Sodium removal from Maramarua CSG waters using Ngakuru zeolites

Coal seam gas (CSG) waters are a by-product of natural gas extraction from un derground coal seams. The main issue with these waters is their elevated sodium content, which in conjunction with their low calcium and magnesium concentrations can generate soil infiltration problems in the long run , as well as short term toxicity effects in plants due to the sodium ion itself. Zeolites are minerals having a porous structure, crystalline characteristics, and an alumino-silicate configuration resulting in an overall negative charge which is balanced by loosely held cations. In New Zealand, Ngakuru zeolites have been mined for commercial use in wastewater treatment applications, cosmetics, and pet litter. This research focuses on assessing the capacity of Ngakuru zeolites to reduce sodium concentrations of CSG waters from Maramarua. Batch and column test (flow through) experiments revealed that Ngakuru zeolites are capable of sorbing sodium cations from concentrated solutions of sodium. In b atch tests, the sodium adsorption capacity ranged from 5.0 to 34.3meq/100g depending on the solution concentration and on the number of times the zeolite had been regenerated. Regeneration with CaCl2 was foun d to be effective. The calculated sodium adsorption capacity of Ngakuru zeolites under flow-through conditions ranged from 11 to 42meq/100g depending on the strength of the solution being treated and on w hether the zeolites had been previously regenerated. The slow kinetics and low cost of the zeolities, coupled with potentially remote sites for gas extraction, could make semi-batch operational processes without regeneration more favourable than in more industrial ion exchange situations.

Encapsulation of transition metal species into zeolites and molecular sieves as redox catalysts: Part I-preparation and characterisation of nanosized TiO2, CdO and ZnO semiconductor particles anchored in NaY zeolite

In this paper, we report the preparation and characterisation of nanometer-sized TiO2, CdO, and ZnO semiconductor particles trapped in zeolite NaY. Preparation of these particles was carried out via the traditional ion exchange method and subsequent calcination procedure. It was found that the smaller cations, i.e., Cd2+ and Zn2+ could be readily introduced into the SI′ and SII′ sites located in the sodalite cages, through ion exchange; while this is not the case for the larger Ti species, i.e., Ti monomer [TiO]2+ or dimer [Ti2O3]2+ which were predominantly dispersed on the external surface of zeolite NaY. The subsequent calcination procedure promoted these Ti species to migrate into the internal surface of the supercages. These semiconductor particles confined in NaY zeolite host exhibited a significant blue shift in the UV-VIS absorption spectra, in contrast to the respective bulk semiconductor materials, due to the quantum size effect (QSE). The particle sizes calculated from the UV-VIS optical absorption spectra using the effective mass approximation model are in good agreement with the atomic absorption data.

Plasmonic nanostructures to enhance catalytic performance of zeolites under visible light

Light absorption efficiency of heterogeneous catalysts has restricted their photocatalytic capability for commercially important organic synthesis. Here, we report a way of harvesting visible light efficiently to boost zeolite catalysis by means of plasmonic gold nanoparticles (Au-NPs) supported on zeolites. Zeolites possess strong Brønsted acids and polarized electric fields created by extra-framework cations. The polarized electric fields can be further intensified by the electric near-field enhancement of Au-NPs, which results from the localized surface plasmon resonance (LSPR) upon visible light irradiation. The acetalization reaction was selected as a showcase performed on MZSM-5 and Au/MZSM-5 (M = H+, Na+, Ca2+, or La3+). The density functional theory (DFT) calculations confirmed that the intensified polarized electric fields played a critical role in stretching the C = O bond of the reactants of benzaldehyde to enlarge their molecular polarities, thus allowing reactants to be activated more efficiently by catalytic centers so as to boost the reaction rates. This discovery should evoke intensive research interest on plasmonic metals and diverse zeolites with an aim to take advantage of sunlight for plasmonic devices, molecular electronics, energy storage, and catalysis.

Determination of acidities of zeolites by photoacoustic spectroscopy

Photoacoustic spectroscopy is found to be a useful technique for determining the acidity of zeolites. The acidity so determined correlates well with temperature programmed vdesorption studies of ammonia and product distribution.

