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Sample records for crystalline aluminosilicate zeolite

  1. A highly crystalline microporous hybrid organic-inorganic aluminosilicate resembling the AFI-type zeolite.

    PubMed

    Bellussi, Giuseppe; Millini, Roberto; Montanari, Erica; Carati, Angela; Rizzo, Caterina; Parker, Wallace O; Cruciani, Giuseppe; de Angelis, Alberto; Bonoldi, Lucia; Zanardi, Stefano

    2012-07-28

    ECS-14, a crystalline microporous hybrid organic-inorganic aluminosilicate, has been synthesized by using 1,4-bis-(triethoxysilyl)-benzene (BTEB) as a source of silica. Its structure contains a system of linear channels with 12-membered ring openings, running along the [001] direction, resembling the pore architecture of the AFI framework type. PMID:22717682

  2. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    SciTech Connect

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-04-29

    A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  3. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    SciTech Connect

    Nicholas, Christopher P; Boldingh, Edwin P

    2013-12-17

    A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  4. Process for the exchange of crystalline zeolites

    SciTech Connect

    Lim, J.; Brady, M.; Humphries, A.

    1984-07-10

    This invention relates to exchanging the sodium contained in a crystalline zeolite by partially removing sodium by exchange with another cation, partially drying the exchanged zeolite and re-exchanging the dried zeolite.

  5. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    SciTech Connect

    Nicholas, Christpher P; Boldingh, Edwin P

    2013-12-17

    A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and show to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hyrdocarbons into hydrocarbons removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  6. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    SciTech Connect

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-10-07

    A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and shown to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub.1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  7. Predicting Large CO2 Adsorption in Aluminosilicate Zeolites for Postcombustion Carbon Dioxide Capture

    SciTech Connect

    Kim, J; Lin, LC; Swisher, JA; Haranczyk, M; Smit, B

    2012-11-21

    Large-scale simulations of aluminosilicate zeolites were conducted to identify structures that possess large CO2 uptake for postcombustion carbon dioxide capture. In this study, we discovered that the aluminosilicate zeolite structures with the highest CO2 uptake values have an idealized silica lattice with a large free volume and a framework topology that maximizes the regions with nearest-neighbor framework atom distances from 3 to 4.5 angstrom. These predictors extend well to different Si:Al ratios and for both Na+ and Ca2+ cations, demonstrating their universal applicability in identifying the best-performing aluminosilicate zeolite structures.

  8. Novel process for the preparation of ZSM-5 aluminosilicate zeolite

    SciTech Connect

    Winquist, B.H.C.

    1989-04-04

    A method of manufacture of ZSM-5 aluminosilicate zeolite is described which consists of crystallizing, at a temperature of from about 185/sup 0/C to about 250/sup 0/C, an aqueous crystallizing gel consisting essentially of a colloidal silica, a colloidal alumina, water, trisodium phosphate and potassium fluoride. Water is present in a range of from about 200 to about 500 moles of water per mole of colloidal alumina, wherein the colloidal silica and the colloidal alumina are present in a molar ratio of greater than about 20 moles of the colloidal silica per mole of the colloidal alumina and less than 50 moles of the colloidal silica per mole of the colloidal alumina. Trisodium phosphate is present in a mole ratio of 1.8 to 2.7 moles of the trisodium phosphate per mole of the colloidal alumina and wherein the potassium fluoride is present in a molar relationship of greater than 0.5 to less than 2.1 moles of potassium fluoride per mole of colloidal alumina.

  9. Zeolites

    NASA Technical Reports Server (NTRS)

    1992-01-01

    Zeolites are crystalline aluminosilicates that have complex framework structures. However, there are several features of zeolite crystals that make unequivocal structure determinations difficult. The acquisition of reliable structural information on zeolites is greatly facilitated by the availability of high-quality specimens. For structure determinations by conventional diffraction techniques, large single-crystal specimens are essential. Alternatively, structural determinations by powder profile refinement methods relax the constraints on crystal size, but still require materials with a high degree of crystalline perfection. Studies conducted at CAMMP (Center for Advanced Microgravity Materials Processing) have demonstrated that microgravity processing can produce larger crystal sizes and fewer structural defects relative to terrestrial crystal growth. Principal Investigator: Dr. Albert Sacco

  10. Formic acid, ethanol in vycor glass, and water in aluminosilicate zeolites

    SciTech Connect

    Loong, C.K.; Trouw, F.; Iton, L.E.

    1993-11-01

    We present results of incoherent inelastic neutron-scattering experiments on formic acid, ethanol in vycor glass, and water in aluminosilicate zeolites performed at Argonne`s spallation neutron source, IPNS. The forming and breaking of hydrogen bonds are discussed in terms of translational and rotational diffusion, and vibrational footprints of various molecular species in these systems.

  11. Energy Analysis of Aluminosilicate Zeolites with Comprehensive Ranges of Framework Topologies, Chemical Compositions, and Aluminum Distributions.

    PubMed

    Muraoka, Koki; Chaikittisilp, Watcharop; Okubo, Tatsuya

    2016-05-18

    The contents and locations of Al in the zeolite frameworks are one of the key factors determining the physicochemical properties of zeolites. Systematic evaluation of the characteristics of zeolites with a wide variety of framework topologies, a wide range of Si/Al ratios, and various locations of Al is of great significance, but very challenging due to the limitation of the realizable ranges of Al contents in zeolites as well as the limited information on the Al locations obtained from the current analytical techniques. Here, we report the systematic analysis of the energetics of aluminosilicate zeolites with 209 existing framework topologies at different Si/Al ratios using molecular mechanics. More than 43 000 initial structures were generated to give comprehensive views of the energetics of zeolites. The results coincide well with the structural knowledge obtained experimentally. It was revealed that the relation between the relative framework energies versus the Al contents varies in accordance with the topologies, suggesting that the relative stability of zeolites depends not only on the topologies, but also on the substituting contents of Al. For particular topologies with the same Al contents, in addition, comparisons between random and specific distributions of Al showed that zeolite with Al at a particular T site is energetically more stable than those with random distributions, suggesting the inherent influences of the Al locations. The contents and locations of Al in zeolites likely have a certain preference that may reflect the range of chemical compositions, the Al distributions, and consequently the physicochemical properties of realizable aluminosilicate zeolites. PMID:27097121

  12. Analysis of the biological and chemical reactivity of zeolite-based aluminosilicate fibers and particulates.

    PubMed Central

    Fach, Estelle; Waldman, W James; Williams, Marshall; Long, John; Meister, Richard K; Dutta, Prabir K

    2002-01-01

    Environmental and/or occupational exposure to minerals, metals, and fibers can cause lung diseases that may develop years after exposure to the agents. The presence of toxic fibers such as asbestos in the environment plus the continuing development of new mineral or vitreous fibers requires a better understanding of the specific physical and chemical features of fibers/particles responsible for bioactivity. Toward that goal, we have tested aluminosilicate zeolites to establish biological and chemical structure-function correlations. Zeolites have known crystal structure, are subject to experimental manipulation, and can be synthesized and controlled to produce particles of selected size and shape. Naturally occurring zeolites include forms whose biological activity is reported to range from highly pathogenic (erionite) to essentially benign (mordenite). Thus, we used naturally occurring erionite and mordenite as well as an extensively studied synthetic zeolite based on faujasite (zeolite Y). Bioactivity was evaluated using lung macrophages of rat origin (cell line NR8383). Our objective was to quantitatively determine the biological response upon interaction of the test particulates/fibers with lung macrophages and to evaluate the efficacy of surface iron on the zeolites to promote the Fenton reaction. The biological assessment included measurement of the reactive oxygen species by flow cytometry and chemiluminescence techniques upon phagocytosis of the minerals. The chemical assessment included measuring the hydroxyl radicals generated from hydrogen peroxide by iron bound to the zeolite particles and fibers (Fenton reaction). Chromatography as well as absorption spectroscopy were used to quantitate the hydroxyl radicals. We found that upon exposure to the same mass of a specific type of particulate, the oxidative burst increased with decreasing particle size, but remained relatively independent of zeolite composition. On the other hand, the Fenton reaction depended on the type of zeolite, suggesting that the surface structure of the zeolite plays an important role. PMID:12417479

  13. Secondary Ion Mass Spectrometry of Zeolite Materials: Observation of Abundant Aluminosilicate Oligomers Using an Ion Trap

    SciTech Connect

    Groenewold, Gary Steven; Kessinger, Glen Frank; Scott, Jill Rennee; Gianotto, Anita Kay; Appelhans, Anthony David; Delmore, James Edward

    2000-12-01

    Oligomeric oxyanions were observed in the secondary ion mass spectra (SIMS) of zeolite materials. The oxyanions have the general composition AlmSinO2(m+n)H(m-1)- (m + n = 2 to 8) and are termed dehydrates. For a given mass, multiple elemental compositions are possible because (Al + H) is an isovalent and isobaric substitute for Si. Using 18 keV Ga+ as a projectile, oligomer abundances are low relative to the monomers. Oligomer abundance can be increased by using the polyatomic projectile ReO4- (~5 keV). Oligomer abundance can be further increased using an ion trap (IT-) SIMS; in this instrument, long ion lifetimes (tens of ms) and relatively high He pressure result in significant collisional stabilization and increased high-mass abundance. The dehydrates rapidly react with adventitious H2O present in the IT-SIMS to form mono-, di-, and trihydrates. The rapidity of the reaction and comparison to aluminum oxyanion hydration suggest that H2O adds to the aluminosilicate oxyanions in a dissociative fashion, forming covalently bound product ions. In addition to these findings, it was noted that production of abundant oligomeric aluminosilicates could be significantly increased by substituting the countercation (NH4+) with the larger alkali ions Rb+ and Cs+. This constitutes a useful tactic for generating large aluminosilicate oligomers for surface characterization and ion-molecule reactivity studies.

  14. Synthesis and Structural Characterization of the Aluminosilicate LZ-135, a Zeolite Related to ZSM-10

    SciTech Connect

    McCusker, Lynne B.; Baerlocher, Christian; Wilson, Stephen T.; Broach, Robert W.

    2009-09-02

    The aluminosilicate LZ-135 was one of the first zeolites to be prepared in the presence of two or more organic structure-directing agents (in this case, Me{sub 4}N{sup +} (TMA) and Et{sub 4}N{sup +} (TEA)) and was patented 20 years ago. However, the material was polycrystalline, and at the time, its aluminosilicate framework structure could not be determined. In view of the fact that methods of structure determination from powder diffraction data have developed considerably in the meantime, a fresh analysis of the problem was undertaken. High-resolution synchrotron powder diffraction data were collected on a calcined sample of LZ-135 (as synthesized composition ca. |Na{sub 26}TMA{sub 6}|[Si{sub 76}Al{sub 32}O{sub 216}]), and the new powder charge-flipping structure-solution algorithm was applied. The framework structure (P6{sub 3}/mmc; a = 31.3830(2) {angstrom}, c = 7.6513(1) {angstrom}) was revealed immediately, and then the positions of the Na{sup +} ions and a few water molecules were located in a series of difference electron density maps. The [001] projection of the framework structure is identical to that of ZSM-10 (P6{sub 3}/mmm), but the (up-down) orientations of the (Si,Al) tetrahedra, and therefore their connectivities, are different, and this leads to a distinctly different topology with two 1-dimensional, 12-ring channel systems with effective pore widths of 7.2 and 6.5 {angstrom}. The new framework has been assigned the framework type code LTF by the International Zeolite Association. The framework structures of LZ-135 and ZSM-10 are related to one another in the same way as are those of mazzite and zeolite L. Approximately 27.5 Na{sup +} ions were located in six different sites, and all are coordinated to oxygen atoms of the framework. Twelve H{sub 2}O molecules per unit cell are associated with one of the Na{sup +} ion positions, where they serve to complete an octahedral coordination geometry around the ion, and 5.2 are located in the larger of the two 12-ring channels, where they make hydrogen-bonding contacts to framework oxygen atoms and are probably associated with protons.

  15. Structure-Directing Behaviors of Tetraethylammonium Cations toward Zeolite Beta Revealed by the Evolution of Aluminosilicate Species Formed during the Crystallization Process.

    PubMed

    Ikuno, Takaaki; Chaikittisilp, Watcharop; Liu, Zhendong; Iida, Takayuki; Yanaba, Yutaka; Yoshikawa, Takeshi; Kohara, Shinji; Wakihara, Toru; Okubo, Tatsuya

    2015-11-18

    Organic structure-directing agents (OSDAs) have been widely used for the synthesis of zeolites. In most cases, OSDAs are occluded in zeolites as an isolated cation or molecule geometrically fitted within the zeolite cavities. This is not the case for zeolite beta synthesized by using tetraethylammonium (TEA(+)) cation as an OSDA, in which a cluster/aggregate of ca. six TEA(+) cations is occluded intact in the cavity (i.e., the channel intersection) of zeolite beta. The structure direction of TEA(+) in such a nontypical, clustered mode has remained elusive. Here, zeolite beta was hydrothermally synthesized using TEA(+) in the absence of other alkali metal cations in order to focus on the structure-directing behaviors of TEA(+) alone. The solid products formed throughout the hydrothermal synthesis were analyzed by an array of characterization techniques including argon adsorption-desorption, high-energy X-ray total scattering, Raman and solid-state NMR spectroscopy, and high-resolution transmission electron microscopy. It was revealed that the formation of amorphous TEA(+)-aluminosilicate composites and their structural, chemical, and textural evolution toward the amorphous zeolite beta-like structure during the induction period is vital for the formation of zeolite beta. A comprehensive scheme of the formation of zeolite beta is proposed paying attention to the clustered behavior of TEA(+) as follows: (i) the formation of the TEA(+)-aluminosilicate composites after heating, (ii) the reorganization of aluminosilicates together with the conformational rearrangement of TEA(+), yielding the formation of the amorphous TEA(+)-aluminosilicate composites with the zeolite beta-like structure, (iii) the formation of zeolite beta nuclei by solid-state reorganization of such zeolite beta-like, TEA(+)-aluminosilicate composites, and (iv) the subsequent crystal growth. It is anticipated that these findings can provide a basis for broadening the utilization of OSDAs in the clustered mode of structure direction in more effective ways. PMID:26509741

  16. A comparison of the amorphization of zeolitic imidazolate frameworks (ZIFs) and aluminosilicate zeolites by ball-milling.

    PubMed

    Baxter, Emma F; Bennett, Thomas D; Cairns, Andrew B; Brownbill, Nick J; Goodwin, Andrew L; Keen, David A; Chater, Philip A; Blanc, Frédéric; Cheetham, Anthony K

    2016-03-01

    X-ray diffraction has been used to investigate the kinetics of amorphization through ball-milling at 20 Hz, for five zeolitic imidazolate frameworks (ZIFs) - ZIF-8, ZIF-4, ZIF-zni, BIF-1-Li and CdIF-1. We find that the rates of amorphization for the zinc-containing ZIFs increase with increasing solvent accessible volume (SAV) in the sequence ZIF-8 > ZIF-4 > ZIF-zni. The Li-B analogue of the dense ZIF-zni amorphizes more slowly than the corresponding zinc phase, with the behaviour showing a correlation with their relative bulk moduli and SAVs. The cadmium analogue of ZIF-8 (CdIF-1) amorphizes more rapidly than the zinc counterpart, which we ascribe primarily to its relatively weak M-N bonds as well as the higher SAV. The results for the ZIFs are compared to three classical zeolites - Na-X, Na-Y and ZSM-5 - with these taking up to four times longer to amorphize. The presence of adsorbed solvent in the pores is found to render both ZIF and zeolite frameworks more resistant to amorphization. X-ray total scattering measurements show that amorphous ZIF-zni is structurally indistinguishable from amorphous ZIF-4 with both structures retaining the same short-range order that is present in their crystalline precursors. By contrast, both X-ray total scattering measurements and (113)Cd NMR measurements point to changes in the local environment of amorphous CdIF-1 compared with its crystalline CdIF-1 precursor. PMID:26575842

  17. Properties of Zeolite A Obtained from Powdered Laundry Detergent: An Undergraduate Chemistry Experiment

    NASA Astrophysics Data System (ADS)

    Lindquist, David A.; Smoot, Alison L.

    1997-05-01

    Zeolites, crystalline porous aluminosilicates, are valued for their ability to absorb ions and molecules as well as function as catalysts. A number of laboratory experiments using zeolites filtered from a suspension of powdered laundry detergent are described. The various experiments illustrate the myriad uses of zeolites as desiccants, ion exchange materials, and catalysts.

  18. Characterization of Aluminosilicate Formation on the Surface of a Crystalline Silicotitanate Ion Exchanger

    SciTech Connect

    Young, James S.; Su, Yali; Li, Liyu; Balmer, M Lou; G W Bailey

    2001-10-30

    Millions of gallons of high-level radioactive waste are contained in underground tanks at U.S. Department of Energy sites such as Hanford and Savannah River. Most of the radioactivity is due to 137Cs and 90Sr, which must be extracted in order to concentrate the waste. An ion exchanger, crystalline silicotitanate IONSIV IE911, is being considered for separation for Cs at the Savannah River Site (SRS). While the performance of this ion exchanger has been well characterized under normal operating conditions, Cs removal at slightly elevated temperatures, such as those that may occur in a process upset, is not clear. Our recent study indicates that during exposure to SRS simulant at 55 degrees Celsius and 80 degrees Celsius, an aluminosilicate coating formed on the exchanger surface. There was concern that the coating would affect its ion exchange properties. A LEO 982 field emission scanning electron microscope (FESEM) and an Oxford ISIS energy dispersive x-ray spectrometer (EDS) were used to characterize the coating.

  19. Poorly Crystalline, Iron-Bearing Aluminosilicates and Their Importance on Mars

    NASA Technical Reports Server (NTRS)

    Baker, L. L.; Strawn, D. G.; McDaniel, P. A.; Nickerosn, R. N.; Bishop, J. L.; Ming, D. W.; Morris, Richard V.

    2011-01-01

    Martian rocks and sediments contain weathering products including evaporite salts and clay minerals that only form as a result of interaction between rocks and water [1-6]. These weathering products are key to studying the history of water on Mars because their type, abundance and location provide clues to past conditions on the surface of the planet, as well as to the possible location of present-day reservoirs of water. Weathering of terrestrial volcanic rocks similar to those on Mars produces nano-sized, variably hydrated aluminosilicate and iron oxide minerals [7-10] including allophane, imogolite, halloysite, hisingerite, and ferrihydrite. The nanoaluminosilicates can contain isomorphically substituted Fe, which affects their spectral and physical properties. Detection and quantification of such minerals in natural environments on earth is difficult due to their variable chemical composition and lack of long-range crystalline order [9, 11, 12]. Despite the difficulty in characterizing these materials, they are common on Earth, and data from orbital remote sensing and rover-based instruments suggest that they are also present on Mars [9, 10, 13-17]. Their accurate detection and quantification require a better understanding of how composition affects their spectral properties. We present here the results of XAFS spectroscopy; these results will be corroborated with planned Mossbauer and reflectance spectroscopy.

  20. The Loewenstein rule: the increase in electron kinetic energy as the reason for instability of Al-O-Al linkage in aluminosilicate zeolites

    NASA Astrophysics Data System (ADS)

    Larin, Alexander V.

    2013-11-01

    Problem of Al-O-Al linkage in aluminosilicate materials or Al-avoidance is discussed for two zeolite structures (phillipsite and brewsterite) exchanged with Mg2+ cations. All models are fully optimized at periodic Hartree-Fock and hybrid density functional theory levels (the CRYSTAL code). Their properties are then calculated at the periodic level with the same basis sets. The reasons for the instability of the zeolite structures including the Al-O-Al moieties are interpreted on the basis of cell energy decomposition. This destabilization comes from an increase in kinetic energy if the Al-O(Mg)-Al moieties are present in zeolites. This effect is discussed in parallel with already known variational evidences in favor of dominating role of kinetic energy for stability of molecular systems.

  1. RBS and PIXE study of gallium depth profiling in ZSM-5 gallo-aluminosilicate zeolites

    NASA Astrophysics Data System (ADS)

    Gabelica, Zelimir; Demortier, Guy

    1998-03-01

    Gallium concentration depth profiling in various as-synthesised and post-synthesis thermally treated Ga- and (Ga,Al)-ZSM-5 zeolites was quantitatively evaluated by RBS. This technique proved for the first time that Ga-ZSM-5 synthesised in the presence of methylamine involves a homogeneous Ga framework distribution. When both Al and Ga are present in the gel precursor, they form mixed complexes with methylamine and incorporate the zeolite lattice at different rates while some unreacted Ga-amino complex overcoats the outer rim of the crystals. Gallosilicates synthesised in the fluoride medium show a fairly homogeneous Ga incorporation with an increased Ga concentration on surface due to its overcoating by residual Ga fluoro complexes. Post-synthesis thermal treatments result in a partial degalliation of the framework that could be quantified by RBS. The nature, mobility and location of the extra framework Ga species markedly depend on the calcination conditions. A rapid calcination in dry conditions leads to the formation of extra framework Ga oxides that migrate towards the crystal core. Under milder heating, these species stay homogeneously partitioned within the crystal channels. Under a humid atmosphere, the extra framework Ga species migrate towards the crystal surface, the migration being enhanced by a partial reduction of Ga during non-oxidative treatments. Humid air treatment maintains the homogeneous distribution of both Ga 2O 3 and residual Ga 3+ framework ions.

  2. Iridium Complexes and Clusters in Dealuminated Zeolite HY: Distribution between Crystalline and Impurity Amorphous Regions

    SciTech Connect

    Martinez-Macias, Claudia; Xu, Pinghong; Hwang, Son-Jong; Lu, Jing; Chen, Cong-Yan; Browning, Nigel D.; Gates, Bruce C.

    2014-07-08

    Dealuminated zeolite HY was used to support Ir(CO)2 complexes formed from Ir(CO)2(C5H7O2). Infrared and X-ray absorption spectra and atomic-resolution electron microscopy images identify these complexes, and the images and 27Al NMR spectra identify impurity amorphous regions in the zeolite where the iridium is more susceptible to aggregation than in the crystalline regions. The results indicate a significant stability limitation of metal in amorphous impurity regions of zeolites.

  3. One-pot synthesis of hierarchical FeZSM-5 zeolites from natural aluminosilicates for selective catalytic reduction of NO by NH3

    PubMed Central

    Yue, Yuanyuan; Liu, Haiyan; Yuan, Pei; Yu, Chengzhong; Bao, Xiaojun

    2015-01-01

    Iron-modified ZSM-5 zeolites (FeZSM-5s) have been considered to be a promising catalyst system to reduce nitrogen oxide emissions, one of the most important global environmental issues, but their synthesis faces enormous economic and environmental challenges. Herein we report a cheap and green strategy to fabricate hierarchical FeZSM-5 zeolites from natural aluminosilicate minerals via a nanoscale depolymerization-reorganization method. Our strategy is featured by neither using any aluminum-, silicon-, or iron-containing inorganic chemical nor involving any mesoscale template and any post-synthetic modification. Compared with the conventional FeZSM-5 synthesized from inorganic chemicals with the similar Fe content, the resulting hierarchical FeZSM-5 with highly-dispersed iron species showed superior catalytic activity in the selective catalytic reduction of NO by NH3. PMID:25791958

  4. One-pot synthesis of hierarchical FeZSM-5 zeolites from natural aluminosilicates for selective catalytic reduction of NO by NH3

    NASA Astrophysics Data System (ADS)

    Yue, Yuanyuan; Liu, Haiyan; Yuan, Pei; Yu, Chengzhong; Bao, Xiaojun

    2015-03-01

    Iron-modified ZSM-5 zeolites (FeZSM-5s) have been considered to be a promising catalyst system to reduce nitrogen oxide emissions, one of the most important global environmental issues, but their synthesis faces enormous economic and environmental challenges. Herein we report a cheap and green strategy to fabricate hierarchical FeZSM-5 zeolites from natural aluminosilicate minerals via a nanoscale depolymerization-reorganization method. Our strategy is featured by neither using any aluminum-, silicon-, or iron-containing inorganic chemical nor involving any mesoscale template and any post-synthetic modification. Compared with the conventional FeZSM-5 synthesized from inorganic chemicals with the similar Fe content, the resulting hierarchical FeZSM-5 with highly-dispersed iron species showed superior catalytic activity in the selective catalytic reduction of NO by NH3.

  5. Growth of zeolite crystals in the microgravity environment of space

    NASA Technical Reports Server (NTRS)

    Sacco, A., Jr.; Sand, L. B.; Collette, D.; Dieselman, K.; Crowley, J.; Feitelberg, A.

    1986-01-01

    Zeolites are hydrated, crystalline aluminosilicates with alkali and alkaling earth metals substituted into cation vacancies. Typically zeolite crystals are 3 to 8 microns. Larger cyrstals are desirable. Large zeolite crystals were produced (100 to 200 microns); however, they have taken restrictively long times to grow. It was proposed if the rate of nucleation or in some other way the number of nuclei can be lowered, fewer, larger crystals will be formed. The microgravity environment of space may provide an ideal condition to achieve rapid growth of large zeolite crystals. The objective of the project is to establish if large zeolite crystals can be formed rapidly in space.

  6. Microsphere zeolite materials derived from coal fly ash cenospheres as precursors to mineral-like aluminosilicate hosts for 135,137Cs and 90Sr

    NASA Astrophysics Data System (ADS)

    Vereshchagina, Tatiana A.; Vereshchagin, Sergei N.; Shishkina, Nina N.; Vasilieva, Nataly G.; Solovyov, Leonid A.; Anshits, Alexander G.

    2013-06-01

    Hollow microsphere zeolite materials with a bilayered zeolite/glass crystalline shell bearing NaP1 zeolite were synthesized by the hydrothermal treatment of coal fly ash cenospheres (Si/Al = 2.7) in an alkaline medium. Cs+ and/or Sr2+ forms of zeolitized cenospheres with the different Cs+ and/or Sr2+ loading were prepared by the ion exchange from nitrate solutions. The resulted (Cs,Na)P1, (Sr,Na)P1 and (Cs,Sr,Na)P1 bearing microsphere zeolites were converted to glass ceramics by heating at 900-1000 °C. The differential scanning calorimetry and quantitative phase analysis were used to monitor the solid-phase transformation of the initial and ion exchanged zeolite materials. It was established that the final solidified forms of Cs+ and/or Sr2+ are glass-crystalline ceramic materials based on pollucite-nepheline, Sr-feldspar-nepheline and Sr-feldspar-pollucite composites including ˜60 wt.% of the major host phases (pollucite, Sr-feldspar) and 10-20 wt.% of glass. The 137Cs leaching rate of 4.1 × 10-7 g cm-2 day-1 was determined for the pollucite glass-ceramic according to Russian State Standard (GOST) No. 52126 P-2003 (7 day, 25 °C, distilled water).

  7. Highly crystalline Zeolite-A from flyash of bituminous and lignite coal combustion.

    PubMed

    Rayalu, S S; Udhoji, J S; Munshi, K N; Hasan, M Z

    2001-11-16

    Flyash is being generated in voluminous amounts by large scale coal combustion process. It poses a serious threat to thermal power industries specifically, in India, wherein the percent of utilisation of flyash is very poor (3-5%). In view of this problem, newer methods of its disposal and utilisation are being explored. The synthesis of zeolite from flyash appears to be one of the most promising alternatives as it has emphasis on value addition to waste material. Flyashes originating from different sources of coal differ in their characteristics and have implications in this work on Zeolite-A production. These factors have been thoroughly investigated and the conditions favourable for formation of Zeolite-A have been delineated. The reactivity of flyash towards zeolite formation is directly dependent on the SiO(2)/Al(2)O(3) ratio, Fe(2)O(3) and CaO content. Amongst the flyashes investigated, so far the sub-bituminous coal based flyash with SiO(2)/Al(2)O(3) ratio of 3.47 appears to be a suitable substrate for Zeolite-A synthesis. These zeolites have been characterised with respect to XRD crystallinity, calcium binding capacity (CBC) and sorption capacity, wherein the crystallinity ranges from 50 to 100%, the CBC ranges from 290 to 560meq/100g and sorption capacity ranges from 16.6 to 23.8%. PMID:11606244

  8. Feasible conversion of solid waste bauxite tailings into highly crystalline 4A zeolite with valuable application

    SciTech Connect

    Ma, Dongyang; Wang, Zhendong; Guo, Min; Zhang, Mei; Liu, Jingbo

    2014-11-15

    Highlights: • Concept to convert waste to valuable product is carried out in this study. • An industrially feasible and cost-effective approach was developed and optimized. • Highly crystalline and well-defined zeolite was produced under moderate conditions. • The zeolite derived from the bauxite tailings displayed high ion exchange capacity. • Bauxite tailings have potential application in heavy metal ions adsorbent. - Abstract: Bauxite tailings are a major type of solid wastes generated in the flotation process. The waste by-products caused significant environmental impact. To lessen this hazardous effect from poisonous mine tailings, a feasible and cost-effective solution was conceived and implemented. Our approach focused on reutilization of the bauxite tailings by converting it to 4A zeolite for reuse in diverse applications. Three steps were involved in the bauxite conversion: wet-chemistry, alkali fusion, and crystallization to remove impurities and to prepare porous 4A zeolite. It was found that the cubic 4A zeolite was single phase, in high purity, with high crystallinity and well-defined structure. Importantly, the 4A zeolite displayed maximum calcium ion exchange capacity averaged at 296 mg CaCO{sub 3}/g, comparable to commercially-available zeolite (310 mg CaCO{sub 3}/g) exchange capacity. Base on the optimal synthesis condition, the reaction yield of zeolite 4A from bauxite tailings achieved to about 38.43%, hence, this study will provide a new paradigm for remediation of bauxite tailings, further mitigating the environmental and health care concerns, particularly in the mainland of PR China.

  9. Feasible conversion of solid waste bauxite tailings into highly crystalline 4A zeolite with valuable application.

    PubMed

    Ma, Dongyang; Wang, Zhendong; Guo, Min; Zhang, Mei; Liu, Jingbo

    2014-11-01

    Bauxite tailings are a major type of solid wastes generated in the flotation process. The waste by-products caused significant environmental impact. To lessen this hazardous effect from poisonous mine tailings, a feasible and cost-effective solution was conceived and implemented. Our approach focused on reutilization of the bauxite tailings by converting it to 4A zeolite for reuse in diverse applications. Three steps were involved in the bauxite conversion: wet-chemistry, alkali fusion, and crystallization to remove impurities and to prepare porous 4A zeolite. It was found that the cubic 4A zeolite was single phase, in high purity, with high crystallinity and well-defined structure. Importantly, the 4A zeolite displayed maximum calcium ion exchange capacity averaged at 296 mg CaCO3/g, comparable to commercially-available zeolite (310 mg CaCO3/g) exchange capacity. Base on the optimal synthesis condition, the reaction yield of zeolite 4A from bauxite tailings achieved to about 38.43%, hence, this study will provide a new paradigm for remediation of bauxite tailings, further mitigating the environmental and health care concerns, particularly in the mainland of PR China. PMID:25153822

  10. Delaminated zeolites: Combining the benefits of zeolites and mesoporous materials for catalytic uses

    SciTech Connect

    Corma, A.; Fornes, V.; Martinez-Triguero, J.; Pergher, S.B.

    1999-08-15

    The delamination of the layered precursor of the MCM-22 zeolite (MWW structure) affords monolayers of a crystalline aluminosilicate with more than 700 m{sup 2}/g of a well defined external surface formed by cups of 0.7 x 0.7 nm. In this layered structure the circular 10-member-ring microporous system is preserved. The resultant material presents the strong acidity and stability characteristic of the zeolites but, at the same time, offers the high accessibility to large molecules characteristic of the amorphous aluminosilicates. The cracking behavior during the process of small and large molecules has been compared with that of the zeolite MCM-22 and pillared laminar precursor MCM-36.

  11. Hydrocarbon zeolite catalyst employed in hydrocracking process

    SciTech Connect

    Ward, J.W.

    1987-05-12

    A hydrocracking process is described which comprises contacting a hydrocarbon feedstock under hydrocracking conditions with hydrogen in the presence of a catalyst comprising at least one hydrogenation component, a crystalline aluminosilicate zeolite having catalytic activity for cracking hydrocarbons, and a dispersion of silica-alumina in a matrix consisting essentially of alumina, wherein the catalyst comprises particles in the shape of a three-leaf clover.

  12. Synthesis of Foam-Shaped Nanoporous Zeolite Material: A Simple Template-Based Method

    ERIC Educational Resources Information Center

    Saini, Vipin K.; Pires, Joao

    2012-01-01

    Nanoporous zeolite foam is an interesting crystalline material with an open-cell microcellular structure, similar to polyurethane foam (PUF). The aluminosilicate structure of this material has a large surface area, extended porosity, and mechanical strength. Owing to these properties, this material is suitable for industrial applications such as…

  13. Synthesis of Foam-Shaped Nanoporous Zeolite Material: A Simple Template-Based Method

    ERIC Educational Resources Information Center

    Saini, Vipin K.; Pires, Joao

    2012-01-01

    Nanoporous zeolite foam is an interesting crystalline material with an open-cell microcellular structure, similar to polyurethane foam (PUF). The aluminosilicate structure of this material has a large surface area, extended porosity, and mechanical strength. Owing to these properties, this material is suitable for industrial applications such as

  14. Combined experimental and computational NMR study of crystalline and amorphous zeolitic imidazolate frameworks.

    PubMed

    Baxter, Emma F; Bennett, Thomas D; Mellot-Draznieks, Caroline; Gervais, Christel; Blanc, Frédéric; Cheetham, Anthony K

    2015-10-14

    Zeolitic imidazolate frameworks (ZIFs) have attracted great interest in recent years due to their high chemical and thermal stability with promising applications in gas storage and separations. We investigate the structures of three different crystalline ZIFs - ZIF-4, ZIF-8, ZIF-zni - and their amorphous counterparts using high field (13)C and (15)N CP MAS NMR. The high field (20 T) allows for the observation of all crystallographically independent carbon and nitrogen atoms in the crystalline ZIFs. Combining our experimental results with density functional theory calculations enabled the assignment of all chemical shifts. The crystalline spectra reveal the potential of high field NMR to distinguish between two ZIF polymorphs, ZIF-4 and ZIF-zni, with identical [Zn(C3H3N2)2] chemical compositions. (13)C and (15)N CP MAS NMR data obtained for the amorphous ZIFs clearly showed signal broadening upon amorphization, confirming the retention of chemical composition and the structural similarity of amorphous ZIF-4 and ZIF-zni. In the case of amorphous ZIF-8, we present evidence for the partial de-coordination of the 2-methyl imidazole linker. PMID:26351979

  15. Flexibility mechanisms in ideal zeolite frameworks.

    PubMed

    Treacy, M M J; Dawson, C J; Kapko, V; Rivin, I

    2014-02-13

    Zeolites are microporous crystalline aluminosilicate materials whose atomic structures can be usefully modelled in purely mechanical terms as stress-free periodic trusses constructed from rigid corner-connected SiO4 and AlO4 tetrahedra. When modelled this way, all of the known synthesized zeolite frameworks exhibit a range of densities, known as the flexibility window, over which they satisfy the framework mechanical constraints. Within the flexibility window internal stresses are accommodated by force-free coordinated rotations of the tetrahedra about their apices (oxygen atoms). We use rigidity theory to explore the folding mechanisms within the flexibility window, and derive an expression for the configurational entropic density throughout the flexibility window. By comparison with the structures of pure silica zeolite materials, we conclude that configurational entropy associated with the flexibility modes is not a dominant thermodynamic term in most bulk zeolite crystals. Nevertheless, the presence of a flexibility window in an idealized hypothetical tetrahedral framework may be thermodynamically important at the nucleation stage of zeolite formation, suggesting that flexibility is a strong indicator that the topology is realizable as a zeolite. Only a small fraction of the vast number of hypothetical zeolites that are known exhibit flexibility. The absence of a flexibility window may explain why so few hypothetical frameworks are realized in nature. PMID:24379426

  16. Interface Induced Growth and Transformation of Polymer-Conjugated Proto-Crystalline Phases in Aluminosilicate Hybrids: A Multiple-Quantum (23)Na-(23)Na MAS NMR Correlation Spectroscopy Study.

    PubMed

    Brus, Jiri; Kobera, Libor; Urbanova, Martina; Doušová, Barbora; Lhotka, Miloslav; Koloušek, David; Kotek, Jiří; Čuba, Pavel; Czernek, Jiri; Dědeček, Jiří

    2016-03-22

    Nanostructured materials typically offer enhanced physicochemical properties because of their large interfacial area. In this contribution, we present a comprehensive structural characterization of aluminosilicate hybrids with polymer-conjugated nanosized zeolites specifically grown at the organic-inorganic interface. The inorganic amorphous Al-O-Si framework is formed by alkali-activated low-temperature transformation of metakaoline, whereas simultaneous copolymerization of organic comonomers creates a secondary epoxide network covalently bound to the aluminosilicate matrix. This secondary epoxide phase not only enhances the mechanical integrity of the resulting hybrids but also introduces additional binding sites accessible for compensating negative charge on the aluminosilicate framework. This way, the polymer network initiates growth and subsequent transformation of protocrystalline short-range ordered zeolite domains that are located at the organic-inorganic interface. By applying an experimental approach based on 2D (23)Na-(23)Na double-quantum (DQ) MAS NMR spectroscopy, we discovered multiple sodium binding sites in these protocrystalline domains, in which immobilized Na(+) ions form pairs or small clusters. It is further demonstrated that these sites, the local geometry of which allows for the pairing of sodium ions, are preferentially occupied by Pb(2+) ions during the ion exchange. The proposed synthesis protocol thus allows for the preparation of a novel type of geopolymer hybrids with polymer-conjugated zeolite phases suitable for capturing and storage of metal cations. The demonstrated (23)Na-(23)Na DQ MAS NMR combined with DFT calculations represents a suitable approach for understanding the role of Na(+) ions in aluminositicate solids and related inorganic-organic hybrids, particularly their specific arrangement and clustering at interfacial areas. PMID:26931131

  17. The influence of hydrothermal temperature and time toward crystallinity of zeolite X supported on glass wool for CO2 adsorption

    NASA Astrophysics Data System (ADS)

    Anggita, R. K. Wardani; Yuniar, V. T. P.; Aini, W. T.; Nurul, W.

    2016-04-01

    In this study, the influence of hydrothermal temperature and time at zeolite X supported on glasswool were investigated. The results of characterization using XRD showed that a single phase zeolite X with highest crystallinity was obtained when hydrothermal temperature and time at 100°C during 24 hours (ZXF100-24H). The CO2 adsorption capacity of ZXF100-24H has reached up to 10.15 wt. %. Kinetics of CO2 adsorption onto zeolite X supported on glasswool was investigated using pseudo-first-order, pseudo-second-order and intra-particle diffusion kinetic models. After evaluating three kinetic models for CO2 adsorption at adsorption temperatures of 30°C, 40°C and 50°C, it was found that intra-particle diffusion kinetic model provided the best fitting for the adsorption data. Furthermore, the thermodynamic parameters of CO2 adsorption were obtained as follows, Gibbs free energy change (ΔG°) are -0.409 kJ/mol at 30°C, -0.274 kJ/mol at 40°C and -0.138 kJ/mol at 50 °C, whereas the enthalpy change (ΔH°) is -4.53 kJ/mol and the entropy change (ΔS°) is -0.0135 kJ/(mol K).

  18. Pure, single phase, high crystalline, chamfered-edge zeolite 4A synthesized from coal fly ash for use as a builder in detergents.

    PubMed

    Hui, K S; Chao, C Y H

    2006-09-01

    Single phase chamfered-edge zeolite 4A samples in pure form with a high crystallinity were synthesized by applying step-change of synthesis temperature during hydrothermal treatment of coal fly ash. The calcium binding capacity of these zeolite 4A samples (prepared from coal fly ash) and the commercial detergent grade zeolite 4A were tested for usage as a detergent builder. The results show that these zeolite 4A samples behaved similarly as the commercial one in removing calcium ions during the washing cycle. Moreover, from the leaching tests (evaluation of toxicological safety), the results show that these zeolite 4A samples leached the same elements (Sb, As, Se and Tl) as the commercial one with the concentrations in the same order of magnitude. This shows that the toxicological effect of the coal fly ash converted zeolite 4A was not worse than that of the commercial sample. Finally, economic and environmental aspects of converting coal fly ash to useful products were discussed. PMID:16621273

  19. Hydrocracking process utilizing a catalyst having a reduced zeolite content

    SciTech Connect

    Abdo, S.F.

    1989-08-15

    This patent describes a process for refining hydrocarbon feedback containing organonitrogen components, organosulfur components or a mixture thereof. The process comprises: contacting the feedback with molecular hydrogen under hydrotreating conditions in the presence of a hydrotreating catalyst comprising a Group VIB metal component and a Group VIII metal component such that a subtantial proportion of the organonitrogen components, organosulfur components or mixture thereof is converted to ammonia, hydrogen sulfide or a mixture thereof; contacting substantially all of the effluent from the first step with molecular hydrogen in a first hydrocracking zone in the presence of a first hydrocracking catalyst comprising a zeolite and a hydrogeneration component to produce a hydrocracking product of substantially lower boiling point; separating the hydrocracking product into a higher boiling fraction and a lower boiling fraction; contacting the higher boiling fraction with molecular hydrogen in a second hydrocracking zone under hydrocracking conditions in an atmosphere which contains no more than about 200 ppmv ammonia and in the presence of a second hydrocracking catalyst to convert the higher boiling fraction into lower boiling products. The second hydrocracking catalysts comprises; a porous, inorganic refractory oxide component; and between about 40 weight percent and about 70 weight percent of a crystalline aluminosilicate Y zeolite having a silica-to-alumina mole ratio above about 6.0 intimately mixed with the refractory oxide component. The crystalline aluminosilicate Y zeolite having been ion-exchanged with Group VIII noble metal cations.

  20. Rapid crystallization of faujasitic zeolites: mechanism and application to zeolite membrane growth on polymer supports.

    PubMed

    Severance, Michael; Wang, Bo; Ramasubramanian, Kartik; Zhao, Lin; Ho, W S Winston; Dutta, Prabir K

    2014-06-17

    Zeolites are microporous, crystalline aluminosilicates with the framework made up of T-O-T (T = Si, Al) bonds and enclosed cages and channels of molecular dimensions. Influencing and manipulating the nucleation and growth characteristics of zeolites can lead to novel frameworks and morphologies, as well as decreased crystallization time. In this study, we show that manipulating the supersaturation during synthesis of zeolite X/Y (FAU) via dehydration led to extensive nucleation. Controlled addition of water to this nucleated state promotes the transport of nutrients, with a 4-fold increase in the rate of crystal growth, as compared to conventional hydrothermal process. Structural signature of the nucleated state was obtained by electron microscopy, NMR, and Raman spectroscopy. This extensively intermediate nucleated state was isolated and used as the starting material for zeolite membrane synthesis on porous polymer supports, with membrane formation occurring within an hour. With this time frame for growth, it becomes practical to fabricate zeolite/polymer membranes using roll-to-roll technology, thus making possible new commercial applications. PMID:24758695

  1. Influence of crystallite size on cation conductivity in faujasitic zeolites.

    PubMed

    Severance, Michael; Zheng, Yangong; Heck, Elizabeth; Dutta, Prabir K

    2013-12-19

    The influence of particle size on the ionic conductivity of ceramic materials is an active area of research, and novel effects are observed as particles approach the nanoscale in size. Zeolites are crystalline aluminosilicates with ion-exchangeable cations that are responsible for ionic conductivity at high temperatures. In this paper, we present systematic results for the first time of ionic conductivity in alkali metal ion-exchanged faujasitic zeolites with morphologies ranging from a zeolite membrane, micrometer-sized, submicrometer, and nanoparticles of zeolite. Using impedance spectroscopy in the range of 10 MHz to 0.1 Hz, we have obtained the activation energy (E(act)) of cation motion with these various morphologies in the temperature range of 525-625 °C. Overall, the E(act) decreases with Si/Al ratio. Surface modification of the zeolite particles was carried out with a silylating agent, which upon high temperature calcination should lead to the formation of a monolayer Si-O-Si film on the particle surface. This surface modification had minimal influence on the E(act) of micrometer-sized zeolites. However, E(act) increased rapidly as the zeolite particle approached the nanoscale. These observations led us to propose that, for the high-temperature, low-frequency (10(4)-10(5) Hz), long-range ionic conduction in zeolites, cation hopping across grain boundaries is relevant to ion transport, especially as the size of the crystallite approaches the nanoscale. Intergrain boundaries are more defective in the nanosized zeolite and contribute to the higher E(act). PMID:24041267

  2. Effect of ultrasound energy on the zeolitization of chemical extracts from fused coal fly ash.

    PubMed

    Bukhari, Syed Salman; Rohani, Sohrab; Kazemian, Hossein

    2016-01-01

    This paper investigates the effects of ultrasound (UTS) energy at different temperatures on the zeolitization of aluminosilicate constituents of coal fly ash. UTS energy irradiated directly into the reaction mixture utilizing a probe immersed into the reaction mixture, unlike previously reported works that have used UTS baths. Controlled synthesis was also conducted at constant stirring and at the same temperatures using conventional heating. The precursor reaction solution was obtained by first fusing the coal fly ash with sodium hydroxide at 550°C followed by dissolution in water and filtration. The synthesized samples were characterized by XRF, XRD, SEM and TGA. The crystallinity of crystals produced with UTS assisted conversion compared to conventional conversion at 85°C was twice as high. UTS energy also reduced the induction time from 60 min to 40 min and from 80 min to 60 min for reaction temperatures of 95°C and 85°C, respectively. Prolonging the UTS irradiation at 95°C resulted in the conversion of zeolite-A crystals to hydroxysodalite, which is a more stable zeolitic phase. It was found that at 85°C coupled with ultrasound energy produced the best crystalline structure with a pure single phase of zeolite-A. It has been shown that crystallization using UTS energy can produce zeolitic crystals at lower temperatures and within 1h, dramatically cutting the synthesis time of zeolite. PMID:26384882

  3. Synthesis of 'unfeasible' zeolites.

    PubMed

    Mazur, Michal; Wheatley, Paul S; Navarro, Marta; Roth, Wieslaw J; Položij, Miroslav; Mayoral, Alvaro; Eliášová, Pavla; Nachtigall, Petr; Čejka, Jiří; Morris, Russell E

    2016-01-01

    Zeolites are porous aluminosilicate materials that have found applications in many different technologies. However, although simulations suggest that there are millions of possible zeolite topologies, only a little over 200 zeolite frameworks of all compositions are currently known, of which about 50 are pure silica materials. This is known as the zeolite conundrum--why have so few of all the possible structures been made? Several criteria have been formulated to explain why most zeolites are unfeasible synthesis targets. Here we demonstrate the synthesis of two such 'unfeasible' zeolites, IPC-9 and IPC-10, through the assembly-disassembly-organization-reassembly mechanism. These new high-silica zeolites have rare characteristics, such as windows that comprise odd-membered rings. Their synthesis opens up the possibility of preparing other zeolites that have not been accessible by traditional solvothermal synthetic methods. We envisage that these findings may lead to a step change in the number and types of zeolites available for future applications. PMID:26673264

  4. Hydrocracking of vacuum gasoil on the novel mesoporous MCM-41 aluminosilicate catalyst

    SciTech Connect

    Corma, A.; Martinez, A.; Martinez-Soria, V.

    1995-04-15

    The performance of NiMo (12 wt% MoO{sub 3}, 3 wt% NiO) supported on the mesoporous crystalline MCM-41 aluminosilicate for mild hydrotreating of a vacuum gasoil has been compared with that of an amorphous silica-alumina and a USY zeolite with the same Ni and Mo loadings. The MCM-41-based catalyst was seen to give superior HDS, HDN, and HC activities to the latter two catalysts in a one-stage operation using an untreated gasoil. The better performance of the former catalyst is explained by its higher surface area, the presence of uniform pores in the mesopore range, mild acidity, and stability. In the case of a two-stage operation using a pretreated feed, the MCM-41 catalyst showed a lower HC activity than USY, but higher than the amorphous silica-alumina while preserving its better selectivity to middle distillates. 13 refs., 4 figs., 7 tabs.

  5. Calibration analysis of zeolites by laser induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Horňáčková, M.; Grolmusová, Z.; Horňáček, M.; Rakovský, J.; Hudec, P.; Veis, P.

    2012-08-01

    Laser induced breakdown spectroscopy was used for calibration analysis of different types of microporous crystalline aluminosilicates with exactly ordered structure — zeolites. The LIBS plasma was generated using a Q-switched Nd:YAG laser operating at the wavelength of 532 nm and providing laser pulses of 4 ns duration. Plasma emission was analysed by echelle type emission spectrometer, providing wide spectral range 200-950 nm. The spectrometer was equipped with intensified CCD camera providing rapid spectral acquisition (gating time from 5 ns). The optimum experimental conditions (time delay, gate width and laser pulse energy) have been determined for reliable use of LIBS for quantitative analysis. Samples of different molar ratios of Si/Al were used to create the calibration curves. Calibration curves for different types of zeolites (mordenite, type Y and ZSM-5) were constructed. Molar ratios of Si/Al for samples used for calibration were determined by classical wet chemical analysis and were in the range 5.3-51.8 for mordenite, 2.3-12.8 for type Y and 14-600 for ZSM-5. Zeolites with these molar ratios of Si/Al are usually used as catalysts in alkylation reactions. Laser induced breakdown spectroscopy is a suitable method for analysis of molar ratio Si/Al in zeolites, because it is simple, fast, and does not require sample preparation compared with classical wet chemical analysis which are time consuming, require difficult sample preparation and manipulation with strong acids and bases.

  6. Hot isostatically-pressed aluminosilicate glass-ceramic with natural crystalline analogues for immobilizing the calcined high-level nuclear waste at the Idaho Chemical Processing Plant

    SciTech Connect

    Raman, S.

    1993-12-01

    The additives Si, Al, MgO, P{sub 2}O{sub 5} were mechanically blended with fluorinelsodium calcine in varying proportions. The batches were vacuum sealed in stainless steel canisters and hot isostatically pressed at 20,000 PSI and 1000 C for 4 hours. The resulting suite of glass-ceramic waste forms parallels the natural rocks in microstructural and compositional heterogeneity. Several crystalline phases ar analogous in composition and structure to naturally occurring minerals. Additional crystalline phases are zirconia and Ca-Mg borate. The glasses are enriched in silica and alumina. Approximately 7% calcine elements occur dissolved in this glass and the total glass content in the waste forms averages 20 wt%. The remainder of the calcine elements are partitioned into crystalline phases at 75 wt% calcine waste loading. The waste forms were tested for chemical durability in accordance with the MCC1-test procedure. The leach rates are a function of the relative proportions of additives and calcine, which in turn influence the composition and abundances of the glass and crystalline phases. The DOE leach rate criterion of less than 1 g/m{sup 2}-day is met by all the elements B, Cs and Na are increased by lowering the melt viscosity. This is related to increased crystallization or devitrification with increases in MgO addition. This exploratory work has shown that the increases in waste loading occur by preferred partitioning of the calcine components among crystalline and glass phases. The determination of optimum processing parameters in the form of additive concentration levels, homogeneous blending among the components, and pressure-temperature stabilities of phases must be continued to eliminate undesirable effects of chemical composition, microstructure and glass devitrification.

  7. Rapid synthesis of beta zeolites

    DOEpatents

    Fan, Wei; Chang, Chun -Chih; Dornath, Paul; Wang, Zhuopeng

    2015-08-18

    The invention provides methods for rapidly synthesizing heteroatom containing zeolites including Sn-Beta, Si-Beta, Ti-Beta, Zr-Beta and Fe-Beta. The methods for synthesizing heteroatom zeolites include using well-crystalline zeolite crystals as seeds and using a fluoride-free, caustic medium in a seeded dry-gel conversion method. The Beta zeolite catalysts made by the methods of the invention catalyze both isomerization and dehydration reactions.

  8. The behaviour of water confined in zeolites: molecular dynamics simulations versus experiment

    NASA Astrophysics Data System (ADS)

    Demontis, P.; Guln-Gonzlez, J.; Masia, M.; Suffritti, G. B.

    2010-07-01

    In order to study the behaviour of water adsorbed in zeolites, which are microporous crystalline aluminosilicates, whose channels and cavities of nanometric dimensions can host many different molecules, we developed a sophisticated empirical potential for water, including the full flexibility of the molecule and the correct response to the electric field generated by the cations and by the charged atoms of the aluminosilicate framework. The reproduction of experimental data by our potential model is similar or even better than that obtained from the first principles methods. The results of molecular dynamics simulations of water confined in a variety of zeolites (worm-like clusters in silicalite, spherical nanoclusters in zeolite A and ice-like nanotubes in AlPO4-5 and SSZ-24) at different temperatures and coverage (loading) are discussed in connection with the experimental data, whose overall good reproduction encourages the attempt of an atomic-scale description of structural and dynamical phenomena occurring in confined water, in particular in the supercooled regime. The results are also compared with simulations and experimental data on bulk water.

  9. Microprobes aluminosilicate ceramic membranes

    DOEpatents

    Anderson, Marc A.; Sheng, Guangyao

    1993-01-01

    Methods have been developed to make mixed alumina-silicate and aluminosilicate particulate microporous ceramic membranes. One method involves the making of separate alumina and silica sols which are then mixed. Another method involves the creation of a combined sol with aluminosilicate particles. The resulting combined alumina and silica membranes have high surface area, a very small pore size, and a very good temperature stability.

  10. Physical, Chemical and Structural Evolution of Zeolite-Containing Waste Forms Produced from Metakaolinite and Calcined Sodium Bearing Waste (HLW and/or LLW)

    SciTech Connect

    Grutzeck, Michael W.

    2005-06-27

    Zeolites are extremely versatile. They can adsorb liquids and gases and serve as cation exchange media. They occur in nature as well cemented deposits. The ancient Romans used blocks of zeolitized tuff as a building material. Using zeolites for the management of radioactive waste is not a new idea, but a process by which the zeolites can be made to act as a cementing agent is. Zeolitic materials are relatively easy to synthesize from a wide range of both natural and man-made substances. The process under study is derived from a well known method in which metakaolin (an impure thermally dehydroxylated kaolinite heated to {approx}700 C containing traces of quartz and mica) is mixed with sodium hydroxide (NaOH) and reacted in slurry form (for a day or two) at mildly elevated temperatures. The zeolites form as finely divided powders containing micrometer ({micro}m) sized crystals. However, if the process is changed slightly and only just enough concentrated sodium hydroxide solution is added to the metakaolinite to make a thick crumbly paste and then the paste is compacted and cured under mild hydrothermal conditions (60-200 C), the mixture will form a hard ceramic-like material containing distinct crystalline tectosilicate minerals (zeolites and feldspathoids) imbedded in an X-ray amorphous hydrated sodium aluminosilicate matrix. Due to its lack of porosity and vitreous appearance we have chosen to call this composite a ''hydroceramic''.

  11. A Highly Ion-Selective Zeolite Flake Layer on Porous Membranes for Flow Battery Applications.

    PubMed

    Yuan, Zhizhang; Zhu, Xiangxue; Li, Mingrun; Lu, Wenjing; Li, Xianfeng; Zhang, Huamin

    2016-02-01

    Zeolites are crystalline microporous aluminosilicates with periodic arrangements of cages and well-defined channels, which make them very suitable for separating ions of different sizes, and thus also for use in battery applications. Herein, an ultra-thin ZSM-35 zeolite flake was introduced onto a poly(ether sulfone) based porous membrane. The pore size of the zeolite (ca. 0.5 nm) is intermediary between that of hydrated vanadium ions (>0.6 nm) and protons (<0.24 nm). The resultant membrane can thus be used to perfectly separate vanadium ions and protons, making this technology useful in vanadium flow batteries (VFB). A VFB with a zeolite-coated membrane exhibits a columbic efficiency of >99 % and an energy efficiency of >81 % at 200 mA cm(-2) , which is by far the highest value ever reported. These convincing results indicate that zeolite-coated membranes are promising in battery applications. PMID:26822866

  12. Examination of the solventlike nature of zeolites based on a solvatochromic indicator

    SciTech Connect

    Dutta, P.K.; Turbeville, W. )

    1991-05-16

    Zeolites are crystalline aluminosilicates with cages and channel systems that can host a variety of organic transformations. This intracrystalline space is akin to a solvent, and description of this space in terms of solventlike properties is appropriate. The concept of solvatochromic indicators has been successfully used to define the physicochemical properties of organic solvents. In this study, the authors have investigated the electronic and Raman spectroscopy of the molecule N-(2-hydroxybenzylidene)aniline and established a quantitative correlation between the spectral intensities of the benzenoid and zwitterionic forms of this molecule and the {alpha}-value of various hydroxylic solvents. The {alpha} value is a measure of the hydrogen bond donor ability of the solvent. This correlation has been used to establish an {alpha} value scale for a series of faujasitic zeolites with varying Si/Al ratios. It was found that the {alpha} value of the zeolite increased with Si/Al ratio to reach a maximum around 7.8, followed by a decrease at higher Si/Al ratios. Since Na{sup +}-exchanged zeolites were examined in all cases, the interaction of the anil molecule in its zwitterionic form with Lewis acids (Na{sup +}) and bases (oxygen of the framework) was considered to be responsible for its formation. The Si/Al ratio of the framework determines the acid-base character of the zeolite and is reflected in a quantitative manner by the {alpha} value determined in this study.

  13. Investigation of structure formation mechanism of a mesoporous ZSM-5 zeolite by mesoscopic simulation

    NASA Astrophysics Data System (ADS)

    Ren, Yanqun; Liu, Baoyu; Kiryutina, Tatyana; Xi, Hongxia; Qian, Yu

    2015-02-01

    Amphiphilic surfactant molecules have a profound influence in directing zeolite crystallization, while the self-assembly process between the functionalized surfactant and aluminosilicate species is the key factor in determining the structure of zeolites. However, such a complex process is extremely difficult to be characterized experimentally. A novel mesoporous ZSM-5 zeolite with hexagonal mesostructures and crystalline microporous frameworks has been synthesized in our previous work. In present research, dissipative particle dynamics (DPD), a mesoscopic simulation method, has been used to investigate the self-assembly process of a surfactant/tetraethylorthosilicate (TEOS)/water system in order to explore the structure formation mechanism of a mesoporous ZSM-5 zeolite. The simulation results show that under a certain composition, the specially designed bifunctional triquaternary ammonium-type surfactant and TEOS can form spherical core-shell micelles. The core (inner section) of a spherical micelle is occupied by hydrophobic beads, while the shell (outer section) is formed by hydrophilic beads. Besides, an ordered, uniform mesophase can be formed under a constant shear rate and transformed into mesoscale structure. The simulation results are consistent with the corresponding experimental results. Overall, the DPD simulation is a valuable tool to investigate the porogenic mechanism of surfactants. The present approach may open a window for investigating the formation mechanism of mesoporous zeolites that involves the surfactant-driven synthesis process.

  14. Core-shell strain structure of zeolite microcrystals

    NASA Astrophysics Data System (ADS)

    Cha, Wonsuk; Jeong, Nak Cheon; Song, Sanghoon; Park, Hyun-Jun; Thanh Pham, Tung Cao; Harder, Ross; Lim, Bobae; Xiong, Gang; Ahn, Docheon; McNulty, Ian; Kim, Jungho; Yoon, Kyung Byung; Robinson, Ian K.; Kim, Hyunjung

    2013-08-01

    Zeolites are crystalline aluminosilicate minerals featuring a network of 0.3-1.5-nm-wide pores, used in industry as catalysts for hydrocarbon interconversion, ion exchangers, molecular sieves and adsorbents. For improved applications, it is highly useful to study the distribution of internal local strains because they sensitively affect the rates of adsorption and diffusion of guest molecules within zeolites. Here, we report the observation of an unusual triangular deformation field distribution in ZSM-5 zeolites by coherent X-ray diffraction imaging, showing the presence of a strain within the crystal arising from the heterogeneous core-shell structure, which is supported by finite element model calculation and confirmed by fluorescence measurement. The shell is composed of H-ZSM-5 with intrinsic negative thermal expansion whereas the core exhibits a different thermal expansion behaviour due to the presence of organic template residues, which usually remain when the starting materials are insufficiently calcined. Engineering such strain effects could have a major impact on the design of future catalysts.

  15. Accelerated crystallization of zeolites via hydroxyl free radicals.

    PubMed

    Feng, Guodong; Cheng, Peng; Yan, Wenfu; Boronat, Mercedes; Li, Xu; Su, Ji-Hu; Wang, Jianyu; Li, Yi; Corma, Avelino; Xu, Ruren; Yu, Jihong

    2016-03-11

    In the hydrothermal crystallization of zeolites from basic media, hydroxide ions (OH(-)) catalyze the depolymerization of the aluminosilicate gel by breaking the Si,Al-O-Si,Al bonds and catalyze the polymerization of the aluminosilicate anions around the hydrated cation species by remaking the Si,Al-O-Si,Al bonds. We report that hydroxyl free radicals (•OH) are involved in the zeolite crystallization under hydrothermal conditions. The crystallization processes of zeolites-such as Na-A, Na-X, NaZ-21, and silicalite-1-can be accelerated with hydroxyl free radicals generated by ultraviolet irradiation or Fenton's reagent. PMID:26965626

  16. Raman spectroscopic study of the synthesis of zeolite Y

    SciTech Connect

    Dutta, P.K.; Shieh, D.C.; Puri, M.

    1987-04-23

    The formation of zeolite Y from colloidal silica and soluble silicate species was investigated by Raman spectroscopy. The role of aging of the reactant mixture was studied. During the nucleation period, the solid amorphous phase consists of predominantly six-membered aluminosilicate rings, which act as building blocks for the formation of zeolite Y. It is essential to have polymeric, highly condensed silicate units as a reactant if zeolite Y crystallization is to take place.

  17. Zeolite with trimodal porosity by desilication of zeolite nanocrystals aggregate

    SciTech Connect

    Wang Yuxin; Liu Kaituo; Graduate School of the Chinese Academy of Sciences, Beijing 100049 ; He Tao; Wu Jinhu; Fang Yunming

    2012-10-15

    Zeolite with trimodal porosity can be synthesized by desilication of zeolite nanocrystal aggregate. In the desilication process, the originally existed intercrystalline mesopores of zeolite nanocrystal aggregate were enlarged into large mesopore, and the new small intracrystalline mesopore channel was created, thus the Zeolite with trimodal porosity was formed. The structure of resulted zeolite, both on aggregate and mesopore level can be fine tuned by the desilication degree. - Graphical abstract: The Si from the edges and boundary of nanocrystals was first removed resulted the surface roughness and enlarges of the originally existed intercrystalline mesopores. As the degree of alkali-treatment increasing, the Si species inside zeolite nanocrystals was also removed, leading to further enlarges the intercrystalline mesopores and the formation of small intracrystalline mesopores. In case the alkali-treatment is serve enough to completely dissolve the bridges between zeolite nanocrystals, zeolite nanocrystals were exfoliated from the aggregate. Highlights: Black-Right-Pointing-Pointer Zeolite with trimodal porosity by desilication of zeolite nanocrystals aggregate. Black-Right-Pointing-Pointer The original intercrystalline mesopores were enlarged into large mesopore. Black-Right-Pointing-Pointer The new intracrystalline mesopores were created as the inside Si extracted out. Black-Right-Pointing-Pointer The aggregate structure, crystallinity and acidity of parent zeolite remained. Black-Right-Pointing-Pointer Desilication is start on the edges then in the inner part of zeolite.

  18. Functionalized Amorphous Aluminosilicates

    NASA Astrophysics Data System (ADS)

    Mesgar, Milad

    Alkali treated aluminosilicate (geopolymer) was functionalized by surfactant to increase the hydrophobicity for making Pickering emulsion for the first part of this work. In the first part of this study, alkali treated metakaolin was functionalized with cetyltrimethylammonium bromide ((C16H33)N(CH 3)3Br, CTAB). The electrostatic interaction between this quaternary ammonium and the surface of the aluminosilicate which has negative charge has taken place. The particles then were used to prepare Pickering emulsion. The resulting stable dispersions, obtained very fast at very simple conditions with low ratio of aluminosilicate to liquid phase. In the second part, the interaction between geopolymer and glycerol was studied to see the covalent grafting of the geopolymer for making geopolymer composite. The composite material would be the basis material to be used as support catalyst, thin coating reagent and flame retardant material and so on, Variety of techniques, Thermogravimetric (TGA), Particle-induced X-ray emission (PIXE), FTIR, Solid state NMR, Powder X-ray diffraction (PXRD), BET surface area, Elemental analysis (CHN), TEM, SEM and Optical microscopy were used to characterize the functionalized geopolymer.

  19. Highly fluorescent C-dots obtained by pyrolysis of quaternary ammonium ions trapped in all-silica ITQ-29 zeolite

    NASA Astrophysics Data System (ADS)

    Baldovi, Herme G.; Valencia, Susana; Alvaro, Mercedes; Asiri, Abdullah M.; Garcia, Hermenegildo

    2015-01-01

    C-dots obtained in the homogeneous phase may exhibit a broad particle size distribution. The formation of C-dots within nanometric reaction cavities could be a methodology to gain control on their size distribution. Among the various possibilities, in the present work, the cavities of small pore size zeolites have been used to confine C-dots generated by the pyrolysis of the organic structure directing agent present in the synthesis of these crystalline aluminosilicates. To explore this methodology, ITQ-29 zeolite having a Linde type A (LTA) structure was prepared as pure silica with 4-methyl-2,3,6,7-tetrahydro-1H,5H-pyrido[3.2.1-ij]quinolinium as the organic structure directing agent. Pyrolysis under an inert atmosphere at 550 °C of a pure-silica ITQ-29 sample (cubic particles of 4 μm edge) renders a highly fluorescent zeolite containing about 15 wt% of the carbonised residue. While another small pore zeolite, ITQ-12 (ITW), also renders photoluminescent C-dots under similar conditions, medium or large pore zeolites, such as silicalite (MFI) or pure silica Beta (BEA), failed to produce fluorescent powders under analogous thermal treatment and only decomposition and complete removal of the corresponding quaternary ammonium ion templates was observed for these zeolites. The dissolution of the pyrolysed ITQ-29 zeolite framework and the extraction of the carbon residue with ethyl acetate have allowed the characterisation of C-dots with particle sizes between 5 and 12 nm and a photoluminescence quantum yield of 0.4 upon excitation at 350 nm that is among the highest reported for non-surface functionalized C-dots. Photoluminescence varies with the excitation wavelength and is quenched by oxygen. Pyrolysed ITQ-29 powders can act as fluorescent oxygen sensors.

  20. Synthesis and characterization of aluminosilicate catalyst impregnated by nickel oxide

    NASA Astrophysics Data System (ADS)

    Maulida, Iffana Dani; Sriatun, Taslimah

    2015-09-01

    Aluminosilicate as a catalyst has been synthesized by pore-engineering using CetylTrimethylAmmonium-Bromide (CTAB) as templating agent. It can produce bigger aluminosilicate pore therefore it will be more suitable for bulky molecule. The aims of this research are to synthesize aluminosilicate supported by Nickel, using CTAB surfactant as templating agent for larger pore radius than natural zeolite and characterize the synthesis product, consist of total acid sites and surface area characteristic. This research has been done with following steps. First, making sodium silicate and sodium aluminate. Second, aluminosilicate was synthesized by direct methods, calcined at 550, 650 and 750°C variation temperature, characterized product by X-RD and FTIR spectrometer. Third, NiCl2 was impregnated to the aluminosilicate that has the best cristallinity and main TO4 functional groups product (550 sample). Variation of NiCl2:aluminosilicate (w/w) ratio were 25%:75%, 50%:50% and 75%:25%. Last but not least characterization of catalytic properties was performed. It comprised total acidity test (gravimetric method) and Surface Area Analyzer. The result shows that the product synthesized by direct method at 550oC calcination temperature has the best cristallinity and main functional groups of TO4. The highest total acid sites was 31.6 mmole/g (Imp-A sample). Surface Area Analyzer shows that Imp-B sample has the best pore distribution and highest total pore volume and specific surface area with value 32.424 cc/g and 46.8287 m2/g respectively. We can draw the conclusion that the most potential catalyst is Imp-A sample compared to Imp-B and Imp-C because it has the highest total acid sites. However the most effective catalyst used for product selectivity was Imp-B sample among all samples.

  1. Synthesis, structure, and carbon dioxide capture properties of zeolitic imidazolate frameworks.

    PubMed

    Phan, Anh; Doonan, Christian J; Uribe-Romo, Fernando J; Knobler, Carolyn B; O'Keeffe, Michael; Yaghi, Omar M

    2010-01-19

    Zeolites are one of humanity's most important synthetic products. These aluminosilicate-based materials represent a large segment of the global economy. Indeed, the value of zeolites used in petroleum refining as catalysts and in detergents as water softeners is estimated at $350 billion per year. A major current goal in zeolite chemistry is to create a structure in which metal ions and functionalizable organic units make up an integral part of the framework. Such a structure, by virtue of the flexibility with which metal ions and organic moieties can be varied, is viewed as a key to further improving zeolite properties and accessing new applications. Recently, it was recognized that the Si-O-Si preferred angle in zeolites (145 degrees ) is coincident with that of the bridging angle in the M-Im-M fragment (where M is Zn or Co and Im is imidazolate), and therefore it should be possible to make new zeolitic imidazolate frameworks (ZIFs) with topologies based on those of tetrahedral zeolites. This idea was successful and proved to be quite fruitful; within the last 5 years over 90 new ZIF structures have been reported. The recent application of high-throughput synthesis and characterization of ZIFs has expanded this structure space significantly: it is now possible to make ZIFs with topologies previously unknown in zeolites, in addition to mimicking known structures. In this Account, we describe the general preparation of crystalline ZIFs, discussing the methods that have been developed to create and analyze the variety of materials afforded. We include a comprehensive list of all known ZIFs, including structure, topology, and pore metrics. We also examine how complexity might be introduced into new structures, highlighting how link-link interactions might be exploited to effect particular cage sizes, create polarity variations between pores, or adjust framework robustness, for example. The chemical and thermal stability of ZIFs permit many applications, such as the capture of CO(2) and its selective separation from industrially relevant gas mixtures. Currently, ZIFs are the best porous materials for the selective capture of CO(2); furthermore, they show exceptionally high capacity for CO(2) among adsorbents operating by physisorption. The stability of ZIFs has also enabled organic transformations to be carried out on the crystals, yielding covalently functionalized isoreticular structures wherein the topology, crystallinity, and porosity of the ZIF structure are maintained throughout the reaction process. These reactions, being carried out on macroscopic crystals that behave as single molecules, have enabled the realization of the chemist's dream of using "crystals as molecules", opening the way for the application of the extensive library of organic reactions to the functionalization of useful extended porous structures. PMID:19877580

  2. Synthesis of ‘unfeasible’ zeolites

    NASA Astrophysics Data System (ADS)

    Mazur, Michal; Wheatley, Paul S.; Navarro, Marta; Roth, Wieslaw J.; Položij, Miroslav; Mayoral, Alvaro; Eliášová, Pavla; Nachtigall, Petr; Čejka, Jiří; Morris, Russell E.

