oxidation of VOCs. They were active at low temperature and totally selective for CO₂ and H₂O. However, their activity depends significantly on the type of zeolite and on the nature of the charge-compensating cation. The activity order for propene and toluene oxidation on FAU catalysts, Pd/CsFAU > Pd/NaFAU > Pd/HFAU, is the reverse of the activity order on BEA catalysts: Pd/HBEA > Pd/NaBEA > Pd/CsBEA. The catalytic activities can be rationalized in terms of the influence of the electronegativity of the charge-compensating cation on the Pd particles, the Pd dispersion, the PdO reducibility and the adsorption energies for VOCs.     

Analysis of the Water Permeability of Linde Type A Zeolites in Reverse Osmosis

In this paper, we apply the Hagan-Poiseuille Model and the resistance model to perform an original analysis of previous experimental studies of water transport through polycrystalline Linde Type A (LTA) zeolite membranes and nanocomposite polymer/LTA membranes. From our analysis we estimate the intrinsic water permeability of LTA zeolites and the zeolite/polymer interface. We find that the permeability of a single LTA crystal is significantly greater than the intrinsic permeability of a commercial seawater reverse osmosis membrane or a commercial cellulose-acetate forward osmosis membrane.     

Preparation for Size-Controlled MOR Zeolite Nanocrystal Using Water/Surfactant/Organic Solvent

Recently, the synthesis of nanometer-sized zeolite crystals has attracted considerable attention from many researchers. In this study, the preparation of Mordenite (MOR zeolite) nanocrystals via hydrothermal synthesis in water/surfactant/organic solvent was carried out. Polyoxyethylene-(15)-oleylether (O-15, non-ionic surfactant) and cyclohexane were employed as a surfactant and organic solvent, respectively. Interestingly, it was found that the crystal sizes and morphology of MOR zeolites depended on the surfactant concentration regardless of the same concentrations of Si and Al sources and template in the water solution. The MOR zeolite nanocrystals with average sizes of approximately 80 nm could be obtained. Moreover, the column-like morphology of MOR zeolite was also observed at a high surfactant concentration (0.75 mol/L). Accordingly, the crystal size and morphology of MOR zeolite can be controlled by the surfactant concentration. This result appears to be due to the difference in the nucleation and growth rates of MOR in the solution.     

Characterization of polymeric LB thin films for sensor applications

The Quartz Crystal Microbalance (QCM) system is utilized to investigate the relationship between mass uptake and associated swelling for Langmuir‐Blodgett (LB) organic thin films obtained from pyrene end‐capped polystyrene (PS). The study was carried out using three different molecular weights of polymeric chains. The changes in resonance frequency associated with mass changes can be attributed to the swelling behavior of polymeric thin films during vapor absorption. This swelling is due to the capturing of organic vapor molecules in the sensor environment. To quantify real‐time QCM data for swelling, early‐time Fick's law of diffusion was adopted to fit the results, and a good linear relationship was observed between the mass uptake and square root of the swelling time. The diffusion coefficients for swelling were thus obtained from the slopes of the fitting curves and was found to be correlation with the amount of organic vapor content in the cell. It was also observed that diffusion of the organic vapor into higher molecular weight polystyrene thin films are much faster than low molecular weight ones in sensor applications. Diffusion coefficients were found to be 0.2–3.0 × 10^?16, 5.0–13 × 10^?16, and 1.0–1.6 × 10^?15 cm²/s for PS1, PS2, and PS3 LB thin films, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Promising zeolite-type hydrocarbon trap catalyst by a knowledge-based combinatorial approach

Libraries consisting of more than 100 zeolite samples were prepared and examined for developing a promising HC trap catalyst. Parallel adsorptions of toluene onto the catalyst samples were conducted over a 10 × 10 array reactor under dry and wet conditions with or without a heating process three knowledge-based conditions for developing an automotive catalyst during the cold-start period. FAU and BEA type zeolites revealed a high performance of toluene adsorption under the dry condition. However, FAU type zeolite significantly decreased the amount of toluene adsorbed in the presence of water in the feed gas stream, mainly due to the hydrophobicity of the catalyst surface. Over Beta type zeolites, the toluene adsorbed was found to be considerably preserved, even after forced desorption temperature-ramping to the warm-up condition of an automotive engine. Li, K, or Ag ion-exchanged Beta zeolites seem to be particularly promising as an HC trap catalyst.     

改性BEA沸石催化香茅醛Meerwein-Ponndor-Verley(MPV)还原合成香茅醇

采用盐酸脱铝-碱金属或碱土金属离子交换制备了改性BEA沸石催化剂,并进行催化剂XRD、SEM表征.以上述改性BEA沸石为催化剂、以异丙醇为氢源,通过MPV反应考察了催化剂还原香茅醛合成香茅醇的性能.结果表明,在环化合成异胡薄荷醇和MPV还原合成香茅醇的两种竞争反应中,脱铝-离子交换改性沸石Cs-BEA对于MPV反应合成...     

Nucleation and growth history of zeolite LTA synthesized from kaolinite by two different methods

The synthesis of zeolite Linde Type A (LTA) from kaolinite by two different routes: (1) conventional hydrothermal alkaline activation and (2) alkaline fusion prior to hydrothermal reaction, as well as its nucleation and growth history, were investigated. Using the first method, co-crystallization of sodalite and cancrinite, probably via an unstable zeolite LTA intermediate, was observed during treatment of kaolinite in NaOH solutions. The addition of a SiO₂ source promoted the co-precipitation of several zeolite phases, including zeolites LTA, X and P, with traces of sodalite and cancrinite. By fusion with NaOH followed by hydrothermal reaction, kaolinite was converted into zeolite LTA. Synthesized materials appeared stable thermodynamically under the experimental conditions. The synthesis products have been characterized by X-ray diffraction, scanning electron microscopy and Fourier Transform Infrared Spectroscopy.     