Equilibrium studies of ammonium exchange with Australian natural zeolites

This paper is concerned with the study of the equilibrium exchange of ammonium ions with two natural zeolite samples sourced in Australia from Castle Mountain Zeolites and Zeolite Australia. A range of sorption models including Langmuir Vageler, Competitive Langmuir, Freundlich, Temkin, Dubinin Astakhov and Brouers–Sotolongo were applied in order to gain an insight as to the exchange process. In contrast to most previous studies, non-linear regression was used in all instances to determine the best fit of the experimental data. Castle Mountain natural zeolite was found to exhibit higher ammonium capacity than Zeolite Australia material when in the freshly received state, and this behavior was related to the greater amount of sodium ions present relative to calcium ions on the zeolite exchange sites. The zeolite capacity for ammonium ions was also found to be dependent on the solution normality, with 35–60% increase inuptake noted when increasing the ammonium concentration from 250 to 1000 mg/L. The optimal fit ofthe equilibrium data was achieved by the Freundlich expression as confirmed by use of Akaikes Information Criteria. It was emphasized that the bottle-point method chosen influenced the isotherm profile in several ways, and could lead to misleading interpretation of experiments, especially if the constant zeolite mass approach was followed. Pre-treatment of natural zeolite with acid and subsequently sodium hydroxide promoted the uptake of ammonium species by at least 90%. This paper highlighted the factors which should be taken into account when investigating ammonium ion exchange with natural zeolites.

Behaviour of natural zeolites used for the treatment of simulated and actual coal seam gas water

Coal seam gas operations produce significant quantities of associated water which often require demineralization. Ion exchange with natural zeolites has been proposed as a possible approach. The interaction of natural zeolites with solutions of sodium chloride and sodium bicarbonate in addition to coal seam gas water is not clear. Hence, we investigated ion exchange kinetics, equilibrium, and column behaviour of an Australian natural zeolite. Kinetic tests suggested that the pseudo first order equation best simulated the data. Intraparticle diffusion was part of the rate limiting step and more than one diffusion process controlled the overall rate of sodium ion uptake. Using a constant mass of zeolite and variable concentration of either sodium chloride or sodium bicarbonate resulted in a convex isotherm which was fitted by a Langmuir model. However, using a variable mass of zeolite and constant concentration of sodium ions revealed that the exchange of sodium ions with the zeolite surface sites was in fact unfavourable. Sodium ion exchange from bicarbonate solutions (10.3 g Na/kg zeolite) was preferred relative to exchange from sodium chloride solutions (6.4 g Na/kg zeolite). The formation of calcium carbonate species was proposed to explain the observed behaviour. Column studies of coal seam gas water showed that natural zeolite had limited ability to reduce the concentration of sodium ions (loading 2.1 g Na/kg zeolite) with rapid breakthrough observed. It was concluded that natural zeolites may not be suitable for the removal of cations from coal seam gas water without improvement of their physical properties.

Towards a green synthesis of isoquinoline: Beckmann rearrangement of E,-cinnamaldoxime over H-zeolites

Isoquinoline was prepared through the Beckmann rearrangement of cinnamaldoxime over different H-zeolites, K-10 montmorillonite clay, amorphous SiO2–Al2O3 and γ-alumina under well-optimized conditions of temperature, weight hourly space velocity and catalyst loading. Cinnamaldoxime under ambient reaction conditions over the catalysts underwent migration of the anti-styryl moiety to electron deficient nitrogen (Beckmann rearrangement) followed by an intramolecular cyclization to yield isoquinoline. Cinnamo-nitrile (dehydration product) and cinnamaldehyde were formed as by-products. Isoquinoline formation was high on zeolite catalysts (ca. >86.5%) and mordenite (ca. 92.3%) was the most efficient in the series. Catalysts were susceptible for deactivation and the decrease in the percentage conversion of oxime with time is associated with a corresponding increase in the acid hydrolysis producing salicylaldehyde at later stages of the reaction. However, these catalysts retain activity considerably and can be recycled without loss of activity and change of product distribution.

Levitation effect in zeolites: Quasielastic neutron scattering and molecular dynamics study of pentane isomers in zeolite NaY

We report the quasielastic neutron scattering (QENS) and molecular dynamics (MD) investigations into diffusion of pentane isomers in zeolite NaY. The molecular cross section perpendicular to the long molecular axis varies for the three isomers while the mass and the isomer-zeolite interaction remains essentially unchanged. Both QENS and MD results show that the branched isomers neopentane and isopentane have higher self-diffusivities as compared with n-pentane at 300 K in NaY zeolite. This result provides direct experimental evidence for the existence of nonmonotonic, anomalous dependence of self-diffusivity on molecular diameter known as the levitation effect. The energetic barrier at the bottleneck derived from MD simulations exists for n-pentane which lies in the linear regime while no such barrier is seen for neopentane which is located clearly in the anomalous regime.Activation energy is in the order E-a(n-pentane)>E-a(isopentane)>E-a(neopentane) consistent with the predictions of the levitation effect. In the liquid phase, it is seen thatD(n pentane)>D(isopentane)>D(neopentane) and E-a(n-pentane)< E-a(isopentane)< E-a(neopentane). Intermediate scattering function for small wavenumbers obtained from MD follows a single exponential decay for neopentane and isopentane. For n-pentane, a single exponential fit provides a poor fit especially at short times. Cage residence time is largest for n-pentane and lowest for neopentane. For neopentane, the width of the self-part of the dynamic structure factor shows a near monotonic decrease with wavenumber. For n-pentane a minimum is seen near k=0.5 A degrees(-1) suggesting a slowing down of motion around the 12-ring window, the bottleneck for diffusion. Finally, the result that the branched isomer has a higher diffusivity as compared with the linear analog is at variation from what is normally seen.