    2016-01-01

    Zeolites are porous aluminosilicate materials that have found applications in many different technologies. However, although simulations suggest that there are millions of possible zeolite topologies, only a little over 200 zeolite frameworks of all compositions are currently known, of which about 50 are pure silica materials. This is known as the zeolite conundrum—why have so few of all the possible structures been made? Several criteria have been formulated to explain why most zeolites are unfeasible synthesis targets. Here we demonstrate the synthesis of two such ‘unfeasible’ zeolites, IPC-9 and IPC-10, through the assembly-disassembly-organization-reassembly mechanism. These new high-silica zeolites have rare characteristics, such as windows that comprise odd-membered rings. Their synthesis opens up the possibility of preparing other zeolites that have not been accessible by traditional solvothermal synthetic methods. We envisage that these findings may lead to a step change in the number and types of zeolites available for future applications.

  3. A new approach to evaluate natural zeolite ability to sorb lead (Pb) from aqueous solutions

    NASA Astrophysics Data System (ADS)

    Drosos, Evangelos I. P.; Karapanagioti, Hrissi K.

    2013-04-01

    Lead (Pb) is a hazardous pollutant commonly found in aquatic ecosystems. Among several methods available, the addition of sorbent amendments to soils or sediments is attractive, since its application is relatively simple, while it can also be cost effective when a low cost and re-usable sorbent is used; e.g. natural zeolites. Zeolites are crystalline aluminosilicates with a three-dimensional structure composed of a set of cavities occupied by large ions and water molecules. Zeolites can accommodate a wide variety of cations, such as Na+, K+, Ca2+, Mg2+, which are rather loosely held and can readily be exchanged for others in an aqueous solution. Natural zeolites are capable of removing cations, such as lead, from aqueous solutions by ion exchange. There is a wide variation in the cation exchange capacity (CEC) of natural zeolites because of the different nature of various zeolites cage structures, natural structural defects, adsorbed ions, and their associated gangue minerals. Naturally occurring zeolites are rarely pure and are contaminated to varying degrees by other minerals, such as clays and feldspars, metals, quartz, or other zeolites as well. These impurities affect the CEC even for samples originated from the same region but from a different source. CEC of the material increases with decreasing impurity content. Potentially exchangeable ions in such impurities do not necessarily participate in ion exchange mechanism, while, in some cases, impurities may additionally block the access to active sites. For zeoliferous rocks having the same percentage of a zeolitic phase, the CEC increases with decreasing Si/Al ratio, as the more Si ions are substituted by Al ions, the more negative the valence of the matrix becomes. Sodium seems to be the most effective exchangeable ion for lead. On the contrary, it is unlikely that the potassium content of the zeolite would be substituted. A pretreatment with high concentration solutions of Na, such as 2 M NaCl, can significantly improve zeolite CEC by bringing the material to near homoionic form. pH and temperature are the critical parameters for using natural zeolites as sorbents. Zeolites should not be used in extremely acidic, neither in extremely basic pH conditions, except for very short times. The exchange of Pb, requires low solution pH, to avoid precipitation but not too low because the H+ are competitive ions for ion exchange; as a result the zeolite CEC related to Pb removal may be downgraded. If pH enters the basic range (e.g. pH>8), more aquatic complexes with lower positive valence than those prevailing in lower pH are produced; these complexes are less attracted by the negative charged zeolitic matrix. Pb uptake is favored at higher temperatures as ion exchange (including the diffusion of exchangeable ions inside the material and the medium, and vice versa) is an endothermic process. With the increase of temperature there is a decrease in hydration of all available exchangeable cations that eases the movement within the channels of the solid matrix. Additionally, the mobility of the potassium ions, present in the zeolitic material, also increases with the temperature resulting in enhanced CEC.

  4. The growth of zeolites A, X and mordenite in space

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.; Bac, N.; Coker, E. N.; Dixon, A. G.; Warzywoda, J.; Thompson, R. W.

    1994-01-01

    Zeolites are a class of crystalline aluminosilicate materials that form the backbone of the chemical process industry worldwide. They are used primarily as adsorbents and catalysts and support to a significant extent the positive balance of trade realized by the chemical industry in the United States (around $19 billion in 1991). The magnitude of their efforts can be appreciated when one realizes that since their introduction as 'cracking catalysts' in the early 1960's, they have saved the equivalent of 60 percent of the total oil production from Alaska's North Slope. Thus the performance of zeolite catalysts can have a profound effect on the U.S. economy. It is estimated that a 1 percent increase in yield of the gasoline fraction per barrel of oil would represent a savings of 22 million barrels of crude oil per year, representing a reduction of $400 million in the United States' balance of payments. Thus any activity that results in improvement in zeolite catalyst performance is of significant scientific and industrial interest. In addition, due to their 'stability,' uniformity, and, within limits, their 'engineerable' structures, zeolites are being tested as potential adsorbents to purify gases and liquids at the parts-per-billion levels needed in today's electronic, biomedical, and biotechnology industries and for the environment. Other exotic applications, such as host materials for quantum-confined semiconductor atomic arrays, are also being investigated. Because of the importance of this class of material, extensive efforts have been made to characterize their structures and to understand their nucleation and growth mechanisms, so as to be able to custom-make zeolites for a desired application. To date, both the nucleation mechanics and chemistry (such as what are the 'key' nutrients) are, as yet, still unknown for many, if not all, systems. The problem is compounded because there is usually a 'gel' phase present that is assumed to control the degree of supersaturation, and this gel undergoes a continuous 'polymerization' type reaction during nucleation and growth. Generally, for structure characterization and diffusion studies, which are useful in evaluating zeolites for improving yield in petroleum refining as well as for many of the proposed new applications (e.g., catalytic membranes, molecular electronics, chemical sensors) large zeolites (greater than 100 to 1000 times normal size) with minimum lattice defects are desired. Presently, the lack of understanding of zeolite nucleation and growth precludes the custom design of zeolites for these or other uses. It was hypothesized that the microgravity levels achieved in an orbiting spacecraft could help to isolate the possible effects of natural convection (which affects defect formation) and minimize sedimentation, which occurs since zeolites are twice as dense as the solution from which they are formed. This was expected to promote larger crystals by allowing growing crystals a longer residence time in a high-concentration nutrient field. Thus it was hypothesized that the microgravity environment of Earth orbit would allow the growth of large, more defect-free zeolite crystals in high yield.

  5. Vapor Phase Transport Synthesis of Zeolites from Sol-Gel Precursors

    SciTech Connect

    THOMA,STEVEN G.; NENOFF,TINA M.

    2000-07-14

    A study of zeolite crystallization from sol-gel precursors using the vapor phase transport synthesis method has been performed. Zeolites (ZSM-5, ZSM-48, Zeolite P, and Sodalite) were crystallized by contacting vapor phase organic or organic-water mixtures with dried sodium silicate and dried sodium alumino-silicate gels. For each precursor gel, a ternary phase system of vapor phase organic reactant molecules was explored. The vapor phase reactant mixtures ranged from pure ethylene diamene, triethylamine, or water, to an equimolar mixture of each. In addition, a series of gels with varied physical and chemical properties were crystallized using the same vapor phase solvent mixture for each gel. The precursor gels and the crystalline products were analyzed via Scanning Electron Microscopy, Electron Dispersive Spectroscopy, X-ray mapping, X-ray powder diffraction, nitrogen surface area, Fourier Transform Infrared Spectroscopy, and thermal analyses. The product phase and purity as a function of the solvent mixture, precursor gel structure, and precursor gel chemistry is discussed.

  6. Reclaiming silver from silver zeolite

    SciTech Connect

    Reimann, G.A.

    1991-10-01

    Silver zeolite is used to capture radioiodines from air cleaning systems in some nuclear facilities at the Idaho National Engineering Laboratory. It may become radioactively contaminated and/or poisoned by hydrocarbon vapors, which diminishes its capacity for iodine. Silver zeolite contains up to 38 wt% silver. A pyrometallurgical process was developed to reclaim the silver before disposing of the unserviceable zeolite as a radioactive waste. A flux was formulated to convert the refractory aluminosilicate zeolite structure into a low-melting fluid slag, with Na{sub 2}O added as NAOH instead of Na{sub 2}CO{sub 3} to avoid severe foaming due to CO{sub 2} evolution. A propane-fired furnace was built to smelt 45 kg charges at 1300C in a carbon-bonded silicon carbide crucible. A total of 218 kg (7000 tr oz) of silver was reclaimed from 1050 kg of unserviceable zeolite. Silver recoveries of 97% were achieved, and the radioisotopes were fixed as stable silicates in a vitreous slag that was disposed of as a low level waste. Recovered silver was refined using oxygen and cast into 100 tr oz bars assaying 99.8+% silver and showing no radioactive contamination.

  7. Reclaiming silver from silver zeolite

    SciTech Connect

    Reimann, G.A.

    1991-10-01

    Silver zeolite is used to capture radioiodines from air cleaning systems in some nuclear facilities at the Idaho National Engineering Laboratory. It may become radioactively contaminated and/or poisoned by hydrocarbon vapors, which diminishes its capacity for iodine. Silver zeolite contains up to 38 wt% silver. A pyrometallurgical process was developed to reclaim the silver before disposing of the unserviceable zeolite as a radioactive waste. A flux was formulated to convert the refractory aluminosilicate zeolite structure into a low-melting fluid slag, with Na[sub 2]O added as NAOH instead of Na[sub 2]CO[sub 3] to avoid severe foaming due to CO[sub 2] evolution. A propane-fired furnace was built to smelt 45 kg charges at 1300C in a carbon-bonded silicon carbide crucible. A total of 218 kg (7000 tr oz) of silver was reclaimed from 1050 kg of unserviceable zeolite. Silver recoveries of 97% were achieved, and the radioisotopes were fixed as stable silicates in a vitreous slag that was disposed of as a low level waste. Recovered silver was refined using oxygen and cast into 100 tr oz bars assaying 99.8+% silver and showing no radioactive contamination.

  8. Crystalline Membranes

    NASA Technical Reports Server (NTRS)

    Tsapatsis, Michael (Inventor); Lai, Zhiping (Inventor)

    2008-01-01

    In certain aspects, the invention features methods for forming crystalline membranes (e.g., a membrane of a framework material, such as a zeolite) by inducing secondary growth in a layer of oriented seed crystals. The rate of growth of the seed crystals in the plane of the substrate is controlled to be comparable to the rate of growth out of the plane. As a result, a crystalline membrane can form a substantially continuous layer including grains of uniform crystallographic orientation that extend through the depth of the layer.

  9. Characterization of Uranium Solids Precipitated with Aluminosilicates

    SciTech Connect

    DUFF, MC

    2004-01-09

    At the Savannah River Site (SRS), the High-Level Waste (HLW) Tank Farms store and process high-level liquid radioactive wastes from the Canyons and recycle water from the Defense Waste Processing Facility. The waste is concentrated using evaporators to minimize the volume of space required for HLW storage. Recently, the 2H Evaporator was shutdown due to the crystallization of sodium aluminosilicate (NAS) solids (such as cancrinite and sodalite) that contained close to 10 weight percent of elementally-enriched uranium (U). Prior to extensive cleaning,the evaporator deposits resided on the evaporator walls and other exposed internal surfaces within the evaporator pot. Our goal is to support the basis for the continued safe operation of SRS evaporators and to gain more information that could be used to help mitigate U accumulation during evaporator operation. To learn more about the interaction between U(VI) and NAS in HLW salt solutions, we performed several fundamental studies to examine the mechanisms of U accumulation with NAS in highly caustic solutions. This larger group of studies focused on the following processes: co-precipitation/structural incorporation, sorption, and precipitation (with or without NAS), which will be reviewed in this presentation. We will present and discuss local atomic structural characterization data about U that has been co-precipitated with NAS solids (such as amorphous zeolite precursor material and sodalite) using X-ray absorption fine-structure (XAFS) spectroscopic techniques.

  10. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium aluminosilicate. 182.2727 Section 182.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  11. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium aluminosilicate. 182.2727 Section 182.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  12. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  13. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  14. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium aluminosilicate. 182.2727 Section 182.2727...) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Anticaking Agents § 182.2727 Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance. This substance is generally recognized...

  15. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Sodium aluminosilicate. 182.2727 Section 182.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  16. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium aluminosilicate. 182.2727 Section 182.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  17. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  18. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  19. 21 CFR 582.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Sodium aluminosilicate. 582.2727 Section 582.2727 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Sodium aluminosilicate. (a) Product. Sodium aluminosilicate (sodium silicoaluminate). (b) Tolerance....

  20. Mineral resource of the month: natural and synthetic zeolites

    USGS Publications Warehouse

    Virta, R.

    2008-01-01

    Robert Virta, mineral commodity specialist for the U.S. Geological Survey, prepared the following information about the zeolite industry. Volcanic rocks containing natural zeolites — hydrated aluminosilicate minerals that contain alkaline and alkaline-earth metals — have been mined worldwide for more than 1,000 years for use as cements and building stone. For centuries, people thought natural zeolites occurred only in small amounts inside cavities of volcanic rock. But in the 1950s and early 1960s, large zeolite deposits were discovered in volcanic tuffs in the western United States and in marine tuffs in Italy and Japan. And since then, similar deposits have been found around the world, from Hungary to Cuba to New Zealand. The discovery of these larger deposits made commercial mining of natural zeolite possible.

  1. Crystallization of zeolite A: a spectroscopic study

    SciTech Connect

    Dutta, P.K.; Shieh, D.C.

    1986-05-22

    The transformation of aluminosilicate gel to zeolite A was investigated by Raman spectroscopy, supported by x-ray diffraction and NMR measurements. The gel, even though amorphous, has a structure consisting of predominantly four-membered rings connected in a random fashion. It is considerably depolymerized, consisting of Si atoms with one and two nonbonded oxygen atoms. For the transformation of this gel to zeolite A to proceed, it is essential to have Al(OH)/sub 4//sup -/ species in solution. During the nucleation period, the gel reorganizes its structure by interaction with these Al(OH)/sub 4//sup -/ ions and forms nuclei of zeolite A. The crystallization curve obtained by Raman spectroscopy closely resembles that from x-ray diffraction.

  2. Mesostructured zeolites: bridging the gap between zeolites and MCM-41.

    PubMed

    Prasomsri, Teerawit; Jiao, Wenqian; Weng, Steve Z; Garcia Martinez, Javier

    2015-05-28

    Surfactant-templating is one of the most versatile and useful techniques to implement mesoporous systems into solid materials. Various strategies based on various interactions between surfactants and solid precursors have been explored to produce new structures. Zeolites are invaluable as size- and shape-selective solid acid catalysts. Nevertheless, their micropores impose limitations on the mass transport of bulky feed and/or product molecules. Many studies have attempted to address this by utilizing surfactant-assisting technology to alleviate the diffusion constraints. However, most efforts have failed due to micro/mesopore phase separation. Recently, a new technique combining the uses of cationic surfactants and mild basic solutions was introduced to synthesise mesostructured zeolites. These materials sustain the unique characteristics of zeolites (i.e., strong acidity, crystallinity, microporosity, and hydrothermal stability), including tunable mesopore sizes and degrees of mesoporosity. The mesostructured zeolites are now commercially available through Rive Technology, and show superior performance in VGO cracking. This feature article provides an overview of recent explorations in the introduction of mesoporosity into zeolites using surfactant-templating techniques. Various porous materials, preparation methods, physical and catalytic properties of mesostructured zeolites will be discussed. PMID:25866848

  3. Crystallization Kinetics of Calcium-magnesium Aluminosilicate (CMAS) Glass

    NASA Technical Reports Server (NTRS)

    Wiesner, Valerie L.; Bansal, Narottam P.

    2015-01-01

    The crystallization kinetics of a calcium-magnesium aluminosilicate (CMAS) glass with composition relevant for aerospace applications, like air-breathing engines, were evaluated using differential thermal analysis (DTA) in powder and bulk forms. Activation energy and frequency factor values for crystallization of the glass were evaluated. X-ray diffraction (XRD) was used to investigate the onset of crystallization and the phases that developed after heat treating bulk glass at temperatures ranging from 690 to 960 deg for various times. Samples annealed at temperatures below 900 deg remained amorphous, while specimens heat treated at and above 900 deg exhibited crystallinity originating at the surface. The crystalline phases were identified as wollastonite (CaSiO3) and aluminum diopside (Ca(Mg,Al) (Si,Al)2O6). Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were employed to examine the microstructure and chemical compositions of crystalline phases formed after heat treatment.

  4. PHYSICAL, CHEMICAL AND STRUCTURAL EVOLUTIION OF ZEOLITE-CONTAINING WASTE FORMS PRODUCED FROM METAKAOLINITE AND CALCINED SODUIM BEARING WASTE (HLW AND/OR LLW)

    SciTech Connect

    Grutzeck, Michael W.

    2004-06-10

    Zeolites are extremely versatile. They can adsorb liquids and gases and serve as cation exchange media. They occur in nature as well cemented deposits. The Romans used blocks of zeolitized tuff as a building material. Using zeolites for the management of radioactive waste is not new, but a process by which the zeolites can be made to act as a cementing agent is. Zeolitic materials are relatively easy to synthesize from a wide range of both natural and man-made precursors. The process under study is derived from a well known method in which metakaolin (thermally dehydroxylated kaolin a mixture of kaolinite and smaller amounts of quartz and mica that has been heated to {approx}700 C) is mixed with sodium hydroxide (NaOH) and water and reacted in slurry form (for a day or two) at mildly elevated temperatures. The zeolites form as finely divided powders containing micrometer ({micro}m) sized crystals. However, if the process is changed slightly and just enough concentrated sodium hydroxide solution is added to the metakaolinite to make a thick paste and then the paste is cured under mild hydrothermal conditions (60-200 C), the mixture forms a concrete-like ceramic material made up of distinct crystalline tectosilicate minerals (zeolites and feldspathoids) imbedded in an X-ray amorphous hydrated sodium aluminosilicate matrix. Due to its vitreous character we have chosen to call this composite a ''hydroceramic''. Similar to zeolite powders, a hydroceramic is able to sequester cations in both lattice positions and within the channels and voids present in its tectosilicate framework structure. It can also accommodate a wide range of salt molecules (e.g., sodium nitrate) within these same openings thus rendering them insoluble. Due to its fine crystallite size and cementing character, the matrix develops significant physical strength. The obvious similarities between a hydroceramic waste form and a waste form based on solidified Portland cement grout are only superficial because their chemistries are entirely different. In addition to being vastly superior to conventional Portland cement grouts with respect to salt retention, standard radwaste leach protocols (PCT, TCLP, etc.) have shown that hydroceramics also do a better job of immobilizing the RCRA-toxic and radioactive components of ''sodium bearing wastes'' (SBWs).

  5. Regenerative Cu/La zeolite supported desulfurizing sorbents

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E. (Inventor); Sharma, Pramod K. (Inventor)

    1991-01-01

    Efficient, regenerable sorbents for removal of H2S from fluid hydrocarbons such as diesel fuel at moderate condition comprise a porous, high surface area aluminosilicate support, suitably a synthetic zeolite, and most preferably a zeolite having a free lattice opening of at least 6 Angstroms containing from 0.1 to 0.5 moles of copper ions, lanthanum ions or their mixtures. The sorbent removes sulfur from the hydrocarbon fuel in high efficiency and can be repetitively regenerated without loss of activity.

  6. Synthesis, Structure, and Carbon Dioxide Capture Properties of Zeolitic Imidazolate Frameworks

    SciTech Connect

    Phan, Anh; Doonan, Christian J; Uribe-Romo, Fernando J; Knobler, Carolyn B; O'Keeffe, Michael; Yaghi, Omar M

    2010-01-19

    Zeolites are one of humanity’s most important synthetic products. These aluminosilicate-based materials represent a large segment of the global economy. Indeed, the value of zeolites used in petroleum refining as catalysts and in detergents as water softeners is estimated at $350 billion per year. A major current goal in zeolite chemistry is to create a structure in which metal ions and functionalizable organic units make up an integral part of the framework. Such a structure, by virtue of the flexibility with which metal ions and organic moieties can be varied, is viewed as a key to further improving zeolite properties and accessing new applications. Recently, it was recognized that the Si−O−Si preferred angle in zeolites (145°) is coincident with that of the bridging angle in the M−Im−M fragment (where M is Zn or Co and Im is imidazolate), and therefore it should be possible to make new zeolitic imidazolate frameworks (ZIFs) with topologies based on those of tetrahedral zeolites. This idea was successful and proved to be quite fruitful; within the last 5 years over 90 new ZIF structures have been reported. The recent application of high-throughput synthesis and characterization of ZIFs has expanded this structure space significantly: it is now possible to make ZIFs with topologies previously unknown in zeolites, in addition to mimicking known structures. In this Account, we describe the general preparation of crystalline ZIFs, discussing the methods that have been developed to create and analyze the variety of materials afforded. We include a comprehensive list of all known ZIFs, including structure, topology, and pore metrics. We also examine how complexity might be introduced into new structures, highlighting how link−link interactions might be exploited to effect particular cage sizes, create polarity variations between pores, or adjust framework robustness, for example. The chemical and thermal stability of ZIFs permit many applications, such as the capture of CO{sub 2} and its selective separation from industrially relevant gas mixtures. Currently, ZIFs are the best porous materials for the selective capture of CO{sub 2}; furthermore, they show exceptionally high capacity for CO{sub 2} among adsorbents operating by physisorption. The stability of ZIFs has also enabled organic transformations to be carried out on the crystals, yielding covalently functionalized isoreticular structures wherein the topology, crystallinity, and porosity of the ZIF structure are maintained throughout the reaction process. These reactions, being carried out on macroscopic crystals that behave as single molecules, have enabled the realization of the chemist’s dream of using “crystals as molecules”, opening the way for the application of the extensive library of organic reactions to the functionalization of useful extended porous structures.

  7. Aluminosilicate Precipitation Impact on Uranium

    SciTech Connect

    WILMARTH, WILLIAM

    2006-03-10

    Experiments have been conducted to examine the fate of uranium during the formation of sodium aluminosilicate (NAS) when wastes containing high aluminate concentrations are mixed with wastes of high silicate concentration. Testing was conducted at varying degrees of uranium saturation. Testing examined typical tank conditions, e.g., stagnant, slightly elevated temperature (50 C). The results showed that under sub-saturated conditions uranium is not removed from solution to any large extent in both simulant testing and actual tank waste testing. This aspect was not thoroughly understood prior to this work and was necessary to avoid criticality issues when actual tank wastes were aggregated. There are data supporting a small removal due to sorption of uranium on sites in the NAS. Above the solubility limit the data are clear that a reduction in uranium concentration occurs concomitant with the formation of aluminosilicate. This uranium precipitation is fairly rapid and ceases when uranium reaches its solubility limit. At the solubility limit, it appears that uranium is not affected, but further testing might be warranted.

  8. Shape selectivity extending to ordered supermicroporous aluminosilicates.

    PubMed

    Fu, Wen Hua; Liang, Xiao Min; Zhang, Haidong; Wang, Yi Meng; He, Ming Yuan

    2015-01-28

    In the synthesis of polyoxymethylene dimethyl ethers (PODEn) catalyzed by ordered supermicroporous aluminosilicates, shape selectivity was observed and the high selectivity for target products (PODE3-8) was attributed to the particular pore diameter. PMID:25487895

  9. Molecular simulations and experimental studies of zeolites

    NASA Astrophysics Data System (ADS)

    Moloy, Eric C.

    Zeolites are microporous aluminosilicate tetrahedral framework materials that have symmetric cages and channels with open-diameters between 0.2 and 2.0 nm. Zeolites are used extensively in the petrochemical industries for both their microporosity and their catalytic properties. The role of water is paramount to the formation, structure, and stability of these materials. Zeolites frequently have extra-framework cations, and as a result, are important ion-exchange materials. Zeolites also play important roles as molecular sieves and catalysts. For all that is known about zeolites, much remains a mystery. How, for example, can the well established metastability of these structures be explained? What is the role of water with respect to the formation, stabilization, and dynamical properties? This dissertation addresses these questions mainly from a modeling perspective, but also with some experimental work as well. The first discussion addresses a special class of zeolites: pure-silica zeolites. Experimental enthalpy of formation data are combined with molecular modeling to address zeolitic metastability. Molecular modeling is used to calculate internal surface areas, and a linear relationship between formation enthalpy and internal surface areas is clearly established, producing an internal surface energy of approximately 93 mJ/m2. Nitrate bearing sodalite and cancrinite have formed under the caustic chemical conditions of some nuclear waste processing centers in the United States. These phases have fouled expensive process equipment, and are the primary constituents of the resilient heels in the bottom of storage tanks. Molecular modeling, including molecular mechanics, molecular dynamics, and density functional theory, is used to simulate these materials with respect to structure and dynamical properties. Some new, very interesting results are extracted from the simulation of anhydrous Na6[Si6Al 6O24] sodalite---most importantly, the identification of two distinct oxygen sites (rather than one), and formation of a new supercell. New calorimetric measurements of enthalpy are used to examine the energetics of the hydrosodalite family of zeolites---specifically, formation enthalpies and hydration energies. Finally, force-field computational methods begin the examination of water in terms of energetics, structure, and radionuclide containment and diffusion.

  10. Synthesis and structure of zeolite ZSM-5: a Raman spectroscopic study

    SciTech Connect

    Dutta, P.K.; Puri, M.

    1987-07-30

    The Raman spectra of the solution and solid phases present during various stages of ZSM-5 synthesis were examined by monitoring the vibrations of the tetrapropylammonium ion. It was found that this cation is trapped into the amorphous solid phase at the earliest stages of the synthesis in the all-trans configuration. Upon crystallization of the zeolite, there is a forced change in the conformation of the trapped tetrapropylammonium cation, such that it can fit into the zig-zag zeolite channels. The Raman spectra of the aluminosilicate zeolite framework is also distinct from other zeolites, such as A, X, and Y, and exhibits a band at 385 cm/sup -1/ characteristic of the five-membered building units of this zeolite.

  11. Selectivity of zeolite catalysts of hydrocracking of paraffin hydrocarbons

    SciTech Connect

    Shakun, A.N.; Il'icheva, L.F.; Nikitina, N.L.; Nefedov, B.K.; Konoval'chikov, L.D.; Alekseeva, T.V.

    1988-09-20

    The selectivity of catalysts of hydrocracking based on three types of zeolites: HKE, HM, and HTsVM was studied in comparable conditions and it was found that in rigorous conditions of conducting the process (longer contact time, deeper conversion of the normal paraffin), the contribution of nonselective hydrocracking which takes place on the external crystalline surface of the zeolites becomes marked on all of the catalysts. Incorporation of a hydrogenating component in the zeolite-containing catalyst results in an increase in nonselective hydrocracking on the external crystalline surface of the zeolites, and addition of significant amounts of molybdenum oxide also results in a decrease in the total conversion of the n-paraffin. The contribution of nonselective hydrocracking decreases with an increase in the intracrystalline activity of the zeolite.

  12. Raman spectroscopic studies of zeolite framework. Hydrated Zeolite A and the influence of cations

    SciTech Connect

    Dutta, P.K.; Del Barco, B.

    1985-05-09

    Raman spectra of hydrated zeolite A completely exchanged with Li/sup +/, Na/sup +/, K/sup +/, Tl/sup +/, and NH/sub 4//sup +/ ions are reported in this paper. The emphasis has been on the high-frequency region between 300 and 1200 cm/sup -1/, where the intramolecular modes of the aluminosilicate framework are expected. The Raman bands cluster in three regions of the spectrum: (a) 300-500 cm/sup -1/, assigned to T-O deformation modes; (b) 650-750 cm/sup -1/, assigned to Al-O stretching vibrations; and (c) 900-1100 cm/sup -1/, assigned to Si-O stretching motions. The Raman spectra of the ion-exchanged zeolites suggest that Li/sup +/ distorts the zeolite framework, whereas in Na/sup +/-, K/sup +/-, and Tl/sup +/-A, the zeolite structure remains unchanged. In NH/sub 4/-A, there is strong spectroscopic evidence for H-bond formation between the cation and the lattice oxygens. 31 references, 2 figures, 1 table.

  13. Effects of ultrasonic treatment on zeolite NaA synthesized from by-product silica.

    PubMed

    Vaičiukynienė, Danutė; Kantautas, Aras; Vaitkevičius, Vitoldas; Jakevičius, Leonas; Rudžionis, Žymantas; Paškevičius, Mantas

    2015-11-01

    The synthesis of zeolite NaA from silica by-product was carried out in the presence of 20 kHz ultrasound at room temperature. Zeolites obtained in this type of synthesis were compared to zeolites obtained by performing conventional static syntheses under similar conditions. The sonication effects on zeolite NaA synthesis were characterized by phase identification, crystallinity etc. The effects of different parameters such as crystallization time and initial materials preparation methods on the crystallinity and morphology of the synthesized zeolites were investigated. The final products were characterized by XRD and FT-IR. It was possible to obtain crystalline zeolite NaA from by-product silica in the presence of ultrasound. PMID:26186874

  14. Noble gas adsorption in two-dimensional zeolites: a combined experimental and density functional theory study

    NASA Astrophysics Data System (ADS)

    Wang, Mengen; Zhong, Jianqiang; Boscoboinik, Jorge Anibal; Lu, Deyu

    Zeolites are important industrial catalysts with porous three-dimensional structures. The catalytically active sites are located inside the pores, thus rendering them inaccessible for surface science measurements. We synthesized a two-dimensional (2D) zeolite model system, consisting of an (alumino)silicate bilayer weakly bound to a Ru (0001) surface. The 2D zeolite is suitable for surface science studies; it allows a detailed characterization of the atomic structure of the active site and interrogation of the model system during the catalytic reaction. As an initial step, we use Ar adsorption to obtain a better understanding of the atomic structure of the 2D zeolite. In addition, atomic level studies of rare gas adsorption and separation by zeolite are important for its potential application in nuclear waste sequestration. Experimental studies found that Ar atoms can be trapped inside the 2D-zeolite, raising an interesting question on whether Ar atoms are trapped inside the hexagonal prism nano-cages or at the interface between the (alumino)silicate bilayer and Ru(0001), or both. DFT calculations using van der Waals density functionals were carried out to determine the preferred Ar adsorption sites and the corresponding adsorption energies. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704.

  15. Dissolution and Separation of Aluminum and Aluminosilicates

    SciTech Connect

    McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; Felker, Leslie Kevin; Mattus, Catherine H.

    2015-12-19

    The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as a function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.

  16. Dissolution and Separation of Aluminum and Aluminosilicates

    DOE PAGESBeta

    McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; Felker, Leslie Kevin; Mattus, Catherine H.

    2015-12-19

    The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as amore » function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.« less

  17. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  18. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium calcium aluminosilicate, hydrated. 182.2729... § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  19. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  20. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  1. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Sodium calcium aluminosilicate, hydrated. 182.2729... § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  2. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  3. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729... Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  4. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium calcium aluminosilicate, hydrated. 182.2729... (CONTINUED) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Anticaking Agents § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium...

  5. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium calcium aluminosilicate, hydrated. 182.2729... § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  6. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium calcium aluminosilicate, hydrated. 182.2729... § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium calcium silicoaluminate). (b) Tolerance. This substance is generally recognized as...

  7. Ammonium removal from high-strength aqueous solutions by Australian zeolite.

    PubMed

    Wijesinghe, D Thushari N; Dassanayake, Kithsiri B; Sommer, Sven G; Jayasinghe, Guttila Y; J Scales, Peter; Chen, Deli

    2016-07-01

    Removal of ammonium nitrogen (NH4(+)-N) particularly from sources which are highly rich in nitrogen is important for addressing environmental pollution. Zeolites, aluminosilicate minerals, are commonly used as commercial adsorbents and ion-exchange medium in number of commercial applications due to its high adsorption capacity of ammonium (NH4(+)). However, detailed investigations on NH4(+) adsorption and ion exchange capacities of Australian natural zeolites are rare, particularly under higher NH4(+) concentrations in the medium. Therefore, this study was conducted to determine NH4(+) adsorption characteristics of Australian natural zeolites at high NH4(+) concentrations with and without other chemical compounds in an aqueous solution. Results showed that initial NH4(+) concentration, temperature, reaction time, and pH of the solution had significant effects on NH4(+) adsorption capacity of zeolite. Increased retention time and temperature generally had a positive impact on adsorption. Freundlich model fitted well with adsorption process of Australian natural zeolites; however, Langmuir model had best fitted for the adsorption process of sodium (Na(+)) treated zeolites. NaCl treatment increased the NH4(+) adsorption capacity of Australian zeolites by 25% at 1000 mg-N, NH4(+) solution. The maximum adsorption capacity of both natural Australian zeolites and Na(+) treated zeolites were estimated as 9.48 and 11.83 mg-N/g, respectively, which is lower than many zeolites from other sources. Compared to the NH4(+) only medium, presence of other competitive ions and acetic acid in the medium (resembling composition in digested swine manure slurries) reduced NH4(+) removal of natural and Na(+) treated zeolites by 44% and 57%, respectively. This suggests detailed investigations are required to determine practically achievable NH4(+) -N removal potential of zeolites for applications in complex mediums such as animal manure slurries. PMID:27050255

  8. ZEOLITES: EFFECTIVE WATER PURIFIERS

    EPA Science Inventory

    Zeolites are known for their adsorption, ion exchange and catalytic properties. Various natural zeolites are used as odor and moisture adsorbents and water softeners. Due to their acidic nature, synthetic zeolites are commonly employed as solid acid catalysts in petrochemical ind...

  9. Synthetic Zeolites as Controlled-Release Delivery Systems for Anti-Inflammatory Drugs.

    PubMed

    Khodaverdi, Elham; Soleimani, Hossein Ali; Mohammadpour, Fatemeh; Hadizadeh, Farzin

    2016-06-01

    Scientists have always been trying to use artificial zeolites to make modified-release drug delivery systems in the gastrointestinal tract. An ideal carrier should have the capability to release the drug in the intestine, which is the main area of absorption. Zeolites are mineral aluminosilicate compounds with regular structure and huge porosity, which are available in natural and artificial forms. In this study, soaking, filtration and solvent evaporation methods were used to load the drugs after activation of the zeolites. Weight measurement, spectroscopy FTIR, thermogravimetry and scanning electronic microscope were used to determine drug loading on the systems. Finally, consideration of drug release was made in a simulated gastric fluid and a simulated intestinal fluid for all matrixes (zeolites containing drugs) and drugs without zeolites. Diclofenac sodium (D) and piroxicam (P) were used as the drug models, and zeolites X and Y as the carriers. Drug loading percentage showed that over 90% of drugs were loaded on zeolites. Dissolution tests in stomach pH environment showed that the control samples (drug without zeolite) released considerable amount of drugs (about 90%) within first 15 min when it was about 10-20% for the matrixes. These results are favorable as NSAIDs irritate the stomach wall and it is ideal not to release much drugs in the stomach. Furthermore, release rate of drugs from matrixes has shown slower rate in comparison with control samples in intestine pH environment. PMID:26705687

  10. Synthesis and characterization of nitrogen substituted zeolites

    NASA Astrophysics Data System (ADS)

    Dogan, Fulya

    The interest in basic solid materials, particularly for basic zeolites has considerably increased in the last two decades because of their potential use in catalysis and separation. Basic zeolites have most often been obtained by ion-exchange or impregnation with alkali metal cations or grafting of organic bases onto zeolite pore walls. Such materials often suffer from instability and/or pore blockage, because none of these approaches places basic sites directly into the zeolite framework. Recently zeolitic materials have been made with some of the bridging oxygen atoms in Si--O--Si and/or Si--O--Al linkages replaced by NH groups, i.e. by substitution of framework oxygen by nitrogen. As a result, the basic strength of the framework increases due to the lower electronegativity of nitrogen with respect to oxygen. In this study, solid base catalysts are obtained by nitrogen substitution of the faujasite type of zeolites under ammonia flow at high temperatures. The efficiency of the reaction is tested by using zeolites with different aluminum contents and extraframework cations and varying the reaction conditions such as ammonia flow rate, reaction temperature and duration. The characterization studies show that high levels of nitrogen substitution can be achieved while maintaining porosity, particularly for NaY and low-aluminum HY zeolites, without a significant loss in the crystallinity. 27Al and 29 Si MAS NMR experiments performed on the nitrogen substituted zeolites show dealumination of the framework and preferential substitution for Si--OH--Al sites at the early stages of the reaction (temperatures at 750--800 °C). No preference is seen for reactions performed at higher temperatures and longer reaction times (e.g., 850 °C and 48 h). X-ray PDF analysis performed on the modified zeolites show that the Si-N distance in the 1st shell is longer than Si-O bond distance and Si-Si/Al bond distance of the Si-O/N-Si/Al linkage decreases, as an indication of a decrease in bond angle. The basicity experiments performed on the zeolites show an increase basicity with increase of the nitrogen content.

  11. Zeolite-like liquid crystals.

    PubMed

    Poppe, Silvio; Lehmann, Anne; Scholte, Alexander; Prehm, Marko; Zeng, Xiangbing; Ungar, Goran; Tschierske, Carsten

    2015-01-01

    Zeolites represent inorganic solid-state materials with porous structures of fascinating complexity. Recently, significant progress was made by reticular synthesis of related organic solid-state materials, such as metal-organic or covalent organic frameworks. Herein we go a step further and report the first example of a fluid honeycomb mimicking a zeolitic framework. In this unique self-assembled liquid crystalline structure, transverse-lying π-conjugated rod-like molecules form pentagonal channels, encircling larger octagonal channels, a structural motif also found in some zeolites. Additional bundles of coaxial molecules penetrate the centres of the larger channels, unreachable by chains attached to the honeycomb framework. This creates a unique fluid hybrid structure combining positive and negative anisotropies, providing the potential for tuning the directionality of anisotropic optical, electrical and magnetic properties. This work also demonstrates a new approach to complex soft-matter self-assembly, by using frustration between space filling and the entropic penalty of chain extension. PMID:26486751

  12. Zeolite-like liquid crystals

    PubMed Central

    Poppe, Silvio; Lehmann, Anne; Scholte, Alexander; Prehm, Marko; Zeng, Xiangbing; Ungar, Goran; Tschierske, Carsten

    2015-01-01

    Zeolites represent inorganic solid-state materials with porous structures of fascinating complexity. Recently, significant progress was made by reticular synthesis of related organic solid-state materials, such as metal-organic or covalent organic frameworks. Herein we go a step further and report the first example of a fluid honeycomb mimicking a zeolitic framework. In this unique self-assembled liquid crystalline structure, transverse-lying π-conjugated rod-like molecules form pentagonal channels, encircling larger octagonal channels, a structural motif also found in some zeolites. Additional bundles of coaxial molecules penetrate the centres of the larger channels, unreachable by chains attached to the honeycomb framework. This creates a unique fluid hybrid structure combining positive and negative anisotropies, providing the potential for tuning the directionality of anisotropic optical, electrical and magnetic properties. This work also demonstrates a new approach to complex soft-matter self-assembly, by using frustration between space filling and the entropic penalty of chain extension. PMID:26486751

  13. Modeling of Macroscopic/Microscopic Transport and Growth Phenomena in Zeolite Crystal Solutions Under Microgravity Conditions

    NASA Technical Reports Server (NTRS)

    Gatsonis, Nikos A.; Alexandrou, Andreas; Shi, Hui; Ongewe, Bernard; Sacco, Albert, Jr.

    1999-01-01

    Crystals grown from liquid solutions have important industrial applications. Zeolites, for instance, a class of crystalline aluminosilicate materials, form the backbone of the chemical process industry worldwide, as they are used as adsorbents and catalysts. Many of the phenomena associated with crystal growth processes are not well understood due to complex microscopic and macroscopic interactions. Microgravity could help elucidate these phenomena and allow the control of defect locations, concentration, as well as size of crystals. Microgravity in an orbiting spacecraft could help isolate the possible effects of natural convection (which affects defect formation) and minimize sedimentation. In addition, crystals will stay essentially suspended in the nutrient pool under a diffusion-limited growth condition. This is expected to promote larger crystals by allowing a longer residence time in a high-concentration nutrient field. Among other factors, the crystal size distribution depends on the nucleation rate and crystallization. These two are also related to the "gel" polymerization/depolymerization rate. Macroscopic bulk mass and flow transport and especially gravity, force the crystals down to the bottom of the reactor, thus forming a sedimentation layer. In this layer, the growth rate of the crystals slows down as crystals compete for a limited amount of nutrients. The macroscopic transport phenomena under certain conditions can, however, enhance the nutrient supply and therefore, accelerate crystal growth. Several zeolite experiments have been performed in space with mixed results. The results from our laboratory have indicated an enhancement in size of 30 to 70 percent compared to the best ground based controls, and a reduction of lattice defects in many of the space grown crystals. Such experiments are difficult to interpret, and cannot be easily used to derive empirical or other laws since many physical parameters are simultaneously involved in the process. At the same time, however, there is increased urgency to develop such an understanding in order to more accurately quantify the process. In order to better understand the results obtained from our prior space experiments, and design future experiments, a detailed fluid dynamic model simulating the crystal growth mechanism is required. This will not only add to the fundamental knowledge on the crystallization of zeolites, but also be useful in predicting the limits of size and growth of these important industrial materials. Our objective is to develop macro/microscopic theoretical and computational models to study the effect of transport phenomena in the growth of crystals grown in solutions. Our effort has concentrated so far in the development of separate macroscopic and microscopic models. The major highlights of our accomplishments are described.

  14. Mesoporous Aluminosilicate Catalysts for the Selective Isomerization of n-Hexane: The Roles of Surface Acidity and Platinum Metal.

    PubMed

    Musselwhite, Nathan; Na, Kyungsu; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

    2015-08-19

    Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brnsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed. PMID:26168190

  15. Double rotation NMR studies of zeolites and aluminophosphate molecular sieves

    SciTech Connect

    Jelinek, R. |

    1993-07-01

    Goal is to study the organization and structures of guest atoms and molecules and their reactions on internal surfaces within pores of zeolites and aluminophosphate molecular sieves. {sup 27}Al and {sup 23}Na double rotation NMR (DOR) is used since it removes the anisotropic broadening in NMR spectra of quadrupolar nuclei, thus increasing resolution. This work concentrates on probing aluminum framework atoms in aluminophosphate molecular sieves and sodium extra framework cations in porous aluminosilicates. In aluminophosphates, ordering and electronic environments of the framework {sup 27}Al nuclei are modified upon adsorption of water molecules within the channels; a relation is sought between the sieve channel topology and the organization of adsorbed water, as well as the interaction between the Al nuclei and the water molecules. Extra framework Na{sup +} cations are directly involved in adsorption processes and reactions in zeolite cavities.

  16. Inelastic X-ray Scattering Studies of Zeolite Collapse

    SciTech Connect

    Greaves, G. Neville; Kargl, Florian; Ward, David; Holliman, Peter; Meneau, Florian

    2009-01-29

    In situ inelastic x-ray scattering (IXS) experiments have been used to probe heterogeneity and deformability in zeolte Y as this thermally collapses to a high density amorphous (HDA) aluminosilicate phase. The Landau-Placzek ratio R{sub LP} falls slowly as amorphisation advances, increasing in the later stages of collapse clearly showing how homogeneity improves non-linearly--behaviour linked closely with the decline in molar volume V{sub Molar}. The Brillouin frequency {omega}{sub Q} also decreases with amorphisation in a similar fashion, signifying a non-uniform decrease in the speed of sound v{sub l}. All of these changes with zeolite amorphisation infer formation of an intermediate low density amorphous (LDA) phase. This low entropy or 'perfect glass' has mechanical properties which are closer to the zeolite rather to the HDA glass--notably a very small value of Poisson's Ratio signifying unusually low resistance to deformation.

  17. Facile Synthesis, Characterization, and Catalytic Behavior of a Large-Pore Zeolite with the IWV Framework.

    PubMed

    Schmidt, Joel E; Chen, Cong-Yan; Brand, Stephen K; Zones, Stacey I; Davis, Mark E

    2016-03-14

    Large-pore microporous materials are of great interest to process bulky hydrocarbon and biomass-derived molecules. ITQ-27 (IWV) has a two-dimensional pore system bounded by 12-membered rings (MRs) that lead to internal cross-sections containing 14 MRs. Investigations into the catalytic behavior of aluminosilicate (zeolite) materials with this framework structure have been limited until now due to barriers in synthesis. The facile synthesis of aluminosilicate IWV in both hydroxide and fluoride media is reported herein using simple, diquaternary organic structure-directing agents (OSDAs) that are based on tetramethylimidazole. In hydroxide media, a zeolite product with Si/Al=14.8-23.2 is obtained, while in fluoride media an aluminosilicate product with Si/Al up to 82 is synthesized. The material produced in hydroxide media is tested for the hydroisomerization of n-hexane, and results from this test reaction suggest that the effective pore size of zeolites with the IWV framework structure is similar to but slightly larger than that of ZSM-12 (MTW), in fairly good agreement with crystallographic data. PMID:26833857

  18. Densification of salt-occluded zeolite a powders to a leach-resistant monolith

    SciTech Connect

    Lewis, M.A.; Fischer, D.F.; Murhpy, C.D.

    1993-10-01

    Pyrochemical processing of spent fuel from the Integral Fast Reactor (IFR) yields a salt waste of LiCl-KCl that contains approximately 6 wt% fission products, primarily as CsCl and SrCl{sub 2}. Past work has shown that zeolite A will preferentially sorb cesium and strontium and will encapsulate the salt waste in a leach-resistant, radiation-resistant aluminosilicate matrix. However, a method is sill needed to convert the salt-occluded zeolite powders into a form suitable for geologic disposal. We are thus investigating a method that forms bonded zeolite by hot pressing a mixture of glass frit and salt-occluded zeolite powders at 990 K (717{degree}C) and 28 MPa. The leach resistance of the bonded zeolite was measured in static leach tests run for 28 days in 363 K (90{degree}C) deionized water. Normalized release rates of all elements in the bonded zeolite were low, <1 g/m{sup 2} d. Thus, the bonded zeolite may be a suitable waste form for IFR salt waste.

  19. Photochemical generation of electrons and holes in germanium-containing ITQ-17 zeolite.

    PubMed

    Alvaro, Mercedes; Atienzar, Pedro; Corma, Avelino; Ferrer, Belén; Garcia, Hermenegildo; Navarro, Maria T

    2005-03-01

    Laser flash photolysis of germanium-containing ITQ-17 zeolite (Ge/ITQ-17, a single polymorph of beta zeolite) at 266 nm generates a transient spectrum decaying in the sub-millisecond time scale that is compatible with the formation of two transient species. The shorter lived transient (tau approximately 45 micros under nitrogen) has been assigned to trapped electrons due to the characteristic spectroscopic absorption (single band at 480 nm) and its quenching by typical electron scavengers such as N(2)O and CH(2)Cl(2). The second longer lived transient (lambda(max) = 500, 540, and 600 nm; tau approximately 390 micros) is not quenched by O(2) or electron scavengers, but it is quenched by methanol as hole scavenger and has been assigned to positive holes. Also there is a remarkable similarity of the transient spectrum of the Ge/ITQ-17 with the optical spectrum reported previously for electron-hole pairs in ZSM-5 zeolite. Under the same irradiation conditions, photoejection of electrons and photogeneration of positive holes has not been observed for conventional aluminosilicate zeolites, all-silica zeolites, or GeO(2)-impregnated zeolites. Therefore this photochemical behavior has been ascribed to the presence of framework germanium atoms opening the way for photoresponsive zeolites. The ability of Ge/ITQ-17 to generate photochemically electrons and holes has been confirmed by adsorbing naphthalene and propyl viologen sulfonate as electron donor and acceptor, respectively, and observing the generation of the corresponding radical ions. PMID:16851409

  20. Zeolite thin films: from computer chips to space stations.

    PubMed

    Lew, Christopher M; Cai, Rui; Yan, Yushan

    2010-02-16

    Zeolites are a class of crystalline oxides that have uniform and molecular-sized pores (3-12 A in diameter). Although natural zeolites were first discovered in 1756, significant commercial development did not begin until the 1950s when synthetic zeolites with high purity and controlled chemical composition became available. Since then, major commercial applications of zeolites have been limited to catalysis, adsorption, and ion exchange, all using zeolites in powder form. Although researchers have widely investigated zeolite thin films within the last 15 years, most of these studies were motivated by the potential application of these materials as separation membranes and membrane reactors. In the last decade, we have recognized and demonstrated that zeolite thin films can have new, diverse, and economically significant applications that others had not previously considered. In this Account, we highlight our work on the development of zeolite thin films as low-dielectric constant (low-k) insulators for future generation computer chips, environmentally benign corrosion-resistant coatings for aerospace alloys, and hydrophilic and microbiocidal coatings for gravity-independent water separation in space stations. Although these three applications might not seem directly related, they all rely on the ability to fine-tune important macroscopic properties of zeolites by changing their ratio of silicon to aluminum. For example, pure-silica zeolites (PSZs, Si/Al = infinity) are hydrophobic, acid stable, and have no ion exchange capacity, while low-silica zeolites (LSZs, Si/Al < 2) are hydrophilic, acid soluble, and have a high ion exchange capacity. These new thin films also take advantage of some unique properties of zeolites that have not been exploited before, such as a higher elastic modulus, hardness, and heat conductivity than those of amorphous porous silicas, and microbiocidal capabilities derived from their ion exchange capacities. Finally, we briefly discuss our more recent work on polycrystalline zeolite thin films as promising biocompatible coatings and environmentally benign wear-resistant and antifouling coatings. When zeolites are incorporated into polymer thin films in the form of nanocrystals, we also show that the resultant composite membranes can significantly improve the performance of reverse osmosis membranes for sea water desalination and proton exchange membrane fuel cells. These diverse applications of zeolites have the potential to initiate new industries while revolutionizing existing ones with a potential economic impact that could extend into the hundreds of billions of dollars. We have licensed several of these inventions to companies with millions of dollars invested in their commercial development. We expect that other related technologies will be licensed in the near future. PMID:20158246

  1. Association of Indigo with Zeolites for Improved Color Stabilization

    NASA Astrophysics Data System (ADS)

    Dejoie, Catherine; Martinetto, Pauline; Dooryhée, Eric; van Elslande, Elsa; Blanc, Sylvie; Bordat, Patrice; Brown, Ross; Porcher, Florence; Anne, Michel

    2010-10-01

    The durability of an organic colour and its resistance against external chemical agents and exposure to light can be significantly enhanced by hybridizing the natural dye with a mineral. In search for stable natural pigments, the present work focuses on the association of indigo blue with several zeolitic matrices (LTA zeolite, mordenite, MFI zeolite). The manufacturing of the hybrid pigment is tested under varying oxidising conditions, using Raman and UV-visible spectrometric techniques. Blending indigo with MFI is shown to yield the most stable composite in all of our artificial indigo pigments. In absence of defects and substituted cations such as aluminum in the framework of the MFI zeolite matrix, we show that matching the pore size with the dimensions of the guest indigo molecule is the key factor. The evidence for the high colour stability of indigo@MFI opens a new path for modeling the stability of indigo in various alumino-silicate substrates such as in the historical Maya Blue pigment.

  2. The effect of TiO2/aluminosilicate nanocomposite additives on the mechanical and thermal properties of polyacrylic coatings

    NASA Astrophysics Data System (ADS)

    Nosrati, Rahimeh; Olad, Ali

    2015-12-01

    The commercial grade polyacrylic latex was modified in order to prepare a mechanical and thermal improved coating. TiO2/Ag-exchanged-aluminosilicate nanocomposites with montmorillonite, zeolite-A and clinoptilolite aluminosilicates were prepared and used as additive in the matrix of polyacrylic latex to achieve a coating with proper mechanical and thermal properties. X-ray diffraction patterns and FESEM were used to characterize the composition, structure, and morphology of the nanocomposite additives. Polyacrylic coatings modified by TiO2/Ag-exchanged-aluminosilicate nanocomposite additives showed higher adhesion strength and hardness compared to unmodified commercial grade polyacrylic coatings. Differential Scanning Calorimetry (DSC) analysis showed lower glass transition temperature for modified polyacrylic coatings than that of unmodified polyacrylic coatings. The tensile tests were also carried out for unmodified and modified polyacrylic coatings. According to the results, the modified polyacrylic based coating with TiO2/Ag-exchanged-clinoptilolite nanocomposite additive was the best coating considering most of useful properties.

  3. High-Aluminum-Affinity Silica Is a Nanoparticle That Seeds Secondary Aluminosilicate Formation

    PubMed Central

    Jugdaohsingh, Ravin; Brown, Andy; Dietzel, Martin; Powell, Jonathan J.

    2013-01-01

    Despite the importance and abundance of aluminosilicates throughout our natural surroundings, their formation at neutral pH is, surprisingly, a matter of considerable debate. From our experiments in dilute aluminum and silica containing solutions (pH ~ 7) we previously identified a silica polymer with an extraordinarily high affinity for aluminium ions (high-aluminum-affinity silica polymer, HSP). Here, further characterization shows that HSP is a colloid of approximately 2.4 nm in diameter with a mean specific surface area of about 1,000 m2 g-1 and it competes effectively with transferrin for Al(III) binding. Aluminum binding to HSP strongly inhibited its decomposition whilst the reaction rate constant for the formation of the β-silicomolybdic acid complex indicated a diameter between 3.6 and 4.1 nm for these aluminum-containing nanoparticles. Similarly, high resolution microscopic analysis of the air dried aluminum-containing silica colloid solution revealed 3.9 ± 1.3 nm sized crystalline Al-rich silica nanoparticles (ASP) with an estimated Al:Si ratio of between 2 and 3 which is close to the range of secondary aluminosilicates such as imogolite. Thus the high-aluminum-affinity silica polymer is a nanoparticle that seeds early aluminosilicate formation through highly competitive binding of Al(III) ions. In niche environments, especially in vivo, this may serve as an alternative mechanism to polyhydroxy Al(III) species binding monomeric silica to form early phase, non-toxic aluminosilicates. PMID:24349573

  4. Synthesis, characterization, and mercury adsorption properties of hybrid mesoporous aluminosilicate sieve prepared with fly ash

    PubMed Central

    Liu, Minmin; Hou, Li-an; Xi, Beidou; Zhao, Ying; Xia, Xunfeng

    2013-01-01

    A novel hybrid mesoporous aluminosilicate sieve (HMAS) was prepared with fly ash and impregnated with zeolite A precursors. This improved the mercury adsorption of HMAS compared to original MCM-41. The HMAS was characterized by X-ray diffraction (XRD), nitrogen adsorption–desorption, Fourier transform infrared (FTIR) analysis, transmission electron microscopy (TEM) images and 29Si and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra. These showed that the HMAS structure was still retained after impregnated with zeolite A. But the surface area and pore diameter of HMAS decreased due to pore blockage. Adsorption of mercury from aqueous solution was studied on untreated MCM-41and HMAS. The mercury adsorption rate of HMAS was higher than that of origin MCM-41. The adsorption of mercury was investigated on HMAS regarding the pH of mercury solution, initial mercury concentration, and the reaction temperature. The experimental data fit well to Langmuir and Freundlich isotherm models. The Dublin–Radushkevich isotherm and the characterization show that the mercury adsorption on HMAS involved the ion-exchange mechanisms. In addition, the thermodynamic parameters suggest that the adsorption process was endothermic in nature. The adsorption of mercury on HMAS followed the first order kinetics. PMID:23687400

  5. Inorganic-organic composite nanoengineered films using self-assembled monolayers for directed zeolite film growth

    SciTech Connect

    Dye, R.C.; Hermes, R.E.; Martinez, M.G.; Peachey, N.M.

    1997-10-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Zeolites, or molecular sieves, are aluminosilicate cage structures that are typically grown from a heterogeneous mixture of organic template molecules, inorganic salts of alumina and silica, and water. These zeolites are used in industry for catalytic cracking of hydrocarbons (gasoline manufacture from oil), and contaminant removal from chemical production processes. Within one year, we developed a viable method for the deposition of a quaternary ammonium salt amphiphile onto silicon wafer substrates. Using a biomimetic growth process, we were also able to demonstrate the first thin-film formation of a zeolite structure from such an organic template. Additionally, we synthesized the precursor to another amphiphile which was to be for further studies.

  6. Fluorine-19 NMR Study of the Environment of Fluorine in Silicate and Aluminosilicate Oxyfluoride Glasses.

    NASA Astrophysics Data System (ADS)

    Kiczenski, T. J.; Stebbins, J. F.

    2002-12-01

    Using a compilation of F-19 NMR chemical shift values for crystalline model compounds, we have explored the local fluorine environment in several silicate and aluminosilicate oxyfluoride glasses. The F-19 MAS NMR spectrum of the Mg-silicate glass consists of a broad peak centered at -170 ppm, which encompasses the F-Mg(3) environments (where "3" is the number of Mg neighbors) of crystalline MgF2 (-195 ppm) and phlogopite (-175 ppm). The predominant environment in the glass is consequently assigned to F-Mg(n), where "n" indicates an unknown number of nearest neighbors. The magnesium aluminosilicate glass spectra all consist of a major feature at about -175 ppm and a shoulder at approximately -145 ppm. Based on the model compound data, the shoulder lies in the region attributed to Al-F-M2+ sites, and it was observed that glasses with a higher Al/Mg ratio featured extra intensity in the high-frequency shoulder. The shoulder is consequently assigned to Al-F-Mg(n), while the major feature is attributed to F-Mg(n) sites. This indicates that Mg is decidedly more effective in bonding to fluorine than either Ca or Ba in aluminosilicate glasses, following the trend established in our previous work on the Ba- and Ca-aluminosilicate glasses (the higher field strength modifier cation is more effective in competing with Al). Fluorine preferentially bonding with the modifier cation over aluminum has, to our knowledge, never been previously observed in aluminosilicate glasses. Spectra for Na-La-silicate glasses are characterized by an extremely wide peak (hundreds of ppm) and a relatively narrow peak at -220 ppm. The narrow peak at -220 ppm is assigned to F-Na(n) due to its proximity to the chemical shift of F-Na(6) (-225 ppm, from crystalline NaF). The small relative area of the F-Na(n) peak indicates a pronounced preference for F-La bonds over F-Na bonds, which is consistent with the findings of the previously discussed aluminosilicates. The massive, broad feature encapsulates the region described by the mixed fluorine environments of crystalline NaLaF4 (-30 to -63 ppm), and has therefore been assigned to a wide variety of fluorine environments, consisting of F-La bonds in a mixed environment with some number of F-Na bonds. In order to explore La-F clustering we have employed "echo" experiments, which can provide information about F-F distances. In the Na-La-silicates, the broad feature decays much faster than the F-Na(n) peak, indicating a shorter F-F distance in the sites associated with La. This is not consistent with random anion distribution but can be easily explained by the formation of fluorine-rich clusters. This may provide insight into the mechanism for the onset of crystallization in glass ceramics. In the long echo-time experiments on the Na-La-silicate glasses, the intensity of the broad feature was virtually gone, and the intensity of the F-Na(n) peak was largely decreased. This allowed us to clearly observe another peak centered at -140 ppm. This is near the peak found for the Si-F-Na(2) structure (-152 ppm) in the model compounds. Further examination of the original one-pulse spectra revealed the presence of this peak in small quantities in all compositions. Its relative intensity (about 2 percent of the total intensity) is comparable to that of Si-F-Ba(n) and Si-F-Na(n) bonding found in the fluorine containing Ba-silicate and Na-silicate glasses (respectively) from our previous studies. This suggests that Si-F bonding is independent of composition and may be an intrinsic characteristic of fluorine-containing silicate glasses.

  7. Wet gringing of zeolite in stirred media mill

    NASA Astrophysics Data System (ADS)

    Mucsi, G.; Bohács, K.

    2016-04-01

    In the present study the results of systematic experimental series are presented with the specific goal of optimizing the zeolite nanoparticles' production using a wet stirred media mill. The diameter of the grinding media as well as the rotor velocity were varied in the experiments. Particle size distribution and "outer" specific surface area of the ground samples were measured by a laser particle size analyser. Additionally, BET, XRD and FT-IR analyses were performed for the characterization of the "total" specific surface area as well as the crystalline and material structure, respectively. Based on the results of the laboratory experiments it was found that wet stirred media milling provided significant reductions in the particle size of zeolite. Furthermore, the crystallinity of the samples also decreased, so not only the physical but the mineralogical characteristics of zeolite can be controlled by stirred media milling.

  8. Dispersible Exfoliated Zeolite Nanosheets and Their Application as a Selective Membrane

    SciTech Connect

    Varoon, Kumar; Zhang, Xueyi; Elyassi, Bahman; Brewer, Damien D.; Gettel, Melissa; Kumar, Sandeep; Lee, J. Alex; Maheshwari, Sundeep; Mittal, Anudha; Sung, Chun-Yi; Cococcioni, Matteo; Francis, Lorraine F.; McCormick, Alon V.; Mkhoyan, K. Andre; Tsapatsis, Michael

    2011-10-06

    Thin zeolite films are attractive for a wide range of applications, including molecular sieve membranes, catalytic membrane reactors, permeation barriers, and low-dielectric-constant materials. Synthesis of thin zeolite films using high-aspect-ratio zeolite nanosheets is desirable because of the packing and processing advantages of the nanosheets over isotropic zeolite nanoparticles. Attempts to obtain a dispersed suspension of zeolite nanosheets via exfoliation of their lamellar precursors have been hampered because of their structure deterioration and morphological damage (fragmentation, curling, and aggregation). We demonstrated the synthesis and structure determination of highly crystalline nanosheets of zeolite frameworks MWW and MFI. The purity and morphological integrity of these nanosheets allow them to pack well on porous supports, facilitating the fabrication of molecular sieve membranes.

  9. Small-angle neutron scattering studies of the template-mediated crystallization of ZSM-5 type zeolite

    SciTech Connect

    Iton, L.E.; Brun, T.O.; Epperson, J.E. . Materials Science and Technology Div.); Trouw, F. . Intense Pulsed Neutron Source Program); White, J.W.; Henderson, S.J. )

    1988-03-01

    Small-angle neutron scattering is a useful new approach to the study of zeolite crystallization from aluminosilicate gels and the action of template molecules. It has been applied to gels for synthesis of zeolite ZSM-5 using tetrapropylammonium ions as templates where the scattering length densities of the gel particles and their texture were determined using contrast variation methods. Gels formulated from soluble silicate incorporate template molecules promptly into an amorphous embryonic'' structure and crystallization ensues via a solid hydrogel transformation mechanism. Gels formulated from colloidal silica show different scattering behavior, and a liquid phase transport mechanism is inferred. 8 refs., 4 figs., 2 tabs.

  10. Aluminosilicates as controlled molecular environments for selective photochemical and catalytic reactions

    SciTech Connect

    Carrado, K.A.

    1986-01-01

    This dissertation concerns research that involves photochemical, catalytic and spectroscopic studies of clays, pillared clays and zeolites. Incorporation of uranyl ions into hectorite, montmorillonite, bentonite and vermiculite clays was monitored by XRD and luminescence methods. Excitation and emission characteristics were studied in order to understand the behavior of uranyl ions in clays after various thermal treatments. Luminescence lifetime measurements elucidated the number of uranyl sites. Uranyl-exchanged clays were found to absorb light at lower energies (445-455nm) than analogous uranyl-exchanged zeolites (425nm). Each uranyl-exchanged clay was tested as a catalyst for the photoassisted oxidation of isopropyl alcohol. Energy transfer (ET) between uranyl and Eu(III) ions in different zeolite framework systems was examined. The efficiency of ET (eta/sub t/) was found to be affected by the type of framework present. Pillared bentonites were examined in the hydrocracking of decane. A catalytically and spectroscopically active dopant ion, Cr(III), was introduced into the clays in both pillared and unpillared forms depending upon synthetic conditions. EPR and DRS were employed to monitor the environment of Cr(III) for determination of its location - whether in the micropore structure or associated with alumina pillars. Catalytic behavior based upon this variability of location was examined. Incorporation of Cr(III) ions into an alumina pillar was found to increase the stability and activity with respect to an alumina PILC catalyst. The results of these studies suggest that selective, efficient catalysts can be designed around inorganic ions in aluminosilicate supports.

  11. Fly ash from a Mexican mineral coal. II. Source of W zeolite and its effectiveness in arsenic (V) adsorption.

    PubMed

    Medina, Adriana; Gamero, Prócoro; Almanza, José Manuel; Vargas, Alfredo; Montoya, Ascención; Vargas, Gregorio; Izquierdo, María

    2010-09-15

    Coal-fired plants in Coahuila (Mexico) produce highly reactive fly ash (MFA), which is used in a one-step process as a raw material in producing zeolite. We explored two routes in the synthesis of zeolite: (a) direct MFA zeolitization, which resulted in the formation of W zeolite with KOH and analcime with NaOH and (b) a MFA fusion route, which resulted in the formation of zeolite W or chabazite with KOH and zeolite X or P with NaOH. No residual crystalline phases were present. When LiOH was employed, ABW zeolite with quartz and mullite were obtained. For both zeolitization routes, the nature of the alkali (KOH, NaOH, LiOH), the alkali/MFA ratio (0.23-1.46), and the crystallization temperature and time (90-175 degrees C; 8-24 h) were evaluated. Additionally, the effect of temperature and time on MFA fusion was studied. W zeolite was obtained by both zeolitization methods. The direct route is preferred because it is a straightforward method using soft reaction conditions that results in a high yield of low cost zeolites with large crystal agglomerates. It was demonstrated that aluminum modified W zeolite has the ability to remove 99% of the arsenic (V) from an aqueous solution of Na(2)HAsO(4).7H(2)O originally containing 740 ppb. PMID:20537461

  12. Synthesis, characterization and reactivity of transition-metal-containing zeolites

    SciTech Connect

    Rossin, J.A.

    1986-01-01

    Transition metal containing zeolites (zeolite A and ZSM-5) were prepared by addition of various transition metal containing substrates to zeolite synthesis gels. Crystal growth data were recorded in order to determine the influence of the transition metal species on the rate of crystal growth. X-ray diffraction, oxygen adsorption, FTIR and SEM were utilized to evaluate crystal purity. X-ray photoelectron spectroscopy (XPS), chemical analysis and electron microprobe analysis were performed in order to ascertain the position (intrazeolitic versus surface) and homogeneity of the transition metal. It was concluded that intrazeolitic transition metals are produced by the novel procedure presented in this work. 1-Hexane hydroformylation by rhodium zeolite A showed intrazeolitic rhodium to migrate to the external surface of the zeolite. However, in the presence of a solution and surface rhodium poison, intrazeolitic rhodium was found to hydroformylate 1-hexene exclusively to heptanal. Ruthenium containing zeolite A was evaluated under CO-hydrogenation conditions. No migration of intrazeolitic ruthenium to the external surface of the zeolite was observed over the course of the reaction. The product distribution obtained for this catalyst did not follow a log normal behavior. Also, loss of zeolite crystallinity was observed following the reaction. Cobalt ZSM-5 was evaluated under CO-hydrogenation conditions. No migration of cobalt to the external surface of the zeolite occurred. XPS analysis of the catalyst following various stages of the reaction indicated that intrazeolitic cobalt was not reduced to the zero valent state. Consequently, the non-zero valent cobalt was not capable of hydrogenating carbon monoxide.

  13. On the potential of positron lifetime spectroscopy for the study of early stages of zeolites formation from their amorphous precursors

    NASA Astrophysics Data System (ADS)

    Bosnar, S.; Kosanović, C.; Subotić, B.; Bosnar, D.; Kajcsos, Zs.; Liszkay, L.; Lohonyai, L.; Molnár, B.; Lázár, K.

    2007-02-01

    The applicability of positron lifetime (LT) spectroscopy to the study of progress of formation of Secondary Building Units (SBU) in gels yielding in FAU and LTA type zeolites was investigated. Samples were prepared from aluminosilicate gels with various degrees of local structural order. LT measurements were performed at room temperature in air and in vacuum. Coexistence of annihilation modi with long lifetime components was shown; a correlation with precursors of nucleation and type of exchanged ions was also indicated.

  14. Diagram of Zeolite Crystals

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Center for Advanced Microgravity Materials Processing (CAMMP) in Cambridge, MA, a NASA-sponsored Commercial Space Center, is working to improve zeolite materials for storing hydrogen fuel. CAMMP is also applying zeolites to detergents, optical cables, gas and vapor detection for environmental monitoring and control, and chemical production techniques that significantly reduce by-products that are hazardous to the environment. Depicted here is one of the many here complex geometric shapes which make them highly absorbent. Zeolite experiments have also been conducted aboard the International Space Station

  15. Zeolites: Exploring Molecular Channels

    SciTech Connect

    Arslan, Ilke; Derewinski, Mirek

    2015-05-22

    Synthetic zeolites contain microscopic channels, sort of like a sponge. They have many uses, such as helping laundry detergent lather, absorbing liquid in kitty litter, and as catalysts to produce fuel. Of the hundreds of types of zeolites, only about 15 are used for catalysis. PNNL catalysis scientists Ilke Arslan and Mirek Derewinksi are studying these zeolites to understand what make them special. By exploring the mystery of these microscopic channels, their fundamental findings will help design better catalysts for applications such as biofuel production.

  16. Technetium (VII) Co-precipitation with Framework Aluminosilicates

    SciTech Connect

    Harsh, James B.; Dickson, Johnbull Otah; Pierce, Eric M.; Bargar, John

    2015-07-13

    Technetium-99 (99Tc), a long-lived radionuclide, is one of the most widespread contaminants within the Hanford subsurface. At some depths, it is only extractable with strong acids, suggesting incorporation into a solid phase. We hypothesized that Tc may have coprecipitated with feldspathoid aluminosilicates under waste tanks that had leaked caustic solutions into the vadose zone. Our objectives were to determine if Tc could be incorporated into the feldspathoids cancrinite and sodalite and under what conditions coprecipitation could occur. Our hypothesis was that sodalite was more likely to incorporate and retain Tc. Our approach was to use known methods of feldspathoid formation in solutions resembling those in Hanford waste tanks contacting sediments in terms of major ion (Na, NO3, OH, Al(OH)4, and Si(OH)4 concentrations. In some cases, Al and Si were supplied from zeolite. We used perrhenate (ReO4) as a surrogate for pertechnetate (TcO4) to avoid the radioactivity. The major findings of this study were 1) ReO4 could be incorporated into either sodalite or cancrinite but the concentration in the solid was < 1% of the competing ion Cl, NO3, or NO2. 2) The small amount of ReO4 incorporated was not exchangeable with NO3 or NO2. 3) In sodalite, NO3 was highly preferred over ReO4 but significant Re-sodalite was formed when the mole fraction in solution (Re/Re+N) exceeded 0.8. 4) A nonlinear relation between the unit cell parameter and amount of Re incorporated suggested that a separate Re-sodalite phase was formed rather than a solid solution. 5) We determined that sodalite preference for sodalite in the presence of different anions increased with the ionic size of the competing anion: Cl < CO3 < NO3 < SO4 < MnO4 < WO4 and significant incorporation did not occur unless the difference in anion radii was less than 12%. 6) Re(VII) was not significantly reduced to Re(IV) under the conditions of this experiment and Re appeared to be a good surrogate for Tc under oxidizing conditions as both oxyanions have the same size. In conclusion, incorporation of TcO4 is unlikely in the close proximity to the tanks where sodalite is likely to form in the presence of high NO3 and other anions much smaller than TcO4.

