A Molecular Dynamic Investigation of the Diffusion of Methane‐Ethane and Methane‐Propane Mixtures in Zeolites

Molecular Dynamic (MD) simulations were carried out to determine the Maxwell‐Stefan (M‐S) diffusivities, ?_i, and self‐diffusivities, D_i,self, of methane (C1), ethane (C2), and propane (C3) for a variety of molecular loadings, q_i, in three classes of zeolite topologies: (1) intersecting channels (MFI, ISV, BEA), (2) one‐dimensional (1D) channels (AFI, TON, FER, MOR, LTL), and (3) cages separated by windows (FAU, LTA, ERI, CHA, DDR). The ?_i are strongly dependent on loading, decreasing to zero at saturation loading in all cases. For 1D channels, the decrease of ?_i with q_i is severe. For cages separated by narrow windows (LTA, ERI, DDR, CHA), the ?_i increase sharply with q_i before eventually reducing to zero at saturation loading. Correlation effects are reflected in the ratio of the self‐ to M‐S diffusivity, D_i,self/?_i; this ratio is seen to be strongly dependent on the topology. Correlation effects are negligibly small in zeolite structures with cages separated by narrow windows. For binary C1–C2 and C1–C3 mixtures in both intersecting channel structures and 1D channels, the D_i,self of the more mobile species, C1, is reduced significantly due to the presence of the more tardy C2 or C3. The mobility of the tardy species is enhanced due to the presence of the mobile C1. For cages separated by narrow windows, the inter‐cage hops are practically independent and there is no accelerating or decelerating effects during mixture diffusion.     

Onsager coefficients for binary mixture diffusion in nanopores

This paper presents a critical appraisal of current estimation methods for the Onsager coefficients L₁₁, L₂₂, and L₁₂ for binary mixture diffusion inside nanopores using pure component diffusivity data inputs. The appraisal is based on extensive sets of molecular dynamics (MD) simulation data on L_ij for a variety of mixtures in zeolites (MFI, AFI, TON, FAU, CHA, DDR, MOR, and LTA), carbon nanotubes (CNTs: armchair and zig-zag configurations), titanosilicates (ETS-4), and metal-organic frameworks (IRMOF-1, CuBTC). The success of the L_ij predictions is crucially dependent on the estimates of the degree of correlations in molecular jumps for different guest-host combinations; these correlations are captured in Maxwell-Stefan approach by the exchange coefficients ?_ij. Three limiting scenarios for correlation effects have been distinguished; for each of these scenarios appropriate expressions for the L_ij are presented. For CNTs, correlation effects are dominant and the interaction factor, defined by , is close to unity. For cage-type zeolites such as LTA, CHA, and DDR with narrow windows separating cages, correlation effects are often, but not always, negligibly small and the assumption of uncoupled diffusion, i.e., α₁₂=0, is a reasonable approximation provided the occupancies are not too high. In other cases such as zeolites with one-dimensional channel structures (AFI, TON), intersecting channels (MFI), cage-type zeolite with large windows (FAU), ETS-4, CuBTC, and in IRMOF-1, it is essential to have a reliable estimation of the ?_ij; MD simulations underline the wide variety of factors that influence the ?_ij.We also highlight two situations where estimations of the L_ij fail completely; in both cases the failure is caused due to segregated adsorption. In adsorption of CO₂-bearing mixtures in LTA and DDR zeolites, CO₂ is preferentially lodged at the narrow window regions and this hinders the diffusion of partner molecules between cages. The second situation arises in MOR zeolite that has one-dimensional channels connected to side pockets. Some molecules such as methane, get preferentially lodged in the side pockets and do not freely participate in the molecular thoroughfare. Current phenomenological models do not cater for segregation effects on mixture diffusion.     

A Molecular Dynamics investigation of the influence of framework flexibility on self-diffusivity of ethane in Zn(tbip) frameworks

Configurational-Bias Monte Carlo simulations of the adsorption isotherm of ethane in Zn(tbip) (H₂tbip = 5-tert-butyl isophthalic acid), a representative of metal-organic frameworks, show an inflection at a loading, q_i = 6 molecules per unit cell. This inflection causes the inverse thermodynamic factor, 1/Γ_i, to display a minimum at q_i = 6, along with a maximum at q_i ≈ 10. Molecular Dynamics (MD) simulations of the self-diffusivity D_i,self, taking account of the framework flexibility of Zn(tbip) show that the D_i,self − q_i dependence follows that of 1/Γ_i − q_i, with a minimum at q_i = 6. Remarkably, MD simulations assuming a rigid framework yield significantly lower values of the self-diffusivities, and show a monotonic decrease of D_i,self with q_i.     

