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Sample records for crystalline aluminosilicate zeolite

  1. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    DOEpatents

    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.

  2. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    DOEpatents

    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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Predicting large CO2 adsorption in aluminosilicate zeolites for postcombustion carbon dioxide capture.

    PubMed

    Kim, Jihan; Lin, Li-Chiang; Swisher, Joseph A; Haranczyk, Maciej; Smit, Berend

    2012-11-21

    Large-scale simulations of aluminosilicate zeolites were conducted to identify structures that possess large CO(2) uptake for postcombustion carbon dioxide capture. In this study, we discovered that the aluminosilicate zeolite structures with the highest CO(2) 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 . These predictors extend well to different Si:Al ratios and for both Na(+) and Ca(2+) cations, demonstrating their universal applicability in identifying the best-performing aluminosilicate zeolite structures. PMID:23137005

  8. Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity.

    PubMed

    Choi, Minkee; Cho, Hae Sung; Srivastava, Rajendra; Venkatesan, Chithravel; Choi, Dae-Heung; Ryoo, Ryong

    2006-09-01

    Zeolites are a family of crystalline aluminosilicate materials widely used as shape-selective catalysts, ion exchange materials, and adsorbents for organic compounds. In the present work, zeolites were synthesized by adding a rationally designed amphiphilic organosilane surfactant to conventional alkaline zeolite synthesis mixtures. The zeolite products were characterized by a complementary combination of X-ray diffraction (XRD), nitrogen sorption, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The analyses show that the present method is suitable as a direct synthesis route to highly mesoporous zeolites. The mesopore diameters could be uniformly tailored, similar to ordered mesoporous silica with amorphous frameworks. The mesoporous zeolite exhibited a narrow, small-angle XRD peak, which is characteristic of the short-range correlation between mesopores, similar to disordered wormhole-like mesoporous materials. The XRD patterns and electron micrographs of the samples taken during crystallization clearly showed the evolution of the mesoporous structure concomitantly to the crystallization of zeolite frameworks. The synthesis of the crystalline aluminosilicate materials with tunable mesoporosity and strong acidity has potentially important technological implications for catalytic reactions of large molecules, whereas conventional mesoporous materials lack hydrothermal stability and acidity. PMID:16892049

  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. Simple strategies for fabrication of a periodic mesoporous aluminosilicate with crystalline walls.

    PubMed

    Do, Manh Huy; Wang, Tuo; Cheng, Dang-guo; Chen, Fengqiu; Zhan, Xiaoli; Rioux, Robert M; Gong, Jinlong

    2014-11-12

    An alkali-assisted cooperative assembly process of two different templating systems with aluminosilicate precursors is described. A highly ordered mesoporous zeolite with the 2D hexagonal symmetry mesospores and MFI zeolitic framework walls is synthesized. This method also allows the preparation of ZSM-5 with c- or b-axis-aligned mesopores. The materials have promising catalytic activities for organic reactions involving bulky molecules. PMID:25049062

  11. 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

  12. Highly mesoporous single-crystalline zeolite beta synthesized using a nonsurfactant cationic polymer as a dual-function template.

    PubMed

    Zhu, Jie; Zhu, Yihan; Zhu, Liangkui; Rigutto, Marcello; van der Made, Alexander; Yang, Chengguang; Pan, Shuxiang; Wang, Liang; Zhu, Longfeng; Jin, Yinying; Sun, Qi; Wu, Qinming; Meng, Xiangju; Zhang, Daliang; Han, Yu; Li, Jixue; Chu, Yueying; Zheng, Anmin; Qiu, Shilun; Zheng, Xiaoming; Xiao, Feng-Shou

    2014-02-12

    Mesoporous zeolites are useful solid catalysts for conversion of bulky molecules because they offer fast mass transfer along with size and shape selectivity. We report here the successful synthesis of mesoporous aluminosilicate zeolite Beta from a commercial cationic polymer that acts as a dual-function template to generate zeolitic micropores and mesopores simultaneously. This is the first demonstration of a single nonsurfactant polymer acting as such a template. Using high-resolution electron microscopy and tomography, we discovered that the resulting material (Beta-MS) has abundant and highly interconnected mesopores. More importantly, we demonstrated using a three-dimensional electron diffraction technique that each Beta-MS particle is a single crystal, whereas most previously reported mesoporous zeolites are comprised of nanosized zeolitic grains with random orientations. The use of nonsurfactant templates is essential to gaining single-crystalline mesoporous zeolites. The single-crystalline nature endows Beta-MS with better hydrothermal stability compared with surfactant-derived mesoporous zeolite Beta. Beta-MS also exhibited remarkably higher catalytic activity than did conventional zeolite Beta in acid-catalyzed reactions involving large molecules. PMID:24450997

  13. 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.

  14. 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

  15. 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

  16. Mesoporous aluminosilicates assembled from dissolved LTA zeolite and triblock copolymer in the presence of tetramethylammonium hydroxide.

    PubMed

    Tanaka, Shunsuke; Okada, Hiroaki; Nakatani, Norihito; Maruo, Takanori; Nishiyama, Norikazu; Miyake, Yoshikazu

    2009-05-15

    Zeolite Na-A crystals dissolved in a HCl solution were used as a single-source of silicon and aluminum for the synthesis of mesoporous aluminosilicates via a template-assisted method with an organic base tetramethylammonium hydroxide (TMAOH). Amphiphilic triblock copolymer Pluronic F127 (EO(106)PO(70)EO(106)) was used as template. Increasing the amount of TMAOH in the synthetic solution resulted in an increase in the aluminum content of the products. On the other hand, mesostructural periodicity was deteriorated with higher content of aluminum incorporated into the mesoporous framework. The samples with low Si/Al ratios less than 5 have wormhole-like pore structure, while the samples with Si/Al ratios more than 7 possess highly ordered mesoporous structure, a body-centered Im3m symmetry, with single crystal like morphology. The samples with Si/Al ratio of 7, which prepared at TMAOH molar concentration of 25 mM in the templating solution, possess BET surface area of 470 m(2)/g, pore size of 6.4 nm, and pore volume of 0.56 cm(3)/g. Aluminum atoms have successfully been incorporated in a tetra-coordinated position and remained stable even after calcination at 600 degrees C. PMID:19223041

  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. Immobilization of Cs and Sr in aluminosilicate matrices derived from natural zeolites

    NASA Astrophysics Data System (ADS)

    Cappelletti, Piergiulio; Rapisardo, Gianmarco; de Gennaro, Bruno; Colella, Abner; Langella, Alessio; Graziano, Sossio Fabio; Bish, David Lee; de Gennaro, Maurizio

    2011-07-01

    Three Italian zeolitized volcanoclastic deposits with predominant phillipsite, chabazite or clinoptilolite were selected to investigate their attitude to form ceramized products of the Cs- and Sr-enriched forms and to evaluate the effectiveness of immobilization by means of leaching tests. The mineralogical evolution was carefully followed after thermal treatments at increasing temperatures (800 C up to 1100 C) which led to the crystallization of prevailing pollucite for Cs-exchanged phillipsite and chabazite and of a Sr-feldspar (about 35 wt.%) along with cristobalite and amorphous matter for all Sr-exchanged zeolites. Cs-enriched clinoptilolite at the same temperature was almost totally amorphous. Leaching tests confirm the substantial immobilization of the polluting cations in the ceramized materials with slight higher values only for the Cs-enriched clinoptilolite, mostly amorphous. Finally, calorimetric tests account for a hydrolysis process widely decreasing after thermal treatments at 1100 C for phillipsite and chabazite, both Cs- and Sr-enriched, substantially similar for Sr-enriched clinoptilolite and definitely increased in the prevailing amorphous Cs-enriched clinoptilolite.

  2. 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

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

    PubMed

    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. 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.

  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. Comparing the activity of aluminum in two B horizons developed from volcanic ash deposits in Japan, dominated by short-range ordered aluminosilicates and crystalline clay minerals, respectively

    NASA Astrophysics Data System (ADS)

    Yagasaki, Yasumi; Mulder, Jan; Okazaki, Masanori

    2006-01-01

    Mechanisms controlling the activity of free aluminum (Al) in Bw1 horizons of soils developed from volcanic ash deposits in Japan were investigated by means of acid-base titrations and kinetic studies. In a Bw1 horizon, with a high content of acid-oxalate extractable Al, soil solution reached equilibrium with short-range ordered aluminosilicates in the order of days. Relatively fast kinetics of the release and precipitation of Al and Si indicate a high reactivity of short-range ordered aluminosilicates in the soil. In the Bw1 horizon of an adjacent soil, with a high content of crystalline clay minerals like halloysite and interlayered vermiculite, solution remained well undersaturated with respect to short-range ordered aluminosilicates and aluminum hydroxide. Apparent equilibrium with respect to halloysite occurred after more than 30 days. This halloysite ( logKso0=3.740.02 (25 C)) has a solubility that is less than that reported in the literature ( logKso0=4.36 (25C)). Our findings suggest that different reactive aluminosilicates may control the activity of free Al in sub-surface horizons of volcanic ash soils with different mineralogy.

  11. 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.

  12. 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.

  13. Conversion of rice husk ash to zeolite beta.

    PubMed

    Prasetyoko, Didik; Ramli, Zainab; Endud, Salasiah; Hamdan, Halimaton; Sulikowski, Bogdan

    2006-01-01

    White rice husk ash (RHA), an agriculture waste containing crystalline tridymite and alpha-cristobalite, was used as a silica source for zeolite Beta synthesis. The crystallization of zeolite Beta from RHA at 150 degrees C in the presence of tetraethylammonium hydroxide was monitored by XRD, FTIR and (29)Si MAS NMR techniques. It was found that zeolite Beta started to form after 12h and the complete crystallization of zeolite Beta phase was achieved after 2d. XRD, (29)Si MAS NMR and solid yield studies indicate that the transformation mechanism of silica present in RHA to zeolite Beta involves dissolution of the ash, formation of an amorphous aluminosilicate after 6h of crystallization, followed by dissolution in the mother liquor and final transformation to pure zeolite Beta crystals. PMID:16274981

  14. 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

  15. 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…

  16. 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

  17. 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

  18. 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

  19. Silicon substituted y zeolite composition lz-210

    SciTech Connect

    Skeels, G.W.; Breck, D.W.

    1987-12-08

    A crystalline zeolitic aluminosilicate is described having at least some of its original framework aluminum atoms replaced by extraneous silicon atoms and having a mole ratio of oxides in the anhydrous state of wherein M is a cation having a valence of ''n''; ''x'' has a value greater than 6.0; has a X-ray powder diffraction pattern having at least the d-spacings of Table A; and has extraneous silicon atoms in the crystal lattice in the form of framework SiO/sub 4/ tetrahedra.

  20. Synthesis strategies in the search for hierarchical zeolites.

    PubMed

    Serrano, D P; Escola, J M; Pizarro, P

    2013-05-01

    Great interest has arisen in the past years in the development of hierarchical zeolites, having at least two levels of porosities. Hierarchical zeolites show an enhanced accessibility, leading to improved catalytic activity in reactions suffering from steric and/or diffusional limitations. Moreover, the secondary porosity offers an ideal space for the deposition of additional active phases and for functionalization with organic moieties. However, the secondary surface represents a discontinuity of the crystalline framework, with a low connectivity and a high concentration of silanols. Consequently, hierarchical zeolites exhibit a less "zeolitic behaviour" than conventional ones in terms of acidity, hydrophobic/hydrophilic character, confinement effects, shape-selectivity and hydrothermal stability. Nevertheless, this secondary surface is far from being amorphous, which provides hierarchical zeolites with a set of novel features. A wide variety of innovative strategies have been developed for generating a secondary porosity in zeolites. In the present review, the different synthetic routes leading to hierarchical zeolites have been classified into five categories: removal of framework atoms, surfactant-assisted procedures, hard-templating, zeolitization of preformed solids and organosilane-based methods. Significant advances have been achieved recently in several of these alternatives. These include desilication, due to its versatility, dual templating with polyquaternary ammonium surfactants and framework reorganization by treatment with surfactant-containing basic solutions. In the last two cases, the materials so prepared show both mesoscopic ordering and zeolitic lattice planes. Likewise, interesting results have been obtained with the incorporation of different types of organosilanes into the zeolite crystallization gels, taking advantage of their high affinity for silicate and aluminosilicate species. Crystallization of organofunctionalized species favours the formation of organic-inorganic composites that, upon calcination, are transformed into hierarchical zeolites. However, in spite of this impressive progress in novel strategies for the preparation of hierarchical zeolites, significant challenges are still ahead. The overall one is the development of methods that are versatile in terms of zeolite structures and compositions, capable of tuning the secondary porosity properties, and being scaled up in a cost-effective way. Recent works have demonstrated that it is possible to scale-up easily the synthesis of hierarchical zeolites by desilication. Economic aspects may become a significant bottleneck for the commercial application of hierarchical zeolites since most of the synthesis strategies so far developed imply the use of more expensive procedures and reagents compared to conventional zeolites. Nevertheless, the use of hierarchical zeolites as efficient catalysts for the production of high value-added compounds could greatly compensate these increased manufacturing costs. PMID:23138888

  1. Process for converting silicon dioxide containing waste flue dust to crystalline zeolitic molecular sieves of type A

    SciTech Connect

    Achenbach, K.; Turk, G.

    1982-01-12

    Silicon dioxide containing waste flue dust from the production of silicon metal and silicon alloys is converted to crystalline zeolite molecular sieves of type A. The process involves: (1) dissolving the flue dust in alkali metal hydroxide solution with the formation of alkali metal silicate solution having a module (SiO/sub 2/:Me/sub 2/IO) in the range of 2.0:1 to 3.5:1 at a temperature of 60/sup 0/-100/sup 0/ C; (2) purifying the thus obtained alkali metal silicate solution from organic constituents by treatment with activated carbon and/or an oxidizing agent and separating the non-decomposable residue from the solution; and, (3) reacting alkali metal aluminate solution present at room temperature with the diluted, purified alkali metal silicate solution with a module (SiO2:Na2O) of 2.0:1 to 5:1 obtained by steps (1) and (2) and subsequent crystallizing the reaction mixture ((2.0-4.4)Na/sub 2/O:Al/sub 2/O/sub 3/; (1.3-1.8)SiO/sub 2/:(90-120)H/sub 2/O) at a temperature of 90/sup 0/-95/sup 0/ C for a period of 6-12 hours, subsequently filtering, washing to ph of about 10-11 and drying to recover a crystalline, zeolitic molecular sieve of type a having a degree of whiteness according to berger (A. Berger, die farbe 8 nr. 4/6 (1959) pages 187-202) at 460 mu in the range of 90-95%.

  2. 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

  3. 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.

  4. 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

  5. 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

  6. 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

  7. Synthesis of 'unfeasible' zeolites.

    PubMed

    Mazur, Michal; Wheatley, Paul S; Navarro, Marta; Roth, Wieslaw J; Poloij, Miroslav; Mayoral, Alvaro; Eliov, Pavla; Nachtigall, Petr; ?ejka, Ji?; 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

  8. 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.

  9. 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.

  10. Microprobes aluminosilicate ceramic membranes

    DOEpatents

    Anderson, Marc A. (2114 Chadbourne Ave., Madison, WI 53705); Sheng, Guangyao (45 N. Orchard St., Madison, WI 53715)

    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.

  11. Rapid synthesis of beta zeolites

    SciTech Connect

    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.

  12. 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.

  13. 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''.

  14. 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.

  15. 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.

  16. Spectroscopic signatures of nitrogen-substituted zeolites.

    PubMed

    Hammond, Karl D; Dogan, Fulya; Tompsett, Geoffrey A; Agarwal, Vishal; Conner, W Curtis; Grey, Clare P; Auerbach, Scott M

    2008-11-12

    Nanoporous acid catalysts such as zeolites form the backbone of catalytic technologies for refining petroleum. With the promise of a biomass economy, new catalyst systems will have to be discovered, making shape-selective base catalysts especially important because of the high oxygen content in biomass-derived feedstocks. Strongly basic zeolites are attractive candidates, but such materials are notoriously difficult to make due to the strong inherent acidity of aluminosilicates. Several research groups have endeavored to produce strongly basic zeolites by treating zeolites with amines, but to date there is no compelling evidence that nitrogen is incorporated into zeolite frameworks. In this communication, we detail synthesis, NMR spectroscopy, and quantum mechanical calculations showing that nitrogen adds onto both surface and interior sites while preserving the framework structure of zeolites. This finding is crucial for the rational design of new biomass-refinement catalysts, allowing 50 years of zeolite science to be brought to bear on the catalytic synthesis of biofuels. PMID:18855470

  17. Zeolite A imidazolate frameworks.

    PubMed

    Hayashi, Hideki; Ct, Adrien P; Furukawa, Hiroyasu; O'Keeffe, Michael; Yaghi, Omar M

    2007-07-01

    Faujasite (FAU) and zeolite A (LTA) are technologically important porous zeolites (aluminosilicates) because of their extensive use in petroleum cracking and water softening. Introducing organic units and transition metals into the backbone of these types of zeolite allows us to expand their pore structures, enhance their functionality and access new applications. The invention of metal-organic frameworks and zeolitic imidazolate frameworks (ZIFs) has provided materials based on simple zeolite structures where only one type of cage is present. However, so far, no metal-organic analogues based on FAU or LTA topologies exist owing to the difficulty imposed by the presence of two types of large cage (super- and beta-cages for FAU, alpha- and beta-cages for LTA). Here, we have identified a strategy to produce an LTA imidazolate framework in which both the link geometry and link-link interactions play a decisive structure-directing role. We describe the synthesis and crystal structures of three porous ZIFs that are expanded analogues of zeolite A; their cage walls are functionalized, and their metal ions can be changed without changing the underlying LTA topology. Hydrogen, methane, carbon dioxide and argon gas adsorption isotherms are reported and the selectivity of this material for carbon dioxide over methane is demonstrated. PMID:17529969

  18. Zeolite A imidazolate frameworks

    NASA Astrophysics Data System (ADS)

    Hayashi, Hideki; Ct, Adrien P.; Furukawa, Hiroyasu; O'Keeffe, Michael; Yaghi, Omar M.

    2007-07-01

    Faujasite (FAU) and zeolite A (LTA) are technologically important porous zeolites (aluminosilicates) because of their extensive use in petroleum cracking and water softening. Introducing organic units and transition metals into the backbone of these types of zeolite allows us to expand their pore structures, enhance their functionality and access new applications. The invention of metal-organic frameworks and zeolitic imidazolate frameworks (ZIFs) has provided materials based on simple zeolite structures where only one type of cage is present. However, so far, no metal-organic analogues based on FAU or LTA topologies exist owing to the difficulty imposed by the presence of two types of large cage (super- and ?-cages for FAU, ?- and ?-cages for LTA). Here, we have identified a strategy to produce an LTA imidazolate framework in which both the link geometry and link-link interactions play a decisive structure-directing role. We describe the synthesis and crystal structures of three porous ZIFs that are expanded analogues of zeolite A; their cage walls are functionalized, and their metal ions can be changed without changing the underlying LTA topology. Hydrogen, methane, carbon dioxide and argon gas adsorption isotherms are reported and the selectivity of this material for carbon dioxide over methane is demonstrated.