  17. Composite zeolite membranes

    DOEpatents

    Nenoff, Tina M.; Thoma, Steven G.; Ashley, Carol S.; Reed, Scott T.

    2002-01-01

    A new class of composite zeolite membranes and synthesis techniques therefor has been invented. These membranes are essentially defect-free, and exhibit large levels of transmembrane flux and of chemical and isotopic selectivity.

  18. ZEOLITE CHARACTERIZATION TESTING

    SciTech Connect

    Jacobs, W; Herbert Nigg, H

    2007-09-13

    The Savannah River Site isolates tritium from its process streams for eventual recycling. This is done by catalyzing the formation of tritiated water (from process streams) and then sorbing that water on a 3A zeolite (molsieve) bed. The tritium is recovered by regenerating the saturated bed into a Mg-based water cracking unit. The process described has been in use for about 15 years. Recently chloride stress corrosion cracking (SCC) was noted in the system piping. This has resulted in the need to replace the corroded piping and associated molecular sieve beds. The source of chlorine has been debated and one possible source is the zeolite itself. Since new materials are being purchased for recently fabricated beds, a more comprehensive analysis protocol for characterizing zeolite has been developed. Tests on archived samples indicate the potential for mobile chloride species to be generated in the zeolite beds.

  19. Flexibility of zeolite frameworks

    NASA Astrophysics Data System (ADS)

    Kapko, Vitaliy; Treacy, Michael; Thorpe, Michael

    2009-03-01

    Zeolites are an important class of industrial catalysts because of their large internal surfaces and molecular-sieving properties. Recent geometric simulations (1) show that almost all of the known zeolites can exist without distortion of their tetrahedra within some range of densities, which we call the flexibility window. Within this window, the framework accommodates density changes by rotations about the shared tetrahedral corners. We argue that the presence of a flexibility window can be used as a topological criterion to select potential candidates for synthesis from millions of hypothetical structures. We also investigate the exceptions to the rule, as well as the shape of the flexibility window and the symmetric properties of zeolites inside it. (1) A. Sartbaeva, S.A. Wells, M.M.J. Treacy and M.F. Thorpe The flexibility window in zeolites, Nature Materials 5, 962-965 (2006); I. Rivin, commentary 931-932.

  20. Stability and thermal transformation studies of Zn2+- and Fe2+- loaded zeolite Y prepared from Egyptian kaolin

    NASA Astrophysics Data System (ADS)

    EL-Mekkawi, Doaa M.; Ibrahim, Fatma A.; Selim, Mohamed M.

    2015-10-01

    The stability and thermal transformation of Zn2+ and Fe2+- zeolites based kaolin were studied with respect to their loading experimental conditions. Zeolite Y prepared from Egyptian kaolin was used in our investigations. Zeolite shows different degrees of framework stability according to the type of cation and the loading experimental conditions. The obtained data indicate the predominance of adsorption and ion exchange mechanisms during Fe2+ and Zn2+ loading, respectively. The loading experimental conditions also greatly affect the solid-solid interactions of transition metal-zeolites at elevated temperatures. ZnAl2O4 and silica phases were formed upon thermal treatment of Zn-Y zeolites. The ratio of ZnAl2O4 to silica phases increases as the amount of loaded Zn2+ increases in the corresponding unheated zeolites. However, nepheline phase was obtained upon heating Fe-Y zeolites loaded at low initial Fe2+ concentrations. Upon increasing of loaded Fe2+, iron oxide beside other amorphous phases from silica, alumina and/or aluminosilicates were obtained.

  1. Heat capacity of magnesium aluminosilicate melts

    NASA Astrophysics Data System (ADS)

    Courtial, Philippe; Richet, Pascal

    1993-03-01

    The heat capacities of six melts of the system MgO-Al 2O 3-SiO 2 have been determined from drop calorimetry measurements made between 900 and 1800 K. These and previously published data show that within the glass-forming region of this system the heat capacity is a linear function of composition. The partial molar heat capacities of SiO 2 and MgO are temperature independent and equal to the values obtained previously for Al-free melts, whereas that of Al 2O 3 increases with temperature and is consistent with the heat capacity of pure alumina liquid. Although melts of the system MgO-Al 2O 3-SiO 2 behave as ideal solutions with respect to the heat capacity, available measurements for other liquids show that this conclusion is not generally valid for aluminosilicates. Some thermochemical and structural implications of this behavior are also discussed.

  2. Characterization of Uranium Solids Precipitated with Aluminosilicates

    SciTech Connect

    DUFF, MC

    2004-04-29

    At the Savannah River Site (SRS), the High-Level Waste (HLW) Tank Farms store and process high-level liquid radioactive wastes from the Canyons and recycle water from the Defense Waste Processing Facility. The waste is concentrated using evaporators to minimize the volume of space required for HLW storage. Recently, the 2H Evaporator was shutdown due to the crystallization of sodium aluminosilicate (NAS) solids (such as cancrinite and sodalite) that contained close to 10 weight percent of elementally-enriched uranium (U). Prior to extensive cleaning,the evaporator deposits resided on the evaporator walls and other exposed internal surfaces within the evaporator pot. Our goal is to support the basis for the continued safe operation of SRS evaporators and to gain more information that could be used to help mitigate U accumulation during evaporator operation.

  3. Hierarchical zeolites from class F coal fly ash

    NASA Astrophysics Data System (ADS)

    Chitta, Pallavi

    Fly ash, a coal combustion byproduct is classified as types class C and class F. Class C fly ash is traditionally recycled for concrete applications and Class F fly ash often disposed in landfills. Class F poses an environmental hazard due to disposal and leaching of heavy metals into ground water and is important to be recycled in order to mitigate the environmental challenges. A major recycling option is to reuse the fly ash as a low-cost raw material for the production of crystalline zeolites, which serve as catalysts, detergents and adsorbents in the chemical industry. Most of the prior literature of fly ash conversion to zeolites does not focus on creating high zeolite surface area zeolites specifically with hierarchical pore structure, which are very important properties in developing a heterogeneous catalyst for catalysis applications. This research work aids in the development of an economical process for the synthesis of high surface area hierarchical zeolites from class F coal fly ash. In this work, synthesis of zeolites from fly ash using classic hydrothermal treatment approach and fusion pretreatment approach were examined. The fusion pretreatment method led to higher extent of dissolution of silica from quartz and mullite phases, which in turn led to higher surface area and pore size of the zeolite. A qualitative kinetic model developed here attributes the difference in silica content to Si/Al ratio of the beginning fraction of fly ash. At near ambient crystallization temperatures and longer crystallization times, the zeolite formed is a hierarchical faujasite with high surface area of at least 360 m2/g. This work enables the large scale recycling of class F coal fly ash to produce zeolites and mitigate environmental concerns. Design of experiments was used to predict surface area and pore sizes of zeolites - thus obviating the need for intense experimentation. The hierarchical zeolite catalyst supports tested for CO2 conversion, yielded hydrocarbons up to C9, a performance attesting the hierarchal pore structure. The preliminary techno-economic feasibility assessment demonstrates a net energy saving of 75% and cost saving of 63% compared to the commercial zeolite manufacturing process.

  4. Sustainable synthesis of zeolites without addition of both organotemplates and solvents.

    PubMed

    Wu, Qinming; Wang, Xiong; Qi, Guodong; Guo, Qiang; Pan, Shuxiang; Meng, Xiangju; Xu, Jun; Deng, Feng; Fan, Fengtao; Feng, Zhaochi; Li, Can; Maurer, Stefan; Mller, Ulrich; Xiao, Feng-Shou

    2014-03-12

    The development of sustainable and environmentally friendly techniques for synthesizing zeolites has attracted much attention, as the use of organic templates and solvents in the hydrothermal synthesis of zeolites is a major obstacle for realizing green and sustainable synthesis ways. Recently, the introduction of the organotemplate-free synthesis method allowed avoiding the use of organic templates, but water as solvent was still required; solvent-free routes on the other hand beared the potential to significantly reduce the amount of polluted wastewater, but organic templates were still present. In this work, we have demonstrated a combined strategy of both organotemplate- and solvent-free conditions to synthesize aluminosilicate zeolites Beta and ZSM-5 (S-Beta and S-ZSM-5), two of the most important zeolites relevant for industry. The samples are thoroughly characterized by XRD patterns, SEM images, N2 sorption isotherms, UV-Raman spectra, and (29)Si and (27)Al MAS NMR spectra. The results demonstrate that S-Beta and S-ZSM-5 zeolites exhibit almost the same textural parameters (e.g., BET surface area and pore volume) and catalytic performance in cumene cracking and m-xylene isomerization as those of conventional Beta and ZSM-5 zeolites synthesized under hydrothermal conditions (C-Beta and C-ZSM-5). The organotemplate- and solvent-free syntheses of S-Beta and S-ZSM-5 take place at a low-pressure regime and are free of harmful gases as well as give high product yields together with highly efficient consumption of the starting raw materials. These advantages plus the very simple procedures opened the pathway to a highly sustainable zeolite synthesis protocol compared to conventional methods currently employed for C-Beta and C-ZSM-5. Very interestingly, this simple synthesis is a good model for understanding zeolite crystallization. The detail characterizations indicate that the S-Beta crystals are formed from the assembly of zeolite building units, mainly 4MRs, while the 5MRs in the framework are just formed in the crystallization of S-ZSM-5, rather than existence in the starting solid mixture. During the crystallization processes, small traces of water play an important role for the hydrolysis and condensation of silica and/or aluminosilicate species. PMID:24552214

  5. Role of ammonium fluoride in crystallization process of beta zeolite

    NASA Astrophysics Data System (ADS)

    Jon, Hery; Oumi, Yasunori; Itabashi, Keiji; Sano, Tsuneji

    2007-09-01

    The addition of Na + cations to the starting gel prepared using NH 4F significantly prolonged the crystallization time of beta zeolite. However, in the case of pure silica beta zeolite an addition of more NH 4F reduced the crystallization time by one-half. From 29Si MAS NMR measurements, the signal attributed to pentacoordinated silicon was found to be more pronounced for pure silica beta zeolite in the presence of Na + cations even in the solid phase with low crystallinity, as compared to that in the absence of Na + cations. Considering the results of theoretical calculation, because of more energetically stable state of Na +[SiO 4/2F] - species, it could be presumed that Na +[SiO 4/2F] - species might exist in pure silica beta zeolite. Furthermore, as confirmed by 19F MAS NMR measurements tetraethylammonium fluoride (TEAF) species were enclathrated intact in solid phase during the initial crystallization stage. This suggests that TEAF species are required for the formation of beta zeolite framework, in other words, as "SDA" which conditions the formation of kinetically favored phase, i.e., beta zeolite. Moreover, since part of TEA + cations is replaced by sodium cations, forming Na +[SiO 4/2F] - species, the amount of TEA +[SiO 4/2F] - species involved in either nucleation or crystal growth decreases and thus the crystallization time becomes longer.

  6. Preparation of functionalized zeolitic frameworks

    DOEpatents

    Yaghi, Omar M; Furukawa, Hiroyasu; Wang, Bo

    2013-07-09

    The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

  7. Preparation of functionalized zeolitic frameworks

    DOEpatents

    Yaghi, Omar M.; Hayashi, Hideki; Banerjee, Rahul; Park, Kyo Sung; Wang, Bo; Cote, Adrien P.

    2014-08-19

    The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

  8. Preparation of functionalized zeolitic frameworks

    DOEpatents

    Yaghi, Omar M; Hayashi, Hideki; Banerjee, Rahul; Park, Kyo Sung; Wang, Bo; Cote, Adrien P

    2012-11-20

    The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

  9. Structural analysis of hierarchically organized zeolites

    PubMed Central

    Mitchell, Sharon; Pinar, Ana B.; Kenvin, Jeffrey; Crivelli, Paolo; Kärger, Jörg; Pérez-Ramírez, Javier

    2015-01-01

    Advances in materials synthesis bring about many opportunities for technological applications, but are often accompanied by unprecedented complexity. This is clearly illustrated by the case of hierarchically organized zeolite catalysts, a class of crystalline microporous solids that has been revolutionized by the engineering of multilevel pore architectures, which combine unique chemical functionality with efficient molecular transport. Three key attributes, the crystal, the pore and the active site structure, can be expected to dominate the design process. This review examines the adequacy of the palette of techniques applied to characterize these distinguishing features and their catalytic impact. PMID:26482337

  10. Structural analysis of hierarchically organized zeolites

    NASA Astrophysics Data System (ADS)

    Mitchell, Sharon; Pinar, Ana B.; Kenvin, Jeffrey; Crivelli, Paolo; Kärger, Jörg; Pérez-Ramírez, Javier

    2015-10-01

    Advances in materials synthesis bring about many opportunities for technological applications, but are often accompanied by unprecedented complexity. This is clearly illustrated by the case of hierarchically organized zeolite catalysts, a class of crystalline microporous solids that has been revolutionized by the engineering of multilevel pore architectures, which combine unique chemical functionality with efficient molecular transport. Three key attributes, the crystal, the pore and the active site structure, can be expected to dominate the design process. This review examines the adequacy of the palette of techniques applied to characterize these distinguishing features and their catalytic impact.

  11. IMPROVED CATALYSTS FOR HEAVY OIL UPGRADING BASED ON ZEOLITE Y NANOPARTICLES ENCAPSULATED IN STABLE NANOPOROUS HOSTS

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2004-06-30

    The focus of this project is to improve the catalytic performance of zeolite Y for heavy petroleum hydrocracking by synthesizing nanoparticles of the zeolite ({approx}20-30 nm) inside nanoporous silicate or aluminosilicate hosts of similar pore diameters. The encapsulated zeolite nanoparticles are expected to possess pores of reduced diffusional path lengths, hence hydrocarbon substrates will diffuse in, are converted and the products quickly diffused out. This is expected to prevent over-reaction, hence minimizing pore blockage and active sites deactivation. In this phase of the project, research activities were focused on refining procedures to: (a) improve the synthesis of ordered, high surface area nanoporous silica, such as SBA-15, with expanded pore size using trimethylbenzene as additive to the parent SBA-15 synthesis mixture; and (b) reduce the particle size of zeolite Y such that they can be effectively incorporated into the nanoporous silicas. The synthesis of high surface ordered nanoporous silica containing enlarged pores of diameter of 25 nm (larger than the standard size of 8.4 nm) using trimethylbenzene as a pore size expander was accomplished. The synthesis of zeolite Y nanoparticles with median pore size of approximately 50 nm (smaller than the 80 nm typically obtained with TMAOH) using combined TMABr/TMAOH as organic additives was also accomplished.

  12. IMPROVED CATALYSTS FOR HEAVY OIL UPGRADING BASED ON ZEOLITE Y NANOPARTICLES ENCAPSULATED IN STABLE NANOPOROUS HOSTS

    SciTech Connect

    Conrad Ingram

    2003-09-03

    The focus of this project is to improve the catalytic performance of zeolite Y for petroleum hydrocracking by synthesizing nanoparticles of the zeolite ({approx}20-25 nm) inside nanoporous silicate or aluminosilicate hosts. The encapsulated zeolite nanoparticles are expected to possess reduced diffusional path lengths, hence hydrocarbon substrates will diffuse in, are converted and the products quickly diffused out. This is expected to prevent over-reaction and the blocking of the zeolite pores and active sites will be minimized. In this phase of the project, procedures for the synthesis of ordered nanoporous silica, such as SBA-15, using block copolymers and nonionic surfactant were successful reproduced. Expansion of the pores sizes of the nanoporous silica using trimethylbenzene is suggested based on shift in the major X-Ray Diffraction peak in the products to lower 2 angles compared with the parent SBA-15 material. The synthesis of ordered nanoporous materials with aluminum incorporated in the predominantly silicate framework was attempted but is not yet successful, and the procedures needs will be repeated and modified as necessary. Nanoparticles of zeolite Y of particle sizes in the range 40 nm to 120 nm were synthesized in the presence of TMAOH as the particle size controlling additive.

  13. Synthesis of zeolite Li-ABW from fly ash by fusion method.

    PubMed

    Yao, Z T; Xia, M S; Ye, Y; Zhang, L

    2009-10-30

    The zeolite Li-ABW was synthesized by fusion method using fly ash as raw material. It comprised alkaline fusion followed by hydrothermal treatment in LiOH x H2O medium. Crystallinity of zeolite as high as 97.8% was attained under the following conditions: LiOH x H2O concentration, 3M; hydrothermal temperature, 180 degrees C; the corresponding aging time, 12 h. The content of Li-ABW increased at the expense of lithium aluminum silicate or quartz with an increase of LiOH x H2O concentration. With increasing hydrothermal temperature and aging time, the soluble species re-crystallized and crystalline phase transformation between different zeolites was observed. Scanning electron microscopy (SEM) observation revealed that the obtained zeolite Li-ABW was a rod-like crystal. The pore size distribution curve indicated the presence of mesopores. PMID:19493616

  14. Investigation of aluminosilicate refractory for solid oxide fuel cell applications

    NASA Astrophysics Data System (ADS)

    Gentile, Paul Steven

    Stationary solid oxide fuel cells (SOFCs) have been demonstrated to provide clean and reliable electricity through electro-chemical conversion of various fuel sources (CH4 and other light hydrocarbons). To become a competitive conversion technology the costs of SOFCs must be reduced to less than $400/kW. Aluminosilicate represents a potential low cost alternative to high purity alumina for SOFC refractory applications. The objectives of this investigation are to: (1) study changes of aluminosilicate chemistry and morphology under SOFC conditions, (2) identify volatile silicon species released by aluminosilicates, (3) identify the mechanisms of aluminosilicate vapor deposition on SOFC materials, and (4) determine the effects of aluminosilicate vapors on SOFC electrochemical performance. It is shown thermodynamically and empirically that low cost aluminosilicate refractory remains chemically and thermally unstable under SOFC operating conditions between 800°C and 1000°C. Energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) of the aluminosilicate bulk and surface identified increased concentrations of silicon at the surface after exposure to SOFC gases at 1000°C for 100 hours. The presence of water vapor accelerated surface diffusion of silicon, creating a more uniform distribution. Thermodynamic equilibrium modeling showed aluminosilicate remains stable in dry air, but the introduction of water vapor indicative of actual SOFC gas streams creates low temperature (<1000°C) silicon instability due to the release of Si(OH)4 and SiO(OH) 2. Thermal gravimetric analysis and transpiration studies identified a discrete drop in the rate of silicon volatility before reaching steady state conditions after 100-200 hours. Electron microscopy observed the preferential deposition of vapors released from aluminosilicate on yttria stabilized zirconia (YSZ) over nickel. The adsorbent consisted of alumina rich clusters enclosed in an amorphous siliceous layer. Silicon penetrated the YSZ along grain boundaries, isolating grains in an insulating glassy phase. XPS did not detect spectra shifts or peak broadening associated with formation of new Si-Zr-Y-O phases. SOFC electrochemical performance testing at 800-1000°C attributed rapid degradation (0.1% per hour) of cells exposed to aluminosilicate vapors in the fuel stream predominately to ohmic polarization. EDS identified silicon concentrations above impurity levels at the electrolyte/active anode interface.

  15. Zeolite-Dye Microlasers

    NASA Astrophysics Data System (ADS)

    Vietze, U.; Krauß, O.; Laeri, F.; Ihlein, G.; Schüth, F.; Limburg, B.; Abraham, M.

    1998-11-01

    We present a new class of micro lasers based on nanoporous molecular sieve host-guest systems. Organic dye guest molecules of 1-ethyl-4-[4-( p-dimethylaminophenyl)-1,3-butadienyl]-pyridinium Perchlorat were inserted into the 0.73-nm-wide channel pores of a zeolite AlPO 4-5 host. The zeolitic microcrystal compounds were hydrothermally synthesized according to a particular host-guest chemical process. The dye molecules are found not only to be aligned along the host channel axis, but to be oriented as well. Single mode laser emission at 687 nm was obtained from a whispering gallery mode oscillating in a 8-μm-diameter monolithic microresonator, in which the field is confined by total internal reflection at the natural hexagonal boundaries inside the zeolitic microcrystals.

  16. Differences in Al distribution and acidic properties between RTH-type zeolites synthesized with OSDAs and without OSDAs.

    PubMed

    Liu, Ming; Yokoi, Toshiyuki; Yoshioka, Masato; Imai, Hiroyuki; Kondo, Junko N; Tatsumi, Takashi

    2014-03-01

    In addition to the original preparation route of the RTH-type zeolites using 1,2,2,6,6-pentamethylpiperidine (PMP) as an organic structure directing agent (OSDA), we have found that simpler organic amines such as N-methylpiperidine and pyridine can be used as alternative OSDAs in place of PMP. Furthermore, we have established a synthesis method for preparing the RTH-type zeolites without using any OSDAs. In this study, RTH-type aluminosilicates were synthesized with different types of OSDA or without using any OSDAs. The obtained zeolites synthesized with different preparation methods were characterized by using various techniques, especially high-resolution (27)Al MAS NMR and in situ FT-IR techniques using CO adsorption. The relationship between the preparation method and the catalytic performance in the methanol to olefins (MTO) reaction was discussed. Finally, the distribution of Al species in the RTH-framework was clarified. PMID:24451998

  17. Effect of temperature and aluminium on calcium (alumino)silicate hydrate chemistry under equilibrium conditions

    SciTech Connect

    Myers, Rupert J.; L'Hôpital, Emilie; Provis, John L.; Lothenbach, Barbara

    2015-02-15

    There exists limited information regarding the effect of temperature on the structure and solubility of calcium aluminosilicate hydrate (C–A–S–H). Here, calcium (alumino)silicate hydrate (C–(A–)S–H) is synthesised at Ca/Si = 1, Al/Si ≤ 0.15 and equilibrated at 7–80 °C. These systems increase in phase-purity, long-range order, and degree of polymerisation of C–(A–)S–H chains at higher temperatures; the most highly polymerised, crystalline and cross-linked C–(A–)S–H product is formed at Al/Si = 0.1 and 80 °C. Solubility products for C–(A–)S–H were calculated via determination of the solid-phase compositions and measurements of the concentrations of dissolved species in contact with the solid products, and show that the solubilities of C–(A–)S–H change slightly, within the experimental uncertainty, as a function of Al/Si ratio and temperature between 7 °C and 80 °C. These results are important in the development of thermodynamic models for C–(A–)S–H to enable accurate thermodynamic modelling of cement-based materials.

  18. Catalytic Fast Pyrolysis of Lignin over High-Surface-Area Mesoporous Aluminosilicates: Effect of Porosity and Acidity.

    PubMed

    Custodis, Victoria B F; Karakoulia, Stamatia A; Triantafyllidis, Kostas S; van Bokhoven, Jeroen A

    2016-05-23

    Catalytic fast pyrolysis (CFP) of lignin with amorphous mesoporous aluminosilicates catalysts yields a high fraction of aromatics and a relatively low amount of char/coke. The relationship between the acidity and porosity of Al-MCM-41, Al-SBA-15, and Al-MSU-J with product selectivity during lignin CFP is determined. The acid sites (mild Brønsted and stronger Lewis) are able to catalyze pyrolysis intermediates towards fewer oxygenated phenols and aromatic hydrocarbons. A generalized correlation of the product selectivity and yield with the aluminum content and acidity of the mesoporous aluminosilicates is hard to establish. Zeolitic strong acid sites are not required to achieve high conversion and selectivity to aromatic hydrocarbon because nanosized MCM-41 produces a high liquid yield and selectivity. The two most essential parameters are diffusion, which is influenced by pore and grain size, and the active site, which may be mildly acidic, but is dominated by Lewis acid sites. Nanosized grains and mild acidity are essential ingredients for a good lignin CFP catalyst. PMID:27079742

  19. Coating of silica sand with aluminosilicate clay.

    PubMed

    Jerez, Jorge; Flury, Markus; Shang, Jianying; Deng, Youjun

    2006-02-01

    The objective of this work was to coat aluminosilicate clays on an inert silica support, and to characterize the properties and stability of the clay-silica coating. Two polymers, polyacrylamide (PAM) and polyvinyl alcohol (PVA), were used to bind kaolinite, illite, and smectite onto silica grains. The clay-polymer composites were studied by X-ray diffraction, FTIR, and electrophoretic mobility. Clay coatings on silica grains were characterized by mass coverage, scanning electron microscopy, specific surface area, and pH stability. Silica sand was successfully coated with clays by using the two polymers, but with PVA, the clay coating had a greater mass coverage and was more stable against pH variations. Less polymer was needed for the clay coating using PVA as compared to using PAM. Clay-polymer complexes and pure clay minerals had similar cation exchange capacities and electrophoretic mobilities, indicating that overall surface charge of the clays was little affected by the polymers. Some decrease in hydrophilicity was observed for illite and smectite when clays where coated with the polymers. The methodology reported here allows the generation of a clay-based porous matrix, with hydraulic properties that can be varied by adjusting the grain size of the inert silica support. PMID:16085082

  20. Uranium Sorption on Sodium Aluminosilicates and Gibbsite

    SciTech Connect

    Duff, M.C.

    2003-02-11

    At the Savannah River Site (SRS), the High-Level Waste (HLW) Tank Farms store and process high-level liquid radioactive wastes from the Canyons and recycle water from the Defense Waste Processing Facility (DWPF). The waste is concentrated using evaporators to minimize the volume of space required for HLW storage. After evaporation, the waste concentrate is transferred to one or more receipt storage tanks. Recently, the 2H Evaporator was shutdown due to the crystallization of sodium aluminosilicates (NAS) solids that contained elementally enriched uranium (U) precipitates. The scale deposits resided on the evaporator walls and other exposed internal surfaces within the evaporator pot. Little is known about U interactions with NAS in HLW solutions. Hence, this research was conducted to improve our basic understanding of one possible mechanism for U accumulation in the evaporators and in other SRS process areas. These studies will help support the basis for the continued safe operation of SRS evaporators and provide information on other issues associated with U behavior in the tank farms. For example, the knowledge of such fundamental information could help mitigate U accumulation during evaporator operation and optimize saltcake dissolution.

  1. Intraframework migration of tetrahedral atoms in a zeolite.

    PubMed

    Shin, Jiho; Ahn, Nak Ho; Camblor, Miguel A; Cho, Sung June; Hong, Suk Bong

    2014-08-18

    The transformation from a disordered into an ordered version of the zeolite natrolite occurs on prolonged heating of this material in the crystallizing medium, but not if the mother liquor is replaced by water or an alkaline solution. This process occurs for both aluminosilicate and gallosilicate analogues of natrolite. In cross experiments, the disordered Al-containing (or Ga-containing) analogue is heated while in contact with the mother liquor of the opposite analogue, that is, the Ga-containing (or Al-containing) liquor. Therefore, strong evidence for the mechanism of the ordering process was obtained, which was thus proposed to proceed by intraframework migration of tetrahedral atoms without diffusion along the pores. Migration is first triggered, then fuelled by surface rearrangement through reactions with the mother liquor, and stops when an almost fully ordered state is attained. Classical dissolution-recrystallization and Ostwald ripening processes do not appear to be relevant for this phase transformation. PMID:24931398

  2. Mimicking high-silica zeolites: highly stable germanium- and tin-rich zeolite-type chalcogenides.

    PubMed

    Lin, Qipu; Bu, Xianhui; Mao, Chengyu; Zhao, Xiang; Sasan, Koroush; Feng, Pingyun

    2015-05-20

    High-silica zeolites, as exemplified by ZSM-5, with excellent chemical and thermal stability, have generated a revolution in industrial catalysis. In contrast, prior to this work, high-silica-zeolite-like chalcogenides based on germanium/tin remained unknown, even after decades of research. Here six crystalline high-germanium or high-tin zeolite-type sulfides and selenides with four different topologies are reported. Their unprecedented framework compositions give these materials much improved thermal and chemical stability with high surface area (Langmuir surface area of 782 m(2)/g(-1)) comparable to or better than zeolites. Among them, highly stable CPM-120-ZnGeS allows for ion exchange with diverse metal or complex cations, resulting in fine-tuning in porosity, fast ion conductivity, and photoelectric response. Being among the most porous crystalline chalcogenides, CPM-120-ZnGeS (exchanged with Cs(+) ions) also shows reversible adsorption with high capacity and affinity for CO2 (98 and 73 cm(3) g(-1) at 273 and 298 K, respectively, isosteric heat of adsorption = 40.05 kJ mol(-1)). Moreover, CPM-120-ZnGeS could also function as a robust photocatalyst for water reduction to generate H2. The overall activity of H2 production from water, in the presence of Na2S-Na2SO3 as a hole scavenger, was 200 ?mol h(-1)/(0.10 g). Such catalytic activity remained undiminished under illumination by UV light for as long as measured (200 h), demonstrating excellent resistance to photocorrosion even under intense UV radiation. PMID:25950820

  3. IMPROVED CATALYSTS FOR HEAVY OIL UPGRADING BASED ON ZEOLITE Y NANOPARTICLES ENCAPSULATED STABLE NANOPOROUS HOST

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2005-03-21

    The objectives of this project are to synthesis nanocrystals of highly acidic zeolite Y, encapsulate them within the channels of mesoporous (nanoporous) silicates or nanoporous organosilicates and evaluate the ''zeolite Y/Nanoporous host'' composites as catalysts for the upgrading of heavy petroleum feedstocks. Our results to date are summarized as follows. The synthesis of high surface ordered nanoporous silica of expanded pore diameter of 25 nm (larger than the standard size of 8.4 nm) using trimethylbenzene as a pore size expander was accomplished. The synthesis of zeolite Y nanoparticles with median pore size of approximately 50 nm (smaller than the 80 nm typically obtained with TMAOH) using combined TMABr/TMAOH as organic additives was also accomplished. The successful synthesis of zeoliteY/Nanoporous host composite materials by sequential combination of zeolite precursors and nanoporous material precursor mixtures was implied based on results from various characterization techniques such as X-Ray diffraction, infrared spectra, thermal analysis, porosimetry data. The resulting materials showed pore sizes up to 11 nm, and infrared band at 570 cm{sup -1} suggesting the presence of both phases. Work in the immediate future will be focused on the following three areas: (1) Further characterization of all-silica and aluminosilicate mesoporous materials with expanded pore sizes up to 30 nm will continue; (2) Research efforts to reduce the average particle size of zeolite nanoparticles down to 35-30 nm will continue; (3) Further synthesis of polymer-SBA15 nanocomposites will be conducted by changing the amount and chemistry of the zeolitic precursors added; and (4) Investigation on the catalytic properties of the materials using probe catalytic reactions (such as cumene cracking), followed by catalytic testing for heavy oil conversion.

  4. Phosphorus promotion and poisoning in zeolite-based materials: synthesis, characterisation and catalysis.

    PubMed

    van der Bij, Hendrik E; Weckhuysen, Bert M

    2015-10-21

    Phosphorus and microporous aluminosilicates, better known as zeolites, have a unique but poorly understood relationship. For example, phosphatation of the industrially important zeolite H-ZSM-5 is a well-known, relatively inexpensive and seemingly straightforward post-synthetic modification applied by the chemical industry not only to alter its hydrothermal stability and acidity, but also to increase its selectivity towards light olefins in hydrocarbon catalysis. On the other hand, phosphorus poisoning of zeolite-based catalysts, which are used for removing nitrogen oxides from exhaust fuels, poses a problem for their use in diesel engine catalysts. Despite the wide impact of phosphorus-zeolite chemistry, the exact physicochemical processes that take place require a more profound understanding. This review article provides the reader with a comprehensive and state-of-the-art overview of the academic literature, from the first reports in the late 1970s until the most recent studies. In the first part an in-depth analysis is undertaken, which will reveal universal physicochemical and structural effects of phosphorus-zeolite chemistry on the framework structure, accessibility, and strength of acid sites. The second part discusses the hydrothermal stability of zeolites and clarifies the promotional role that phosphorus plays. The third part of the review paper links the structural and physicochemical effects of phosphorus on zeolite materials with their catalytic performance in a variety of catalytic processes, including alkylation of aromatics, catalytic cracking, methanol-to-hydrocarbon processing, dehydration of bioalcohol, and ammonia selective catalytic reduction (SCR) of NOx. Based on these insights, we discuss potential applications and important directions for further research. PMID:26051875

  5. Phosphorus promotion and poisoning in zeolite-based materials: synthesis, characterisation and catalysis

    PubMed Central

    van der Bij, Hendrik E.

    2015-01-01

    Phosphorus and microporous aluminosilicates, better known as zeolites, have a unique but poorly understood relationship. For example, phosphatation of the industrially important zeolite H-ZSM-5 is a well-known, relatively inexpensive and seemingly straightforward post-synthetic modification applied by the chemical industry not only to alter its hydrothermal stability and acidity, but also to increase its selectivity towards light olefins in hydrocarbon catalysis. On the other hand, phosphorus poisoning of zeolite-based catalysts, which are used for removing nitrogen oxides from exhaust fuels, poses a problem for their use in diesel engine catalysts. Despite the wide impact of phosphorus–zeolite chemistry, the exact physicochemical processes that take place require a more profound understanding. This review article provides the reader with a comprehensive and state-of-the-art overview of the academic literature, from the first reports in the late 1970s until the most recent studies. In the first part an in-depth analysis is undertaken, which will reveal universal physicochemical and structural effects of phosphorus–zeolite chemistry on the framework structure, accessibility, and strength of acid sites. The second part discusses the hydrothermal stability of zeolites and clarifies the promotional role that phosphorus plays. The third part of the review paper links the structural and physicochemical effects of phosphorus on zeolite materials with their catalytic performance in a variety of catalytic processes, including alkylation of aromatics, catalytic cracking, methanol-to-hydrocarbon processing, dehydration of bioalcohol, and ammonia selective catalytic reduction (SCR) of NOx. Based on these insights, we discuss potential applications and important directions for further research. PMID:26051875

  6. Effect of synthetic conditions on the adsorption properties of the resulting offretite-type zeolite

    NASA Astrophysics Data System (ADS)

    Gorshunova, K. K.; Travkina, O. S.; Kapustin, G. I.; Kustov, L. M.; Pavlov, M. L.; Kutepov, B. I.

    2015-05-01

    The effect of the nature of the silicon-containing component of the reaction mixture and that of the crystallization conditions on characteristics of the resulting offretite-type zeolite powder, including its degree of crystallinity, particle-size distribution, and adsorption properties with respect to toluene, cyclohexane, n-hexane, and water molecules, are considered. The thermal desorption of toluene from cationic forms of the offretite-type zeolite is reported. The K-forms of this zeolite can retain adsorbed toluene up to 300-400°C.

  7. The influence of using Jordanian natural zeolite on the adsorption, physical, and mechanical properties of geopolymers products.

    PubMed

    Yousef, Rushdi Ibrahim; El-Eswed, Bassam; Alshaaer, Mazen; Khalili, Fawwaz; Khoury, Hani

    2009-06-15

    Geopolymers consist of an amorphous, three-dimensional structure resulting from the polymerization of aluminosilicate monomers that result from dissolution of kaolin in an alkaline solution at temperatures around 80 degrees C. One potential use of geopolymers is as Portland cement replacement. It will be of great importance to provide a geopolymer with suitable mechanical properties for the purpose of water storage and high adsorption capacity towards pollutants. The aim of this work is to investigate the effect of using Jordanian zeolitic tuff as filler on the mechanical performance and on the adsorption capacity of the geopolymers products. Jordanian zeolitic tuff is inexpensive and is known to have high adsorption capacity. The results confirmed that this natural zeolitic tuff can be used as a filler of stable geopolymers with high mechanical properties and high adsorption capacity towards methylene blue and Cu(II) ions. The XRD measurements showed that the phillipsite peaks (major mineral constituent of Jordanian zeolite) were disappeared upon geopolymerization. The zeolite-based geopolymers revealed high compressive strength compared to reference geopolymers that employ sand as filler. Adsorption experiments showed that among different geopolymers prepared, the zeolite-based geopolymers have the highest adsorption capacity towards methylene blue and copper(II) ions. PMID:19036505

  8. Synthesis and characterization of zeolites prepared from industrial fly ash.

    PubMed

    Franus, Wojciech; Wdowin, Magdalena; Franus, Małgorzata

    2014-09-01

    In this paper, we present the possibility of using fly ash to produce synthetic zeolites. The synthesis class F fly ash from the Stalowa Wola SA heat and power plant was subjected to 24 h hydrothermal reaction with sodium hydroxide. Depending on the reaction conditions, three types of synthetic zeolites were formed: Na-X (20 g fly ash, 0.5 dm(3) of 3 mol · dm(-3) NaOH, 75 °C), Na-P1 (20 g fly ash, 0.5 dm(3) of 3 mol · dm(-3) NaOH, 95 °C), and sodalite (20 g fly ash, 0.8 dm(3) of 5 mol · dm(-3) NaOH + 0.4 dm(3) of 3 mol · dm(-3) NaCl, 95 °C). As synthesized materials were characterized to obtain mineral composition (X-ray diffractometry, Scanning electron microscopy-energy dispersive spectrometry), adsorption properties (Brunauer-Emmett-Teller surface area, N2 isotherm adsorption/desorption), and ion exchange capacity. The most effective reaction for zeolite preparation was when sodalite was formed and the quantitative content of zeolite from X-ray diffractometry was 90 wt%, compared with 70 wt% for the Na-X and 75 wt% for the Na-P1. Residues from each synthesis reaction were the following: mullite, quartz, and the remains of amorphous aluminosilicate glass. The best zeolitic material as characterized by highest specific surface area was Na-X at almost 166 m(2) · g(-1), while for the Na-P1 and sodalite it was 71 and 33 m(2) · g(-1), respectively. The ion exchange capacity decreased in the following order: Na-X at 1.8 meq · g(-1), Na-P1 at 0.72 meq · g(-1), and sodalite at 0.56 meq · g(-1). The resulting zeolites are competitive for commercially available materials and are used as ion exchangers in industrial wastewater and soil decontamination. PMID:24838802

  9. Synthesis, deposition and characterization of magnesium hydroxide nanostructures on zeolite 4A

    SciTech Connect

    Koh, Pei-Yoong; Yan, Jing; Ward, Jason; Koros, William J.; Teja, Amyn S.; Xu, Bo

    2011-03-15

    Research highlights: {yields} Reports a simple precipitation-growth method to produce nanostructures of Mg(OH){sub 2} on the surface of zeolite 4A. {yields} Able to control the growth of the nanostructures by manipulating the experimental procedure. {yields} Able to deposit Mg(OH){sub 2} onto specific sites namely bridging hydroxyl protons (SiOHAl) on the surface of zeolite 4A. -- Abstract: The precipitation and self-assembly of magnesium hydroxide Mg(OH){sub 2} nanopetals on dispersed zeolite 4A particles was investigated. Mg(OH){sub 2}/zeolite nanocomposites were produced from magnesium chloride solutions and characterized via X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Fourier transform infrared analysis (FTIR), and solid state NMR. It was determined that Mg(OH){sub 2} interacted with bridging hydroxyl protons (SiOHAl) on the zeolite surface, but not with silanol or aluminol groups. NMR analysis showed that 13% of the tetrahedral Al sites on the zeolite were converted to octahedral Al. The zeolite structure and crystallinity remained intact after treatment, and no dealumination reactions were detected. This suggests that the deposition-precipitation process at ambient conditions is a facile method for controlling Mg(OH){sub 2} nanostructures on zeolites.

  10. Applications of high resolution NMR to geochemistry: crystalline, glass, and molten silicates

    SciTech Connect

    Schneider, E.

    1985-11-01

    The nuclear spin interactions and the associated quantum mechanical dynamics which are present in solid state NMR are introduced. A brief overview of aluminosilicate structure is presented and crystalline structure is then reviewed, with emphasis on the contributions made by /sup 29/Si NMR spectroscopy. The local structure of glass aluminosilicates as observed by NMR, is presented with analysis of the information content of /sup 29/Si spectra. A high-temperature (to 1300/sup 0/C) NMR spectroscopic investigation of the local environment and dynamics of molecular motion in molten aluminosilicates is described. A comparison is made of silicate liquid, glass, and crystalline local structure. The atomic and molecular motions present in a melt are investigated through relaxation time (T/sub 1/ and T/sub 2/) measurements as a function of composition and temperature for /sup 23/Na and /sup 29/Si.

  11. Microstructural and phase evolution in metakaolin geopolymers with different activators and added aluminosilicate fillers

    NASA Astrophysics Data System (ADS)

    Sarkar, Madhuchhanda; Dana, Kausik; Das, Sukhen

    2015-10-01

    This work aims to investigate the microstructural and phase evolution of alkali activated metakaolin products with different activators and added aluminosilicate filler phases. The added filler phases have different reactivity to the alkali activated metakaolin system. Microstructural evolution in the alkali activated products has been investigated by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Field Emission Scanning Electron Microscope (FESEM). Variation in strength development in alkali activated metakaolin products was followed by compressive strength measurement test. Microstructural study shows that in case of metakaolin with NaOH activator crystalline sodalite formed in all the product samples irrespective of the added filler phases. The microstructure of these NaOH activated products investigated by FESEM showed crystalline and inhomogeneous morphology. Mixed activator containing both NaOH and sodium silicate in a fixed mass ratio formed predominantly amorphous phase. Microstructure of these samples showed more homogeneity than that of NaOH activated metakaolin products. The study further shows that addition of α-Al2O3 powder, non reactive phase to the alkali activated metakaolin system when used in larger amount increased crystalline phase in the matrix. α-Al2O3 powder addition increased the compressive strength of the product samples for both the activator compositions. Added phase of colloidal silica, reactive to the alkali activated metakaolin system when used in larger amount was found to increase amorphous nature of the matrix. Addition of colloidal silica influenced the compressive strength property differently with different activator compositions.

  12. Magic-angle-spinning NMR studies of zeolite SAPO-5

    NASA Astrophysics Data System (ADS)

    Freude, D.; Ernst, H.; Hunger, M.; Pfeifer, H.; Jahn, E.

    1988-01-01

    SAPO-5 was synthesized using triethylamine as template. Magic-angle-spinning (MAS) NMR of 1H, 27Al, 29Si and 31P was used to study the silicon incorporation into the framework and the nature of the Brønsted sites. 1H MAS NMR shows two types of bridging hydroxyl groups. 29Si MAS NMR indicates that silicon substitutes mostly for phosphorus and that there is a small amount of crystalline SiO 2 in the zeolite powder.

  13. Zeolite crystal growth in space

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.; Thompson, Robert W.; Dixon, Anthony G.

    1991-01-01

    The growth of large, uniform zeolite crystals in high yield in space can have a major impact on the chemical process industry. Large zeolite crystals will be used to improve basic understanding of adsorption and catalytic mechanisms, and to make zeolite membranes. To grow large zeolites in microgravity, it is necessary to control the nucleation event and fluid motion, and to enhance nutrient transfer. Data is presented that suggests nucleation can be controlled using chemical compounds (e.g., Triethanolamine, for zeolite A), while not adversely effecting growth rate. A three-zone furnace has been designed to perform multiple syntheses concurrently. The operating range of the furnace is 295 K to 473 K. Teflon-lined autoclaves (10 ml liquid volume) have been designed to minimize contamination, reduce wall nucleation, and control mixing of pre-gel solutions on orbit. Zeolite synthesis experiments will be performed on USML-1 in 1992.

  14. Recycling of aluminosilicate waste: Impact onto geopolymer formation

    NASA Astrophysics Data System (ADS)

    Essaidi, N.; Gharzouni, A.; Vidal, L.; Gouny, F.; Joussein, E.; Rossignol, S.

    2015-07-01

    Geopolymers are innovative ecomaterials resulting from the activation of an aluminosilicate source by an alkaline solution. Their properties depend on the used raw materials. This paper focuses on the possibility to obtain geopolymer materials with aluminosilicate laboratory waste. The effect of these additions on the geopolymer properties was studied by FTIR spectroscopy and mechanical test. It was evidenced a slowdown of the polycondensation reaction as well as the compressive strength due to the addition of laboratory waste which decreases the Si/K ratio of mixture.

  15. Disilane-modified mordenite zeolites

    SciTech Connect

    Yan, Y.; Vansant, E.F. )

    1990-03-22

    The effective pore size of H-mordenite zeolite can be decreased by implantation of disilyl compounds. Chemisorption of disilane at high temperature results in denser packing of the implanted entities on the external surface. This in turn enhances the pore narrowing effect. After hydrolysis-dehydration, the external surface of the disilanated zeolite can be reactivated by partial rehydration; thus a successive modification of the zeolite surface is possible.

  16. Structure of soda-lime aluminosilicate glasses

    NASA Astrophysics Data System (ADS)

    Cormier, L.; Neuville, D. R.

    2003-04-01

    The SiO2-CaO-Na2O-Al2O3 system is one of the most important in glass industry or geological processses but there have been relatively few structural studies in this system and, in particular, on the environment around non-network former cations (Na and Ca). Calcium and sodium in presence of alumina have a double structural role either as modifier, participating to the network depolymerization, or as charge compensator, near the (AlO4)- tetrahedra. The local and medium range environment may be affected by the structural role played in the network by these cations. Here we present experimental and simulation results on this system. We investigated several glasses to study the Si/Al substitution with a constant Na2O/CaO ratio, in order to determine the structural modifications between cations acting as pure modifiers and cations acting progressively as modifiers. Moreover, the Ca/Na substitution has been studied in silicate and aluminosilicate glasses to assess the effect of replacing Ca by Na. X-ray absorption data have been obtained at the Na and Ca K-edge at LURE (Orsay, France). XANES spectra indicate that the Ca environment in the studied glasses is close to the distorted site observed for c-anorthite, which corresponds to a coordination number of 6-7. A structural relaxation around Ca, with a decrease of the site distortion, is observed as SiO2 content increases. The two main peaks in the Na XANES spectra become broader as Na is replacing Ca. Conversely, the Si/Al substitution as little effect on both the Na and Ca XANES spectra. Raman spectra were collected with a T64000 spectrometer of Jobin-Yvon. When replacing Al by Si with constant Na2O/CaO ratio, a rapid decrease of the high frequency region (1100 cm-1) is observed. These decrease can be attributed to the substitution of Si by Al. The anionic units are Q4, Q3 and Q2 where tetrahedrally coordinated Al3+ is probably partitioned between these units. These experimental results are coupled with Molecular Dynamics simulations performed with Born-Mayer Huggins potentials and three body terms, in order to better assess the chemical dependence of the polymerized network and of the cations environment.

  17. SO2 REMOVAL FROM FLUE GASES USING UTILITY SYNTHESIZED ZEOLITES

    SciTech Connect

    MICHAEL GRUTZECK

    1998-10-31

    It is well known that natural and synthetic zeolites (molecular sieves) can adsorb gaseous SO2 from flue gas and do it more efficiently than lime based scrubbing materials. Unfortunately their cost ($500-$800 per ton) has deterred their use in this capacity. It is also known that zeolites are easy to synthesize from a variety of natural and man-made materials. The overall objective of the current work has been to evaluate the feasibility of having a utility synthesize its own zeolites, on-site, from fly ash and other recycled materials and then use these zeolites to adsorb SO2 from their flue gases. Work to date has shown that the efficiency of the capture process is related to the degree of crystallinity and the type of zeolite that forms in the samples. Normally, those samples cured at 150°C contained a greater proportion of zeolite and as such were more SO2 adsorptive than their low-temperature counterparts. However, in order for the project to be successful, on site synthesis must remain an option, i.e. _100°C synthesis. In light of this, the experimental focus now has two aspects. First, compositions of the starting materials are being altered by blending the current suite of fly ashes with other fly ashes, ground glass cullet and silica fume to promote the formation and growth of well crystallized and highly adsorptive zeolites. Second, greater degrees of reaction at significantly lower temperatures are being promote by ball milling the fly ash prior to use, by the use of more concentrated caustic solutions, and by the addition of zeolite seeds to the reactants. In all cases studies will focus on the effect of structure type and degree of conversion on SO2 adsorption. Future work will concentrate on the study of the effect of weathering on the suitability of converting fly ash into zeolites. This is an especially important study, considering the acres of fly ash now in storage throughout the country.

  18. SO2 REMOVAL FROM FLUE GASES USING UTILITY SYNTHESIZED ZEOLITES

    SciTech Connect

    Michael Grutzeck

    1999-04-30

    It is well known that natural and synthetic zeolites (molecular sieves) can adsorb gaseous SO{sub 2} from flue gas and do it more efficiently than lime based scrubbing materials. Unfortunately their cost ($500-$800 per ton) has deterred their use in this capacity. It is also known that zeolites are easy to synthesize from a variety of natural and man-made materials. The overall objective of the current work has been to evaluate the feasibility of having a utility synthesize its own zeolites, on-site, from fly ash and other recycled materials and then use these zeolites to adsorb SO{sub 2} from their flue gases. Work to date has shown that the efficiency of the capture process is related to the degree of crystallinity and the type of zeolite that forms in the samples. Normally, those samples cured at 150 C contained a greater proportion of zeolite and as such were more SO{sub 2} adsorptive than their low-temperature counterparts. However, in order for the project to be successful, on site synthesis must remain an option, i.e. 100 C synthesis. In light of this, the experimental focus now has two aspects. First, compositions of the starting materials are being altered by blending the current suite of fly ashes with ground glass cullet and silica fume to promote the formation and growth of well crystallized and highly adsorptive zeolites. Second, greater degrees of reaction at significantly lower temperatures are being promote by ball milling the fly ash prior to use, by the use of more concentrated caustic solutions, and by the addition of zeolite seeds to the reactants. In all cases studies will focus on the effect of structure type and degree of conversion on SO{sub 2} adsorption. Future work will concentrate on the study of the effect of weathering on the suitability of converting fly ash into zeolites. This is an especially important study, considering the acres of fly ash now in storage throughout the US.

  19. Hydrothermal synthesis and characterization of aluminum-free Mn-β zeolite: a catalyst for phenol hydroxylation.

    PubMed

    He, Zhen; Wu, Juan; Gao, Bingying; He, Hongyun

    2015-02-01

    Zeolite beta, especially heteroatomic zeolite beta, has been widely used in the industries of fine chemicals and petroleum refining because of its outstanding thermal stability, acid resistance, and unique 3-D open-frame structure. In this paper, aluminum-free Mn-β zeolite was hydrothermally synthesized in the SiO2-MnO2-(TEA)2O-NaF-H2O system. The effect of the chemical composition of the precursor mixture to the crystallization of the Al-free Mn-β zeolite was investigated. The synthesized Al-free Mn-β zeolite was characterized by inductively coupled plasma (ICP), XRD, thermogravimetric/differential thermal analysis (TG/DTA), N2 adsorption-desorption, FT-IR, UV-vis, X-ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM). The results show that the synthesized zeolite has a structure of β zeolite with good crystallinity and Mn ions present in the framework of the zeolite. The synthesized Al-free Mn-β zeolite shows great catalytic activity toward the phenol hydroxylation reaction using H2O2 as the oxidant. Approximately 35% of phenol conversion and ∼98% of dihydroxybenzene selectivity can be obtained under the optimal conditions. PMID:25556927

  20. Sodium Aluminosilicate Formation in Tank 43H Simulants

    SciTech Connect

    Wilmarth, W.R.; Walker, D.D.; Fink, S.D.

    1997-11-01

    This work studied the formation of a sodium aluminosilicate, Na{sub 8}Al{sub 6}Si{sub 6}O{sub 24}(NO{sub 3}){sub 2?4}H{sub 2}O, at 40{degree} 110{degree} C in simulated waste solutions with varied amounts of silicon and aluminum. The data agree well with literature solubility data for sodalite, the analogous chloride salt. The following conclusions result from this work: (1) The study shows, by calculation and experiments, that evaporation of the September 1997 Tank 43H inventory will only form minor quantities of the aluminosilicate. (2) The data indicate that the rate of formation of the nitrate enclathrated sodalite solid at these temperatures falls within the residence time ({lt}; 4 h) of liquid in the evaporator. (3) The silicon in entrained Frit 200 transferred to the evaporator with the Tank 43H salt solution will quantitatively convert to the sodium aluminosilicate. One kilogram of Frit 200 produces 2.1 kg of the sodium aluminosilicate.

  1. Molecular Chemistry in a Zeolite: Genesis of a Zeolite Y-Supported Ruthenium Complex Catalyst

    SciTech Connect

    Ogino, I.; Gates, B.C.

    2009-05-22

    Dealuminated zeolite Y was used as a crystalline support for a mononuclear ruthenium complex synthesized from cis-Ru(acac){sub 2}(C{sub 2}H{sub 4}){sub 2}. Infrared (IR) and extended X-ray absorption fine structure spectra indicated that the surface species were mononuclear ruthenium complexes, Ru(acac)(C{sub 2}H{sub 4}){sub 2}{sup 2+}, tightly bonded to the surface by two Ru-O bonds at Al{sup 3+} sites of the zeolite. The maximum loading of the anchored ruthenium complexes was one complex per two Al{sup 3+} sites; at higher loadings, some of the cis-Ru(acac){sub 2}(C{sub 2}H{sub 4}){sub 2} was physisorbed. In the presence of ethylene and H{sub 2}, the surface-bound species entered into a catalytic cycle for ethylene dimerization and operated stably. IR data showed that at the start of the catalytic reaction, the acac ligand of the Ru(acac)(C{sub 2}H{sub 4}){sub 2}{sup 2+} species was dissociated and captured by an Al{sup 3+} site. Ethylene dimerization proceeded 600 times faster with a cofeed of ethylene and H{sub 2} than without H{sub 2}. These results provide evidence of the importance of the cooperation of the Al{sup 3+} sites in the zeolite and the H{sub 2} in the feed for the genesis of the catalytically active species. The results presented here demonstrate the usefulness of dealuminated zeolite Y as a nearly uniform support that allows precise synthesis of supported catalysts and detailed elucidation of their structures.

  2. IMPROVED CATALYSTS FOR HEAVY OIL UPGRADING BASED ON ZEOLITE Y NANOPARTICLES ENCAPSULATED IN STABLE NANOPOROUS HOST

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2005-03-31

    The objectives of this project are to synthesis nanocrystals of highly acidic zeolite Y, encapsulate them within the channels of mesoporous (nanoporous) silicates or nanoporous organosilicates and evaluate the ''zeolite Y/Nanoporous host'' composites as catalysts for the upgrading of heavy petroleum feedstocks. Our results to date are summarized as follows. The synthesis of high surface ordered nanoporous silica of expanded pore diameter of 25 nm (larger than the standard size of 8.4 nm) using trimethylbenzene as a pore size expander was accomplished. The synthesis of zeolite Y nanoparticles with median pore size of approximately 50 nm (smaller than the 80 nm typically obtained with TMAOH) using combined TMABr/TMAOH as organic additives was also accomplished. The successful synthesis of zeoliteY/Nanoporous host composite materials by sequential combination of zeolite precursors and nanoporous material precursor mixtures was implied based on results from various characterization techniques such as X-Ray diffraction, infrared spectra, thermal analysis, porosimetry data. The resulting materials showed pore sizes up to 11 nm, and infrared band at 570 cm{sup -1} suggesting the presence of both phases. New results indicated that good quality highly ordered nanoporous silica host can be synthesized in the presence of zeolite Y seed precursor depending on the amount of precursor added. Preliminary research on the catalytic performance of the materials is underway. Probe acid catalyzed reactions, such as the cracking of cumene is currently being conducted. Work in the immediate future will be focused on the following three areas: (1) Further characterization of all-silica and aluminosilicate mesoporous materials with expanded pore sizes up to 30 nm will continue; (2) Research efforts to reduce the average particle size of zeolite nanoparticles down to 35-30 nm will continue; (3) Further synthesis of ZeoliteY/Nanoporous host composite catalysts of improved structural and physicochemical characteristics will be conducted by changing the amount and chemistry of the zeolitic precursors added; and (4) Investigation on the catalytic properties of the materials using probe catalytic reactions (such as cumene cracking), followed by catalytic testing for heavy oil conversion.

  3. Preparation of zeolites in space

    NASA Astrophysics Data System (ADS)

    Stöcker, Michael; Akporiaye, Duncan; Andersen, Arnfinn G.; Lillerud, Karl Petter; Seip, Knut L.; Røneid, Turid

    The synthesis of the zeolite offretite under microgravity conditions is planned during the EURECA-1 mission in 1991. The main experimental goal is the preparation of large single crystals with a perfect structure. Zeolites are of special interest with respect to heterogenous catalysis and adsorbents in connection with several industrial processes.

  4. Hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design.

    PubMed

    Prez-Ramrez, Javier; Christensen, Claus H; Egeblad, Kresten; Christensen, Christina H; Groen, Johan C

    2008-11-01

    The introduction of synthetic zeolites has led to a paradigm shift in catalysis, separations, and adsorption processes, due to their unique properties such as crystallinity, high-surface area, acidity, ion-exchange capacity, and shape-selective character. However, the sole presence of micropores in these materials often imposes intracrystalline diffusion limitations, rendering low utilisation of the zeolite active volume in catalysed reactions. This critical review examines recent advances in the rapidly evolving area of zeolites with improved accessibility and molecular transport. Strategies to enhance catalyst effectiveness essentially comprise the synthesis of zeolites with wide pores and/or with short diffusion length. Available approaches are reviewed according to the principle, versatility, effectiveness, and degree of reality for practical implementation, establishing a firm link between the properties of the resulting materials and the catalytic function. We particularly dwell on the exciting field of hierarchical zeolites, which couple in a single material the catalytic power of micropores and the facilitated access and improved transport consequence of a complementary mesopore network. The carbon templating and desilication routes as examples of bottom-up and top-down methods, respectively, are reviewed in more detail to illustrate the benefits of hierarchical zeolites. Despite encircling the zeolite field, this review stimulates intuition into the design of related porous solids (116 references). PMID:18949124

  5. Adamantanes from petroleum, with zeolites

    SciTech Connect

    Rollmann, L.D.; Green, L.A.; Bradway, R.A.

    1995-12-31

    Experiments with zeolite Beta and zeolite {Upsilon} demonstrate that adamantane and methyl adamantanes can be isolated very effectively from modern refinery streams by mild hydrocracking over Pt- and Pd-containing large pore zeolites. Yield depends importantly on individual refinery crude source and process configuration. Heavy crudes and refineries with conventional hydrocracking and FCC feed hydrotreater facilities are particularly desirable, and an ideal feed for adamantane isolation in such a situation is the 150{degrees}-250{degrees}C fraction of the hydrocracker (HDC) recycle stream. When Pt- or Pd-containing zeolite Beta was used with such a stream, temperatures of some 250{degrees}C and pressures below 3.5 mPa (500 psig) sufficed to remove selectively well over 90% of the non-adamantane hydrocarbon, with little conversion of adamantanes. High selectivity for adamantanes is attributed in large part to size-selective exclusion of these molecules from the pores of zeolite Beta.

  6. Temperature dependent thermal conductivity of pure silica MEL and MFI zeolite thin films

    NASA Astrophysics Data System (ADS)

    Fang, Jin; Huang, Yi; Lew, Christopher M.; Yan, Yushan; Pilon, Laurent

    2012-03-01

    This paper reports the temperature dependent cross-plane thermal conductivity of pure silica zeolite (PSZ) MFI and MEL thin films measured using the 3ω method between 30 and 315 K. PSZ MFI thin films were b-oriented, fully crystalline, and had a 33% microporosity. PSZ MEL thin films consisted of MEL nanoparticles embedded in a nonuniform and porous silica matrix. They featured porosity, relative crystallinity, and particle size ranging from 40% to 59%, 23% to 47%, and 55 to 80 nm, respectively. Despite their crystallinity, MFI films had smaller thermal conductivity than that of amorphous silica due to strong phonon scattering by micropores. In addition, the effects of increased relative crystallinity and particle size on thermal conductivity of MEL thin films were compensated by the simultaneous increase in porosity. Finally, thermal conductivity of MFI zeolite was predicted and discussed using the Callaway model based on the Debye approximation.

  7. Zeolite formation from coal fly ash and its adsorption potential

    SciTech Connect

    Duangkamol Ruen-ngam; Doungmanee Rungsuk; Ronbanchob Apiratikul; Prasert Pavasant

    2009-10-15

    The possibility in converting coal fly ash (CFA) to zeolite was evaluated. CFA samples from the local power plant in Prachinburi province, Thailand, were collected during a 3-month time span to account for the inconsistency of the CFA quality, and it was evident that the deviation of the quality of the raw material did not have significant effects on the synthesis. The zeolite product was found to be type X. The most suitable weight ratio of sodium hydroxide (NaOH) to CFA was approximately 2.25, because this gave reasonably high zeolite yield with good cation exchange capacity (CEC). The silica (Si)-to-aluminum (Al) molar ratio of 4.06 yielded the highest crystallinity level for zeolite X at 79% with a CEC of 240 meq/100 g and a surface area of 325 m{sup 2}/g. Optimal crystallization temperature and time were 90{sup o}C and 4 hr, respectively, which gave the highest CEC of approximately 305 meq/100 g. Yields obtained from all experiments were in the range of 50-72%. 29 refs., 5 tabs., 7 figs.

  8. Oxygen and hydrogen isotope geochemistry of zeolites

    NASA Technical Reports Server (NTRS)

    Karlsson, Haraldur R.; Clayton, Robert N.

    1990-01-01

    Oxygen and hydrogen isotope ratios for natural samples of the zeolites analcime, chabazite, clinoptilolite, laumontite, mordenite, and natrolite have been obtained. The zeolite samples were classified into sedimentary, hydrothermal, and igneous groups. The ratios for each species of zeolite are reported. The results are used to discuss the origin of channel water, the role of zeolites in water-rock interaction, and the possibility that a calibrated zeolite could be used as a low-temperature geothermometer.

  9. Effect of metal loading processes on the stability and thermal transformation of Co{sup 2+}- and Cu{sup 2+}-zeolite Y prepared from Egyptian kaolin

    SciTech Connect

    EL-Mekkawi, Doaa M. Selim, Mohamed M.

    2012-07-15

    This paper aims to assess the effect of the transition metals (TM) loading procedure on the incorporation of Co{sup 2+} and Cu{sup 2+} in zeolite Y, and their relevance to stability of the zeolite, particularly with respect to the thermal transformation to the spinel phases. In this work, zeolite Y prepared from Egyptian kaolin was used. XRF, XRD, TEM, UV/visible absorption measurements, and atomic absorption analyses in addition to the visual observations are recorded. XRF has been used to investigate the materials composition. TEM and XRD indicate the presence of nanoparticle spinel upon the calcination of the TM-zeolites at 1000 Degree-Sign C. In addition to spinel particles, XRD shows the formation of metal oxides, SiO{sub 2} and alumino-silicate phases. According to the transition metal and the cation loading process, different phases were detected. UV/visible absorption measurements and the visual observations are used to determine the experimental condition of the highest spinel content. It has been noticed that the experimental conditions of the metal sorption processes greatly affect the phase transformation. Stability and thermal transformation of zeolite depend on the initial concentration of the transition cation solutions and the number of loading cycles. - Highlights: Black-Right-Pointing-Pointer We study the effects of loading procedure in the incorporation of TM in zeolite Y. Black-Right-Pointing-Pointer Synthetic zeolite Y prepared from Egyptian kaolin has been used. Black-Right-Pointing-Pointer The type of TM affects the stability and thermal transformation of zeolite. Black-Right-Pointing-Pointer Loading processes affect the stability and thermal transformation of zeolite.

  10. Tailoring Zeolite ZSM-5 Crystal Morphology/Porosity through Flexible Utilization of Silicalite-1 Seeds as Templates: Unusual Crystallization Pathways in a Heterogeneous System.

    PubMed

    Zhang, Hongbin; Zhao, Yang; Zhang, Hongxia; Wang, Peicheng; Shi, Zhangping; Mao, Jianjiang; Zhang, Yahong; Tang, Yi

    2016-05-17

    Diffusion limitation in micropores of zeolites leads to a demand for optimization of zeolite morphology and/or porosity. However, tailoring crystallization processes to realize targeted morphology/porosity is a major challenge in zeolite synthesis. On the basis of previous work on the salt-aided, seed-induced route, the template effect of seeds on the formation of micropores, mesopores and even macropores was further explored to selectively achieve desired hierarchical architectures. By carefully investigating the crystallization processes of two typical samples with distinct crystal morphologies, namely, 1) nanocrystallite-oriented self-assembled ZSM-5 zeolite and 2) enriched intracrystal mesoporous ZSM-5 zeolite, a detailed mechanism is proposed to clarify the role of silicalite-1 seeds in the formation of diverse morphologies in a salt-rich heterogeneous system, combined with the transformation of seed-embedded aluminosilicate gel. On the basis of these conclusions, the morphologies/porosities of products were precisely tailored by deliberately adjusting the synthesis parameters (KF/Si, tetrapropylammonium bromide/Si and H2 O/Si ratios and type of organic template) to regulate the kinetics of seed dissolution and seed-induced recrystallization. This work may not only provide a practical route to control zeolite crystallization for tailoring crystal morphology, but also expands the knowledge of crystal growth mechanisms in a heterogeneous system. PMID:27073032

  11. Solid-state radioluminescent zeolite-containing composition and light sources

    DOEpatents

    Clough, Roger L. (Albuquerque, NM); Gill, John T. (Miamisburg, OH); Hawkins, Daniel B. (Fairbanks, AK); Renschler, Clifford L. (Tijeras, NM); Shepodd, Timothy J. (Livermore, CA); Smith, Henry M. (Overland Park, KS)

    1992-01-01

    A new type of RL light source consisting of a zeolite crystalline material, the intralattice spaces of which a tritiated compound and a luminophore are sorbed, and which material is optionally further dispersed in a refractive index-matched polymer matrix.

  12. Ultrafast synthesis of nano-sized zeolite SAPO-34 with excellent MTO catalytic performance.

    PubMed

    Sun, Qiming; Wang, Ning; Guo, Guanqi; Yu, Jihong

    2015-11-25

    Nano-sized SAPO-34 zeolites with high crystallinity are obtained in 10 minutes by fast heating the reaction gel in a stainless steel tubular reactor combined with the seed-assisted method, which show outstanding performance in methanol-to-olefin (MTO) reaction. PMID:26412585

  13. Dispersion and orientation of zeolite ZSM-5 crystallites within a fluid catalytic cracking catalyst particle.

    PubMed

    Sprung, Christoph; Weckhuysen, Bert M

    2014-03-24

    Confocal fluorescence microscopy was employed to selectively visualize the dispersion and orientation of zeolite ZSM-5 domains inside a single industrially applied fluid catalytic cracking (FCC) catalyst particle. Large ZSM-5 crystals served as a model system together with the acid-catalyzed fluorostyrene oligomerization reaction to study the interaction of plane-polarized light with these anisotropic zeolite crystals. The distinction between zeolite and binder material, such as alumina, silica, and clay, within an individual FCC particle was achieved by utilizing the anisotropic nature of emitted fluorescence light arising from the entrapped fluorostyrene-derived carbocations inside the zeolite channels. This characterization approach provides a non-invasive way for post-synthesis characterization of an individual FCC catalyst particle in which the size, distribution, orientation, and amount of zeolite ZSM-5 aggregates can be determined. It was found that the amount of detected fluorescence light originating from the stained ZSM-5 aggregates corresponds to about 15?wt?%. Furthermore, a statistical analysis of the emitted fluorescence light indicated that a large number of the ZSM-5 domains appeared in small sizes of about 0.015-0.25??m(2), representing single zeolite crystallites or small aggregates thereof. This observation illustrated a fairly high degree of zeolite dispersion within the FCC binder material. However, the highest amount of crystalline material was aggregated into larger domains (ca. 1-5??m(2)) with more or less similarly oriented zeolite crystallites. It is clear that this visualization approach may serve as a post-synthesis quality control on the dispersion of zeolite ZSM-5 crystallites within FCC particles. PMID:24616006

  14. Laser control of zeolite nucleation.

    PubMed

    Navarro, Marta; Mayoral, Alvaro; Mateo, Ester; Lahoz, Ruth; de la Fuente, Germán F; Coronas, Joaquín

    2012-02-01

    Precursor solutions for the synthesis of zeolites are irradiated by means of a Nd-YAG laser. These solutions are subsequently submitted to a hydrothermal treatment and the results analyzed by X-ray diffraction and electron microscopy. Laser irradiation promotes the formation of silica nanoparticles that nucleate into zeolite (silicalite-1), following a hydrothermal treatment. The average crystal size (in the 0.6-3.6 μm range) of the zeolite exponentially decreases as a function of laser irradiation time. In addition, a longer irradiation time results in a narrower crystal size distribution. PMID:22266775

  15. The structural behavior of ferric and ferrous iron in aluminosilicate glass near meta-aluminosilicate joins

    NASA Astrophysics Data System (ADS)

    Mysen, Bjorn O.

    2006-05-01

    Iron-57 resonant absorption Mössbauer spectroscopy was used to describe the redox relations and structural roles of Fe 3+ and Fe 2+ in meta-aluminosilicate glasses. Melts were formed at 1500 °C in equilibrium with air and quenched to glass in liquid H 2O with quenching rates exceeding 200 °C/s. The aluminosilicate compositions were NaAlSi 2O 6, Ca 0.5AlSi 2O 6, and Mg 0.5AlSi 2O 6. Iron oxide was added in the form of Fe 2O 3, NaFeO 2, CaFe 2O 4, and MgFe 2O 4 with total iron oxide content in the range ˜0.9 to ˜5.6 mol% as Fe 2O 3. The Mössbauer spectra, which were deconvoluted by assuming Gaussian distributions of the hyperfine field, are consistent with one absorption doublet of Fe 2+ and one of Fe 3+. From the area ratios of the Fe 2+ and Fe 3+ absorption doublets, with corrections for differences in recoil-fractions of Fe 3+ and Fe 2+, the Fe 3+/ΣFe is positively correlated with increasing total iron content and with decreasing ionization potential of the alkali and alkaline earth cation. There is a distribution of hyperfine parameters from the Mössbauer spectra of these glasses. The maximum in the isomer shift distribution function of Fe 3+, δFe 3+, ranges from about 0.25 to 0.49 mm/s (at 298 K relative to Fe metal) with the quadrupole splitting maximum, ΔFe 3+, ranging from ˜1.2 to ˜1.6 mm/s. Both δFe 3+ and δFe 2+ are negatively correlated with total iron oxide content and Fe 3+/ΣFe. The dominant oxygen coordination number Fe 3+ changes from 4 to 6 with decreasing Fe 3+/ΣFe. The distortion of the Fe 3+-O polyhedra of the quenched melts (glasses) decreases as the Fe 3+/ΣFe increases. These polyhedra do, however, coexist with lesser proportions of polyhedra with different oxygen coordination numbers. The δFe 2+ and ΔFe 2+ distribution maxima at 298 K range from ˜0.95 to 1.15 mm/s and 1.9 to 2.0 mm/s, respectively, and decrease with increasing Fe 3+/ΣFe. We suggest that these hyperfine parameter values for the most part are more consistent with Fe 2+ in a range of coordination states from 4- to 6-fold. The lower δFe 2+-values for the most oxidized melts are consistent with a larger proportion of Fe 2+ in 4-fold coordination compared with more reduced glasses and melts.