The change of the unit cell dimension of different zeolite types by heating and its influence on supported membrane layers

In comparison with the well-known swelling of organic polymer membranes, zeolite membranes have been considered for a long time as relatively stiff. The problem of the different thermal expansion coefficients of the α-Al₂O₃ support and the zeolite layer was usually reduced on a possible crack formation during the template removal of MFI membranes. However, the crack formation could be avoided by an extremely slow heating rate and by membrane layers formed of small and non-oriented zeolite crystallites. Several papers have shown that the isomorphous incorporation of Al into the MFI structure (silicalite → ZSM-5) results in an increase of the non-selective intercrystalline transport and – as a consequence – the separation selectivity drops. In accordance with this observation, no shape-selective gas separation is reported for the Al-rich zeolite membranes MOR, FAU and LTA. On the other hand, these membranes allow the highly selective separation of water from organic mixtures due to hydrophilic interactions. In the present paper the change of the unit cell dimension (UCD) for zeolites LTA, FAU, MOR and MFI was studied as a function of temperature and water content using Rietveld refinement. Parallel to the determination of the linear and volume expansion coefficients by in situ-heating XRD, the de-watering and de-templating was studied by thermogravimetry (TGA). A strong UCD-change was found for all Al-rich zeolite types as a result of the de-watering. In contrast, the smallest changes of the UCD in the temperature range 50–450 °C were found for MFI crystals. Nevertheless, also for MFI membrane layers with rising temperature an increasing tension between the expanding α-Al₂O₃ support and the slightly shrinking membrane layer takes place. Zeolite layers of small crystals with either a random or a preferential crystal orientation relative to the support and an only partial de-watering in the case of Al-rich zeolite layers can minimize the tension in the support-membrane system. Thus, the irreversible formation of macroscopic cracks can be avoided and the formation of small intercrystalline pores in the mesopore region becomes reversible.     

Interzeolite Conversion of FAU Type Zeolite into CHA and its Application in NH3-SCR

In this work we studied the potential feasibility to synthesize small pore zeolites, such as chabazite (CHA) via interzeolite conversion of FAU type zeolite. We have thereafter used CHA as the starting material to obtain Cu–CHA. When CHA in NH₄ ⁺ form was used to prepare Cu–CHA, the large size of the potassium cation present in the structure caused pore blockage in the chabazite framework, and diminished the adsorption and exchange capacity. However, Cu–CHA with comparable Selective Catalytic Reduction performance to the commercial catalyst was obtained via ion exchange if Cu-exchange was performed from H⁺–CHA form. Still, the main challenge was to fully eliminate K⁺ from the zeolite structure in order to further improve its catalytic performance and high temperature stability.     

Validating the Darken Relation for Diffusivities in Fluid Mixtures of Varying Densities by Use of MD Simulations

Molecular Dynamics (MD) simulations have been carried out to determine the self‐diffusivities, D_i,self, of the pure hydrocarbons methane (C1), ethane (C2), propane (C3), and n‐hexane (nC6) at various fluid densities. The MD simulations are in reasonable agreement with published experimental data. The influence of fluid density on both D_i,self and the Maxwell‐Stefan (M‐S) diffusivities, ?_ij, in binary C1‐C2, C1‐C3, C2‐C3, and C1‐nC6 mixtures was also investigated. The MD simulations show that the M‐S diffusivities in binary fluid mixtures can be estimated with good accuracy using the Darken relation.     