Electrical conductivity of LTA‐zeolite in the presence of poly(vinyl alcohol) and poly(vinyl pyrrolidone) polymers

In this work we studied the electrical behavior of Linde type A zeolite (K⁺) in the presence of two polymers, poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP), with excellent film forming properties. Homogeneous composite thin films of PVA/LTA‐zeolite and PVP/LTA‐zeolite were prepared with different zeolite concentrations. The current?voltage (I?V) characteristics of the composites were measured at different applied voltages. The results show that the conductivity properties are composition‐ratio‐dependent and are also related to the type of polymers. Moreover, a well‐defined step‐like change was detected in the I?V curve of PVP/LTA‐zeolite at very high applied voltage. © 2013 Society of Chemical Industry     

Positron lifetimes in pores of some low-silica zeolites: influence of water content, crystal size and structural type

Positron annihilation lifetime spectroscopy has been used for observation of the free voids in low silica zeolites, of LTA and FAU structure and different crystal size, before and after their heating at different temperatures below 200 °C. Sizes of crystals of the zeolite samples, as well as their structures and water contents, were characterized by X-ray diffraction, scanning electron microscopy, thermogravimetry, and particle size distribution measurements. The number of positron lifetime components as well as their values and intensities, after water removal from the zeolite structure, vary. However, changes are not uniform in all investigated zeolites. The differences are compared and discussed in the dependence of different structure types and crystal sizes of investigated zeolites.     

Use of zeolite films to improve the selectivity of reactive gas sensors

Semiconductor (Pd-doped SnO₂) gas sensors covered with zeolitic films (MFI or LTA) have been developed and used for gas phase sensing of different species (methane, propane, and ethanol) at different humidity levels. The dynamic responses obtained with these sensors were compared with the response of a reference sensor without a zeolitic layer. The results clearly indicate that a suitable zeolite layer strongly reduces, and in some cases suppresses, the response of the sensor to paraffins, thereby increasing the sensor selectivity to the alcohol, while the reference sensor could not discriminate between these molecules. This clearly shows the potential of zeolite-based sensors to achieve a higher selectivity/sensitivity in gas sensing applications.     

Synthesis of Dihydropyrimidinones Using Large Pore Zeolites

Abstract  

A series of dihydropyrimidin-2(1H)-one (DHPM) belongs to one of the important class of therapeutic and pharmacological active compound, were synthesized through the multicomponent reactions (MCRs) of aldehydes, ethyl acetoacetate and urea, followed by the heterogeneous catalyzed Biginelli reaction. In the present endeavour, medium (ZSM-5) and large pore zeolites (Y, BEA and MOR) as well as dealuminated zeolites BEA, were studied as catalysts. An excellent activity for DHPMs synthesis is achieved by optimizing accessibility of the reactants to the active sites and the surface polarity of zeolite catalysts. Moreover, the mechanism of Biginelli reaction was studied by means of GAUSSVIEW energy calculations of adsorbed acylimine intermediate on zeolite by using the density functional method (DFT).     

A study of PVDF Langmuir‐Blodgett thin film using quartz crystal microbalance

Poly(vinylidene fluoride) (PVDF) was deposited onto a quartz crystal microbalance (QCM), using a standard Langmuir–Blodgett (LB) thin film deposition procedure. QCM technique was used to monitor the reproducibility of the LB film monolayer, and the fabricated QCM sensor was employed to detect the dimethyl methyl phosphonate (DMMP) vapor, a simulant of nerve agents. The results show that PVDF was successfully deposited from the water surface onto the quartz crystal substrate. The PVDF LB film is found to be highly sensitive to DMMP vapor, and frequency shifts are linear to the concentrations. The response of the sensor against DMMP is fast, large, and reversible. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and Properties of Carbon/Zeolite Composites with Corrugated Structure

Composites of carbon/zeolite with corrugated structures were prepared by carbonization, steam activation and/or hydrothermal treatment of corrugated paper. No zeolite formation resulted from conventional hydrothermal treatment of the carbonized and activated samples in NaOH solution but zeolite Na P1 was formed by addition of silica to the solution. By contrast, zeolites Na P1 and Na A were formed by the in-situ crystallization method (hydrothermal treatment of solid samples impregnated with NaOH solution). With higher impregnating NaOH concentrations, longer reaction times and higher reaction temperatures, the products changed to sodalite- and cancrinite-type compounds. Hydrothermal treatment was effective in increasing the specific surface area of the products by the formation of zeolite from amorphous calcium aluminosilicate, and also increased the mechanical strength by gluing together the carbon fibers in the samples. The resulting samples showed enhanced adsorption for polar molecules such as ammonia, water vapor and methanol due to the formation of composites of activated carbon with hydrophilic zeolites.     

Acidic property of BEA zeolite synthesized by seed-directed method

The acidic property of a BEA zeolite prepared by a seed-directed synthesis (SDS) method without organic structure directing agent (OSDA) was analyzed by a method of ammonia infrared/mass spectroscopic temperature-programmed desorption. The number of Brønsted acid sites on the SDS-BEA zeolite was larger than that on a conventional BEA zeolite synthesized from using OSDA. The enthalpy of ammonia desorption, distributed mainly in a range between 115 and 145 kJ mol^?1, was in agreement with the acid strength region generated by isomorphous substitution of Si⁴⁺ by Al³⁺ in the BEA framework. These observations confirm that the microstructure around the incorporated Al in the SDS-BEA zeolite was equivalent to that in the conventional one.