  19. Sonochemical synthesis of zeolite NaP from clinoptilolite.

    PubMed

    Behin, Jamshid; Kazemian, Hossein; Rohani, Sohrab

    2016-01-01

    In the present work, natural clinoptilolite was converted to zeolite NaP using ultrasonic energy, in which the transformation time shortened remarkably. The effect of post-synthesis treatment using conventional hydrothermal was also investigated. The synthesized powders were characterized by XRD, TGA/DTA, SEM, and PSD analysis. The results showed that, increasing the sonication time (energy) has no significant effect on the product's morphology. The crystallinity of the synthesized samples increased slightly with increasing sonication time, but their yield remained relatively unchanged. Furthermore, post-synthesis hydrothermal treatment showed very little influence on properties of the final product. Because the ultrasonic irradiation creates acoustic cavitation cracks on the surface structure of clinoptilolite particulates and increases the concentration of soluble alumino-silicate species, which favors the prevailing super-saturation, crystallization and crystal growth of zeolite NaP happen faster. The particles of zeolite NaP synthesized by ultrasonic irradiation consist of small crystallites of uniform size. PMID:26341462

  20. 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

  1. Photochemical charge separation in zeolites: Electron transfer dynamics, nanocrystals and zeolitic membranes. Final technical report

    SciTech Connect

    Dutta, Prabir K.

    2001-09-30

    Aluminosilicate zeolites provide an excellent host for photochemical charge separation. Because of the constraints provided by the zeolite, the back electron transfer from the reduced acceptor to the oxidized sensitizer is slowed down. This provides the opportunity to separate the charge and use it in a subsequent reaction for water oxidation and reduction. Zeolite-based ruthenium oxide catalysts have been found to be efficient for the water splitting process. This project has demonstrated the usefulness of zeolite hosts for photolytic splitting of water.

  2. 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.

  3. Ionic Liquid assisted Synthesis of Zeolite-TON

    PubMed Central

    Tian, Yuyang; McPherson, Matthew J; Wheatley, Paul S; Morris, Russell E

    2014-01-01

    An ionic liquid assisted strategy for the synthesis of zeolitic material is reported. This strategy is a solid state synthetic method and the ionic liquid is employed as structure directing agent. A TON-type zeolite, which contains one-dimensional 10-member-ring, is successfully synthesized with the assistance of the ionic liquid, 1-ethyl-3-methylimidazolium bromide. This finding improves our understanding about the challenge of ionothermally synthesizing siliceous and aluminosilicate zeolites. PMID:26213423

  4. 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.

  5. 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.

  6. SODIUM ZEOLITE A SUPPLEMENTATION TO DAIRY CALVES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sodium zeolite A (SZA), an aluminosilicate, has been used in a number of animal studies, but alterations in mineral metabolism and tissue composition have not been fully investigated. The objective of this study was to determine the effects of SZA on mineral metabolism and tissue mineral composition...

  7. 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.

  8. Demonstrating the benefits and pitfalls of various acidity characterization techniques by a case study on bimodal aluminosilicates.

    PubMed

    Van Oers, Cynthia J; Gra-Marek, Kinga; Prelot, Bndicte; Datka, Jerzy; Meynen, Vera; Cool, Pegie

    2014-02-25

    A new combination of a volumetric with a dynamic method to investigate the acidity properties of aluminosilicates is introduced. In the first step, the total acidity is determined volumetrically by the measurement of two-cycle adsorption (TCA) isotherms with ammonia as a probe, directly followed by a dynamic temperature-programmed desorption (TPD) experiment to define the acid strength distribution. Furthermore, the results obtained by the new direct combination of TCA and TPD are validated by comparison with an in-situ FTIR (Fourier transform infrared) study with the same probe molecule on the same materials. Both acidity characterization techniques are compared, and we comment on their complementarity, benefits, and pitfalls. The material under investigation is a new type of bimodal microporous and mesoporous material with zeolitic characteristics, synthesized by a mesotemplate-free method. The acidic nature of the novel material is compared to two reference materials: a crystalline zeolite and a mesoporous aluminum incorporated mesocellular foam (Al-MCF) with amorphous characteristics. PMID:24471941

  9. 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.

  10. Synthesis and testing of nanosized zeolite Y

    NASA Astrophysics Data System (ADS)

    Karami, Davood

    This work focuses on the synthesis and testing of nanosized zeolite Y. The synthesis formulations of faujasite-type structure of zeolite Y prepared in nanosized form are described. The synthetic zeolite Y is the most widely employed for the preparation of fluid catalytic cracking (FCC) catalysts. The synthesis of zeolite Y is very complicated process. The mean particle size of zeolite Y is 1800 nm. The major challenge of this work involved reducing this average particle size to less than 500 nm. The preliminary experiments were conducted to obtain the pure zeolite Y using the soluble silicates as a silica source. This was achieved by applying the experimental design approach to study the effects of many parameters. The ageing time turned out to be the most significant variable affecting product purity. Based on the preliminary results, a detailed investigation was carried out to determine the effects of silica-alumina precursor preparations on zeolite Y synthesis. Aluminosilicate precursors were prepared by gelling and precipitation of soluble silicate. The as-prepared precursors were used for the hydrothermal synthesis of zeolite Y. The procedure of the precipitation of soluble silicate yielded pure zeolite Y at the conventional synthesis conditions. The extent of purity of zeolite Y depends on the surface areas of aluminosilicate precursors. A novel approach to zeolite Y synthesis was employed for the preparation of the pure nanosized zeolite Y. This was achieved by applying the method of impregnation of precipitated silica. This novel method of impregnation for zeolite Y preparation allows eliminating the vigorous agitation step required for the preparation of a homogeneous silica solution, thereby simplifying the synthesis of zeolite Y in one single vessel. In case of the synthesis of nanosized zeolite Y, the effect of varying the organic templates on the formation of nanosized particles of zeolite Y was investigated, while all other reaction parameters were kept constant. The extent to which the nanosized zeolite Y was formed depended on the types and amount of the organic templates as well as the ageing duration. The activity testing of four FCC catalysts prepared by using CREY (Calcined Rare Earth ion-exchanged) zeolites with different particle sizes was carried out in a fluidized bench-scale batch riser simulator reactor. The starting zeolites NaY of different particle sizes were subjected to two cycles of ion exchange treatment. The particle size of the supported zeolites was varied between 150 and 1800 nm. The preparation of FCC catalysts was conducted by mixing the CREY zeolite with silica-alumina matrix and silica sol binder. Each catalyst contained 25% zeolite. The results of catalytic cracking demonstrated the significant effect of size reduction of the starting zeolite Y on catalytic performance of FCC catalyst. Keywords. Zeolite NaY, Faujasite, Nanosized particles, Nanozeolite, Nanotechnology, Synthesis, Crystallization, Seeding, Ageing, Precipitated silica, Sylopol silica, Fumed silica, Silica sol, Soluble silicates, Alumina, SAR or SiO2/Al2O3 Ratios, Sodium hydroxide, Sodium aluminate, Organic templates, TMAOH, Surfactant (CTAB), Ammonium Sulfate, BET surface area, BJH Pore Size Distribution, Zetasizer Particle Size Distribution, Powder XRD, 27Al Solid-State NMR, Catalytic Impregnation, CREY Zeolite, Silica-Alumina Matrix, Ion Exchange, FCC Catalyst, Catalytic cracking, Riser SimulatorRTM, Steaming, Zeolite HY, Utrastable Zeolite Y (USY)

  11. 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 humanitys 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 chemists 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.

  12. 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.

  13. Process for preparing silicon substituted zeolite compositions

    SciTech Connect

    Skeels, G.W.

    1991-02-26

    This patent describes the process for substituting silicon into the crystal lattice of zeolites in place of extracted lattice aluminum atoms to achieve zeolite products of higher silicon content. It comprises: providing a starting aluminosilicate zeolite having a framework SiO{sub 2}/Al{sub 2}O{sub 3} molar ratio of at least 2 and pore diameters of at least 3 Angstroms; contacting the starting zeolite at a temperature of 25{degrees} C. to 95{degrees} C. with an aqueous solution of a fluorosilicate salt containing from 0.5 to 1.5 moles per liter of the fluorosilicate salt dissolved therein, the proportions of zeolite and fluorosilicate salt being at least 0.1 moles of salt per 100 grams of anhydrous zeolite; maintaining contact between the zeolite and the salt solution for a period not in excess of 5 hours; removing from contact with the zeolite the liquid medium containing at least 90 percent of the by-product fluoroaluminate salt produced by the reaction of the fluorosilicate salt with the zeolite.

  14. 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.

  15. 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.

  16. Density functional modelling of silicate and aluminosilicate dimerisation solution chemistry.

    PubMed

    White, Claire E; Provis, John L; Kearley, Gordon J; Riley, Daniel P; van Deventer, Jannie S J

    2011-02-14

    Common throughout sol-gel chemistry, including zeolite synthesis, aluminosilicate glass formation and geopolymerisation, is the process of inorganic oxide polymerisation and deprotonation. In this investigation, some of the fundamental reactions occurring during zeolite synthesis and geopolymerisation at high pH are investigated using density functional theory (DFT), and are compared with: (i) existing values reported in the literature, and (ii) new and previously published DFT-derived data for similar silicate reactions at near-neutral pH. From the results it is seen that the energetics of deprotonation and dimerisation reactions depend greatly on the pH value, and these results correlate well with existing experimental values and trends. Hence, this investigation exemplifies that an accurate replication of the solution environment is crucial for obtaining useful theoretical results for species dissolved in non-ideal environments. PMID:21180742

  17. 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.

  18. 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.

  19. Constructing Hierarchical Porous Zeolites via Kinetic Regulation.

    PubMed

    Ding, Kunlun; Corma, Avelino; Maci-Agull, Juan Antonio; Hu, Jerry G; Krmer, Stephan; Stair, Peter C; Stucky, Galen D

    2015-09-01

    Zeolites are crystalline inorganic solids with microporous structures, having widespread applications in the fields of catalysis, separation, adsorption, microelectronics, and medical diagnosis. A major drawback of zeolites is the mass transfer limitation due to the small size of the micropores (less than 1 nm). Numerous efforts have been dedicated to integrating mesopores with the microporous zeolite structures by using templating and/or destructive approaches. Here we provide a new strategy for hierarchical pore size zeolite synthesis, without using supramolecular or hard templates. The branching epitaxial growth behavior, as a result of aluminum-zoning, contributes to the formation of the hierarchical porous zeolite structures. PMID:26322625

  20. 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.

  1. 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.

  2. Aluminosilicate nanoparticles for catalytic hydrocarbon cracking.

    PubMed

    Liu, Yu; Pinnavaia, Thomas J

    2003-03-01

    Aluminosilicate nanoparticles containing 9.0-20 nm mesopores were prepared through the use of protozeolitic nanoclusters as the inorganic precursor and starch as a porogen. The calcined, porogen-free composition containing 2 mol % aluminum exhibited the porosity, hydrothermal stability, and acidity needed for the cracking of very large hydrocarbons. In fact, the hydrothermal stability of the nanoparticles to pure steam at 800 degrees C, along with the cumene cracking activity, surpassed the analogous performance properties of ultrastable Y zeolite, the main catalyst component of commercial cracking catalysts. The remarkable hydrothermal stability and catalytic reactivity of the new nanoparticles are attributable to a unique combination of two factors, the presence of protozeolitic nanoclusters in the pore walls and the unprecedented pore wall thickness (7-15 nm). In addition, the excellent catalytic longevity of the nanoparticles is most likely facilitated by the small domain size of the nanoparticles that greatly improves access to the acid sites on the pore walls and minimizes the diffusion length of coke precursors out of the pores. PMID:12603109

  3. Aluminosilicate sources of Cs + ions

    NASA Astrophysics Data System (ADS)

    Ong, P. P.; Tan, T. L.

    1994-12-01

    Synthetic cesium aluminosilicates in the form of ?-eucryptite (Cs2O?Al2O3?2SiO2) and spodumene (Cs2O?Al2O3?4SiO2) were used to construct thermionic emitters of Cs+ ions. Total ion emission current and purity of ion emission of Cs+ ions for these two forms of aluminosilicates were studied and compared at four different material surface temperatures over 50 h of continuous heating. In addition, the ion emission characteristics were investigated for three other compositions of cesium aluminosilicates. It was revealed that as a Cs+ ion source, ?-eucryptite gives the optimum ion emission at the temperature of 1100 C.

  4. 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....

  5. 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....

  6. 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....

  7. 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....

  8. 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....

  9. 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....

  10. 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....

  11. 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...

  12. 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....

  13. 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....

  14. Structural and diffusion characterizations of steam-stable mesostructured zeolitic UL-ZSM-5 materials.

    PubMed

    Vinh-Thang, Hoang; Huang, Qinglin; Ungureanu, Adrian; Ei?, Mladen; Trong-On, Do; Kaliaguine, Serge

    2006-05-01

    A series of mesoporous UL-ZSM-5 materials (Si/Al = 50) with different micro- and mesoporosity as well as crystallinity was prepared following the procedure proposed in one of our recent studies (Trong-On, D.; Kaliaguine, S. Angew. Chem. Int. Ed. 2001, 40, 3248-3251. Trong-On, D.; Kaliaguine, S. U.S. Patent 6,669,924, B1, 2003). These materials have zeolitic structure in the form of nanoparticles intergrown in the walls of the amorphous wormhole-like aluminosilicate mesopores of Al-Meso-50, which was used as a precursor in the synthesis. The structure, crystallinity, and textural properties of the synthesized materials, as well as a reference ZSM-5 zeolite sample, were determined by X-ray diffraction (XRD), transmission electron microscopy (TEM)/scanning electron microscoy (SEM) analyses, Fourier transform infrared spectroscopy (FTIR), 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR), and nitrogen adsorption/desorption techniques. The acid properties were examined by FTIR of adsorbed pyridine. UL-ZSM-5 materials were shown to be highly hydrothermally stable. The diffusion of two C7 hydrocarbons, i.e., n-heptane and toluene, in four UL-ZSM-5 materials with different microporosities, related acidities, and crystallinities were investigated using the zero-length column (ZLC) method. Furthermore, the wormhole-like mesostructured aluminosilicate precursor (Al-Meso-50) and a reference MFI zeolite sample were also investigated using the same technique. A theoretical model considering a combination of mesopore diffusion (with surface slip in the main channels) with an activated, mainly surface diffusion mechanism in the intrawall biporous structure, was proposed and employed to interpret the experimental ZLC results. A classical Knudsen type of diffusion was replaced by an activated surface slip type of diffusion mechanism in the mesopores. The transport of n-heptane in UL-ZSM-5 materials was found to be mainly controlled by mesopore diffusion in the main-channel structure, while that of toluene was dominated by the intrawall diffusion process. Diffusion activation energies of n-heptane are about 2 times higher in comparison to toluene, which has a larger kinetic diameter. The main mesopore channel structure seems to appreciably contribute to the overall mass transport. Furthermore, the effect of hydrothermal treatment (20% steam at 800 degrees C for 24 h) on the diffusion of these two sorbates on UL-ZSM-5 materials was also evaluated. PMID:16649795

  15. 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.

  16. 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.

  17. Synthesis of novel perfluoroalkylglucosides on zeolite and non-zeolite catalysts.

    PubMed

    Nowicki, Janusz; Mokrzycki, ?ukasz; Sulikowski, Bogdan

    2015-01-01

    Perfluoroalkylglucosides comprise a very important class of fluorine-containing surfactants. These compounds can be synthesized by using the Fisher reaction, starting directly from glucose and the required perfluoroalcohols. We wish to report on the use of zeolite catalysts of different structure and composition for the synthesis of perfluoroalkylglucosides when using glucose and 1-octafluoropentanol as substrates. Zeolites of different pore architecture have been chosen (ZSM-5, ZSM-12, MCM-22 and Beta). Zeolites were characterized by XRD, nitrogen sorption, scanning electron microscopy (SEM) and solid-state 27Al MAS NMR spectroscopy. The activity of the zeolite catalysts in the glycosidation reaction was studied in a batch reactor at 100 C below atmospheric pressure. The performance of zeolites was compared to other catalysts, an ion-exchange resin (Purolite) and a montmorillonite-type layered aluminosilicate. The catalytic performance of zeolite Beta was the highest among the zeolites studied and the results were comparable to those obtained over Purolite and montmorillonite type catalysts. PMID:25856063

  18. Anomalous strain behavior in CO2-saturated zeolitic tuffs

    NASA Astrophysics Data System (ADS)

    Dralus, D. E.; Vanorio, T.; Mavko, G. M.

    2012-12-01

    Zeolites are aluminosilicate minerals with open, cage-like structures and negatively charged frames. Some naturally-occurring zeolites are stabile at geothermal temperatures and have cage structures large enough that small molecules can traverse the intracrystalline cage network easily. This, in addition to their negatively-charged frames, makes these zeolites strong adsorbents (and potentially absorbents) of carbon dioxide. We present a short series of experiments to determine what mechanical effects result from carbon dioxide interaction with zeolitic tuff samples. Three samples were tested: a non-zeolitized grey tuff from the Campi Flegrei region, a zeolitized yellow tuff from the same region, and a zeolite-rich tuff from southern California. The samples were tested in a hydrostatic pressure vessel up to 12 MPa confining pressure. Strains and ultrasonic acoustic velocities were measured under dry conditions as well as during helium injection and carbon dioxide injection. Results show acoustic velocities depend only on differential pressure and not on pore fluid type. Both zeolitized tuffs show decreased strain with gaseous carbon dioxide in the pore space; the decreased strain (or swelling) represents an 8%-16% deviation from the total strain in the helium-saturated case. This indicates that it is the interaction between zeolite minerals and carbon dioxide causing the anomalous strain readings.

  19. 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

  20. Density of molten sodium aluminosilicates

    SciTech Connect

    Stein, D.J.; Stebbins, J.F.; Carmichael, I.S.E.

    1986-05-01

    In order to address controversial discrepancies among earlier measurements, the densities of eight sodium aluminosilicate melts were measured at 1100/sup 0/ to 1550/sup 0/C. The double-bob Archimedean method was used; it is the most accurate available technique and one not used in previous density measurements in this system. The results of a regression of molar volume with temperature and composition in terms of oxides are presented. The variation of molar volume with composition is linear within the range of the data. The standard error of the fit is <0.2%.

  1. 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.

  2. Amphiphilic Organic-Inorganic Hybrid Zeotype Aluminosilicate like a Nanoporous Crystallized Langmuir-Blodgett Film.

    PubMed

    Ikeda, Takuji; Hiyoshi, Norihito; Matsuura, Shun-ichi; Kodaira, Tetsuya; Nakaoka, Takuma; Irisa, Ami; Kawano, Miki; Yamamoto, Katsutoshi

    2015-06-26

    A new organic-inorganic hybrid zeotype compound with amphiphilic one-dimensional nanopore and aluminosilicate composition was developed. The framework structure is composed of double aluminosilicate layers and 12-ring nanopores; a hydrophilic layer pillared by Q(2) silicon atom species and a lipophilic layer pillared by phenylene groups are alternately stacked, and 12-ring nanopores perpendicularly penetrate the layers. The framework topology looks similar to that of an AFI-type zeolite but possesses a quasi-multidimensional pore structure consisting of a 12-ring channel and intersecting small pores equivalent to 8-rings. The hybrid material with alternately laminated lipophilic and hydrophilic nanospaces can be assumed as a crystallized Langmuir-Blodgett film. It demonstrates microporous adsorption for both hydrophilic and lipophilic adsorptives, and its outer surface tightly adsorbs lysozyme whose molecular size is much larger than its micropore opening. Our results suggest the possibility of designing porous adsorbent with high amphipathicity. PMID:26012531

  3. 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).

  4. 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.

  5. Zeolite-like liquid crystals

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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 ?-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.

  6. Preparation and characterization of zeolitic membrane

    SciTech Connect

    Shuanshi Fan; Chunhua Li; Jinqu Wang

    1994-12-31

    Zeolites with less than 10 {angstrom} pores are desirable membrane materials, due to their crystallinity, resistance to high temperature, and chemical inertness. Although several works have been done on them, zeolitic membranes have not been developed so perfect at present. In this paper, the authors reported the preparation and some properties of an asymmetric zeolitic membrane synthesized by hydrothermal process on the intermediate layer which was made on a porous ceramic support, meanwhile the results of separation of ethanol-water mixture on pervaporation were discussed.