Kinetics of the anionic ring‐opening polymerization of octamethylcyclotetrasiloxane initiated by potassium isopropoxide

Kinetics of the anionic ring‐opening polymerization of octamethylcyclotetrasiloxane (D₄) in bulk initiated by potassium isopropoxide was studied. Several promoters including N‐methyl‐2‐pyrrolidinone (NMP), N,N‐dimethylformamide (DMF), and diglyme were used. It is indicated that the reactions are first‐order in D₄ during the initial stage of polymerization. The polymerization rate of D₄ is influenced by a number of factors, such as the nature of promoters, the molar ratio of promoter to initiator (C_p/C_i ratio), and the reaction temperatures. With the use of NMP as promoter, the polymerization rate constant at 30°C is 10.482 h^?1 with the C_p/C_i ratio equal to 3.0. As the C_p/C_i ratio increases, the polymerization rate constant increases sharply and the cyclic oligomers content in polymer decreases evidently. The back‐biting reaction that leads to the formation of decamethylcyclopentasiloxane (D₅) occurred in the polymerization of D₄. The rate of the D₅ formation relatively to the rate of D₄ conversion increases with the conversion of D₄. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3510–3516, 2006     

Selective ethylene‐permeable zeolite composite double‐layered film for novel modified atmosphere packaging

The composite double‐layered films, for the packaging application of postharvest fruits and vegetables, were prepared by laminating low‐density polyethylene (LDPE) and poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) modified with zeolite ZSM‐5. The film was characterized by scanning electron microscope and differential scanning calorimeter and tested for permeation of ethylene (C₂H₄), oxygen (O₂), carbon dioxide (CO₂), and water vapor. It was found that the C₂H₄ permeability of the films was improved because of an enhanced adsorption of C₂H₄ by the incorporated zeolite (0–10 wt%). The preconcentrated layer (zeolite/SEBS) leads to a higher C₂H₄ concentration gradient across the film. Moreover, the high dispersion of zeolite increased the C₂H₄ permeation. When compared with O₂ and CO₂, the composite films were more selective to C₂H₄. However, the C₂H₄ permeation decreased in the presence of O₂ because of a competitive adsorption. In addition, the films possessed appreciate tensile properties for packaging application. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Hydrothermal conversion of FAU zeolite into aluminous MTN zeolite

The hydrothermal conversion of FAU zeolite into aluminous MTN zeolite is described here. In the presence of both benzyltrimethylammonium hydroxide (BTMAOH) and sodium chloride (NaCl) the highly crystalline and pure MTN zeolites with Si/Al ratios of 21-23 could be obtained from the hydrothermal conversion of FAU zeolite. Based on powder XRD refinement and ¹³C CP/MAS NMR spectra, BTMA⁺ ions were not present in cages of the obtained zeolites, but TMA⁺ ions existed instead. It means that BTMAOH underwent degradation during the conversion. Moreover, the effects of Si/Al ratio of starting FAU zeolite, synthesis parameters (BTMAOH/SiO₂ and H₂O/SiO₂ ratios) and the addition of alkali metal chlorides on the hydrothermal conversion of FAU zeolite into MTN zeolite are discussed. As compared to amorphous SiO₂/γ-Al₂O₃, which produced impurity, the hydrothermal conversion of FAU zeolite showed a fast crystallization rate and a high selectivity to MTN zeolite formation. These phenomena indicate that the assembly of locally ordered aluminosilicate species coming from the decomposition or dissolution of FAU zeolite should be taking part in the conversion process.     

New evidence derived from the discrimination of Henry and Langmuir modes parameters in glassy polymeric film revealed by the Freeze‐Purged‐Desorption method

The Freeze‐Purged‐Desorption (FPD) method was developed for the experimental measurement of gas permeability coefficients as a new technique using a desorption curve of gas immobilized in polymeric films. The FPD method was effectively used to evaluate four gas permeation parameters (C_D, C_H, D_D, and D_H) of glassy polymeric films (polycarbonate and polystyrene) by using CO_2. The modes of the CO₂ gas desorption response curve (D‐curve) obtained were sensitively characterized by the proportion of sorption in the Henry and Langmuir modes in the polymeric films accompanied by their own gas diffusivity. A graphical analysis of the D‐curve of CO₂ reasonably proposed a linear relation between the desorption rate and the sorption amount of CO_2, which was strongly influenced by the kind of sorption gas, film, temperature, and other factors. The desorption rate of sorbed CO₂ gas for the PC and PS films gave a characteristic straight line with an inflection point indicating a shift in the gas‐diffusion mechanism from the complex type of the Henry and the Langmuir modes to the Langmuir mode. The characteristic D‐curves obtained were graphically analyzed, and they clearly discriminated the Henry mode part and the Langmuir mode part. This discrimination process quantitatively and individually evaluated C_D, C_H, D_D, and D_H. By using the four parameters evaluated, a mathematical model to describe the D‐curve was proposed, and it consistently explained the experimental D‐curves. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 934–941, 2004     