  16. Structure-Property Relationships of Inorganically Surface-Modified Zeolite Molecular Sieves for Nanocomposite Membrane Fabrication

    SciTech Connect

    Lydon, Megan E; Unocic, Kinga A; Jones, Christopher W; Nair, Sankar

    2012-01-01

    A multiscale experimental study of the structural, compositional, and morphological characteristics of aluminosilicate (LTA) and pure-silica (MFI) zeolite materials surface-modified with MgO{sub x}H{sub y} nanostructures is presented. These characteristics are correlated with the suitability of such materials in the fabrication of LTA/Matrimid mixed-matrix membranes (MMMs) for CO{sub 2}/CH{sub 4} separations. The four functionalization methods studied in this work produce surface nanostructures that may appear superficially similar under SEM observation but in fact differ considerably in shape, size, surface coverage, surface area/roughness, degree of attachment to the zeolite surface, and degree of zeolite pore blocking. The evaluation of these characteristics by a combination of TEM, HRTEM, N{sub 2} physisorption, multiscale compositional analysis (XPS, EDX, and ICP-AES elemental analysis), and diffraction (ED and XRD) allows improved understanding of the origin of disparate gas permeation properties observed in MMMs made with four types of surface-modified zeolite LTA materials, as well as a rational selection of the method expected to result in the best enhancement of the desired properties (in the present case, CO{sub 2}/CH{sub 4} selectivity increase without sacrificing permeability). A method based on ion exchange of the LTA with Mg{sup 2+}, followed by base-induced precipitation and growth of MgOxHy nanostructures, deemed 'ion exchange functionalization' here, offers modified particles with the best overall characteristics resulting in the most effective MMMs. LTA/Matrimid MMMs containing ion exchange functionalized particles had a considerably higher CO{sub 2}/CH{sub 4} selectivity (40) than could be obtained with the other functionalization techniques (30), while maintaining a CO{sub 2} permeability of 10 barrers. A parallel study on pure silica MFI surface nanostructures is also presented to compare and contrast with the zeolite LTA case.

  17. Hard x-ray nanotomography of amorphous aluminosilicate cements.

    SciTech Connect

    Provis, J. L.; Rose, V.; Winarski, R. P.; van Deventer, J. S. J.

    2011-08-01

    Nanotomographic reconstruction of a sample of low-CO{sub 2} 'geopolymer' cement provides the first three-dimensional view of the pore structure of the aluminosilicate geopolymer gel, as well as evidence for direct binding of geopolymer gel onto unreacted fly ash precursor particles. This is central to understanding and optimizing the durability of concretes made using this new class of binder, and demonstrates the value of nanotomography in providing a three-dimensional view of nanoporous inorganic materials.

  18. Template-free nanosized faujasite-type zeolites

    NASA Astrophysics Data System (ADS)

    Awala, Hussein; Gilson, Jean-Pierre; Retoux, Richard; Boullay, Philippe; Goupil, Jean-Michel; Valtchev, Valentin; Mintova, Svetlana

    2015-04-01

    Nanosized faujasite (FAU) crystals have great potential as catalysts or adsorbents to more efficiently process present and forthcoming synthetic and renewable feedstocks in oil refining, petrochemistry and fine chemistry. Here, we report the rational design of template-free nanosized FAU zeolites with exceptional properties, including extremely small crystallites (10-15 nm) with a narrow particle size distribution, high crystalline yields (above 80%), micropore volumes (0.30 cm3 g-1) comparable to their conventional counterparts (micrometre-sized crystals), Si/Al ratios adjustable between 1.1 and 2.1 (zeolites X or Y) and excellent thermal stability leading to superior catalytic performance in the dealkylation of a bulky molecule, 1,3,5-triisopropylbenzene, probing sites mostly located on the external surface of the nanosized crystals. Another important feature is their excellent colloidal stability, which facilitates a uniform dispersion on supports for applications in catalysis, sorption and thin-to-thick coatings.

  19. Template-free nanosized faujasite-type zeolites.

    PubMed

    Awala, Hussein; Gilson, Jean-Pierre; Retoux, Richard; Boullay, Philippe; Goupil, Jean-Michel; Valtchev, Valentin; Mintova, Svetlana

    2015-04-01

    Nanosized faujasite (FAU) crystals have great potential as catalysts or adsorbents to more efficiently process present and forthcoming synthetic and renewable feedstocks in oil refining, petrochemistry and fine chemistry. Here, we report the rational design of template-free nanosized FAU zeolites with exceptional properties, including extremely small crystallites (10-15 nm) with a narrow particle size distribution, high crystalline yields (above 80%), micropore volumes (0.30 cm(3) g(-1)) comparable to their conventional counterparts (micrometre-sized crystals), Si/Al ratios adjustable between 1.1 and 2.1 (zeolites X or Y) and excellent thermal stability leading to superior catalytic performance in the dealkylation of a bulky molecule, 1,3,5-triisopropylbenzene, probing sites mostly located on the external surface of the nanosized crystals. Another important feature is their excellent colloidal stability, which facilitates a uniform dispersion on supports for applications in catalysis, sorption and thin-to-thick coatings. PMID:25559425

  20. Barium aluminosilicate reinforced in situ with silicon nitride

    SciTech Connect

    Richardson, K.K.; Freitag, D.W.; Hunn, D.L.

    1995-10-01

    Advanced ceramic composite materials that exhibit high strength and toughness with good thermal shock resistance are needed for emerging high-temperature engineering applications. A recently developed in situ reinforced barium aluminosilicate glass-ceramic shows promise of meeting many of the requirements for these types of applications with the added benefit of low-cost fabrication through densification by pressureless sintering. The material is toughened through in situ growth of rodlike {beta}-Si{sub 3}N{sub 4} grains resulting from the {alpha}-{beta} silicon nitride phase transformation. Microstructural development and material properties for temperatures up to 1,400 C are discussed. When compared to monolithic barium aluminosilicate, barium aluminosilicate reinforced with 70% by volume of Si{sub 3}N{sub 4} shows a significant increase in flexural strength (from 80 to 565 MPa) and fracture toughness (from 1.8 to 5.74 MPa {center_dot} m{sup 1/2}) with a high resistance to thermal shock.

  1. Development of Li+ alumino-silicate ion source

    SciTech Connect

    Roy, P.K.; Seidl, P.A.; Waldron, W.; Greenway, W.; Lidia, S.; Anders, A.; Kwan, J.

    2009-04-21

    To uniformly heat targets to electron-volt temperatures for the study of warm dense matter, one strategy is to deposit most of the ion energy at the peak of energy loss (dE/dx) with a low (E< 5 MeV) kinetic energy beam and a thin target[1]. Lower mass ions have a peak dE/dx at a lower kinetic energy. To this end, a small lithium (Li+) alumino-silicate source has been fabricated, and its emission limit has been measured. These surface ionization sources are heated to 1000-1150 C where they preferentially emit singly ionized alkali ions. Alumino-silicates sources of K+ and Cs+ have been used extensively in beam experiments, but there are additional challenges for the preparation of high-quality Li+ sources: There are tighter tolerances in preparing and sintering the alumino-silicate to the substrate to produce an emitter that gives uniform ion emission, sufficient current density and low beam emittance. We report on recent measurements ofhigh ( up to 35 mA/cm2) current density from a Li+ source. Ion species identification of possible contaminants is being verified with a Wien (E x B) filter, and via time-of-flight.

  2. Mechanisms of zinc incorporation in aluminosilicate crystalline structures and the leaching behaviour of product phases.

    PubMed

    Tang, Yuanyuan; Shih, Kaimin

    2015-01-01

    This study quantitatively evaluates a waste-to-resource strategy of blending zinc-laden sludge and clay material for low-cost ceramic products. Using ZnO as the simulated zinc-laden sludge to sinter with kaolinite, both zinc aluminate spinel (ZnAl₂O₄) and willemite (Zn₂SiO₄) phases were formed during the sintering process. To analyse the details of zinc incorporation reactions, γ-Al₂O₃and quartz were further used as precursors to observe ZnAl₂O₄and Zn₂SiO₄formations. By firing the ZnO mixtures and their corresponding precursors at 750-1350°C for 3 h, the efficiency of zinc transformation was determined through Rietveld refinement analyses of X-ray diffraction data. The results also show different incorporation behaviour for kaolinite and mullite precursors during the formation of ZnAl2O₄and Zn2SiO₄in the system. In addition, with a competitive formation between ZnAl₂O₄and Zn₂SiO₄, the ZnAl₂O₄spinel phase is predominant at temperatures higher than 1050°C. This study used a prolonged leaching test modified from the US Environmental Protection Agency's toxicity characteristic leaching procedure to evaluate ZnO, ZnAl₂O₄, and Zn₂SiO₄product phases. The zinc concentrations in ZnO and Zn₂SiO₄leachates were about two orders of magnitude higher than that of ZnAl₂O₄ leachate at the end of the experiment, indicating that ZnAl₂O₄formation is the preferred stabilization mechanism for incorporating zinc in ceramic products. PMID:25399963

  3. Determination of the crystalline structure of scale solids from the 16H evaporator gravity drain line to tank 38H

    SciTech Connect

    Oji, L. N.

    2015-10-01

    August 2015, scale solids from the 16H Evaporator Gravity Drain Line (GDL) to the Tank 38H were delivered to SRNL for analysis. The desired analytical goal was to identify and confirm the crystalline structure of the scale material and determine if the form of the aluminosilicate mineral was consistent with previous analysis of the scale material from the GDL.

  4. Hydrocracking process using zeolite beta

    SciTech Connect

    Angevine, P.J.; Mitchell, K.M.; Oleck, S.M.; Shih, S.S.

    1986-09-16

    A process is described for the hydrocracking and dewaxing of a petroleum fraction comprising waxy components boiling above 345/sup 0/C., which comprises passing the fraction over a hydrocracking catalyst comprising zeolite beta and a matrix material in the presence of hydrogen and under hydrocracking conditions, the proportion of zeolite beta in the hydrocracking catalyst increasing in the direction in which the fraction is passed.

  5. Copper-containing zeolite catalysts

    DOEpatents

    Price, Geoffrey L.; Kanazirev, Vladislav

    1996-01-01

    A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl.sub.2, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

  6. Copper-containing zeolite catalysts

    DOEpatents

    Price, G.L.; Kanazirev, V.

    1996-12-10

    A catalyst useful in the conversion of nitrogen oxides or in the synthesis of nitriles or imines from amines, is formed by preparing an intimate mechanical mixture of a copper (II)-containing species, such as CuO or CuCl{sub 2}, or elemental copper, with a zeolite having a pore mouth comprising 10 oxygen atoms, such as ZSM-5, converting the elemental copper or copper (II) to copper (I), and driving the copper (I) into the zeolite.

  7. Photoinduced formation of selenium molecules in zeolites: A resonant Raman spectroscopy study

    SciTech Connect

    Goldbach, A.; Grimsditch, M.; Iton, L.; Saboungi, M.L.

    1997-01-16

    After excitation of selenium encapsulated in Y-zeolite with 476 nm radiation, decomposition of the initially present semiconductor chains is observed. The fragmentation is influenced by the nature of the cations that counterbalance the negative charges of the aluminosilicate framework of the zeolite. In La{sup 3+}- and Nd{sup 3+}-exchanged Y-zeolite, Se{sub 2}{sup -} is formed upon irradiation with 476 nm laser light while Se{sub 3} is generated in the Ca{sup 2+}-exchanged form under the same conditions. Both species are identified by their resonance Raman spectra. The vibrational constants obtained for the electronic ground state of Se{sub 3} in Ca-Y are {omega}{sub 0} = 315 cm{sup -1} and {omega}{sub 0}{chi}{sub 0} = 0.5 cm{sup -1}, the respective values for Se{sub 2}{sup -} in La-Y are {omega}{sub 0} = 329 cm{sup -1} and {omega}{sub 0}{chi}{sub 0} = 0.8 cm{sup -1}. 22 refs., 6 figs., 1 tab.

  8. Surface analysis of zeolites: An XPS, variable kinetic energy XPS, and low energy ion scattering study

    NASA Astrophysics Data System (ADS)

    Bare, Simon R.; Knop-Gericke, Axel; Teschner, Detre; Hävacker, Michael; Blume, Raoul; Rocha, Tulio; Schlögl, Robert; Chan, Ally S. Y.; Blackwell, N.; Charochak, M. E.; ter Veen, Rik; Brongersma, Hidde H.

    2016-06-01

    The surface Si/Al ratio in a series of zeolite Y samples has been obtained using laboratory XPS, synchrotron (variable kinetic energy) XPS, and low energy ion scattering (LEIS) spectroscopy. The non-destructive depth profile obtained using variable kinetic energy XPS is compared to that from the destructive argon ion bombardment depth profile from the lab XPS instrument. All of the data indicate that the near surface region of both the ammonium form and steamed Y zeolites is strongly enriched in aluminum. It is shown that when the inelastic mean free path of the photoelectrons is taken into account the laboratory XPS of aluminosilicates zeolites does not provide a true measurement of the surface stoichiometry, while variable kinetic energy XPS results in a more surface sensitive measurement. A comprehensive Si/Al concentration profile as a function of depth is developed by combining the data from the three surface characterization techniques. The LEIS spectroscopy reveals that the topmost atomic layer is further enriched in Al compared to subsequent layers.

  9. Hierarchical hybrid organic-inorganic materials with tunable textural properties obtained using zeolitic-layered precursor.

    PubMed

    Opanasenko, Maksym; Parker, Wallace O'Neil; Shamzhy, Mariya; Montanari, Erica; Bellettato, Michela; Mazur, Michal; Millini, Roberto; Čejka, Jiří

    2014-02-12

    Novel layered zeolitic organic-inorganic materials have been synthesized using a two-dimensional zeolite precursor IPC-1P prepared by a top-down approach from zeolite UTL. The formation of porous materials containing organic linkers or polyhedral oligomeric siloxane covalently bonded to zeolite layers in the interlayer space was confirmed by a variety of characterization techniques (N2/Ar sorption analysis, XRD, (29)Si and (13)C NMR, TEM). The organic-inorganic porous hybrids obtained by intercalation with silsesquioxane posessed layered morphology and contained large crystalline domains. The hybrids exhibited mesoporous or hierarchical micro-/mesoporous systems, stable up to 350 °C. Textural properties of the formed zeolitic organic-inorganic materials can be controlled by varying the linker or synthetic conditions over a broad range. Surface areas and pore volumes of synthesized hybrids significantly exceed those for parent zeolite UTL and corresponding swollen material; the amount of micropores increased with increasing rigidity and size of the organic linker in the order biphenyl > phenylene > ethanediyl. PMID:24451039

  10. Ultrastrong Alkali-Resisting Lanthanide-Zeolites Assembled by [Ln60] Nanocages.

    PubMed

    Dong, Jie; Cui, Ping; Shi, Peng-Fei; Cheng, Peng; Zhao, Bin

    2015-12-30

    Zeolites, as one of the most important porous materials, are most widely utilized in sorbents, catalysis, and ion-exchange fields. However, the multi-functional lanthanide-zeolites constructed exclusively by lanthanide ions and oxygen linkers are to our knowledge unknown hitherto. Herein, we, for the first time, report the unique structure and multifunctions of lanthanide zeolites (1·Gd, 1·Tb, 1·Dy), featuring 60 nuclear [Ln60] nanocages as building blocks and ultrastrong alkali-resisting. These compounds possess extremely high stability and still retain single crystallinity after treatment in boiling water, 0.1 M HCl, and 20 M NaOH aqueous solutions. Magnetic studies revealed 1·Gd has large magnetocaloric effect with -ΔSm(max) = 66.5 J kg(-1) K(-1), falling among the largest values known to date. Importantly, these lanthanide-zeolites themselves can efficiently catalyze the cycloaddition of CO2 with epoxides under mild conditions. Our finding extends the conventional zeolites to lanthanide counterparts, opening a new space for seeking novel and/or multifunctional zeolites. PMID:26653619

  11. Zeolites as catalysts in organic reactions: condensation of aldehydes with benzene derivatives

    SciTech Connect

    Climent, M.J.; Corma, A.; Garcia, H.; Primo, J. )

    1991-07-01

    Reactions of four aldehydes with five aromatic compounds have been carried out on a series of USY zeolites with unit cell size in the 24.56 to 24.25-{angstrom} range. Conversion decreased in the order formaldehyde > benzaldehyde > acetaldehyde > propionaldehyde and also in the series anisole > toluene > benzene > chlorobenzene. For aliphatic aldehydes a mixture of ortho-ortho, ortho-para, and para-para diarylmethanes was obtained. USY zeolites show a higher para-directing selectivity than AlCl{sub 3}. Benzaldehyde reacted with benzene derivatives to afford mixtures of diaryl- and triarylmethanes. Formation of ditolyl- and dianisylmethanes in the corresponding reactions indicated that bulky triarylmethanes, once formed inside the crystalline framework, have strong diffusional limitations to get out of the zeolite cavities and can undergo subsequent protolytic cleavage. A decrease in the activity of the zeolite to catalyze hydride transfer reactions lead to a decrease on the diphenylmethane yield. Finally, diphenylmethane appears as a primary product indicating that a series of consecutive reactions such as the formation of diarylcarbinols followed by protonation, water elimination, and hydride abstraction are taking place inside the pores of the zeolite before the real primary product comes out from the zeolite.

  12. Catalytic performance of Metal-Organic-Frameworks vs. extra-large pore zeolite UTL in condensation reactions

    PubMed Central

    Shamzhy, Mariya; Opanasenko, Maksym; Shvets, Oleksiy; Čejka, Jiří

    2013-01-01

    Catalytic behavior of isomorphously substituted B-, Al-, Ga-, and Fe-containing extra-large pore UTL zeolites was investigated in Knoevenagel condensation involving aldehydes, Pechmann condensation of 1-naphthol with ethylacetoacetate, and Prins reaction of β-pinene with formaldehyde and compared with large-pore aluminosilicate zeolite beta and representative Metal-Organic-Frameworks Cu3(BTC)2 and Fe(BTC). The yield of the target product over the investigated catalysts in Knoevenagel condensation increases in the following sequence: (Al)beta < (Al)UTL < (Ga)UTL < (Fe)UTL < Fe(BTC) < (B)UTL < Cu3(BTC)2 being mainly related to the improving selectivity with decreasing strength of active sites of the individual catalysts. The catalytic performance of Fe(BTC), containing the highest concentration of Lewis acid sites of the appropriate strength is superior over large-pore zeolite (Al)beta and B-, Al-, Ga-, Fe-substituted extra-large pore zeolites UTL in Prins reaction of β-pinene with formaldehyde and Pechmann condensation of 1-naphthol with ethylacetoacetate. PMID:24790940

  13. Cost-effective two-stage varying-temperature rapid crystallization of zeolite T and SAPO-34

    NASA Astrophysics Data System (ADS)

    Yin, Xiaoyan; Chu, Naibo; Lu, Xuewei; Li, Zhongfang; Guo, Hong

    2016-05-01

    In this paper, zeolite T and SAPO-34 have been synthesized by two-stage varying temperature crystallization method (TVTC method). The feature of this method is dividing the hydrothermal process into two steps. The first step is lower temperature treatment which is favorable for the crystals nucleation and the second step is higher temperature treatment which is helpful to the crystals growth. The advantage of this method is that it greatly reduces the crystallization time and particle size compared to conventional constant temperature crystallization method (CCTC method). The influences of different initial and final temperatures on the zeolite crystallinity, morphology and particle size have been investigated in detail. Ultimately, the optimal crystallization conditions of zeolite T and SAPO-34 using this method have been summarized. The samples prepared with TVTC method and CCTC method also have been contrasted. With TVTC method, the synthesis time of zeolite T crystals is reduced from 7 days to 4 days and the synthesis time of SAPO-34 crystals is reduced from 48 h to 16 h. Furthermore, the sample prepared by TVTC method has higher crystallinity compared with the sample prepared by CCTC method. The particle size distributions of samples prepared by two methods have strongly confirmed that TVTC method is beneficial to form uniform and small zeolite particles. This paper provides an efficient and economical route to the industrial preparation of zeolite T and SAPO-34.

  14. Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Ahlborg, Nadia L.; Zhu, Dongming

    2013-01-01

    The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

  15. Atomic Structure of a Cesium Aluminosilicate Geopolymer: A Pair Distribution Function Study

    SciTech Connect

    Bell, J.; Sarin, P; Provis, J; Haggerty, R; Driemeyer, P; Chupas, P; van Deventer, J; Kriven, W

    2008-01-01

    The atomic pair distribution function (PDF) method was used to study the structure of cesium aluminosilicate geopolymer. The geopolymer was prepared by reacting metakaolin with cesium silicate solution followed by curing at 50C for 24 h in a sealed container. Heating of Cs-geopolymer above 1000C resulted in formation of crystalline pollucite (CsAlSi{sub 2}O{sub 6}). PDF refinement of the pollucite phase formed displayed an excellent fit over the 10-30 {angstrom} range when compared with a cubic pollucite model. A poorer fit was attained from 1-10 {angstrom} due to an additional amorphous phase present in the heated geopolymer. On the basis of PDF analysis, unheated Cs-geopolymer displayed structural ordering similar to pollucite up to a length scale of 9 {angstrom}, despite some differences. Our results suggest that hydrated Cs{sup +} ions were an integral part of the Cs-geopolymer structure and that most of the water present was not associated with Al-OH or Si-OH bonds.

  16. Microstructure and Cs Behavior of Ba-Doped Aluminosilicate Pollucite Irradiated with F+ Ions

    SciTech Connect

    Jiang, Weilin; Kovarik, Libor; Zhu, Zihua; Varga, Tamas; Engelhard, Mark H.; Bowden, Mark E.; Nenoff, Tina M.; Garino, Terry

    2014-06-24

    Radionuclide 137Cs is one of the major fission products that dominate heat generation in spent fuels over the first 300 hundred years. A durable waste form for 137Cs that decays to 137Ba is needed to minimize its environmental impact. Aluminosilicate pollucite CsAlSi2O6 is selected as a model waste form to study the decay-induced structural effects. While Ba-containing precipitates are not present in charge-balanced Cs0.9Ba0.05AlSi2O6, they are found in Cs0.9Ba0.1AlSi2O6 and identified as monoclinic Ba2Si3O8. Pollucite is susceptible to electron irradiation induced amorphization. The threshold density of the electronic energy deposition for amorphization is determined to be ~235 keV/nm3. Pollucite can be readily amorphized under F+ ion irradiation at 673 K. A significant amount of Cs diffusion and release from the amorphized pollucite is observed during the irradiation. However, cesium is immobile in the crystalline structure under He+ ion irradiation at room temperature. The critical temperature for amorphization is not higher than 873 K under F+ ion irradiation. If kept at or above 873 K all the time, the pollucite structure is unlikely to be amorphized; Cs diffusion and release are improbable. A general discussion regarding pollucite as a potential waste form is provided in this report.

  17. RESULTS OF CAUSTIC DISSOLUTION OF ALUMINOSILICATE SCALE AND CHARACTERIZATION DATA FOR SAMPLES FROM THE EVAPORATOR POT AND GRAVITY DRAIN LINE

    SciTech Connect

    Wilmarth, B; Rita Sullivan, R; Chris Martino, C

    2006-08-21

    The build-up of sodium aluminosilicate scale in the 2H Evaporator system continues to cause operational difficulties. The use of a nitric acid cleaning operation proved successful in 2001. However, the operation required additional facilities to support spent cleaning solution neutralization and was quite costly. A proposed caustic cleaning flowsheet has many advantages over the acid flowsheet. Therefore, samples were retrieved from the evaporator system (gravity drain line and pot) for both chemical and radiological characterization and dissolution testing. The characterization of these scale samples showed the presence of nitrated cancrinite along with a dehydrated zeolite. Small amounts of depleted uranium were also found in these samples as expected and the amount of uranium ranged from 0.5 wt% to 2 wt%. Dissolution in sodium hydroxide solutions of various caustic concentrations showed that the scale slowly dissolves at elevated temperature (90 C). Data from similar testing indicate that the scale removed from the GDL in 2005 dissolves slower than that removed in 1997. Differences in the particle size of these samples of scale may well explain the measured dissolution rate differences.

  18. New nanocomposites based on layered aluminosilicate and guanidine containing polyelectrolytes

    SciTech Connect

    Khashirov, Azamat A.; Zhansitov, Azamat A.; Khashirova, Svetlana Yu.; Zaikov, Genadiy E.

    2014-05-15

    The new functional nanomaterials based on layered aluminosilicate and guanidine containing polyelectrolytes combining high bactericidal activity with an increased ability to bind to heavy metals and organic pollutants were received. To prove the chemical structure of the model compounds (zwitterionic delocalized resonance structures AG/MAG and PAG/PMAG), as well as the presence of such structures in nanocomposites received on their basis and the MMT, IR, {sup 1}H NMR spectroscopy, X-ray diffraction studies and nanoindentation/sclerometry followed by scanning the surface in the area of the indentation were used.

  19. Characterisation of frequency doubling in Eu(2+) doped aluminosilicate fibres

    NASA Technical Reports Server (NTRS)

    Driscoll, T. J.; Lawandy, N. M.; Killian, A.; Rienhart, L.; Morse, T. F.

    1991-01-01

    The results of a series of experiments on efficient second-harmonic generation in a fiber with a Eu(2+)-doped aluminosilicate core are reported. The fiber was prepared by the seeding method with CW mode-locked radiation at 1.06 micron and produced ultrastable peak conversion efficiencies of 0.001 during mode-locked readout. Experiments were performed to determine the IR preparation intensity dependence, the stability of the output, and the type of erasure mechanisms which occur. The results are compared with those of germanosilicate fibers and some similarities and differences are discussed.

  20. Cesium adsorption on composite ferrocyanide-aluminosilicate adsorbents

    SciTech Connect

    Panasyugin, A.S.; Rat`ko, A.I.; Trofimenko, N.E.

    1995-11-01

    The formation of composite ferrocyanide adsorbents prepared on the basis of clinoptilolite is studied by potentiometric titration, X-ray diffraction analysis, and IR spectroscopy, and the nature of ion-exchanging complex is established. Exchange capacity, selectivity, and hydrolytic stability of the sorbents are characterized. Distribution coefficients with modified samples can be as large as 10000 for {sup 137}Cs; however, with increase of the background salt concentration above 0.17 g l{sup -1}, competing ions have noticeable effect on the adsorption properties of the aluminosilicates.

  1. Selective preparation of zeolite X and A from flyash and its use as catalyst for biodiesel production.

    PubMed

    Volli, Vikranth; Purkait, M K

    2015-10-30

    This work discusses the utilization of flyash for synthesis of heterogeneous catalyst for transesterification. Different types of zeolites were synthesized from alkali fusion followed by hydrothermal treatment of coal flyash as source material. The synthesis conditions were optimized to obtain highly crystalline zeolite based on degree of crystallinity and cation exchange capacity (CEC). The effect of CEC, acid treatment, Si/Al ratio and calcination temperature (800, 900 and 1000 °C) on zeolite formation was also studied. Pure, single phase and highly crystalline zeolite was obtained at flyash/NaOH ratio (1:1.2), fusion temperature (550 °C), fusion time (1 h), hydrothermal temperature (110 °C) and hydrothermal time (12h). The synthesized zeolite was ion-exchanged with potassium and was used as catalyst for transesterification of mustard oil to obtain a maximum conversion of 84.6% with 5 wt% catalyst concentration, 12:1 methanol to oil molar ratio, reaction time of 7 h at 65 °C. The catalyst was reused for 3 times with marginal reduction in activity. PMID:25956640

  2. Cobalt and nickel supported on HY zeolite: Synthesis, characterization and catalytic properties

    SciTech Connect

    Garrido Pedrosa, Anne M. . E-mail: annemgp@yahoo.com; Souza, Marcelo J.B.; Melo, Dulce M.A.; Araujo, Antonio S.

    2006-06-15

    Bifunctional catalysts consisting of cobalt and nickel supported on HY zeolite were synthesized by solvent excess impregnation and characterized by X-ray diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, atomic absorption spectroscopy, thermogravimetric analysis and nitrogen adsorption. The profiles of metal reduction on zeolite were obtained by temperature-programmed reduction. The catalytic properties of the bifunctional catalysts were verified by n-hexane hydroconversion. X-ray diffraction and microstructural analyses showed the presence of crystalline phases in HY zeolite and in samples after impregnation. A decrease in the micropore surface area was observed by nitrogen adsorption experiments and attributed to a reduction in the accessibility to micropores. The catalysts showed catalytic activity in the hydroconversion of n-hexane with selectivity to branched hydrocarbons. Such catalytic activity was related to the acid and metallic properties of the bifunctional catalysts used.

  3. Entrapping of Cs and Sr in heat-treated zeolite matrices

    NASA Astrophysics Data System (ADS)

    Liguori, B.; Caputo, D.; Iucolano, F.; Aprea, P.; de Gennaro, B.

    2013-04-01

    A solidification-stabilization procedure aiming at immobilizing Cs+ and Sr2+, two of the radioactive species more frequently present in nuclear power plant wastewaters, was successfully tested. Both cations were simultaneously exchanged by a blend of two zeolites, a phillipsite-rich tuff, selective for Cs+, and a synthetic zeolite Linde-type A, selective for Sr2+. The contaminated material was then heat treated up to 1200 C with the result of safely immobilizing both cations, as demonstrated by leaching estimation with three different procedures. X-ray studies of the single cation-loaded zeolites or mixture of them helped to interpret the immobilization mechanism, involving cation trapping in chemically stable crystalline/amorphous matrices formed as a result of firing.

  4. Synthesis of Silicate Zeolite Analogues Using Organic Sulfonium Compounds as Structure-Directing Agents.

    PubMed

    Jo, Changbum; Lee, Sungjune; Cho, Sung June; Ryoo, Ryong

    2015-10-19

    A microporous crystalline silica zeolite of the MEL structure type and three other zeolite analogues composed of germanosilicate frameworks were synthesized using tributylsulfonium, triphenylsulfonium, or tri(para-tolyl)sulfonium as the structure-directing agent. The germanosilicates thus obtained had ISV, ITT, or a new zeolite structure depending on the synthesis conditions. The structure of the new germanosilicate was solved using X-ray powder diffraction data with the aid of a charge-flipping method. The solution indicated a crystal structure belonging to the P63/mmc space group with cell parameters of a=16.2003 Å and c=21.8579 Å. After calcination, the new germanosilicate material exhibited two types of accessible micropores with diameters of 0.61 and 0.78 nm. PMID:26302889

  5. Effective Sequestration of Clostridium difficile Protein Toxins by Calcium Aluminosilicate

    PubMed Central

    Pokusaeva, Karina; Carpenter, Robert

    2015-01-01

    Clostridium difficile is a leading cause of antibiotic-associated diarrhea and the etiologic agent responsible for C. difficile infection. Toxin A (TcdA) and toxin B (TcdB) are nearly indispensable virulence factors for Clostridium difficile pathogenesis. Given the toxin-centric mechanism by which C. difficile pathogenesis occurs, the selective sequestration with neutralization of TcdA and TcdB by nonantibiotic agents represents a novel mode of action to prevent or treat C. difficile-associated disease. In this preclinical study, we used quantitative enzyme immunoassays to determine the extent by which a novel drug, calcium aluminosilicate uniform particle size nonswelling M-1 (CAS UPSN M-1), is capable of sequestering TcdA and TcdB in vitro. The following major findings were derived from the present study. First, we show that CAS UPSN M-1 efficiently sequestered both TcdA and TcdB to undetectable levels. Second, we show that CAS UPSN M-1's affinity for TcdA is greater than its affinity for TcdB. Last, we show that CAS UPSN M-1 exhibited limited binding affinity for nontarget proteins. Taken together, these results suggest that ingestion of calcium aluminosilicate might protect gastrointestinal tissues from antibiotic- or chemotherapy-induced C. difficile infection by neutralizing the cytotoxic and proinflammatory effects of luminal TcdA and TcdB. PMID:26149988

  6. Formation of cobalt hydrotalcite by cation exchange of Co2+-substitued zeolite X

    NASA Astrophysics Data System (ADS)

    Jeong, H. Y.; Lee, K.

    2013-12-01

    Zeolite has been utilized to sequester heavy metals and nuclides due to the high cation exchange capacity. However, once-immobilized cations by zeolite tend to be re-exchanged by other cations (Ca2+, Mg2+, Na+, etc) present in groundwater. Thus, it is important to understand the mechanism associated with re-exchange reactions to predict the environmental fate and behavior of the metal cations sequestered by zeolite. In this study, we performed a series of cation exchange experiments using Co2+-substituted zeolite X (Co-X) in concentrated CaCl2 solutions. The radioactive isotope of cobalt (60Co2+), commonly found in low-to-intermediate level nuclear wastes, undergoes radioactive decay, likely altering the physicochemical properties of zeolite by generating heat and irradiation. To simulate such effects, Co-X was thermally treated at 400 and 600oC before re-exchange experiments. At the higher treatment temperature, the re-exchanged amount of Co2+ in Co-X by Ca2+ was found to decrease. According to X-ray diffraction, the re-exchange led to little change in the zeolite crystallinity for thermally untreated samples, but the significantly decreased crystallinity was noted for re-exchanged, thermally treated samples. Nonetheless, 27Al MAS NMR spectra of all re-exchanged samples revealed that the peaks corresponding to 4-fold coordinated Al became broader with their position shifting as a result of the re-exchange, suggesting that the re-exchange caused a short-range order structural distortion for both thermally untreated and treated samples. Also, Co-K edge X-ray absorption spectroscopy (XAS) was employed to examine the mechanism(s) involved in the re-exchange. By comparison of XAS spectra between re-exchanged samples and model compounds, Co2+ was likely to be either present as an extraframwork cation within zeolite or incorporated into a cobalt hydrotalcite (Co6Al2(OH)16(An-)2/n where An- is an interlayer anion) phase. The relative contribution of an extraframwork Co2+ versus cobalt hydrotalcite in re-exchanged samples was determined using the least squares fitting of EXAFS spectra. Formation of cobalt hydrotalcite became greater with the increasing treatment temperature. Taken together, thermally-induced structural distortion of zeolite enhanced the dealumination of zeolite and the subsequent formation of cobalt hydrotalcite.

  7. Metal immobilization in soils using synthetic zeolites.

    PubMed

    Oste, Leonard A; Lexmond, Theo M; Van Riemsdijk, Willem H

    2002-01-01

    In situ immobilization of heavy metals in contaminated soils is a technique to improve soil quality. Synthetic zeolites are potentially useful additives to bind heavy metals. This study selected the most effective zeolite in cadmium and zinc binding out of six synthetic zeolites (mordenite-type, faujasite-type, zeolite X, zeolite P, and two zeolites A) and one natural zeolite (clinoptilolite). Zeolite A appeared to have the highest binding capacity between pH 5 and 6.5 and was stable above pH 5.5. The second objective of this study was to investigate the effects of zeolite addition on the dissolved organic matter (DOM) concentration. Since zeolites increase soil pH and bind Ca, their application might lead to dispersion of organic matter. In a batch experiment, the DOM concentration increased by a factor of 5 when the pH increased from 6 to 8 as a result of zeolite A addition. A strong increase in DOM was also found in the leachate of soil columns, particularly in the beginning of the experiment. This resulted in higher metal leaching caused by metal-DOM complexes. In contrast, the free ionic concentration of Cd and Zn strongly decreased after the addition of zeolites, which might explain the reduction in metal uptake observed in plant growth experiments. Pretreatment of zeolites with acid (to prevent a pH increase) or Ca (to coagulate organic matter) suppressed the dispersion of organic matter, but also decreased the metal binding capacity of the zeolites due to competition of protons or Ca. PMID:12026084

  8. Enhanced selectivity of zeolites by controlled carbon deposition

    SciTech Connect

    Nenoff, Tina M.; Thoma, Steven G.; Kartin, Mutlu

    2006-05-09

    A method for carbonizing a zeolite comprises depositing a carbon coating on the zeolite pores by flowing an inert carrier gas stream containing isoprene through a regenerated zeolite at elevated temperature. The carbonized zeolite is useful for the separation of light hydrocarbon mixtures due to size exclusion and the differential adsorption properties of the carbonized zeolite.

  9. A novel concept for photovoltaic cells: clusters of titanium dioxide encapsulated within zeolites as photoactive semiconductors.

    PubMed

    Alvaro, Mercedes; Carbonell, Esther; Atienzar, Pedro; García, Hermenegildo

    2006-09-11

    Discrete clusters of TiO(2) (of only a few titanium atoms) are prepared within the internal micropore space of zeolite Y (4.8 wt % Ti loading) and characterized by Raman spectroscopy (rutile- and anatase-like structures), electron microscopy combined with elemental analyses (coincident Si and Ti spatial distribution), and X-ray diffraction (minor zeolite crystallinity decrease). The parent TiO(2)@Y sample is modified either by adsorption of acid-organic compounds (benzoic and 4-aminobenzoic acids or catechol) or by nitrogen doping. After modification, the optical UV/Vis spectrum of the parent TiO(2)@Y (onset of the absorption band at wavelengths <300 nm and bandgap of 4.2 eV) changes, and the appearance of new bands expanding to the visible region is observed. In contrast to the inactive zeolite Y matrix, all the zeolite-encapsulated TiO(2) species exhibit a photovoltaic response. The influence of the I(2)/I(3) (-) concentration in the electrolyte solution on the temporal profile of the photovoltage clearly shows that I(2)/I(3) (-) is also a suitable carrier for the positive charge in zeolite-based photovoltaic devices. The photocurrent response and the efficiency of the photovoltaic cell based on zeolite-encapsulated TiO(2) materials depend on the nature of the organic modifier and on the N-doping. The most efficient photovoltaic cell is that based on N-doped TiO(2)@Y, which exhibits a V(OC) (voltage at open circuit) of 270 mV, an I(SC) of 5.8 muA (current at short circuit), and a fill factor (FF) of 0.4. Although these values are low compared to current dye-sensitized TiO(2) solar cells, our findings could open up a promise for a stimulating research on the photovoltaic activity of zeolite-based host-guest solids. PMID:16921574

  10. One-pot pseudomorphic crystallization of mesoporous porous silica to hierarchical porous zeolites

    SciTech Connect

    Xing, Jun-Ling; Jiang, Shu-Hua; Pang, Jun-Ling; Yuan, En-Hui; Ma, Xiao-Jing; Lam, Koon-Fung; Xue, Qing-Song; Zhang, Kun

    2015-09-15

    Hierarchically porous silica with mesopore and zeolitic micropore was synthesized via pseudomorphic crystallization under high-temperature hydrothermal treatment in the presence of cetyltrimethylammonium tosylate and tetrapropylammonium ions. A combined characterization using small-angle X-ray diffraction (XRD), nitrogen adsorption, high-resolution transmission electron microscopy (TEM), thermogravimetric analysis (TG), and elemental analysis showed that dual templates, CTA{sup +} and TPA{sup +} molecules, can work in a cooperative manner to synthesize mesoporous zeolite in a one-pot system by precisely tuning the reaction conditions, such as reaction time and temperature, and type and amount of heterometal atoms. It is found that the presence of Ti precursor is critical to the successful synthesis of such nanostructure. It not only retards the nucleation and growth of crystalline MFI domains, but also acts as nano-binder or nano-glue to favor the assembly of zeolite nanoblocks. - Graphical abstract: Display Omitted - Highlights: • A facile method to synthesize mesoporous zeolites with hierarchical porosity was presented. • It gives a new insight into keeping the balance between mesoscopic and molecular ordering in hierarchical porous materials. • A new understanding on the solid–solid transformation mechanism for the synthesis of titanosilicate zeolites was proposed.

  11. A novel magnetic 4A zeolite adsorbent synthesised from kaolinite type pyrite cinder (KTPC)

    NASA Astrophysics Data System (ADS)

    Wang, Weiqing; Feng, Qiming; Liu, Kun; Zhang, Guofan; Liu, Jing; Huang, Yang

    2015-01-01

    As a solid waste, kaolinite type pyrite cinder (KTPC) is a special pyrite cinder, its mineral components include metakaolin and magnetite, and the chemical compositions of these minerals include SiO2, Al2O3, FeO and Fe2O3. In this study, a novel magnetic 4A zeolite adsorbent was synthesised from KTPC using the hydrothermal method, and the optimum hydrothermal synthesis conditions were investigated using X-ray diffraction (XRD) and by determining the specific surface area (SSA) and the saturated cation exchange adsorption capacity (SCEAC) to Cs+. Under the optimum hydrothermal synthesis conditions, the magnetic 4A zeolite adsorbent can be synthesised with high crystallinity, and the SSA and SCEAC to Cs+ are 24.49 m2/g and 106.63 mg/g, respectively. The further characterisations of pore size distribution, scanning electron microscopy (SEM), energy dispersive X-ray (EDX), thermogravimetry-derivative thermogravimetry-differential thermal analysis (TG-DTG-DTA), Fourier transform infrared spectroscopy (FTIR), vibrating sample magnetometer (VSM) were performed. The results revealed that magnetic particles are coated onto the zeolite surface and further form magnetic aggregates, and the existing magnetic particles in KTPC do not change their crystal structure and do not affect the synthesis of the 4A zeolite. In addition, the synthesised 4A zeolite adsorbent can be used as a magnetic adsorbent in wastewater treatment with high magnetic sensitivity and is thermally stable up to approximately 900 °C.

  12. Absence of Non-Bridging Oxygen on the Metaluminous Join in Potassium Aluminosilicate Glasses

    NASA Astrophysics Data System (ADS)

    Thompson, L. M.; Stebbins, J. F.

    2009-12-01

    In aluminosilicate melts and glasses, non-bridging oxygen (NBO) have a significant influence on thermodynamic and transport properties such as configurational entropy and viscosity. However, both its role and the extent of its influence are not yet fully understood, particularly in metaluminous and peraluminous compositions. Viscosity measurements from sodium, calcium, and magnesium aluminosilicate melts first suggested the presence of NBO on the metaluminous join (e.g. CaAl2O4-SiO2) (Toplis et al., 1996, 2004); direct observation with 17O nuclear magnetic resonance (NMR) spectroscopy has so far been limited to calcium aluminosilicate glasses, where it has been observed in both metalumious and peraluminous compositions (Stebbins et al., 2008). Potassium aluminosilicate glasses are another candidate for exploring the possibility of NBO on the metaluminous join, as the NBO peak is partially resolved from the bridging oxygen peak even in the one dimensional magic angle spinning (MAS) spectrum. However, preliminary analysis of 17O NMR spectra of slightly peraluminous potassium aluminosilicate glasses shows no detectable signal (<1% of total oxygen) in the area expected for NBO. Calcium aluminosilicate glasses of similar compositions have an NBO content of approximately 4.5%. This comparison shows an influence by the field strength of the network modifying cation on the presence of NBO and fraction of five-coordinated aluminum at the glass transition. However, understanding the extent of this impact in melts requires additional work exploring the temperature effects on speciation in the potassium aluminosilicate glasses.

  13. SODIUM ALUMINOSILICATE FOULING AND CLEANING OF DECONTAMINATED SALT SOLUTION COALESCERS

    SciTech Connect

    Poirier, M; Thomas Peters, T; Fernando Fondeur, F; Samuel Fink, S

    2008-10-28

    During initial non-radioactive operations at the Modular Caustic Side Solvent Extraction Unit (MCU), the pressure drop across the decontaminated salt solution coalescer reached {approx}10 psi while processing {approx}1250 gallons of salt solution, indicating possible fouling or plugging of the coalescer. An analysis of the feed solution and the 'plugged coalescer' concluded that the plugging was due to sodium aluminosilicate solids. MCU personnel requested Savannah River National Laboratory (SRNL) to investigate the formation of the sodium aluminosilicate solids (NAS) and the impact of the solids on the decontaminated salt solution coalescer. Researchers performed developmental testing of the cleaning protocols with a bench-scale coalescer container 1-inch long segments of a new coalescer element fouled using simulant solution. In addition, the authors obtained a 'plugged' Decontaminated Salt Solution coalescer from non-radioactive testing in the MCU and cleaned it according to the proposed cleaning procedure. Conclusions from this testing include the following: (1) Testing with the bench-scale coalescer showed an increase in pressure drop from solid particles, but the increase was not as large as observed at MCU. (2) Cleaning the bench-scale coalescer with nitric acid reduced the pressure drop and removed a large amount of solid particles (11 g of bayerite if all aluminum is present in that form or 23 g of sodium aluminosilicate if all silicon is present in that form). (3) Based on analysis of the cleaning solutions from bench-scale test, the 'dirt capacity' of a 40 inch coalescer for the NAS solids tested is calculated as 450-950 grams. (4) Cleaning the full-scale coalescer with nitric acid reduced the pressure drop and removed a large amount of solid particles (60 g of aluminum and 5 g of silicon). (5) Piping holdup in the full-scale coalescer system caused the pH to differ from the target value. Comparable hold-up in the facility could lead to less effective cleaning and precipitation of bayerite solid particles. (6) Based on analysis of the cleaning solutions from the full-scale test, the 'dirt capacity' of a 40 inch coalescer for these NAS solids was calculated to be 40-170 grams.

  14. Dynamic Reduction of FeO-Bearing, Anhydrous Aluminosilicate Melts

    NASA Astrophysics Data System (ADS)

    Everman, R. L.; Cooper, R. F.

    2004-12-01

    We have studied the reduction dynamics of FeO-bearing aluminosilicate melts at oxygen activities sufficiently low to form metallic iron. The experiments involved reacting droplets, suspended from refractory metal wires, with a high-temperature ( ˜1400oC), controlled-oxygen-activity environment maintained by a dynamic CO:CO2 buffer. In the case of an FeO-doped magnesium aluminosilicate ("Fe-MAS") melt ( ˜5 mol% FeO) exposed to an oxygen activity of 2x10-13 ("QIF-2"; CO:CO2=240:1), the reduction dynamic is rate-limited by chemical diffusion of Mg2+: oxygen chemically ablates from the free surface and the network-modifying cations diffuse inward, charge-compensated by a counterflux of electron holes (the "semiconductor condition" holds for diffusion dynamics in this melt [e.g., Cook and Cooper, 2000]); nm-scale crystals of pure α -Fe nucleate at an internal front. Diffusion of an oxygen species is not involved. In the case of FeO-doped calcium-magnesium aluminosilicate (Fe-CMAS) melt ( ˜8 mol% FeO) exposed to an oxygen activity of 2x10-15 (QIF-4; CO:CO2=1750:1), the dynamic changes: molten Fe-C-Si alloy droplets form near the surface, and bubbles are seen to form internally, truncating at an internal front. Further, the reaction occurs more slowly than that seen for the similarly polymerized Fe-MAS melt. The results suggests that molecular CO diffuses inward, consuming electron holes so as to form carbonate ion species in the melt [cf. Brooker et al., 2001]. Quenching produces a driving potential to reverse the internal reduction reaction, so creating the bubbles. Consumption of the electron holes by reaction with the carbon species dramatically reduces the reduction-to-metal kinetics. Brooker RA, Kohn SC, Holloway JR, McMillan PF (2001) Chem Geol 174:241-254; Cook GB, Cooper RF (2000) Am Mineral 85:397-406

  15. Hydrogen Selective Exfoliated Zeolite Membranes

    SciTech Connect

    Tsapatsis, Michael; Daoutidis, Prodromos; Elyassi, Bahman; Lima, Fernando; Iyer, Aparna; Agrawal, Kumar; Sabnis, Sanket

    2015-04-06

    The objective of this project was to develop and evaluate an innovative membrane technology at process conditions that would be representative of Integrated Gasification Combined Cycle (IGCC) advanced power generation with pre-combustion capture of carbon dioxide (CO2). This research focused on hydrogen (H2)-selective zeolite membranes that could be utilized to separate conditioned syngas into H2-rich and CO2-rich components. Both experiments and process design and optimization calculations were performed to evaluate the concept of ultra-thin membranes made from zeolites nanosheets. In this work, efforts in the laboratory were made to tackle two fundamental challenges in application of zeolite membranes in harsh industrial environments, namely, membrane thickness and membrane stability. Conventional zeolite membranes have thicknesses in the micron range, limiting their performance. In this research, we developed a method for fabrication of ultimately thin zeolite membranes based on zeolite nanosheets. A range of layered zeolites (MWW, RWR, NSI structure types) suitable for hydrogen separation was successfully exfoliated to their constituent nanosheets. Further, membranes were made from one of these zeolites, MWW, to demonstrate the potential of this group of materials. Moreover, long-term steam stability of these zeolites (up to 6 months) was investigated in high concentrations of steam (35 mol% and 95 mole%), high pressure (10 barg), and high temperatures (350 °C and 600 °C) relevant to conditions of water-gas-shift and steam methane reforming reactions. It was found that certain nanosheets are stable, and that stability depends on the concentration of structural defects. Additionally, models that represent a water-gas-shift (WGS) membrane reactor equipped with the zeolite membrane were developed for systems studies. These studies had the aim of analyzing the effect of the membrane reactor integration into IGCC plants in terms of performance and economic aspects of the plants. Specifically, simulation and design optimization studies were performed using the developed stand-alone membrane reactor models to identify the membrane selectivity and permeance characteristics necessary to achieve desired targets of CO2 capture and H2 recovery, as well as guide the selection of the optimal reactor design that minimizes the membrane cost as a function of its surface area required. The isothermal membrane reactor model was also integrated into IGCC system models using both the MATLAB and Aspen software platforms and techno-economic analyses of the integrated plants have been carried out to evaluate the feasibility of replacing current technologies for pre-combustion capture by the proposed novel approach in terms of satisfying stream constraints and achieving the DOE target goal of 90% CO2 capture. The results of the performed analyses based on present value of annuity calculations showed break even costs for the membrane reactor within the feasible range for membrane fabrication. However, the predicted membrane performance used in these simulations exceeded the performance achieved experimentally. Therefore, further work is required to improve membrane performance.

  16. Enhancing stability and oxidation activity of cytochrome C by immobilization in the nanochannels of mesoporous aluminosilicates.

    PubMed

    Lee, Chia-Hung; Lang, Jun; Yen, Chun-Wan; Shih, Pei-Chun; Lin, Tien-Sung; Mou, Chung-Yuan

    2005-06-30

    Hydrothermally stable and structrurally ordered mesoporous and microporous aluminosilicates with different pore sizes have been synthesized to immobilize cytochrome c (cyt c): MAS-9 (pore size 90 A), MCM-48-S (27 A), MCM-41-S (25 A), and Y zeolites (7.4 A). The amount of cyt c adsorption could be increased by the introduction of aluminum into the framework of pure silica materials. Among these mesoprous silicas (MPS), MAS-9 showed the highest loading capacity due to its large pore size. However, cyt c immobilized in MAS-9 could undergo facile unfolding during hydrothermal treatments. MCM-41-S and MCM-48-S have the pore sizes that match well the size of cyt c (25 x 25 x 37 A). Hence the adsorbed cyt c in these two medium pore size MPS have the highest hydrothermal stability and overall catalytic activity. On the other hand, the pore size of NaY zeolite is so small that cyt c is mostly adsorbed only on the outer surface and loses its enzymatic activity rapidly. The improved stability and high catalytic activity of cyt c immobilized in MPS are attributed to the electrostatic attraction between the pore surface and cyt c and the confinement provided by nanochannels. We further observed that cyt c immobilized in MPS exists in both high and low spin states, as inferred from the ESR and UV-vis studies. This is different from the native cyt c, which shows primarily the low spin state. The high spin state arises from the replacement of Met-80 ligands of heme Fe (III) by water or silanol group on silica surface, which could open up the heme groove for easy access of oxidants and substrates to iron center and facilitate the catalytic activity. In the catalytic study, MAS-9-cyt c showed the highest specific activity toward the oxidation of polycyclic aromatic hydrocarbons (PAHs), which arises from the fast mass transfer rate of reaction substrate due to its large pore size. For pinacyanol (a hydrophilic substrate), MCM-41-S-cyt c and MCM-48-S-cyt c showed higher specific activity than NaY-cyt c and MAS-9-cyt c. The result indicated that cyt c embedded in the channels of MCM-41-S and MCM-48-S was protected against unfolding and loss of activity. By increasing the concentration of the spin trapping agent, 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in ESR experiments, we showed that cyt c catalyzes a homolytic cleavage of the O-O bond of hydroperoxide and generates a protein cation radical (g = 2.00). Possible mechanisms for MPS-cyt c catalytic oxidation of hydroperoxides and PAHs are proposed based on the spectroscopic characterizations of the systems. PMID:16852515

  17. UTILITY OF ZEOLITES IN HAZARDOUS METAL REMOVAL FROM WATER

    EPA Science Inventory

    Zeolites are well known for their ion exchange, adsorption and acid catalysis properties. Different inorganic pollutants have been removed from water at room temperature by using synthetic zeolites. Zeolite Faujasite Y has been used to remove inorganic pollutants including arseni...

  18. Adsorption of β-galactosidase on silica and aluminosilicate adsorbents

    NASA Astrophysics Data System (ADS)

    Atyaksheva, L. F.; Dobryakova, I. V.; Pilipenko, O. S.

    2015-03-01

    It is shown that adsorption of β-galactosidase of Aspergillus oryzae fungi on mesoporous and biporous silica and aluminosilicate adsorbents and the rate of the process grow along with the diameter of the pores of the adsorbent. It is found that the shape of the adsorption isotherms changes as well, depending on the texture of the adsorbent: the Michaelis constant rises from 0.3 mM for the enzyme in solution to 0.4-0.5 mM for the enzyme on a surface in the hydrolysis of o-nitrophenyl-β-D-galactopyranoside. It is concluded that β-galactosidase displays its maximum activity on the surface of biporous adsorbents.

  19. Selective laser densification of lithium aluminosilicate glass ceramic tapes

    NASA Astrophysics Data System (ADS)

    Zocca, Andrea; Colombo, Paolo; Günster, Jens; Mühler, Thomas; Heinrich, Jürgen G.

    2013-01-01

    Tapes, cast by blade deposition of a lithium aluminosilicate glass slurry, were sintered using a YAG-fiber laser, with the aim of finding suitable parameters for an additive manufacturing process based on layer-wise slurry deposition and selective laser densification. The influence of the laser parameters (output power and scan velocity) on the sintering was evaluated, by scanning electron microscopy and by X-ray diffraction, on the basis of the quality of the processed layer. Well densified samples could be obtained only in a small window of values for the output power and the scan velocity. The measurement of the width of a set of single scanned lines allowed also to estimate the minimum resolution of the system along the layer plane.

  20. Multiple-quantum NMR studies of spin clusters in liquid crystals and zeolites

    SciTech Connect

    Pearson, J. . Dept. of Chemistry Lawrence Berkeley Lab., CA )

    1991-07-01

    This work will describe the use of MQ NMR to study spin clusters in anisotropic materials. A technique known as multiple-quantum spin counting was used to determine average spin cluster sizes liquid crystalline materials and in faujacitic zeolites containing aromatic hydrocarbons. The first half of the thesis will describe MQ NMR and the MQ spin counting technique, and the second half of the thesis will describe the actual experiments and their results.

  1. Spin probes of chemistry in zeolites

    SciTech Connect

    Werst, D.W.; Trifunac, A.D.

    1997-09-01

    Electron spin resonance (EPR) studies in zeolites are reviewed in which radiolysis was used to ionize the zeolite lattice, create reactive intermediates, spin label reaction products and to provide a window onto chemistry and transport of adsorbates and matrix control of chemistry. The review examines reactions of radical cations and the influence of the geometry constraints inside the zeolite, explores how zeolite model systems can be used to learn about energy and charge transfer in solids and illustrates the use of radiolysis and EPR for in situ spectroscopic studies of solid-acid catalysis. The various spin probes created inside the zeolite pores report on properties of the zeolites as well as shed light on radiolytic processes.

  2. Osmium(0) nanoclusters stabilized by zeolite framework; highly active catalyst in the aerobic oxidation of alcohols under mild conditions.

    PubMed

    Zahmakiran, Mehmet; Akbayrak, Serdar; Kodaira, Tetsuya; Ozkar, Saim

    2010-08-28

    Osmium(0) nanoclusters stabilized by zeolite-Y framework were reproducibly prepared by a simple two step procedure involving the incorporation of osmium(III) cations into the zeolite matrix by ion-exchange, followed by their reduction within the cavities of zeolite with sodium borohydride in aqueous solution all at room temperature. The composition and morphology of osmium(0) nanoclusters stabilized by zeolite framework, as well as the integrity and crystallinity of the host material were investigated by using ICP-OES, XRD, XPS, SEM, TEM, HRTEM, TEM/EDX, mid-IR, far-IR spectroscopies, and N(2)-adsorption/desorption technique. The results of the multiprong analysis reveal the formation of osmium(0) nanoclusters within the cavities of zeolite-Y without causing alteration in the framework lattice, formation of mesopores, or loss in the crystallinity of the host material. More importantly, far-IR studies showed that after the reduction of Os(3+) cations by sodium borohydride the Na(+) cations reoccupy their authentic cation sites restoring the integrity of zeolite-Y. The catalytic activity of osmium(0) nanoclusters stabilized by zeolite framework was tested in the aerobic oxidation of activated, unactivated and heteroatom containing alcohols to carbonyl compounds and was found to provide high activity and selectivity even under mild conditions (80 degrees C and 1 atm O(2) or air). Moreover, they were found to be stable enough to be isolated and bottled as solid material, which can be reused as active catalyst under the identical conditions of the first run. PMID:20614055

  3. Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2006-09-30

    The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of mesoporous aluminosilicate catalyst, Al-SBA-15, containing strong Broensted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt% Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst will be evaluated for the conversion of heavy petroleum feedstocks to naphtha and middle distillates.

  4. Increased thermal conductivity monolithic zeolite structures

    DOEpatents

    Klett, James; Klett, Lynn; Kaufman, Jonathan

    2008-11-25

    A monolith comprises a zeolite, a thermally conductive carbon, and a binder. The zeolite is included in the form of beads, pellets, powders and mixtures thereof. The thermally conductive carbon can be carbon nano-fibers, diamond or graphite which provide thermal conductivities in excess of about 100 W/mK to more than 1,000 W/mK. A method of preparing a zeolite monolith includes the steps of mixing a zeolite dispersion in an aqueous colloidal silica binder with a dispersion of carbon nano-fibers in water followed by dehydration and curing of the binder is given.

  5. The impact of aqueous medium on zeolite framework integrity

    SciTech Connect

    Vjunov, Aleksei; Fulton, John L.; Camaioni, Donald M.; Hu, Jian Z.; Burton, Sarah D.; Arslan, Ilke; Lercher, Johannes A.

    2015-05-12

    Understanding the zeolite framework stability in aqueous phase is crucial to develop stable catalysts. Al K–edge, extended X–ray absorption fine structure and 27Al MAS NMR spectroscopies in combination with DFT calculations have been used to monitor both qualitative and quantitative structural changes of two well–characterized samples with BEA structure. The effects of various properties on stability were explored, including Al concentration, Al distribution, particle size and structural defects. As the samples were degraded by treatment in hot liquid water, the local structure about the Al T–site remained mostly intact, including the Al–O–Si angles and bond distances, while the nano–scale crystalline structure as measured by XRD and TEM was disrupted. The combined data suggest a three–step mechanism in which, initially, the HBEA framework crystallinity decreases via hydrolysis of T–O bonds along polymorph stacking faults and inter–grain boundaries in a mode similar to crack propagation in glass. With prolonged exposure, amorphization occurs via hydrolysis of surface Si–OH groups propagating inward through the zeolite lattice. In parallel, cracks propagate within the crystalline micro–domains along paths through specific T–O–T groups. Authors thank B. W. Arey (PNNL) for HIM measurements, T. Huthwelker for support during Al XAFS measurements at the Swiss Light Source (PSI, Switzerland) and M. Y. Hu (PNNL) for support during NMR experiments. This work was supported by the U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. NMR experiments were performed at the Environmental Molecular Science Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research, and Physical Science Laboratory both located at Pacific Northwest National Laboratory (PNNL). PNNL is a multi–program national laboratory operated for DOE by Battelle under Contract No. DE–AC05–76RL01830.

  6. Superior performance of metal-organic frameworks over zeolites as solid acid catalysts in the Prins reaction: green synthesis of nopol.

    PubMed

    Opanasenko, Maksym; Dhakshinamoorthy, Amarajothi; Hwang, Young Kyu; Chang, Jong-San; Garcia, Hermenegildo; Čejka, Jiří

    2013-05-01

    The catalytic performance of a set of metal-organic frameworks [CuBTC, FeBTC, MIL-100(Fe), MIL-100(Cr), ZIF-8, MIL-53(Al)] was investigated in the Prins condensation of β-pinene with formaldehyde and compared with the catalytic behavior of conventional aluminosilicate zeolites BEA and FAU and titanosilicate zeolite MFI (TS-1). The activity of the investigated metal-organic frameworks (MOFs) increased with the increasing concentration of accessible Lewis acid sites in the order ZIF-8zeolites BEA and FAU, which showed significantly lower selectivity to the target nopol than the MOFs. Its high activity, the preservation of its structure and active sites, and the possibility to use it in at least three catalytic cycles without loss of activity make MIL-100 (Fe) the best performing catalyst of the series for the Prins condensation of β-pinene and paraformaldehyde. Our report exemplifies the advantages of MOFs over zeolites as solid catalysts in liquid-phase reactions for the production of fine chemicals. PMID:23592600

  7. Zeolites Remove Sulfur From Fuels

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E.; Sharma, Pramod K.

    1991-01-01

    Zeolites remove substantial amounts of sulfur compounds from diesel fuel under relatively mild conditions - atmospheric pressure below 300 degrees C. Extracts up to 60 percent of sulfur content of high-sulfur fuel. Applicable to petroleum refineries, natural-gas processors, electric powerplants, and chemical-processing plants. Method simpler and uses considerably lower pressure than current industrial method, hydro-desulfurization. Yields cleaner emissions from combustion of petroleum fuels, and protects catalysts from poisoning by sulfur.

  8. Synthesis, characterization and catalytic activity of indium substituted nanocrystalline Mobil Five (MFI) zeolite

    SciTech Connect

    Shah, Kishor Kr.; Nandi, Mithun; Talukdar, Anup K.

    2015-06-15

    Highlights: • In situ modification of the MFI zeolite by incorporation of indium. • The samples were characterized by XRD, FTIR, TGA, UV–vis (DRS), SAA, EDX and SEM. • The incorporation of indium was confirmed by XRD, FT-IR, UV–vis (DRS), EDX and TGA. • Hydroxylation of phenol reaction was studied on the synthesized catalysts. - Abstract: A series of indium doped Mobil Five (MFI) zeolite were synthesized hydrothermally with silicon to aluminium and indium molar ratio of 100 and with aluminium to indium molar ratios of 1:1, 2:1 and 3:1. The MFI zeolite phase was identified by XRD and FT-IR analysis. In XRD analysis the prominent peaks were observed at 2θ values of around 6.5° and 23° with a few additional shoulder peaks in case of all the indium incorporated samples suggesting formation of pure phase of the MFI zeolite. All the samples under the present investigation were found to exhibit high crystallinity (∼92%). The crystallite sizes of the samples were found to vary from about 49 to 55 nm. IR results confirmed the formation of MFI zeolite in all cases showing distinct absorbance bands near 1080, 790, 540, 450 and 990 cm{sup −1}. TG analysis of In-MFI zeolites showed mass losses in three different steps which are attributed to the loss due to adsorbed water molecules and the two types TPA{sup +} cations. Further, the UV–vis (DRS) studies reflected the position of the indium metal in the zeolite framework. Surface area analysis of the synthesized samples was carried out to characterize the synthesized samples The analysis showed that the specific surface area ranged from ∼357 to ∼361 m{sup 2} g{sup −1} and the pore volume of the synthesized samples ranged from 0.177 to 0.182 cm{sup 3} g{sup −1}. The scanning electron microscopy studies showed the structure of the samples to be rectangular and twinned rectangular shaped. The EDX analysis was carried out for confirmation of Si, Al and In in zeolite frame work. The catalytic activities of the synthesized samples were investigated with respect to hydroxylation of phenol, in which catechol and hydroquinone were found to be the major products. It is observed that under all reaction conditions catechol selectivity was higher than the hydroquinone selectivity. In-MFI zeolites were successfully synthesized and were used as an effective catalyst for the hydroxylation of phenol to synthesize catechol and hydroquinone as the major product.

  9. Electrical properties of the zeolite composites prepared by using zeolite and copper powders

    NASA Astrophysics Data System (ADS)

    Orbukh, V. I.; Lebedeva, N. N.; Ozturk, S.; Salamov, B. G.

    2013-02-01

    We present the electrical characterization of a zeolite plate and its composites prepared by using zeolite and copper powders. The experimentally obtained electronic and ionic conductivities and their interactions are discussed. It is established that electrical properties of the powder of natural zeolite which included 10% of the metallic Cu powder is fundamentally changed. However, the non-steady state decaying current in a pure zeolite powder is replaced with the steady state current, strongly dependent on the gas pressure. It is assumed that there is the gas discharge ignition in the nanopores of zeolite, initiated by electrons emission from Cu metal particles.

  10. Enhancing nitrification at low temperature with zeolite in a mining operations retention pond.

    PubMed

    Miazga-Rodriguez, Misha; Han, Sukkyun; Yakiwchuk, Brian; Wei, Kai; English, Colleen; Bourn, Steven; Bohnert, Seth; Stein, Lisa Y

    2012-01-01

    Ammonium nitrate explosives are used in mining operations at Diavik Diamond Mines Inc. in the Northwest Territories, Canada. Residual nitrogen is washed into the mine pit and piped to a nearby retention pond where its removal is accomplished by microbial activity prior to a final water treatment step and release into the sub-Arctic lake, Lac de Gras. Microbial removal of ammonium in the retention pond is rapid during the brief ice-free summer, but often slows under ice cover that persists up to 9 months of the year. The aluminosilicate mineral zeolite was tested as an additive to retention pond water to increase rates of ammonium removal at 4°C. Water samples were collected across the length of the retention pond monthly over a year. The structure of the microbial community (bacteria, archaea, and eukarya), as determined by denaturing gradient gel electrophoresis of PCR-amplified small subunit ribosomal RNA genes, was more stable during cold months than during July-September, when there was a marked phytoplankton bloom. Of the ammonia-oxidizing community, only bacterial amoA genes were consistently detected. Zeolite (10 g) was added to retention pond water (100 mL) amended with 5 mM ammonium and incubated at 12°C to encourage development of a nitrifying biofilm. The biofilm community was composed of different amoA phylotypes from those identified in gene clone libraries of native water samples. Zeolite biofilm was added to fresh water samples collected at different times of the year, resulting in a significant increase in laboratory measurements of potential nitrification activity at 4°C. A significant positive correlation between the amount of zeolite biofilm and potential nitrification activity was observed; rates were unaffected in incubations containing 1-20 mM ammonium. Addition of zeolite to retention ponds in cold environments could effectively increase nitrification rates year-round by concentrating active nitrifying biomass. PMID:22866052

  11. Enhancing Nitrification at Low Temperature with Zeolite in a Mining Operations Retention Pond

    PubMed Central

    Miazga-Rodriguez, Misha; Han, Sukkyun; Yakiwchuk, Brian; Wei, Kai; English, Colleen; Bourn, Steven; Bohnert, Seth; Stein, Lisa Y.

    2012-01-01

    Ammonium nitrate explosives are used in mining operations at Diavik Diamond Mines Inc. in the Northwest Territories, Canada. Residual nitrogen is washed into the mine pit and piped to a nearby retention pond where its removal is accomplished by microbial activity prior to a final water treatment step and release into the sub-Arctic lake, Lac de Gras. Microbial removal of ammonium in the retention pond is rapid during the brief ice-free summer, but often slows under ice cover that persists up to 9 months of the year. The aluminosilicate mineral zeolite was tested as an additive to retention pond water to increase rates of ammonium removal at 4°C. Water samples were collected across the length of the retention pond monthly over a year. The structure of the microbial community (bacteria, archaea, and eukarya), as determined by denaturing gradient gel electrophoresis of PCR-amplified small subunit ribosomal RNA genes, was more stable during cold months than during July–September, when there was a marked phytoplankton bloom. Of the ammonia-oxidizing community, only bacterial amoA genes were consistently detected. Zeolite (10 g) was added to retention pond water (100 mL) amended with 5 mM ammonium and incubated at 12°C to encourage development of a nitrifying biofilm. The biofilm community was composed of different amoA phylotypes from those identified in gene clone libraries of native water samples. Zeolite biofilm was added to fresh water samples collected at different times of the year, resulting in a significant increase in laboratory measurements of potential nitrification activity at 4°C. A significant positive correlation between the amount of zeolite biofilm and potential nitrification activity was observed; rates were unaffected in incubations containing 1–20 mM ammonium. Addition of zeolite to retention ponds in cold environments could effectively increase nitrification rates year-round by concentrating active nitrifying biomass. PMID:22866052

  12. PHYSICAL, CHEMICAL AND STRUCTURAL EVOLUTIION OF ZEOLITE-CONTAINING WASTE FORMS PRODUCED FROM METAKAOLINITE AND CALCINED SODUIM BEARING WASTE (HLW AND/OR LLW)

    SciTech Connect

    Grutzeck, Michael W.

    2003-06-15

    Zeolites can adsorb liquids and gases, take part in catalytic reactions and serve as cation exchange media. They are commercially available as finely divided powders. Using zeolites to manage radioactive waste is not new, but a process by which zeolites can be made to act both as a host phase and a cementing agent is. It is notable that zeolites occur in nature as well consolidated/cemented deposits. The Romans used blocks of Neapolitan zeolitized tuff as a building material and some of these buildings are still standing. Zeolites are easy to synthesize from a wide range of both natural and man-made precursor materials. The method of making a ''hydroceramic'' is derived from a process in which metakaolinite (thermally dehydroxylated kaolinite) is slurried with a dilute sodium hydroxide (NaOH) solution and then reacted for hours to days at mildly elevated temperatures (60-200 C). The zeolites that form in solution are finely divided powders containing micrometer sized crystals. However, if the process is changed and only enough concentrated sodium hydroxide solution (e.g. 12 M) is added to the metakaolinite to give the mixture a putty-like consistency and the mixture is then cured under similar conditions, the mixture becomes a very hard ceramic-like material containing distinct tectosilicate crystallites (zeolites and feldspathoids) imbedded in an X-ray amorphous sodium aluminosilicate hydrate matrix. Due to the material's vitreous character, the composite has been called a hydroceramic. Similar to zeolite/feldspathoid powders, a hydroceramic is able to sequester cations and a wide range of salt molecules (e.g., nitrate, nitrite and sulfate) in lattice positions and within structural channels and voids thus rendering them ''insoluble'' and making them an ideal contingency waste form for solidifying radioactive waste. The obvious similarities between a hydroceramic waste form and a waste form based on solidified Portland-cement grout are superficial because their chemistries are entirely different. In addition to being vastly superior to conventional Portland cement grouts with respect to salt retention, standard radwaste leach protocols (PCT, TCLP) have shown that hydroceramics also do a better job of immobilizing the RCRA-toxic and radioactive components of liquid sodium bearing waste (SBW) now in storage at DOE's Hanford, Savannah River and Idaho sites.