  7. Acidity of two-dimensional zeolites.

    PubMed

    Rybicki, Marcin; Sauer, Joachim

    2015-11-01

    Hybrid quantum mechanics:molecular mechanics (QM/MM) calculations of absolute deprotonation energies are performed with periodic boundary conditions for Brnsted sites of aluminosilicate bilayers with various Al/Si ratios (two-dimensional zeolite). The supercell method is applied and density functional theory is used. Much lower values are obtained (1042, 1069 and 1091 kJ mol(-1) for Al/Si = 1/63, 1/7 and 1/3, respectively) than those for bulk zeolites (1233 kJ mol(-1) for H-chabazite with Al/Si = 1/11). We ascribe the much lower deprotonation energy to the smaller effective dielectric constant (1.6-1.9) of an ultra-thin dielectric in a vacuum compared to that of the corresponding bulk systems (3.0 for H-chabazite), which leads to a better stabilization of the charge created upon deprotonation. PMID:26437870

  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. Conversion of fly ash into mesoporous aluminosilicate

    SciTech Connect

    Chang, H.L.; Shi, W.H.; Chu, C.M.; Aksay, I.A.

    1999-03-01

    Mesoporous aluminosilicate in the hexagonal phase (MCM-41) has been synthesized from fused fly ash solutions and cationic cetyltrimethylammonium bromide (CTAB) surfactants. The authors provide direct evidence that an MCM-41 aluminosilicate with a homogeneous chemical composition of Si/Al = 13.4 can be prepared with cationic surfactant. Results indicate that coal combustion byproducts can be utilized for producing mesoporous molecular sieves even though they contain significant amounts of impurities.

  10. Preparation and characterization of Na-LTA zeolite from Tunisian sand and aluminum scrap

    NASA Astrophysics Data System (ADS)

    Tounsi, H.; Mseddi, S.; Djemel, S.

    2009-11-01

    Pure Na-A (LTA) zeolite has been prepared from aluminosilicate gel obtained by a mixture of metasilicate and aluminate solutions. Metasilicate sol; used as silica source; was prepared from an alkaline attack of Tunisian sand in an autoclave under agitation at 220 ?C and pressure of 27 bar. The aluminate solution was obtained by dissolution of aluminium scraps in NaOH solution. The crystallization of Na-LTA zeolite is controlled by the alkalinity of the mixture and the reaction time. At 90 ?C, well crystallized LTA have been obtained after 3h. The Zeolite LTA converts into the more stable HS after long reaction times according to Ostwald's law. The alkalinity of the reaction mixture changes the nature of the obtained zeolite. At lower NaOH concentration (0.1 M), Na-X zeolite was obtained; whereas the crystallization of LTA was promoted at higher NaOH concentration (3M).

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. Physical, chemical and catalytic properties of high modules Y zeolite obtained by direct synthesis compared with ultrastable Y zeolite

    SciTech Connect

    Levinbuk, M.I.; Melnikov, V.B.; Pavlov, M.L.

    1996-10-01

    Industrial preparation of Y zeolites is widely spread throughout the world. However, unlike the zeolites of pentasil (ZSM) series, their catalytic activity and selectivity are controlled by molar SiO{sub 2}; Al{sub 2}O{sub 3} ratio, which is varied by the method of post synthesis modification and not by direct synthesis. Zeolites obtain in such a way (hydrothermal - USY or chemical treatments-LZ-210) with the modulus above 5.5 are called ultrastable. Defects of ultrastable zeolites are: partial distortions of the crystalline framework, appearance of the aluminum in the sample beyond the framework, and the higher cost of zeolite product at expense of construction and operating charges. These additional expenses are due to the necessity of special blocks for modification of NaY zeolite with modulus 4.5-5.0 synthesized by traditional methods.

  17. 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...

  18. 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...

  19. 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...

  20. 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...

  1. 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...

  2. 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...

  3. 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...

  4. 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...

  5. 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...

  6. 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...

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

    PubMed

    Vai?iukynien?, Danut?; Kantautas, Aras; Vaitkevi?ius, Vitoldas; Jakevi?ius, Leonas; Rudionis, ymantas; Pakevi?ius, 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

  8. 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.

  9. Energetics and structural evolution of Na-Ca exchanged zeolite A during heating.

    PubMed

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

    2015-04-14

    The properties of zeolite A change significantly upon sodium-calcium exchange. The impact of cation composition on the temperature-induced phase transformations and energetics of Na-Ca exchanged zeolite A was studied systematically using powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and high-temperature oxide melt solution calorimetry. As the temperature increases, the structural evolution of each Na-Ca exchanged zeolite A sample undergoes three distinct stages - dehydration, amorphization, and densification/recrystallization. Initially complete dehydration does not result in framework degradation, but further heating leads to zeolite phase degradation into other aluminosilicate phases. Both amorphization and recrystallization shift to higher temperatures as the calcium content increases. On the other hand, the enthalpies of formation for the high temperature aluminosilicate phases, the amorphous phase (AP) and the dense phase (DP), appear to be a linear function of calcium content (average ionic potential) with diminishing of energetic stability upon increasing the Ca content. 100% Na-A heated at 1200 C has the most exothermic enthalpy of formation from oxides (-65.87 0.87 kJ mol(-1)- TO2), while 97.9% CaNa-A heated at 945 C has the least exothermic value (-5.26 0.62 kJ mol(-1)- TO2). For different aluminosilicates with the same chemical composition, the dense phase (DP) assemblage is more stable than the amorphous phase (AP). PMID:25760889

  10. Factors that Determine Zeolite Stability in Hot Liquid Water.

    PubMed

    Zhang, Lu; Chen, Kuizhi; Chen, Banghao; White, Jeffery L; Resasco, Daniel E

    2015-09-16

    The susceptibility of zeolites to hot liquid water may hamper their full utilization in aqueous phase processes, such as those involved in biomass conversion and upgrading reactions. Interactions of zeolites with water strongly depend on the presence of hydrophilic moieties including Brnsted acid sites (BAS), extraframework cations, and silanol defects, which facilitate wetting of the surface. However, it is not clear which of these moieties are responsible for the susceptibility of zeolites to liquid water. Previous studies have offered contradictory explanations because the role of each of these characteristics has not been investigated independently. In this work, a systematic comparison has been attempted by relating crystallinity losses to the variation of each of the five zeolite characteristics that may influence their stability in liquid water, including number of BAS, Si-O-Si bonds, framework type, silanol defects, and extraframework Al. In this study, we have systematically monitored the crystallinity changes of a series of HY, H-ZSM-5, and H-? zeolite samples with varying Si/Al ratio, density of BAS, zeolite structure, and density of silanol defects upon exposure to liquid water at 200 C. The results of this comparison unambiguously indicate that the density of silanol defects plays the most crucial role in determining susceptibility of zeolites to hot liquid water. By functionalizing the silanol defects with organosilanes, the hydrophobicity of defective zeolite is increased and the tolerance to hot liquid water is significantly enhanced. PMID:26301890

  11. 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

  12. Zeolite coatings on metal alloys for corrosion resistance, hydrophilicity, and microbiocidal activity

    NASA Astrophysics Data System (ADS)

    Beving, Derek Eugene

    The recent advent of polycrystalline zeolite coatings on metal alloys has heralded a paradigm shift in zeolitic application and function as well as their requisite synthesis. The prevailing paradigm for zeolite utilization and employment was through the exploitation of their uniform microporosity. We have demonstrated the utility of the non-porous as-synthesized form of high-silica-zeolite (HSZ) MFI coatings on aluminum alloys for corrosion resistance. A single chemical formulation was able to generate excellent corrosion-resistant HSZ MFI coatings on all aluminum alloys studied. Functional zeolite coatings have traditionally been synthesized as coatings comprised of single zeolite species. We have successfully generated functional zeolite hybrid coatings comprised of disparate zeolite species with controlled composition. A three-layer zeolite coating was developed to apply a low-silica-zeolite (LSZ), zeolite Y (ZY), to aluminum substrates. The middle layer was a zeolite hybrid coating of ZY crystals embedded within a MFI matrix. The mixed zeolite middle layer allowed for the adhesion of the single species HSZ MFI bottom layer to the single species LSZ ZY, top layer. A two-layer hydrophilic and antimicrobial hybrid zeolite coating on aluminum alloys was also developed. The base layer was a HSZ MFI coating and the top layer consisted of zeolite A (ZA) crystals embedded within a matrix of HSZ MFI. The ZA crystals are still present at the surface of the hybrid layer, as such; their hydrophilicity is accessible and can be exploited for their hydrophilic and antimicrobial potential. The great utility of the zeolite hybrid layer is realized with the formation of single-layer hybrid coatings on metal alloys. The hybrid coating is made of mixed inorganic crystalline species imbedded in a matrix of HSZ MFI. The inorganic species used is not limited to zeolite types; other inorganic crystalline species can be used. We have generated hybrid coatings made from LSZ ZY and HSZ MR, and hybrid coatings made from hydrotalcite, an inorganic crystalline species distinctly different from zeolite, and HSZ MFI. The single layer hybrid coatings have great utility and their function and application can be easily tuned by changing the zeolite or crystalline inorganic species used to generate them.

  13. 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...

  14. Lithium alumino-silicate ion source development

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

    We report experimental progress on Li+ source development in preparation for warm dense matter heating experiments. To uniformly heat targets to electron-volt temperatures for the study of warm dense matter, we are pursuing the use of a low (E < 5 MeV) kinetic energy singly ionized lithium beam and a thin target. Two kinds of lithium (Li+) alumino-silicate ion sources, ?-spodumene and ?-eucryptite, each of area 0.31 cm2, have been fabricated for ion emission measurements. These surface ionization sources are heated to 1200 to 1300 C where they preferentially emit singly ionized alkali ions. Tight process controls were necessary in preparing and sintering the alumino-silicate to the porous tungsten substrate to produce an emitter that gives uniform ion emission, sufficient current density and low beam emittance. Current density limit of the two kinds have been measured, and ion species identification of possible contaminants has been verified with a Wien (E x B) filter.

  15. 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 ?-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

  16. 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

  17. 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.

  18. Zeolite catalysis: technology

    SciTech Connect

    Heinemann, H.

    1980-07-01

    Zeolites have been used as catalysts in industry since the early nineteen sixties. The great majority of commercial applications employ one of three zeolite types: zeolite Y; Mordenite; ZSM-5. By far the largest use of zeolites is in catalytic cracking, and to a lesser extent in hydrocracking. This paper reviews the rapid development of zeolite catalysis and its application in industries such as: the production of gasoline by catalytic cracking of petroleum; isomerization of C/sub 5/ and C/sub 6/ paraffin hydrocarbons; alkylation of aromatics with olefins; xylene isomerization; and conversion of methanol to gasoline.

  19. Hydrocracking with a zeolite in an alumina binder peptized in the presence of a surfactant

    SciTech Connect

    O'Hara, M.J.

    1984-11-27

    A process for the conversion of a hydrocarbon charge stock is disclosed. The process comprises reacting the charge stock with hydrogen at hydrocracking conditions in contact with a catalytic composite having improved selectivity to middle distillate product during hydrocracking. The catalyst composite comprises alumina, a crystalline aluminosilicate, a Group VIB metal component and a Group VIII metal component and is prepared by the method comprising: admixing the alumina and crystalline aluminosilicate with a peptizing agent and an aqueous solution of a modified linear aliphatic polyether surfactant to form a dough; extruding the dough into discrete particles; and calcining and drying the particles.

  20. 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

  1. 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.

  2. 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.

  3. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks

    PubMed Central

    Park, Kyo Sung; Ni, Zheng; Ct, Adrien P.; Choi, Jae Yong; Huang, Rudan; Uribe-Romo, Fernando J.; Chae, Hee K.; OKeeffe, Michael; Yaghi, Omar M.

    2006-01-01

    Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) have been synthesized as crystals by copolymerization of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, respectively. In addition, one example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m2/g), high thermal stability (up to 550C), and remarkable chemical resistance to boiling alkaline water and organic solvents. PMID:16798880

  4. 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.

  5. Silanization-Based Zeolite Crystallization: Participation Degree and Pathway.

    PubMed

    Yan, Yueer; Azhati, Arepati; Guo, Xiao; Zhang, Yahong; Tang, Yi

    2015-08-17

    A clear and deep understanding of zeolite crystallization with the addition of organosilane is desirable for the reasonable design and preparation of hierarchical zeolites. Herein, the effects of different organosilanes on zeolite crystallization were systematically studied. It was found that organosilane plays the role of an inhibitor in the silanization-based zeolite preparation, and this inhibition effect was determined by its participation degree. An organosilane with a high participation degree can result in the prolongation of nucleation and growth periods of zeolite as well as the variation of product properties. More importantly, a dynamic participation pathway of organosilane is proposed, that is, the growth of zeolite is accompanied by the continuous removal of organosilane, leading to an increase of product crystallinity as well as the decrease of mesoporosity. This study gives a new insight into the role that organosilane plays in zeolite crystallization, which will help to direct the rational selection of organosilane and design of crystallization condition for the optimal synthesis of hierarchical zeolites. PMID:26173899

  6. 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

  7. The recyclable synthesis of hierarchical zeolite SAPO-34 with excellent MTO catalytic performance.

    PubMed

    Xi, Dongyang; Sun, Qiming; Chen, Xiaoxin; Wang, Ning; Yu, Jihong

    2015-08-01

    A facile and green route has been developed for the synthesis of hierarchical zeolite catalysts by recycling of waste mother-liquors. After three recycles of mother-liquors, the obtained hierarchical SAPO-34 zeolites retain high crystallinity, texture properties, and acidity, as well as excellent MTO catalytic performance as compared to the initially prepared catalysts. PMID:26121259

  8. 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

  9. 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.

  10. 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

  11. 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.

  12. Association of Indigo with Zeolites for Improved Color Stabilization

    NASA Astrophysics Data System (ADS)

    Dejoie, Catherine; Martinetto, Pauline; Dooryhe, 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

    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.

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

    PubMed

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

    2013-05-15

    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 (29)Si and (27)Al 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

  15. 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

  16. Statistical Approach to the Transformation of Fly Ash into Zeolites

    NASA Astrophysics Data System (ADS)

    Derkowski, Arkadiusz; Michalik, Marek

    2007-01-01

    The experimental conversion of F-class fly ash into zeolites is described. The ash, composed mainly of aluminosilicate glass, mullite and quartz, was collected in the Cracow power plant (southern Poland). The experiments involved the heating of fly ash samples in PTFE vessels. Time, temperature and solution composition were the reaction parameters considered in the experiments and in the subsequent modeling. A series of reactions with 0.5, 3 and 5M NaOH solutions (and some with additional 3M NaCl) were carried out at 70, 100 and 150C for 12-48 hours under autogenic pressure (not measured) and at a constant ash-to-solution ratio of 33.3 g/l. The following zeolite phases were synthesized: sodalite (SOD structure), hydroxysodalite (SOD), CAN type phases, Na-X (FAU), and NaP1 (GIS). Statistically calculated relationships based on the mineral- and chemical compositions of the reaction products support the conclusion that the type of zeolite phase that crystallizes depends on the concentration of OH- and Cl- in solution and on the temperature of the reaction. The duration of reaction, if on the order of tens of hours, is of less significance. The nature of the zeolite phase that crystalises is controlled by the intensity and selectivity of the substrate dissolution. That dissolution can favour, in sequence, one or other of the components in the substrate, resulting in Si/Al variation in the reaction solutions. Mullite dissolution (decreasing solution Si/Al) characterizes the most advanced reaction stages. The sequence of crystallization of the zeolite phases mirrors the sequential dissolution of substrate components, and the composition of the crystallizing zeolite crystals reflects the changes in the solution Si/Al.

  17. Non-framework cation migration and irreversible pressure-induced hydration in a zeolite.

    PubMed

    Lee, Yongjae; Vogt, Thomas; Hriljac, Joseph A; Parise, John B; Hanson, Jonathan C; Kim, Sun Jin

    2002-12-01

    Zeolites crystallize in a variety of three-dimensional structures in which oxygen atoms are shared between tetrahedra containing silicon and/or aluminium, thus yielding negatively charged tetrahedral frameworks that enclose cavities and pores of molecular dimensions occupied by charge-balancing metal cations and water molecules. Cation migration in the pores and changes in water content associated with concomitant relaxation of the framework have been observed in numerous variable-temperature studies, whereas the effects of hydrostatic pressure on the structure and properties of zeolites are less well explored. The zeolite sodium aluminosilicate natrolite was recently shown to undergo a volume expansion at pressures above 1.2 GPa as a result of reversible pressure-induced hydration; in contrast, a synthetic analogue, potassium gallosilicate natrolite, exhibited irreversible pressure-induced hydration with retention of the high-pressure phase at ambient conditions. Here we report the structure of the high-pressure recovered phase and contrast it with the high-pressure phase of the sodium aluminosilicate natrolite. Our findings show that the irreversible hydration behaviour is associated with a pronounced rearrangement of the non-framework metal ions, thus emphasizing that they can clearly have an important role in mediating the overall properties of zeolites. PMID:12466838

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Sodium clusters in zeolites

    NASA Astrophysics Data System (ADS)

    Grobet, P. J.; Martens, L. R. M.; Vermeiren, W. J. M.; Huybrechts, D. R. C.; Jacobs, P. A.

    1989-03-01

    The method of loading sodium clusters in zeolites, consisting of the controlled thermal decomposition of physisorbed sodium azide, is discussed. The influence of the azide loading, the azide decomposition rate and the sintering process on the amount of ionic and metallic sodium clusters in zeolite Y was followed by ESR. The method is compared to other metal deposition techniques.

  3. 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.

  4. 3D Study of the Morphology and Dynamics of Zeolite Nucleation.

    PubMed

    Melinte, Georgian; Georgieva, Veselina; Springuel-Huet, Marie-Anne; Nossov, Andre; Ersen, Ovidiu; Guenneau, Flavien; Gedeon, Antoine; Pal?i?, Ana; Bozhilov, Krassimir N; Pham-Huu, Cuong; Qiu, Shilun; Mintova, Svetlana; Valtchev, Valentin

    2015-12-01

    The principle aspects and constraints of the dynamics and kinetics of zeolite nucleation in hydrogel systems are analyzed on the basis of a model Na-rich aluminosilicate system. A detailed time-series EMT-type zeolite crystallization study in the model hydrogel system was performed to elucidate the topological and temporal aspects of zeolite nucleation. A comprehensive set of analytical tools and methods was employed to analyze the gel evolution and complement the primary methods of transmission electron microscopy (TEM) and nuclear magnetic resonance (NMR) spectroscopy. TEM tomography reveals that the initial gel particles exhibit a core-shell structure. Zeolite nucleation is topologically limited to this shell structure and the kinetics of nucleation is controlled by the shell integrity. The induction period extends to the moment when the shell is consumed and the bulk solution can react with the core of the gel particles. These new findings, in particular the importance of the gel particle shell in zeolite nucleation, can be used to control the growth process and properties of zeolites formed in hydrogels. PMID:26503177

  5. 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.

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

    PubMed

    Medina, Adriana; Gamero, Prcoro; Almanza, Jos Manuel; Vargas, Alfredo; Montoya, Ascencin; Vargas, Gregorio; Izquierdo, Mara

    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

  7. 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

  8. 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.

  9. 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.

  10. Microwave assisted two-step process for rapid synthesis of Na-A zeolite from coal fly ash

    SciTech Connect

    Tanaka, H.; Fujimoto, S.; Fujii, A.; Hino, R.; Kawazoe, T.