Rare earth exchanged (Ce3+, La3+ and RE3+) H-Y zeolites as solid acid catalysts for the synthesis of linear alkyl benzenes

Rare earth exchanged H–Y zeolites were prepared by simple ion exchange methods at 353 K and have been characterized using different physicochemical techniques. A strong peak around 58 ppm in the 27Al{1H} MAS NMR spectra of these zeolites suggests a tetrahedral coordination for the framework aluminium. Small peak at or near 0 ppm is due to hexa-coordinated extra-framework aluminium and a shoulder peak near 30 ppm is a penta-coordinated aluminium species; [Al(OH)4]−. The vapor-phase benzene alkylation with 1-decene and 1-dodecene was investigated with these catalytic systems. Under the reaction conditions of 448 K, benzene/olefin molar ratio of 20 and time on stream 3 h, the most efficient catalyst was CeH–Y which showed more than 70% of olefin conversion with 48.5% 2-phenyldecane and 46.8%, 2-phenyldodecane selectivities with 1-decene and 1-dodecene respectively.

Towards a green synthesis of LAB's: Effect of rare earth metal ions on the benzene alkylation with 1-dodecene over NaFAU-Y zeolites

Chemically modified microporous materials can be prepared as robust catalysts suitable for application in vapor phase processes such as Friedel-Crafts alkylation. In the present paper we have investigated the use of rare earth metal (Ce3+, La3+, RE3+, and Sm3+) exchanged Na-Y zeolites as catalysts for the alkylation of benzene with long chain linear 1-olefin; 1-dodecene. Thermodesorption studies of 2,6-dimethylpyridine adsorbed catalysts (in the temperature range 573 to 873 K) show that the rare earth zeolites are highly Bronsted acidic in nature. A perfect correlation between catalyst selectivity towards the desired product (2-phenyldodecane) and Bronsted acid sites amount has been observed. (c) 2006 Springer Science + Business Media, Inc.

Diffusion of sorbates in zeolites Y and A novel dependence on sorbate size and strength of sor ba t e-Zeoli t e interaction

A systematic investigation of monatomic spherical sorbates in the supercages of zeolites Y and A by molecular dynamics technique is presented. Rates of intercage diffusion, rates of cage visits, and the diffusion coefficients have been calculated as a function of the sorbate-zeolite interaction strength. These properties exhibit markedly different dependences on interaction strength for the two zeolites. The observed behavior is shown to be a consequence of the two principal mechanisms of intercage diffusion and the energetic barrier associated with them. The diffusion coefficient and other properties associated with intercage diffusion are found to be directly proportional to the reciprocal of the square of the sorbate diameter when the sorbate diameter is significantly smaller than the window diameter. As the sorbate diameter increases, a peak is observed in all the transport properties investigated including the diffusion coefficient. We call this surprising effect as the ring or levitation effect and it explains several anomalous results reported in the literature and suggests a breakdown of the geometrical criterion for diffusion of sorbates. It shows that under certain conditions nongeometrical factors play a major role and geometrical factors become secondary in the determination of the molecular sieve property. A generalized parameter has been proposed which suggests conditions under which one can expect the ring or levitation effect in any porous medium. Inverse size selectivity becomes operative under these conditions.

Probing potential energy surfaces in confined systems: behavior of mean-square displacement in zeolites

Time evolution of mean-squared displacement based on molecular dynamics for a variety of adsorbate-zeolite systems is reported. Transition from ballistic to diffusive behavior is observed for all the systems. The transition times are found to be system dependent and show different types of dependence on temperature. Model calculations on a one-dimensional system are carried out which show that the characteristic length and transition times are dependent on the distance between the barriers, their heights, and temperature. In light of these findings, it is shown that it is possible to obtain valuable information about the average potential energy surface sampled under specific external conditions.