  13. SEQUESTERING MANURE N WITH SYNTHETIC ZEOLITES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Natural zeolites have a long and successful history of agricultural use in Japan and more recently in the U.S. However the price (often > $US500 Mg -1) limits their use in agriculture. Zeolites can be synthesized from fly ash by reaction with sodium hydroxide solutions and low temperature. The proje...

  14. Metal/zeolite catalysts of methane dehydroaromatization

    NASA Astrophysics Data System (ADS)

    Mamonov, N. A.; Fadeeva, E. V.; Grigoriev, D. A.; Mikhailov, M. N.; Kustov, Leonid M.; Alkhimov, S. A.

    2013-06-01

    Results of studying methane dehydroaromatization over metal/zeolite catalysts have been reviewed. Special attention has focused on molybdenum catalysts based on HZSM-5 zeolites. The effect of catalyst synthesis and reaction conditions on the catalytic properties of the systems has been scrutinized. Information on the mechanism of the process and the nature of active sites has been reported. The bibliography includes 137 references.

  15. Crystalline and Crystalline International Disposal Activities

    SciTech Connect

    Viswanathan, Hari S.; Chu, Shaoping; Reimus, Paul William; Makedonska, Nataliia; Hyman, Jeffrey De'Haven; Karra, Satish; Dittrich, Timothy M.

    2015-12-21

    This report presents the results of work conducted between September 2014 and July 2015 at Los Alamos National Laboratory in the crystalline disposal and crystalline international disposal work packages of the Used Fuel Disposition Campaign (UFDC) for DOE-NE’s Fuel Cycle Research and Development program.

  16. Dissolution of lanthanide alumino-silicate oxynitride glasses

    NASA Astrophysics Data System (ADS)

    Bois, L.; Barré, N.; Guillopé, S.; Guittet, M. J.; Gautier-Soyer, M.; Duraud, J. P.; Trocellier, P.; Verdier, P.; Laurent, Y.

    2000-01-01

    The aqueous corrosion behavior of lanthanide aluminosilicate glasses has been studied under static conditions ( T=96°C, duration=1 and 3 months, glass surface area/leachate volume, S/ V=0.3 cm -1) by means of solution and solid analyses. It was found that these glasses exhibit a high chemical durability. The influence of yttrium, magnesium and nitrogen, which are supposed to improve the mechanical properties, on the chemical durability, has been investigated. After a one-month experiment, lanthanum and yttrium releases were found to be about 10 -7 mol l -1, while silicon and aluminum releases were about 10 -5 mol l -1. Yttrium seems to improve the chemical durability. The presence of nitrogen does not seem to modify the glass constituents releases, but seems to improve the surface state of the altered glass. XPS experiments reveal that lanthanum and yttrium are more concentrated near the surface (20-30 Å) of the glass after the leaching test.

  17. MoO3 incorporation in magnesium aluminosilicate glasses

    NASA Astrophysics Data System (ADS)

    Tan, Shengheng; Ojovan, Michael I.; Hyatt, Neil C.; Hand, Russell J.

    2015-03-01

    Molybdate has a very low solubility in silicate and borosilicate glass systems and its excess presence in nuclear waste glass can cause the formation of a readily soluble "yellow phase". In this study, the incorporation of molybdenum oxide (MoO3) in a magnesium aluminosilicate glass system has been investigated. The prepared glasses show a higher than 90% molybdenum retention rate and up to 5.34 mol% (12.28 wt%) MoO3 can be incorporated into these glasses without causing visible phase separation. The incorporation of MoO3 increases glass density, decreases glass transition and crystallisation temperatures and intensifies Raman bands assigned to vibrations of MoO42- units. When excess molybdate is added liquid-liquid phase separation and crystallisation occurs. The separated phase is spherical, 200-400 nm in diameter and randomly dispersed. Based on powder X-ray diffraction, Raman spectroscopy and transmission electron microscopy, the separated phase is identified as MgMoO4.

  18. Mixed alkaline earth effect in the compressibility of aluminosilicate glasses

    NASA Astrophysics Data System (ADS)

    Smedskjaer, Morten M.; Rzoska, Sylwester J.; Bockowski, Michal; Mauro, John C.

    2014-02-01

    The mixed modifier effect (MME) in oxide glasses manifests itself as a non-additive variation in certain properties when one modifier oxide species is substituted by another one at constant total modifier content. However, the structural and topological origins of the MME are still under debate. This study provides new insights into the MME by investigating the effect of isostatic compression on density and hardness of mixed MgO/CaO sodium aluminosilicate glasses. This is done using a specially designed setup allowing isostatic compression of bulk glass samples up to 1 GPa at elevated temperature. A mixed alkaline earth effect is found in the compressibility and relative change of hardness, viz., a local maximum of density as a function of Mg/Ca ratio appears following compression, whereas a local minimum of hardness in the uncompressed glasses nearly disappears after compression. Moreover, the densification of these glasses is found to occur at temperatures much below the glass transition temperature, indicating that a non-viscous mechanism is at play. This is further supported by the fact that density relaxes in a stretched exponential manner upon subsequent annealing at ambient pressure with an exponent of ˜0.62. This is close to the Phillips value of 3/5 for relaxation in three dimensions when both short- and long-range interactions are activated.

  19. Dehydration, dehydroxylation, and rehydroxylation of single-walled aluminosilicate nanotubes.

    PubMed

    Kang, Dun-Yen; Zang, Ji; Wright, Elizabeth R; McCanna, Arthur L; Jones, Christopher W; Nair, Sankar

    2010-08-24

    Single-walled metal oxide (aluminosilicate) nanotubes are excellent candidates for addressing the long-standing issue of functionalizing nanotube interiors, due to their high surface reactivity and controllable dimensions. However, functionalization of the nanotube interior is impeded by its high surface silanol density (9.1 -OH/nm(2)) and resulting hydrophilicity. Controlled dehydration of the nanotubes is critical for the success of functionalization efforts. We employ a range of solid-state characterization tools to elucidate dehydration and dehydroxylation phenomena in the nanotubes as a function of heat treatment up to 450 degrees C. Vibrational spectroscopy (Fourier transform infrared, FT-IR), thermogravimetric analysis-mass spectrometry (TGA-MS), nitrogen physisorption, solid-state NMR, and X-ray diffraction (XRD) reveal that a completely dehydrated condition is achieved at 250 degrees C under vacuum and that the maximum pore volume is achieved at 300 degrees C under vacuum due to partial dehydroxylation of the dehydrated nanotube. Beyond 300 degrees C, further dehydroxylation partially disorders the nanotube wall structure. However, a unique rehydroxylation mechanism can partially reverse these structural changes upon re-exposure to water vapor. Finally, detailed XRD simulations and experiments allow further insight into the nanotube packing, the dimensions, and the dependence of nanotube XRD patterns on the water content. PMID:20684571

  20. Surface functionalization of aluminosilicate nanotubes with organic molecules

    PubMed Central

    Ma, Wei; Yah, Weng On; Otsuka, Hideyuki

    2012-01-01

    Summary The surface functionalization of inorganic nanostructures is an effective approach for enriching the potential applications of existing nanomaterials. Inorganic nanotubes attract great research interest due to their one-dimensional structure and reactive surfaces. In this review paper, recent developments in surface functionalization of an aluminosilicate nanotube, “imogolite”, are introduced. The functionalization processes are based on the robust affinity between phosphate groups of organic molecules and the aluminol (AlOH) surface of imogolite nanotubes. An aqueous modification process employing a water soluble ammonium salt of alkyl phosphate led to chemisorption of molecules on imogolite at the nanotube level. Polymer-chain-grafted imogolite nanotubes were prepared through surface-initiated polymerization. In addition, the assembly of conjugated molecules, 2-(5’’-hexyl-2,2’:5’,2’’-terthiophen-5-yl)ethylphosphonic acid (HT3P) and 2-(5’’-hexyl-2,2’:5’,2’’-terthiophen-5-yl)ethylphosphonic acid 1,1-dioxide (HT3OP), on the imogolite nanotube surface was achieved by introducing a phosphonic acid group to the corresponding molecules. The optical and photophysical properties of these conjugated-molecule-decorated imogolite nanotubes were characterized. Moreover, poly(3-hexylthiophene) (P3HT) chains were further hybridized with HT3P modified imogolite to form a nanofiber hybrid. PMID:22428100

  1. SODIUM ALUMINOSILICATE SOLIDS AFFINITY FOR CESIUM AND ACTINIDES

    SciTech Connect

    Peters, T; Bill Wilmarth, B; Samuel Fink, S

    2007-07-31

    Washed sodium-aluminosilicate (NAS) solids at initial concentrations of 3.55 and 5.4 g/L sorb or uptake virtually no cesium over 288 hours, nor do any NAS solids generated during that time. These concentrations of solids are believed to conservatively bound current and near-term operations. Hence, the NAS solids should not have affected measurements of the cesium during the mass transfer tests and there is minimal risk of accumulating cesium during routine operations (and hence posing a gamma radiation exposure risk in maintenance). With respect to actinide uptake, it appears that NAS solids sorb minimal quantities of uranium - up to 58 mg U per kg NAS solid. The behavior with plutonium is less well understood. Additional study may be needed for radioactive operations relative to plutonium or other fissile component sorption or trapping by the solids. We recommend this testing be incorporated in the planned tests using samples from Tank 25F and Tank 49H to extend the duration to bound expected inventory time for solution.

  2. UTILITY OF ZEOLITES IN ARSENIC REMOVAL FROM WATER

    EPA Science Inventory

    Zeolites are well known for their ion exchange and adsorption properties. So far the cation exchanger properties of zeolites have been extensively studied and utilized. The anion exchanger properties of zeolites are less studied. Zeolite Faujasite Y has been used to remove arseni...

  3. Preliminary study on calcium aluminosilicate glass as a potential host matrix for radioactive 90Sr--an approach based on natural analogue study.

    PubMed

    Sengupta, Pranesh; Fanara, Sara; Chakraborty, Sumit

    2011-06-15

    Given the environmental-, safety- and security risks associated with sealed radioactive sources it is important to identify suitable host matrices for (90)Sr that is used for various peaceful applications. As SrO promotes phase separation within borosilicate melt, aluminosilicate bulk compositions belonging to anorthite-wollastonite-gehlenite stability field are studied in this work. Tests for their homogeneity, microstructural characteristics and resistance to phase separation narrowed the choice down to the composition CAS11 (CaO=35 wt%, Al(2)O(3)=20 wt%, SiO(2)=45 wt%). We find that up to 30 wt% SrO can be loaded in this glass without phase separation (into Ca, Sr-rich and Sr-poor, Si-rich domains). Leaching behaviour of the glasses differs depending on the content and distribution of Sr. In general, the elemental leach rates determined from conventional PCT experimental procedure yield values better than 10(-7)gcm(-2)day(-1) for both CAS11 base glass as well as SrO doped glass. It was noted that leach rates calculated on the basis of Ca(2+) and Sr(2+) were of the same order and bit higher compared to those calculated on the basis of Si(4+) and Al(3+). During accelerated leaching tests, zeolite and zeolite+epidote were found to have developed on CAS11 base glass and SrO doped glasses respectively. The Sr bulk diffusion coefficients is found to vary from ∼ 10(-15) to 10(-13)cm(2)/s at temperature intervals as high as 725-850°C. Based on the experimental observations, it is suggested that CAS11 glass can be used as host matrix of (90)Sr for various applications of radioactive Sr-pencils. PMID:21477923

  4. Dealumination of hexagonal (EMT)/cubic (FAU) zeolite intergrowth materials: A SEM and HRTEM study

    SciTech Connect

    Ohsuna, Tetsu; Watanabe, Denjiro; Terasaki, Osamu; Anderson, M.W.; Carr, S.W.

    1994-12-01

    The aim of this paper is to describe the effects of mild dealumination of the end members (FAU, EMT) and intergrowths produced using crown ethers on the nature of the resultant zeolite. The end members and intergrowths were prepared as described previously and dealuminated according to the following procedure. The intergrowth was prepared from a mixture of crown ethers; 66% 18-crown-6 and 33% 15-crown-5 to give an ordered intergrowth. The zeolites were first calcined to remove the crown ether template (600{degree}C, flowing air, 16 h) and then exchanged with ammonium ions. The zeolite (6 g) was slurried in ammonium acetate solution (450 cm{sup 3}, 0.8 M), and to this was added slowly 15.6 cm{sup 3} of ammonium hexafluorosilicate solution (0.5 M). The mixture was stirred at 75{degree}C for 3 h. The zeolite was collected and carefully washed with water (3 x 100 cm{sup 3}). The dealuminated samples were characterized by {sup 29}Si and {sup 27}Al MAS NMR, X-ray powder diffraction and adsorption measurements. These data indicate that the resultant materials are highly crystalline and showed no signs of structural degradation both in short-range order ({sup 27}Al, {sup 29}Si MAS NMR) and long-range order (XRD). However, the SEM and high-resolution images were particularly informative.

  5. Zeolites on Mars: Prospects for Remote Sensing

    NASA Technical Reports Server (NTRS)

    Gaffney, E. S.; Singer, R. B.; Kunkle, T. D.

    1985-01-01

    The Martian surface composition measured by Viking can be represented by several combinations of minerals incorporating major fractions of zeolites known to occur in altered mafic rocks and polar soils on Earth. The abundant occurrence of zeolites on Mars is consistent with what is known about both the physical and chemical environment of that planet. The laboratory reflectance spectra (0.65 to 2.55 microns) of a number of relatively pure zeolite minerals and some naturally occurring zeolite-clay soils were measured. All of the spectra measured are dominated by strong absorption near 1.4 and 1.9 microns and a steep reflectance drop longward of about 2.2 microns, all of which are due to abundant H2O. Weaker water overtone bands are also apparent, and in most cases there is spectral evidence for minor Fe(3+). In these features the zeolite spectra are similar to spectra of smectite clays which have abundant interlayer water. The most diagnostic difference between clay and zeolite spectra is the total absence in the zeolites of the weak structural OH absorption.

  6. Water nanodroplets confined in zeolite pores.

    PubMed

    Coudert, François-Xavier; Cailliez, Fabien; Vuilleumier, Rodolphe; Fuchs, Alain H; Boutin, Anne

    2009-01-01

    We provide a comprehensive depiction of the behaviour of a nanodroplet of approximately equal to 20 water molecules confined in the pores of a series of 3D-connected isostructural zeolites with varying acidity, by means of molecular simulations. Both grand canonical Monte Carlo simulations using classical interatomic forcefields and first-principles Car-Parrinello molecular dynamics were used in order to characterise the behaviour of confined water by computing a range of properties, from thermodynamic quantities to electronic properties such as dipole moment, including structural and dynamical information. From the thermodynamic point of view, we have identified the all-silica zeolite as hydrophobic, and the cationic zeolites as hydrophilic; the condensation transition in the first case was demonstrated to be of first order. Furthermore, in-depth analysis of the dynamical and electronic properties of water showed that water in the hydrophobic zeolite behaves as a nanodroplet trying to close its hydrogen-bond network onto itself, with a few short-lived dangling OH groups, while water in hydrophilic zeolites "opens up" to form weak hydrogen bonds with the zeolite oxygen atoms. Finally, the dipole moment of confined water is studied and the contributions of water self-polarisation and the zeolite electric field are discussed. PMID:19227366

  7. Structure-Entropy Relationships in Aluminosilicate Garnets (Invited)

    NASA Astrophysics Data System (ADS)

    Geiger, C. A.; Dachs, E.

    2013-12-01

    Aluminosilicate garnet (X3Al2Si3O12) is a key rock-forming mineral whose geological occurrence is widespread. Various petrologic, geochemical and geophysical processes can be best interpreted if garnet's structure and thermodynamic properties are understood. Extensive research has been done on garnet's crystal-chemical properties using diffraction and spectroscopic measurements as well as computational methods. The level of understanding is, in general, good. In terms of macroscopic thermodynamic properties, there has also been much work done over the years. Here, however, the level of understanding is less. Consider the crystal chemistry and entropy behavior of two binary solid solutions, namely pyrope-grossular (Py-Gr) [(MgxCa1-x)3Al2Si3O12] and almandine-spessartine (Al-Sp) [(FexMn1-x)3Al2Si3O12]. The heat capacity, Cp, of a series of well characterized natural and synthetic almandine-spessartine garnets was recently measured between 3 and 300 K (Dachs et al., submitted). All garnets show a λ-type anomaly at low temperatures resulting from a paramagnetic-antiferromagnetic phase transition. The lattice heat capacity, Cp,vib, was calculated for each garnet member by applying the phonon dispersion model of Komada and Westrum (1997). This allows a decomposition of S298 into its vibrational (Svib) and magnetic (Smag) contributions. A full analysis shows that the Al-Sp binary is entropically ideal with ΔSex ≈ 0 at 298 K. Previously published calorimetric work on Py-Gr garnets shows, in contrast, substantial positive ΔSex across the join at 298 K (Dachs and Geiger, 2006). Why the difference? The vibrational behavior of the divalent X cations plays an important role in affecting macroscopic Cp,vib and Svib in aluminosilicate garnets. X-ray single-crystal diffraction and XAFS measurements show that the mean square amplitudes of vibration for Fe2+ in Al and Mn2+ in Sp are similar and, moreover, they do not vary significantly in magnitude as a function of composition across the Al-Sp binary. Vibrational modes in IR and Raman spectra of Al-Sp garnets show mostly continuous and linear variation in wavenumber across the binary. These results are fully consistent with the calorimetric work indicating ΔSex ≈ 0 at 298 K. In contrast, the mean square amplitudes of vibration of Mg and Ca in Py-Gr garnets are substantially different from each other. The behavior of IR and Raman modes in spectra of Py-Gr garnets are also quite different than the spectra of Al-Sp garnets. Low energy modes related to Ca and especially Mg do not shift linearly in energy across the Py-Gr join but soften in intermediate compositions. This behavior is considered to be the cause of the large positive ΔSex behavior. Al-Sp garnets differ, of course, from Py-Gr garnets because of their magnetic and electronic contributions to Cp and S.

  8. Structure of Ca and Mg aluminosilicate melts under pressure

    NASA Astrophysics Data System (ADS)

    Urakawa, S.; Kikegawa, T.

    2007-12-01

    Viscosity and density are important physical properties to control the transportation of magma in the Earth's interior, which are affected by microscopic structure of magma. Magmas have been considered to be densified by structural change with increasing pressure. Recently, Allwardt et al. (2005) found the structure change in auminosilicate glasses quenched under pressure using the NMR spectroscopy, in which an average coordination number of aluminium increases from four to five up to about 10 GPa. We carried out direct observation of structural change in aluminsilicate melts by using in-situ X-ray diffraction method. High-pressure and high-temperature experiments were conducted using MAX80 installed at AR-NE5C of Photon Factory, Tsukuba, Japan. Energy dispersive X-ray diffraction method is applied to acquire diffraction patterns from molten samples. X-ray diffraction spectra were acquired for Ca3Al2Si6O18 and Mg3Al2Si6O18 composition melts up to 5 GPa and 2000 K. Signs of pressure-induced structural change are observed in radial distribution functions as well as in diffraction patterns. The first sharp diffraction peaks (FSDP) shift to higher-Q side with increasing pressure, indicating reduction of the size of the intermediate rage structure, such as rings or chains composed of SiO4 and AlO4 tetrahedra. Radial distribution function also changes with pressure. The nearest neighbour T-O peak (composed of Si-O and Al-O interactions) becomes asymmetric, indicating the coordination increase of the nearest neighbour ions. These observations are consistent with the densification of high-pressure quenched aluminosilicate glasses.

  9. Aqueous dissolution of sodium aluminosilicate geopolymers derived from metakaolin

    NASA Astrophysics Data System (ADS)

    Aly, Z.; Vance, E. R.; Perera, D. S.

    2012-05-01

    In dilute aqueous solutions, the elemental releases of Na, Al and Si from a metakaolin-based sodium aluminosilicate geopolymer were not very sensitive to pH in the range of 4-10 but increased outside this range, particularly on the acidic side. To minimise pH drifts, experiments were carried out using small amounts of graded powders in relatively large volumes of water. In deionised water, the Na dissolution rate in 7 days was dominant and increased by at least a factor of ˜4 on heating from 18 to 90 °C, with greater increases in the extractions of Al and Si. At 18 °C the elemental extractions in deionised water increased approximately linearly with time over the 1-7 days period. Further exposure led to a slower extraction into solution for Na and Si, with a decrease in extraction of Al. It was deduced that framework dissolution was important in significantly acidic or alkaline solutions, but that contributions from water transfer from pores to elemental extractions were present, even at low temperatures in neutral solutions. It was also deduced from the Na release data that the Na leaching kinetics of geopolymer in deionised water (dilute solutions) followed the pseudo-second-order kinetic model and the pseudo-second-order rate constant evaluated. Contact with KCl, KHCO3, and pH ˜6 and 10 potassium phthalate buffer solutions gave rise to a high degree of Na+ ↔ K+ exchange and rendered the framework ions less leachable in water.

  10. Imogolite: an aluminosilicate nanotube endowed with low cytotoxicity and genotoxicity.

    PubMed

    Rotoli, Bianca Maria; Guidi, Patrizia; Bonelli, Barbara; Bernardeschi, Margherita; Bianchi, Massimiliano G; Esposito, Serena; Frenzilli, Giada; Lucchesi, Paolo; Nigro, Marco; Scarcelli, Vittoria; Tomatis, Maura; Zanello, Pier Paolo; Fubini, Bice; Bussolati, Ovidio; Bergamaschi, Enrico

    2014-07-21

    High-aspect-ratio nanomaterials (HARN) (typically, single-walled carbon nanotubes (SWCNT) or multiwalled carbon nanotubes (MWCNT)) impair airway barrier function and are toxic to macrophages. Here, we assess the biological effects of nanotubes of imogolite (INT), a hydrated alumino-silicate [(OH)3Al2O3SiOH] occurring as single-walled NT, on murine macrophages and human airway epithelial cells. Cell viability was assessed with resazurin. RT-PCR was used to study the expression of Nos2 and Arg1, markers of classical or alternative macrophage activation, respectively, and nitrite concentration in the medium was determined to assess NO production. Epithelial barrier integrity was evaluated from the trans-epithelial electrical resistance (TEER). Potential genotoxicity of INT was assessed with comet and cytokinesis-block micronucleus cytome assays. Compared to MWCNT and SWCNT, INT caused much smaller effects on RAW264.7 and MH-S macrophage viability. The incubation of macrophages with INT at doses as high as 120 μg/cm(2) for 72 h did not alter either Nos2 or Arg1 expression nor did it increase NO production, whereas IL6 was induced in RAW264.7 cells but not in MH-S cells. INT did not show any genotoxic effect in RAW264.7 and A549 cells except for a decrease in DNA integrity observed in epithelial A549 cells after treatment with the highest dose (80 μg/cm(2)). No significant change in permeability was recorded in Calu-3 epithelial cell monolayers exposed to INT, whereas comparable doses of both SWCNT and MWCNT lowered TEER. Thus, in spite of their fibrous nature, INT appear not to be markedly toxic for in vitro models of lung-blood barrier cells. PMID:24933079

  11. Dominant toughening mechanisms in barium aluminosilicate (BAS) glass-ceramics

    NASA Astrophysics Data System (ADS)

    Griggs, Jason Alan

    The purpose of this study was to develop a barium aluminosilicate (BAS) glass-ceramic with improved strength and fracture toughness by controlling the morphology of the constituent phases through a series of thermal crystallization treatments. The specific objectives of this study were to (1) determine which toughening mechanisms are active in the BAS system, (2) provide quantitative estimates of the relative contributions of those mechanisms, and (3) identify the processing conditions that correspond to a glass-ceramic with optimal fracture toughness. The BAS system was chosen for this study because of its potential applications in CAD-CAM production of dental prostheses. It is concluded that load sharing and crack deflection are the only major sources of toughening in the BAS system. Theoretical predictions for toughening increases due to load sharing and crack deflection are insufficient to account for 100% of the increases observed. The excess increase in fracture toughness is produced by thermal mismatch between and crystal and glass phases. The strength and fracture toughness of BAS glass-ceramics are shown to increase with increasing crystal growth time over the entire range of treatments studied. The strength and fracture toughness increased from 63 ± 8 MPa and 0.89 ± 0.05 MPa*msp{1/2}, respectively for BAS glass to 141 ± 8 MPa and 1.87 ± 0.07 MPa*msp{1/2} respectively for a glass-ceramic treated for 256 h at 975sp°C. Fracture toughness was also shown to increase with increasing mean crystal size. A non-stoichiometric glass composition results in thermal compatibility between the glass and crystal phases, eliminating the weakening at large crystal sizes that can be associated with a spontaneous microcracking mechanism.

  12. The role of zeolite in the Fischer-Tropsch synthesis over cobalt-zeolite catalysts

    NASA Astrophysics Data System (ADS)

    Sineva, L. V.; Asalieva, E. Yu; Mordkovich, V. Z.

    2015-11-01

    The review deals with the specifics of the Fischer-Tropsch synthesis for the one-stage syncrude production from CO and H2 in the presence of cobalt-zeolite catalytic systems. Different types of bifunctional catalysts (hybrid, composite) combining a Fischer-Tropsch catalyst and zeolite are reviewed. Special attention focuses on the mechanisms of transformations of hydrocarbons produced in the Fischer-Tropsch process on zeolite acid sites under the synthesis conditions. The bibliography includes 142 references.

  13. Copper-Exchanged Zeolite L Traps Oxygen

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K.; Seshan, Panchalam K.

    1991-01-01

    Brief series of simple chemical treatments found to enhance ability of zeolite to remove oxygen from mixture of gases. Thermally stable up to 700 degrees C and has high specific surface area which provides high capacity for adsorption of gases. To increase ability to adsorb oxygen selectively, copper added by ion exchange, and copper-exchanged zeolite reduced with hydrogen. As result, copper dispersed atomically on inner surfaces of zeolite, making it highly reactive to oxygen, even at room temperature. Reactivity to oxygen even greater at higher temperatures.

  14. Photoinduced electron transfer reactions in zeolite cages

    SciTech Connect

    Dutta, P.K.

    1992-01-01

    This report summarizes work in the two areas of zeolites and layered double hydroxides. Results of studies on structural aspects of Ru(bpy)[sub 3][sup 2+]-zeolite Y are summarized. Photoinduced electron transfer between entrapped Ru(bpy)[sub 3][sup 2+] and methylviologen (MV) in neighboring supercages was examined. Benzylviologen was also used. Since molecules larger than 13 [angstrom] cannot be accomodated in zeolite cages, the layered double metal hydroxides (LDH) LiAl[sub 2](OH)[sub 6][sup +]X[sup [minus

  15. Pulsed laser deposition of zeolitic membranes

    SciTech Connect

    Peachey, N.M.; Dye, R.C.; Ries, P.D.

    1995-02-01

    The pulsed laser deposition of zeolites to form zeolitic thin films is described. Films were grown using both mordenite and faujasite targets and were deposited on various substrates. The optimal films were obtained when the target and substrate were separated by 5 cm. These films are comprised of small crystallites embedded in an amorphous matrix. Transmission electron microscopy reveals that the amorphous material is largely porous and that the pores appear to be close to the same size as the parent zeolite. Zeolotic thin films are of interest for sensor, gas separation, and catalytic applications.

  16. CuO nanoparticles incorporated in hierarchical MFI zeolite as highly active electrocatalyst for non-enzymatic glucose sensing.

    PubMed

    Dong, Junping; Tian, Taolei; Ren, Linxiao; Zhang, Yuan; Xu, Jiaqiang; Cheng, Xiaowei

    2015-01-01

    A hierarchical MFI zeolite, with typical micro/meso bimodal pore structures, was prepared by desilication method. CuO nanoparticles (NPs) were incorporated into the hierarchical MFI zeolite by impregnation method. CuO/hierarchical zeolite composites were characterized by X-ray diffraction, transmission electron microscopy and nitrogen sorption. It is shown that the CuO nanoparticles are mostly dispersed in the mesopores with remaining of the crystallinity and morphology of the host zeolite. CuO nanoparticles located in hierarchical zeolite exhibit the excellent electrocatalytic performances to oxidation of glucose in alkaline media. The electrocatalytic activity enhances with increasing the loading content of CuO from 5% to 15%. The composites were fabricated for nonenzyme glucose sensing. Under the optimal conditions, the sensor shows a wide linear range from 5×10(-7) to 1.84×10(-2) M with a low detection limit of 3.7×10(-7) M. The sensor also exhibits good repeatability, long-term stability as well as high selectivity against interfering species. PMID:25499226

  17. Studies on the formation of hierarchical zeolite T aggregates with well-defined morphology in different template systems

    NASA Astrophysics Data System (ADS)

    Yin, Xiaoyan; Chu, Naibo; Lu, Xuewei; Li, Zhongfang; Guo, Hong

    2016-01-01

    In this paper, the disk-like and pumpkin-like hierarchical zeolite T aggregates consisted of primary nano-grains have been hydrothermally synthesized with and without the aid of the second template. The first template is used with tetramethylammonium hydroxide (TMAOH) and the second template is used with triethanolamine (TEA) or polyving akohol (PVA). A combination of characterization techniques, including XRD, SEM, TEM and N2 adsorption-desorption to examine the crystal crystallinity, morphology and surface properties of hierarchical zeolite T aggregates. In the single-template preparation process, the two-step varying-temperature treatment has been used to improve the meso-porosity of zeolite T aggregates. In the double-template preparation process, the amounts of PVA or TEA on the crystallinity, morphology and meso-porosity of zeolite T aggregates have been studied. It has been proved that the interstitial voids between the primary grains of aggregates are the origin of additional mesopores of samples. The micro- and meso-porosities of samples prepared with and without the second template have been contrasted in detail at last. In particular, the sample synthesized with the addition of PVA presents a hierarchical pore structure with the highest Sext value of 122 m2/g and Vmeso value of 0.255 cm3/g.

  18. Synthesis and immobilization of silver nanoparticles on aluminosilicate nanotubes and their antibacterial properties

    NASA Astrophysics Data System (ADS)

    Ipek Yucelen, G.; Connell, Rachel E.; Terbush, Jessica R.; Westenberg, David J.; Dogan, Fatih

    2016-04-01

    A novel colloidal method is presented to synthesize silver nanoparticles on aluminosilicate nanotubes. The technique involves decomposition of AgNO3 solution to Ag nanoparticles in the presence of aluminosilicate nanotubes at room temperature without utilizing of reducing agents or any organic additives. Aluminosilicate nanotubes are shown to be capable of providing a unique chemical environment, not only for in situ conversion of Ag+ into Ag0, but also for stabilization and immobilization of Ag nanoparticles. The synthesis strategy described here could be implemented to obtain self-assembled nanoparticles on other single-walled metal oxide nanotubes for unique applications. Finally, we demonstrated that nanotube/nanoparticle hybrid show strong antibacterial activity toward Gram-positive Staphylococcus epidermidis and Gram-negative Escherichia coli.

  19. Evidence for lithium-aluminosilicate supersaturation of pegmatite-forming melts

    NASA Astrophysics Data System (ADS)

    Maneta, Victoria; Baker, Don R.; Minarik, William

    2015-07-01

    New experimental data on the solubility of lithium (Li) at spodumene (LiAlSi2O6) and petalite (LiAlSi4O10) saturation at 500 MPa and 550-750 °C reveal evidence for lithium supersaturation of pegmatite-forming melts before the formation of Li-aluminosilicates. The degree of Li enrichment in granitic melts can reach ~11,000 ppm above the saturation value before the crystallization of Li-aluminosilicate minerals at lower temperatures. Comparison of the experimental results with the spodumene-rich Moblan pegmatite (Quebec) is consistent with extreme Li enrichment of the pegmatite-forming melt prior to emplacement, which cannot be explained with equilibrium crystallization of Li-aluminosilicates from a common granitic melt. The results of this study support the model of disequilibrium fractional crystallization through liquidus undercooling as the most plausible mechanism for the generation of such Li-rich ore resources.

  20. Li+ alumino-silicate ion source development for the Neutralized Drift Compression Experiment (NDCX)

    SciTech Connect

    Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.; Seidl, Peter A.; Waldron, William L.; Wu, James K.

    2010-10-01

    We report results on lithium alumino-silicate ion source development in preparation for warmdense-matter heating experiments on the new Neutralized Drift Compression Experiment (NDCXII). The practical limit to the current density for a lithium alumino-silicate source is determined by the maximum operating temperature that the ion source can withstand before running into problems of heat transfer, melting of the alumino-silicate material, and emission lifetime. Using small prototype emitters, at a temperature of ~;;1275 oC, a space-charge-limited Li+ beam current density of J ~;;1 mA/cm2 was obtained. The lifetime of the ion source was ~;;50 hours while pulsing at a rate of 0.033 Hz with a pulse duration of 5-6 mu s.

  1. Synthesis and immobilization of silver nanoparticles on aluminosilicate nanotubes and their antibacterial properties

    NASA Astrophysics Data System (ADS)

    Ipek Yucelen, G.; Connell, Rachel E.; Terbush, Jessica R.; Westenberg, David J.; Dogan, Fatih

    2015-06-01

    A novel colloidal method is presented to synthesize silver nanoparticles on aluminosilicate nanotubes. The technique involves decomposition of AgNO3 solution to Ag nanoparticles in the presence of aluminosilicate nanotubes at room temperature without utilizing of reducing agents or any organic additives. Aluminosilicate nanotubes are shown to be capable of providing a unique chemical environment, not only for in situ conversion of Ag+ into Ag0, but also for stabilization and immobilization of Ag nanoparticles. The synthesis strategy described here could be implemented to obtain self-assembled nanoparticles on other single-walled metal oxide nanotubes for unique applications. Finally, we demonstrated that nanotube/nanoparticle hybrid show strong antibacterial activity toward Gram-positive Staphylococcus epidermidis and Gram-negative Escherichia coli.

  2. Studies on sorption properties of zeolite derived from Indian fly ash.

    PubMed

    Mishra, T; Tiwari, S K

    2006-09-01

    Indian fly ash has been completely converted to crystalline porous 13X zeolite by NaOH fusion at 600 degrees C followed by hydrothermal treatment at 105 degrees C for 20 h. Obtained materials were characterized by XRD, SEM and surface area measurement. Prepared material was used for the sorption study of different metal ions (Cu(2+), Co(2+) and Ni(2+)) at different pH, temperature. Thermodynamic data (DeltaS, DeltaH and DeltaG) corresponding to different metal ion uptake were evaluated from Langmuir equation. In all the experiment sorption capacity of prepared zeolite was found to be quite high than that of fly ash at acidic pH. However, the uptake selectivity order for both the materials is Cu(2+)>Co(2+)>Ni(2+). PMID:16563613

  3. Zeolite membranes fabricated by pulsed laser deposition

    SciTech Connect

    Peachey, N.M.; Espinoza, B.F.; Dye, R.C.

    1995-12-01

    The well-defined cavities of the zeolite cage provides an attractive structure around which a membrane can be constructed. However, the fabrication of useful thin film zeolite membranes has presented difficulties since these crystals are not readily formed into thin, defect-free materials. Recently, pulsed laser deposition (PLD) has been used to make thin film sensors. In this process, a laser beam is used to create a plume of particles having reactive edges or dangling bonds. These can then react on a support material to form porous zeolites embedded in a dense phase material. The use of differing wavelengths of laser light can provide a degree of control of the energy of the particles oblated from the target. These novel thin film zeolites provide a unique approach to the synthesis of separation membranes and sensors.

  4. Effect of vanadium contamination on the framework and micropore structure of ultra stable Y-zeolite.

    PubMed

    Etim, U J; Xu, B; Ullah, Rooh; Yan, Z

    2016-02-01

    Y-zeolites are the main component of fluid catalytic cracking (FCC) catalyst for conversion of crude petroleum to products of high demand including transportation fuel. We investigated effects of vanadium which is present as one of the impurities in FCC feedstock on the framework and micropore structure of ultra-stable (US) Y-zeolite. The zeolite samples were prepared and characterized using standard techniques including: (1) X-ray diffraction, (2) N2 adsorption employing non local density functional theory method, NLDFT, (3) Transmittance and Pyridine FTIR, (4) Transmittance electron microscopy (TEM), and (5) (27)Al and (29)Si MAS-NMR. Results revealed that in the presence of steam, vanadium caused excessive evolution of non inter-crystalline mesopores and structural damage. The evolved mesopore size averaged about 25.0nm at 0.5wt.% vanadium loading, far larger than mesopore size in zeolitic materials with improved hydrothermal stability and performance for FCC catalyst. A mechanism of mesopore formation based on accelerated dealumination has been proposed and discussed. Vanadium immobilization experiments conducted to mitigate vanadium migration into the framework clearly showed vanadium is mobile at reaction conditions. From the results, interaction of vanadium with the passivator limits and decreases mobility and activity of vanadium into inner cavities of the zeolite capable of causing huge structure breakdown and acid sites destruction. This study therefore deepens insight into the causes of alteration in activity and selectivity of vanadium contaminated catalyst and hints on a possible mechanism of passivation in vanadium passivated FCC catalyst. PMID:26520826

  5. Spectroscopic and XRD characterisation of zeolite catalysts active for the oxidative methylation of benzene with methane

    NASA Astrophysics Data System (ADS)

    Adebajo, Moses O.; Long, Mervyn A.; Frost, Ray L.

    2004-03-01

    The benzene methylation with methane over zeolite catalysts was previously shown in our laboratory to require the presence of oxygen. Thus, a two-step mechanism involving the intermediate formation of methanol by partial oxidation of methane followed by the methylation of benzene with methanol in the second step, was postulated. This paper now reports the results of the characterisation of the zeolite catalysts used for the oxidative benzene methylation reaction in order to provide some information about their composition, structure, properties and their behaviour before and after the reaction. The catalysts were characterised by X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray fluorescence (XRF), FT-IR and solid state NMR. XRD results indicate that the crystalline structures of all the ZSM-5 and H-beta catalysts remained unchanged after batch reaction of benzene with methane over the catalysts in agreement with the observation that the catalysts recovered from the reactor could be reused without loss of activity. Elemental analyses and FT-IR data show that as the level of metal ion exchange increases, the Brnsted acid concentration decreases but this metal ion exchange does not totally remove Brnsted acidity. FT-IR results further show that only a small amount of acid sites is actually necessary for a catalyst to be active since used catalysts containing highly reduced Brnsted acidity are found to be reusable without any loss of their activity. 29Si and 27Al magic angle spinning (MAS) NMR together with FT-IR spectra also show that all the active zeolites catalysts contain some extra-framework octahedral aluminium in addition to the normal tetrahedral framework aluminium. The presence of this extra-lattice aluminium does not, however, have any adverse effect on the crystallinity of the catalysts both before and after oxidative benzene methylation reaction. There appears also to be no significant dealumination of the zeolite catalysts during reaction since their catalytic performance was retained after use.

  6. The zeolite deposits of Greece

    USGS Publications Warehouse

    Stamatakis, M.G.; Hall, A.; Hein, J.R.

    1996-01-01

    Zeolites are present in altered pyroclastic rocks at many localities in Greece, and large deposits of potential economic interest are present in three areas: (1) the Evros region of the province of Thrace in the north-eastern part of the Greek mainland; (2) the islands of Kimolos and Poliegos in the western Aegean; and (3) the island of Samos in the eastern Aegean Sea. The deposits in Thrace are of Eocene-Oligocene age and are rich in heulandite and/or clinoptilolite. Those of Kimolos and Poliegos are mainly Quaternary and are rich in mordenite. Those of Samos are Miocene, and are rich in clinoptilolite and/or analcime. The deposits in Thrace are believed to have formed in an open hydrological system by the action of meteoric water, and those of the western Aegean islands in a similar way but under conditions of high heat flow, whereas the deposits in Samos were formed in a saline-alkaline lake.

  7. Properties of glass-bonded zeolite monoliths

    SciTech Connect

    Lewis, M.A.; Fischer, D.F.; Murphy, C.D.

    1994-05-01

    It has been shown that mineral waste forms can be used to immobilize waste salt generated during the pyrochemical processing of spent fuel from the Integral Fast Reactor (IFR). Solid, leach resistant monoliths were formed by hot-pressing mixtures of salt-occluded zeolite A powders and glass frit at 990 K and 28 MPa. Additional samples have now been fabricated and tested. Normalized release rates for all elements, including iodide and chloride, were less than 1 g/m{sup 2}d in 28-day tests in deionized water and in brine at 363 K (90{degrees}C). Preliminary results indicate that these rates fall with time with both leachants and that the zeolite phase in the glass-bonded zeolite does not function as an ion exchanger. Some material properties were measured. The Poisson ratio and Young`s modulus were slightly smaller in glass-bonded zeolite than in borosilicate glass. Density depended on zeolite fraction. The glass-bonded zeolite represents a promising mineral waste form for IFR salt.

  8. Thermodynamic modeling of natural zeolite stability

    SciTech Connect

    Chipera, S.J.; Bish, D.L.

    1997-06-01

    Zeolites occur in a variety of geologic environments and are used in numerous agricultural, commercial, and environmental applications. It is desirable to understand their stability both to predict future stability and to evaluate the geochemical conditions resulting in their formation. The use of estimated thermodynamic data for measured zeolite compositions allows thermodynamic modeling of stability relationships among zeolites in different geologic environments (diagenetic, saline and alkaline lakes, acid rock hydrothermal, basic rock, deep sea sediments). This modeling shows that the relative cation abundances in both the aqueous and solid phases, the aqueous silica activity, and temperature are important factors in determining the stable zeolite species. Siliceous zeolites (e.g., clinoptilolite, mordenite, erionite) present in saline and alkaline lakes or diagenetic deposits formed at elevated silica activities. Aluminous zeolites (e.g., natrolite, mesolite/scolecite, thomsonite) formed in basic rocks in association with reduced silica activities. Likewise, phillipsite formation is favored by reduced aqueous silica activities. The presence of erionite, chabazite, and phillipsite are indicative of environments with elevated potassium concentrations. Elevated temperature, calcic water conditions, and reduced silica activity help to enhance the laumontite and wairakite stability fields. Analcime stability increases with increased temperature and aqueous Na concentration, and/or with decreased silica activity.

  9. Three Mile Island zeolite vitirification demonstration program

    SciTech Connect

    Siemens, D.H.; Knowlton, D.E.; Shupe, M.W.

    1981-06-01

    The cleanup of the high-activity-level water at Three Mile Island (TMI) provides an opportunity to further develop waste management technology. Approximately 790,000 gallons of high-activity-level water at TMI's Unit-2 Nuclear Power Station will be decontaminated at the site using the submerged demineralizer system (SDS). In the SDS process, the cesium and strontium in the water are sorbed onto zeolite that is contained within metal liners. The Department of Energy has asked the Pacific Northwest Laboratory (PNL) to take a portion of the zeolite from the SDS process and demonstrate, on a production scale, that this zeolite can be vitrified using the in-can melting process. This paper is a brief overview of the TMI zeolite vitrification program. The first section discusses the formulation of a glass suitable for immobilizing SDS zeolite. The following section describes a feed system that was developed to feed zeolite to the in-can melter. It also describes the in-can melting process and the government owned facilities in which the demonstrations will take place. Finally, the schedule for completing the program activities is outlined.

  10. Kinetics of zeolite dealumination in steam

    SciTech Connect

    Hughes, C.D.; Labouriau, A.; Crawford, S.N.; Romero, R.; Quirin, J.; Earl, W.L.

    1998-08-01

    Zeolite dealumination is a well known phenomenon that contributes to the deactivation or activation of catalysts in several different applications. The most obvious effect is in acid catalysis where dealumination under reaction conditions removes the Broensted sites, thus deactivating the catalyst. The authors are interested in the use of cation exchanged zeolites as selective reduction catalysts for removal of NO{sub x} from exhaust streams, particularly from automotive exhaust. In this case, copper exchanged ZSM-5 has been shown to be an effective catalyst for the generic reaction of NO{sub x} with hydrocarbons. However, high temperature and steam in combustion exhaust causes dealumination and consequent migration of copper out of the zeolite structure resulting in rapid deactivation of the catalyst. Dealumination of zeolites has been reported by many authors in uncountable papers and cannot be reviewed here. However, to the authors` knowledge there are no reports on the kinetics of dealumination under varying conditions of temperature and steam. By measuring the kinetics of dealumination with different zeolites and exchange cations they expect to develop working models of the dealumination process that will allow control of zeolite deactivation. This manuscript is a description of the basic techniques used and a progress report on the very beginning of this study.

  11. Influence of zeolite crystal size on zeolite-polyamide thin film nanocomposite membranes.

    PubMed

    Lind, Mary L; Ghosh, Asim K; Jawor, Anna; Huang, Xiaofei; Hou, William; Yang, Yang; Hoek, Eric M V

    2009-09-01

    Zeolite-polyamide thin film nanocomposite membranes were coated onto polysulfone ultrafiltration membranes by interfacial polymerization of amine and acid chloride monomers in the presence of Linde type A zeolite nanocrystals. A matrix of three different interfacial polymerization chemistries and three different-sized zeolite crystals produced nanocomposite thin films with widely varying structure, morphology, charge, hydrophilicity, and separation performance (evaluated as reverse osmosis membranes). Pure polyamide film properties were tuned by changing polymerization chemistry, but addition of zeolite nanoparticles produced even greater changes in separation performance, surface chemistry, and film morphology. For fixed polymer chemistry, addition of zeolite nanoparticles formed more permeable, negatively charged, and thicker polyamide films. Smaller zeolites produced greater permeability enhancements, but larger zeolites produced more favorable surface properties; hence, nanoparticle size may be considered an additional "degree of freedom" in designing thin film nanocomposite reverse osmosis membranes. The data presented offer additional support for the hypothesis that zeolite crystals alter polyamide thin film structure when they are present during the interfacial polymerization reaction. PMID:19527039

  12. Zeolite LTA Nanoparticles Prepared by Laser-Induced Fracture of Zeolite Microcrystals.

    PubMed

    Nichols, William T; Kodaira, Tetsuya; Sasaki, Yukichi; Shimizu, Yoshiki; Sasaki, Takeshi; Koshizaki, Naoto

    2006-01-12

    Zeolite LTA nanoparticles are prepared by laser-induced fragmentation of zeolite LTA microparticles using a pulsed laser. Zeolite nanoparticle formation is attributed to absorption of the laser at impurities or defects within the zeolite microcrystal generating thermoelastic stress that mechanically fractures the microparticle into smaller nanoparticle fragments. Experimentally, it is found that nanoparticles have a wide size and morphology distribution. Large nanoparticles (>200 nm) are typically irregularly shaped crystals of zeolite LTA, whereas small nanoparticles (<50 nm) tend to be spherical, dense, and amorphous, indicative of destruction of the original LTA crystal structure. Results of the fragmentation versus laser parameters show that shorter laser wavelengths are more efficient at producing zeolite nanoparticles, which is explained based on a larger cross section for optical absorption in the zeolite crystal. Increasing the laser energy density irradiating the sample was found to be a trade-off between increasing the amount of fragmentation and increasing the amount of structural damage to the zeolite crystal. It is suggested that in the presence of strongly absorbing defects, plasma formation is induced resulting in dramatically higher temperatures. On the basis of these results it is suggested the optimal laser processing conditions are 355 nm and 10 mJ/pulse laser energy for our LTA samples. PMID:16471503

  13. Synthesis and structural characterization of Al-containing interlayer-expanded-MWW zeolite with high catalytic performance.

    PubMed

    Yokoi, Toshiyuki; Mizuno, Shun; Imai, Hiroyuki; Tatsumi, Takashi

    2014-07-21

    Treatment of the zeolitic layered precursor of Al-MWW, so-called Al-MWW(P), with diethoxydimethylsilane (DEDMS) in acidic media leads to the formation of an aluminosilicate-type interlayer-expanded zeolite MWW (Al-IEZ-MWW) with expanded 12-membered ring (12-MR) micropores. However, the silylation process under acidic conditions simultaneously causes dealumination from the MWW framework, resulting in a decrease in the acid amount. We have developed a method for preparing Al-IEZ-MWW without leaching of the Al species. The strategy is to conduct the silylation under weakly acidic conditions; the silylation was conducted in an aqueous solution of an ammonium salt, e.g., NH4Cl, instead of HNO3. Subsequent additional acid treatment led to the formation of Al-IEZ-MWW that shows a high catalytic performance in the acylation of anisole compared to typical Al-MWW as well as Al-IEZ-MWW directly prepared under acidic conditions. The change in the state of Al atoms during the preparation process was investigated by high-resolution solid-state (27)Al MAS NMR and (27)Al MQMAS NMR techniques. PMID:24798349

  14. Effect of different glasses in glass bonded zeolite

    SciTech Connect

    Lewis, M.A.; Ackerman, J.P.; Verma, S.

    1995-05-01

    A mineral waste form has been developed for chloride waste salt generated during the pyrochemical treatment of spent nuclear fuel. The waste form consists of salt-occluded zeolite powders bound within a glass matrix. The zeolite contains the salt and immobilizes the fission products. The zeolite powders are hot pressed to form a mechanically stable, durable glass bonded zeolite. Further development of glass bonded zeolite as a waste form requires an understanding of the interaction between the glass and the zeolite. Properties of the glass that enhance binding and durability of the glass bonded zeolite need to be identified. Three types of glass, boroaluminosilicate, soda-lime silicate, and high silica glasses, have a range of properties and are now being investigated. Each glass was hot pressed by itself and with an equal amount of zeolite. MCC-1 leach tests were run on both. Soda-lime silicate and high silica glasses did not give a durable glass bonded zeolite. Boroaluminosilicate glasses rich in alkaline earths did bind the zeolite and gave a durable glass bonded zeolite. Scanning electron micrographs suggest that the boroaluminosilicate glasses wetted the zeolite powders better than the other glasses. Development of the glass bonded zeolite as a waste form for chloride waste salt is continuing.

  15. EFFECT OF IMPURITIES ASSOCIATED WITH ALUMINOSILICATES ON ARSENIC SORPTION AND OXIDATION

    EPA Science Inventory

    Arsenite, As(III), and arsenate, As(V), are of increasing environmental concern. Risk assessment and risk management of arsenic contaminated sites requires a better understanding of arsenic-mineral interactions. Aluminosilicate minerals, such as feldspars and clays, are the mos...

  16. Spectroscopy and crystal-field analysis for Cr(IV) in alumino-silicate glasses

    NASA Astrophysics Data System (ADS)

    Feng, Xian; Tanabe, Setsuhisa

    2002-08-01

    Racah parameters of Cr 4+ ions in alumino-silicate glasses have been calculated, indicating most Cr 4+ ions are located at low-field sites. Using three-peak Gauss fitting for the luminescence lineshape of Cr 4+:alumino-silicate glass at low temperatures, the existence of Cr 4+ at high-field sites has been demonstrated for the first time in the alumino-silicate glass. The temperature dependence of the emission of low-Cr 2O 3 glass shows blue shift because most of the Cr 4+ ions are in the low-field sites, in which the Cr 4+ ions show the large difference of the thermal population at different excited states due to the non-radiative processes. On the other hand, the concentration dependence of the emission of Cr 4+ ions in alumino-silicate glass shows red shift, caused by the energy transfer between Cr 4+ ions in different crystal-field sites, and subsequently the mechanism of energy transfer between Cr 4+ ions at low-field sites and at high-field sites has been proposed.

  17. Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2007-03-31

    The addition of hydrothermally-aged zeolite Y precursor to an SBA-15 synthesis mixture under a mildly acidic condition resulted in the formation of a mesoporous aluminosilicate catalyst, AlSBA-15. The Al-SBA-15 mesoporous catalyst contains strong Br{umlt o}nsted acid sites and aluminum (Al) stabilized in a totally tetrahedral coordination. The physicochemical characteristics of the catalyst varied as a function of the synthesis conditions. The catalyst possessed surface areas ranging between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm, and pore volumes up 1.03 cm{sup 3}, which were comparable to the parent SBA-15 synthesized under similar conditions. Two wt % Al was present in the catalyst that was obtained from the reaction mixture that contained the highest Al content. The Al remained stable in totally tetrahedral coordination after calcination at a temperature of 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and the activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. In preparation for the final phase of the project, the catalyst was embedded into a psuedoboemite alumina (catapal B) matrix and then formed into pellets. In the final phase of the project, the pelletized catalyst is being evaluated for the conversion of a heavy petroleum feedstock to naphtha and middle distillates. This phase was significantly delayed during the past six months due to a serious malfunction of the fume hoods in the Clark Atlanta University's Research Center for Science and Technology, where the project is being conducted. The fume hood system was repaired and the catalyst evaluation is now underway.

  18. 11. EASTERN END OF ZEOLITE BUILDING. NOTE DIAL TO LEFT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    11. EASTERN END OF ZEOLITE BUILDING. NOTE DIAL TO LEFT OF CLOCK GAUGING TOTAL ZEOLITE INFLUENT IN MILLIONS OF GALLONS PER DAY. - F. E. Weymouth Filtration Plant, 700 North Moreno Avenue, La Verne, Los Angeles County, CA

  19. Preparation of environmentally friendly alkylglucoside surfactants using zeolites as catalysts

    SciTech Connect

    Corma, A.; Iborra, S.; Miquel, S.; Primo, J.

    1996-07-01

    Acid zeolites were evaluated for glycosidation activity of D-glucose and n-butanol. Zeolites with high Si/Al ratios such as faujasite and beta are the most suitable catalysts. 24 refs., 7 figs., 5 tabs.

  20. Corrosion behavior of sodium aluminosilicate glasses and crystals

    NASA Astrophysics Data System (ADS)

    Hamilton, James Patrick

    1999-12-01

    A comprehensive study of the effects of structure and composition on the pH-dependent corrosion behavior of sodium-aluminosilicate glasses and crystals at 25C, was investigated by a combination of various solution and surface analysis techniques. These techniques were used to measure solution stoichiometry relative to the glass and crystal, surface composition, surface layer thickness, and structure of the surface layer. The room temperature dissolution rates of glasses and crystals with the albite composition (NaAlSi3O8) were essentially identical over the acidic-weakly basic pH region. Differences in density and tetrahedral ring structure between the glass and crystal structures, however, led to more extensive Na and Al depletion from the glass surface. Nevertheless, the outermost 17A of the glass and crystal surface were compositionally similar, suggesting that this region of the solid controls the dissolution rate. The corrosion behavior of glasses in the NBO (Na2O-xAl 2O3-(3-x)SiO2) and mineral (Na2O-Al 2O3-y SiO2) series were investigated over the pH range of 1--12. The NBO glass series tested the effects of alumina and non-bridging oxygen (NBO) concentration on corrosion behavior without any change in soda content. The mineral glass series tested the effect of Al/Si ratio on corrosion behavior in glasses with fully polymerized structures and no NBO sites. The elimination of some NBO sites by the initial addition of alumina to the glass with x = 0.0 composition caused a significant reduction in the dissolution rate. However, the dissolution rates of glasses with x > 0.2 (in the NBO series) and all glasses in the mineral series were controlled by Al-O-Si and Si-O-Si bonding. In the NBO series, NBO concentration controlled the formation and thickness of leached surface layers. In the absence of NBO sites, Al-O-Si and Si-O-Si bonding controlled the leaching behavior. Transformation of the glass surfaces during corrosion at any pH led to the formation leached layers with structures that were different from their corresponding bulk glass structures and not a relic of them. NBO concentration, pH, and Al-O-Si and Si-O-Si bonding dictated the structures of leached layers. The results of this study show that dissolution rate may not be a simple function of leached layer formation. All of these observations are consistent with a model in which leached layer formation is controlled by the diffusion rate of molecular water into the glass network, whereas dissolution is controlled by the hydrolytic stability of the metal-oxide bonds at the pH of the solution.

  1. An efficient synthesis of nanocrystalline MFI zeolite using different silica sources: A green approach

    SciTech Connect

    Kalita, Banani; Talukdar, Anup K.

    2009-02-04

    Nanocrystalline MFI zeolite was synthesized with a very broad range of silica to alumina ratios using an autoclave for periods of 7 h at 473 K under autogeneous pressure without seeding gel, promoter, organic solvent or sulfuric acid. The procedure has been successfully employed for the synthesis of MFI samples using fumed silica, colloidal silica, aerosil and tetraethylorthosilicate as silica sources. The synthesized samples were characterized by different techniques such as X-ray diffraction, Fourier transform infrared spectroscopy, Scanning electron microscopy. Their average crystallite size ranges from about 26 to 55 nm and they exhibit high crystallinity.

  2. Kilogram scale production of EMT zeolite: Optimization of the synthesis conditions

    SciTech Connect

    Anglerot, D.; Fitoussi, F.; Schulz, P.

    1995-12-01

    Faujasite type zeolites have found Widespread use in industrial applications, both as catalysts and as adsorbents. EMT (Elf Mulhouse Two), the hexagonal polymorph of faujasite, is prepared in 8 days at 110{degrees}C from a synthesis gel containing 18-crown-6 as organic template. In this work it was aimed at developing a reproducible method to prepare kilogram batches of highly crystalline and pure EMT, focusing in particular on the raw material quality, the template content and the influence of agitation (type and rate) on the ageing and crystallization periods. The characterization of the obtained materials is also reported (XRD, chemical and thermal analyses, SEM, NMR spectroscopy ... ).

  3. Flexibility of the zeolite RHO framework. In situ X-ray and neutron powder structural characterization of cation-exchanged BePO and BeAsORHO analogs

    SciTech Connect

    Nenoff, T.M.; Parise, J.B.; Jones, G.A.; Galya, L.G.; Corbin, D.R.; Stucky, G.D.

    1996-08-15

    This is an extensive study of the non-aluminosilicate analogs of the zeolite RHO. This molecular sieve is of great interest commercially because of its catalytic properties. In the absence of rigid supporting structural subunits (smaller cages or channels), the aluminosilicate RHO exhibits atypical framework flexibility with large displacivere arrangements. The beryllophosphate and beryalloarsenate analogs are easily synthesized under very mild reaction conditions and therefore maybe of interest for inexpensive and rapid commercial production. However,t hey have decreased thermal stability. In an effort to increase thermal stability and explore framework flexibility, we have synthesized and characterized a series of analogs of the non-aluminosilicate RHO framework. All materials crystallize in the space group I23, ranging from a = 13.584-(2) A for Li-BePO RHO to a = 14.224(4) A for Ba-RbBeAsO RHO for hydrated phases. The extra framework cations are distributed over the double 8-ring, single 8-ring, and two single 6-ring sites. Partially and fully dehydrated phases were also studied for changes in framework stability. Predictive trends based on the type of cation exchanged into the framework were determined by {sup 9}Be and {sup 31}P MAS NMR. 50 refs., 8 figs., 6 tabs.

  4. Monitoring early zeolite formation via in situ electrochemical impedance spectroscopy.

    PubMed

    Brabants, G; Lieben, S; Breynaert, E; Reichel, E K; Taulelle, F; Martens, J A; Jakoby, B; Kirschhock, C E A

    2016-04-01

    Hitherto zeolite formation has not been fully understood. Although electrochemical impedance spectroscopy has proven to be a versatile tool for characterizing ionic solutions, it was never used for monitoring zeolite growth. We show here that EIS can quantitatively monitor zeolite formation, especially during crucial early steps where other methods fall short. PMID:27020096

  5. Fly ash zeolite catalyst support for Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Campen, Adam

    This dissertation research aimed at evaluating a fly ash zeolite (FAZ) catalyst support for use in heterogeneous catalytic processes. Gas phase Fischer-Tropsch Synthesis (FTS) over a fixed-bed of the prepared catalyst/FAZ support was identified as an appropriate process for evaluation, by comparison with commercial catalyst supports (silica, alumina, and 13X). Fly ash, obtained from the Wabash River Generating Station, was first characterized using XRD, SEM/EDS, particle size, and nitrogen sorption techniques. Then, a parametric study of a two-step alkali fusion/hydrothermal treatment process for converting fly ash to zeolite frameworks was performed by varying the alkali fusion agent, agent:flyash ratio, fusion temperature, fused ash/water solution, aging time, and crystallization time. The optimal conditions for each were determined to be NaOH, 1.4 g NaOH: 1 g fly ash, 550 °C, 200 g/L, 12 hours, and 48 hours. This robust process was applied to the fly ash to obtain a faujasitic zeolite structure with increased crystallinity (40 %) and surface area (434 m2/g). Following the modification of fly ash to FAZ, ion exchange of H+ for Na+ and cobalt incipient wetness impregnation were used to prepare a FTS catalyst. FTS was performed on the catalysts at 250--300 °C, 300 psi, and with a syngas ratio H2:CO = 2. The HFAZ catalyst support loaded with 11 wt% cobalt resulted in a 75 % carbon selectivity for C5 -- C18 hydrocarbons, while methane and carbon dioxide were limited to 13 and 1 %, respectively. Catalyst characterization was performed by XRD, N2 sorption, TPR, and oxygen pulse titration to provide insight to the behavior of each catalyst. Overall, the HFAZ compared well with silica and 13X supports, and far exceeded the performance of the alumina support under the tested conditions. The successful completion of this research could add value to an underutilized waste product of coal combustion, in the form of catalyst supports in heterogeneous catalytic processes.

  6. Zeolites as catalysts in oil refining.

    PubMed

    Primo, Ana; Garcia, Hermenegildo

    2014-11-21

    Oil is nowadays the main energy source and this prevalent position most probably will continue in the next decades. This situation is largely due to the degree of maturity that has been achieved in oil refining and petrochemistry as a consequence of the large effort in research and innovation. The remarkable efficiency of oil refining is largely based on the use of zeolites as catalysts. The use of zeolites as catalysts in refining and petrochemistry has been considered as one of the major accomplishments in the chemistry of the XXth century. In this tutorial review, the introductory part describes the main features of zeolites in connection with their use as solid acids. The main body of the review describes important refining processes in which zeolites are used including light naphtha isomerization, olefin alkylation, reforming, cracking and hydrocracking. The final section contains our view on future developments in the field such as the increase in the quality of the transportation fuels and the coprocessing of increasing percentage of biofuels together with oil streams. This review is intended to provide the rudiments of zeolite science applied to refining catalysis. PMID:24671148

  7. Italian zeolitized rocks of technological interest

    NASA Astrophysics Data System (ADS)

    de'Gennaro, M.; Langella, A.

    1996-09-01

    Large areas of Italian territory are covered by thick and widespread deposits of zeolite-bearing volcaniclastic products. The main zeolites are phillipsite and chabazite spread over the whole peninsula, and clinoptilolite recorded only in Sardinia. A trachytic to phonolitic glassy precursor accounts for the formation of the former zeolites characterized by low Si/Al ratios (?3.00), while clinoptilolite is related to more acidic volcanism. The genesis of most of these zeolitized deposits is linked to pyroclastic flow emplacement mechanisms characterized by quite high temperatures and by the presence of abundant fluids. The main utilization of these materials has been and still is as dimension stones in the building industry. Currently, limited amounts are also employed in animal farming (dietary supplement, pet litter and manure deodorizer) and in agriculture as soil improvement and slow-release fertilizers. New fields of application have been proposed for these products on account of their easy availability, very low cost, their high-grade zeolites (50 70%), and good technological features such as high cation exchange capacities and adsorption properties.

  8. Molecular recognition in cation-exchanged zeolites

    NASA Astrophysics Data System (ADS)

    Pidko, Evgeny A.; van Santen, Rutger A.

    The concepts of confinement- and molecular recognition-driven chemical reactivity of cation-exchanged zeolites is illustrated by our recent results from periodic and cluster density functional theory (DFT) calculations. The reactivity of alkali-earth- and alkaline-exchanged low-silica zeolites for selective photo-oxidation of alkenes with molecular oxygen and for N2O4 disproportionation is shown to be mainly due to the specific arrangement and the size of the cations in the zeolite cage. An attempt is made to separate the effects of basicity of the framework, the Lewis acidity of the extra-framework cations and the electrostatic field in the zeolite cage as well as its geometrical properties for the respective reactions. The importance of the favorable adsorption fashion of the reagents controlled by noncovalent interactions with the microporous matrix is shown. The role of the weak interactions with the zeolite walls and the factors, which determine the preference for a particular adsorption mode, are discussed by the example of light alkanes adsorption to Mg- and Ca-exchanged faujasites.

  9. Topological crystalline insulator nanostructures

    NASA Astrophysics Data System (ADS)

    Shen, Jie; Cha, Judy J.

    2014-11-01

    Topological crystalline insulators are topological insulators whose surface states are protected by the crystalline symmetry, instead of the time reversal symmetry. Similar to the first generation of three-dimensional topological insulators such as Bi2Se3 and Bi2Te3, topological crystalline insulators also possess surface states with exotic electronic properties such as spin-momentum locking and Dirac dispersion. Experimentally verified topological crystalline insulators to date are SnTe, Pb1-xSnxSe, and Pb1-xSnxTe. Because topological protection comes from the crystal symmetry, magnetic impurities or in-plane magnetic fields are not expected to open a gap in the surface states in topological crystalline insulators. Additionally, because they have a cubic structure instead of a layered structure, branched structures or strong coupling with other materials for large proximity effects are possible, which are difficult with layered Bi2Se3 and Bi2Te3. Thus, additional fundamental phenomena inaccessible in three-dimensional topological insulators can be pursued. In this review, topological crystalline insulator SnTe nanostructures will be discussed. For comparison, experimental results based on SnTe thin films will be covered. Surface state properties of topological crystalline insulators will be discussed briefly.

  10. Production of biofuel from waste cooking palm oil using nanocrystalline zeolite as catalyst: process optimization studies.

    PubMed

    Taufiqurrahmi, Niken; Mohamed, Abdul Rahman; Bhatia, Subhash

    2011-11-01

    The catalytic cracking of waste cooking palm oil to biofuel was studied over different types of nano-crystalline zeolite catalysts in a fixed bed reactor. The effect of reaction temperature (400-500 °C), catalyst-to-oil ratio (6-14) and catalyst pore size of different nanocrystalline zeolites (0.54-0.80 nm) were studied over the conversion of waste cooking palm oil, yields of Organic Liquid Product (OLP) and gasoline fraction in the OLP following central composite design (CCD). The response surface methodology was used to determine the optimum value of the operating variables for maximum conversion as well as maximum yield of OLP and gasoline fraction, respectively. The optimum reaction temperature of 458 °C with oil/catalyst ratio=6 over the nanocrystalline zeolite Y with pore size of 0.67 nm gave 86.4 wt% oil conversion, 46.5 wt% OLP yield and 33.5 wt% gasoline fraction yield, respectively. The experimental results were in agreement with the simulated values within an experimental error of less than 5%. PMID:21924606

  11. Catalytically active and hierarchically porous SAPO-11 zeolite synthesized in the presence of polyhexamethylene biguanidine.

    PubMed

    Liu, Yan; Qu, Wei; Chang, Weiwei; Pan, Shuxiang; Tian, Zhijian; Meng, Xiangju; Rigutto, Marcello; van der Made, Alexander; Zhao, Lan; Zheng, Xiaoming; Xiao, Feng-Shou

    2014-03-15

    Hierarchically porous SAPO-11 zeolite (H-SAPO-11) is rationally synthesized from a starting silicoaluminophosphate gel in the presence of polyhexamethylene biguanidine as a mesoscale template. The sample is well characterized by XRD, N2 sorption, SEM, TEM, NMR, XPS, NH3-TPD, and TG techniques. The results show that the sample obtained has good crystallinity, hierarchical porosity (mesopores at ca. 10 nm and macropores at ca. 50-200 nm), high BET surface area (226 m(2)/g), large pore volume (0.25 cm(3)/g), and abundant medium and strong acidic sites (0.36 mmol/g). After loading Pt (0.5 wt.%) on H-SAPO-11 by using wet impregnation method, catalytic hydroisomerization tests of n-dodecane show that the hierarchical Pt/SAPO-11 zeolite exhibits high conversion of n-dodecane and enhanced selectivity for branched products as well as reduced selectivity for cracking products, compared with conventional Pt/SAPO-11 zeolite. This phenomenon is reasonably attributed to the presence of hierarchical porosity, which is favorable for access of reactants on catalytically active sites. The improvement in catalytic performance in long-chain paraffin hydroisomerization over Pt/SAPO-11-based catalyst is of great importance for its industrial applications in the future. PMID:24461835

  12. Magnetic and Mössbauer study of metal-zeolite interaction in catalysts

    NASA Astrophysics Data System (ADS)

    Pannaparayil, Thomas; Oskooie-Tabrizi, M.; Lo, C.; Mulay, L. N.; Melson, G. A.; Rao, V. U. S.

    1984-03-01

    Molecular sieve aluminosilicates, such as ZSM-5 and mordenite, when impregnated with highly dispersed Fe, yield catalysts for the selective conversion of coal-derived syngas (CO+H2) to liquid hydrocarbon fuels. Fe performs the primary Fischer-Tropsch (FT) syngas to yield light olefins which are converted by the acidic (H+) and shape-selective function of the zeolite to high octane gasoline components. The physical aspects of the Fe-mordenite interaction studied by magnetic measurements, Mössbauer, and IR spectroscopy are reported and correlations with the catalytic properties are drawn. Mordenite samples with [SiO2/Al2O3] ratio in the range 12 - 60 were impregnated with 15 wt. % Fe using Fe3(CO)12; decarbonylation yielded superparamagmetic dispersions of γ-Fe2O3, in the range 1.4-5.0 nm; the smallest particles were obtained for a ratio=17. Hydrogen chemisorption also revealed a similar trend in Fe dispersions. No samples, other than the one with a ratio=60 and containing the largest particles could be carbided under usual conditions. The acidity of the mordenite and the aromatics fraction in liquid hydrocarbons from syngas conversion also showed maxima at a ratio=17. The presence of a strong metal-support interaction between Fe and mordenite was thus influenced by the varying ratios in the mordenite in a manner that paralleled the acidity and catalytic activity.

  13. Optimizing the crystallinity and acidity of H-SAPO-34 by fluoride for synthesizing Cu/SAPO-34 NH3-SCR catalyst.

    PubMed

    Ma, Jing; Si, Zhichun; Wu, Xiaodong; Weng, Duan; Ma, Yue

    2016-03-01

    A series of H-SAPO-34 zeolites were synthesized by a hydrothermal method in fluoride media. The as-synthesized H-SAPO-34 zeolites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 physisorption, temperature-programmed desorption of NH3 (NH3-TPD) and nuclear magnetic resonance (NMR) measurements. The results showed that a certain concentration of F(-) anions promoted the nucleation and crystallization of H-SAPO-34. The H-SAPO-34 synthesized in the fluoride media showed high crystallinity, uniform particle size distribution, large specific surface area and pore volume, and enhanced acidity. Therefore, Cu/SAPO-34 based on the fluoride-assisted zeolite showed a broadened temperature window for the selective catalytic reduction of NO by NH3 (NH3-SCR) reaction due to the enhanced acidity of the zeolite and the improved dispersion of copper species. PMID:26969071

  14. Hydrogen Purification Using Natural Zeolite Membranes

    NASA Technical Reports Server (NTRS)

    DelValle, William

    2003-01-01

    The School of Science at Universidad del Turabo (UT) have a long-lasting investigation plan to study the hydrogen cleaning and purification technologies. We proposed a research project for the synthesis, phase analysis and porosity characterization of zeolite based ceramic perm-selective membranes for hydrogen cleaning to support NASA's commitment to achieving a broad-based research capability focusing on aerospace-related issues. The present study will focus on technology transfer by utilizing inorganic membranes for production of ultra-clean hydrogen for application in combustion. We tested three different natural zeolite membranes (different particle size at different temperatures and time of exposure). Our results show that the membranes exposured at 900 C for 1Hr has the most higher permeation capacity, indicated that our zeolite membranes has the capacity to permeate hydrogen.