    2008-01-15

    Using the amorphous aluminosilicate of coal fly ash (FA), Na-A zeolite was synthesized. The FA particles mechanically treated with ball mill were added into a tube made of cellulose filter paper, and they were pretreated with a NaOH solution by refluxing under microwave (MW) irradiation for 60 min. The amorphous aluminosilicate of FA was dissolved during the pretreatment. After pretreatment, the tube was removed and NaAlO{sub 2} solution was added to the residual solution to control the SiO{sub 2}/Al{sub 2}O{sub 3} molar ratio of the solution ranging from 0.5 to 4.0. The precipitates thus formed were aged by refluxing under MW irradiation for 60 min. After aging, white precipitates were yielded over the whole SiO{sub 2}/Al{sub 2}O{sub 3} range. At SiO{sub 2}/Al{sub 2}O{sub 3} = 0.51.0, the materials were identified as Na-A zeolite with a little amount of hydroxysodalite. The amorphous aluminosilicate emerged slightly at SiO{sub 2}/Al{sub 2}O{sub 3} = 2.0. The diffraction peaks of Na-A zeolite and hydroxysodalite disappeared at SiO{sub 2}/Al{sub 2}O{sub 3} = 4.0. The cation exchange capacity of Na-A zeolite formed at SiO{sub 2}/Al{sub 2}O{sub 3} = 0.5 and 1.0 was 4.32 and 4.70 meq.gP{sup -1}, respectively. The results obtained led to the conclusion that Na-A zeolite can be synthesized from milled FA for 120 min under MW irradiation.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. Dietary aluminosilicate supplement enhances immune activity in mice and reinforces clearance of porcine circovirus type 2 in experimentally infected pigs.

    PubMed

    Jung, Bock-Gie; Toan, Nguyen Tat; Cho, Sun-Ju; Ko, Jae-hyung; Jung, Yeon-Kwon; Lee, Bong-Joo

    2010-07-14

    Aluminosilicate is the major component of clay minerals such as zeolite, bentonite and clinoptilolite. The minerals possess a number of beneficial activities, especially in regulating the immune system. The aims of the present study were to evaluate immune enhancing effects of dietary aluminosilicate supplement (DAS) in mice, and to demonstrate clearance effects of DAS against porcine circovirus type 2 (PCV2) in experimentally infected pigs as an initial step towards the development of an antibiotic substitute for use in pigs. Relative messenger RNA expression levels of interferon-gamma, interleukin-4 and tumor necrosis factor-alpha, phagocytic activities of polymorphonuclear leucocytes, serum antibody production level and spleen B cell ratio were significantly increased in the DAS groups of mice compared with the control group (each feeding group had three replications with 5 mice each). The results indicated that general immune activity including cellular and humoral immunity could be enhanced by DAS in mice. In experimentally PCV2-infected pigs, the load of viral genome in nasal swab, serum and lung of the DAS group of pigs was significantly decreased compared with the control group at 28 days post-infection (each group three pigs). Corresponding histopathological analyses demonstrated that pigs in the DAS group displayed mild and less severe abnormal changes compared with the control group, indicating that DAS reinforces clearance of PCV2 in experimentally infected pigs. This may relate to general immune enhancing effects of DAS in mice. Therefore DAS will help the health of animal, especially in swine. PMID:20022715

  16. Hydraulic conductivity of compacted zeolites.

    PubMed

    Oren, A Hakan; Ozdamar, Tu?e

    2013-06-01

    Hydraulic conductivities of compacted zeolites were investigated as a function of compaction water content and zeolite particle size. Initially, the compaction characteristics of zeolites were determined. The compaction test results showed that maximum dry unit weight (?(dmax)) of fine zeolite was greater than that of granular zeolites. The ?(dmax) of compacted zeolites was between 1.01 and 1.17 Mg m(-3) and optimum water content (w(opt)) was between 38% and 53%. Regardless of zeolite particle size, compacted zeolites had low ?(dmax) and high w(opt) when compared with compacted natural soils. Then, hydraulic conductivity tests were run on compacted zeolites. The hydraulic conductivity values were within the range of 2.0 10(-3) cm s(-1) to 1.1 10(-7) cm s(-1). Hydraulic conductivity of all compacted zeolites decreased almost 50 times as the water content increased. It is noteworthy that hydraulic conductivity of compacted zeolite was strongly dependent on the zeolite particle size. The hydraulic conductivity decreased almost three orders of magnitude up to 39% fine content; then, it remained almost unchanged beyond 39%. Only one report was found in the literature on the hydraulic conductivity of compacted zeolite, which is in agreement with the findings of this study. PMID:23460541

  17. Structural analysis of hierarchically organized zeolites

    NASA Astrophysics Data System (ADS)

    Mitchell, Sharon; Pinar, Ana B.; Kenvin, Jeffrey; Crivelli, Paolo; Krger, Jrg; Prez-Ramrez, 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.

  18. 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

  19. Structural analysis of hierarchically organized zeolites.

    PubMed

    Mitchell, Sharon; Pinar, Ana B; Kenvin, Jeffrey; Crivelli, Paolo; Krger, Jrg; Prez-Ramrez, 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. Microstructural and phase evolution in metakaolin geopolymers withdifferent 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 ?-Al2O3 powder, non reactive phase to the alkali activated metakaolin system when used in larger amount increased crystalline phase in the matrix. ?-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.

  9. 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

  10. 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

  11. 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

  12. 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.

  13. Changes in the Vibrational Spectra of Zeolites Due to Sorption of Heavy Metal Cations

    NASA Astrophysics Data System (ADS)

    Krl, M.; Mozgawa, W.; Barczyk, K.; Bajda, T.; Kozanecki, M.

    2013-11-01

    This work presents the results of spectroscopic (MIR and Raman) studies of zeolite structures after immobilization of heavy metal cations from aqueous solutions. The sorption of Ag+, Cu2+, Cd2+, Pb2+, Zn2+, and Cr3+ ions has been conducted on zeolites belonging to different structural groups, i.e., sodium forms of natural chabazite, mordenite, ferrierite, and clinoptilolite, as well as on synthetic zeolite Y. Systematic changes in intensities and positions of the bands corresponding to the characteristic ring vibrations have been observed in the measured spectra. The most visible changes are observed in the FT-IR spectra of the samples in the range of 850-450 cm-1, and in the Raman spectra in the range of 600-250 cm-1. Depending on the zeolite structure, the bands, which can be regarded as a kind of indicator of ion exchange, were indentifi ed. For example, in the case of IR spectra, these bands are at 766, 703, 648, 578, and 506 cm-1 for zeolite Y, at 733 and 560 cm-1 for mordenite, at 675 cm-1 for clinoptilolite, etc. The degree of changes depends on both the type of cation and its concentration in the initial solution. This is connected with the way of binding of metal ions to the zeolite aluminosilicate framework, i.e., a proportion of the ion exchange and chemisorption in the process. Cations mainly undergoing ion exchange, such as Cd2+ or Pb2+, have the greatest impact on the character of the spectra. On the other hand, Cr3+ ions practically do not modify the spectra of zeolites. Results of IR and Raman spectroscopic studies have been compared with those obtained by atomic absorption spectroscopy (AAS), from which the proportion of ion exchange to chemisorption in the process and the effective cation exchange capacity of the individual samples have been estimated.

  14. Aluminosilicate and aluminosilicate based polymer composites: Present status, applications and future trends

    NASA Astrophysics Data System (ADS)

    Lopes, A. C.; Martins, P.; Lanceros-Mendez, S.

    2014-08-01

    Aluminosilicates have traditionally been important materials for applications related to adsorbents, water softeners, catalysis and mechanical and thermal reinforcement due to their high surface area, excellent thermal/hydrothermal stability, high shape-selectivity and superior ion-exchange ability. Recently, their use as polymer fillers has allowed to increasingly extending their application range to innovative areas such as medical and biological fields as well as in sensors, filtration membranes, energy storage and novel catalysis routes. Further, the large versatility and tailoring possibilities of both filler and matrix indicates this area as one of the enabling key technologies of the near future. This work summarizes the main developments up to date in this increasingly interesting field, focuses on the main applications already developed as well as on the key challenges for the near future.

  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. In-situ growth of porous alumino-silicates and fabrication of nano-porous membranes

    NASA Astrophysics Data System (ADS)

    Kodumuri, Pradeep

    2009-12-01

    Feasibility of depositing continuous films of nano-porous alumino-silicates, primarily zeolites and MCM-41, on metallic and non-metallic substrates was examined with an aim to develop membranes for separation of gaseous mixtures and also for application as hydrogen storage material. Mesoporous silica was deposited in-side the pores of these nano-porous disks with an aim to develop membranes for selective separations. Our study involves supported zeolite film growth on substrates using in-situ hydrothermal synthesis. Faujasite, Silicalite and Mesoporous silica have been grown on various metallic and non-metallic supports. Metallic substrates used for film growth included anodized titanium, sodium hydroxide treated Titanium, Anodized aluminum, and sintered copper. A non-metallic substrate used was nano-porous aluminum oxide. Zeolite film growth was characterized using Scanning Electron Microscope (AMRAY 1820) and High Resolution Transmission electron microscope. Silicalite was found to grow uniformly on all the substrates to form a uniform and closely packed film. Faujasite tends to grow in the form of individual particles which do not inter-grow like silicalite to form a continuous film. Mesoporous silica was found to grow uniformly on anodized aluminum compared to growth on sintered copper and anodized titanium. Mesoporous silica growth on AnodiscRTM was found to cover more than half the surface of the substrate. Commercially obtained AnodiscRTM was found to have cylindrical channels of the pore branching into each other and since we needed pore channels of uniform dimension for Mesoporous silica growth, we have fabricated nano-porous alumina with uniform pore channels. Nano-porous alumina membranes containing uniform distribution of through thickness cylindrical pore channels were fabricated using anodization of aluminum disks. Free-standing nano-porous alumina membranes were used as templates for electro-deposition in order to fabricate nickel and palladium nano-wire mesh with large surface area to volume ratio. Such nano-wire metallic alloy meshes have a strong potential for application as advanced hydrogen storage material. Statistical image analysis techniques were used to determine the dependence of the pore morphology and distribution on the crystal orientation by anodizing single crystal aluminum disks that were oriented with their surface normal along [111], [110] and [111] directions. The [100] oriented disks were found to have the highest tendency to anodize in oxalic acid electrolytic solutions.

  17. Luminescent properties of bismuth centres in aluminosilicate optical fibres

    SciTech Connect

    Bulatov, Lenar I; Mashinskii, Valerii M; Dvoirin, Vladislav V; Dianov, Evgenii M; Kustov, Evgenii F

    2010-02-28

    The shape and spectral position of the luminescence bands of bismuth-doped aluminosilicate glass fibres are shown to depend on excitation power and wavelength. This indicates that the red and IR luminescence bands are composed of several components. The absorption and radiative transitions involved are identified, and a diagram of energy levels and transitions is obtained for four modifications of a bismuth centre in different environments in the aluminosilicate glass network. The effect of local environment on the optical properties of the bismuth centres is examined. (optical fibres and waveguides)

  18. 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.

  19. 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

  20. Binding and catalytic reduction of NO by transition metal aluminosilicates

    SciTech Connect

    Klier, K.; Herman, R.G.; Hou, S.

    1992-06-01

    Na, Co{sup 2+}, Ce{sup 3+}, and Co{sup 2+}Ce{sup 3+} exchanged A type zeolite have been tested for NO and N{sub 2}O adsorption and decomposition at room temperature. Dynamic temperature programmed desorption (TPD) studies were also carried out with these four zeolites, as well as with CeO{sub 2} and CoA zeolite mixed with CeO{sub 2}. It was demonstrated that NO was especially decomposed into N{sub 2}, with some N{sub 2}, with some N{sub 2}O, over the doubly ion exchanged CoCeA zeolite that contained 1.77 Co and 2 Ce per unit cell. Some segregation of CeO{sub 2} occurred during these experiments, and a lower content of Ce in the CoCeA zeolite might be utilizable.

  1. 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.

  2. 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

  3. Iron silicates, iron-modulated zeolite catalysts, and molecular models thereof.

    PubMed

    Pinkert, Denise; Limberg, Christian

    2014-07-21

    Iron centres incorporated in silicate frameworks or located in their pores have been shown to possess unique catalytic properties. As compared to aluminosilicates this area of zeolite chemistry is much younger and in the first part of this review the findings made so far are summarised. Molecular model compounds may help to understand the formation, corrosion and reactivity of such materials or to even develop new ones. Hence, the subsequent parts deal with molecular iron siloxides, the number of which is still quite limited, and their behaviour also in relation to the iron-modified zeolites is outlined. At first, compounds based on an incompletely condensed cubic silsequioxane are discussed, before iron(III) complexes of more basic siloxide ligands with varying steric demands are described. Finally, recent developments based on branched polydentate siloxides are presented. PMID:24939619

  4. 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.

  5. Clinoptilolite zeolitized tuff from Central Alborz Range, North Iran

    NASA Astrophysics Data System (ADS)

    Taghipour, Batoul

    2010-05-01

    Zeolites are hydrated alumino-silicates of the alkaline and alkaline earth cations, principally sodium, potassium, calcium, and magnesium (Iijima 1980; Hay 1981). Zeolites occur principally in unmetamorphosed sedimentary rocks and are particularly widespread in volcani-clastic strata (Hay, 1978). Clinoptilolite is a natural zeolite of the heulandite group with the simplified formula of (Na, K)6 Si30 Al6 O72 .nH2. It is the most common natural zeolite found mainly in sedimentary rocks of volcanic origin. Alborz zone is one of the important geological divisions in Iran. This zone is restricted to Kopeh dagh zone in North & Central Iranian zone in South and is a region of active deformation within the broad Arabian-Eurasia collision zone (Allen et al. 2003). The zeolitized green tuff belt from Central Alborz which introduce here are made of volcanoclastic sequence of Karaj Formation. This belt is about 40 km long along Alborz Range and is Eocene in age. Zeolites and associated minerals of this altered vitric tuff studied. Zeolitization took place in some beds of Karaj Formations, with average range of 3 to 300 meters thickness. There are several gypsum lenses which interbed with a widespread green tuff succession in the studied area. On the basis of chemical composition these tuffs are in the range of acid to intermediate volcanic rocks. Also magmatic affinity is calc-alkaline and geological setting of the area belongs to volcanic arc granitoid. Petrographic data has shown that various shape and size of shard glass are the main component of tuffs. Based on the field studies, detail microscopy, XRD and electron microprobe analysis (EMPA), the following main minerals are determined: Clinoptilolite+montmorillonite+crystobalite. Clinoptilolite and smectite are predominant minerals in all altered samples. Concerning the Si/Al ratio of 40 point analyses of glass shards the Alborz tuff has clinoptilolite composition. Otherwise the chemical composition of altered shard glass is very similar to clinoptilolite structural formula. By using medium results of chemical data the structural formula for Firuzkuh clinoptilolite is as follow: Si 29.91 Al 6.01 Fe2+ 951 Mg2+ 0.393 Ca 0.222 Na 3.162 K 1.422 Paleogeographic conditions have provided a marginal shallow seawater environment which has been filled by volcanoclastics sequence. In Eocene the zeolitization occur as layers which are confined stratigraphically, it seems this process that took place only in preferred tuffaceous horizons which enriched by shard glass. So the term staratabound can be used for this type zeolitization. In altered tuffs there are a close relationship between clinoptiloite and montmorilonite in some deposits. Alborz range, there was an occasionally marine environment (existence of marine microfossils) with humid climate (remnants of plants in some points). Transformation process (glass zeolite + smectite) provides a further silica contribution to the system, which finally in supersaturation and decreasing pH favors the precipitation of silica in altered tuff. This may have occurred when ground water flow become to mix with saline water to lowering the pH.

  6. 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.

  7. Synthesis of new zeolite structures.

    PubMed

    Li, Jiyang; Corma, Avelino; Yu, Jihong

    2015-10-21

    The search for new zeolites is of continuous interest in the field of zeolite science because of their widespread application in catalysis and adsorption-separation. To this end, considerable efforts have been devoted to the preparation of new zeolites with novel porous architectures and compositions. Taking account of the key factors governing the formation of zeolites (e.g., guest species, framework elements, construction processes, etc.), several synthetic strategies have been developed recently. These allow the discovery of many new zeolites with unprecedented structural features, such as hierarchical pores, odd-ring numbers (11-, 15-rings), extra-large pores (16-, 18-, 20-, 28-, and 30-rings), chiral pores, and extremely complex framework topologies, etc. In this review, we will present the advances in the synthesis of new zeolite structures in the last decade, which are achieved by utilization of the synthetic strategies based on pre-designed structure-directing agents, heteroatom substitution, and topotactic transformations. PMID:25740693

  8. 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.

  9. Zeolite exposure and associated pneumoconiosis

    SciTech Connect

    Casey, K.R.; Shigeoka, J.W.; Rom, W.N.; Moatamed, F.

    1985-06-01

    Naturally occurring zeolite minerals are aluminum silicates widespread in the earth's crust. Several of these minerals have fibrous forms and have been implicated as a possible cause of benign and malignant diseases of the lung and pleura in Turkey. This report describes a patient, living in an area of Nevada rich in zeolites, who presented with idiopathic pleural thickening and pulmonary fibrosis associated with extensive pulmonary deposition of zeolites.

  10. 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 150C 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. _100C 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.

  11. 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.

  12. 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.

  13. 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.

  14. Study of ethylene adsorption on zeolite NaY modified with group I metal ions

    NASA Astrophysics Data System (ADS)

    Sue-aok, Niramai; Srithanratana, Tipaporn; Rangsriwatananon, Kunwadee; Hengrasmee, Sunantha

    2010-04-01

    The adsorption of ethylene by zeolite NaY and zeolite NaY modified by cation exchange with potassium, rubidium, and cesium ions was studied. Cation exchanges were carried out using KNO 3, RbNO 3, and CsNO 3 in the concentration ranges of 0.2-10 mM. XRD patterns and specific surface areas illustrated that modification of NaY zeolite by very dilute solutions containing K +, Rb + and Cs + did not lead to significant changes in the crystallinity. Analysis of metals content (ICP-OES) showed that Cs + can replace Na + better than Rb + and K +. Particle analysis indicated slight decreases in surface area but pore volumes and pore diameters remained unchanged. Ethylene adsorption isotherms indicated that Na-Y zeolite which was modified by 5.0 mM KNO 3, 0.5 mM RbNO 3 and 1.0 mM CsNO 3 could adsorb ethylene better than zeolite Na-Y. K-NaY zeolite adsorbed up to 102.45 cm 3/g ethylene, while Rb-NaY and Cs-NaY zeolites adsorbed up to 98.50 cm 3/g and 90.15 cm 3/g ethylene, respectively. Ethylene adsorption capacities depended on number of adsorption sites and surface interactions.

  15. 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

  16. Enhanced ion mobility in aluminosilicate/polysiloxane network polyelectrolytes

    SciTech Connect

    Siska, D.P.; Shriver, D.F.

    2000-07-01

    A new series of polysiloxane-based single-ion conductors was prepared. These contain solvating oligoether sidechains and covalently linked aluminosilicate or alkoxy/siloxy-aluminate anions attached to the polysiloxane backbone. Of these two systems, the polymers containing aluminosilicate [(SiO){sub 4}Al]{sup {minus}} anions show higher room temperature conductivities (10{sup {minus}6} S/cm) than those with alkoxy/siloxyaluminate [(SiO){sub 2}(CH{sub 2}O){sub 2}Al]{sup {minus}} anions (10{sup {minus}7} S/cm). The incorporation of longer covalent tethers between the alkoxy/siloxyaluminate anion and the polymer backbone results in enhanced room temperature conductivities at high ion loadings. Differential scanning calorimetry data provide a rationale for the high conductivity.

  17. 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 3? 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. Further studies of effects of sodium aluminosilicate on egg shell quality.