Gaseous ozone decomposition over high silica zeolitic frameworks

For several decades, it has been known that ozone emissions are harmful to humans, plants, and animals. Heterogeneous catalytic decomposition is an efficient process for removing ozone from air. This study examines the effect of the zeolite's framework and pore width on efficiency for decomposing gaseous ozone. Four highly hydrophobic zeolites are used: a large cavity zeolite (Faujasite/H‐FAU), a medium pore zeolite with parallel channel (Mordenite/H‐MOR), and two medium pore zeolites with interconnected channels (H‐ZSM‐5/H‐MFI and Na‐ZSM‐5/Na‐MFI). Experiments were conducted in fixed‐bed flow reactors loaded with zeolite at ambient conditions (20 °C and 101 kPa). Zeolite surfaces were analyzed during the experiments in order to understand the influence of physical and chemical surface properties on the ozone decomposition mechanism. A higher amount of ozone is eliminated using H‐MOR, compared with the zeolite samples H‐FAU, H‐MFI, and Na‐MFI. Pore width and micropore framework size distribution (channel and cages) appear to be key factors. A narrow channel or cage, slightly larger than the ozone molecule size, seems to promote ozone interactions with Lewis acid sites. Fourier transform infrared spectroscopy shows that Lewis acid sites (LAS), located on the walls of zeolite pores, decompose ozone. This leads to the formation of atomic oxygen species that could react with another ozone molecule to form dioxygen. Hence, LAS are regenerated, ready to decompose another ozone molecule once more.

     

Preparation of CPB-modified FAU zeolite for the removal of tannery wastewater contaminants

The preparation of organomodified zeolites with different framework structures (FAU, LTA and MOR) using N-cetylpyridinium bromide (CPB) as tailoring agent was studied. The sorption properties of CPB-modified zeolites were evaluated in the removal of tannery contaminants from aqueous solution. The CPB-modified FAU-type zeolite presented the highest Cr(VI) retention capacity (37 mmol/kg) due to the higher Cr(VI) retention of its unmodified form (larger pore opening) and its high CPB sorption capacity. CPB-modified FAU zeolite also exhibited high thermal stability as consequence of special interactions between the CPB molecules and the zeolite surface. In addition, the intrinsic Cr(III) exchange capacity of FAU zeolite increased with CPB loading (162–527 mmol/kg), which appear to be due to an additional retention mechanism provided by the sorbed cetylpyridinium surfactant layer. On other hand, CPB-modified FAU zeolite also exhibited high toluene retention capacity (62 mmol/kg) due to of the hydrophobic character of its surfactant-modified surface and toluene adsorption on internal sorption sites of FAU zeolite. Thus, CPB-modified FAU zeolite appears as a promising adsorbent for simultaneous removal of Cr(III), Cr(VI) and toluene contaminants from aqueous solution.     

The skeletal isomerization of C4-C7 1-olefins over ferrierite and ZSM-5 zeolite catalysts

The skeletal isomerization of C₄-C₇ 1-olefins was studied on ferrierite (FER) and ZSM-5 (MFI) zeolites to elucidate the effect of the molecular distribution in zeolite pores on the selectivity foriso-olefin formation. Regardless of the difference in molecular length of 1-olefins, the FER zeolite showed high selectivity foriso-olefins, while the selectivity became slightly low at the skeletal isomerization of long olefin molecules. The drastic decrease in the selectivity of MFI zeolites by increasing the conversion is concurrently observed in the skeletal isomerization of C₄-C₇ 1-olefins. The high selectivity of FER zeolites is explained by their sparse distributions of olefin molecules in pores, which induces a high preference for monomolecular skeletal isomerization.     

Pyrotechnic Countermeasures. III: The Influence of Oxygen Balance of an Aromatic Fuel on the Color Ratio of Spectral Flare Compositions

The influence of the oxygen balance, Λ, of an anthracene‐type aromatic fuel in flare compositions on the spectral color ratio, that is the ratio of radiation emitted in band A (λ=1.8–2.5 μm) versus radiation emitted in band B (λ=3.5–4.8 μm), is investigated. Eight compositions based on potassium perchlorate, polychloroprene binder and either of the following fuels, anthracene, C₁₄H₁₀ ( 1 ), anthracene‐d¹⁰, C₁₄D₁₀ ( 2 ), phenanthrene C₁₄H₁₀ ( 3 ), anthrone, C₁₄H₁₀O ( 4 ), anthraquinone, C₁₄H₈O₂ ( 5 ), 1‐aminoanthraquinone, C₁₄H₉NO₂ ( 6 ), 1,5‐dihydroxyanthraquinone, C₁₄H₈O₄ ( 7 ) and 1,5‐dinitroanthraquinone, C₁₄H₆N₂O₆ ( 8 ) were prepared and radiometrically investigated.     