  15. Preparation, Processing, and Characterization of Oriented Polycrystalline Zeolite and Aluminophosphate Membranes

    NASA Astrophysics Data System (ADS)

    Stoeger, Jared Andrew

    Since the advent of zeolite membranes, speculation on their industrial applicability has been closely monitored, although widespread commercialization has been hampered by limitations in fabrication and post-synthesis processing. Economical, energy-efficient technology breakthroughs require an evaluation of a range of material candidates which show robustness and reliability. Straightforward manufacturing techniques should be devised to generate thousands of square meters of membrane area; however, this demands control of structural characteristics on the scale of nanometers. As described in this dissertation, the path forward will be forged by exploiting the intrinsic crystalline properties of zeolites or aluminophosphates for the next advancement in membrane technology. A facile method is described for the preparation of silicalite-1 (MFI zeolite type) membranes using the secondary growth technique on symmetric porous stainless steel tubes. Activation through rapid thermal processing (RTP), a lamp-based heat-treatment process used as a critical fabrication step in silicon integrated circuit manufacturing, is proven to reduce the density of non-zeolitic transport pathways which are detrimental to high-resolution molecular sieving. RTP-treated membranes are shown to have enhanced performance in the binary separation of vapor-phase isomers (p-/o-xylene), gas-phase isomers (n-/i-butane), and alcohol/water when compared to membranes activated at a much slower heating rate but otherwise similarly-prepared. The performance is discussed in the context of the market potential for industrially-attractive separations: the recovery of p-xylene from an isomeric mixture or alcohol biofuels from aqueous post-fermentation streams. Hydrothermal growth techniques for the preparation and characterization of continuous aluminophosphate (AFI zeolite type) membranes with a preferential crystallographic alignment on porous alpha-Al2O3 disc supports are demonstrated. A mechanism is proposed for flake-like crystal formation in the early stages of in-plane crystalline intergrowth between oriented columnar crystals by electric heating. It is shown that elevated temperatures induce a phase transformation to a densified aluminophosphate phase despite framework metal substitution or alternative heat-treatment conditions. Additionally, stability and membrane characteristics following in situ microwave growth using a TiO2-coated support are examined. Indications of improved quality validate the candidacy of the microwave-grown membranes with regard to the potential for carbon nanotube synthesis in the aligned one-dimensional channels for high flux, high separation factor membrane fabrication.

  16. Evidence of energy transfer in an aluminosilicate glass codoped with Si nanoaggregates and Er{sup 3+} ions

    SciTech Connect

    Enrichi, F.; Mattei, G.; Sada, C.; Trave, E.; Pacifici, D.; Franzo, G.; Priolo, F.; Iacona, F.; Prassas, M.; Falconieri, M.; Borsella, E.

    2004-10-01

    The enhancement of the Er{sup 3+} ions' photoluminescence (PL) emission at 1.54 {mu}m in a Si and Er coimplanted aluminosilicate glass is investigated in detail. A postimplantation thermal treatment has been performed to recover the damage induced by the implantation process and to promote Si aggregation. It will be shown that 1 h treatment in N{sub 2} atmosphere is not sufficient to induce Si precipitation for temperatures up to 500 deg. C. Nevertheless, the most intense Er{sup 3+} PL emission at 1.54 {mu}m is achieved after a thermal treatment at 400 deg. C. Such emission has been investigated by pumping in and out of resonance, showing a very efficient energy transfer process in the whole excitation wavelength range (360-515 nm). These results suggest that good energy transfer mediators could be small Si aggregates and not only crystalline clusters. For the best performing sample, the effective Er excitation cross section has been measured to be higher than 10{sup -17} cm{sup 2} at 379 and 390 nm and about 2x10{sup -16} cm{sup 2} at 476 nm, that is, several orders of magnitude higher than the Er direct absorption cross section (of the order of 10{sup -21} cm{sup 2} in this glass). Moreover the coefficient of cooperative upconversion has been evaluated to be 2.7x10{sup -18} cm{sup 3} s{sup -1}. The structural and optical properties of this material are discussed and compared to those found for Si and Er codoped silica.

  17. Detecting Nanophase Weathering Products with CheMin: Reference Intensity Ratios of Allophane, Aluminosilicate Gel, and Ferrihydrite

    NASA Technical Reports Server (NTRS)

    Rampe, E. B.; Bish, D. L.; Chipera, S. J.; Morris, R. V.; Achilles, C. N.; Ming, D W.; Blake, D. F.; Anderson, R. C.; Bristow, T. F.; Crisp, A.; DesMarais, D. J.; Downs, R. T.; Farmer, J. D.; Morookian, J. M.; Morrison, S. M.; Sarrazin, P.; Spanovich, N.; Stolper, E. M.; Treiman, A. H.; Vaniman, D. T.; Yen, A. S.

    2013-01-01

    X-ray diffraction (XRD) data collected of the Rocknest samples by the CheMin instrument on Mars Science Laboratory suggest the presence of poorly crystalline or amorphous materials [1], such as nanophase weathering products or volcanic and impact glasses. The identification of the type(s) of X-ray amorphous material at Rocknest is important because it can elucidate past aqueous weathering processes. The presence of volcanic and impact glasses would indicate that little chemical weathering has occurred because glass is highly susceptible to aqueous alteration. The presence of nanophase weathering products, such as allophane, nanophase iron-oxides, and/or palagonite, would indicate incipient chemical weathering. Furthermore, the types of weathering products present could help constrain pH conditions and identify which primary phases altered to form the weathering products. Quantitative analysis of phases from CheMin data is achieved through Reference Intensity Ratios (RIRs) and Rietveld refinement. The RIR of a mineral (or mineraloid) that relates the scattering power of that mineral (typically the most intense diffraction line) to the scattering power of a separate mineral standard such as corundum [2]. RIRs can be calculated from XRD patterns measured in the laboratory by mixing a mineral with a standard in known abundances and comparing diffraction line intensities of the mineral to the standard. X-ray amorphous phases (e.g., nanophase weathering products) have broad scattering signatures rather than sharp diffraction lines. Thus, RIRs of X-ray amorphous materials are calculated by comparing the area under one of these broad scattering signals with the area under a diffraction line in the standard. Here, we measured XRD patterns of nanophase weathering products (allophane, aluminosilicate gel, and ferrihydrite) mixed with a mineral standard (beryl) in the CheMinIV laboratory instrument and calculated their RIRs to help constrain the abundances of these phases in the Rocknest samples.

  18. Crystal engineering of zeolites with graphene

    NASA Astrophysics Data System (ADS)

    Gebhardt, Paul; Pattinson, Sebastian W.; Ren, Zhibin; Cooke, David J.; Elliott, James A.; Eder, Dominik

    2014-06-01

    Achieving control over the morphology of zeolite crystals at the nanoscale is crucial for enhancing their performance in diverse applications including catalysis, sensors and separation. The complexity and sensitivity of zeolite synthesis processes, however, often make such control both highly empirical and difficult to implement. We demonstrate that graphene can significantly alter the morphology of titanium silicalite (TS-1) particles, in particular being able to reduce their dimensions from several hundreds to less than 10 nm. Through electron microscopy and molecular mechanics simulations we propose a mechanism for this change based on the preferential interaction of specific TS-1 surfaces with benzyl-alcohol-mediated graphene. These findings suggest a facile new means of controlling the zeolite morphology and thereby also further demonstrate the potential of graphene in hybrid materials. Moreover, the generality of the mechanism points the way to a new avenue of research in using two-dimensional materials to engineer functional inorganic crystals.Achieving control over the morphology of zeolite crystals at the nanoscale is crucial for enhancing their performance in diverse applications including catalysis, sensors and separation. The complexity and sensitivity of zeolite synthesis processes, however, often make such control both highly empirical and difficult to implement. We demonstrate that graphene can significantly alter the morphology of titanium silicalite (TS-1) particles, in particular being able to reduce their dimensions from several hundreds to less than 10 nm. Through electron microscopy and molecular mechanics simulations we propose a mechanism for this change based on the preferential interaction of specific TS-1 surfaces with benzyl-alcohol-mediated graphene. These findings suggest a facile new means of controlling the zeolite morphology and thereby also further demonstrate the potential of graphene in hybrid materials. Moreover, the generality of the mechanism points the way to a new avenue of research in using two-dimensional materials to engineer functional inorganic crystals. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00320a

  19. Improving the osteointegration of Ti6Al4V by zeolite MFI coating

    SciTech Connect

    Li, Yong; Jiao, Yilai; Li, Xiaokang; Guo, Zheng

    2015-05-01

    Osteointegration is crucial for success in orthopedic implantation. In recent decades, there have been numerous studies aiming to modify titanium alloys, which are the most widely used materials in orthopedics. Zeolites are solid aluminosilicates whose application in the biomedical field has recently been explored. To this end, MFI zeolites have been developed as titanium alloy coatings and tested in vitro. Nevertheless, the effect of the MFI coating of biomaterials in vivo has not yet been addressed. The aim of the present work is to evaluate the effects of MFI-coated Ti6Al4V implants in vitro and in vivo. After surface modification, the surface was investigated using field emission scanning electron microscopy (FE-SEM) and energy dispersive spectroscopy (EDS). No difference was observed regarding the proliferation of MC3T3-E1 cells on the Ti6Al4V (Ti) and MFI-coated Ti6Al4V (M−Ti) (p > 0.05). However, the attachment of MC3T3-E1 cells was found to be better in the M−Ti group. Additionally, ALP staining and activity assays and quantitative real-time RT-PCR indicated that MC3T3-E1 cells grown on the M−Ti displayed high levels of osteogenic differentiation markers. Moreover, Van-Gieson staining of histological sections demonstrated that the MFI coating on Ti6Al4V scaffolds significantly enhanced osteointegration and promoted bone regeneration after implantation in rabbit femoral condylar defects at 4 and 12 weeks. Therefore, this study provides a method for modifying Ti6Al4V to achieve improved osteointegration and osteogenesis. - Highlights: • Osteointegration is a crucial factor for orthopedic implants. • We coated MFI zeolite on Ti6Al4V substrates and investigated the effects in vitro and in vivo. • The MFI coating displayed good biocompatibility and promoted osteogenic differentiation in vitro. • The MFI coating promoted osteointegration and osteogenesis peri-implant in vivo.

  20. Determination of trace elements in zeolites by laser ablation ICP-MS.

    PubMed

    Pickhardt, C; Brenner, I B; Becker, J S; Dietze, H J

    2000-09-01

    Laser ablation inductively coupled plasma mass spectrometry using a quadrupole-based mass spectrometer (LA-ICP-QMS) was applied for the analysis of powdered zeolites (microporous aluminosilicates) used for clean-up procedures. For the quantitative determination of trace element concentrations three geological reference materials, granite NIM-G, lujavrite NIM-L and syenite NIM-S, from the National Institute for Metallurgy (South Africa) with a matrix composition corresponding to the zeolites were employed. Both the zeolites and reference materials were fused with a lithium borate mixture to increase the homogeneity and to eliminate mineralogical effects. In order to compare two different approaches for the quantification of analytical results in LA-ICP-MS relative sensitivity coefficients (RSCs) of chemical elements and calibration curves were measured using the geostandards. The experimentally obtained RSCs are in the range of 0.2-6 for all elements of interest. Calibration curves for trace elements were measured without and with Li or Ti as internal standard element. With a few exceptions the regression coefficients of the calibration curves are better than 0.993 with internal standardization. NIM-G granite reference material was employed to evaluate the accuracy of the technique. Therefore, the measured concentrations were corrected with RSCs which were determined using lujavrite reference material NIM-L. This quantification method provided analytical results with deviations of 1-11% from the recommended and proposed values in granite reference material NIM-G, except for Co, Cs, La and Tb. The relative standard deviation (RSD) of the determination of the trace element concentration (n = 5) is about 1% to 6% using Ti as internal standard element. Detection limits of LA-ICP-QMS in the lower microg/g range (from 0.03 microg/g for Lu, Ta and Th to 7.3 microg/g for Cu, with the exception of La) have been achieved for all elements of interest. Under the laser ablation conditions employed (lambda: 266 nm, repetition frequency: 10 Hz, pulse energy: 10 mJ, laser power density: 6 x 10(9) W/cm2) fractionation effects of the determined elements relative to the internal standard element Ti were not observed. PMID:11220836

  1. Crystalline Silica Primer

    USGS Publications Warehouse

    Staff- Branch of Industrial Minerals

    1992-01-01

    substance and will present a nontechnical overview of the techniques used to measure crystalline silica. Because this primer is meant to be a starting point for anyone interested in learning more about crystalline silica, a list of selected readings and other resources is included. The detailed glossary, which defines many terms that are beyond the scope of this publication, is designed to help the reader move from this presentation to a more technical one, the inevitable next step.

  2. A cationic cesium continuum in zeolite x.

    PubMed

    Sun, T; Seff, K; Heo, N H; Petranovskii, V P

    1993-01-22

    A cesium continuum that fills the channels and cavities of zeolite X has been prepared, and its structure has been determined by single-crystal x-ray crystallography. The three-dimensional continuum is cationic to balance the negative charge of the zeolite framework. Its valence electrons, only 0.3 per Cs(+) ion, are widely delocalized over 95 percent of the cesium ions in the crystal. The continuum has a unit cell formula of (Cs(122))(86+) and contains Cs(13) and Cs(14) clusters (one per supercage) arranged like the atoms in diamond, with one Cs(2) appendix (in the sodalite cavity) per cluster. PMID:17734168

  3. A Cationic Cesium Continuum in Zeolite X

    NASA Astrophysics Data System (ADS)

    Sun, Tao; Seff, Karl; Heo, Nam Ho; Petranovskii, Vitalli P.

    1993-01-01

    A cesium continuum that fills the channels and cavities of zeolite X has been prepared, and its structure has been determined by single-crystal x-ray crystallography. The three-dimensional continuum is cationic to balance the negative charge of the zeolite framework. Its valence electrons, only 0.3 per Cs^+ ion, are widely delocalized over 95 percent of the cesium ions in the crystal. The continuum has a unit cell formula of (Cs122)86+ and contains Cs13 and Cs14 clusters (one per supercage) arranged like the atoms in diamond, with one Cs_2 appendix (in the sodalite cavity) per cluster.

  4. A Site-Isolated Iridium Diethylene Complex Supported on Highly Dealuminated Y Zeolite: Synthesis And Characterization

    SciTech Connect

    Uzun, A.; Bhirud, V.A.; Kletnieks, P.W.; Haw, J.F.; Gates, B.C.

    2009-06-04

    Highly dealuminated Y zeolite-supported mononuclear iridium complexes with reactive ethylene ligands were synthesized by chemisorption of Ir(C{sub 2}H{sub 4}){sub 2}(C{sub 5}H{sub 7}O{sub 2}). The resultant structure and its treatment in He, CO, ethylene, and H2 were investigated with infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectroscopies. The IR spectra show that Ir(C{sub 2}H{sub 4}){sub 2}(C{sub 5}H{sub 7}O{sub 2}) reacted readily with surface OH groups of the zeolite, leading to the removal of C{sub 5}H{sub 7}O{sub 2} ligands and the formation of supported mononuclear iridium complexes, confirmed by the lack of Ir-Ir contributions in the EXAFS spectra. The EXAFS data show that each Ir atom was bonded to four carbon atoms at an average distance of 2.10 {angstrom}, consistent with the presence of two ethylene ligands per Ir atom and in agreement with the IR spectra indicating {pi}-bonded ethylene ligands. The EXAFS data also indicate that each Ir atom was bonded to two oxygen atoms of the zeolite at a distance of 2.15 {angstrom}. The supported iridium-ethylene complex reacted with H{sub 2} to give ethane, and it also catalyzed ethylene hydrogenation at atmospheric pressure and 294 K. Treatment of the sample in CO led to the formation of Ir(CO){sub 2} complexes bonded to the zeolite. The sharpness of the V{sub CO} bands indicates a high degree of uniformity of these complexes on the support. The iridium-ethylene complex on the crystalline zeolite support is inferred to be one of the most nearly uniform supported metal complex catalysts. The results indicate that it is isostructural with a previously reported rhodium complex on the same zeolite; thus, the results are a start to a family of analogous, structurally well-defined supported metal complex catalysts.

  5. Influence of Boehmite Precursor on Aluminosilicate Aerogel Pore Structure, Phase Stability and Resistance to Densification at High Temperatures

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.; Guo, Haiquan; Newlin, Katy N.

    2011-01-01

    Aluminosilicate aerogels are of interest as constituents of thermal insulation systems for use at temperatures higher than those attainable with silica aerogels. It is anticipated that their effectiveness as thermal insulators will be influenced by their morphology, pore size distribution, physical and skeletal densities. The present study focuses on the synthesis of aluminosilicate aerogel from a variety of Boehmite (precursors as the Al source, and tetraethylorthosilicate (TEOS) as the Si source, and the influence of starting powder on pore structure and thermal stability.

  6. Nuclear Magnetic Resonance Studies of Aluminosilicate Gels Prepared in High-Alkaline and Salt-Concentrated Solutions

    SciTech Connect

    Wang, Li Q.; Mattigod, Shas V.; Parker, Kent E.; Hobbs, David T.; McCready, David E.

    2005-01-11

    We have examined the formation of aluminosilicate in high alkaline and salt concentrated solutions characteristic of nuclear tank wastes. Information on the mechanism and kinetics of the phase formation under hydrothermal conditions was obtained by characterization the structures of gel phases as a function of time and composition using multinuclear NMR techniques in combination with x-ray diffraction. This work offers a new insight into the aluminum and aluminosilicate chemistry in simulated nuclear tank wastes.

  7. The effect of the zeolite clinoptilolite on serum chemistry and hematopoiesis in mice.

    PubMed

    Martin-Kleiner, I; Flegar-Mestric, Z; Zadro, R; Breljak, D; Stanovic Janda, S; Stojkovic, R; Marusic, M; Radacic, M; Boranic, M

    2001-07-01

    Zeolites are natural or synthetic crystalline alumosilicates with ion exchanging properties. Supplied in fodder, they promote biomass production and animal health. Our aim was to assess the effects of the natural zeolite, clinoptilolite, on hematopoiesis, serum electrolytes and essential biochemical indicators of kidney and liver function in mice. Two preparations differing in particle size were tested: a powderized form obtained by countercurrent mechanical treatment of the clinoptilolite (MTCp) and normally ground clinoptilolite (NGCp). Young adult mice were supplied with food containing 12.5, 25 or 50% clinoptilolite powder. Control animals received the same food ration without the clinoptilolite. After 10, 20, 30 and 40 days, six animals from each group were exsanguinated to obtain blood for hematological and serum for biochemical measurements as well as to collect femoral bone marrow for determination of hematopoietic activity. Clinoptilolite ingestion was well tolerated, as judged by comparable body masses of treated and control animals. A 20% increase of the potassium level was detected in mice receiving the zeolite-rich diet, without other changes in serum chemistry. Erythrocyte, hemoglobin and platelet levels in peripheral blood were not materially affected. NGCp caused leukocytosis, with concomitant decline of the GM-CFU content in the bone marrow, which was attributed to intestinal irritation by rough zeolite particles. The mechanically treated clinoptilolite preparation caused similar, albeit less pronounced, changes. In a limited experiment, mice having transplanted mammary carcinoma in the terminal stage showed increased potassium and decreased sodium and chloride levels, severe anemia and leukocytosis, decreased bone marrow cellularity and diminished content of hematopoietic progenitor cells in the marrow. The clinoptilolite preparations ameliorated the sodium and chloride decline, whereas the effects on hematopoiesis were erratic. PMID:11397518

  8. Stability of glucose oxidase and catalase adsorbed on variously activated 13X zeolite.

    PubMed

    Pifferi, P G; Vaccari, A; Ricci, G; Poli, G; Ruggeri, O

    1982-10-01

    The use of 13X zeolite (0.1-0.4-mm granules), treated with 2N and 0.01N HCI, 0.01M citric acid, 0.1M citric-phosphate buffer (pH 3.6), and in untreated form to adsorb glucose oxidase of fungal origin and microbial catalase was examined. Physicochemical analysis of the support demonstrated that its crystalline structure, greatly altered by the HCl and buffer, could be partially maintained with citric acid. The specific adsorption of the enzymes increased with decreasing pH and proved to be considerable for all the supports. The stability with storage at 25 degrees C is strictly correlated with the titrable acidity of the activated zeolite expressed as meq NaOH/g and with pH value of the activation solution. It proved to be lower than 55 h for both enzymes if adsorbed on zeolite treated with 2N HCl, and 15-fold and 30-fold higher for glucose oxidase and catalase adsorbed, respectively, on zeolite treated with the 0.1M citric-phosphate buffer and 0.01M citric acid. The specific adsorption of glucose oxidase and catalase was, respectively, 1840 U/g at pH 3.0 and 6910 U/g at pH 5.0. Their half-life at 25 degrees C with storage at pH 3.5 for the former and at pH 5.0 for the latter was 800 and 1560 h vs. 40 and 110 h for the corresponding free enzymes. PMID:18546124

  9. Towards liquid fuels from biosyngas: effect of zeolite structure in hierarchical-zeolite-supported cobalt catalysts.

    PubMed

    Sartipi, Sina; Alberts, Margje; Meijerink, Mark J; Keller, Tobias C; Pérez-Ramírez, Javier; Gascon, Jorge; Kapteijn, Freek

    2013-09-01

    Wax on, wax off: Bifunctional cobalt-based catalysts on zeolite supports are applied for the valorization of biosyngas through Fischer-Tropsch chemistry. By using these catalysts, waxes can be hydrocracked to shorter-chain hydrocarbons, increasing the selectivity towards the C5 -C11 (gasoline) fraction. The zeolite topology and the amount and strength of acid sites are key parameters to maximize the performance of these bifunctional catalysts, steering Fischer-Tropsch product selectivity towards liquid hydrocarbons. PMID:23765635

  10. Maximizing the catalytic function of hydrogen spillover in platinum-encapsulated aluminosilicates with controlled nanostructures.

    PubMed

    Im, Juhwan; Shin, Hyeyoung; Jang, Haeyoun; Kim, Hyungjun; Choi, Minkee

    2014-01-01

    Hydrogen spillover has been studied for several decades, but its nature, catalytic functions and even its existence remain topics of vigorous debate. This is a consequence of the lack of model catalysts that can provide direct evidences of the existence of hydrogen spillover and simplify the catalytic interpretation. Here we use platinum encapsulated in a dense aluminosilicate matrix with controlled diffusional properties and surface hydroxyl concentrations to elucidate the catalytic functions of hydrogen spillover. The catalytic investigation and theoretical modelling show that surface hydroxyls, presumably Brønsted acids, are crucial for utilizing the catalytic functions of hydrogen spillover on the aluminosilicate surface. The catalysts with optimized nanostructure show remarkable activities in hydro-/dehydrogenation, but virtually no activity for hydrogenolysis. This distinct chemoselectivity may be beneficial in industrially important hydroconversions such as propane dehydrogenation to propylene because the undesired hydrogenolysis pathway producing light hydrocarbons of low value (methane and ethane) is greatly suppressed. PMID:24566616

  11. Adsorption of water-methanol mixtures in carbon and aluminosilicate pores: a molecular simulation study

    NASA Astrophysics Data System (ADS)

    Shevade, Abhijit V.; Jiang, Shaoyi; Gubbins, Keith E.

    A theoretical study is reported of the adsorption behaviour of water-methanol mixtures in slit carbon and in uncharged alumino-silicate micropores. The adsorption isotherms are obtained for a pore of width of 2 nm and at a temperature of 298K from grand canonical ensemble Monte Carlo simulations. The results show that the graphite and uncharged silicate surfaces are covered by a dense layer of flatly adsorbed water and methanol molecules having weaker hydrogen bonding. In the interior of the pore, the fluid exhibits bulk-like behaviour with a stronger hydrogen bonded structure. Solvation forces are also calculated as a function of pore size. The positive values found for the solvation force for all pore sizes reflect the hydrophobic interactions of the mixture with the carbon and uncharged alumino-silicate walls.

  12. Zeolite 5A Catalyzed Etherification of Diphenylmethanol

    ERIC Educational Resources Information Center

    Cooke, Jason; Henderson, Eric J.; Lightbody, Owen C.

    2009-01-01

    An experiment for the synthetic undergraduate laboratory is described in which zeolite 5A catalyzes the room temperature dehydration of diphenylmethanol, (C[subscript 6]H[subscript 5])[subscript 2]CHOH, producing 1,1,1',1'-tetraphenyldimethyl ether, (C[subscript 6]H[subscript 5])[subscript 2]CHOCH(C[subscript 6]H[subscript 5])[subscript 2]. The…

  13. ARSENIC SEPARATION FROM WATER USING ZEOLITES

    EPA Science Inventory

    Arsenic is known to be a hazardous contaminant in drinking water. The presence of arsenic in water supplies has been linked to arsenical dermatosis and skin cancer . Zeolites are well known for their ion exchange capacities. In the present work, the potential use of a variety of ...

  14. ARSENIC SEPARATION FROM WATER USING ZEOLITES: SYMPOSIUM

    EPA Science Inventory

    NRMRL-ADA-01134 Shevade, S, Ford*, R., and Puls*, R.W. "Arsenic Separation from Water Using Zeolites." In: 222nd ACS National Meeting, ACS Environmental Chemistry Division Symposia, Chicago, IL, 08/26-30/2001. 2001. 04/23/2001 This...

  15. Multicomponent liquid ion exchange with chabazite zeolites

    SciTech Connect

    Robinson, S.M.; Arnold, W.D. Jr.; Byers, C.W.

    1993-10-01

    In spite of the increasing commercial use of zeolites for binary and multicomponent sorption, the understanding of the basic mass-transfer processes associated with multicomponent zeolite ion-exchange systems is quite limited. This study was undertaken to evaluate Na-Ca-Mg-Cs-Sr ion exchange from an aqueous solution using a chabazite zeolite. Mass-transfer coefficients and equilibrium equations were determined from experimental batch-reactor data for single and multicomponent systems. The Langmuir isotherm was used to represent the equilibrium relationship for binary systems, and a modified Dubinin-Polyani model was used for the multicomponent systems. The experimental data indicate that diffusion through the microporous zeolite crystals is the primary diffusional resistance. Macropore diffusion also significantly contributes to the mass-transfer resistance. Various mass-transfer models were compared to the experimental data to determine mass-transfer coefficients. Effective diffusivities were obtained which accurately predicted experimental data using a variety of models. Only the model which accounts for micropore and macropore diffusion occurring in series accurately predicted multicomponent data using single-component diffusivities. Liquid and surface diffusion both contribute to macropore diffusion. Surface and micropore diffusivities were determined to be concentration dependent.

  16. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, Wolfgang M. H.; Tzou, Ming-Shin; Jiang, Hui-Jong

    1987-01-01

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  17. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, W.M.H.; Tzou, M.S.; Jiang, H.J.

    1987-03-31

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  18. MERCURY SEPARATION FROM POLLUTANT WATER USING ZEOLITES

    EPA Science Inventory

    Arsenic is known to be a hazardous contaminant in drinking water that causes arsenical dermatitis and skin cancer. In the present work, the potential use of a variety of synthetic zeolites for removal of arsenic from water has been examined at room temperature. Experiments have...

  19. Chemical interactions in multimetal/zeolite catalysts

    SciTech Connect

    Sachtler, W.M.H.

    1992-02-07

    Mechanistic explanations have been found for the migration of atoms and ions through the zeolite channels leading to specific distribution of ions and the metal clusters. In this report, we summarize the state of understanding attained on a number of topics in the area of mono- and multimetal/zeolite systems, to which our recent research has made significant contributions. The following topics are discussed: (1) Formation of isolated metal atoms in sodalite cages; (2) differences of metal/zeolite systems prepared by ion reduction in channels or via isolated atoms; (3) rejuvenation of Pd/NaY and Pd/HY catalysts by oxidative redispersion of the metal; (4) formation of mono- or bimetal particles in zeolites by programmed reductive decomposition of volatile metal complexes; (5) cation-cation interaction as a cause of enhanced reducibility; (6) formation of palladium carbonyl clusters in supercages; (7) enhanced catalytic activity of metal particle-proton complexes for hydrocarbon conversion reactions; (8) stereoselectivity of catalytic reactions due to geometric constraints of particles in cages.

  20. Source fabrication and lifetime for Li{sup +} ion beams extracted from alumino-silicate sources

    SciTech Connect

    Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.

    2012-04-15

    A space-charge-limited beam with current densities (J) exceeding 1 mA/cm{sup 2} have been measured from lithium alumino-silicate ion sources at a temperature of {approx}1275 deg. C. At higher extraction voltages, the source appears to become emission limited with J{>=} 1.5 mA/cm{sup 2}, and J increases weakly with the applied voltage. A 6.35 mm diameter source with an alumino-silicate coating, {<=}0.25 mm thick, has a measured lifetime of {approx}40 h at {approx}1275 deg. C, when pulsed at 0.05 Hz and with pulse length of {approx}6 {mu}s each. At this rate, the source lifetime was independent of the actual beam charge extracted due to the loss of neutral atoms at high temperature. The source lifetime increases with the amount of alumino-silicate coated on the emitting surface, and may also be further extended if the temperature is reduced between pulses.

  1. Impact Of Sodium Oxalate, Sodium Aluminosilicate, and Gibbsite/Boehmite on ARP Filter Performance

    SciTech Connect

    Poirier, M.; Burket, P.

    2015-11-01

    The Savannah River Site (SRS) is currently treating radioactive liquid waste with the Actinide Removal Process (ARP) and the Modular Caustic Side Solvent Extraction Unit (MCU). Recently, the low filter flux through the ARP of approximately 5 gallons per minute has limited the rate at which radioactive liquid waste can be treated. Salt Batch 6 had a lower processing rate and required frequent filter cleaning. Savannah River Remediation (SRR) has a desire to understand the causes of the low filter flux and to increase ARP/MCU throughput. SRR requested SRNL to conduct bench-scale filter tests to evaluate whether sodium oxalate, sodium aluminosilicate, or aluminum solids (i.e., gibbsite and boehmite) could be the cause of excessive fouling of the crossflow or secondary filter at ARP. The authors conducted the tests by preparing slurries containing 6.6 M sodium Salt Batch 6 supernate, 2.5 g MST/L slurry, and varying concentrations of sodium oxalate, sodium aluminosilicate, and aluminum solids, processing the slurry through a bench-scale filter unit that contains a crossflow primary filter and a dead-end secondary filter, and measuring filter flux and transmembrane pressure as a function of time. Among the conclusions drwn from this work are the following: (1) All of the tests showed some evidence of fouling the secondary filter. This fouling could be from fine particles passing through the crossflow filter. (2) The sodium oxalate-containing feeds behaved differently from the sodium aluminosilicate- and gibbsite/boehmite-containing feeds.

  2. The effects of intrapleural injections of alumina and aluminosilicate (ceramic) fibres.

    PubMed

    Pigott, G H; Ishmael, J

    1992-04-01

    Groups of rats, 24 male and 24 female, approximately 8 weeks old, were dosed by a single intrapleural injection with a saline suspension of refractory alumina fibres (Saffil fibres ICI plc) either as manufactured or after extensive thermal ageing; or one of two aluminosilicate ('ceramic') fibres with different diameter distributions. Similar groups were dosed with a suspension of UICC chrysotile A asbestos or saline solution to serve as positive and negative controls respectively. Rats were maintained to 85% mortality and all decedents and terminal sacrifices were closely examined for the presence of mesothelioma. Malignant mesothelioma was diagnosed in ten rats, seven dosed with asbestos and three dosed with aluminosilicate fibre B. No mesothelioma was detected in any rat dosed with Saffil fibres or aluminosilicate fibre A or in negative controls. The results support the predicted inert nature of Saffil alumina fibres and provide further evidence for the importance of fibre dimension in the induction of mesothelioma. The implication of the results for inhalation exposures is discussed. PMID:1571274

  3. STUDIES OF POTENTIAL INHIBITORS OF SODIUM ALUMINOSILICATE SCALES IN HIGH-LEVEL WASTE EVAPORATION

    SciTech Connect

    Wilmarth, B; Lawrence Oji, L; Terri Fellinger, T; David Hobbs, D; Nilesh Badheka, N

    2008-02-27

    The Savannah River Site (SRS) has 49 underground storage tanks used to store High Level Waste (HLW). The tank space in these tanks must be managed to support the continued operation of key facilities. The reduction of the tank volumes in these tanks are accomplished through the use of three atmospheric pressure HLW evaporators. For a decade, evaporation of highly alkaline HLW containing aluminum and silicates has produced sodium aluminosilicate scales causing both operation and criticality hazards in the 2H Evaporator System. Segregation of aluminum-rich wastes from silicate-rich wastes minimizes the amount of scale produced and reduces cleaning expenses, but does not eliminate the scaling nor increases operation flexibility in waste process. Similar issues have affected the aluminum refining industry for many decades. Over the past several years, successful commercial products have been identified to eliminate aluminosilicate fouling in the aluminum industry, but have not been utilized in a nuclear environment. Laboratory quantities of three proprietary aluminosilicate scale inhibitors have been produced and been shown to prevent formation of scales. SRNL has been actively testing these potential inhibitors to examine their radiation stability, radiolytic degradation behaviors, and downstream impacts to determine their viability within the HLW system. One of the tested polymers successfully meets the established criteria for application in the nuclear environment. This paper will describe a summary of the methodology used to prioritize laboratory testing protocols based on potential impacts/risks identified for inhibitor deployment at SRS.

  4. Source fabrication and lifetime for Li+ ion beams extracted from alumino-silicate sources.

    PubMed

    Roy, Prabir K; Greenway, Wayne G; Kwan, Joe W

    2012-04-01

    A space-charge-limited beam with current densities (J) exceeding 1 mA/cm(2) have been measured from lithium alumino-silicate ion sources at a temperature of ∼1275 °C. At higher extraction voltages, the source appears to become emission limited with J ≥ 1.5 mA/cm(2), and J increases weakly with the applied voltage. A 6.35 mm diameter source with an alumino-silicate coating, ≤0.25 mm thick, has a measured lifetime of ∼40 h at ∼1275 °C, when pulsed at 0.05 Hz and with pulse length of ∼6 μs each. At this rate, the source lifetime was independent of the actual beam charge extracted due to the loss of neutral atoms at high temperature. The source lifetime increases with the amount of alumino-silicate coated on the emitting surface, and may also be further extended if the temperature is reduced between pulses. PMID:22559528

  5. Origins of saccharide-dependent hydration at aluminate, silicate, and aluminosilicate surfaces

    PubMed Central

    Smith, Benjamin J.; Rawal, Aditya; Funkhouser, Gary P.; Roberts, Lawrence R.; Gupta, Vijay; Israelachvili, Jacob N.; Chmelka, Bradley F.

    2011-01-01

    Sugar molecules adsorbed at hydrated inorganic oxide surfaces occur ubiquitously in nature and in technologically important materials and processes, including marine biomineralization, cement hydration, corrosion inhibition, bioadhesion, and bone resorption. Among these examples, surprisingly diverse hydration behaviors are observed for oxides in the presence of saccharides with closely related compositions and structures. Glucose, sucrose, and maltodextrin, for example, exhibit significant differences in their adsorption selectivities and alkaline reaction properties on hydrating aluminate, silicate, and aluminosilicate surfaces that are shown to be due to the molecular architectures of the saccharides. Solid-state 1H, 13C, 29Si, and 27Al nuclear magnetic resonance (NMR) spectroscopy measurements, including at very high magnetic fields (19 T), distinguish and quantify the different molecular species, their chemical transformations, and their site-specific adsorption on different aluminate and silicate moieties. Two-dimensional NMR results establish nonselective adsorption of glucose degradation products containing carboxylic acids on both hydrated silicates and aluminates. In contrast, sucrose adsorbs intact at hydrated silicate sites and selectively at anhydrous, but not hydrated, aluminate moieties. Quantitative surface force measurements establish that sucrose adsorbs strongly as multilayers on hydrated aluminosilicate surfaces. The molecular structures and physicochemical properties of the saccharides and their degradation species correlate well with their adsorption behaviors. The results explain the dramatically different effects that small amounts of different types of sugars have on the rates at which aluminate, silicate, and aluminosilicate species hydrate, with important implications for diverse materials and applications. PMID:21562207

  6. Liquid crystalline composites containing phyllosilicates

    DOEpatents

    Chaiko, David J.

    2004-07-13

    The present invention provides phyllosilicate-polymer compositions which are useful as liquid crystalline composites. Phyllosilicate-polymer liquid crystalline compositions of the present invention can contain a high percentage of phyllosilicate while at the same time be transparent. Because of the ordering of the particles liquid crystalline composite, liquid crystalline composites are particularly useful as barriers to gas transport.

  7. Early age hydration and pozzolanic reaction in natural zeolite blended cements: Reaction kinetics and products by in situ synchrotron X-ray powder diffraction

    SciTech Connect

    Snellings, R.; Mertens, G.; Cizer, O.; Elsen, J.

    2010-12-15

    The in situ early-age hydration and pozzolanic reaction in cements blended with natural zeolites were investigated by time-resolved synchrotron X-ray powder diffraction with Rietveld quantitative phase analysis. Chabazite and Na-, K-, and Ca-exchanged clinoptilolite materials were mixed with Portland cement in a 3:7 weight ratio and hydrated in situ at 40 {sup o}C. The evolution of phase contents showed that the addition of natural zeolites accelerates the onset of C{sub 3}S hydration and precipitation of CH and AFt. Kinetic analysis of the consumption of C{sub 3}S indicates that the enveloping C-S-H layer is thinner and/or less dense in the presence of alkali-exchanged clinoptilolite pozzolans. The zeolite pozzolanic activity is interpreted to depend on the zeolite exchangeable cation content and on the crystallinity. The addition of natural zeolites alters the structural evolution of the C-S-H product. Longer silicate chains and a lower C/S ratio are deduced from the evolution of the C-S-H b-cell parameter.

  8. Conversion of Ethanol to Hydrocarbons on Hierarchical HZSM-5 Zeolites

    SciTech Connect

    Ramasamy, Karthikeyan K.; Zhang, He; Sun, Junming; Wang, Yong

    2014-02-22

    This study reports synthesis, characterization, and catalytic activity of the nano-size hierarchical HZSM-5 zeolite with high mesoporosity produced via a solvent evaporation procedure. Further, this study compares hierarchical zeolites with conventional HZSM-5 zeolite with similar Si/Al ratios for the ethanol-to-hydrocarbon conversion process. The catalytic performance of the hierarchical and conventional zeolites was evaluated using a fixed-bed reactor at 360 °C, 300 psig, and a weight hourly space velocity of 7.9 h-1. For the low Si/Al ratio zeolite (~40), the catalytic life-time for the hierarchical HZSM-5 was approximately 2 times greater than the conventional HZSM-5 despite its coking amount deposited 1.6 times higher than conventional HZSM-5. For the high Si/Al ratio zeolite (~140), the catalytic life-time for the hierarchical zeolite was approximately 5 times greater than the conventional zeolite and the amount of coking deposited was 2.1 times higher. Correlation was observed between catalyst life time, porosity, and the crystal size of the zeolite. The nano-size hierarchical HZSM-5 zeolites containing mesoporosity demonstrated improved catalyst life-time compared to the conventional catalyst due to faster removal of products, shorter diffusion path length, and the migration of the coke deposits to the external surface from the pore structure.

  9. Zeolite Nanoparticles for Selective Sorption of Plasma Proteins

    PubMed Central

    Rahimi, M.; Ng, E.-P.; Bakhtiari, K.; Vinciguerra, M.; Ahmad, H. Ali; Awala, H.; Mintova, S.; Daghighi, M.; Bakhshandeh Rostami, F.; de Vries, M.; Motazacker, M. M.; Peppelenbosch, M. P.; Mahmoudi, M.; Rezaee, F.

    2015-01-01

    The affinity of zeolite nanoparticles (diameter of 8–12 nm) possessing high surface area and high pore volume towards human plasma proteins has been investigated. The protein composition (corona) of zeolite nanoparticles has been shown to be more dependent on the plasma protein concentrations and the type of zeolites than zeolite nanoparticles concentration. The number of proteins present in the corona of zeolite nanoparticles at 100% plasma (in vivo state) is less than with 10% plasma exposure. This could be due to a competition between the proteins to occupy the corona of the zeolite nanoparticles. Moreover, a high selective adsorption for apolipoprotein C-III (APOC-III) and fibrinogen on the zeolite nanoparticles at high plasma concentration (100%) was observed. While the zeolite nanoparticles exposed to low plasma concentration (10%) exhibited a high selective adsorption for immunoglobulin gamma (i.e. IGHG1, IGHG2 and IGHG4) proteins. The zeolite nanoparticles can potentially be used for selectively capture of APOC-III in order to reduce the activation of lipoprotein lipase inhibition during hypertriglyceridemia treatment. The zeolite nanoparticles can be adapted to hemophilic patients (hemophilia A (F-VIII deficient) and hemophilia B (F-IX deficient)) with a risk of bleeding, and thus might be potentially used in combination with the existing therapy. PMID:26616161

  10. Energetics of sodium-calcium exchanged zeolite A.

    PubMed

    Sun, H; Wu, D; Guo, X; Shen, B; Navrotsky, A

    2015-05-01

    A series of calcium-exchanged zeolite A samples with different degrees of exchange were prepared. They were characterized by powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC). High temperature oxide melt drop solution calorimetry measured the formation enthalpies of hydrated zeolites CaNa-A from constituent oxides. The water content is a linear function of the degree of exchange, ranging from 20.54% for Na-A to 23.77% for 97.9% CaNa-A. The enthalpies of formation (from oxides) at 25 C are -74.50 1.21 kJ mol(-1) TO2 for hydrated zeolite Na-A and -30.79 1.64 kJ mol(-1) TO2 for hydrated zeolite 97.9% CaNa-A. Dehydration enthalpies obtained from differential scanning calorimetry are 32.0 kJ mol(-1) H2O for hydrated zeolite Na-A and 20.5 kJ mol(-1) H2O for hydrated zeolite 97.9% CaNa-A. Enthalpies of formation of Ca-exchanged zeolites A are less exothermic than for zeolite Na-A. A linear relationship between the formation enthalpy and the extent of calcium substitution was observed. The energetic effect of Ca-exchange on zeolite A is discussed with an emphasis on the complex interactions between the zeolite framework, cations, and water. PMID:25827491

  11. Zeolite Nanoparticles for Selective Sorption of Plasma Proteins

    NASA Astrophysics Data System (ADS)

    Rahimi, M.; Ng, E.-P.; Bakhtiari, K.; Vinciguerra, M.; Ahmad, H. Ali; Awala, H.; Mintova, S.; Daghighi, M.; Bakhshandeh Rostami, F.; de Vries, M.; Motazacker, M. M.; Peppelenbosch, M. P.; Mahmoudi, M.; Rezaee, F.

    2015-11-01

    The affinity of zeolite nanoparticles (diameter of 8-12 nm) possessing high surface area and high pore volume towards human plasma proteins has been investigated. The protein composition (corona) of zeolite nanoparticles has been shown to be more dependent on the plasma protein concentrations and the type of zeolites than zeolite nanoparticles concentration. The number of proteins present in the corona of zeolite nanoparticles at 100% plasma (in vivo state) is less than with 10% plasma exposure. This could be due to a competition between the proteins to occupy the corona of the zeolite nanoparticles. Moreover, a high selective adsorption for apolipoprotein C-III (APOC-III) and fibrinogen on the zeolite nanoparticles at high plasma concentration (100%) was observed. While the zeolite nanoparticles exposed to low plasma concentration (10%) exhibited a high selective adsorption for immunoglobulin gamma (i.e. IGHG1, IGHG2 and IGHG4) proteins. The zeolite nanoparticles can potentially be used for selectively capture of APOC-III in order to reduce the activation of lipoprotein lipase inhibition during hypertriglyceridemia treatment. The zeolite nanoparticles can be adapted to hemophilic patients (hemophilia A (F-VIII deficient) and hemophilia B (F-IX deficient)) with a risk of bleeding, and thus might be potentially used in combination with the existing therapy.

  12. Topological nonsymmorphic crystalline superconductors

    NASA Astrophysics Data System (ADS)

    Wang, Qing-Ze; Liu, Chao-Xing

    2016-01-01

    Topological superconductors possess a nodeless superconducting gap in the bulk and gapless zero energy modes, known as "Majorana zero modes," at the boundary of a finite system. In this work, we introduce a new class of topological superconductors, which are protected by nonsymmorphic crystalline symmetry and thus dubbed "topological nonsymmorphic crystalline superconductors." We construct an explicit Bogoliubov-de Gennes type of model for this superconducting phase in the D class and show how Majorana zero modes in this model are protected by glide plane symmetry. Furthermore, we generalize the classification of topological nonsymmorphic crystalline superconductors to the classes with time reversal symmetry, including the DIII and BDI classes, in two dimensions. Our theory provides guidance to search for new topological superconducting materials with nonsymmorphic crystal structures.

  13. One-pot synthesis of MWW zeolite nanosheets using a rationally designed organic structure-directing agent

    PubMed Central

    Luo, Helen Y.; Michaelis, Vladimir K.; Hodges, Sydney; Griffin, Robert G.

    2015-01-01

    A new material MIT-1 comprised of delaminated MWW zeolite nanosheets is synthesized in one-pot using a rationally designed organic structure-directing agent (OSDA). The OSDA is comprised of a hydrophilic head segment that resembles the OSDA used to synthesize the zeolite precursor MCM22(P), a hydrophobic tail segment that resembles the swelling agent used to swell MCM22(P), and a di-quaternary ammonium linker that connects both segments. MIT-1 features high crystallinity and surface areas exceeding 500 m2g?1, and can be synthesized over a wide synthesis window that includes Si/Al ratios ranging from 13 to 67. Characterization data reveal high mesoporosity and acid strength with no detectable amorphous silica phases. Compared to MCM-22 and MCM-56, MIT-1 shows a three-fold increase in catalytic activity for the Friedel-Crafts alkylation of benzene with benzyl alcohol. PMID:26478803

  14. CO2 SEPARATIONS USING ZEOLITE MEMBRANES

    SciTech Connect

    Richard D. Noble; John L. Falconer

    2001-06-30

    Zeolite and other inorganic molecular sieve membranes have shown potential for separations based on molecular size and shape because of their small pore sized, typically less than 1 nm, and their narrow pore size distribution. The high thermal and chemical stability of these inorganic crystals make them ideal materials for use in high temperature applications such as catalytic membrane reactors. Most of the progress with zeolite membranes has been with MFI zeolites prepared on porous disks and tubes. The MFI zeolite is a medium pore size structure having nearly circular pores with diameters between .53 and .56 nm. Separation experiments through MFI membranes indicate that competitive adsorption separates light gas mixtures. Light gas selectivities are typically small, however, owing to small differences in adsorption strengths and their small sizes relative to the MFI pore opening. Furthermore, competitive adsorption does not work well at high temperature where zeolite membranes are stable and have potential application. Separation by differences in size has a greater potential to work at high temperature than competitive adsorption, but pores smaller than those in MFI zeolites are required. Therefore, some studies focused on the synthesis of a small, 8-membered-pore structures such as zeolite A (0.41-nm pore diameter) and SAPO-34, a chabazite (about .4-nm pore diameter with about 1.4 nm cages) analog. The small pore size of the zeolite A and SAPO-34 structures made the separation of smaller molecules by differences in size possible. Zeolite MFI and SAPO-34 membranes were prepared on the inside surface of porous alumina tubes by hydrothermal synthesis, and single gas and binary mixture permeances were measured to characterize the membrane's performance. A mathematical diffusion model was developed to determine the relative quantities of zeolite and non-zeolite pores in different membranes by modeling the permeation date of CO{sub 2}. This model expresses the total flux through the membrane as the sum of surface diffusion through zeolite pores and viscous flow and Knudsen diffusion through non-zeolite pores. As predicted by the model, the permeance of CO{sub 2} decrease with increasing pressure at constant pressure drop for membranes with few non-zeolite pores, but the permeance increased through viscous flow pores and was constant through pores allowing Knudsen diffusion. Membranes having more non-zeolite pores had lower CO{sub 2}/CH{sub 4} selectivities. The SAPO-34 membranes were characterized for light gas separation applications, and the separation mechanisms were identified. Single gas permeances of CO{sub 2}, N{sub 2}, and CH{sub 4} decreased with increasing kinetic diameter. For the best membrane at 300K, the He and H{sub 2} permeances were less than that of CO{sub 2}, because He, H{sub 2} and CO{sub 2} were small compared to the SAPO-34 pore, and differences in the heat of adsorption determined the permeance order. The small component permeated the fastest in CO{sub 2}/CH{sub 4}, CO{sub 2}/N{sub 2}, N{sub 2}/CH{sub 4}, H{sub 2}/CH{sub 4}, and H{sub 2}/N{sub 2} mixtures between 300 and 470 K. For H{sub 2}/CO{sub 2} mixtures, which were separated by competitive adsorption at room temperature, the larger component permeated faster below 400K. The room temperature CO{sub 2}/CH{sub 4} selectivity was 36 and decreased with temperature. The H{sub 2}/CH{sub 4} mixture selectivity was 8 and constant with temperature up to 480 K. Calcination, slow temperature cycles, and exposure to water vapor had no permanent effect on membrane performance, but temperature changes of approximately 30 K/min decreased the membrane's effectiveness. The effects of humidity on gas permeation were studied with SAPO-34 membranes of different qualities. Membranes with high CO{sub 2}/CH{sub 4} selectivities (greater than 20) were stable in water vapor under controlled conditions, but degradation was seen for some membranes. The degradation opened non-SAPO-34 pores that were larger than SAPO-34 pores as shown by the IC{sub 4}H{sub 10} permeance, CO{sub 2}/CH{sub 4} selectivity, and CO{sub 2} flux pressure dependence. In SAPO-34 pores, water apparently adsorbed and increased the gas permeances. Thus, the effect of water on gas permeation is a useful indicator of the membrane quality.

  15. UTILITY OF ZEOLITES IN REMOVAL OF INORGANIC AND ORGANIC WATER POLLUTANTS

    EPA Science Inventory

    Zeolites are well known for their ion exchange, adsorption and acid catalysis properties. Different inorganic and organic pollutants have been removed from water at room temperature using various zeolites. Synthetic zeolite Faujasite Y has been used to remove inorganic pollutants...

  16. One-step synthesis of hierarchical aluminosilicate aggregates using bifunctional alkanolamine as single template

    NASA Astrophysics Data System (ADS)

    Chen, Li; Zhu, Shu Yan; Wang, Hai Man; Wang, Yi Meng

    2011-11-01

    Highly active, hierarchical zeolite ZSM-5 aggregates have been prepared in a one-step synthesis using alkanolamine as single template. The effects of SiO 2/Al 2O 3, pH and H 2O/SiO 2 on the aggregate morphology of the ZSM-5 nanocrystals were investigated. The obtained aggregate zeolites characterized by SEM, TEM and BET possessed significant textual porosity (up to 0.22 cm 3/g), which could be tuned by the number of substituents in the alkanolamine molecules and the amount of aluminum in the synthetic mixtures. These zeolite aggregates showed high activities for Friedel-Crafts alkylations and may curtail the filtration difficulties during the synthesis and applications to some extent.

  17. Characteristic of fly ash derived-zeolite and its catalytic performance for fast pyrolysis of Jatropha waste.

    PubMed

    Vichaphund, S; Aht-Ong, D; Sricharoenchaikul, V; Atong, D

    2014-01-01

    Fly ash from pulp and paper industries was used as a raw material for synthesizing zeolite catalyst. Main compositions of fly ash consisted of 41 wt%SiO2, 20 wt%Al2O3, 14 wt%CaO, and 8 wt% Fe2O3. High content of silica and alumina indicated that this fly ash has potential uses for zeolite synthesis. Fly ash was mixed with 1-3 M NaOH solution. Sodium silicate acting as silica source was added into the solution to obtain the initial SiO2/Al2O3 molar ratio of 23.9. The mixtures were then crystallized at 160 degrees C for 24 and 72 h. Zeolites synthesized after a long synthesis time of 72 h showed superior properties in terms of high crystallinity, less impurity, and small particle size. The catalytic activities of fly ash-derived zeolites were investigated via fast pyrolysis of Jatropha wastes using analytical pyrolysis-gas chromatograph/mass spectrometer (GC/MS). Pyrolysis temperature was set at 500 degrees C with Jatropha wastes to catalyst ratio of 1:1, 1:5, and 1:10. Results showed that higher amounts of catalyst have a positive effect on enhancing aromatic hydrocarbons as well as decreasing in the oxygenated and N-containing compounds. Zeolite Socony Mobil-5 (ZSM-5) treated with 3 M NaOH at 72 h showed the highest hydrocarbon yield of 97.4%. The formation of hydrocarbon led to the high heating value of bio-oils. In addition, the presence of ZSM-5 derived from fly ash contributed to reduce the undesirable oxygenated compounds such as aldehydes, acids, and ketones which cause poor quality of bio-oil to only 0.8% while suppressed N-compounds to 1.7%. Overall, the ZSM-5 synthesized from fly ash proved to be an effective catalyst for catalytic fast pyrolysis application. PMID:25145178

  18. Zeolite catalysis in conversion of cellulosics. Annual report

    SciTech Connect

    Tsao, G.T.

    1994-02-01

    The authors have studied the kinetics of oxylose/xylulose isomerization in significant detail over a variety of zeolites and obtained the pseudo-first order reaction rate constants. The authors have found that HY zeolite is still the best material and zeolites are more selective than homogeneous acid catalysts where decomposition of the sugar compounds is much faster. They have completed, as described in the Year 2 Work Plan, the study of cellobiose hydrolysis with an ion exchange resin. The kinetics of the solid-catalyzed reaction is qualitatively similar to that for catalysis by homogeneous acids. The planned program of NMR studies has revealed the dynamics of sugar molecules within the zeolite cavities. Two chemisorbed and a physisorbed state have been identified in HY zeolite. A new state, accounting for as much as a half of the sugar, has been found in ZSM-5 zeolite.

  19. Preparation of Robust, Thin Zeolite Membrane Sheet for Molecular Separation

    SciTech Connect

    Liu, Wei; Zhang, Jian; Canfield, Nathan L.; Saraf, Laxmikant V.

    2011-10-19

    This paper reports a feasibility study on the preparation of zeolite membrane films on a thin, porous metal support sheet (50-{micro}m thick). Zeolite sodium A (NaA) and silicalite zeolite frameworks are chosen to represent synthesis of respective hydrophilic-type and hydrophobic-type zeolite membranes on this new support. It is found that a dense, continuous inter-grown zeolite crystal layer at a thickness less than 2 {micro}m can be directly deposited on such a support by using direct and secondary growth techniques. The resulting membrane shows excellent adhesion on the metal sheet. Molecular-sieving functions of the prepared membranes are characterized with ethanol/water separation, CO2 separation, and air dehumidification. The results show great potential to make flexible metal-foil-like zeolite membranes for a range of energy conversion and environmental applications.

  20. Atomic sites and stability of Cs+ captured within zeolitic nanocavities

    PubMed Central

    Yoshida, Kaname; Toyoura, Kazuaki; Matsunaga, Katsuyuki; Nakahira, Atsushi; Kurata, Hiroki; Ikuhara, Yumi H.; Sasaki, Yukichi

    2013-01-01

    Zeolites have potential application as ion-exchangers, catalysts and molecular sieves. Zeolites are once again drawing attention in Japan as stable adsorbents and solidification materials of fission products, such as 137Cs+ from damaged nuclear-power plants. Although there is a long history of scientific studies on the crystal structures and ion-exchange properties of zeolites for practical application, there are still open questions, at the atomic-level, on the physical and chemical origins of selective ion-exchange abilities of different cations and detailed atomic structures of exchanged cations inside the nanoscale cavities of zeolites. Here, the precise locations of Cs+ ions captured within A-type zeolite were analyzed using high-resolution electron microscopy. Together with theoretical calculations, the stable positions of absorbed Cs+ ions in the nanocavities are identified, and the bonding environment within the zeolitic framework is revealed to be a key factor that influences the locations of absorbed cations. PMID:23949184

  1. Density of mechanisms within the flexibility window of zeolites.

    PubMed

    Kapko, V; Dawson, C; Rivin, I; Treacy, M M J

    2011-10-14

    By treating idealized zeolite frameworks as periodic mechanical trusses, we show that the number of flexible folding mechanisms in zeolite frameworks is strongly peaked at the minimum density end of their flexibility window. 25 of the 197 known zeolite frameworks exhibit an extensive flexibility, where the number of unique mechanisms increases linearly with the volume when long wavelength mechanisms are included. Extensively flexible frameworks therefore have a maximum in configurational entropy, as large crystals, at their lowest density. Most real zeolites do not exhibit extensive flexibility, suggesting that surface and edge mechanisms are important, likely during the nucleation and growth stage. The prevalence of flexibility in real zeolites suggests that, in addition to low framework energy, it is an important criterion when searching large databases of hypothetical zeolites for potentially useful realizable structures. PMID:22107389

  2. Zeolite and swine inoculum effect on poultry manure biomethanation

    NASA Astrophysics Data System (ADS)

    Kougias, P. G.; Fotidis, I. A.; Zaganas, I. D.; Kotsopoulos, T. A.; Martzopoulos, G. G.

    2013-03-01

    Poultry manure is an ammonia-rich substrate that inhibits methanogenesis, causing severe problems to the anaerobic digestion process. In this study, the effect of different natural zeolite concentrations on the mesophilic anaerobic digestion of poultry waste inoculated with well-digested swine manure was investigated. A significant increase in methane production was observed in treatments where zeolite was added, compared to the treatment without zeolite.Methane production in the treatment with 10 g dm-3 of natural zeolite was found to be 109.75% higher compared to the treatment without zeolite addition. The results appear to be influenced by the addition of zeolite, which reduces ammonia toxicity in anaerobic digestion and by the ammonia-tolerant swine inoculum.

  3. Cation locations and dislocations in zeolites

    NASA Astrophysics Data System (ADS)

    Smith, Luis James

    The focus of this dissertation is the extra-framework cation sites in a particular structural family of zeolites, chabazite. Cation sites play a particularly important role in the application of these sieves for ion exchange, gas separation, catalysis, and, when the cation is a proton, acid catalysis. Structural characterization is commonly performed through the use of powder diffraction and Rietveld analysis of powder diffraction data. Use of high-resolution nuclear magnetic resonance, in the study of the local order of the various constituent nuclei of zeolites, complements well the long-range order information produced by diffraction. Recent developments in solid state NMR techniques allow for increased study of disorder in zeolites particularly when such phenomena test the detection limits of diffraction. These two powerful characterization techniques, powder diffraction and NMR, offer many insights into the complex interaction of cations with the zeolite framework. The acids site locations in SSZ-13, a high silica chabazite, and SAPO-34, a silicoaluminophosphate with the chabazite structure, were determined. The structure of SAPO-34 upon selective hydration was also determined. The insensitivity of X-rays to hydrogen was avoided through deuteration of the acid zeolites and neutron powder diffraction methods. Protons at inequivalent positions were found to have different acid strengths in both SSZ-13 and SAPO-34. Other light elements are incorporated into zeolites in the form of extra-framework cations, among these are lithium, sodium, and calcium. Not amenable by X-ray powder diffraction methods, the positions of such light cations in fully ion-exchanged versions of synthetic chabazite were determined through neutron powder diffraction methods. The study of more complex binary cation systems were conducted. Powder diffraction and solid state NMR methods (MAS, MQMAS) were used to examine cation site preferences and dislocations in these mixed-akali chabazites. Lithium cations were found to prefer high-symmetry positions in the six-ring windows of the framework. Sodium cations preferred positions in the eight-ring window when not hindered by the presence of other cations in the supercage.

  4. Large zeolites - Why and how to grow in space

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.

    1991-01-01

    The growth of zeolite crystals which are considered to be the most valuable catalytic and adsorbent materials of the chemical processing industry are discussed. It is proposed to use triethanolamine as a nucleation control agent to control the time release of Al in a zeolite A solution and to increase the average and maximum crystal size by 25-50 times. Large zeolites could be utilized to make membranes for reactors/separators which will substantially increase their efficiency.

  5. Zeolite (clinoptilolite) as feed additive to reduce manure mineral content.

    PubMed

    Leung, S; Barrington, S; Wan, Y; Zhao, X; El-Husseini, B

    2007-12-01

    Clinoptilolite (a species of zeolite) as grower hog feed additive can potentially improve nutrient ingestion and lower manure nutrient levels. A first objective was to establish the optimal particle size of the zeolite powder, as a fine size increases the adsorption surface while a coarse size can facilitate handling. The second objective tested the effect of feeding zeolite on manure nutrient levels. For the first objective, three zeolite powders (250-500 microm; 50-250 microm, and 50-500 microm) were exposed to an NH(4)(+) solution under a pH of either 7.0 or 2.0. The resulting solutions were tested for cation exchange. A commercial zeolite was also tested for the pH of 2.0 to evaluate zeolite stability. At 0%, 5% and 10% humidity, the same three particle size powders were subjected to shear tests to determine the zeolite's angle of friction. For the second objective using metabolic cages, female hogs were subjected to one of four rations (a control and three with zeolite) while collecting and analyzing their manures. For the first objective, the coarse particle zeolite performed best, adsorbing 158 and 123 Cmol(+)/kg of NH(4)(+) under neutral and acid pH, respectively, and releasing an equivalent amount of minerals only under neutral pH. The commercial zeolite with less clinoptilolite released more Al, Fe, Cu and Pb, showing less stability. The high internal angle of friction of zeolite did not vary with particle size and moisture, indicating funnel flow under gravity. For the second objective, hogs fed a zeolite diet produced manure with 15% and 22% less N and P, respectively, and demonstrated a better feed conversion, although not statistically significant (P>0.05). These results show that there is some potential in using high quality clinoptilolite in the ration of grower hogs. PMID:16905313

  6. Comparing gas separation performance between all known zeolites and their zeolitic imidazolate framework counterparts.

    PubMed

    Gómez-Álvarez, Paula; Hamad, Said; Haranczyk, Maciej; Ruiz-Salvador, A Rabdel; Calero, Sofia

    2015-12-14

    To find optimal porous materials for adsorption-based separations is a challenging task due to the extremely large number of possible pore topologies and compositions. New porous material classes such as Metal Organic Frameworks (MOFs) are emerging, and hope to replace traditionally used materials such as zeolites. Computational screening offers relatively fast searching for candidate structures as well as side-by-side comparisons between material families. This work is pioneering at examining the families comprised by the experimentally known zeolites and their respective Zeolitic Imidazolate Framework (ZIF) counterparts in the context of a number of environmental and industrial separations involving carbon dioxide, nitrogen, methane, oxygen, and argon. Additionally, unlike related published work, here all the targeted structures have been previously relaxed through energy minimization. On the first level of characterization, we considered a detailed pore characterization, identifying 24 zeolites as promising candidates for gas separation based on adsorbate sizes. The second level involved interatomic potential-based calculations to assess the adsorption performance of the materials. We found no correlation in the values of heat of adsorption between zeolites and ZIFs sharing the same topology. A number of structures were identified as potential experimental targets for CO2/N2, and CO2/CH4 affinity-based separations. PMID:26600432

  7. Peculiarities of the dielectric response of natural zeolite composites prepared by using zeolite and silicon powders

    NASA Astrophysics Data System (ADS)

    Ozturk Koc, S.; Orbukh, V. I.; Eyvazova, G. M.; Lebedeva, N. N.; Salamov, B. G.

    2016-03-01

    We present the real and imaginary part of the dielectric permittivity of natural zeolite composites prepared by using zeolite and silicon powders. The dielectric response (DR) dependences on the frequency (3-300 GHz) of electric field and different Si concentrations (5-33%) are non-monotonic and a maximum peak is observed. This peak position is practically independent on the frequency and its maximum is observed in zeolite composites which included 9% of the Si-powder. Also the maximum peak is decreased by about an order of magnitude when frequency increases from 500 Hz to 5 kHz. Addition of the conductive Si-particles to zeolite-powder leads to two opposite effects. Firstly, the movement of electrons in the Si-particles provides increase of DR. Secondly, cations which leaving from zeolite pores can be neutralized by the particles of Si in the intercrystalline-space. Such a peculiar mechanism for recombination of Si electrons and cations from pores leads to a reduction of DR for large silicon concentrations. Due to the fact that the contribution of free carriers in the decreasing of the DR as the frequency increases, it is consistent with the suggestion that the maximum peak decreases with increasing frequency.

  8. Method for the recovery of silver from silver zeolite

    DOEpatents

    Reimann, G.A.

    1985-03-05

    High purity silver is recovered from silver exchanged zeolite used to capture radioactive iodine from nuclear reactor and nuclear fuel reprocessing environments. The silver exchanged zeolite is heated with slag formers to melt and fluidize the zeolite and release the silver, the radioactivity removing with the slag. The silver containing metallic impurities is remelted and treated with oxygen and a flux to remove the metal impurities. About 98% of the silver in the silver exchanged zeolite having a purity of 99% or better is recoverable by the method.

  9. Method for the recovery of silver from silver zeolite

    DOEpatents

    Reimann, George A.

    1986-01-01

    High purity silver is recovered from silver exchanged zeolite used to capture radioactive iodine from nuclear reactor and nuclear fuel reprocessing environments. The silver exchanged zeolite is heated with slag formers to melt and fluidize the zeolite and release the silver, the radioactivity removing with the slag. The silver containing metallic impurities is remelted and treated with oxygen and a flux to remove the metal impurities. About 98% of the silver in the silver exchanged zeolite having a purity of 99% or better is recoverable by the method.

  10. Dry method for recycling iodine-loaded silver zeolite

    DOEpatents

    Thomas, Thomas R.; Staples, Bruce A.; Murphy, Llewellyn P.

    1978-05-09

    Fission product iodine is removed from a waste gas stream and stored by passing the gas stream through a bed of silver-exchanged zeolite until the zeolite is loaded with iodine, passing dry hydrogen gas through the bed to remove the iodine and regenerate the bed, and passing the hydrogen stream containing the hydrogen iodide thus formed through a lead-exchanged zeolite which adsorbs the radioactive iodine from the gas stream and permanently storing the lead-exchanged zeolite loaded with radioactive iodine.

  11. Zeolite Crystal Growth in Microgravity and on Earth

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Center for Advanced Microgravity Materials Processing (CAMMP), a NASA-sponsored Research Partnership Center, is working to improve zeolite materials for storing hydrogen fuel. CAMMP is also applying zeolites to detergents, optical cables, gas and vapor detection for environmental monitoring and control, and chemical production techniques that significantly reduce by-products that are hazardous to the environment. Shown here are zeolite crystals (top) grown in a ground control experiment and grown in microgravity on the USML-2 mission (bottom). Zeolite experiments have also been conducted aboard the International Space Station.

  12. Natural zeolites in diet or litter of broilers.

    PubMed

    Schneider, A F; Almeida, D S De; Yuri, F M; Zimmermann, O F; Gerber, M W; Gewehr, C E

    2016-04-01

    This study aims to analyse the influence of adding natural zeolites (clinoptilolite) to the diet or litter of broilers and their effects on growth performance, carcass yield and litter quality. Three consecutive flocks of broilers were raised on the same sawdust litter, from d 1 to d 42 of age, and distributed in three treatments (control with no added zeolites, addition of 5 g/kg zeolite to diet and addition of 100 g/kg zeolites to litter). The addition of zeolites to the diet or litter did not affect growth performance or carcass yield. The addition of zeolites to the diet did not influence moisture content of the litter, ammonia volatilisation was reduced only in the first flock and pH of litter was reduced in the second and third flock. However, the addition of zeolites to the litter reduced moisture content, litter pH and ammonia volatilisation in all flocks analysed. The addition of 5 g/kg zeolite to the diet in three consecutive flocks was not effective in maintaining litter quality, whereas the addition of 100 g/kg natural zeolites to sawdust litter reduced litter moisture and ammonia volatilisation in three consecutive flocks raised on the same litter. PMID:26879673

  13. Pf/Zeolite Catalyst for Tritium Stripping

    SciTech Connect

    Hsu, R.H.

    2001-03-26

    This report described promising hydrogen (protium and tritium) stripping results obtained with a Pd/zeolite catalyst at ambient temperature. Preliminary results show 90-99+ percent tritium stripping efficiency may be obtained, with even better performance expected as bed configuration and operating conditions are optimized. These results suggest that portable units with single beds of the Pd/zeolite catalyst may be utilized as ''catalytic absorbers'' to clean up both tritium gas and tritiated water. A cart-mounted prototype stripper utilizing this catalyst has been constructed for testing. This portable stripper has potential applications in maintenance-type jobs such as tritium line breaks. This catalyst can also potentially be utilized in an emergency stripper for the Replacement Tritium Facility.

  14. Calculation of the 13C NMR shieldings of the C0 2 complexes of aluminosilicates

    NASA Astrophysics Data System (ADS)

    Tossell, J. A.

    1995-04-01

    13C NMR shieldings have been calculated using the random-phase-approximation, localized-orbital local-origins version of ab initio coupled Hartree-Fuck perturbation theory for CO 2 and and for several complexes formed by the reaction of CO 2 with molecular models for aluminosilicate glasses, H 3TOT'H3 3-n, T,T' = Si,Al. Two isomeric forms of the CO 2-aluminosilicate complexes have been considered: (1) "CO 2-like" complexes, in which the CO 2 group is bound through carbon to a bridging oxygen and (2) "CO 3-like" complexes, in which two oxygens of a central CO 3 group form bridging bonds to the two TH 3 groups. The CO 2-like isomer of CO 2-H 3SiOSiH 3 is quite weakly bonded and its 13C isotropic NMR shielding is almost identical to that in free CO 2. As Si is progressively replaced by Al in the - H terminated aluminosilicate model, the CO 2-like isomers show increasing distortion from the free CO 2 geometry and their 13C NMR shieldings decrease uniformly. The calculated 13C shielding value for H 3AlO(CO 2)AlH 3-2 is only about 6 ppm larger than that calculated for point charge stabilized CO 3-2. However, for a geometry of H 3SiO(CO 2) AlH 3-1, in which the bridging oxygen to C bond length has been artificially increased to that found in the - OH terminated cluster (OH) 3SiO(CO 2)Al(OH) 3-1, the calculated 13C shielding is almost identical to that for free CO 2. The CO 3-like isomers of the CO 2-aluminosili-cate complexes show carbonate like geometries and 13C NMR shieldings about 4-9 ppm larger than those of carbonate for all T,T' pairs. For the Si,Si tetrahedral atom pair the CO 2-like isomer is more stable energetically, while for the Si,Al and Al,Al cases the CO 3-like isomer is more stable. Addition of Na + ions to the CO 3-2 or H 3AlO(CO 2)AlH 3-2 complexes reduces the 13C NMR shieldings by about 10 ppm. Complexation with either Na + or CO 2 also reduces the 29Si NMR shieldings of the aluminosilicate models, while the changes in 27Al shielding with Na + or CO 2 complexation are much smaller. Complexation with CO 2 greatly increases the electric field gradient at the bridging oxygen of H 3AlOAlH 3-2, raising it to a value similar to that found for SiOSi linkages. Comparison of these results with the experimental 13C NMR spectra support the formation of CO 2-like complexes at SiOSi bridges in albite glasses and CO 3-like complexes at SiOAl and AlOAl bridges in albite and nepheline glasses. Changes in the calculated shieldings as Na + ions are added to the complexes suggest that some of the observed complexes may be similar in their CO 2-aluminosilicate interactions, but different with respect to the positions of the charge-compensating Na + ions.