    PubMed

    Roland, D A

    1988-04-01

    Five experiments were conducted using 36 dietary treatments to compare chloride salts and HCl as chemical sources of Cl for the adjustment of dietary Cl when using sodium aluminosilicate (SAS), to compare SAS to natural zeolites (clinoptilolite and mordenite), and to determine the appropriate level of dietary SAS for optimum egg specific gravity. The methods of Na and Cl correction used in the various treatments included altering the levels of NaCl, calcium chloride (CaCl2), potassium chloride (KCl), magnesium chloride (MgCl2), iron chloride (FeCl3), or hydrochloric acid (HCl). Experimental diets were fed for 6 to 8 wk. Results of all experiments (except Experiment 2) indicated that the addition of SAS to layer diets improved egg specific gravity and that correction for Na by removal of NaCl and the addition of HCl was not necessary for SAS to be effective. No beneficial effects of dietary SAS on egg specific gravity were observed when Na and Cl corrections were made using CaCl2, KCl, MgCl2, or FeCl3. The feeding of SAS has no influence on egg production in Experiments 1 and 3 but significantly improved egg production in Experiment 4, when it was added to diets containing 2.75% Ca. An adverse effect on production of feeding SAS was observed, especially at the higher levels of SAS in Experiments 2 and 5. In general, SAS tended to reduce feed consumption, with no effect on egg weight. It was concluded that .75% SAS will improve egg specific gravity approximately 1 to 3 units and that correction for Na was not necessary for SAS to be effective. PMID:2841658

  3. Mesoporous aluminosilicate ropes with improved stability from protozeolitic nanoclusters

    SciTech Connect

    Zheng Junlin; Kong Dejin; Yang Weimin; Xie Zaiku; Wu Dong; Sun Yuhan

    2007-02-15

    Mesoporous aluminosilicate ropes with improved hydrothermal stability have been prepared through S{sup +}X{sup -}I{sup +} route via self-assembly of protozeolitic nanoclusters with cetyltrimethylammonium bromides (CTAB) template micelles in HNO{sub 3} solution. SEM observation confirmed that high-yield aluminosilicate ropes could be produced under proper HNO{sub 3} concentration. NO{sub 3} {sup -} ions had strong binding strength to the CTA{sup +} ions and tended to form more elongated surfactant micelles, thus fibrous products were fabricated under the direction of these long rod micelles in shearing flow. At the same time, the NO{sub 3} {sup -} ions combining with CTA{sup +} ions generated more active (CTA{sup +}NO{sub 3} {sup -}) assembly, which effectively catalysed the polymerization of protozeolitic nanoclusters with large volume into highly ordered mesostructures. Compared with normal MCM-41 silica synthesized through S{sup +}X{sup -}I{sup +} route in acidic media, the hydrothermal stability was improved considerably. These protozeolitic nanoclusters survived strongly acidic media and entered into mesostructured framework, which contributed to the improvement of hydrothermal stability. - Graphical abstract: Mesoporous aluminosilicate ropes with enhanced hydrothermal stability were fabricated from protozeolitic nanoclusters through S{sup +}X{sup -}I{sup +} route in HNO{sub 3} solution under the direction of CTAB templates.

  4. 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.

  5. 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.

  6. 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.

  7. Composition-solubility-structure relationships in calcium (alkali) aluminosilicate hydrate (C-(N,K-)A-S-H).

    PubMed

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

    2015-08-14

    The interplay between the solubility, structure and chemical composition of calcium (alkali) aluminosilicate hydrate (C-(N,K-)A-S-H) equilibrated at 50 C is investigated in this paper. The tobermorite-like C-(N,K-)A-S-H products are more crystalline in the presence of alkalis, and generally have larger basal spacings at lower Ca/Si ratios. Both Na and K are incorporated into the interlayer space of the C-(N,K-)A-S-H phases, with more alkali uptake observed at higher alkali and lower Ca content. No relationship between Al and alkali uptake is identified at the Al concentrations investigated (Al/Si ? 0.1). More stable C-(N,K-)A-S-H is formed at higher alkali content, but this factor is only significant in some samples with Ca/Si ratios ?1. Shorter chain lengths are formed at higher alkali and Ca content, and cross-linking between (alumino)silicate chains in the tobermorite-like structure is greatly promoted by increasing alkali and Al concentrations. The calculated solubility products do not depend greatly on the mean chain length in C-(N,K-)A-S-H at a constant Ca/(Al + Si) ratio, or the Al/Si ratio in C-(N,K-)A-S-H. These results are important for understanding the chemical stability of C-(N,K-)A-S-H, which is a key phase formed in the majority of cements and concretes used worldwide. PMID:26134354

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

    PubMed

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

    2009-10-01

    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 m2/g. Optimal crystallization temperature and time were 90 degrees 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%. PMID:19842322

  9. 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.

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

    PubMed

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

    2015-11-01

    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

  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. 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.

  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. 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.

  15. 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

  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. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

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

    PubMed Central

    Shamzhy, Mariya; Opanasenko, Maksym; Shvets, Oleksiy; ?ejka, Ji?

    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 ?-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 ?-pinene with formaldehyde and Pechmann condensation of 1-naphthol with ethylacetoacetate. PMID:24790940

  6. 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.

  7. Copper-containing zeolite catalysts

    DOEpatents

    Price, Geoffrey L. (Baton Rouge, LA); Kanazirev, Vladislav (Sofia, BG)

    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.

  8. 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.

  9. Epitaxial Growth of ZSM-5@Silicalite-1: A Core-Shell Zeolite Designed with Passivated Surface Acidity.

    PubMed

    Ghorbanpour, Arian; Gumidyala, Abhishek; Grabow, Lars C; Crossley, Steven P; Rimer, Jeffrey D

    2015-04-28

    The design of materials with spatially controlled chemical composition has potential advantages for wide-reaching applications that span energy to medicine. Here, we present a method for preparing a core-shell aluminosilicate zeolite with continuous translational symmetry of nanopores and an epitaxial shell of tunable thickness that passivates Brnsted acid sites associated with framework Al on exterior surfaces. For this study, we selected the commercially relevant MFI framework type and prepared core-shell particles consisting of an aluminosilicate core (ZSM-5) and a siliceous shell (silicalite-1). Transmission electron microscopy and gas adsorption studies confirmed that silicalite-1 forms an epitaxial layer on ZSM-5 crystals without blocking pore openings. Scanning electron microscopy and dynamic light scattering were used in combination to confirm that the shell thickness can be tailored with nanometer resolution (e.g., 5-20 nm). X-ray photoelectron spectroscopy and temperature-programmed desorption measurements revealed the presence of a siliceous shell, while probe reactions using molecules that were either too large or adequately sized to access MFI pores confirmed the uniform shell coverage. The synthesis of ZSM-5@silicalite-1 offers a pathway for tailoring the physicochemical properties of MFI-type materials, notably in the area of catalysis, where surface passivation can enhance product selectivity without sacrificing catalyst activity. The method described herein may prove to be a general platform for zeolite core-shell design with potentially broader applicability to other porous materials. PMID:25824422

  10. Brillouin scattering properties of lanthano-aluminosilicate optical fiber.

    PubMed

    Dragic, P D; Kucera, C; Ballato, J; Litzkendorf, D; Dellith, J; Schuster, K

    2014-09-01

    Utilizing measurements on a lanthano-aluminosilicate core optical fiber, the specific effects of lanthana (La2O3) on the Brillouin characteristics of silica-based oxide glass optical fibers are described. Lanthana is an interesting species to investigate since it possesses a wide transparency window covering the common fiber laser and telecom system wavelengths. As might be expected, it is found that the properties of lanthana are very similar to those of ytterbia (Yb2O3), namely, low acoustic velocity, wide Brillouin spectral width, and a negative photoelastic constant, with the latter two properties affording significant reductions to the Brillouin gain coefficient. However, lanthana possesses thermo-acoustic and strain-acoustic coefficients (acoustic velocity versus temperature or strain, TAC and SAC, respectively) with signs that are opposed to those of ytterbia. The lanthano-aluminosilicate (SAL) fiber utilized in this study is Brillouin-athermal (no dependence of the Brillouin frequency on temperature), but not atensic (is dependent upon the strain), which is believed to be, to the best of our knowledge, the first demonstration of such a glass fiber utilizing a compositional engineering approach. PMID:25321361

  11. 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

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

    PubMed

    Sturino, Joseph M; Pokusaeva, Karina; Carpenter, Robert

    2015-12-01

    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

  13. 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

  14. 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.

  15. 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.

  16. Controlled Embedding of Metal Oxide Nanoparticles in ZSM-5 Zeolites through Preencapsulation and Timed Release.

    PubMed

    Lai, Yungchieh; Rutigliano, Michael N; Veser, Gtz

    2015-09-29

    We report a straightforward and transferrable synthesis strategy to encapsulate metal oxide nanoparticles (NPs) in mesoporous ZSM-5 via the encapsulation of NPs into silica followed by conversion of the NP@silica precursor to NP@ZSM-5. The systematic bottom-up approach allows for straightforward, precise control of both the metal weight loading and size of the embedded NP and yields uniform NP@ZSM-5 microspheres composed of stacked ZSM-5 nanorods with substantial mesoporosity. Key to the synthesis is the timed release of the embedded NPs during dissolution of the silica matrix in the hydrothermal conversion step, which finely balances the rate of NP release with the rate of SiO2 dissolution and the subsequent nucleation of aluminosilicate. The synthesis approach is demonstrated for Zn, Fe, and Ni oxide encapsulation in ZSM-5 but can be expected to be broadly transferrable for the encapsulation of metal and metal oxide nanoparticles into other zeolite structures. PMID:26352788

  17. 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? and c=21.8579?. After calcination, the new germanosilicate material exhibited two types of accessible micropores with diameters of 0.61 and 0.78?nm. PMID:26302889

  18. 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.

  19. 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.

  20. 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.

  1. The aluminosilicate fraction of North Pacific manganese nodules

    USGS Publications Warehouse

    Bischoff, J.L.; Piper, D.Z.; Leong, K.

    1981-01-01

    Nine nodules collected from throughout the deep North Pacific were analyzed for their mineralogy and major-element composition before and after leaching with Chester-Hughes solution. Data indicate that the mineral phillipsite accounts for the major part (> 75%) of the aluminosilicate fraction of all nodules. It is suggested that formation of phillipsite takes place on growing nodule surfaces coupled with the oxidation of absorbed manganous ion. All the nodules could be described as ternary mixtures of amorphous iron fraction (Fe-Ti-P), manganese oxide fraction (Mn-Mg Cu-Ni), and phillipsite fraction (Al-Si-K-Na), these fractions accounting for 96% of the variability of the chemical composition. ?? 1981.

  2. 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.

  3. Parameters influencing zeolite incorporation in PDMS membranes

    SciTech Connect

    Vankelecom, I.F.J.; Scheppers, E.; Heus, R.; Uytterhoeven, J.B. )

    1994-11-24

    The incorporation of several types of zeolite in PDMS membranes is studied, by measuring the tensile strength, xylene sorption, and density of the membranes. The zeolite is shown to be involved in the cross-linking of the membrane. The interaction between the PDMS matrix and the zeolites results in reinforced membranes in the case of zeolite Y. The parameters influencing the dispersion of the zeolite in the membrane are investigated, as well as several aspects of the preparation method. Finally, the idea of cross-linking is applied to explain the results of water/ethanol pervaporation. 25 refs., 9 figs., 4 tabs.

  4. Zeolites with Continuously Tuneable Porosity**

    PubMed Central

    Wheatley, Paul S; Chlubn-Eliov, Pavla; Greer, Heather; Zhou, Wuzong; Seymour, Valerie R; Dawson, Daniel M; Ashbrook, Sharon E; Pinar, Ana B; McCusker, Lynne B; Opanasenko, Maksym; ?ejka, Ji?; Morris, Russell E

    2014-01-01

    Zeolites are important materials whose utility in industry depends on the nature of their porous structure. Control over microporosity is therefore a vitally important target. Unfortunately, traditional methods for controlling porosity, in particular the use of organic structure-directing agents, are relatively coarse and provide almost no opportunity to tune the porosity as required. Here we show how zeolites with a continuously tuneable surface area and micropore volume over a wide range can be prepared. This means that a particular surface area or micropore volume can be precisely tuned. The range of porosity we can target covers the whole range of useful zeolite porosity: from small pores consisting of 8-rings all the way to extra-large pores consisting of 14-rings. PMID:25284344

  5. Suspending Zeolite Particles In Tanks

    SciTech Connect

    Poirier, M.R.

    1999-01-19

    The Savannah River Site (SRS) is in the process of removing waste (sludge and salt cake) from million gallon waste tanks. The current practice for removing waste from the tanks is adding water, agitating the tanks with long shaft vertical centrifugal pumps, and pumping the sludge/salt solution from the tank to downstream treatment processes. This practice has left sludge heels ({tilde} 30,000 gallons) in the bottom of the tanks. SRS is evaluating shrouded axial impeller mixers for removing the sludge heels in the waste tanks. The authors conducted a test program to determine mixer requirements for suspending sludge heels using the shrouded axial impeller mixers. The tests were performed with zeolite in scaled tanks which have diameters of 1.5, 6.0, and 18.75 feet. The mixer speeds required to suspend zeolite particles were measured at each scale. The data were analyzed with various scaling methods to compare their ability to describe the suspension of insoluble solids with the mixers and to apply the data to a full-scale waste tank. The impact of changes in particle properties and operating parameters was also evaluated. The conclusions of the work are: Scaling of the suspension of fast settling zeolite particles was best described by the constant power per unit volume method. Increasing the zeolite particle concentration increased the required mixer power needed to suspend the particles. Decreasing the zeolite particle size from 0.7 mm ? 0.3 mm decreased the required mixer power needed to suspend the particles. Increasing the number of mixers in the tank decreased the required mixer power needed to suspend the particles. A velocity of 1.6 ft/sec two inches above the tank bottom is needed to suspend zeolite particles.

  6. Structural Characterization of Zeolite Beta

    NASA Astrophysics Data System (ADS)

    Newsam, J. M.; Treacy, M. M. J.; Koetsier, W. T.; de Gruyter, C. B.

    1988-12-01

    Crystallographic faulting in zeolite structures affects both the catalytic and sorption properties, and can greatly complicate attempts at structural characterization. A near extreme example of stacking disorder is provided by zeolite beta, a large pore, high-silica zeolite that was first reported in 1967. We describe here the determination of the framework structure of zeolite beta, using primarily high-resolution electron microscopy, electron diffraction, computer-assisted modelling and powder X-ray diffraction. Zeolite beta can be regarded as a highly intergrown hybrid of two distinct, but closely related structures that both have fully three-dimensional pore systems with 12-rings as the minimum constricting apertures. One end member, polymorph A, forms an enantiomorphic pair, space group symmetries P4_122 and P4_322, with a = 1.25 nm, c = 2.66 nm. Polymorph B is achiral, space group C2/c with a = 1.76 nm, b = 1.78 nm, c = 1.44 nm, ? = 114.5^circ. Both structures are constructed from the same centrosymmetric tertiary building unit (TBU), arranged in layers that, successively, interconnect in either a left- (L) or a right- (R) handed fashion. Polymorph A represents an uninterrupted sequence of RRRR... (or LLLL...) stacking. Polymorph B has an alternating RLRL... stacking sequence. The TBU has no intrinsic preference for either mode of connection, enabling both to occur with almost equal probability in zeolite beta, giving rise to a near random extent of interplanar stacking faults and, to a lesser extent, intraplanar defects terminated by hydroxyl groups. The faulting does not significantly affect the accessible pore volume, but influences the tortuosity of the pore connectivity along the c direction. The high stacking fault densities give rise to complex powder X-ray diffraction (PXD) patterns for zeolite beta materials that comprise both sharp and broad features. By exploiting recursive relations between possible stacking sequences, PXD patterns have been calculated as a function of faulting probability. Reasonable agreement with observed PXD profiles is observed for a ca. 60% faulting probability in the chiral stacking sequence, suggesting a slight preference for polymorph B. The framework building units observed in zeolite beta can also be used to construct other frameworks.

  7. Enhanced selectivity of zeolites by controlled carbon deposition

    DOEpatents

    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.

  8. 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

  9. Selective Chlorination of Toluene to p-Chlorotoluene Catalyzed by Nanosized Zeolite K-L Catalysts.

    PubMed

    Zhu, Xiaoyan; Fu, Yujun; Yin, Hengbo; Feng, Yonghai; Shen, Lingqin; Wang, Aili; Li, Jitai; Ni, Wenxiu; Xie, Xulan

    2015-08-01

    Nanosized zeolite K-L catalysts were synthesized by the hydrothermal method starting from silica sol and potassium aluminate. The crystallinities of the zeolite K-L catalysts increased with increasing the SiO2/Al2O3 mole ratio of reaction solution and prolonging the autoclaving time. Nanosized and well-dispersed zeolite K-L catalysts were synthesized when the SiO2/Al2O3 mole ratio was more than 26:1. Well-crystallized and nanosized zeolite K-L catalysts showed high catalytic activity for the chlorination of toluene to p-chlorotoluene. When the nanosized zeolite K-L catalyst was synthesized with the SiO2/Al2O3 mole ratio of 31:1 at the autoclaving temperature of 150 C for 96 h, the selectivities of p-chlorotoluene and o-chlorotoluene were 76.2% and 20.0%, respectively, at the complete conversion of toluene. PMID:26369216

  10. 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.

  11. Luminescent properties of Tb3+ and Gd3+ ions doped aluminosilicate oxyfluoride glasses.

    PubMed

    Zuo, Chenggang; Lu, Anxian; Zhu, Ligang; Zhou, Zhihua; Long, Woyun

    2011-11-01

    Tb(3+) and Gd(3+) ions doped lithium-barium-aluminosilicate oxyfluoride glasses have been prepared. The transmission, emission and excitation spectra were measured. It has been found that those Tb(3+)-doped lithium-barium-aluminosilicate oxyfluoride glasses exhibit good UV-excited luminescence. The luminescence intensity of Tb(3+) ion increases for those (Tb(3+), Gd(3+))-codoped glasses. Energy transfer process from Gd(3+) ion to Tb(3+) ion is indicated. PMID:21831699

  12. 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.

  13. 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.

  14. 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.

  15. 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...

  16. 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.

  17. 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

  18. 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.

  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. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  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. Increased thermal conductivity monolithic zeolite structures

    DOEpatents

    Klett, James (Knoxville, TN); Klett, Lynn (Knoxville, TN); Kaufman, Jonathan (Leonardtown, MD)

    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.

  7. 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

  8. 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

  9. 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

  10. 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.

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

    SciTech Connect

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

    2007-01-01

    Highly dealuminated Y zeolite-supported mononuclear iridium complexes with reactive ethylene ligands were synthesized by chemisorption of Ir(C2H4)2(C5H7O2). 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(C2H4)2(C5H7O2) reacted readily with surface OH groups of the zeolite, leading to the removal of C5H7O2 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 Angstroms, consistent with the presence of two ethylene ligands per Ir atom and in agreement with the IR spectra indicating p-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 Angstroms . The supported iridium-ethylene complex reacted with H2 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)2 complexes bonded to the zeolite. The sharpness of the ?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.