Prediction of induction time for natural gas components during gas hydrate formation in the presence of kinetic hydrate inhibitors in a flow mini‐loop apparatus

The objective of this work is the prediction of induction time (t_i) for simple gas hydrate formation in the presence or absence of kinetic hydrate inhibitors at various conditions based on the Kashchiev and Firoozabadi model in a flow mini‐loop apparatus. For this purpose, the t_i model is developed for simple gas hydrate formation in batch system for natural gas components during hydrate formation in a flow mini‐loop apparatus. A laboratory flow mini‐loop apparatus is designed and built up to measure the t_i for simple gas hydrate formation when a hydrate former (such as C₁, C₃, CO₂ and i‐C₄) is contacted with water in the absence or presence of dissolved inhibitor, such as poly vinylpyrrolidone, PVCap and L ‐tyrosine. In each experiment, a water blend saturated with pure gas is circulated up to a required pressure. Pressure is maintained at a constant value during experimental runs by means of the required gas make‐up. The average absolute deviation (AAD) of the predicted t_i values from the corresponding experimental data are found to be about 11% and 9.4% for gas hydrate formation t_i in the presence or absence of kinetic hydrate inhibitors, respectively. © 2012 Canadian Society for Chemical Engineering     

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     

Notable Effects of Aluminum Alkyls and Solvents for Highly Efficient Ethylene (Co)polymerizations Catalyzed by (Arylimido)‐ (aryloxo)vanadium Complexes

The effects of both Al cocatalyst and solvent on catalytic activity in the ethylene polymerization by the (arylmido)(aryloxo)vanadium(V) complex, VCl₂(N‐2,6‐Me₂C₆H₃)(O‐2,6‐Me₂C₆H₃) ( 1 ), have been explored in detail. The activity of 5.84×10⁵ kg PE/mol V⋅h (TOF 2.08×10⁷ h⁻¹) has been achieved by 1 /EtAlCl₂ catalyst in CH₂Cl₂ at 0 °C, and the activity in toluene increased in the order: i‐Bu₂AlCl>EtAlCl₂>Me₂AlCl>Et₂AlCl> Et₂Al(OEt), AlEt₃, AlMe₃ (negligible activities). Both aluminum alkyl cocatalyst and solvent also affected the catalytic activity and the norbornene (NBE) incorporation in the ethylene/NBE copolymerization using complex 1 , whereas the NBE contents were not strongly affected by the kind of aryl oxide ligand in VCl₂(N‐2,6‐Me₂C₆H₃)(OAr) [OAr=O‐2,6‐Me₂C₆H₃ ( 1 ), O‐2,6‐i‐Pr₂C₆H₃ ( 2 ), O‐2,6‐Ph₂C₆H₃ ( 3 )].     

Understanding the Behavior of Native Point Defects in ZrC by First‐Principles Calculations

Phase stability and macroscopic performances of ZrC are closely related to the behavior of native point defects. In this study, structures and stabilities of native point defects in ZrC as well as diffusion of C‐related defects are investigated by first‐principles calculations. It is shown that the carbon vacancy (V_C) and interstitials (C_is) are the dominant native point defects in ZrC. Six types of C_i configurations: two C‐trimers, one C‐tetrahedron, and three C‐dimers are identified with low defect formation energies. The V_C has a high migration energy (4.39 eV) which suggests its low mobility in ZrC. The C_is have low diffusion energy barriers (from 0.26 to 1.29 eV) which lead to their high mobility. In addition, the impact of defects (V_C, V_Zr, Zr_C, and C_Zr) on bonding strengths of neighboring Zr–C bonds is discussed. Especially near V_C, the 1NN (nearest neighboring) and 2NN Zr–C bonds are strengthened but 4NN Zr–C bonds are weakened. Interestingly, the 3NN Zr–C bonds are almost not affected by the presence of V_C. These results may be closely related to the short‐range interactions and ordering of V_C in nonstoichiometric ZrC.