  15. Development of a Composite Non-Electrostatic Surface Complexation Model Describing Plutonium Sorption to Aluminosilicates

    SciTech Connect

    Powell, B A; Kersting, A; Zavarin, M; Zhao, P

    2008-10-28

    Due to their ubiquity in nature and chemical reactivity, aluminosilicate minerals play an important role in retarding actinide subsurface migration. However, very few studies have examined Pu interaction with clay minerals in sufficient detail to produce a credible mechanistic model of its behavior. In this work, Pu(IV) and Pu(V) interactions with silica, gibbsite (Aloxide), and Na-montmorillonite (smectite clay) were examined as a function of time and pH. Sorption of Pu(IV) and Pu(V) to gibbsite and silica increased with pH (4 to 10). The Pu(V) sorption edge shifted to lower pH values over time and approached that of Pu(IV). This behavior is apparently due to surface mediated reduction of Pu(V) to Pu(IV). Surface complexation constants describing Pu(IV)/Pu(V) sorption to aluminol and silanol groups were developed from the silica and gibbsite sorption experiments and applied to the montmorillonite dataset. The model provided an acceptable fit to the montmorillonite sorption data for Pu(V). In order to accurately predict Pu(IV) sorption to montmorillonite, the model required inclusion of ion exchange. The objective of this work is to measure the sorption of Pu(IV) and Pu(V) to silica, gibbsite, and smectite (montmorillonite). Aluminosilicate minerals are ubiquitous at the Nevada National Security Site and improving our understanding of Pu sorption to aluminosilicates (smectite clays in particular) is essential to the accurate prediction of Pu transport rates. These data will improve the mechanistic approach for modeling the hydrologic source term (HST) and provide sorption Kd parameters for use in CAU models. In both alluvium and tuff, aluminosilicates have been found to play a dominant role in the radionuclide retardation because their abundance is typically more than an order of magnitude greater than other potential sorbing minerals such as iron and manganese oxides (e.g. Vaniman et al., 1996). The sorption database used in recent HST models (Carle et al., 2006) and upscaled for use in CAU models (Stoller-Navarro, 2008) includes surface complexation constants for U, Am, Eu, Np and Pu (Zavarin and Bruton, 2004). Generally, between 15 to 30 datasets were used to develop the constants for each radionuclide. However, the constants that describe Pu sorption to aluminosilicates were developed using only 10 datasets, most of which did not specify the oxidation state of Pu in the experiment. Without knowledge or control of the Pu oxidation state, a high degree of uncertainty is introduced into the model. The existing Pu surface complexation model (e.g. Zavarin and Bruton, 2004) drastically underestimates Pu sorption and, thus, will overestimate Pu migration rates (Turner, 1995). Recent HST simulations at Cambric (Carle et al., 2006) suggest that the existing surface complexation model may underpredict Pu K{sub d}s by as much as 3 orders of magnitude. In order to improve HST and CAU-scale transport models (and, as a result, reduce the conservative nature Pu migration estimates), sorption experiments were performed over a range of solution conditions that brackets the groundwater chemistry of the Nevada National Security Site. The aluminosilicates examined were gibbsite, silica, and montmorillonite.

  16. Effects of Fiber Content on Mechanical Properties of CVD SiC Fiber-Reinforced Strontium Aluminosilicate Glass-Ceramic Composites

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.

    1996-01-01

    Unidirectional CVD SiC(f)(SCS-6) fiber-reinforced strontium aluminosilicate (SAS) glass-ceramic matrix composites containing various volume fractions, approximately 16 to 40 volume %, of fibers were fabricated by hot pressing at 1400 C for 2 h under 27.6 MPa. Monoclinic celsian, SrAl2Si2O8, was the only crystalline phase formed, with complete absence of the undesired hexacelsian phase, in the matrix. Room temperature mechanical properties were measured in 3-point flexure. The matrix microcracking stress and the ultimate strength increased with increase in fiber volume fraction, reached maximum values for V(sub f) approximately equal to 0.35, and degraded at higher fiber loadings. This degradation in mechanical properties is related to the change in failure mode, from tensile at lower V(sub f) to interlaminar shear at higher fiber contents. The extent of fiber loading did not have noticeable effect on either fiber-matrix debonding stress, or frictional sliding stress at the interface. The applicability of micromechanical models in predicting the mechanical properties of the composites was also examined. The currently available theoretical models do not appear to be useful in predicting the values of the first matrix cracking stress, and the ultimate strength of the SCS-6/SAS composites.

  17. In situ evolution of Ni environment in magnesium aluminosilicate glasses and glass-ceramics-Influence of ZrO2 and TiO2 nucleating agents

    NASA Astrophysics Data System (ADS)

    Dugué, A.; Dymshits, O.; Cormier, L.; Cochain, B.; Lelong, G.; Zhilin, A.; Belin, S.

    2015-03-01

    The evolution of Ni2+ environment has been systematically investigated using optical and in situ X-ray absorption spectroscopy (XAS) to determine the influence of nucleating agents (TiO2 and/or ZrO2) during the formation of spinel in magnesium aluminosilicate glass-ceramics. The results were complemented by in situ X-ray diffraction data. According to XAS and optical spectroscopy, the nature of nucleating agents does not modify significantly the Ni environment in initial glasses. However, it has a relatively strong influence in the observed crystallization sequence. Ni2+ ions do not enter the Zr-containing crystalline phase of ZrO2 or ZrTiO4 but a Ni2+ coordination change from the fivefold coordinated sites, with a small amount of tetrahedral sites in parent glasses, to [6]Ni2+ and [4]Ni2+ sites in spinel (in glasses nucleated by ZrO2 and/or TiO2) or in β-quartz solid solutions (in glasses nucleated by ZrO2) has been found.

  18. Anchoring strategies for bimetallic species in zeolites

    SciTech Connect

    Bein, T.

    1993-03-01

    We explore a new approach by introducing heterobinuclear organometallic compounds for linking catalytic functions to zeolite frameworks. With two different metals present, the complexes are being anchored to the support via one oxophilic metal, ligand exchange and catalytic reactions may proceed at the second metal center. Anchoring chemistry, thermal stability and reactivity of Me[sub 3]SnMn(CO)[sub 5] in zeolite NaY and acid forms of zeolite Y was studied with X-ray absorption spectroscopy (Sn, Mn edge EXAFS) and in-situ FTIR/TPD-MS techniques. Subsequently, the tin-cobalt complex Me[sub 3]SnCo(CO)[sub 4] has been a focus of detailed synthetic and spectroscopic studies. The reactivity of tricarbonyl (cyclopentadienyl) (trimethylstannyl) molybdenum in new mesoporous hosts has been explored. A recent development is the design of vanadium oxo species in different micro- and mesoporous hosts. These are of great interest for the selective reduction of nitrogen oxides by ammonia, and selective oxidation of different hydrocarbons, such as xylenes, olefines and alkanes. Combination analytical techniques used to probe local structural changes at the molecular level, include EXAFS (Extended X-Ray Absorption Fine Structure) spectroscopy utilizing synchrotron radiation, in situ FT-IR coupled to thermodesorption/MS, UV-NIR, and CCD Raman.

  19. Crystalline color superconductors

    NASA Astrophysics Data System (ADS)

    Anglani, Roberto; Casalbuoni, Roberto; Ciminale, Marco; Ippolito, Nicola; Gatto, Raoul; Mannarelli, Massimo; Ruggieri, Marco

    2014-04-01

    Inhomogeneous superconductors and inhomogeneous superfluids appear in a variety of contexts including quark matter at extreme densities, fermionic systems of cold atoms, type-II cuprates, and organic superconductors. In the present review the focus is on properties of quark matter at high baryonic density, which may exist in the interior of compact stars. The conditions realized in these stellar objects tend to disfavor standard symmetric BCS pairing and may favor an inhomogeneous color superconducting phase. The properties of inhomogeneous color superconductors are discussed in detail and in particular of crystalline color superconductors. The possible astrophysical signatures associated with the presence of crystalline color superconducting phases within the core of compact stars are also reviewed.

  20. Layered Topological Crystalline Insulators.

    PubMed

    Kim, Youngkuk; Kane, C L; Mele, E J; Rappe, Andrew M

    2015-08-21

    Topological crystalline insulators (TCIs) are insulating materials whose topological property relies on generic crystalline symmetries. Based on first-principles calculations, we study a three-dimensional (3D) crystal constructed by stacking two-dimensional TCI layers. Depending on the interlayer interaction, the layered crystal can realize diverse 3D topological phases characterized by two mirror Chern numbers (MCNs) (μ1,μ2) defined on inequivalent mirror-invariant planes in the Brillouin zone. As an example, we demonstrate that new TCI phases can be realized in layered materials such as a PbSe (001) monolayer/h-BN heterostructure and can be tuned by mechanical strain. Our results shed light on the role of the MCNs on inequivalent mirror-symmetric planes in reciprocal space and open new possibilities for finding new topological materials. PMID:26340198

  1. Layered Topological Crystalline Insulators

    NASA Astrophysics Data System (ADS)

    Kim, Youngkuk; Kane, C. L.; Mele, E. J.; Rappe, Andrew M.

    2015-08-01

    Topological crystalline insulators (TCIs) are insulating materials whose topological property relies on generic crystalline symmetries. Based on first-principles calculations, we study a three-dimensional (3D) crystal constructed by stacking two-dimensional TCI layers. Depending on the interlayer interaction, the layered crystal can realize diverse 3D topological phases characterized by two mirror Chern numbers (MCNs) (μ1,μ2 ) defined on inequivalent mirror-invariant planes in the Brillouin zone. As an example, we demonstrate that new TCI phases can be realized in layered materials such as a PbSe (001) monolayer/h -BN heterostructure and can be tuned by mechanical strain. Our results shed light on the role of the MCNs on inequivalent mirror-symmetric planes in reciprocal space and open new possibilities for finding new topological materials.

  2. Metallic nanoparticles and their medicinal potential. Part II: aluminosilicates, nanobiomagnets, quantum dots and cochleates.

    PubMed

    Loomba, Leena; Scarabelli, Tiziano

    2013-09-01

    Metallic miniaturization techniques have taken metals to nanoscale size where they can display fascinating properties and their potential applications in medicine. In recent years, metal nanoparticles such as aluminium, silicon, iron, cadmium, selenium, indium and calcium, which find their presence in aluminosilicates, nanobiomagnets, quantum dots (Q-dots) and cochleates, have caught attention of medical industries. The increasing impact of metallic nanoparticles in life sciences has significantly advanced the production techniques for these nanoparticles. In this Review, the various methods for the synthesis of nanoparticles are outlined, followed by their physicochemical properties, some recent applications in wound healing, diagnostic imaging, biosensing, assay labeling, antimicrobial activity, cancer therapy and drug delivery are listed, and finally their toxicological impacts are revised. The first half of this article describes the medicinal uses of two noble nanoparticles - gold and silver. This Review provides further information on the ability of aluminum, silicon, iron, selenium, indium, calcium and zinc to be used as nanoparticles in biomedical sciences. Aluminosilicates find their utility in wound healing and antibacterial growth. Iron-oxide nanoparticles enhance the properties of MRI contrast agents and are also used as biomagnets. Cadmium, selenium, tellurium and indium form the core nanostructures of tiny Q-dots used in cellular assay labeling, high-resolution cell imaging and biosensing. Cochleates have the bivalent nano ions calcium, magnesium or zinc imbedded in their structures and are considered to be highly effective agents for drug and gene delivery. The aluminosilicates, nanobiomagnets, Q-dots and cochleates are discussed in the light of their properties, synthesis and utility. PMID:24024515

  3. Contribution of aluminas and aluminosilicates to the formation of PCDD/Fs on fly ashes.

    PubMed

    Potter, Phillip M; Dellinger, Barry; Lomnicki, Slawomir M

    2016-02-01

    Chlorinated aromatics undergo surface-mediated reactions with metal oxides to form Environmentally Persistent Free Radicals (EPFRs) which can further react to produce polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Previous work using laboratory-made fly ash surrogates composed of transition metal oxides deposited on silica powder has confirmed their ability to mimic fly ash in the production of PCDD/Fs. However, little is known about the propensity of aluminas and aluminosilicates, other components of fly ash, to form PCDD/Fs. A fly ash sample containing both alumina and mullite, an aluminosilicate, was tested for PCDD/F formation ability and compared to PCDD/F yields from the thermal degradation of 2-monochlorophenol (2-MCP) precursor over γ-alumina, α-alumina, and mullite. A packed-bed flow reactor was used to investigate the thermal degradation of 2-MCP over the various catalysts at 200-600 °C. Fly ash gave similar PCDD/F yields to surrogates made with similar transition metal content. γ-alumina, which is thermodynamically unfavorable, was very catalytically active and gave low PCDD/F yields despite a high destruction of 2-MCP. Mullite and α-alumina, the thermodynamically favorable form of alumina, yielded higher concentrations of dioxins and products with a higher degree of chlorine substitution than γ-alumina. The data suggest that certain aluminas and aluminosilicates, commonly found in fly ash, are active catalytic surfaces in the formation of PCDD/Fs in the post-flame cool zones of combustion systems and should be considered as additional catalytic surfaces active in the process. PMID:26615490

  4. In vitro osteogenic/dentinogenic potential of an experimental calcium aluminosilicate cement

    PubMed Central

    Eid, Ashraf A.; Niu, Li-na; Primus, Carolyn M.; Opperman, Lynne A.; Watanabe, Ikuya; Pashley, David H.; Tay, Franklin R.

    2013-01-01

    Introduction Calcium aluminosilicate cements are fast-setting, acid-resistant, bioactive cements that may be used as root-repair materials. This study examined the osteogenic/dentinogenic potential of an experimental calcium aluminosilicate cement (Quick-Set) using a murine odontoblast-like cell model. Methods Quick-Set and white ProRoot MTA (WMTA) were mixed with the proprietary gel or deionized water, allowed to set completely in 100% relative humidity and aged in complete growth medium for 2 weeks until rendered non-cytotoxic. Similarly-aged Teflon discs were used as negative control. The MDPC-23 cell-line was used for evaluating changes in mRNA expressions of genes associated with osteogenic/dentinogenic differentiation and mineralization (qRT-PCR) alkaline phosphatase enzyme production and extracellular matrix mineralization (Alizarin red-S staining). Results After MDPC-23 cells were incubated with the materials in osteogenic differentiation medium for 1 week, both cements showed upregulation in ALP and DSPP expression. Fold increases in these two genes were not significantly different between Quick-Set and WMTA. Both cements showed no statistically significant upregulation/downregulation in RUNX2, OCN, BSP and DMP1 gene expression compared with Teflon. Alkaline phosphatase activity of cells cultured on Quick-Set and WMTA were not significantly different at 1 week or 2 weeks, but were significantly higher (p<0.05) than Teflon in both weeks. Both cements showed significantly higher calcium deposition compared with Teflon after 3 weeks of incubation in mineralizing medium (p<0.001). Differences between Quick-Set and WMTA were not statistically significant. Conclusions The experimental calcium aluminosilicate cement exhibits similar osteogenic/dentinogenic properties to WMTA and may be a potential substitute for commercially-available tricalcium silicate cements. PMID:23953291

  5. Efficient adsorbents of nanoporous aluminosilicate monoliths for organic dyes from aqueous solution.

    PubMed

    El-Safty, Sherif A; Shahat, Ahmed; Awual, Md Rabiul

    2011-07-01

    Growing public awareness on the potential risk to humans of toxic chemicals in the environment has generated demand for new and improved methods for toxicity assessment and removal, rational means for health risk estimation. With the aim of controlling nanoscale adsorbents for functionality in molecular sieving of organic pollutants, we fabricated cubic Im3m mesocages with uniform entrance and large cavity pores of aluminosilicates as highly promising candidates for the colorimetric monitoring of organic dyes in an aqueous solution. However, a feasible control over engineering of three-dimensional (3D) mesopore cage structures with uniform entrance (~5 nm) and large cavity (~10 nm) allowed the development of nanoadsorbent membranes as a powerful tool for large-quantity and high-speed (in minutes) adsorption/removal of bulk molecules such as organic dyes. Incorporation of high aluminum contents (Si/Al=1) into 3D cubic Im3m cage mesoporous silica monoliths resulted in small, easy-to-use optical adsorbent strips. In such adsorption systems, natural surfaces of active acid sites of aluminosilicate strips strongly induced both physical adsorption of chemically responsive dyes and intraparticle diffusion into cubic Im3m mesocage monoliths. Results likewise indicated that although aluminosilicate strips with low Si/Al ratios exhibit distortion in pore ordering and decrease in surface area and pore volume, enhancement of both molecular converges and intraparticle diffusion onto the network surfaces and into the pore architectures of adsorbent membranes was achieved. Moreover, 3D mesopore cage adsorbents are reversible, offering potential for multiple adsorption assays. PMID:21514595

  6. Liquid crystalline composites containing phyllosilicates

    DOEpatents

    Chaiko; David J.

    2007-05-08

    The present invention provides barrier films having reduced gas permeability for use in packaging and coating applications. The barrier films comprise an anisotropic liquid crystalline composite layer formed from phyllosilicate-polymer compositions. Phyllosilicate-polymer liquid crystalline compositions of the present invention can contain a high percentage of phyllosilicate while remaining transparent. Because of the ordering of the particles in the liquid crystalline composite, barrier films comprising liquid crystalline composites are particularly useful as barriers to gas transport.

  7. Crystalline titanate catalyst supports

    DOEpatents

    Anthony, R.G.; Dosch, R.G.

    1993-01-05

    A series of new crystalline titanates (CT) are shown to have considerable potential as catalyst supports. For Pd supported catalyst, the catalytic activity for pyrene hydrogenation was substantially different depending on the type of CT, and one was substantially more active than Pd on hydrous titanium oxide (HTO). For 1-hexene hydrogenation the activities of the new CTs were approximately the same as for the hydrous metal oxide supports.

  8. Crystalline titanate catalyst supports

    DOEpatents

    Anthony, Rayford G.; Dosch, Robert G.

    1993-01-01

    A series of new crystalline titanates (CT) are shown to have considerable potential as catalyst supports. For Pd supported catalyst, the catalytic activity for pyrene hydrogenation was substantially different depending on the type of CT, and one was substantially more active than Pd on hydrous titanium oxide (HTO). For 1-hexene hydrogenation the activities of the new CTs were approximately the same as for the hydrous metal oxide supports.

  9. Liquid crystalline dendrimers.

    PubMed

    Donnio, Bertrand; Buathong, Saïwan; Bury, Izabela; Guillon, Daniel

    2007-09-01

    In recent years, there has been an increasing interest in the field of liquid crystalline dendrimers. Such a fast development is, among other things, driven by the multiple possibilities offered by combining the mesomorphic properties of single mesogenic subunits with the supermolecular and versatile architectures of dendrimers to yield a new class of highly functional materials. The induction and the control of the mesomorphic properties (phase type and stability) in dendrimers can be achieved by a dedicated molecular design which depends on the chemical nature and structure of both the functional groups and the dendritic matrix. In particular, the intrinsic connectivity of the dendrimer such as the multivalency of the focal core and the multiplicity of the branches, both controlling the geometrical rate of growth, or the dendritic generation, plays a crucial role and influences at various stages the subtle relationships between the supermolecular structure and the mesophase structure and stability. In this critical review article, an account of the various types of dendritic systems that form liquid-crystalline mesophases along with a description of the self-organization of representative case-study supermolecules into liquid crystalline mesophases will be discussed. Some basics of thermotropic liquid crystals and dendrimers will be given in the introduction. Then, in the following sections, selected examples including side-chain, main-chain, fullerodendrimers, shape-persistent dendrimers, supramolecular dendromesogens and metallodendrimers, as representative families of LC dendrimers, will be described. In the conclusion some further developments will be highlighted. This review will not cover liquid crystalline hyperbranched and dendronized polymers that might be considered as being somehow less structurally "perfect". PMID:17660881

  10. New antiaxillary odour deodorant made with antimicrobial Ag-zeolite (silver-exchanged zeolite).

    PubMed

    Nakane, T; Gomyo, H; Sasaki, I; Kimoto, Y; Hanzawa, N; Teshima, Y; Namba, T

    2006-08-01

    The causative substances for axillary osmidrosis, which are often found in apocrine sweat, are the decomposed/denatured products of short-chain fatty acid and other biological metabolite compounds produced by axillary-resident bacteria. Conventional underarm deodorants suppress the process of odour production mostly by the following mechanism: (1) suppression of perspiration, (2) reduction in numbers of resident bacteria, (3) deodorization and (4) masking. The most important and effective method to reduce odour is to suppress the growth of resident bacteria with antimicrobials, which have several drawbacks, especially in their safety aspect. To solve these problems, we focused on Ag-zeolite (silver-exchanged zeolite) that hold stable Ag, an inorganic bactericidal agent, in its structure, and therefore, poses less risk in safety. Its bactericidal effect on skin-resident bacteria was found to be excellent and comparable with that of triclosan, a most frequently used organic antimicrobial in this product category. The dose-response study of Ag-zeolite powder spray (0-40 w/w%) using 39 volunteers revealed that 5-40 w/w% Ag-zeolite could show a sufficient antimicrobial effect against skin-resident bacteria. The comparison study using 0.2 w/w% triclosan as the control and 10 w/w% Ag-zeolite indicated that: (1) one application of the powder spray containing 10 w/w% Ag-zeolite could show a sufficient antimicrobial effect against the resident bacteria and its effect continued for 24 h, (2) a powder spray containing 0.2 w/w% triclosan was unable to show a sufficient antimicrobial effect, and (3) no adverse event was observed. These studies show that Ag-zeolite has a superior antimicrobial ability that is rarely found in conventional antimicrobials used in deodorant products and a strong antiaxillary odour deodorant ability because of its long-lasting effect. During clinical study, patch tests with humans and other clinical studies of this product showed no adverse events related to the treatment with the Ag-zeolite product. PMID:18489270

  11. Thermotropic liquid crystalline drugs.

    PubMed

    Bunjes, Heike; Rades, Thomas

    2005-07-01

    Crystalline solids are characterized by long-range positional and orientational order in three dimensions, whereas amorphous liquids lack long-range order in any dimension. Liquid crystals (mesophases) show structural, mechanical and optical properties intermediate to those of crystalline solids and the amorphous, liquid state of matter. There are two principle types of liquid crystals: thermotropic liquid crystals (TLCs) and lyotropic liquid crystals (LLCs). TLCs can be formed by heating a crystalline solid or by cooling an isotropic melt of a TLC-forming molecule (mesogen). In the first part of this review the types of liquid crystals are defined and classified and the structural properties of mesogens are explained. In the second part, ten case studies of thermotropic mesomorphous drugs and pharmaceutically relevant molecules (arsphenamine, nafoxidine hydrochloride, L-660711, palmitoyl propranolol hydrochloride, penbutolol sulfate, itraconazole hydrochloride, fenoprofen sodium, fenoprofen calcium, ciclosporin and cholesteryl esters) are presented and their thermotropic mesomorphism is described. The review closes with a brief discussion of the unusual properties of drug mesophases and a potential use of drugs and excipients in this fourth state of matter. PMID:15969938

  12. DuraLith Alkali-Aluminosilicate Geopolymer Waste Form Testing for Hanford Secondary Waste

    SciTech Connect

    Gong, W. L.; Lutz, Werner; Pegg, Ian L.

    2011-07-21

    The primary objective of the work reported here was to develop additional information regarding the DuraLith alkali aluminosilicate geopolymer as a waste form for liquid secondary waste to support selection of a final waste form for the Hanford Tank Waste Treatment and Immobilization Plant secondary liquid wastes to be disposed in the Integrated Disposal Facility on the Hanford Site. Testing focused on optimizing waste loading, improving waste form performance, and evaluating the robustness of the waste form with respect to waste variability.

  13. Optical absorption and luminescence study of cobalt-doped magnesium aluminosilicate glass ceramics

    NASA Astrophysics Data System (ADS)

    Malyarevich, A. M.; Denisov, I. A.; Yumashev, K. V.; Dymshits, O. S.; Zhilin, A. A.

    2002-08-01

    Linear and nonlinear optical properties of cobalt-doped magnesium aluminosilicate transparent glass ceramics that were prepared under different conditions have been studied. It has been shown that absorption and luminescence spectra and absorption bleaching of these glass ceramics are defined mainly by tetrahedrally coordinated Co 2+ ions located in magnesium aluminum spinel nanocrystals. The lifetimes of the 4 T 1 ( 4 F) and 4 T 2 ( 4 F) excited states of the tetrahedral Co 2+ ions were found to be in the ranges 2540 and 120450 ns, respectively, depending on the Co concentration. 2002 Optical Society of America

  14. Aluminosilicate ceramic proppant for gas and oil well fracturing and method of forming same

    SciTech Connect

    Watson, D. R.; Carithers, V. G.; McDaniel, L. T.

    1985-11-26

    An aluminosilicate ceramic product or article and a method of forming the article from as-mined ore. The product is useful as a proppant in gas and oil well fracturing. The ratio, on a calcined basis, of alumina to silica is between approximately 2.2 to 4.0. The amount of iron in the product is controlled as a function of the alumina to silica ratio so as to produce products having less than ten percent (10%) crush loss when subjected to a force of 10,000 psi.

  15. Physical properties of a natural lamellar aluminosilicate structure, rich in Fe

    NASA Astrophysics Data System (ADS)

    Andrade, B. C.; Machado, R.; Jorge, A. M.; Gravina, E. G.; Macêdo, M. A.

    2012-07-01

    We present a natural sample from the coast of Sergipe, a state of Brazil, with a lamellar aluminosilicate structure characterized by three major components: phlogopite (K2(Mg,Fe2+)6[Si6Al2O20](OH)4), clinochlore (Mg,Al)6[Si3AlO10](OH)8 and goethite (αFeOOH). Ferrimagnetic behavior was found at room temperature with a Curie temperature TC>300 K. At low temperatures, the zero field cooling curve showed a peak at 6 K attributed to frustration caused by a ferrimagnetic-antiferromagnetic coupling between the lamellar structure (ferrimagnetic) and the grains of the antiferromagnetic goethite.

  16. Advanced NMR characterization of zeolite catalysts. Final technical report

    SciTech Connect

    Welsh, L.B.; Oldfield, E.

    1986-03-01

    The effort described in this report involved a joint industry-university program between the Signal Research Center, Inc., and the University of Illinois, designed to advance the state of knowledge of zeolite catalyst characterization technology for application to zeolite catalysts useful in coal liquefaction related processes. The program involved the application of new and improved high resolution solid state nuclear magnetic resonance (NRM) techniques to the characterization of zeolite catalysts and other related microporous materials. The NMR experiments were performed in the state-of-the-art NMR laboratory at the University of Illinois. In this report the first comprehensive investigation of /sup 17/O NMR of A and Y zeolites by means of static, MASS and VASS (variable angle sample spinning) NMR techniques is presented. The determination of the /sup 17/O isotropic chemical shifts, nuclear quadrupole coupling constants and electric field gradient tensor asymmetry parameters provides valuable supplementary information on zeolite structure. As an extension of the /sup 17/O NMR investigation of zeolites, results for gallosilicates and for several aluminophosphate materials have also been obtained. The work presented in this study demonstrates the ability of using /sup 17/O NMR to observe chemical changes in the oxygen environment of zeolites. This has important implications for the study of zeolite based catalysts. Chemical modifications of catalysts, such as framework substitutions or ion exchange which are commonly used to modify zeolite catalyst activity can be directly studied for their effect on the oxygen rich surface of the zeolite. It is also possible that this technique could be used to directly probe the interactions between the zeolite surface and reactant molecules. 29 refs., 14 figs., 7 tabs.

  17. Reactive oxygen species mediated DNA damage in human lung alveolar epithelial (A549) cells from exposure to non-cytotoxic MFI-type zeolite nanoparticles.

    PubMed

    Bhattacharya, Kunal; Naha, Pratap C; Naydenova, Izabela; Mintova, Svetlana; Byrne, Hugh J

    2012-12-17

    Increasing utilization of engineered nanoparticles in the field of electronics and biomedical applications demands an assessment of risk associated with deliberate or accidental exposure. Metal based nanoparticles are potentially most important of all the nanoparticles in terms of health risks. Microporous alumino-silicates and pure silicates named as zeolites and zeo-type materials with variety of structures, chemical compositions, particle sizes and morphologies have a significant number of industrial uses such as in catalysis, sorption and ion-exchange processes. In particular, the nanosized particles due to their unique properties are used in hybrid organic-inorganic materials for photography, photonics, electronics, labeling, imaging, and sensing. The aim of the current study is to investigate pure silica MFI-type zeolites nanoparticles with sizes of 50nm and 100nm (samples MFI-50 and MFI-100) under suspended conditions and their toxicological effects on human lung alveolar (A549) cells under in vitro conditions. Live cell imaging showed that the nanoparticles precipitated from the colloidal suspension of cell culture media as large agglomerates, coming in contact with the cell surface through sedimentation. A cellular proliferative capacity test showed the zeolite nanoparticles to exhibit no significant cytotoxicity below a concentration of 100μg/ml. However, both the MFI-50 and MFI-100 nanoparticles induced high intracellular reactive oxygen species (ROS) generation and elevated mitochondrial membrane potential in the A549 cells over the measured time period of 12h and at concentrations up to ≤50μg/ml. DNA fragmentation analysis using the comet assay showed that the MFI-50 and MFI-100 nanoparticles cause genotoxicity in a concentration dependent manner. Furthermore, the rate at which maximum genomic damage was caused by MFI-100 nanoparticles in the A549 cells was found to be high as compared to the MFI-50 nanoparticles. However, the damage caused by the MFI-50 nanoparticles was found to accumulate over a longer period of time as compared to MFI-100 nanoparticles. The study therefore points towards the capability of the non-cytotoxic zeolite nanoparticles to induce oxidative stress resulting in short-term altered cellular metabolism up-regulation and genomic instability. Although the damage was found to be short-lived, its persistence over longer durations, or stabilization cannot be neglected. Further studies are in progress to yield a better understanding of the mechanisms for oxidative stress and resulting cascade of events leading to genetic damage in the human lung alveolar epithelial cells following exposure to zeolite nanoparticles of different sizes. PMID:23103338

  18. Characterization and antibacterial activity of silver exchanged regenerated NaY zeolite from surfactant-modified NaY zeolite.

    PubMed

    Salim, Mashitah Mad; Malek, Nik Ahmad Nizam Nik

    2016-02-01

    The antibacterial activity of regenerated NaY zeolite (thermal treatment from cetyltrimethyl ammonium bromide (CTAB)-modified NaY zeolite and pretreatment with Na ions) loaded with silver ions were examined using the broth dilution minimum inhibitory concentration (MIC) method against Escherichia coli (E. coli ATCC 11229) and Staphylococcus aureus (S. aureus ATCC 6538). X-ray diffraction (XRD), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) and chemical elemental analyses were used to characterize the regenerated NaY and AgY zeolites. The XRD patterns indicated that the calcination and addition of silver ions on regenerated NaY zeolite did not affect the structure of the regenerated NaY zeolite as the characteristic peaks of the NaY zeolite were retained, and no new peaks were observed. The regenerated AgY zeolite showed good antibacterial activity against both bacteria strains in distilled water, and the antibacterial activity of the samples increased with increasing Ag loaded on the regenerated AgY zeolite; the regenerated AgY zeolite was more effective against E. coli than S. aureus. However, the antibacterial activity of the regenerated AgY was not effective in saline solution for both bacteria. The study showed that CTAB-modified NaY zeolite materials could be regenerated to NaY zeolite using thermal treatment (550°C, 5h) and this material has excellent performance as an antibacterial agent after silver ions loading. PMID:26652350

  19. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, H.; Blatter, F.; Sun, H.

    1999-06-22

    A process is described for selective thermal oxidation or photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts. 19 figs.

  20. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    2001-01-01

    A process for a combined selective thermal oxidation and photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly combined selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  1. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    1999-01-01

    A process for selective thermal oxidation or photooxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation and photooxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls in solvent free zeolites under dark thermal conditions or under irradiation with visible light. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  2. Selective thermal oxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    2000-01-01

    A process for selective thermal oxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls is carried out in solvent free zeolites under dark thermal conditions. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  3. Crewmember working on the mid deck Zeolite Crystal Growth experiment.

    NASA Technical Reports Server (NTRS)

    1992-01-01

    View showing Payload Specialist Bonnie Dunbar, in the mid deck, conducting the Zeolite Crystal Growth (ZCG) Experiment in the mid deck stowage locker work area. View shows assembly of zeolite sample in the metal autoclave cylinders prior to insertion into the furnace.

  4. CATION CONTROLLED SINGLET OXYGEN MEDIATED OXIDATION OF OLEFINS WITHIN ZEOLITES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Oxidation of trialkyl olefins has been performed within zeolites employing thionin as the singlet oxygen sensitizer. Unusual selectivity in favor of secondary hydroperoxides is observed within zeolites. In light of the fact that in solution such a selectivity is never observed the selectivity report...

  5. Zeolites in the Pine Ridge Indian Reservation, South Dakota

    USGS Publications Warehouse

    Raymond, William H.; Bush, Alfred L.; Gude, Arthur J., 3rd

    1982-01-01

    Zeolites of possible commercial value occur in the Brule Formation of Oligocene age and the Sharps Formation (Harksen, 1961) of Miocene age which crop out in a wide area in the northern part of the Pine Ridge Indian Reservation. The thickness of the zeolite-bearing Interval and the extent of areas within the Interval which contain significant amounts of zeolites are far greater than was expected prior to this investigation. The shape of the zeolite-bearing Interval is tabular and the dimensions of Its exposure are roughly 10 ml x 200 mi x 150 ft (16 km x 160 km x 45 m) thick. Within the study area, there are tracts in which the zeolite resource potential is significant (see pl. 2). This report is intended to inform the Oglala Sioux Tribe of some of the most promising zeolite occurrences. Initial steps can then be taken by the Tribe toward possible development of the resources, should they wish to do so. The data contained herein identify areas of high zeolite potential, but are not adequate to establish economic value for the deposits. If development is recommended by the tribal government, we suggest that the tribal government contact companies involved in research and production of natural zeolites and provide them with the data in this report.

  6. Ion exchange in a zeolite-molten chloride system

    SciTech Connect

    Woodman, R.H.; Pereira, C.

    1997-07-01

    Electrometallurgical treatment of spent nuclear fuel results in a secondary waste stream of radioactive fission products dissolved in chloride salt. Disposal plans include a waste form that can incorporate chloride forms featuring one or more zeolites consolidated with sintered glass. A candidate method for incorporating fission products in the zeolites is passing the contaminated salt over a zeolite column for ion exchange. To date, the molten chloride ion-exchange properties of four zeolites have been investigated for this process: zeolite A, IE95{reg_sign}, clinoptilolite, and mordenite. Of these, zeolite A has been the most promising. Treating zeolite 4A, the sodium form of zeolite A , with the solvent salt for the waste stream-lithium-potassium chloride of eutectic melting composition, is expected to provide a material with favorable ion-exchange properties for the treatment of the waste salt. The authors constructed a pilot-plant system for the ion-exchange column. Initial results indicate that there is a direct relationship between the two operating variable of interest, temperature, and initial sodium concentration. Also, the mass ratio has been about 3--5 to bring the sodium concentration of the effluent below 1 mol%.

  7. FUNDAMENTALS AND APPLICATIONS OF PERVAPORATION THROUGH ZEOLITE MEMBRANES

    EPA Science Inventory

    Zeolite membranes are well suited for separating liquid-phase mixtures by pervaporation because of their molecular-sized pores and their hydrophilic/hydrophobic nature, and the first commercial application of zeolite membranes has been for dehydrating organics [1]. Because of ...

  8. Antibacterial activity of heavy metal-loaded natural zeolite.

    PubMed

    Hrenovic, Jasna; Milenkovic, Jelena; Ivankovic, Tomislav; Rajic, Nevenka

    2012-01-30

    The antibacterial activity of natural zeolitized tuffs containing 2.60wt.% Cu(2+), 1.47 Zn(2+) or 0.52 Ni(2+) were tested. Antibacterial activities of the zeolites against Escherichia coli and Staphylococcus aureus were tested after 1h and 24h of exposure to 1g of the zeolite in 100mL of three different media, namely Luria Bertani, synthetic wastewater and secondary effluent wastewater. The antibacterial activities of the zeolites in Luria Bertani medium were significantly lower than those in the other media and negatively correlated with the chemical oxygen demand of the media. The Ni-loaded zeolite showed high leaching of Ni(2+) (3.44-9.13wt.% of the Ni(2+) loaded) and weak antibacterial activity in the effluent water. Since Cu-loaded zeolite did not leach Cu(2+) and the leaching of Zn(2+) from Zn-loaded zeolite was low (1.07-1.61wt.% of the Zn(2+) loaded), the strong antibacterial activity classified the Cu- and Zn-loaded zeolite as promising antibacterial materials for disinfection of secondary effluent water. PMID:22178285

  9. A zeolite ion exchange membrane for redox flow batteries.

    PubMed

    Xu, Zhi; Michos, Ioannis; Wang, Xuerui; Yang, Ruidong; Gu, Xuehong; Dong, Junhang

    2014-03-01

    The zeolite-T membrane was discovered to have high proton permselectivity against vanadium ions and exhibit low electrical resistance in acidic electrolyte solutions because of its enormous proton concentration and small thickness. The zeolite membrane was demonstrated to be an efficient ion exchange membrane in vanadium redox flow batteries. PMID:24396857

  10. Infrared spectroscopic characterization of dehydration and accompanying phase transition behaviors in NAT-topology zeolites

    SciTech Connect

    Wang, Hsiu-Wen; Bishop, David

    2012-01-01

    Relative humidity (PH2O, partial pressure of water)-dependent dehydration and accompanying phase transitions in NAT-topology zeolites (natrolite, scolecite, and mesolite) were studied under controlled temperature and known PH2O conditions by in situ diffuse-reflectance infrared Fourier transform spectroscopy and parallel X-ray powder diffraction. Dehydration was characterized by the disappearance of internal H2O vibrational modes. The loss of H2O molecules caused a sequence of structural transitions in which the host framework transformation path was coupled primarily via the thermal motion of guest Na?/Ca2? cations and H2O molecules. The observation of different interactions of H2O molecules and Na?/Ca2? cations with host aluminosilicate frameworks under highand low-PH2O conditions indicated the development of different local strain fields, arising from cation H2O interactions in NAT-type channels. These strain fields influence the Si O/Al O bond strength and tilting angles within and between tetrahedra as the dehydration temperature is approached. The newly observed infrared bands (at 2,139 cm-1 in natrolite, 2,276 cm-1 in scolecite, and 2,176 and 2,259 cm-1 in mesolite) result from strong cation H2O Al Si framework interactions in NAT-type channels, and these bands can be used to evaluate the energetic evolution of Na?/Ca2? cations before and after phase transitions, especially for scolecite and mesolite. The 2,176 and 2,259 cm-1 absorption bands in mesolite also appear to be related to Na?/Ca2? order disorder that occur when mesolite loses its Ow4 H2O molecules.

  11. Modified zeolite-based catalyst for effective extinction hydrocracking

    SciTech Connect

    Yan, T.Y. )

    1989-10-01

    The shape selectivity of zeolites makes them generally ineffective for extinction hydrocracking of polycyclic aromatic feeds. To overcome this problem, the zeolite can be modified with an amorphous cracking component to form a composite catalyst. This composite catalyst will be effective for extinction hydrocracking and retain the superior performance characteristics of a zeolite catalyst at the same time because the zeolite and the amorphous components of the catalyst operate complementarily. To illustrate this principle, NiW/REX-NiW/SiO/sub 2/Al/sub 2/O/sub 3/ composite catalyst was tested in the pilot plant. It was active, low in aging rate, resistant to nitrogen poisoning and high in selectivities for naphthas. The aged catalyst could be oxidatively regenerated to fully recover the activity and the product selectivities. This composite catalyst was superior to both individual (zeolite and amorphous) components for extinction hydrocracking. Catalysts similar to this have been used commercially for many years.

  12. Fly ash based zeolitic pigments for application in anticorrosive paints

    NASA Astrophysics Data System (ADS)

    Shaw, Ruchi; Tiwari, Sangeeta

    2016-04-01

    The purpose of this work is to evaluate the utilization of waste fly ash in anticorrosive paints. Zeolite NaY was synthesized from waste fly ash and subsequently modified by exchanging its nominal cation Na+ with Mg2+ and Ca2+ ions. The metal ion exchanged zeolite was then used as anticorrosive zeolitic pigments in paints. The prepared zeolite NaY was characterized using X-Ray diffraction technique and Scanning electron microscopy. The size, shape and density of the prepared fly ash based pigments were determined by various techniques. The paints were prepared by using fly ash based zeolitic pigments in epoxy resin and the percentages of pigments used in paints were 2% and 5%. These paints were applied to the mild steel panels and the anticorrosive properties of the pigments were assessed by the electrochemical spectroscopy technique (EIS).

  13. A pair distribution function analysis of zeolite beta

    SciTech Connect

    Martinez-Inesta, M.M.; Peral, I.; Proffen, T.; Lobo, R.F.

    2010-07-20

    We describe the structural refinement of zeolite beta using the local structure obtained with the pair distribution function (PDF) method. A high quality synchrotron and two neutron scattering datasets were obtained on two samples of siliceous zeolite beta. The two polytypes that make up zeolite beta have the same local structure; therefore refinement of the two structures was possible using the same experimental PDF. Optimized structures of polytypes A and B were used to refine the structures using the program PDFfit. Refinements using only the synchrotron or the neutron datasets gave results inconsistent with each other but a cyclic refinement with the two datasets gave a good fit to both PDFs. The results show that the PDF method is a viable technique to analyze the local structure of disordered zeolites. However, given the complexity of most zeolite frameworks, the use of both X-ray and neutron radiation and high-resolution patterns is essential to obtain reliable refinements.

  14. Synthesis and catalytic applications of combined zeolitic/mesoporous materials

    PubMed Central

    Vernimmen, Jarian; Cool, Pegie

    2011-01-01

    Summary In the last decade, research concerning nanoporous siliceous materials has been focused on mesoporous materials with intrinsic zeolitic features. These materials are thought to be superior, because they are able to combine (i) the enhanced diffusion and accessibility for larger molecules and viscous fluids typical of mesoporous materials with (ii) the remarkable stability, catalytic activity and selectivity of zeolites. This review gives an overview of the state of the art concerning combined zeolitic/mesoporous materials. Focus is put on the synthesis and the applications of the combined zeolitic/mesoporous materials. The different synthesis approaches and formation mechanisms leading to these materials are comprehensively discussed and compared. Moreover, Ti-containing nanoporous materials as redox catalysts are discussed to illustrate a potential implementation of combined zeolitic/mesoporous materials. PMID:22259762

  15. Health implications of natural fibrous zeolites for the Intermountain west

    SciTech Connect

    Rom, W.N.; Casey, K.R.; Parry, W.T.; Mjaatvedt, C.H.; Moatamed, F.

    1983-02-01

    Fibrous zeolites have recently been implicated in an endemic outbreak of malignant pleural mesothelioma in several villages in Cappadocia in central Turkey. The possible association between fibrous zeolites and mesothelioma and the potential biological activity of fibrous erionite from the United States are reviewed. The zeolite minerals comprise a group of over forty hydrated aluminum silicates. More than 300 probable deposits of various natural zeolites are located in 25 states in the United States. Reserves of perhaps 10 trillion tons are present in the western United States; about 120 million tons are deposited near the surface. Several zeolites, including erionite and mordenite, may occur with a fibrous habit. Fibrous erionite is found in several well-defined deposits in Arizona, Nevada, Oregon, and Utah, where it occurs as thin, pure beds within sedimentary tuff sequences, or as outcrops in desert valleys of the Intermountain region. (JMT)

  16. Potential and actual uses of zeolites in crop protection.

    PubMed

    De Smedt, Caroline; Someus, Edward; Spanoghe, Pieter

    2015-10-01

    In this review, it is demonstrated that zeolites have a potential to be used as crop protection agents. Similarly to kaolin, zeolites can be applied as particle films against pests and diseases. Their honeycomb framework, together with their carbon dioxide sorption capacity and their heat stress reduction capacity, makes them suitable as a leaf coating product. Furthermore, their water sorption capacity and their smaller particle sizes make them effective against fungal diseases and insect pests. Finally, these properties also ensure that zeolites can act as carriers of different active substances, which makes it possible to use zeolites for slow-release applications. Based on the literature, a general overview is provided of the different basic properties of zeolites as promising products in crop protection. PMID:25727795

  17. Computational characterization of zeolite porous networks: an automated approach.

    PubMed

    First, Eric L; Gounaris, Chrysanthos E; Wei, James; Floudas, Christodoulos A

    2011-10-14

    An automated method has been developed to fully characterize the three-dimensional structure of zeolite porous networks. The proposed optimization-based approach starts with the crystallographic coordinates of a structure and identifies all portals, channels, and cages in a unit cell, as well as their connectivity. We apply our algorithms to known zeolites, hypothetical zeolites, and zeolite-like structures and use the characterizations to calculate important quantities such as pore size distribution, accessible volume, surface area, and largest cavity and pore limiting diameters. We aggregate this data over many framework types to gain insights about zeolite selectivity. Finally, we develop a continuous-time Markov chain model to estimate the probability of occupancy of adsorption sites throughout the porous network. ZEOMICS, an online database of structure characterizations and web tool for the automated approach is freely available to the scientific community (http://helios.princeton.edu/zeomics/). PMID:21881655

  18. Zeolites in Eocene basaltic pillow lavas of the Siletz River Volcanics, Central Coast Range, Oregon.

    USGS Publications Warehouse

    Keith, T.E.C.; Staples, L.W.

    1985-01-01

    Zeolites and associated minerals occur in a tholeiitic basaltic pillow lava sequence. Although the zeolite assemblages are similar to those found in other major zeolite occurrences in basaltic pillow lavas, regional zoning of the zeolite assemblages is not apparent. The formation of the different assemblages is discussed.-D.F.B.

  19. Formation of superacid centers in the structure of zeolite ZSM-5

    NASA Astrophysics Data System (ADS)

    Kitaev, L. E.; Kolesnikova, E. E.; Biryukova, E. N.; Kolesnichenko, N. V.; Khadzhiev, S. N.

    2013-04-01

    The structural changes and acid characteristics of the zeolite ZSM-5 modified with titanium and sulfur were studied. The modifier components were chemically bonded to the zeolite structure. The acid characteristics of zeolite changed and superacid centers appeared. A physicochemical study showed that treatment of zeolite with titanium tetrachloride and sulfuryl chloride did not change its structure and molecular-sieve properties.

  20. Viscosity-temperature relations and structure in fully polymerized aluminosilicate melts from ion dynamics simulations

    NASA Astrophysics Data System (ADS)

    Scamehorn, C. A.; Angell, C. A.

    1991-03-01

    Results of a series of molecular dynamics simulations indicate that the Al:Si ratio (and to a lesser extent the type of charge-balancing countercation) present in aluminosilicate melts induces a "chemical pressure" that significantly influences the temperature dependence of the melt viscosity. The temperature dependence of the T-O bond length and T-O-T angle in the melt has been calculated for albite, anorthite, nepheline, and MgAl 2Si 2O 8 (a magnesium analog of anorthite) at their experimental melt densities at atmospheric pressure and for pure silica at two different densities corresponding to V/V 0 = 1.0 ( 1 atm) and V/V 0 = 0.8 ( ~4 GPa) . These simulations show that melt fragility can be correlated to increasing T-O length and decreasing T-O-T angle, both of which are characteristics of silicate melts under increasing pressure. Framework cations with coordination numbers greater than four are observed in these aluminosilicate melts and are shown to be related to fragile behavior. Finally, for nepheline and anorthite we infer a large contribution to fragility from configurational disordering of Al-O-Si links which are known to be dominant in the glasses but are found to be absent from the simulated melts.

  1. Compressibility of magnesium silicate glasses in comparison with those of aluminosilicate glasses

    NASA Astrophysics Data System (ADS)

    Kuryaeva, R. G.

    2013-10-01

    The refractive index of the Na2MgSi6O14 glass in the pressure range up to 6.0 GPa has been measured using a polarization-interference microscope and an apparatus with diamond anvils. The changes in relative density which characterize the compressibility of the glass have been estimated in the pressure range under investigation from the measured refractive indices within the framework of the theory of photoelasticity. The results have been compared with the data previously obtained for the NaAlSi3O8 and CaAl2Si6O16 glasses. A comparison of the changes in relative density of the aluminosilicate and magnesium silicate glasses has been demonstrated that the difference in the compressibility is not so much significant as should be expected from the replacement of network-forming ions by modifiers ions. Estimated by different methods the degree of depolymerization of the Na2MgSi6O14 glass (NBO/T ≅ 0.2) is compared to those for the aluminosilicate glasses. The decrease in the compressibility in the series NaAlSi3O8, CaAl2Si6O16, Na2MgSi6O14 glasses is in agreement with an increase of the degree of depolymerization in the same series.

  2. A HIGH CURRENT DENSITY LI+ ALUMINO-SILICATE ION SOURCE FOR TARGET HEATING EXPERIMENTS

    SciTech Connect

    Roy, Prabir K.; Greenway, Wayne G.; Kwan, Joe W.; Seidl, Peter A.; Waldron, William L.

    2011-03-23

    The NDCX-II accelerator for target heating experiments has been designed to use a large diameter ({approx_equal} 10.9 cm) Li{sup +} doped alumino-silicate source with a pulse duration of 0.5 {micro}s, and beam current of {approx_equal} 93 mA. Characterization of a prototype lithium alumino-silicate sources is presented. Using 6.35mm diameter prototype emitters (coated on a {approx_equal} 75% porous tungsten substrate), at a temperature of {approx_equal} 1275 C, a space-charge limited Li{sup +} beam current density of {approx_equal} 1 mA/cm{sup 2} was measured. At higher extraction voltage, the source is emission limited at around {approx_equal} 1.5 mA/cm{sup 2}, weakly dependent on the applied voltage. The lifetime of the ion source is {approx_equal} 50 hours while pulsing the extraction voltage at 2 to 3 times per minute. Measurements show that the life time of the ion source does not depend only on beam current extraction, and lithium loss may be dominated by neutral loss or by evaporation. The life time of a source is around {ge} 10 hours in a DC mode extraction, and the extracted charge is {approx_equal} 75% of the available Li in the sample. It is inferred that pulsed heating may increase the life time of a source.

  3. Water solubility in calcium aluminosilicate glasses investigated by first principles techniques

    SciTech Connect

    Bouyer, Frederic; Geneste, Gregory; Ispas, Simona; Kob, Walter; Ganster, Patrick

    2010-12-15

    First-principles techniques have been employed to study the reactivity of water into a calcium aluminosilicate glass. In addition to the well known hydrolysis reactions Si-O-Si+H{sub 2}O{yields}Si-OH+Si-OH and Si-O-Al+H{sub 2}O{yields}Si-OH+Al-OH, a peculiar mechanism is found, leading to the formation of an AlO{sub 3}-H{sub 2}O entity and the breaking of Al-O-Si bond. In the glass bulk, most of the hydrolysis reactions are endothermic. Only a few regular sites are found reactive (i.e. in association with an exothermic reaction), and in that case, the hydrolysis reaction leads to a decrease of the local disorder in the amorphous vitreous network. Afterwards, we suggest that ionic charge compensators transform into network modifiers when hydrolysis occurs, according to a global process firstly suggested by Burnham in 1975. Our theoretical computations provide a more general model of the first hydrolysis steps that could help to understand experimental data and water speciation in glasses. -- Graphical Abstract: Reactivity within glass bulk: structures obtained after hydrolyses reactions (endothermic and exothermic processes) and mechanisms involving Si-OH, Al-OH, Si-OH-Al groups within aluminosilicates glasses (through ab initio molecular dynamics): formation of the Si-OH-Al entity coupled with an H exchange-Frederic Bouyer and Gregory Geneste. Display Omitted

  4. The Brillouin gain coefficient of Yb-doped aluminosilicate glass optical fibers

    NASA Astrophysics Data System (ADS)

    Dragic, Peter D.; Ballato, John; Morris, Stephanie; Hawkins, Thomas

    2013-07-01

    Provided herein is a detailed analysis of the Brillouin spectroscopy of the ytterbia (Yb2O3) dopant in aluminosilicate glass optical fibers. Yb-doped fiber lasers have become ubiquitous, and the results presented here may be used to design lasers and amplifiers for narrow linewidth systems and applications. It is found, with a high degree of certainty, that Yb2O3 has an acoustic velocity that is lower than that of silica, a Brillouin spectral width (or material acoustic damping coefficient) that is about 80 times greater than that of silica, and photoelastic constants (Pockels' coefficients) that are negative. It is found that the primary influence of ytterbia in concentrations typical of active fibers is to broaden the Brillouin gain spectrum, thereby reducing the peak Brillouin gain. A set of design curves is provided outlining the Brillouin gain coefficient as a function of alumina concentration for several ytterbia concentrations, which can be utilized to design fiber structures with reduced Brillouin gain. The Yb-doped aluminosilicate fiber system is compared to the Yb-doped phosphosilicate system, and a high degree of similarity is found between them at low Al2O3 or P2O5 doping levels. However, for fiber produced utilizing conventional techniques, the phosphosilicates are found to have the potential for lower Brillouin gain since more P2O5 can be reliably incorporated into the glassy matrix.

  5. 29Si NMR study of structural ordering in aluminosilicate geopolymer gels.

    PubMed

    Duxson, Peter; Provis, John L; Lukey, Grant C; Separovic, Frances; van Deventer, Jannie S J

    2005-03-29

    A systematic series of aluminosilicate geopolymer gels was synthesized and then analyzed using 29Si magic-angle spinning nuclear magnetic resonance (MAS NMR) in combination with Gaussian peak deconvolution to characterize the short-range ordering in terms of T-O-T bonds (where T is Al or Si). The effect of nominal Na2O/(Na2O + K2O) and Si/Al ratios on short-range network ordering was quantified by deconvolution of the 29Si MAS NMR spectra into individual Gaussian peaks representing different Q4(mAl) silicon centers. The deconvolution procedure developed in this work is applicable to other aluminosilicate gel systems. The short-range ordering observed here indicates that Loewenstein's Rule of perfect aluminum avoidance may not apply strictly to geopolymeric gels, although further analyses are required to quantify the degree of aluminum avoidance. Potassium geopolymers appeared to exhibit a more random Si/Al distribution compared to that of mixed-alkali and sodium systems. This work provides a quantitative account of the silicon and aluminum ordering in geopolymers, which is essential for extending our understanding of the mechanical strength, chemical and thermal stability, and fundamental structure of these systems. PMID:15779981

  6. Ordered hexagonal mesoporous aluminosilicates with low Si/Al ratio: synthesis, characterization, and catalytic application.

    PubMed

    Liu, Aifeng; Che, Hongwei; Liu, Chuanzhi; Fu, Quanrong; Jiang, Ruijiao; Wang, Cheng; Wang, Liang

    2014-06-01

    Ordered hexagonal mesoporous aluminosilicates with lower Si/Al ratio below 5 have been successfully synthesized via the co-assembly of preformed aluminosilicate precursors with Gemini surfactant [C12H25N+(CH3)2(CH2)6N+(CH3)2C12H25] x 2Br(-) as the template. Powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, N2 adsorption-desorption isotherm measurements, Fourier transform infrared spectroscopy, 27Al nuclear magnetic resonance, thermogravimetric analysis, and temperature-programmed desorption of cyclohexylamine are employed to characterize the resulting samples. The phenol alkylation reaction is carried out to evaluate their catalytic performances. These studies indicate that the sample with a low Si/Al ratio of 3 still retains a highly ordered hexagonal mesoporous structure. And it also possesses the highest acidity of 0.96 mmol among the samples with lower Si/Al ratios below 5 due to its higher specific surface area together with more content of tetrahedrally coordinated Al in the framework. The catalytic tests confirm that the acidity of the samples plays a key role in determining their catalytic performances. PMID:24738433

  7. Cellular morphology of organic-inorganic hybrid foams based on alkali alumino-silicate matrix

    SciTech Connect

    Verdolotti, Letizia; Capasso, Ilaria; Lavorgna, Marino; Liguori, Barbara; Caputo, Domenico; Iannace, Salvatore

    2014-05-15

    Organic-inorganic hybrid foams based on an alkali alumino-silicate matrix were prepared by using different foaming methods. Initially, the synthesis of an inorganic matrix by using aluminosilicate particles, activated through a sodium silicate solution, was performed at room temperature. Subsequently the viscous paste was foamed by using three different methods. In the first method, gaseous hydrogen produced by the oxidization of Si powder in an alkaline media, was used as blowing agent to generate gas bubbles in the paste. In the second method, the porous structure was generated by mixing the paste with a “meringue” type of foam previously prepared by whipping, under vigorous stirring, a water solution containing vegetal proteins as surfactants. In the third method, a combination of these two methods was employed. The foamed systems were consolidated for 24 hours at 40°C and then characterized by FTIR, X-Ray diffraction, scanning electron microscopy (SEM) and compression tests. Low density foams (∼500 Kg/m{sup 3}) with good cellular structure and mechanical properties were obtained by combining the “meringue” approach with the use of the chemical blowing agent based on Si.

  8. Fate of Uranium during Sodium Aluminosilicate Formation under Waste Tank Conditions

    SciTech Connect

    Wilmarth, B

    2005-06-22

    Experiments have been conducted to examine the fate of uranium during the formation of sodium aluminosilicate (NAS) when wastes containing high aluminate concentrations are mixed with wastes of high silicate concentration. Testing was conducted at varying degrees of uranium saturation. Testing examined typical tank conditions, e.g., stagnant, slightly elevated temperature (50 C). The results showed that under sub-saturated conditions uranium is not removed from solution to any large extent in both simulant testing and actual tank waste testing. There are data supporting a small removal due to sorption of uranium on sites in the NAS. Above the solubility limit the data are clear that a reduction in uranium concentration occurs with the formation of aluminosilicate. This uranium precipitation is fairly rapid and ceases when uranium reaches its solubility limit. At the solubility limit, it appears that uranium is not affected, but further testing might be warranted. Lastly, analysis of the uranium speciation in a Tank 49H set of samples showed the uranium to be soluble. Analysis of the solution composition and subsequent use of the Hobb's uranium solubility model indicated a uranium solubility limit of 32 mg/L. The measured value of uranium in the Tank 49H matched the model prediction.

  9. Barrier properties of hydrogenated acrylonitrile-butadiene rubber composites containing modified layered aluminosilicates

    NASA Astrophysics Data System (ADS)

    Krzemińska, S.; Rzymski, W. M.

    2011-12-01

    The resistance to permeation by the selected solvents of flat membranes made of cured hydrogenated acrylonitrile-butadiene rubber (HNBR) materials without any fillers and containing 5 phr of layered aluminosilicate nanofiller (bentonite), modified with various types of ammonium salts or N330 type carbon black, was investigated. The barrier properties were assessed on the basis of the breakthrough time of a liquid with low (cyclohexane) or average (butyl acetate) thermodynamic affinity to HNBR, determined according to EN 6529:2001, through a cured elastomer sample. The addition of bentonite, irrespectively of the method of modification of its particles, was found to increase the cured HNBR breakthrough time by 20 - 35 % in the case of slowly permeating non-polar cyclohexane, and by 50 - 130 % in the case of polar butyl acetate permeating more rapidly, in comparison with the barrier material containing no filler. The layered aluminosilicate nanofillers increased the breakthrough time of the material sample for both the tested solvents. In particular, the breakthrough time for polar butyl acetate was even longer than for conventional carbon black. Additionally, the increase of the breakthrough time was observed to depend on the modifier of bentonite particle surface.

  10. Electromagnetic and Mechanical Properties of Silica-Aluminosilicates Plasma Sprayed Composite Coatings

    NASA Astrophysics Data System (ADS)

    Cipri, F.; Bartuli, C.; Valente, T.; Casadei, F.

    2007-12-01

    The physico-chemical and thermo-mechanical properties of aluminosilicate ceramics (high-melting point, low thermal expansion coefficient, excellent thermal shock resistance, low-density and good corrosion resistance) make this class of materials a good option for high-temperature structural applications. Al2O3-SiO2 compounds show an excellent refractory behavior allowing a wide use as wear-resistant thermal barrier coatings, in metallurgical and glass plants and in high temperature heat exchangers. Moreover, the low values of thermal expansion coefficient and of complex permittivity allow to extend the use of this ceramic for microelectronic devices, radome for antennas and electromagnetic windows for microwaves and infrared. The present article presents the results of an extensive experimental activity carried out to produce thick aluminosilicate coatings by plasma-spray technique. The APS deposition parameters were optimized on the basis of a surface response approach, as specified by design of experiments (DoE) methodologies. Samples were tested for phase composition, total porosity, microstructure, microhardness, deposition efficiency, fracture toughness, and modulus of rupture. Finally, coatings were characterized for their particularly interesting electromagnetic properties: complex permittivity was measured at microwave frequency using a network analyzer with wave guide.

  11. Development of a New Ferrous Aluminosilicate Refractory Material for Investment Casting of Aluminum Alloys

    NASA Astrophysics Data System (ADS)

    Yuan, Chen; Jones, Sam; Blackburn, Stuart

    2012-12-01

    Investment casting is a time-consuming, labour intensive process, which produces complex, high value-added components for a variety of specialised industries. Current environmental and economic pressures have resulted in a need for the industry to improve current casting quality, reduce manufacturing costs and explore new markets for the process. Alumino-silicate based refractories are commonly used as both filler and stucco materials for ceramic shell production. A new ceramic material, norite, is now being produced based on ferrous aluminosilicate chemistry, having many potential advantages when used for the production of shell molds for casting aluminum alloy. This paper details the results of a direct comparison made between the properties of a ceramic shell system produced with norite refractories and a typical standard refractory shell system commonly used in casting industry. A range of mechanical and physical properties of the systems was measured, and a full-scale industrial casting trial was also carried out. The unique properties of the norite shell system make it a promising alternative for casting aluminum based alloys in the investment foundry.

  12. Aqueous dissolution, solubilities and thermodynamic stabilities of common aluminosilicate clay minerals: Kaolinite and smectites

    USGS Publications Warehouse

    May, Howard M.; Klnniburgh, D.G.; Helmke, P.A.; Jackson, M.L.

    1986-01-01

    Determinations of the aqueous solubilities of kaolinite at pH 4, and of five smectite minerals in suspensions set between pH 5 and 8, were undertaken with mineral suspensions adjusted to approach equilibrium from over- and undersaturation. After 1,237 days, Dry Branch, Georgia kaolinite suspensions attained equilibrium solubility with respect to the kaolinite, for which Keq = (2.72 ?? 0.35) ?? 107. The experimentally determined Gibbs free energy of formation (??Gf,2980) for the kaolinite is -3,789.51 ?? 6.60 kj mol-1. Equilibrium solubilities could not be determined for the smectites because the composition of the solution phase in the smectite suspensions appeared to be controlled by the formation of gibbsite or amorphous aluminum hydroxide and not by the smectites, preventing attempts to determine valid ??Gf0 values for these complex aluminosilicate clay minerals. Reported solubility-based ??Gf0 determinations for smectites and other variable composition aluminosilicate clay minerals are shown to be invalid because of experimental deficiencies and of conceptual flaws arising from the nature of the minerals themselves. Because of the variable composition of smectites and similar minerals, it is concluded that reliable equilibrium solubilities and solubility-derived ??Gf0 values can neither be rigorously determined by conventional experimental procedures, nor applied in equilibriabased models of smectite-water interactions. ?? 1986.

  13. Cellular morphology of organic-inorganic hybrid foams based on alkali alumino-silicate matrix

    NASA Astrophysics Data System (ADS)

    Verdolotti, Letizia; Liguori, Barbara; Capasso, Ilaria; Caputo, Domenico; Lavorgna, Marino; Iannace, Salvatore

    2014-05-01

    Organic-inorganic hybrid foams based on an alkali alumino-silicate matrix were prepared by using different foaming methods. Initially, the synthesis of an inorganic matrix by using aluminosilicate particles, activated through a sodium silicate solution, was performed at room temperature. Subsequently the viscous paste was foamed by using three different methods. In the first method, gaseous hydrogen produced by the oxidization of Si powder in an alkaline media, was used as blowing agent to generate gas bubbles in the paste. In the second method, the porous structure was generated by mixing the paste with a "meringue" type of foam previously prepared by whipping, under vigorous stirring, a water solution containing vegetal proteins as surfactants. In the third method, a combination of these two methods was employed. The foamed systems were consolidated for 24 hours at 40C and then characterized by FTIR, X-Ray diffraction, scanning electron microscopy (SEM) and compression tests. Low density foams (500 Kg/m3) with good cellular structure and mechanical properties were obtained by combining the "meringue" approach with the use of the chemical blowing agent based on Si.

  14. Probing zeolites with organic molecules: Supercages of X and Y zeolites are superpolar

    SciTech Connect

    Uppili, S.; Thomas, K.J.; Crompton, E.M.; Ramamurthy, V.

    2000-01-11

    Supercages of Li{sup +}- and Na{sup +}-exchanged X and Y zeolites are much more polar than even water. The extent of polarity depends on the nature and the number of cations present within a supercage. The polarity of Li{sup +}- and Na{sup +}-exchanged X and Y zeolites decreases in the presence of water. In presence of water the contribution of cations toward polarity is much smaller than water itself. In this study polarity has been monitored with organic probe molecules, Nile red, pyrene 1-carboxaldehyde and coumarin-500. A connection between polarity and electric field within a cage has also been established. Since the supercages are much more polar than all organic solvents, they can be characterized as superpolar. Because of this one may be able to achieve excited-state switching of carbonyl compounds within a zeolite while such may not be possible in organic solvents. The n{pi}*-{pi}{pi}* state switching of acetophenones is easily achieved within a zeolite while such does not occur in polar solvent methanol-ethanol mixture.

  15. Influence of NaA Zeolite Crystal Expansion/Contraction on Zeolite Membrane Separations

    SciTech Connect

    Sorenson, Stephanie G; Payzant, E Andrew; Gibbons, Will T; Soydas, Belma; Kita, Hidetoshi; Noble, Richard D; Falconer, John L.

    2011-01-01

    In-situ powder XRD measurements showed that the NaA zeolite unit cell contracts and expands upon adsorption, and these changes in zeolite crystal size correlate with permeation changes through NaA zeolite membranes. These membranes had high pervaporation selectivities, even though gas permeation was mainly through defects, as indicated by Knudsen selectivities for gases. At 300 K and a thermodynamic activity of 0.03, water contracted the NaA crystals by 0.22 vol%, and this contraction increased the helium flux through two NaA membranes by approximately 80%. Crystal contraction also increased the fluxes of i-butane during vapor permeation and i-propanol (IPA) during pervaporation (~ 0.03 wt% water). At activities above 0.07, water expanded NaA crystals and correspondingly decreased the membrane fluxes of helium, i-butane, and IPA. Similarly, methanol contracted NaA crystals by 0.05 vol% at an activity of 0.02, and this contraction slightly increased the helium and i-butane fluxes through a NaA membrane. Above an activity of 0.06, methanol expanded the crystals, and the fluxes of helium and i-butane through a NaA membrane decreased. The adsorbate-induced changes explain some pervaporation behavior reported by others, and they indicate that crystal expansion and contraction may increase or decrease zeolite NaA membrane selectivity by changing the defect sizes.

  16. Organosilane with Gemini-Type Structure as the Mesoporogen for the Synthesis of the Hierarchical Porous ZSM-5 Zeolite.

    PubMed

    Zhu, Haibo; Abou-Hamad, Edy; Chen, Yin; Saih, Youssef; Liu, Weibing; Kumar Samal, Akshaya; Basset, Jean-Marie

    2016-03-01

    A new kind of organosilane (1,6-bis(diethyl(3-trimethoxysilylpropyl)ammonium) hexane bromide) with a gemini-type structure was prepared and used as a mesoporogen for the synthesis of hierarchical porous ZSM-5 zeolite. There are two quaternary ammonium centers along with double-hydrolyzable -RSi(OMe)3 fragments in the organosilane, which results in a strong interaction between this mesoporogen and silica-alumina gel. The organosilane can be easily incorporated into the ZSM-5 zeolite structure during the crystallization process, and it was finally removed by calcination, leading to secondary pores in ZSM-5. The synthesized ZSM-5 has been systematically studied by XRD, nitrogen adsorption, SEM, TEM, TG, and solid-state one-dimensional (1D) and two-dimensional (2D) NMR, which reveal information on its detailed structure. It has a hierarchical porosity system, which combines the intrinsic micropores coming from the crystalline structure and irregular mesopores created by the organosilane template. Moreover, the mesoposity including pore size and volume within ZSM-5 can be systematically tuned by changing the organosilane/TEOS ratio, which confirms that this organosilane has high flexibility of use as a template for the synthesis of hierarchical porous zeolite. PMID:26854763

  17. Preparation and screening of crystalline zeolite and hydrothermally-synthesized materials

    DOEpatents

    Schultz, Peter G.; Xiang, Xiaodong; Goldwasser, Isy; Briceno, Gabriel; Sun, Xiao-Dong; Wang, Kai-An

    2005-03-08

    Methods and apparatus for the preparation and use of a substrate having an array of diverse materials in predefined regions thereon. A substrate having an array of diverse materials thereon is generally prepared by delivering components of materials to predefined regions on a substrate, and simultaneously reacting the components to form at least two materials. Materials which can be prepared using the methods and apparatus of the present invention include, for example, covalent network solids, ionic solids and molecular solids. More particularly, materials which can be prepared using the methods and apparatus of the present invention include, for example, inorganic materials, intermetallic materials, metal alloys, ceramic materials, organic materials, organometallic materials, non-biological organic polymers, composite materials (e.g., inorganic composites, organic composites, or combinations thereof), etc. Once prepared, these materials can be screened for useful properties including, for example, electrical, thermal, mechanical, morphological, optical, magnetic, chemical, or other properties. Thus, the present invention provides methods for the parallel synthesis and analysis of novel materials having useful properties.