  12. Nanocrystalline Zeolites: Synthesis, Mechanism, and Applications

    NASA Astrophysics Data System (ADS)

    Severance, Michael Andrew

    Nanocrystalline zeolite particles are becoming an important material in many technical applications (e.g. zeolite membranes). Synthetic methods that minimize the zeolite crystal diameter, while providing a narrow particle size distribution, are of primary importance in these technical applications. However, there are several limitations to currently existing synthetic routes aimed at producing nanozeolites and zeolite membrane devices. For example, zeolite growth in these contexts typically requires days to weeks at high temperature to crystallize. Despite excellent performance of zeolite membranes in several separation applications, the long synthesis times required undermine any practical application of these technologies. This work focuses on chemical manipulation of zeolite nucleation processes in sol gel systems in effort to address such limitations. The primary findings indicate that careful control of the nucleation stage of a clear zeolite synthesis (optically transparent sol gel) allow the formation of zeolite Y nanocrystals less than 50 nm in diameter with a polydispersity index less than 0.2. Furthermore, chemical perturbations made during the nucleation stage of zeolite Y hydrogel synthesis is shown to accelerate crystal growth by a factor of 3-4, depending on the specific sol gel chemistry. These findings are applied to the nanocrystal seeding and rapid hydrothermal growth of zeolite Y membranes on inexpensive polymeric supports. A novel synthetic method is developed to this end. Also, the chemical and physical properties of monodisperse nanocrystalline zeolite Y synthesized herein are explored by electrochemical impedance spectroscopy. It is found that the particle interface plays an important role in the ionic conductivity of nanocrystalline zeolites in contrast to their larger zeolite counterparts in analogy to other ceramic and metal oxide ion conductors. Finally, the possibility to produce novel organic and inorganic composite systems through zeolite host-guest chemistry is explored. A nanozeolite-silver nanoparticle host-guest system is synthesized and a mechanism describing its evolution is developed. Also, the photochemistry of a colloidal nanozeolite-organic dye host-guest system is explored with ultrafast transient UV-Vis absorption spectroscopy. This allows some of the fastest chemical events to be probed within the host-guest system.

  13. 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.

  14. 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.

  15. Novel aluminosilicate hollow sphere as a catalyst support for methane decomposition to COx-free hydrogen production

    NASA Astrophysics Data System (ADS)

    Awadallah, A. E.; Ahmed, W.; El-Din, M. R. Noor; Aboul-Enein, A. A.

    2013-12-01

    Novel Ni and Co supported on aluminosilicate hollow sphere catalysts were investigated to decompose methane into CO and CO2 free hydrogen and carbon nanotube. The hollow sphere structure was prepared by reverse microemulsion method and then Ni and Co were loaded by the impregnation method. The fresh catalysts and deposited carbon were characterized by several microscopic and spectroscopic techniques. The catalytic results showed that the Co based catalyst exhibited higher activity and durability at longer reaction time, due to the higher number and distribution of metal sites. The hollow sphere structure of the support could protect the metal particles against aggregation during the catalytic reactions. Accordingly, higher metal dispersion, stabilization and catalytic performance were achieved. The formation of nickel silicate is the main reason for the lower decomposition activity of Ni based catalyst at longer reaction time. TEM and Raman spectroscopic data revealed that the Co-based catalyst produced a relatively uniform diameter of MWCNTs with higher crystallinity and graphitization degree compared to the Ni-based catalyst.

  16. 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.

  17. 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...

  18. Li{sup +} alumino-silicate ion source development for the neutralized drift compression experiment

    SciTech Connect

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

    2011-01-15

    We report results on lithium alumino-silicate ion source development in preparation for warm dense matter heating experiments on the new neutralized drift compression experiment II. 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 {approx_equal}1275 deg. C, a space-charge limited Li{sup +} beam current density of J {approx_equal}1 mA/cm{sup 2} was obtained. The lifetime of the ion source was {approx_equal}50 h while pulsing at a rate of 0.033 Hz with a pulse duration of 5-6 {mu}s.

  19. 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.

  20. 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.

  1. 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.

  2. Aluminosilicate filled with aluminum oxyhydroxide used as a dielectric substrate for LED devices

    NASA Astrophysics Data System (ADS)

    Ivanov, A. A.; Tuev, V. I.

    2015-10-01

    New aluminosilicate filled with aluminum oxyhydroxide (AlO(OH)) is offered as a dielectric substrate (DS) for LED devices. The DS obtained from these substances has high thermal conductivity up to ? = 133.61 W/mK and its value depends on the amount of AlO(OH) in the DS. Such high thermal conductivity is achieved by the homogeneous distribution of a large number of AlO(OH) nanosized particles in crowns of dendrimer aluminosilicate ensembles. The AlO(OH) particles size is comparable to that of voids between branches in the aluminosilicate crowns. The adhesive strength of the filled alumosilicate (80% of AlO(OH)) applied under a shear on the aluminum plate (its roughness is 11.3 ?m) is 47 N/mm2.

  3. 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...

  4. Noble metal acidic zeolites for isomerization

    SciTech Connect

    Schweizer, A.E.

    1991-02-12

    This patent describes a method for producing a noble metal containing zeolite catalyst for isomerization of paraffinic hydrocarbons. Contacting a zeolite material selected from the group consisting of acidic fayjasites. LZ-210 faujasites, and mordenite with a noble-metal compound selected from Pt(acetylacetonate){sub 2} and Pd(acetylacetonate){sub 2} for an effective amount of time to incorporate Pt and/or Pd into the pore surface regions of the zeolite, but not to disperse the Pt and/or Pd throughout the entire zeolite; and calcining the so treated zeolite at a temperature from about 250 {degrees} C, to about 600 {degrees} C. for an effective amount of time.

  5. [Spectroscopic analysis of the crystallization mechanism of synthesized zeolite with XRD and FTIR approaches].

    PubMed

    Fan, Chun-hui; Ma, Hong-rui; Hua, Li

    2012-04-01

    Zeolites were synthesized from fly ash using modified one-stage method. The changes in cation exchange capacity (CEC) and chemical elements of zeolite were investigated during the synthesis process to reveal the materials and elements transformation in solid-liquid system. The approaches of XRD, SEM and FTIR were used to indicate the crystallization characteristics and mechanism. The zeolite NaP1 was synthesized, and the CEC value reached to the maximum of 135 mmol/100g at 24 h. After the hydrothermal reaction for 12 h, the characteristic peak and metastable crystalline structure of zeolite NaP1 appeared, then the hydroxy sodalite products formed at 48 h. The crystallization process was the result of materials transformation: the elements of fly ash released into the liquid system for the melting effect of alkali solution, and the solid system played the role of skeleton in crystallization process, being the "source" and the "sink" of the reaction, respectively, and the achievements presented the crystallization mechanism of liquid-phase and solid-phase transformation. PMID:22715798

  6. 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.

  7. Calculation of the Aluminosilicate Half-Life Formation Time in the 2H Evaporator

    SciTech Connect

    Fondeur, F.F.

    2000-09-21

    The 2H Evaporator contains large quantities of aluminosilicate solids deposited on internal fixtures. The proposed cleaning operations will dissolve the solids in nitric acid. Operations will then neutralize the waste prior to transfer to a waste tank. Combining recent calculations of heat transfer for the 2H Evaporator cleaning operations and laboratory experiments for dissolution of solid samples from the pot, the authors estimated the re-formation rate for aluminosilicates during cooling. The results indicate a half-life formation of 17 hours when evaporator solution cools from 60 degrees C and 9 hours when cooled from 90 degrees C.

  8. The Yb-doped aluminosilicate fibers photodarkening mechanism based on the charge-transfer state excitation

    NASA Astrophysics Data System (ADS)

    Rybaltovsky, A. A.; Bobkov, K. K.; Velmiskin, V. V.; Umnikov, A. A.; Shestakova, I. A.; Guryanov, A. N.; Likhachev, M. E.; Bubnov, M. M.; Dianov, E. M.

    2014-03-01

    We have studied the photodarkening effect in fiber preforms with an ytterbium-doped aluminosilicate glass core. The room-temperature stable Yb2+ ions formation in the glass matrix under both UV- and NIR-pumping irradiation was revealed by the method of absorption spectra analysis and the fluorescence spectroscopy technique. Comparative studies of preforms and crystals samples luminescence spectra, obtained under UV-excitation, were performed. A general mechanism of Yb2+ ions and aluminium oxygen-hole centers (Al-OHC) formation as a result of photoinduced process of Yb3+ ions excitation to "charge-transfer state" (CTS) was found for both Yb:YAG crystal and aluminosilicate glass.

  9. 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.

  10. 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 510(-7) to 1.8410(-2) M with a low detection limit of 3.710(-7) M. The sensor also exhibits good repeatability, long-term stability as well as high selectivity against interfering species. PMID:25499226

  11. Water nanodroplets confined in zeolite pores.

    PubMed

    Coudert, Franois-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

  12. 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.

  13. 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.

  14. 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

  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. One-pot surfactant assisted synthesis of aluminosilicate macrochannels with tunable micro- or mesoporous wall structure.

    PubMed

    Lonard, Alexandre; Blin, Jean-Luc; Su, Bao-Lian

    2003-10-21

    A one-step surfactant assisted synthesis pathway was developed leading to novel hierarchical macro-meso- (or micro-)porous aluminosilicates made of an assembly of macrochannels with openings between 0.5 and 2.0 microm and wormhole-like amorphous walls with tunable pore sizes. PMID:14594284

  17. State-of-the-art alumino-silicate refractories for al electrolysis cells

    NASA Astrophysics Data System (ADS)

    Siljan, Ole-Jacob; Schoning, Christian; Grande, Tor

    2002-05-01

    The refractory material of choice for aluminum cell bottom linings worldwide is alumino-silicates, due to high availability, relatively low cost, and empirically good performance. During operation of aluminum electrolysis cells, the alumino-silicates are subjected to infiltration and attack by molten electrolyte components. The penetration of sodium and molten fluorides through the cathode causes significant mineralogical transformation in the refractory, and, in extreme situations, it may terminate the pot life. This paper reviews the current understanding of deterioration mechanisms for refractory materials used in bottom lining of aluminum reduction cells. The silica content of the alumino-silicate refractories is the major single factor affecting deterioration rates through the formation of viscous melts and a glass-like barrier in the reacted lining. In addition, reactions between metallic sodium and alumino-silicate refractories may cause volume expansions in the exposed lining. The present review concludes that firebricks with an optimum silica content are probably still the best penetration barriers available.

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. Liquid crystalline bispropargyl thermosets

    SciTech Connect

    Langlois, D.A.; Benicewicz, B.C.; Douglas, E.P.

    1998-11-01

    A series of rigid-rod bispropargyl thermoset monomers have been synthesized. These monomers were examined by differential scanning calorimetry (DSC) and hot stage polarized optical microscopy. Enantiotropic or monotropic nematic liquid crystalline phases were observed for all but two monomers. Partial curing of these reactive liquid crystalline monomers resulted in the formation of stable liquid crystalline phases with broad nematic phase after partial curing. DSC investigations indicated that the onset temperature of thermally induced cross-linking was approximately 260 C and insensitive to the phase type. The rate of cure was insensitive to the phase in which the cure occurred due to the unusual reaction mechanism for the propargyl end group.

  5. 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

  6. 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.

  7. Mixing of zeolite powders and molten salt

    SciTech Connect

    Pereira, C.; Zyryanov, V.N.; Lewis, M.A.; Ackerman, J.P.

    1996-05-01

    Transuranics and fission products in a molten salt can be incorporated into zeolite A by an ion exchange process and by a batch mixing or blending process. The zeolite is then mixed with glass and consolidated into a monolithic waste form for geologic disposal. Both processes require mixing of zeolite powders with molten salt at elevated temperatures (>700 K). Complete occlusion of salt and a uniform distribution of chloride and fission products are desired for incorporation of the powders into the final waste form. The relative effectiveness of the blending process was studied over a series of temperature, time, and composition profiles. The major criteria for determining the effectiveness of the mixing operations were the level and uniformity of residual free salt in the mixtures. High operating temperatures (>775 K) improved salt occlusion. Reducing the chloride levels in the mixture to below 80% of the full salt capacity of the zeolite significantly reduced the free salt level in the final product.

  8. Complexation of porphyrins with nanoparticles of zeolite

    NASA Astrophysics Data System (ADS)

    Gyulkhandanyan, Anna G.; Zakoyan, Anna A.; Sargsyan, Hakob H.; Ghazaryan, Robert K.; Sheyranyan, Marina A.; Gyulkhandanyan, Grigor V.

    2015-06-01

    The binding of nanoparticles zeolite with a number of cationic porphyrins are studied. Previously, it was established that the main mechanism of binding the zeolite nanoparticles with cationic porphyrins is an ionic bond. Since binding of porphyrins as ligands to nanoparticles at the initial stage of interaction is determined by the Brownian motion of porphyrins, it is obvious that the interaction of porphyrins with nanoparticles may depend on the temperature. In the present paper by methods of absorption and fluorescence spectroscopy was studied the complexation of porphyrins with zeolite nanoparticles at different temperature conditions. It was established that there is a clear temperature dependence of the complexation of cationic metalloporphyrins with zeolite naonoparticles, and for correct determination of the percentage of binding must be strict thermostating of the experimental conditions.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Probing zeolites by vibrational spectroscopies.

    PubMed

    Bordiga, Silvia; Lamberti, Carlo; Bonino, Francesca; Travert, Arnaud; Thibault-Starzyk, Frdric

    2015-10-21

    This review addresses the most relevant aspects of vibrational spectroscopies (IR, Raman and INS) applied to zeolites and zeotype materials. Surface Brnsted and Lewis acidity and surface basicity are treated in detail. The role of probe molecules and the relevance of tuning both the proton affinity and the steric hindrance of the probe to fully understand and map the complex site population present inside microporous materials are critically discussed. A detailed description of the methods needed to precisely determine the IR absorption coefficients is given, making IR a quantitative technique. The thermodynamic parameters of the adsorption process that can be extracted from a variable-temperature IR study are described. Finally, cutting-edge space- and time-resolved experiments are reviewed. All aspects are discussed by reporting relevant examples. When available, the theoretical literature related to the reviewed experimental results is reported to support the interpretation of the vibrational spectra on an atomic level. PMID:26435467

  14. 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.

  15. 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

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. 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 ... ).

  2. 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.

  3. 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.

  4. 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

  5. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

    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 Brnsted 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.

  7. 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.

  8. 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.

  9. Mechanism of the etching rate change of aluminosilicate glass in HF acid with micro-indentation

    NASA Astrophysics Data System (ADS)

    Saito, Yasuhiro; Okamoto, Shinya; Inomata, Hiroyuki; Kurachi, Junji

    2008-12-01

    The etching rate of some kind of glass decreases with micro-indentation. This paper is concerned chiefly with the mechanism for aluminosilicate glass. The change of glass surface condition arising from the indentation and the etching has been examined with X-ray photoelectron spectroscopy (XPS). It was found that the leaching reaction observed through the HF acid etching at non-indented area was restricted at the indented area. The etching rate change should be attributed to the leaching mechanism.

  10. Synthesis and catalytic properties of metal clusters encapsulated within small-pore (SOD, GIS, ANA) zeolites.

    PubMed

    Goel, Sarika; Wu, Zhijie; Zones, Stacey I; Iglesia, Enrique

    2012-10-24

    The synthesis protocols for encapsulation of metal clusters reported here expand the diversity in catalytic chemistries made possible by the ability of microporous solids to select reactants, transition states, and products on the basis of their molecular size. We report a synthesis strategy for the encapsulation of noble metals and their oxides within SOD (Sodalite, 0.28 nm 0.28 nm), GIS (Gismondine, 0.45 nm 0.31 nm), and ANA (Analcime, 0.42 nm 0.16 nm) zeolites. Encapsulation was achieved via direct hydrothermal synthesis for SOD and GIS using metal precursors stabilized by ammonia or organic amine ligands, which prevent their decomposition or precipitation as colloidal hydroxides at the conditions of hydrothermal synthesis (<380 K) and favor interactions between metal precursors and incipient aluminosilicate nuclei during self-assembly of microporous frameworks. The synthesis of ANA requires higher crystallization temperatures (~415 K) and high pH (>12), thereby causing precipitation of even ligand-stabilized metal precursors as hydroxides. As a result, encapsulation was achieved by the recrystallization of metal clusters containing GIS into ANA, which retained these metal clusters within voids throughout the GIS-ANA transformation. PMID:23016946

  11. 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.

  12. 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

  13. Hydrogen isotope separation using molecular sieve of synthetic zeolite 3A

    SciTech Connect

    Kotoh, K.; Kimura, K.; Nakamura, Y.; Kudo, K.

    2008-07-15

    It is known that hydrogen isotope molecules can be adsorbed easily onto synthetic zeolite 4A, 5A, and 13X at the liquid-nitrogen temperature of 77.4 K. We show here that hydrogen and deuterium are not adsorptive onto zeolite 3A at the same temperature. This phenomenon is explained by assuming the molecular sieve function in zeolite-3A-crystalline lattice structure. From a series of pseudo-isobaric experiments, it is also shown that the sieving phenomenon appears in a range above 77.4 K. This behavior is interpreted as resulting on the dependence of sieve's mesh size on temperature, where the sieving effect is considered to appear at a certain temperature. In this interpretation, an isotopic difference between hydrogen and deuterium is suggested to exist in the sieving effect appearance temperatures. This is endorsed in the result of pseudo-isobaric experiments. This temperature deference is very significant because that indicates the possibility of an effective method of hydrogen isotope separation. This possibility is verified through an experimental series of adsorption-desorption with a mixture of H{sub 2} and D{sub 2}, where the gas samples adsorbed through the sieve operated at intentionally selected temperatures are isolated and then analyzed. The result demonstrates remarkable values of isotope separation factor. (authors)

  14. 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

  15. 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.

  16. Hydration effects on the structural and vibrational properties of yttrium aluminosilicate glasses for in situ radiotherapy.

    PubMed

    Malik, Jahangir; Tilocca, Antonio

    2013-11-21

    The performances of silicate glasses as containment matrices or vectors of radioactive ions in nuclear waste storage and in situ radiotherapy are influenced by the effect of interstitial water on the glass durability. In order to assess how hydration determines changes to atomistic structural features which control the glass degradation, we have carried out molecular dynamics simulations of a typical yttrium aluminosilicate (YAS) glass employed in radiotherapy, incorporating different water contents. The analysis of the models allows us to discuss the way in which hydroxyl groups are distributed in the glass structure and modify or disrupt the aluminosilicate glass network. Hydration affects the silicate and aluminate connectivity to a different extent, resulting in a different degree of disruption (depolymerization) of the Si and Al network. The simulations also highlight a strong tendency of all hydrated compositions to form Y(3+)- and OH(-)-rich domains, separated from the aluminosilicate matrix. The implications of these structural effects for the durability and ion release behavior of the glass are discussed, as well as the vibrational signatures of the various hydrous species identified in the models. PMID:24206236

  17. Sorption of 137Cs, 133Ba and 154Eu by synthesized sodium aluminosilicate (Na-AS).

    PubMed

    Singh, B K; Tomar, Radha; Kumar, Sumit; Jain, Aishwarya; Tomar, B S; Manchanda, V K

    2010-06-15

    Sodium aluminosilicate has been synthesized by solution route for use as a sorbent for various radionuclides. It was characterized by XRD, zeta potential, BET surface area, FTIR spectroscopy and site density measurement. Sorption studies of (137)Cs, (133)Ba and (154)Eu on synthesized sodium aluminosilicate have been carried out at varying pH (3-10). Sorption of all the metal ions was found to increase with pH of suspension with the saturation value increasing with the oxidation state of metal ion. Effect of Aldrich humic acid (2mg/l) on sorption was also investigated. In case of (137)Cs, the sorption was not affected by the presence of humic acid, while in case of (133)Ba and (154)Eu, sorption was enhanced at lower pH and decreased at higher pH in presence of HA. A series of experiments were carried out for (154)Eu sorption on sodium aluminosilicate at various conditions. Sorption of europium was analyzed by different sorption isotherms, viz., Freundlich and D-R isotherm. Thermodynamic data reveal sorption phenomena as endothermic and spontaneous. Studies were further extended to find out effect of diverse ions (Ca(2+) and CO(3)(2-)) on sorption of europium. PMID:20236759

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

    PubMed Central

    Pigott, G. H.; Ishmael, J.

    1992-01-01

    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

  19. 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 (19T), 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

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

    SciTech Connect

    Greenway, W. G.; Kwan, J. W.