Monte Carlo and molecular dynamics simulation of argon clusters andn-alkanes in the confined regions of zeolites

Geometry and energy of argon clusters confined in zeolite NaCaA are compared with those of free clusters. Results indicate the possible existence of magic numbers among the confined clusters. Spectra obtained from instantaneous normal mode analysis of free and confined clusters give a larger percentage of imaginary frequencies for the latter indicating that the confined cluster atoms populate the saddle points of the potential energy surface significantly. The variation of the percentage of imaginary frequencies with temperature during melting is akin to the variation of other properties. It is shown that confined clusters might exhibit inverse surface melting, unlike medium-to-large-sized free clusters that exhibit surface melting. Configurational-bias Monte Carte (CBMC) simulations of n-alkanes in zeolites Y and A are reported. CBMC method gives reliable estimates of the properties relating to the conformation of molecules. Changes in the conformational properties of n-butane and other longer n-alkanes such as n-hexane and n-heptane when they are confined in different zeolites are presented. The changes in the conformational properties of n-butane and n-hexane with temperature and concentration is discussed. In general, in zeolite Y as well as A, there is significant enhancement of the gauche population as compared to the pure unconfined fluid.

Statistical thermodynamics of lattice models in zeolites: Implications of local versus global mean field interactions

The statistical thermodynamics of adsorption in caged zeolites is developed by treating the zeolite as an ensemble of M identical cages or subsystems. Within each cage adsorption is assumed to occur onto a lattice of n identical sites. Expressions for the average occupancy per cage are obtained by minimizing the Helmholtz free energy in the canonical ensemble subject to the constraints of constant M and constant number of adsorbates N. Adsorbate-adsorbate interactions in the Brag-Williams or mean field approximation are treated in two ways. The local mean field approximation (LMFA) is based on the local cage occupancy and the global mean field approximation (GMFA) is based on the average coverage of the ensemble. The GMFA is shown to be equivalent in formulation to treating the zeolite as a collection of interacting single site subsystems. In contrast, the treatment in the LMFA retains the description of the zeolite as an ensemble of identical cages, whose thermodynamic properties are conveniently derived in the grand canonical ensemble. For a z coordinated lattice within the zeolite cage, with epsilon(aa) as the adsorbate-adsorbate interaction parameter, the comparisons for different values of epsilon(aa)(*)=epsilon(aa)z/2kT, and number of sites per cage, n, illustrate that for -1 0. We compare the isotherms predicted with the LMFA with previous GMFA predictions [K. G. Ayappa, C. R. Kamala, and T. A. Abinandanan, J. Chem. Phys. 110, 8714 (1999)] (which incorporates both the site volume reduction and a coverage-dependent epsilon(aa)) for xenon and methane in zeolite NaA. In all cases the predicted isotherms are very similar, with the exception of a small steplike feature present in the LMFA for xenon at higher coverages. (C) 1999 American Institute of Physics. [S0021-9606(99)70333-8].

Direct and sensitized (energy and electron transfer) geometric isomerization of stilbene within zeolites: a comparison between solution and zeolite as reaction media

The trans- and cis-stilbenes upon inclusion in NaY zeolite are thermally stable. Direct excitation and triplet sensitization results in geometric isomerization and the excited state behavior under these conditions are similar to that in solution. Upon direct excitation, a photostationary state consisting of 65% cis and 35% trans isomers is established. Triplet sensitization with 2-acetonaphthone gave a photostationary state consisting of 63% cis and 37% trans isomers. These numbers are similar to the ones obtained in solution. Thus, the presence of cations and the confined space within the zeolite have very little influence on the overall chemistry during direct and triplet sensitization. However, upon electron transfer sensitization with N-methylacridinium (NMA) as the sensitizer within NaY, isomerization from cis-stilbene radical cation to trans-stilbene occurs and the recombination of radical ions results in triplet stilbene. Prolonged irradiation gave a photostationary state (65% cis and 35% trans) similar to triplet sensitization. This behavior is unique to the zeolite and does not take place in solution. Steady state fluorescence measurements showed that the majority of stilbene molecules are close to the N-methylacridinium sensitizer. Diffuse reflectance flash photolysis studies established that independent of the isomer being sensitized only trans radical cation is formed. Triplet stilbene is believed to be generated via recombination of stilbene radical cation and sensitizer radical anion. One should be careful in using acidic HY zeolite as a medium for photoisomerization of stilbenes. In our hands, in these acidic zeolites isomerization dominated the photoisomerization. (C) 2002 Elsevier Science B.V. All rights reserved.