  18. Oxidative regeneration of toluene-saturated natural zeolite by gaseous ozone: the influence of zeolite chemical surface characteristics.

    PubMed

    Alejandro, Serguei; Valdés, Héctor; Manéro, Marie-Hélène; Zaror, Claudio A

    2014-06-15

    In this study, the effect of zeolite chemical surface characteristics on the oxidative regeneration of toluene saturated-zeolite samples is investigated. A Chilean natural zeolite (53% clinoptilolite, 40% mordenite and 7% quartz) was chemically modified by acid treatment with hydrochloric acid and by ion-exchange with ammonium sulphate. Thermal pre-treatments at 623 and 823K were applied and six zeolite samples with different chemical surface characteristics were generated. Chemical modification of natural zeolite followed by thermal out-gassing allows distinguishing the role of acidic surface sites on the regeneration of exhausted zeolites. An increase in Brønsted acid sites on zeolite surface is observed as a result of ammonium-exchange treatment followed by thermal treatment at 623K, thus increasing the adsorption capacity toward toluene. High ozone consumption could be associated to a high content of Lewis acid sites, since these could decompose ozone into atomic active oxygen species. Then, surface oxidation reactions could take part among adsorbed toluene at Brønsted acid sites and surface atomic oxygen species, reducing the amount of adsorbed toluene after the regenerative oxidation with ozone. Experimental results show that the presence of adsorbed oxidation by-products has a negative impact on the recovery of zeolite adsorption capacity. PMID:24794812

  19. Applying hexagonal nanostructured zeolite particles for acetone removal.

    PubMed

    Lin, Yu-Chih; Bai, Hsunling; Chang, Chung-Liang

    2005-06-01

    This study examines the performance of a new adsorbent, hexagonal nanostructured zeolite particles (HNZP) for acetone adsorption and compares the results with that of commercial mobil synthetic zeolite-5 (ZSM-5) type zeolite. The HNZP is a pure siliceous adsorbent with different values of pore diameter and surface area being adjustable by the manufacturing condition. The results indicate that a slight increase in the average pore diameter (d) of HNZP from 2 to 2.5 nm leads to an increase in the acetone adsorption capacity, although its surface area is decreased, in which case (d = 2.5 nm) the adsorption capacity of fresh HNZP is better than that of ZSM-5 zeolite. Even for the fresh HNZP (d = 2 nm) of which the adsorption capacity is less than that of the ZSM-5 zeolite at relative humidity (RH) of 0%, its adsorption capacity is not deteriorated after repeated regeneration, but the adsorption capacity of regenerated ZSM-5 zeolite decays markedly. Thus, after only one regeneration, the adsorption capacity of HNZP (d = 2 nm) becomes better than that of the ZSM-5 zeolite. The decrease in the adsorption capacity of regenerated ZSM-5 zeolite might be because of its aluminum content that catalyzes the acetone into coke and, thus, blocks the adsorption sites. Furthermore, result on the moisture effect shows that because the pure siliceous HNZP was more hydrophobic than the ZSM-5 zeolite, the acetone adsorption efficiency of fresh HNZP (d = 2 nm) is better than that of ZSM-5 zeolite at RH = 50%. PMID:16022421

  20. Molecular heterogeneous catalysis: a single-site zeolite-supported rhodium complex for acetylene cyclotrimerization.

    PubMed

    Kletnieks, Philip W; Liang, Ann J; Craciun, Raluca; Ehresmann, Justin O; Marcus, David M; Bhirud, Vinesh A; Klaric, Meghan M; Hayman, Miranda J; Guenther, Darryl R; Bagatchenko, Olesya P; Dixon, David A; Gates, Bruce C; Haw, James F

    2007-01-01

    By anchoring metal complexes to supports, researchers have attempted to combine the high activity and selectivity of molecular homogeneous catalysis with the ease of separation and lack of corrosion of heterogeneous catalysis. However, the intrinsic nonuniformity of supports has limited attempts to make supported catalysts truly uniform. We report the synthesis and performance of such a catalyst, made from [Rh(C(2)H(4))(2)(CH(3)COCHCOCH(3))] and a crystalline support, dealuminated Y zeolite, giving {Rh(C(2)H(4))(2)} groups anchored by bonds to two zeolite oxygen ions, with the structure determined by extended X-ray absorption fine structure (EXAFS) spectroscopy and the uniformity of the supported complex demonstrated by (13)C NMR spectroscopy. When the ethylene ligands are replaced by acetylene, catalytic cyclotrimerization to benzene ensues. Characterizing the working catalyst, we observed evidence of intermediates in the catalytic cycle by NMR spectroscopy. Calculations at the level of density functional theory confirmed the structure of the as-synthesized supported metal complex determined by EXAFS spectroscopy. With this structure as an anchor, we used the computational results to elucidate the catalytic cycle (including transition states), finding results in agreement with the NMR spectra. PMID:17685381

  1. Molecular Heterogeneous Catalysis: a Single-Site Zeolite-Supported Rhodium Complex for Acetylene Cyclotrimerization

    SciTech Connect

    Kletnieks, P.W.; Liang, A.J.; Craciun, R.; Ehresmann, J.O.; Marcus, D.M.; Bhirud, V.A.; Klaric, M.M.; Hayman, M.J.; Guenther, D.R.; Bagatchenko, O.P.; Dixon, D.A.; Gates, B.C.; Haw, J.F.

    2009-06-01

    By anchoring metal complexes to supports, researchers have attempted to combine the high activity and selectivity of molecular homogeneous catalysis with the ease of separation and lack of corrosion of heterogeneous catalysis. However, the intrinsic nonuniformity of supports has limited attempts to make supported catalysts truly uniform. We report the synthesis and performance of such a catalyst, made from [Rh(C{sub 2}H{sub 4}){sub 2}(CH{sub 3}COCHCOCH{sub 3})] and a crystalline support, dealuminated Y zeolite, giving {l_brace}Rh(C{sub 2}H{sub 4}){sub 2}{r_brace} groups anchored by bonds to two zeolite oxygen ions, with the structure determined by extended X-ray absorption fine structure (EXAFS) spectroscopy and the uniformity of the supported complex demonstrated by {sup 13}C NMR spectroscopy. When the ethylene ligands are replaced by acetylene, catalytic cyclotrimerization to benzene ensues. Characterizing the working catalyst, we observed evidence of intermediates in the catalytic cycle by NMR spectroscopy. Calculations at the level of density functional theory confirmed the structure of the as-synthesized supported metal complex determined by EXAFS spectroscopy. With this structure as an anchor, we used the computational results to elucidate the catalytic cycle (including transition states), finding results in agreement with the NMR spectra.

  2. Design of Lewis-acid centres in zeolitic matrices for the conversion of renewables.

    PubMed

    Dapsens, Pierre Y; Mondelli, Cecilia; Pérez-Ramírez, Javier

    2015-10-21

    The catalytic conversion of renewable feedstocks into chemicals is pursued as a means to sustainably fulfil future societal needs. Due to the oxygen-rich nature of bio-derived substrates, isomerisation, transfer-hydrogenation and retro-aldol reactions have emerged as relevant transformations to produce commodity chemicals and polymer building blocks. In this context, porous materials containing Lewis-acid metals (e.g., Al, Ga, Sn, Ti, Zr) play an important role. Among these, tin-containing zeolites have demonstrated superior catalytic properties which have mainly been attributed to their hydrophobicity and crystallinity. This review evaluates the versatility and the scalability of bottom-up and top-down approaches to introduce Lewis-acid functionalities in zeolitic matrices. A precise characterisation is shown to be crucial to determine the structure, acidity and environment of the sites introduced. In this regard, we highlight the limitations of conventional techniques and the advantages of analytical and modelling tools recently applied to gain an improved understanding of these solids. Thereafter, property-performance relations and important aspects for the industrial amenability of new synthetic routes are exemplified through case studies. Finally, we put forward the need for gathering deeper knowledge of the site location, surface properties and stability to aid the design of next-generation Lewis-acid catalysts. PMID:25917850

  3. Photophysical properties of pyrene in zeolites: Adsorption and distribution of pyrene molecules on the surfaces of zeolite L and mordenite

    SciTech Connect

    Liu, Xinsheng; Thomas, J.K.

    1994-12-01

    Adsorption of pyrene on the surfaces of zeolites L and mordenite is investigated using photophysical techniques. Although the internal surfaces of both zeolites are polar, their external surfaces may not be the same. A difference is observed for mordenite. No pyrene excimers can be produced in mordenite, while excimers are readily formed in zeolite L. Due to structural constraints, 30-35% of pyrene adsorbed in mordenite cannot be quenched by O{sub 2}. Rotational movement of pyrene molecules in mordenite is also restricted by the zeolite structure. Laser photolysis produces pyrene cation and anion radicals, the former having a larger yield than the latter in both zeolites. 31 refs., 5 figs., 2 tabs.

  4. [Zeolite catalysis in conversion of cellulosics

    SciTech Connect

    Tsao, G.T.

    1992-01-01

    To transform biomass into fermentable substrate for yeast, we are using zeolites instead of enzymes to catalyze the two bottleneck reactions in biomass conversion, xylose isomerization and ceuobiose hydrolysis. The experimental results on these reactions carried out over various zeolites and other catalysts are presented herein. The advantages and disadvantages of using these catalysts over enzymes are also discussed. Heterogeneous solid catalysts other than zeolites has been employed for cellobiose-to-glucose hydrolysis. The size and shape selectivity that makes zeoutes unique for some reactions can add diffusional hindrance. We have spent some time screening various known solid acidic catalysts. We report that a class of cationic ion exchange resins in the acidified form (e.g. Amberlite) has worked well as an acidic catalyst in hydrolyzing cellobiose to glucose. Our experimental results, together with those obtained from a homogeneous acid catalyst (e.g. sulfuric acid) for comparison are provided. Having succeeded in finding an alternative solid acid catalyst for hydrolysis, we explored other solid resin or other homogeneous but non-enzyme catalyst to carry out the xylose-to-xylulose isomerization. A fairly extensive search has been made. We explored the use of sodium aluminates in the homogeneous phase isomerization of glucose to fructose and obtained a very high conversion of glucose to fructose with the final mixture containing 85% of fructose instead of the common 45%. Fructose apparently complexes with aluminates, and its equilibrium concentration is shifted to considerably higher values than permitted by simple glucose/fructose equilibrium. We have recently found a number of catalysts capable of promoting isomerization between aldoses and ketoses. One solid resin, known as polyvinyl pyridine (PVP), is able to convert xylose to xylulose at a pH below 7. Our usage of alternative isomerization catalysts, including PVP, are described.

  5. [Zeolite catalysis in conversion of cellulosics

    SciTech Connect

    Tsao, G.T.

    1992-12-31

    To transform biomass into fermentable substrate for yeast, we are using zeolites instead of enzymes to catalyze the two bottleneck reactions in biomass conversion, xylose isomerization and ceuobiose hydrolysis. The experimental results on these reactions carried out over various zeolites and other catalysts are presented herein. The advantages and disadvantages of using these catalysts over enzymes are also discussed. Heterogeneous solid catalysts other than zeolites has been employed for cellobiose-to-glucose hydrolysis. The size and shape selectivity that makes zeoutes unique for some reactions can add diffusional hindrance. We have spent some time screening various known solid acidic catalysts. We report that a class of cationic ion exchange resins in the acidified form (e.g. Amberlite) has worked well as an acidic catalyst in hydrolyzing cellobiose to glucose. Our experimental results, together with those obtained from a homogeneous acid catalyst (e.g. sulfuric acid) for comparison are provided. Having succeeded in finding an alternative solid acid catalyst for hydrolysis, we explored other solid resin or other homogeneous but non-enzyme catalyst to carry out the xylose-to-xylulose isomerization. A fairly extensive search has been made. We explored the use of sodium aluminates in the homogeneous phase isomerization of glucose to fructose and obtained a very high conversion of glucose to fructose with the final mixture containing 85% of fructose instead of the common 45%. Fructose apparently complexes with aluminates, and its equilibrium concentration is shifted to considerably higher values than permitted by simple glucose/fructose equilibrium. We have recently found a number of catalysts capable of promoting isomerization between aldoses and ketoses. One solid resin, known as polyvinyl pyridine (PVP), is able to convert xylose to xylulose at a pH below 7. Our usage of alternative isomerization catalysts, including PVP, are described.

  6. Process wastewater treatment with hydrogen-form CST and chabazite zeolite

    SciTech Connect

    DePaoli, S.M.; Bostick, D.T.

    1998-05-01

    Ion-exchange materials have been investigated for the removal of radionuclides from near-neutral-pH wastewaters containing competing cations at concentrations greater than those of the targeted species. Natural chabazite zeolite was chosen as the baseline material for the removal of fission products, namely {sup 90}Sr and {sup 137}Cs, from wastewater and groundwater. The sorbent IONSIV{reg_sign} IE-911, a crystalline silicotitanate manufactured by UOP, was recently tested in this capacity and found to compare extremely well against the baseline material in removing {sup 90}Sr and {sup 137}Cs from process wastewater. This paper presents results of similar column tests performed using both materials, as well as results from batch experiments on actual wastewaters using IONSIV{reg_sign} IE-911.

  7. Reduction of nitrogen oxides with catalytic acid resistant aluminosilicate molecular sieves and ammonia

    DOEpatents

    Pence, Dallas T.; Thomas, Thomas R.

    1980-01-01

    Noxious nitrogen oxides in a waste gas stream such as the stack gas from a fossil-fuel-fired power generation plant or other industrial plant off-gas stream is catalytically reduced to elemental nitrogen and/or innocuous nitrogen oxides employing ammonia as reductant in the presence of a zeolite catalyst in the hydrogen or sodium form having pore openings of about 3 to 10 A.

  8. Mechanism of methanol conversion over zeolite

    SciTech Connect

    Ono, Y.

    1983-01-01

    Details of the reaction mechanisms of conversions of methanol to various alkanes and alkenes were investigated. A discussion of the autocatalytic phenomena of the conversion of methanol over ZSM-5 zeolite was included. The temperature dependence and acidity aspects of the reaction rate were discussed. Also the use of Nafion-H and heteropolyacids as catalysts of conversion was also included. A detailed description of the self-condensation of methyl iodine over Ag/sub 3/PW/sub 12/O/sub 40/ was given. The distribution of hydrocarbon products on the reaction at various temperatures, reaction times, and molar ratios of reactants was given in tabular form.

  9. Growth of large zeolite crystals in space

    NASA Technical Reports Server (NTRS)

    Sacco, A., Jr.; Dixon, A.; Thompson, R.; Scott, G.; Ditr, J.

    1988-01-01

    Synthesis studies performed using close analogs of triethanolamine (TEA) have shown that all three hydroxyl groups and the amine group in this molecule are necessary to provide nucleation suppression. Studies using C-13 nuclear magnetic resonance (NMR) revealed that the hydroxyl ions and the amine group are involved in the formation of an aluminum complex. It was also shown that silicate species fo not interact this way with TEA in an alkaline solution. These results suggest that successful aluminum complexation leads to nucleation in zeolite-A crystallization.

  10. Electron trapping in polar-solvated zeolites.

    PubMed

    Ellison, Eric H

    2005-11-01

    Of current interest in our laboratory is the nature of photoinduced processes in the cavities of zeolites completely submerged in polar solvents, or polar-solvated zeolites (PSZ). The present study addresses the nature of electron trapping in PSZ with emphasis on the zeolites NaX and NaY. Free electrons were generated by two-photon, pulsed-laser excitation of either pyrene or naphthalene included in zeolite cavities. Trapped electrons were monitored by diffuse transmittance, transient absorption spectroscopy at visible wavelengths. In anhydrous alcohols, electron trapping by Na(4)(4+) ion clusters was observed in both NaX and NaY. The resulting trapped electrons decayed over the course of tens of milliseconds. No evidence for alcohol-solvated electrons was found. More varied results were observed in solvents containing water. In NaX submerged in CH(3)OH containing 5% or higher water, species having microsecond lifetimes characteristic of solvated electrons were observed. By contrast, a 2 h exposure of NaY to 95/5 CH(3)OH/H(2)O had no effect on electron trapping relative to anhydrous CH(3)OH. The difference between NaX and NaY was explained by how fast water migrates into the sodalite cage. Prolonged exposure to water at room temperature or exposure to water at elevated temperatures was necessary to place water in the sodalite cages of NaY and deactivate Na(4)(4+) as an electron trap. Additional studies in NaY revealed that solvent clusters eventually become lower energy traps than Na(4)(4+) as the water content in methanol increases. In acetonitrile-water mixtures, electron trapping by Na(4)(4+) was eliminated and no equivalent species characteristic of solvated electrons in methanol-water mixtures was observed. This result was explained by the formation of low energy solvated electrons which cannot be observed in the visible region of the spectrum. Measurements of the rate of O(2) quenching in anhydrous solvents revealed rate constants for the quenching of ion cluster trapped electrons that were 2-4 times higher than that for pyrene triplets. In NaX, the rate constant in methanol was 10(4) times smaller than that in cyclohexane, showing greater inhibition of O(2) reactivity in the medium of PSZ. The results of this study point out the conditions under which Na(4)(4+) is active as an electron trap in PSZ and that water must be present in the sodalite cage to produce solvated electrons in the supercage. PMID:16853643

  11. Zeolite-sorbate interactions from Raman spectroscopy

    SciTech Connect

    Buckley, R.G. ); Deckman, H.W.; Witzke, H.; McHenry, J.A. )

    1990-11-01

    Raman spectroscopy has been used as a direct structural probe to study sorbate-framework interactions for water sorption into the zeolite potassium-ZK5. Equilibrium adsorbate-induced deformations of intertetrahedral angles are quantitatively measured and analyzed in terms of a structural isotherm for each counterion site. All of the structural changes result from the first molecules sorbed. Kinetic studies of the structural deformation are used to determine a diffusion coefficient for the water molecules deforming the six-membered ring site of {approximately} 10{sup {minus}12} cm{sup 2} s{sup {minus}1}.

  12. Zeolitic imidazolate framework as formaldehyde gas sensor.

    PubMed

    Chen, Er-Xia; Yang, Hui; Zhang, Jian

    2014-06-01

    Traditional semiconducting metal oxide-based gas sensors are always limited on low surface areas and high operating temperatures. Considering the high surface area and high stability of zeolitic imidazolate framework (ZIF), ZIF-67 (surface area of 1832.2 m(2) g(-1)) was first employed as a promising formaldehyde gas sensor at a low operating temperature (150 °C), and the gas sensor could detect formaldehyde as low as 5 ppm. This work develops a new promising application approach for porous metal-organic frameworks. PMID:24813234

  13. Zeolite/methanol: The adsorption heat pump

    NASA Astrophysics Data System (ADS)

    Haerkoenen, Martti

    1988-02-01

    This work deals with adsorption heat pump processes. The adsorption process was studied both theoretically and experimentally. Experiments were carried out using different types of synthetic zeolites as an adsorbent and methanol vapor as an adsorbate. Adsorption equilibrium curves were determined, heat of adsorption was measured calorimetrically and sorption kinetics was studied. The pump process was tested experimentally using the pairs 5A/CH(sub 3)OH, 13X/CH(sub 3)OH and 5A/H(sub 2)O. In order to study the effect of various parameters on the process, a simple numerical simulation model was developed and tested.

  14. Hydrogen storage in Chabazite zeolite frameworks.

    PubMed

    Regli, Laura; Zecchina, Adriano; Vitillo, Jenny G; Cocina, Donato; Spoto, Giuseppe; Lamberti, Carlo; Lillerud, Karl P; Olsbye, Unni; Bordiga, Silvia

    2005-09-01

    We have recently highlighted that H-SSZ-13, a highly siliceous zeolite (Si/Al = 11.6) with a chabazitic framework, is the most efficient zeolitic material for hydrogen storage [A. Zecchina, S. Bordiga, J. G. Vitillo, G. Ricchiardi, C. Lamberti, G. Spoto, M. Bjørgen and K. P. Lillerud, J. Am. Chem. Soc., 2005, 127, 6361]. The aim of this new study is thus to clarify both the role played by the acidic strength and by the density of the polarizing centers hosted in the same framework topology in the increase of the adsorptive capabilities of the chabazitic materials towards H2. To achieve this goal, the volumetric experiments of H2 uptake (performed at 77 K) and the transmission IR experiment of H2 adsorption at 15 K have been performed on H-SSZ-13, H-SAPO-34 (the isostructural silico-aluminophosphate material with the same Brønsted site density) and H-CHA (the standard chabazite zeolite: Si/Al = 2.1) materials. We have found that a H2 uptake improvement has been obtained by increasing the acidic strength of the Brønsted sites (moving from H-SAPO-34 to H-SSZ-13). Conversely, the important increase of the Brønsted sites density (moving from H-SSZ-13 to H-CHA) has played a negative role. This unexpected behavior has been explained as follows. The additional Brønsted sites are in mutual interaction via H-bonds inside the small cages of the chabazitic framework and for most of them the energetic cost needed to displace the adjacent OH ligand is higher than the adsorption enthalpy of the OH...H2 adduct. From our work it can be concluded that proton exchanged chabazitic frameworks represent, among zeolites, the most efficient materials for hydrogen storage. We have shown that a proper balance between available space (volume accessible to hydrogen), high contact surface, and specific interaction with strong and isolated polarizing centers are the necessary characteristics requested to design better materials for molecular H2 storage. PMID:16240032

  15. Design and characterization of chitosan/zeolite composite films--Effect of zeolite type and zeolite dose on the film properties.

    PubMed

    Barbosa, Gustavo P; Debone, Henrique S; Severino, Patrícia; Souto, Eliana B; da Silva, Classius F

    2016-03-01

    Chitosan films can be used as wound dressings for the treatment of chronic wounds and severe burns. The antimicrobial properties of these films may be enhanced by the addition of silver. Despite the antimicrobial activity of silver, several studies have reported the cytotoxicity as a factor limiting its biomedical applications. This problem may, however, be circumvented by the provision of sustained release of silver. Silver zeolites can be used as drug delivery platforms to extend the release of silver. The objective of this study was to evaluate the addition of clinoptilolite and A-type zeolites in chitosan films. Sodium zeolites were initially subjected to ion-exchange in a batch reactor. Films were prepared by casting technique using a 2% w/w chitosan solution and two zeolite doses (0.1 or 0.2% w/w). Films were characterized by thermal analysis, color analysis, scanning electron microscopy, X-ray diffraction, and water vapor permeation. The results showed that films present potential for application as dressing. The water vapor permeability is one of the main properties in wound dressings, the best results were obtained for A-type zeolite/chitosan films, which presented a brief reduction of this property in relation to zeolite-free chitosan film. On the other hand, the films containing clinoptilolite showed lower water vapor permeation, which may be also explained by the best distribution of the particles into the polymer which also promoted greater thermal resistance. PMID:26706528

  16. Zeolite Crystal Growth (ZCG) Flight on USML-2

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.; Bac, Nurcan; Warzywoda, Juliusz; Guray, Ipek; Marceau, Michelle; Sacco, Teran L.; Whalen, Leah M.

    1997-01-01

    The extensive use of zeolites and their impact on the world's economy has resulted in many efforts to characterize their structure, and improve the knowledge base for nucleation and growth of these crystals. The zeolite crystal growth (ZCG) experiment on USML-2 aimed to enhance the understanding of nucleation and growth of zeolite crystals, while attempting to provide a means of controlling the defect concentration in microgravity. Zeolites A, X, Beta, and Silicalite were grown during the 16 day - USML-2 mission. The solutions where the nucleation event was controlled yielded larger and more uniform crystals of better morphology and purity than their terrestrial/control counterparts. The external surfaces of zeolite A, X, and Silicalite crystals grown in microgravity were smoother (lower surface roughness) than their terrestrial controls. Catalytic studies with zeolite Beta indicate that crystals grown in space exhibit a lower number of Lewis acid sites located in micropores. This suggests fewer structural defects for crystals grown in microgravity. Transmission electron micrographs (TEM) of zeolite Beta crystals also show that crystals grown in microgravity were free of line defects while terrestrial/controls had substantial defects.

  17. Synthetic zeolites as a new tool for drug delivery.

    PubMed

    Rimoli, Maria G; Rabaioli, Maria R; Melisi, Daniela; Curcio, Annalisa; Mondello, Sandro; Mirabelli, Rosella; Abignente, Enrico

    2008-10-01

    Synthetic zeolites were studied in order to investigate their ability to encapsulate and to release drugs. In particular, a zeolite X and a zeolitic product obtained from a cocrystallization of zeolite X and zeolite A were examined. These materials were characterized by chemical analyses (ICP-AES), X-ray diffraction, nitrogen adsorption isotherm, scanning electron microscopy, laser diffraction, and infrared spectroscopy. Since ketoprofen was chosen as a model drug for the formulation of controlled-release dosage forms, it was encapsulated into these two types of synthetic zeolites by a soaking procedure. Drug-loaded matrices were then characterized for entrapped drug amount and thermogravimetric behavior. In both types of activated zeolites, the total amount of ketoprofen (800 mg) was encapsulated in 2 g of matrix. By using HPLC measurements, ketoprofen release studies were done at different pH conditions so as to mimick gastrointestinal fluids. The absence of release in acid conditions and a double phased release, at two different pH values (5 and 6.8), suggest that after activation these materials offer good potential for a modified release delivery system of ketoprofen. PMID:18085645

  18. Distribution of metal and adsorbed guest species in zeolites

    SciTech Connect

    Chmelka, B.F.

    1989-12-01

    Because of their high internal surface areas and molecular-size cavity dimensions, zeolites are used widely as catalysts, shape- selective supports, or adsorbents in a variety of important chemical processes. For metal-catalyzed reactions, active metal species must be dispersed to sites within the zeolite pores that are accessible to diffusing reactant molecules. The distribution of the metal, together with transport and adsorption of reactant molecules in zeolite powders, are crucial to ultimate catalyst performance. The nature of the metal or adsorbed guest distribution is known, however, to be dramatically dependent upon preparatory conditions. Our objective is to understand, at the molecular level, how preparatory treatments influence the distribution of guest species in zeolites, in order that macroscopic adsorption and reaction properties of these materials may be better understood. The sensitivity of xenon to its adsorption environment makes {sup 129}Xe NMR spectroscopy an important diagnostic probe of metal clustering and adsorbate distribution processes in zeolites. The utility of {sup 129}Xe NMR depends on the mobility of the xenon atoms within the zeolite-guest system, together with the length scale of the sample heterogeneity being studied. In large pore zeolites containing dispersed guest species, such as Pt--NaY, {sup 129}Xe NMR is insensitive to fine structural details at room temperature.

  19. Electron transfer reactions within zeolites: Radical cation from benzonorbornadiene

    SciTech Connect

    Pitchumani, K.; Ramamurthy, V.; Corbin, D.R.

    1996-08-28

    Zeolites are being used as solid acid catalysts in a number of commercial processes. Occasionally zeolites are also reported to perform as electron transfer agents. Recently, we observed that radical cations of certain olefins and thiophene oligomers can be generated spontaneously within ZSM-5 zeolites. We noticed that these radical cations generated from diphenyl polyenes and thiophene oligomers were remarkably stable (at room temperature) within ZSM-5 and can be characterized spectroscopically at leisure. We have initiated a program on electron transfer processes within large pore zeolites. The basis of this approach is that once a cation radical is generated within a large pore zeolite, it will have sufficient room to undergo a molecular transformation. Our aim is to identify a condition under which electron transfer can be routinely and reliably carried out within large pore zeolites such as faujasites. To our great surprise, when benzonorbornadiene A and a number of olefins were included in divalent cation exchanged faujasites. they were transformed into products very quickly (<15 min). This observation allowed us to explore the use of zeolites as oxidants. Results of our studies on benzonorbornadiene are presented in this communication. 16 refs., 1 fig.

  20. Compositional effects on aluminum and silicon coordination changes in high pressure aluminosilicate glasses: NMR results

    NASA Astrophysics Data System (ADS)

    Kelsey, K. E.; Stebbins, J. F.; Asimow, P. D.; Mosenfelder, J. L.

    2007-12-01

    Understanding the structure of high pressure aluminosilicate glasses can better constrain the macroscopic properties and igneous processes in the upper mantle. As melts densify, bond angles and distances change and the average coordination number (CN) for the cations increases. Both Al and Si can increase CN, and are affected by the type and amount of network modifying cation (i.e. Ca, Mg, Na, K, etc...) present. This study uses nuclear magnetic resonance (NMR) spectroscopy to investigate several aspects of the compositional controls on the structure of aluminosilicate glasses quenched from liquids at high pressure. 29Si MAS NMR spectra of 6GPa Na2Si4O9 glasses show the presence of 2 % [5]Si and 2 % [6]Si. A similar glass with 1.2 wt % Al2O3 and the same nominal NBO/T has very similar Si coordinations, even though the Al has an average CN of 5.4. Thus, although Al increases CN more readily than does Si, the addition of Al does not inhibit the formation of high coordination Si. Extending the previously investigated range of modifier cation field strength, 27Al MAS NMR spectra of LaAlSi3O9 glasses show a substantial increase in average Al CN, from about 4.21 to 5.07 from ambient P to 8GPa, while Li3AlSi3O9 glasses have consistently lower average Al CN, increasing from 4.02 to 4.48 from ambient P to 6 GPa. This agrees with previously noted trends with modifier cation field strength. However, at 6 and 8 GPa the average Al CN is less than expected in the La-containing glasses, suggesting that the La3+ environment changes as well. 17O 3QMAS NMR spectra of the Li-containing glasses are consistent with previously proposed mechanisms for the generation of [5],[6]Al at the expense of non-bridging oxygen, but the La-containing glasses have nearly unchanged oxygen environments with increasing pressure. Finally, we present 27Al MAS NMR spectra of Na+Ca-bearing aluminosilicate glasses with up to 5 wt % FeO quenched from melts at 5 GPa and conclude that the substitution of small amounts of Fe2+ for Ca2+ does not significantly affect the average Al CN.

  1. Preparation and characterization of cesium-137 aluminosilicate pellets for radioactive source applications

    SciTech Connect

    Schultz, F.J.; Tompkins, J.A.; Haff, K.W.; Case, F.N.

    1981-07-01

    Twenty-seven fully loaded /sup 137/Cs aluminosilicate pellets were fabricated in a hot cell by the vacuum hot pressing of a cesium carbonate/montmorillonite clay mixture at 1500/sup 0/C and 570 psig. Four pellets were selected for characterization studies which included calorimetric measurements, metallography, scanning electron microscope and electron backscattering (SEM-BSE), electron microprobe, x-ray diffraction, and cesium ion leachability measurements. Each test pellet contained 437 to 450 curies of /sup 137/Cs as determined by calorimetric measurements. Metallographic examinations revealed a two-phase system: a primary, granular, gray matrix phase containing large and small pores and small pore agglomerations, and a secondary fused phase interspersed throughout the gray matrix. SEM-BSE analyses showed that cesium and silicon were uniformly distributed throughout both phases of the pellet. This indicated that the cesium-silicon-clay reaction went to completion. Aluminum homogeneity was unconfirmed due to the high background noise associated with the inherent radioactivity of the test specimens. X-ray diffraction analyses of both radioactive and non-radioactive aluminosilicate pellets confirmed the crystal lattice structure to be pollucite. Cesium ion quasistatic leachability measurements determined the leach rates of fully loaded /sup 137/Cs sectioned pollucite pellets to date to be 4.61 to 34.4 x 10/sup -10/ kg m/sup -2/s/sup -1/, while static leach tests performed on unsectioned fully loaded pellets showed the leach rates of the cesium ion to date to be 2.25 to 3.41 x 10/sup -12/ kg m/sup -2/s/sup -1/. The cesium ion diffusion coefficients through the pollucite pellet were calculated using Fick's first and second laws of diffusion. The diffusion coefficients calculated for three tracer level /sup 137/Cs aluminosilicate pellets were 1.29 x 10/sup -16/m/sup 2/s/sup -1/, 6.88 x 10/sup -17/m/sup 2/s/sup -1/, and 1.35 x 10/sup -17/m/sup 2/s/sup -1/, respectively.

  2. Liquid crystalline polymers

    NASA Technical Reports Server (NTRS)

    1990-01-01

    The remarkable mechanical properties and thermal stability of fibers fabricated from liquid crystalline polymers (LCPs) have led to the use of these materials in structural applications where weight savings are critical. Advances in processing of LCPs could permit the incorporation of these polymers into other than uniaxial designs and extend their utility into new areas such as nonlinear optical devices. However, the unique feature of LCPs (intrinsic orientation order) is itself problematic, and current understanding of processing with control of orientation falls short of allowing manipulation of macroscopic orientation (except for the case of uniaxial fibers). The current and desirable characteristics of LCPs are reviewed and specific problems are identified along with issues that must be addressed so that advances in the use of these unique polymers can be expedited.

  3. Single crystalline magnetite nanotubes.

    PubMed

    Liu, Zuqin; Zhang, Daihua; Han, Song; Li, Chao; Lei, Bo; Lu, Weigang; Fang, Jiye; Zhou, Chongwu

    2005-01-12

    We descried a method to synthesize single crystalline Fe3O4 nanotubes by wet-etching the MgO inner cores of MgO/Fe3O4 core-shell nanowires. Homogeneous Fe3O4 nanotubes with controllable length, diameter, and wall thickness have been obtained. Resistivity of the Fe3O4 nanotubes was estimated to be approximately 4 x 10-2 Omega cm at room temperature. Magnetoresistance of approximately 1% was observed at T = 77 K when a magnetic field of B = 0.7 T was applied. The synthetic strategy presented here may be extended to a variety of materials such as YBCO, PZT, and LCMO which should provide ideal candidates for fundamental studies of superconductivity, piezoelectricity, and ferromagnetism in nanoscale structures. PMID:15631421

  4. Novel long-term immobilization method for radioactive iodine-129 using a zeolite/apatite composite sintered body.

    PubMed

    Watanabe, Yujiro; Ikoma, Toshiyuki; Yamada, Hirohisa; Suetsugu, Yasushi; Komatsu, Yu; Stevens, Geoffrey W; Moriyoshi, Yusuke; Tanaka, Junzo

    2009-07-01

    The amount of radioactive iodine generated from nuclear power plants is expected to increase with the proliferation of nuclear energy production, and long-term immobilization methods for such radioactive elements need to be developed to make nuclear energy sustainable. The standard immobilization method of radioactive elements, vitrification, is not very effective for radioactive iodine-129 because of the low solubility of iodine in silicate melts, its very high volatility at standard vitrification process temperatures, and its instability in the alkaline environment of deep geological layers below 300 m. We have developed a novel three-phase ceramic composite produced by a sintering process. Iodine adsorbed onto Ca-type zeolite A was covered with a hydroxyapatite nanolayer through the exchange reaction of ammonium with calcium. Clusters of iodine of 30 nm within the zeolite structure were found to be thermally stable up to 1253 K because of the partial blockage of the alpha-cage apertures by ammonium ions and the partial change from a crystalline phase to an amorphous phase at 473 K. No gasification of iodine molecules was found to occur during the sintering process. The outer phase was highly crystalline hydroxyfluorapatite in which the hydroxyapatite nanolayer plays an important role for successful sintering. The elution of iodine in low-dioxygen water, similar to that found within the Earth's crust, was investigated and was found to occur only in the surface layer of the sintered body. PMID:20355964

  5. Quantitatively Probing the Al Distribution in Zeolites

    SciTech Connect

    Vjunov, Aleksei; Fulton, John L.; Huthwelker, Thomas; Pin, Sonia; Mei, Donghai; Schenter, Gregory K.; Govind, Niranjan; Camaioni, Donald M.; Hu, Jian Z.; Lercher, Johannes A.

    2014-06-11

    The degree of substitution of Si4+ by Al3+ in the oxygen-terminated tetrahedra (Al T-sites) of zeolites determines the concentration of ion-exchange and Brønsted acid sites. As the location of the tetrahedra and the associated subtle variations in bond angles influence the acid strength, quantitative information about Al T-sites in the framework is critical to rationalize catalytic properties and to design new catalysts. A quantitative analysis is reported that uses a combination of extended X-ray absorption fine structure (EXAFS) analysis and 27Al MAS NMR spectroscopy supported by DFT-based molecular dynamics simulations. To discriminate individual Al atoms, sets of ab initio EXAFS spectra for various T-sites are generated from DFT-based molecular dynamics simulations allowing quantitative treatment of the EXAFS single- and multiple-photoelectron scattering processes out to 3-4 atom shells surrounding the Al absorption center. It is observed that identical zeolite types show dramatically different Al-distributions. A preference of Al for T-sites that are part of one or more 4-member rings in the framework over those T-sites that are part of only 5- and 6-member rings in the HBEA150 sample has been determined from a combination of these methods. This work was supported by the U. S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences.

  6. Direct vibrational energy transfer in zeolites

    NASA Astrophysics Data System (ADS)

    Brugmans, Marco J. P.; Bakker, Huib J.; Lagendijk, Ad

    1996-01-01

    With two-color picosecond infrared laser spectroscopy the dynamics of O-H and O-D stretch vibrations in zeolites are investigated. Zeolites appear to be good model systems to study transfer of vibrational energy in a solid. For the O-D vibrations, transient spectral holes are burnt in the inhomogeneously broadened absorption bands by saturating the absorption with a strong pump pulse. From the spectral hole widths the homogeneous absorption linewidths are obtained. The excited population lifetimes are determined using a time-resolved pump-probe technique, and in combination with the homogeneous linewidth the pure dephasing time is revealed as well. For high concentrations of O-H oscillators the vibrational stretch excitations are found to diffuse spectrally through the inhomogeneous absorption band. This spectral diffusion process is explained by direct site-to-site transfer of the excitations due to dipole-dipole coupling (Förster transfer). The dependences of the transient spectral signals on oscillator concentration and the results of one-color polarization resolved experiments confirm this explanation. The spectral transients are satisfactorily described by simulations in which the site-to-site transfer by dipole-dipole coupling is taken into account.

  7. Gallium Zeolites for Light Paraffin Aromatization

    SciTech Connect

    Price, G.L.; Dooley, K.M.

    1999-02-10

    The primary original goal of this project was to investigate the active state of gallium-containing MFI catalysts for light paraffin aromatization, in particular the state of gallium in the active material. Our original hypothesis was that the most active and selective materials were those which contained gallium zeolitic cations, and that previously reported conditions for the activation of gallium-containing catalysts served to create these active centers. We believed that in high silica materials such as MFI, ion-exchange is most effectively accomplished with metals in their 1+ oxidation state, both because of the sparsity of the anionic ion-exchange sites associated with the zeolite, and because the large hydration shells associated with aqueous 3+ cations hinder transport. Metals such as Ga which commonly exist in higher oxidation states need to be reduced to promote ion-exchange and this is the reason that reduction of gallium-containing catalysts for light paraffin aromatization often yields a dramatic enhancement in catalytic activity. We have effectively combined reduction with ion-exchange and we term this combined process ''reductive solid-state ion-exchange''. Our hypothesis has largely been proven true, and a number of the papers we have published directly address this hypothesis.

  8. Method of preparing sodalite from chloride salt occluded zeolite

    DOEpatents

    Lewis, Michele A. (Naperville, IL); Pereira, Candido (Lisle, IL)

    1997-01-01

    A method for immobilizing waste chloride salts containing radionuclides and hazardous nuclear material for permanent disposal starting with a substantially dry zeolite and sufficient glass to form leach resistant sodalite with occluded radionuclides and hazardous nuclear material. The zeolite and glass are heated to a temperature up to about 1000.degree. K. to convert the zeolite to sodalite and thereafter maintained at a pressure and temperature sufficient to form a sodalite product near theoretical density. Pressure is used on the formed sodalite to produce the required density.

  9. Zeolite crystal growth in space - What has been learned

    NASA Technical Reports Server (NTRS)

    Sacco, A., Jr.; Thompson, R. W.; Dixon, A. G.

    1993-01-01

    Three zeolite crystal growth experiments developed at WPI have been performed in space in last twelve months. One experiment, GAS-1, illustrated that to grow large, crystallographically uniform crystals in space, the precursor solutions should be mixed in microgravity. Another experiment evaluated the optimum mixing protocol for solutions that chemically interact ('gel') on contact. These results were utilized in setting the protocol for mixing nineteen zeolite solutions that were then processed and yielded zeolites A, X and mordenite. All solutions in which the nucleation event was influenced produced larger, more 'uniform' crystals than did identical solutions processed on earth.

  10. Radiation effects on a zeolite ion exchanger and a pollucite

    SciTech Connect

    Komarneni, S.; Palau, G.L.; Pillay, K.K.S.

    1983-01-01

    Cation exchange capacity and selective Cs and Sr ion sorption measurements were found to be too insensitive to detect radiation effects on irradiated Ionsiv-IE-95 zeolite. However, leaching the zeolite while under ..gamma..-irradiation caused a modest increase in the desorption of exchangeable ions. Gamma-irradiation and subsequent leaching of a natural pollucite also slightly enhanced the leachability of this material. The increased desorption of ions from the zeolite and the enhanced leachability of the pollucite are apparently caused by a decrease in pH due to the generation of acidic species during irradiation.

  11. Method of preparing sodalite from chloride salt occluded zeolite

    DOEpatents

    Lewis, M.A.; Pereira, C.

    1997-03-18

    A method is described for immobilizing waste chloride salts containing radionuclides and hazardous nuclear material for permanent disposal starting with a substantially dry zeolite and sufficient glass to form leach resistant sodalite with occluded radionuclides and hazardous nuclear material. The zeolite and glass are heated to a temperature up to about 1000 K to convert the zeolite to sodalite and thereafter maintained at a pressure and temperature sufficient to form a sodalite product near theoretical density. Pressure is used on the formed sodalite to produce the required density.

  12. Electrical Characteristics of Mesoporous Pure-Silica-Zeolite Film

    NASA Astrophysics Data System (ADS)

    Seo, Toshiki; Yoshino, Takenobu; Cho, Yoshinori; Hata, Nobuhiro; Kikkawa, Takamaro

    2007-09-01

    The dependence of the electrical characteristics of hydrothermally crystallized pure-silica-zeolite films on the water concentration in the precursor was investigated. Zeolite was crystallized in a silica-zeolite composite film after spin-coating the precursor, which was composed of tetraethylorthosilicate, tetrabutylammonium hydroxide, ethylalcohol, and deionized (DI) water, followed by calcinations at 400 °C. The results of Fourier-transform infrared (FT-IR) spectroscopy indicated that the number of Si-OH and O-H bonds decreased with an increase in the water concentration in the precursor. The dielectric constant of the film decreased with an increase in water concentration, while the leakage current increased.

  13. Alkylation of phenol with methanol on high-silica zeolites

    SciTech Connect

    Agaev, A.A.; Tagrev, D.B.

    1986-06-01

    This paper presents results obtained in a study of alkylation of phenol with methanol on high-silica zeolites of the TsVM type. The results of the study of alklation at different temperatures show that at relatively low temperatures the predominant reaction product on HTsVM zeolite is anisole, the yield of which reaches 45.7-65.7%. Rise of temperature influences the isomeric composition of cresols, favoring formation of the meta isomer. It is shown that Pd cations have a beneficial effect on the activity and selectivity of zeolite catalysts inthis reaction.

  14. High pressure synthesis of novel, zeolite based nano-composite materials

    NASA Astrophysics Data System (ADS)

    Santoro, Mario

    2013-06-01

    Meso/micro-porous solids such as zeolites are complex materials exhibiting an impressive range of applications, including molecular sieve, gas storage, catalysis, electronics and photonics. We used these materials, particularly non catalytic zeolites in an entirely different fashion. In fact, we performed high pressure (0.5-30 GPa) chemical reactions of simple molecules on a sub-nanometer scale in the channels of a pure SiO2 zeolite, silicalite to obtain unique nano-composite materials with drastically modified physical and chemical properties. Our material investigations are based on a combination of X-ray diffraction and optical spectroscopy techniques in the diamond anvil cell. I will first briefly show how silicalite can be easily filled by simple molecules such as Ar, CO2 and C2H4 among others from the fluid phase at high pressures, and how this efficient filling removes the well known pressure induced amorphization of the silica framework (Haines et al., JACS 2010). I will then present on a silicon carbonate crystalline phase synthesized by reacting silicalite and molecular CO2 that fills the nano-pores, at 18-26 GPa and 600-980 K; after the synthesis the compound is temperature quenched and it results to be slightly metastable at room conditions (Santoro et al., PNAS 2011). On the other hand, a stable at room condition spectacular crystalline nano-composite is obtained by photo-polymerizing ethylene at 0.5-1.5 GPa under UV (351-364 nm) irradiation in the channels of silicalite (Santoro et al., Nat. Commun, in press 2013). For this composite we obtained a structure with single polyethylene chains adapting very well to the confining channels, which results in significant increases in bulk modulus and density, and the thermal expansion coefficient changes sign from negative to positive with respect to the original silicalite host. Mechanical properties may thus be tuned by varying the amount of polymerized ethylene. We then think our findings could allow the high pressure, catalyst free synthesis of a unique generation of technological, functional materials based on simple hydrocarbons polymerized in confining meso/micro-porous solids.

  15. Laser-induced refractive index gratings formed in Pr3+-doped sodium-magnesium-aluminosilicate glasses

    NASA Astrophysics Data System (ADS)

    Hamad, Abdulatif Y.; Wicksted, James P.

    2005-03-01

    We report a systematic study of grating formation in which the Pr2O3 concentration [Pr2O3] in sodium-magnesium-aluminosilicate glasses is varied from 0.5to5mol%. The grating kinetics is reported as functions of the [Pr2O3] and the write-beam irradiance. The maximum persistent change in the index of refraction was 1×10-5. The persistent change in the index of refraction initially decreased linearly as a function of the [Pr2O3] and showed a limiting behavior at the highest [Pr2O3]. No appreciable transient change in the index of refraction, Δntran, was measured. This was attributed to the low probability of the multiphonon relaxation of the P03 level of the Pr3+ ions as determined through fluorescence measurements. The results of this study are consistent with a recently developed small modifier diffusion model.

  16. Passive Q-switching of erbium glass laser by magnesium aluminosilicate sitall with cobalt ions

    NASA Astrophysics Data System (ADS)

    Volk, Yu. V.; Malyarevich, A. M.; Yumashev, K. V.; Dymshits, O. S.; Shashkin, A. V.; Zhilin, A. A.

    2007-01-01

    We have studied the radiation output parameters for an erbium glass laser, lasing at a wavelength of 1.54 µm, with passive Q-switching by means of a cobalt-containing magnesium aluminosilicate sitall compared with a saturable absorber based on a magnesium aluminum spinel crystal with cobalt ions. We have shown that the output characteristics of the laser emission when using sitall are not inferior to the analogous characteristics of a laser based on a spinel crystal, and are practically independent of the temperature of the saturable absorber in the range 0°C 80°C. The duration (energy) of the output pulses was 70 nsec (˜4 mJ), the energy dispersion of the radiation pulse relative to the average value was no greater than 3%, the beam divergence was 2.8 mrad, the laser beam quality factor was M2 = 1.2.

  17. Spectroscopic properties of magnesium aluminosilicate glass-ceramics doped with divalent cobalt ions

    NASA Astrophysics Data System (ADS)

    Malyarevich, A. M.; Denisov, I. A.; Yumashev, K. V.; Dymshits, O. S.; Zhilin, A. A.; Shashkin, A. V.

    2002-10-01

    Electronic absorption and luminescence spectra and nonlinear optical properties of magnesium aluminosilicate glass-ceramics doped with divalent cobalt ions are studied in relation to their synthesis conditions. The lifetimes of the 4 T 1(4 P) and 4 T 1(4 F) excited levels of tetracoordinate Co2+ ions in these glass-ceramics are found to depend on the cobalt concentration and lie within the ranges from 25 to 40 and from 120 to 450 ns, respectively. Using the absorption saturation curves, the ground state absorption cross section for the wave-length of 1.54 μm is estimated to be σGSA=3.3×10-19cm2. The induced emission of the tetrahedrally coordinated Co2+ ion, which dominates over the absorption from the excited state in the spectral range from 640 to 690 nm (4 T 1(4 P)→4 A 2 transition), is found.

  18. Effect of additions of aluminosilicate and silicate materials on the softening temperature of chromite ore

    NASA Astrophysics Data System (ADS)

    Zhdanov, A. V.; Nurmaganbetova, B. N.; Pavlov, V. A.

    2015-07-01

    The temperatures of the beginning and end of softening and the temperature range of softening of the fines of the rich chromite ore of the Donskoy Ore Mining & Processing Plant in Kazakhstan are experimentally determined. The following natural and technical silica-containing materials, which are considered as fluxing additions to decrease the melting temperature of the chromite ore, are investigated: aluminosilicate clays, microsilica, and quartzite of various fractions. The effect of additions of the natural and technical silica-containing materials on the temperatures of the beginning and end of softening and the temperature range of softening of the chromite ore of DODPE is analyzed. The influences of various materials and their fraction compositions on the temperature of softening of the chromite ores are compared.

  19. Tailoring of Boehmite-Derived Aluminosilicate Aerogel Structure and Properties: Influence of Ti Addition

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.; Guo, Haiquan; Sheets, Erik J.; Miller, Derek R.; Newlin, Katy N.

    2010-01-01

    Aluminosilicate aerogels offer potential for extremely low thermal conductivities at temperatures greater than 900 C, beyond where silica aerogels reach their upper temperature limits. Aerogels have been synthesized at various Al:Si ratios, including mullite compositions, using Boehmite (AlOOH) as the Al source, and tetraethoxy orthosilicate as the Si precursor. The Boehmite-derived aerogels are found to form by a self-assembly process of AlOOH crystallites, with Si-O groups on the surface of an alumina skeleton. Morphology, surface area and pore size varies with the crystallite size of the starting Boehmite powder, as well as with synthesis parameters. Ternary systems, including Al-Si-Ti aerogels incorporating a soluble Ti precursor, are possible with careful control of pH. The addition of Ti influences sol viscosity, gelation time pore structure and pore size distribution, as well as phase formation on heat treatment.

  20. Interactions between C.I. Basic Blue 41 and aluminosilicate sorbents.

    PubMed

    Roulia, Maria; Vassiliadis, Alexandros A

    2005-11-01

    Four aluminosilicate sorbents (montmorillonite, bentonite, raw perlite, and expanded perlite) were employed for retention of the cationic dye C.I. Basic Blue 41. Interactions between the clay and the dyestuff were investigated at several temperatures and clay:dye ratios. The mechanism behind the adsorption involves the formation of H-aggregates of the dye on both clays, followed by dye migration into the interlayer in the case of montmorillonite. Time-dependent absorbance spectra revealed the presence of various dye species in montmorillonite. Introduction of the dye molecules into the interlamellar space occurs more rapidly in bentonite than in montmorillonite. The dye molecules inserted between the clay leaves adopt different orientations and, eventually, stack in layers at increased dye loadings for both montmorillonite and bentonite. Higher dye aggregates are then present as suggested by diffuse reflectance spectroscopy. Dye sorption on both raw and expanded perlite proceeds via H-aggregate formation as well. PMID:15990108

  1. Advanced analyses of 57Fe Mössbauer data of alumino-silicate glasses

    NASA Astrophysics Data System (ADS)

    Rossano, S.; Behrens, H.; Wilke, M.

    2008-03-01

    57Fe Mössbauer spectra of iron bearing alumino-silicate glasses are analysed by two complementary methods (SID and x-VBF) especially adapted for the analysis of disordered systems by taking into account distributions of hyperfine Mössbauer parameters. Qualitative and quantitative information about the oxidation state of iron are obtained as well as information about the distribution of local environments of iron. The possibility to separate the signal of ferric iron from that of ferrous iron allows to derive precise redox ratio in favourable cases but also to analyse more sharply the different contributions to Mössbauer spectra. Using two different glass series (feldspar composition, haplo-tonalitic composition), the characteristics of the two methods are described and employed to study the effect of composition, water incorporation and oxidation state on the glass structure. Optical absorption spectroscopy is used to support the interpretation of the Mössbauer spectra in case of the feldspar glasses.

  2. Martian volatiles in shergottite EETA 79001 - New evidence from oxidized sulfur and sulfur-rich aluminosilicates

    NASA Technical Reports Server (NTRS)

    Gooding, J. L.; Muenow, D. W.

    1986-01-01

    Two equivalent chips of lithology A (lith-A) and lithology C (lith-C) taken from the same interior portion of EETA 79001 shergottite have been analyzed for volatile species produced by high-vacuum pyrolysis. The lith-C was found to contain an oxidized sulfur component that does not occur in lith-A. The preterrestrial origin of this component in lith-C is supported by the occurrence in lith-C of sulfur- and chlorine-rich aluminosilicates that are not the same as Antarctic weathering products found in the control samples. The oxidation state and distribution of sulfur found in lith-C are consistent with the interpretation of EETA 79001 as a rock from Mars.

  3. Calcium-magnesium Aluminosilicate (CMAS) Interactions with Advanced Environmental Barrier Coating Material

    NASA Technical Reports Server (NTRS)

    Wiesner, Valerie L.; Bansal, Narottam P.

    2015-01-01

    Particulates, like sand and volcanic ash, threaten the development of robust environmental barrier coatings (EBCs) that protect next-generation silicon-based ceramic matrix composite (CMC) turbine engine components from harsh combustion environments during service. The siliceous particulates transform into molten glassy deposits of calcium-magnesium aluminosilicate (CMAS) when ingested by an aircraft engine operating at temperatures above 1200C. In this study, a sample of desert sand was melted into CMAS glass to evaluate high-temperature interactions between the sand glass and an advanced EBC material. Desert sand glass was added to the surface of hot-pressed EBC substrates, which were then heated in air at temperatures ranging from 1200C to 1500C. Scanning electron microscopy and X-ray energy-dispersive spectroscopy were used to evaluate microstructure and phase compositions of specimens and the CMASEBC interface after heat treatments.

  4. Enhanced room-temperature emission in Cr4+ ions containing alumino-silicate glasses

    NASA Astrophysics Data System (ADS)

    Batchelor, C.; Chung, W. J.; Shen, S.; Jha, A.

    2003-06-01

    The Bi2O3 modified alumino-silicate glasses, when excited at 800 nm exhibited a broadband emission of Cr4+ in the range of 1.2 to ˜1.6 μm at room temperature. The mean lifetime of (1E-3A2)→3T1 transition in Cr4+-doped glass at RT was as long as ˜426 μs, enabling the realization of both tunable lasers and broadband fiber amplifiers. The Cr4+ emission at RT also showed the dependency on the excitation wavelength and site distribution within the chosen glass host. A photoinduced charge transfer process from the Cr3+ ion into Cr4+ ion appears to be responsible for the excitation of Cr4+.

  5. Structure and properties of sodium aluminosilicate glasses from molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Xiang, Ye; Du, Jincheng; Smedskjaer, Morten M.; Mauro, John C.

    2013-07-01

    Addition of alumina to sodium silicate glasses considerably improves the mechanical properties and chemical durability and changes other properties such as ionic conductivity and melt viscosity. As a result, aluminosilicate glasses find wide industrial and technological applications including the recent Corning® Gorilla® Glass. In this paper, the structures of sodium aluminosilicate glasses with a wide range of Al/Na ratios (from 1.5 to 0.6) have been studied using classical molecular dynamics simulations in a system containing around 3000 atoms, with the aim to understand the structural role of aluminum as a function of chemical composition in these glasses. The short- and medium-range structures such as aluminum coordination, bond angle distribution around cations, Qn distribution (n bridging oxygen per network forming tetrahedron), and ring size distribution have been systematically studied. In addition, the mechanical properties including bulk, shear, and Young's moduli have been calculated and compared with experimental data. It is found that aluminum ions are mainly four-fold coordinated in peralkaline compositions (Al/Na < 1) and form an integral part of the rigid silicon-oxygen glass network. In peraluminous compositions (Al/Na > 1), small amounts of five-fold coordinated aluminum ions are present while the concentration of six-fold coordinated aluminum is negligible. Oxygen triclusters are also found to be present in peraluminous compositions, and their concentration increases with increasing Al/Na ratio. The calculated bulk, shear, and Young's moduli were found to increase with increasing Al/Na ratio, in good agreement with experimental data.

  6. Prospects and challenges of iron pyroelectrolysis in magnesium aluminosilicate melts near minimum liquidus temperature.

    PubMed

    Ferreira, N M; Kovalevsky, A V; Mikhalev, S M; Costa, F M; Frade, J R

    2015-04-14

    Although steel production by molten oxide electrolysis offers potential economic and environmental advantages over classic extractive metallurgy, its feasibility is far from being convincingly demonstrated, mainly due to inherent experimental difficulties exerted by harsh conditions and lack of knowledge regarding relevant mechanisms and physico-chemical processes in the melts. The present work was intended to demonstrate the concept of pyroelectrolysis at very high temperature near the minimum liquidus point of magnesium aluminosilicate, being conducted under electron-blocking conditions using yttria-stabilized zirconia cells, and to provide a new insight into electrochemistry behind this process. Significant current yields are possible for pyroelectrolysis performed in electron-blocking mode using a solid electrolyte membrane to separate the anode and the molten electrolyte. Parasitic electrochemical processes rise gradually as the concentration of iron oxide dissolved in the molten electrolytes is depleted, impairing faradaic efficiency. Reduction of silica to metallic silicon was identified as a significant contribution to those parasitic currents, among other plausible processes. Direct pyroelectrolysis without electron blocking was found much less plausible, due to major limitations on faradaic efficiency imposed by electronic leakage and insufficient ionic conductivity of the aluminosilicate melt. Ohmic losses may consume an excessive fraction of the applied voltage, thus failing to sustain the Nernst potential required for reduction to metallic iron. The results suggest the need for further optimization of the molten electrolyte composition to promote ionic conductivity and to suppress electronic transport contribution, possibly, by tuning the Al/Si ratio and altering the network-forming/modifying behaviour of the iron cations. PMID:25760633

  7. Thermal conductivity of pure silica MEL and MFI zeolite thin films

    NASA Astrophysics Data System (ADS)

    Coquil, Thomas; Lew, Christopher M.; Yan, Yushan; Pilon, Laurent

    2010-08-01

    This paper reports the room temperature cross-plane thermal conductivity of pure silica zeolite (PSZ) MEL and MFI thin films. PSZ MEL thin films were prepared by spin coating a suspension of MEL nanoparticles in 1-butanol solution onto silicon substrates followed by calcination and vapor-phase silylation with trimethylchlorosilane. The mass fraction of nanoparticles within the suspension varied from 16% to 55%. This was achieved by varying the crystallization time of the suspension. The thin films consisted of crystalline MEL nanoparticles embedded in a nonuniform and highly porous silica matrix. They featured porosity, relative crystallinity, and MEL nanoparticles size ranging from 40% to 59%, 23% to 47% and 55 nm to 80 nm, respectively. PSZ MFI thin films were made by in situ crystallization, were b-oriented, fully crystalline, and had a 33% porosity. Thermal conductivity of these PSZ thin films was measured at room temperature using the 3? method. The cross-plane thermal conductivity of the MEL thin films remained nearly unchanged around 1.020.10 W m-1 K-1 despite increases in (i) relative crystallinity, (ii) MEL nanoparticle size, and (iii) yield caused by longer nanoparticle crystallization time. Indeed, the effects of these parameters on the thermal conductivity were compensated by the simultaneous increase in porosity. PSZ MFI thin films were found to have similar thermal conductivity as MEL thin films even though they had smaller porosity. Finally, the average thermal conductivity of the PSZ films was three to five times larger than that reported for amorphous sol-gel mesoporous silica thin films with similar porosity and dielectric constant.

  8. Isobutane/2-butene alkylation on ultrastable Y zeolites: Influence of zeolite unit cell size

    SciTech Connect

    Corma, A.; Martinez, A.; Martinez, C. )

    1994-03-01

    The alkylation reaction of isobutane with trans-2-butene has been carried out on a series of steam-dealuminated Y zeolites with unit cell sizes ranging from 2.450 to 2.426 nm. A fixed-bed reactor connected to an automatized multiloop sampling system allowed differential product analysis from very short (1 min or less) to longer times on stream. A maximum in the initial 2-butene conversion was found on samples with unit cell sizes between 2.435 and 2.450 nm. However, the TMP/DMH ratio, i.e., the alkylation-to-oligomerization ratio, continuously increased with zeolite unit cell size. The concentration of reactants in the pores, the strength distribution of Bronsted acid sites, and the extent of hydrogen transfer reactions, which in turn depend on the framework Si/Al ratio of a given zeolite, were seen to affect activity and product distribution of the catalysts. Finally, the influence of these factors on the aging characteristics of the samples was also discussed. 17 refs., 7 figs., 4 tabs.

  9. 12. INTERIOR OF BUILDING 2, ORIGINAL ZEOLITE PLANT, AT WEYMOUTH ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    12. INTERIOR OF BUILDING 2, ORIGINAL ZEOLITE PLANT, AT WEYMOUTH LOOKING WEST TO FOUNTAIN. STAIRWAY RUNS DOWN TO FILTRATION BAYS. - F. E. Weymouth Filtration Plant, 700 North Moreno Avenue, La Verne, Los Angeles County, CA

  10. Influence of the cluster formation on the zeolite crystal lattice

    NASA Astrophysics Data System (ADS)

    Barnakov, Yurii A.; Mitypov, Bair B.; Petranovskii, Vitalii P.; Poborchii, Vladimir V.; Kasuya, Atsuo; Peralez Perez, Oskar J.

    1999-06-01

    Clusters of CdS were prepared inside the framework voids of zeolites NaX and chabazite by multistage ion exchange chemical reaction. It was observed that each stage of reaction affects the structure of zeolites crystals. Aluminum atoms change their coordination state at the first stage because of hydrolytic decomposition of some Al-O tetrahedral bonds. Partially reversible relaxation of aluminum atoms of zeolite framework occurs during the second stage of chemical reaction. This spontaneous transition of the coordination number of aluminum atoms took place without changing of their positions of framework atoms. Such kind of the interaction between framework atoms of alumosilicates and doping ions, which are precursors of the clusters in the zeolite hosts, give indirect information about mechanism of the `ship-in-the-bottle' synthesis of semiconductor materials.

  11. Zeolite - A Natural Filter Material for Lead Polluted Water

    NASA Astrophysics Data System (ADS)

    Neamţu, Corina Ioana; Pică, Elena Maria; Rusu, Tiberiu

    2014-11-01

    Reducing the concentration of lead ions in a wastewater using zeolite has proven to be a successful water treatement method, all over the world. Putting the two media (solid and liquid) in contact in static conditions had good results regarding the concentration of the filtered solution, the pH and the electric conductivity, depending on the values of certain parameters such as the amount of the zeolite, volume of the solution or interaction time. The present study highlights the zeolite ability to retain the lead ions from a solution, in dynamic interaction conditions between the two environments, in a short interaction time. The results confirmed the effectiveness of ion exchange water treatment method in the conditions set, emphasizing once again the properties of the filter material - the zeolite

  12. Comparative study of the removal of coke from protonic zeolites

    SciTech Connect

    Gnep, N.S.; Roger, P.; Magnoux, P.; Guisnet, M.

    1993-12-31

    The transformation of methanol was carried out at 400{degrees}C on four protonic zeolites: USHY (framework Si/Al ratio equal to 5), HZSM5 (Si/Al = 45), two mordenites HMOR (Si/Al = 7.5) and HMORDA (Si/Al = 80) prepared by dealumination of HMOR through hydrothermal and acid treatments. The composition of coke determined through the method developed in the authors` laboratory depended slightly on the zeolite. The amount of coke removed for the zeolites through oxidative treatment was determined as function of the temperature and for various coke contents. The rate of coke removal depended slightly on the coke content and on the coke composition by very much on the zeolite. In particular the coke of HMORDA and of HZSM5 was eliminated at high temperature only.

  13. CO2 capture using zeolite 13X prepared from bentonite

    NASA Astrophysics Data System (ADS)

    Chen, Chao; Park, Dong-Wha; Ahn, Wha-Seung

    2014-02-01

    Zeolite 13X was prepared using bentonite as the raw material by alkaline fusion followed by a hydrothermal treatment without adding any extra silica or alumina sources. The prepared zeolite 13X was characterized by X-ray powder diffraction, N2-adsorption-desorption measurements, and scanning electron microscopy. The CO2 capture performance of the prepared zeolite 13X was examined under both static and flow conditions. The prepared zeolite 13X showed a high BET surface area of 688 m2/g with a high micropore volume (0.30 cm3/g), and exhibited high CO2 capture capacity (211 mg/g) and selectivity to N2 (CO2/N2 = 37) at 25 °C and 1 bar. In addition, the material showed fast adsorption kinetics, and stable CO2 adsorption-desorption recycling performance at both 25 and 200 °C.

  14. Iba of Zeolites Exchanged with Lithium for Co2 Retention

    NASA Astrophysics Data System (ADS)

    Andrade, E.; Alfaro, S.; Valenzuela, M. A.; Solis, C.; Zaval, E. P.; Rocha, M. F.; Cruz, J.; Pfeiffer, H.; Bosch, P.; Contreras, C.; Baptiste, J.

    2009-03-01

    A great concern on the global climatic change, partially due to industry CO2 expelled to the atmosphere, has motivated the search of new materials able to retain this gas. Clays, perovskites, zeolites and membranes have been utilized to trap the CO2. Zeolites are widely used as molecular sieves in different industrial processes related to gas purification or gas separation. Synthetic zeolites exchanged with lithium were prepared as potential material for CO2 retention. A NRA method using the 7Li (p,α)4He was performed in order to measure the the Li contents. With SEM-EDS the atomic concentrations of elements as C, Na, Si, Al, K, Ca, Fe, etc. were determined. Zeolites were also characterized by XRD.

  15. Studies on zeolites: Molecular mechanics, framework stability, and crystal growth

    NASA Astrophysics Data System (ADS)

    Devosburchart, Erik

    Molecular mechanics, framework stability, and crystal growth of zeolites and aluminophosphates, are studied. Both materials belong to the class of molecular sieves, which are important in the industry as ion exchangers, catalysts and adsorbents. The faujasite structure is discussed with respect to the distribution of aluminum atoms and acid sites. Ordered growths between the zeolites X and A are described. Molecular mechanics of MFI type zeolites are studied for: effect of p-xylene adsorption in the zeolite structure; isomorphous substitution by aluminum; the monoclinic orthorhombic phase transition; energetics of crystal growth directing agents; alpha/beta quartz transition. Summation methods for the nonbonded interactions are compared. A consistent molecular mechanics force field for aluminophosphates was developed. A general discussion and conclusion is given covering optimization of force field, parameter set, and computer code.

  16. Topological Crystalline Insulators

    NASA Astrophysics Data System (ADS)

    Hsieh, Timothy

    2015-03-01

    Topological crystalline insulators (TCI) are new phases of matter in which nontrivial band topology and crystal symmetry unite to protect metallic states on the boundary. Remarkably, TCIs have been predicted and observed in the conveniently simple rocksalt SnTe class of IV-VI semiconductors. Despite the simple crystal structure, the interplay between topology and crystal symmetry in these materials have led to a rich variety of new phenomena, including the coexistence of massless and massive Dirac fermions arising from ferroelectric distortion and strain-induced flat band superconductivity. These new physical mechanisms are not only of intrinsic interest but may also find application in new transistor devices. After discussing the topological nature and potential uses of IV-VI family TCIs, I will present recent predictions of TCIs in several anti-perovskite materials. The origin of TCI in this new class of materials is strikingly different and involves the band inversion of two J = 3/2 quartets of Dirac fermions, which together form a ``Dirac octet.'' As interactions play a significant role in many anti-perovskites, this prediction serves as first step toward realizing TCIs in strongly correlated systems. This work is supported by NSF Graduate Research Fellowship No. 0645960 and DOE Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-SC0010526.

  17. Metal Oxide/Zeolite Combination Absorbs H2S

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E.; Sharma, Pramod K.

    1989-01-01

    Mixed copper and molybdenum oxides supported in pores of zeolite found to remove H2S from mixture of gases rich in hydrogen and steam, at temperatures from 256 to 538 degree C. Absorber of H2S needed to clean up gas streams from fuel processors that incorporate high-temperature steam reformers or hydrodesulfurizing units. Zeolites chosen as supporting materials because of their high porosity, rigidity, alumina content, and variety of both composition and form.

  18. Commander Bowersox Tends to Zeolite Crystal Samples Aboard Space Station

    NASA Technical Reports Server (NTRS)

    2003-01-01

    Expedition Six Commander Ken Bowersox spins Zeolite Crystal Growth sample tubes to eliminate bubbles that could affect crystal formation in preparation of a 15 day experiment aboard the International Space Station (ISS). Zeolites are hard as rock, yet are able to absorb liquids and gases like a sponge. By using the ISS microgravity environment to grow better, larger crystals, NASA and its commercial partners hope to improve petroleum manufacturing and other processes.

  19. Structural Role of Alkali Cations in Calcium Aluminosilicate Glasses as Examined Using Oxygen-17 Solid-State Nuclear Magnetic Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sukenaga, Sohei; Kanehashi, Koji; Shibata, Hiroyuki; Saito, Noritaka; Nakashima, Kunihiko

    2016-05-01

    The structural roles of alkali and calcium cations are important for understanding the physical and chemical properties of aluminosilicate melts and glasses. Recently, oxygen-17 nuclear magnetic resonance (17O NMR) studies of calcium-sodium aluminosilicate glasses showed that these structural roles are not randomly given, but rather each cation has its own preferential role. However, the relationship between cation type and role preference in calcium aluminosilicate glass is not completely understood. In the present study, the structural roles of lithium, sodium, and potassium cations in selected calcium aluminosilicate glasses are investigated using 17O solid-state NMR experiments. Data from these experiments clearly show that potassium cations have a notably stronger tendency to act as charge compensators within the network structure, compared to sodium and lithium cations. The result of 17O NMR experiment also showed that sodium and lithium cations in part act as network modifier alongside with calcium cations.

  20. A Novel Conversion Process for Waste Slag: The Preparation of Aluminosilicate Glass with Evaluation of the Dielectric Properties from Blast Furnace Slag

    NASA Astrophysics Data System (ADS)

    Li, Sheng; Huang, Sanxi; Liu, Hongting; Wu, Fengnian; Chang, Ziyuan; Yue, Yunlong

    2015-11-01

    In this paper, aluminosilicate glass was prepared from blast furnace slag and quartz sand. Fourier transform infrared, differential scanning calorimetry and density measurements were carried out to investigate the effects of SiO2 on the aluminosilicate glass network rigidity. The results indicate that glass structure would be enhanced if more SiO2 was introduced into the glass system. Meanwhile, both the glass transition temperature ( T g) and the glass crystallization temperature ( T c) increase slightly; the increase in density of the glass being further evidence of the enhancement in glass network rigidity. Dielectric measurements show that the dielectric constant and dielectric loss decrease with more SiO2. The properties of the prepared aluminosilicate glasses are comparable to those of E glass, indicating that blast furnace slags are suitable for producing aluminosilicate glass with low dielectric constant and dielectric loss.