    2012-02-10

    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 ∼1275{degrees}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 source with an alumino-silicate coating 6.35 mm in diameter and ≤0.25 mm thick, has a lifetime of ∼40 hours at ∼1275{degrees}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. Furthermore, the source lifetime increases with the amount of alumino-silicate coated on the emitting surface, and may also be extended if the temperature is reduced between pulses.

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

    SciTech Connect

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

    2012-03-05

    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 #24;~1275#14;{degrees} C. At higher extraction voltages, the source appears to become emission limited with J #21;{>=} 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, {<=}#20;0.25 mm thick, has a measured lifetime of ~#24;40 hours at ~#24;1275#14;{degrees} C, when pulsed at 0.05 Hz and with pulse length of #24;~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.

  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. 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

  5. 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.

  6. 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.

  7. 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

  8. Substitution clustering in a non-stoichiometric celsian synthesized by the thermal transformation of barium exchanged zeolite X

    SciTech Connect

    Clayden, Nigel J. . E-mail: N.Clayden@uea.ac.uk; Esposito, Serena; Ferone, Claudio; Pansini, Michele

    2006-07-15

    The thermal transformation of Ba exchanged zeolite X to celsian has been studied by {sup 27}Al and {sup 29}Si MAS NMR spectroscopy. Evidence for the degradation of the zeolite framework is present in the {sup 29}Si NMR spectra after thermal treatment at 850 deg. C. Confirmation is provided by the {sup 29}Si NMR data that synthesis of celsian via the decomposition of Ba exchanged zeolite leads to a single defect phase. Clustering of the isomorphous replacement of aluminium by silicon must occur to explain the observed {sup 29}Si chemical shifts. The {sup 27}Al NMR data show distorted aluminium co-ordination sites upon the thermal transformation of Ba exchanged zeolite X. The distortions present in the amorphous matrix are greater than those present in the monoclinic and hexagonal crystalline phases of celsian. - Graphical abstract: Monte Carlo simulation of the Q {sub 4}(mAl) silicon connectivity in the {alpha}-hexagonal celsian lattice, for a Si/Al ratio of 1:1. Si atoms are shown in yellow and the Al atoms in black.

  9. Pressure-Induced Amorphization of Small Pore Zeolites-the Role of Cation-H2O Topology and Anti-glass Formation.

    PubMed

    Chan Hwang, Gil; Joo Shin, Tae; Blom, Douglas A; Vogt, Thomas; Lee, Yongjae

    2015-01-01

    Systematic studies of pressure-induced amorphization of natrolites (PIA) containing monovalent extra-framework cations (EFC) Li(+), Na(+), K(+), Rb(+), Cs(+) allow us to assess the role of two different EFC-H2O configurations within the pores of a zeolite: one arrangement has H2O molecules (NATI) and the other the EFC (NATII) in closer proximity to the aluminosilicate framework. We show that NATI materials have a lower onset pressure of PIA than the NATII materials containing Rb and Cs as EFC. The onset pressure of amorphization (PA) of NATII materials increases linearly with the size of the EFC, whereas their initial bulk moduli (P1 phase) decrease linearly. Only Cs- and Rb-NAT reveal a phase separation into a dense form (P2 phase) under pressure. High-Angle Annular Dark Field Scanning Transmission Electron Microscopy (HAADF-STEM) imaging shows that after recovery from pressures near 25 and 20?GPa long-range ordered Rb-Rb and Cs-Cs correlations continue to be present over length scales up to 100?nm while short-range ordering of the aluminosilicate framework is significantly reduced-this opens a new way to form anti-glass structures. PMID:26455345

  10. 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.

  11. Spectroscopic characterization of bismuth embedded Y zeolites

    NASA Astrophysics Data System (ADS)

    Sun, Hong-Tao; Sakka, Yoshio; Miwa, Yuji; Shirahata, Naoto; Fujii, Minoru; Gao, Hong

    2010-09-01

    Bismuth embedded Y zeolites were studied by using UV-vis- near infrared (NIR) diffuse reflectance, Raman, and steady-state NIR photoluminescence spectroscopy. The results suggest that Bi53+ and Bi+ active centers coexist in the dehydrated and hydrated zeolite framework, both of which contribute to NIR emission. Furthermore, it was revealed that the high-temperature annealing leads to the formation of Bi2O3 clusters, which act as blocks for selectively closing down the "in-out windows" of H2O and O2 molecules in the zeolites. It is believed that these materials can find a wide array of applications as active media of broadly tunable micro or nano-optical sources.

  12. 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.

  13. 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

  14. Studies of anions sorption on natural zeolites.

    PubMed

    Barczyk, K; Mozgawa, W; Krl, M

    2014-12-10

    This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method. PMID:25002191

  15. Natural zeolite reactivity towards ozone: the role of compensating cations.

    PubMed

    Valds, Hctor; Alejandro, Serguei; Zaror, Claudio A

    2012-08-15

    Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L(-1)). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH(3)-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal. PMID:22633878

  16. 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

  17. Formation of Gold Nanoparticles in Zeolites

    NASA Astrophysics Data System (ADS)

    Pestryakov, A.; Tuzovskaya, I.; Smolentseva, E.; Bogdanchikova, N.; Jentoft, F. C.; Knop-Gericke, A.

    The formation of gold nanoparticles in mordenites has been studied by the methods of FTIR spectroscopy of adsorbed CO and diffuse reflectance UV-visible spectroscopy. Different states of ionic and metallic gold were detected in the zeolite cavities and on the external surface of the zeolite - Au+ and Au3+ ions, charged clusters Aun?+, and neutral nanoparticles Aum. The relative amount of these states depends on the method of sample preparation, type of redox treatment and the SiO2/Al2O3 molar ratio.

  18. 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.

  19. Electrostatic potential and field approximation for aluminosilicates in cation-substituted forms

    NASA Astrophysics Data System (ADS)

    Larin, A. V.; Semenyuk, R. A.; Trubnikov, D. N.; Vercauteren, D. P.

    2007-04-01

    Water molecules were removed from the X-ray structure models of zeolites with comparatively small-sized unit cells (BIK, BRE, EDI, GIS, GOO, LAU, and PHI), and cations were replaced by cations of only one type (Mg or Zn). The dehydrated zeolite models obtained were optimized with the Bush and Catlow force fields. The dependences of atomic multipole moments up to the fourth order along the so-called cumulative coordinate were calculated for these models by the density functional method with periodic boundary conditions. These dependences were used to estimate the electrostatic potential and electric field in the cross section of a zeolite that was not used to calculate them. The data obtained with atomic charges borrowed directly from calculation results were quite satisfactory.

  20. 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.

  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. High permeate flux of PVA/PSf thin film composite nanofiltration membrane with aluminosilicate single-walled nanotubes.

    PubMed

    Baroa, Garry Nathaniel B; Choi, Mijin; Jung, Bumsuk

    2012-11-15

    A new type of thin film nanocomposite (TFN) membranes for nanofiltration was successfully prepared by incorporating aluminosilicate single-walled nanotubes (SWNTs) within the poly(vinyl alcohol) (PVA) matrix. The nanocomposite PVA film was composed of well dispersed synthesized aluminosilicate SWNT with up to 20% volume fraction cast on a polysulfone support. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) revealed that the TFN membranes have characteristic bands at 920-1010 cm(-1) corresponding to Si-OH and Si-O-Al stretching vibration of the aluminosilicate SWNT. This insinuated the successful incorporation of aluminosilicate SWNT into the polymer matrix, which was further confirmed and quantified by X-ray photoelectron spectroscopy (XPS). The PVA layers, in the range of 0.99-1.36 ?m, are free from large defects or cracks as observed in the scanning electron microscopy (SEM) images. The membrane surface hydrophilicity increased as the membrane roughness decreased and as the contact angles decreased from 64.2 to 59.4-50.5. The increase in water flux is due to the presence of hydrophilic nanotubes. With the incorporation of the aluminosilicate single-walled nanotubes, higher permeate water flux was achieved, while sustaining high rejection of divalent ions (97%) and monovalent ions (59%). PMID:22918049

  3. Liquid crystalline composites containing phyllosilicates

    DOEpatents

    Chaiko; David J. (Naperville, IL)

    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.

  4. 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.

  5. 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

  6. 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.

  7. 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

  8. COLLIDING CRYSTALLINE BEAMS.

    SciTech Connect

    WEI, J.

    1998-06-26

    The understanding of crystalline beams has advanced to the point where one can now, with reasonable confidence, undertake an analysis of the luminosity of colliding crystalline beams. Such a study is reported here. It is necessary to observe the criteria, previously stated, for the creation and stability of crystalline beams. This requires, firstly, the proper design of a lattice. Secondly, a crystal must be formed, and this can usually be done at various densities. Thirdly, the crystals in a colliding-beam machine are brought into collision. We study all of these processes using the molecular dynamics (MD) method. The work parallels what was done previously, but the new part is to study the crystal-crystal interaction in collision. We initially study the zero-temperature situation. If the beam-beam force (or equivalent tune shift) is too large then overlapping crystals can not be created (rather two spatially separated crystals are formed). However, if the beam-beam force is less than but comparable to that of the space-charge forces between the particles, we find that overlapping crystals can be formed and the beam-beam tune shift can be of the order of unity. Operating at low but non-zero temperature can increase the luminosity by several orders of magnitude over that of a usual collider. The construction of an appropriate lattice, and the development of adequately strong cooling, although theoretically achievable, is a challenge in practice.

  9. Colliding crystalline beams

    SciTech Connect

    Wei, J.; Sessler, A.M.

    1998-08-01

    The understanding of crystalline beams has advanced to the point where one can now, with reasonable confidence, undertake an analysis of the luminosity of colliding crystalline beams. Such a study is reported here. It is necessary to observe the criteria, previously stated, for the creation and stability of crystalline beams. This requires, firstly, the proper design of a lattice. Secondly, a crystal must be formed, and this can usually be done at various densities. Thirdly, the crystals in a colliding-beam machine are brought into collision. The authors study all of these processes using the molecular dynamics (MD) method. The work parallels what was done previously, but the new part is to study the crystal-crystal interaction in collision. They initially study the zero-temperature situation. If the beam-beam force (or equivalent tune shift) is too large then overlapping crystals can not be created (rather two spatially separated crystals are formed). However, if the beam-beam force is less than but comparable to that of the space-charge forces between the particles, they find that overlapping crystals can be formed and the beam-beam tune shift can be of the order of unity. Operating at low but non-zero temperature can increase the luminosity by several orders of magnitude over that of a usual collider. The construction of an appropriate lattice, and the development of adequately strong cooling, although theoretically achievable, is a challenge in practice.

  10. 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…

  11. 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.

  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. Framework Al zoning in zeolite ECR-1.

    PubMed

    Shin, Jiho; Ahn, Nak Ho; Cho, Sung June; Ren, Limin; Xiao, Feng-Shou; Hong, Suk Bong

    2014-02-25

    Rietveld analyses of the synchrotron X-ray diffraction data for various cation forms of zeolite ECR-1 have demonstrated framework Al zoning, which parallels the alternation of Al-rich maz and Al-poor mor layers. This can be further supported by notable differences in the average bond valence of its 10 crystallographically distinct tetrahedral sites. PMID:24409461

  14. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, Wolfgang M. H. (Evanston, IL); Tzou, Ming-Shin (Evanston, IL); Jiang, Hui-Jong (Evanston, IL)

    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.

  15. 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.

  16. 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...

  17. 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...

  18. 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 ...

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Zeolite Nanoparticles for Selective Sorption of Plasma Proteins.

    PubMed

    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

  4. 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.

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

    SciTech Connect

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

    2014-12-15

    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.

  6. 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

  7. 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

  8. 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

  9. 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

  10. 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

  11. 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 ?-alumina, ?-alumina, and mullite. A packed-bed flow reactor was used to investigate the thermal degradation of 2-MCP over the various catalysts at 200-600C. Fly ash gave similar PCDD/F yields to surrogates made with similar transition metal content. ?-alumina, which is thermodynamically unfavorable, was very catalytically active and gave low PCDD/F yields despite a high destruction of 2-MCP. Mullite and ?-alumina, the thermodynamically favorable form of alumina, yielded higher concentrations of dioxins and products with a higher degree of chlorine substitution than ?-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

  12. Impact of Zeolite Aging in Hot Liquid Water on Activity for Acid-Catalyzed Dehydration of Alcohols.

    PubMed

    Vjunov, Aleksei; Derewinski, Miroslaw A; Fulton, John L; Camaioni, Donald M; Lercher, Johannes A

    2015-08-19

    The location and stability of Brnsted acid sites catalytically active in zeolites during aqueous phase dehydration of alcohols were studied on the example of cyclohexanol. The catalytically active hydronium ions originate from Brnsted acid sites (BAS) of the zeolite that are formed by framework tetrahedral Si atom substitution by Al. Al K-edge extended X-ray absorption fine structure (EXAFS) and (27)Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopies in combination with density functional theory (DFT) calculations are used to determine the distribution of tetrahedral Al sites (Al T-sites) both qualitatively and quantitatively for both parent and HBEA catalysts aged in water prior to catalytic testing. The aging procedure leads to partial degradation of the zeolite framework evidenced from the decrease of material crystallinity (XRD) as well as sorption capacity (BET). With the exception of one commercial zeolite sample, which had the highest concentration of framework silanol-defects, there is no evidence of Al coordination modification after aging in water. The catalyst weight-normalized dehydration rate correlated best with the sum of strong and weak Brnsted acidic protons both able to generate the hydrated hydronium ions. All hydronium ions were equally active for the acid-catalyzed reactions in water. Zeolite aging in hot water prior to catalysis decreased the weight normalized dehydration reaction rate compared to that of the parent HBEA, which is attributed to the reduced concentration of accessible Brnsted acid sites. Sites are hypothesized to be blocked due to reprecipitation of silica dissolved during framework hydrolysis in the aging procedure. PMID:26237038

  13. 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

  14. 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...

  15. Physical chemical studies of dispersed aluminosilicate wastes for obtaining the burned building materials

    NASA Astrophysics Data System (ADS)

    Iuriev, I. Y.; Skripnikova, N. K.; Volokitin, G. G.; Volokitin, O. G.; Lutsenko, A. V.; Kosmachev, P. V.

    2015-01-01

    This paper presents results of the studies that determined that grinding can be one of the ways to modify aluminosilicate wastes. The optimal grinding modes were defined in laboratory conditions. Physical and chemical studies of modified ashes were carried out by means of X-ray phase analysis, differential thermal analysis and microscopy. The results have shown that modified ashes of thermal power stations when being applied in production of ceramic brick influence positively the processing properties of raw materials and the ready products.

  16. Potential Sites for Ice Nucleation on Aluminosilicate Clay Minerals and Related Materials.

    PubMed

    Freedman, Miriam Arak

    2015-10-01

    Few aerosol particles in clouds nucleate the formation of ice. The surface sites available for nucleus formation, which can include surface defects and functional groups, determine in part the activity of an aerosol particle toward ice formation. Although ice nucleation on particles has been widely studied, exploration of the specific sites at which the initial germ forms has been limited, but is important for predicting the microphysical properties of clouds, which impact climate. This Perspective focuses on what is currently known about surface sites for ice nucleation on aluminosilicate clay minerals, which are commonly found in ice residuals, as well as related materials. PMID:26722881

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. Direct ?O NMR experimental evidence for Al-NBO bonds in Si-rich and highly polymerized aluminosilicate glasses.

    PubMed

    Jaworski, Aleksander; Stevensson, Baltzar; Edn, Mattias

    2015-07-28

    By using solid-state (17)O NMR spectroscopy, we provide the first direct experimental evidence for bonds between Al and non-bridging oxygen (NBO) ions in aluminosilicate glasses based on rare-earth (RE) elements, where RE = {Lu, Sc, Y}. The presence of ?10% Al-NBO moieties out of all NBO species holds regardless of the precise glass composition, at odds with the conventional structural view that Al-NBO bonds are absent in highly polymerized and Si-rich aluminosilicate glass networks. PMID:26118845

  2. Chemical Interactions in Multimetal/Zeolite Catalysts

    SciTech Connect

    Sachtler, Wolfgang M. H.

    2004-04-16

    This two-year project has led to a significant improvement in the fundamental understanding of the catalytic action of zeolite-supported redox catalysts. It turned out to be essential that we could combine four strategies for the preparation of catalysts containing transition metal (TM) ions in zeolite cavities: (1) ion exchange from aqueous solution; (2) chemical vapor deposition (CVD) of a volatile halide onto a zeolite in its acidic form; (3) solid state ion exchange; and (4) hydrothermal synthesis of a zeolite having TM ions in its lattice, followed by a treatment transporting these ions to ''guest positions''. Technique (2) enables us to position more TM ions into cavities than permitted by the conventional technique (1).viz one positive charge per Al centered tetrahedron in the zeolite lattice. The additional charge is compensated by ligands to the TM ions, for instance in oxo-ions such as (GaO){sup +} or dinuclear [Cu-O-Cu]{sup 2+}. While technique (3) is preferred over CVD where volatile halides are not available, technique (4) leads to rather isolated ''ex lattice'' oxo-ions. Such oxo-ions tend to be mono-nuclear, in contrast to technique (2) which preferentially creates dinuclear oxo-ions of the same TM element. A favorable element for the present research was that the PI is also actively engaged in a project on the reduction of nitrogen oxides, sponsored by EMSI program of the National Science Foundation and the US Department of Energy, Office of Science. This combination created a unique opportunity to test and analyze catalysts for the one step oxidation of benzene to phenol and compare them with catalysts for the reduction of nitrogen oxides, using hydrocarbons as the reductant. In both projects catalysts have been used which contain Fe ions or oxo-ions in the cavities the zeolite MFI, often called ZSM-5. With Fe as the TM-element and MFI as the host zeolite we found that catalysts with high Fe content, prepared by technique (2) were optimal for the De-NO{sub x} reaction, but extremely unselective for benzene oxidation to phenol. Conversely, the catalysts prepared with (4) had the highest turnover frequency for benzene oxidation, but performed very poorly for NO{sub x} reduction with so-butane. In fact the Fe concentration in the former catalysts were so low that it was necessary to design a special experimental program for the sole purpose of showing that it is really the Fe which catalyzes the benzene oxidation, not some acid center as has been proposed by other authors. For this purpose we used hydrogen sulfide to selectively poison the Fe sites, without deactivating the acidic sites. In addition we could show that the hydrothermal treatment of catalysts prepared by technique (4) is essential to transform iron ions in the zeolite lattice to ''ex lattice ions'' in guest positions. That line of the work required very careful experimentation, because a hydrothermal treatment of a zeolite containing Fe ions in its cavities can also lead to agglomeration of such ions to nano-particles of iron oxide which lowers the selectivity for the desired formation of phenol. This part of the program showed convincingly that indeed Fe is responsible for the benzene oxidation catalysis. The results and conclusion of this work, including the comparison of different catalysts, was published in a number of papers in the scientific literature, listed in the attached list. In these papers also our analysis of the reaction orders and the possible mechanism of the used test reaction are given.

  3. The use of zeolites as slow release anthelmintic carriers.

    PubMed

    Dyer, A; Morgan, S; Wells, P; Williams, C

    2000-06-01

    This work examines the ability of commercial zeolite Y to act as a slow release agent for a number of anthelmintic drugs. Administration to rats, dosed with Nippostrongylus brasiliensis, of pyrantel and/or fenbendazole and pigs, dosed with Ascaris and Oesophagostomum, of dichlorvos (DDVP) loaded onto zeolite Y was more successful in killing adult worms than administration of the pure drug alone. The zeolite Y was used as supplied for initial studies and then later dealuminated for further studies. The drug loadings were monitored by thermal analysis and the loaded zeolites were used in several field trials. The results indicate that zeolite Y is a suitable vehicle for the slow release of some anthelmintics. The slow release of drug from the zeolite matrix improved its efficacy. PMID:10881284

  4. 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.

  5. 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

  6. The ADOR mechanism for the synthesis of new zeolites.

    PubMed

    Eliov, Pavla; Opanasenko, Maksym; Wheatley, Paul S; Shamzhy, Mariya; Mazur, Michal; Nachtigall, Petr; Roth, Wieslaw J; Morris, Russell E; ?ejka, Ji?

    2015-10-21

    A novel methodology, called ADOR (assembly-disassembly-organisation-reassembly), for the synthesis of zeolites is reviewed here in detail. The ADOR mechanism stems from the fact that certain chemical weakness against a stimulus may be present in a zeolite framework, which can then be utilized for the preparation of new solids through successive manipulation of the material. In this review, we discuss the critical factors of germanosilicate zeolites required for application of the ADOR protocol and describe the mechanism of hydrolysis, organisation and condensation to form new zeolites starting from zeolite UTL. Last but not least, we discuss the potential of this methodology to form other zeolites and the prospects for future investigations. PMID:25946705

  7. 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.

  8. Advanced zeolites used in FCC catalysts boost motor octane number

    SciTech Connect

    Letzsch, W.S.; Magee, J.S.; Upson, L.L.; Valeri, F. )

    1988-10-31

    Fluid catalytic cracking catalysts that contain an advanced zeolite called LZ-210, have been shown, by commercial trials, to increase the motor octane number (MON) of the FCC gasoline produced. The zeolite crystal utilizes lower unit cell size, lower sodium in the zeolite, less alumina debris in the zeolite structure, and silica reinsertion into the zeolite structure to accomplish the MON increase. Data from commercial trials are presented to support the MON increases, along with some explanations of how the advanced zeolite accomplishes them. A strong gasoline market and the removal of lead have combined to place a premium on clear gasoline octanes. Because gasoline from fluid catalytic cracking units is the largest segment of the refinery pool (up to 40%), its octane numbers are particularly important. Traditional emphasis has been on the research octance number (RON) but motor octanes frequently limit the blending process.

  9. 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.

  10. Binding and catalytic reduction of NO by transition metal aluminosilicates. Technical progress report, March 1992--May 1992

    SciTech Connect

    Klier, K.; Herman, R.G.; Hou, S.

    1992-06-01

    Na, Co{sup 2+}, Ce{sup 3+}, and Co{sup 2+}Ce{sup 3+} exchanged A type zeolite have been tested for NO and N{sub 2}O adsorption and decomposition at room temperature. Dynamic temperature programmed desorption (TPD) studies were also carried out with these four zeolites, as well as with CeO{sub 2} and CoA zeolite mixed with CeO{sub 2}. It was demonstrated that NO was especially decomposed into N{sub 2}, with some N{sub 2}, with some N{sub 2}O, over the doubly ion exchanged CoCeA zeolite that contained 1.77 Co and 2 Ce per unit cell. Some segregation of CeO{sub 2} occurred during these experiments, and a lower content of Ce in the CoCeA zeolite might be utilizable.

  11. Zeolite membranes - a review and comparison with MOFs.

    PubMed

    Rangnekar, N; Mittal, N; Elyassi, B; Caro, J; Tsapatsis, M

    2015-10-21

    The latest developments in zeolite membranes are reviewed, with an emphasis on the synthesis techniques, including seed assembly and secondary growth methods. This review also discusses the current industrial applications of zeolite membranes, the feasibility of their use in membrane reactors and their hydrothermal stability. Finally, zeolite membranes are compared with metal-organic framework (MOF) membranes and the latest advancements in MOF and mixed matrix membranes are highlighted. PMID:26155855

  12. 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

  13. 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.

  14. Fluoride-assisted synthesis of bimodal microporous SSZ-13 zeolite.

    PubMed

    Zhu, Xiaochun; Kosinov, Nikolay; Hofmann, Jan P; Mezari, Brahim; Qian, Qingyun; Rohling, Roderigh; Weckhuysen, Bert M; Ruiz-Martnez, Javier; Hensen, Emiel J M

    2016-02-11

    The presence of small amount of fluoride in alkaline hydrothermal synthesis of SSZ-13 zeolite yields bimodal microporous particles with substantially improved performance in the methanol-to-olefins (MTO) reaction. Hydrocarbon uptake measurements and fluorescence microspectroscopy of spent catalysts demonstrate enhanced diffusion through micropores at the grain boundaries of nanocrystals running through the zeolite particles. Fluoride-assisted SSZ-13 synthesis is a cheap and scalable approach to optimize the performance of MTO zeolite catalysts. PMID:26810114

  15. Crystalline beam ground state

    SciTech Connect

    Wei, Jie ); Li, Xiao-Ping; Sessler, A.M. )

    1993-01-01

    In order to employ Molecular Dynamics method, commonly used in condensed matter physics, we have derived the equations of motion for a beam of charged particles in the rotating rest frame of the reference particle. We include in the formalism that the particles are confined by the guiding and focusing magnetic fields, and that they are confined in a conducting vacuum pipe while interacting with each other via a Coulomb force. Numerical simulations has been performed to obtain the equilibrium structure. The effects of the shearing force, centrifugal force, and azimuthal variation of the focusing strength are investigated. It is found that a constant gradient storage ring can not give a crystalline beam, but that an alternating-gradient (AG) structure can. In such a machine the ground state is, except for one-dimensional (1-D) crystals, time-dependent. The ground state is a zero entropy state, despite the time-dependent, periodic variation of the focusing force. The nature of the ground state, similar to that found by Rahman and Schiffer, depends upon the density and the relative focusing strengths in the transverse directions. At low density, the crystal is 1-D. As the density increases, it transforms into various kinds of 2-D and 3-D crystals. If the energy of the beam is higher than the transition energy of the machine, the crystalline structure can not be formed for lack of radial focusing.

  16. Crystalline beam ground state

    SciTech Connect

    Wei, Jie; Li, Xiao-Ping; Sessler, A.M.

    1993-06-01

    In order to employ Molecular Dynamics method, commonly used in condensed matter physics, we have derived the equations of motion for a beam of charged particles in the rotating rest frame of the reference particle. We include in the formalism that the particles are confined by the guiding and focusing magnetic fields, and that they are confined in a conducting vacuum pipe while interacting with each other via a Coulomb force. Numerical simulations has been performed to obtain the equilibrium structure. The effects of the shearing force, centrifugal force, and azimuthal variation of the focusing strength are investigated. It is found that a constant gradient storage ring can not give a crystalline beam, but that an alternating-gradient (AG) structure can. In such a machine the ground state is, except for one-dimensional (1-D) crystals, time-dependent. The ground state is a zero entropy state, despite the time-dependent, periodic variation of the focusing force. The nature of the ground state, similar to that found by Rahman and Schiffer, depends upon the density and the relative focusing strengths in the transverse directions. At low density, the crystal is 1-D. As the density increases, it transforms into various kinds of 2-D and 3-D crystals. If the energy of the beam is higher than the transition energy of the machine, the crystalline structure can not be formed for lack of radial focusing.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Toxicity of /sup 90/Y in relatively insoluble fused aluminosilicate particles when inhaled by mice

    SciTech Connect

    Lundgren, D.L.; Hahn, F.F.; McClellan, R.O.

    1981-12-01

    A life span study in mice of the toxicity of a short-half-lived (64.2 hr) ..beta..-emitting radionuclide, /sup 90/Y, inhaled in insoluble fused aluminosilicate particles was conducted. Mice were exposed to achieve initial lung burdens between 1 and 140 ..mu..Ci of /sup 90/Y with each microcurie of /sup 90/Y deposited in lung delivering an absorbed lung dose of 150 rad. The cumulative survival rates of mice in groups with initial lung burdens of 1 to 10 ..mu..Ci (1100 +/- 380 rad to lungs) and 11 to 20 ..mu..Ci (2300 +/- 400 rad to lungs) were not significantly different from that of control mice. Initial lung burdens of more than 20 ..mu..Ci (>3000 rad to lungs) resulted in radiation pneumonitis and a significant shortening of the life span. The incidences of all lung tumors and other lesions in mice exposed to /sup 90/Y in fused aluminosilicate particles were similar to those of the control mice, except pulmonary adenomas, found more frequently in groups of mice with initial lung burdens of 1 to 10 and 11 to 20 ..mu..Ci. The early occurring biological effects observed in mice in this study were similar to those observed in beagle dogs exposed to /sup 90/Y in the same form.

  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. 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

  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 40C 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. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. Coreactant-induced modifications of catalytic behavior in zeolitic systems

    SciTech Connect

    Martin, A.M.; Chen, J.-K.; John, V.T. )

    1989-11-01

    The complex feed processing over zeolite catalysts, competitive reaction between the feed components results in observed rates and selectivities that cannot be predicted from pure component data alone. Hydroisomerization of paraffins over various Pt/zeolites in the presence of an aromatic cofeed is considered as an illustration. The aromatic affects paraffin reaction rates by occupying catalytic sites and perhaps also by partially blocking the pores. Analysis of Arrhenius plots helps in correlations of zeolite structure and the extent to which the paraffin reaction is affected. It is shown that the coreactant can induce selectivity to a zeolite that would otherwise not be shape selective.

  15. 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.

  16. 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.

  17. Ion exchange properties of Japanese natural zeolites in seawater.

    PubMed

    Wajima, Takaaki

    2013-01-01

    Ion exchange properties of five different Japanese natural zeolites in seawater were examined. Sodium ions could be reduced by all zeolites, although anions, Cl(-) and SO(4)(2-), in seawater showed barely changes. Natural zeolite desalination treatment mainly depends on the ion exchange between Na(+), K(+) and Mg(2+) in seawater and Ca(2+) in natural zeolite. This study found that mordenite is superior to clinoptilolite for use in Na(+) reduction. Mordenite with high cation exchange capacity containing Ca(2+) resulted in the highest Na(+) reduction from seawater. PMID:23303099

  18. 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.

  19. 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 100?g/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 ?50?g/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

  20. Electrical Response of PEDOT-PSS/FAU Zeolite Composites toward SO2: Controlling the Adsorption Properties of FAU Zeolite

    NASA Astrophysics Data System (ADS)

    Chanthaanont, Pojjawan; Sirivat, Anuvat

    2012-02-01

    In our work, we propose to combine a conductive polymer, Poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonic acid) (PEDOT-PSS), with FAU zeolites to investigate the potential of the composites for use as SO2 sensing materials.Composites with PEDOT-PSS as a matrix containing faujasite zeolites of various cation types (divalent transition metal ions: Fe^2+, Co^2+, Ni^2+ and Cu^2+), were fabricated to investigate the effect of the cation type of the faujasite zeolites on the electrical conductivity response when exposed to SO2. The composite was tested through repeated sensing and recovery processes to investigate the reversibility and reproducibility. During the recovery process, the electrical conductivity of the composites were recovered, which proves that the sensing characteristics are repeatable. Responses and the interaction mechanism of the conductive polymer/zeolite composites were investigated. The composite with 20% (v/v) of zeolite content gives the highest sensitivity. The electrical conductivity responses of PEDOT-PSS/Zeolite composites can be altered due to the available adsorption sites for gas molecules. The addition of zeolites to the pristine PEDOT-PSS improved the electrical conductivity sensitivity of the composites by enhancing the interaction between PEDOT-PSS and SO2. The type of cation in the zeolite pores effected the sensitivity of the composites, depending on the acidity of the ion-exchanged zeolites.

  1. 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.

  2. Nanocomposites with Crystalline Polymers

    NASA Astrophysics Data System (ADS)

    Kumar, Sanat

    2015-03-01

    The creation of ordered (layered) biomimetic materials typically follows a series of steps: first mix nanoparticles with water, organize the NPs by ice templating, evaporate the ice and then back fill with metal or polymer. We propose a simple method exploiting the in situ self-assembly of a crystalline polymer in the presence of nanoparticles to facilitate this process, and provide a completely new pathway for the synthesis of biomimetic materials. A suite of complementary experimental tools are used in this analysis. In parallel, we are developing theoretical tools to a priori predict the morphologies adopted by semicrystalline polymers. The convergence of these novel experimental and theoretical developments in the venerable field of semicrystalline polymers could lead to new applications for this largest class of commercially relevant polymeric materials. With Jacques Jestin, Brian Benicewicz, Dan Zhao, Longxi Zhao

  3. Color centers produced by {gamma}-irradiation and seeding of samarium-, terbium-, and erbium-doped aluminosilicate optical fibers

    SciTech Connect

    Kornienko, L.S.; Stupina, V.I.; Chernov, P.V.

    1995-09-01

    The absorption spectra induced by {gamma}-irradiation and by the recording of writing the quadratic-susceptibility {chi}{sup (2)} gratings are obtained for the samarium-, terbium-, and erbium-doped aluminosilicate optical fibers. The nature of the color centers, which are responsible for microscopic changes in the glass structure, is investigated.

  4. 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

  5. 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.

  6. 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.

  7. Infrared spectroscopic characterization of dehydration and accompanying phase transition behaviors in NAT-topology zeolites

    NASA Astrophysics Data System (ADS)

    Wang, Hsiu-Wen; Bish, David L.

    2012-04-01

    Relative humidity ( P_{{{text{H}}_{ 2} {text{O}}}} , 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 P_{{{text{H}}_{ 2} {text{O}}}} 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 high- and low- P_{{{text{H}}_{ 2} {text{O}}}} 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.

  8. 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.

  9. 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.

  10. 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.

  11. Conversion of crude oil feeds by catalytic cracking

    SciTech Connect

    Long, G.N.; Pellet, R.J.; Rabo, J.A.

    1991-02-12

    This patent describes the catalytic cracking process for converting a crude oil feed to hydrocarbon products including gasoline, contacting a crude oil feed at effective catalytic cracking conditions at an effective catalytic cracking temperature between about 400 {degrees} F and about 1400 {degrees} F with a catalyst. The catalyst comprises at least one crystalline zeolitic aluminosilicate cracking catalyst selected from the group consisting of Zeolite Y, zeolite LZ-210 and Zeolite LZ-10 and at least one molecular sieve selected from the group consisting of the silicoaluminophospates SAPO-5 and SAPO-11.

  12. In Situ SAXS/WAXS of Zeolite Microwave Synthesis: NaY, NaA, and Beta Zeolites

    SciTech Connect

    Panzarella,B.; Tompsett, G.; Conner, W.; Jones, K.

    2007-01-01

    A custom waveguide apparatus is constructed to study the microwave synthesis of zeolites by in situ small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). The WR-284 waveguide is used to heat precursor solutions using microwaves at a frequency of 2.45 GHz. The reaction vessels are designed to include sections of thin-walled glass, which permit X-rays to pass through the precursor solutions with minimal attenuation. Slots were machined into the waveguide to provide windows for X-ray energy to enter and scatter from solutions during microwave heating. The synthesis of zeolites with conventional heating is also studied using X-ray scattering in the same reactor. SAXS studies show that the crystallization of beta zeolite and NaY zeolite is preceded by a reorganization of nanosized particles in their precursor solutions or gels. The evolution of these particles during the nucleation and crystallization stages of zeolite formation depends on the properties of the precursor solution. The synthesis of NaA and NaX zeolites and sodalite from a single zeolite precursor is studied by microwave and conventional heating. Microwave heating shifts the selectivity of this synthesis in favor of NaA and NaX over sodalite; conventional heating leads to the formation of sodalite for synthesis from the same precursor. The use of microwave heating also led to a more rapid onset of NaA zeolite product crystallization compared to conventional heating. Pulsed and continuous microwave heating are compared for zeolite synthesis. The resulting rates of formation of the zeolite products, and the relative amounts of the products determined from the WAXS spectra, are similar when either pulsed or continuous microwave heating is applied in the reactor while maintaining the same synthesis temperature. The consequences of these results in terms of zeolite synthesis are discussed.

  13. 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

  14. 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.

  15. 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 ...

  16. 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%.

  17. Zeolitization of tuffaceous rocks of the green river formation, wyoming.

    PubMed

    Goodwin, J H; Surdam, R C

    1967-07-21

    The alkali-rich zeolites mordenite and clinoptilolite have been discovered in tuffaceous rocks of the Green River Formation, Wyoming. This occurrence strongly supports the alteration of glass to alkali-rich zeolite to analcime as the paragenetic sequence of alteration of tuffaceous rocks deposited in ancient Lake Gosiute. PMID:17734226

  18. 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.

  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

    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.

  1. 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.

  2. 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...

  3. 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.

  4. Some observations on the synthesis of fully-dispersible nanocrystalline zeolite ZSM-5.

    PubMed

    Selvin, Rosilda; Chiang, Anthony S T

    2014-09-01

    A facile method for the rapid synthesis of fully-dispersible ZSM-5 (Si/Al = 100) of about 30 nm size in high yield (about 91%) is described. The method comprises three steps, viz., concentration of an initial clear solution, low-temperature (80 degrees C) ageing of concentrated sol, and high-temperature (175 degrees C) hydrothermal treatment or microwave heating (175 degrees C) of aged concentrated sol. A simple vacuum-concentration method was used for the extraction of pure NPs of ZSM-5 in solution. XRD, FT-IR, TGA and ASAP characterizations showed that the NPs were partially crystalline. The concentration step accelerated the aggregation of primary units, which helps in the production of a large number of nucleation centers protected by TPA+ ions against aggregation. During low-temperature ageing, the number of critical sized nuclei increases, growing into zeolite. The high-temperature heating results in the complete growth of unreacted silica, giving high yields. A key factor for generating small non-aggregated zeolite crystals is the amount of water in the synthesis sol. The three-step method presented here produces a target material of small and uniform sized, non-aggregated ZSM-5 of about 30 nm in a short reaction time. The results are significant, as the synthesis method adopted here produces much uniform, non-aggregated nanocrystalline ZSM-5 in a shorter time with high yield. PMID:25924414

  5. Monoethanol amine modified zeolite 13X for CO{sub 2} adsorption at different temperatures

    SciTech Connect

    P.D. Jadhav; R.V. Chatti; R.B. Biniwale; N.K. Labhsetwar; S. Devotta; S.S. Rayalu . s_rayalu@neeri.res.in

    2007-12-15

    Zeolite 13X has been modified with monoethanol amine (MEA). MEA loadings of 0.5-25 wt % have been achieved using the impregnation method in different solvents. The mode of incorporation based on methanol with stirring at room temperature appears to be the most feasible. The adsorbent has been characterized for crystallinity, surface area, pore volume, and pore size. The thermal stability of the adsorbent is studied using a thermal analyzer. The CO{sub 2} adsorption capacity of adsorbents is evaluated using the breakthrough adsorption method with a packed column on a 10 g scale. The adsorption capacities of adsorbents are estimated in the temperature range 30-120{sup o}C. The adsorbents show improvement in CO{sub 2} adsorption capacity over the unmodified zeolite by a factor of ca. 1.6 at 30{sup o}C, whereas at 120{sup o}C the efficiency improved by a factor of 3.5. For adsorption at these temperatures, different MEA loading levels were found to be suitable as per the governing adsorption phenomena, that is, physical or chemical. The adsorbent is also studied for CO{sub 2} selectivity over N{sub 2} at 75{sup o}C. The MEA-modified adsorbent shows better CO{sub 2} selectivity, which was improved further in the presence of moisture. 25 refs., 6 figs., 3t abs.

  6. Chemical durability of soda-lime-aluminosilicate glass for radioactive waste vitrification

    SciTech Connect

    Eppler, F.H.; Yim, M.S.

    1998-09-01

    Vitrification has been identified as one of the most viable waste treatment alternatives for nuclear waste disposal. Currently, the most popular glass compositions being selected for vitrification are the borosilicate family of glasses. Another popular type that has been around in glass industry is the soda-lime-silicate variety, which has often been characterized as the least durable and a poor candidate for radioactive waste vitrification. By replacing the boron constituent with a cheaper substitute, such as silica, the cost of vitrification processing can be reduced. At the same time, addition of network intermediates such as Al{sub 2}O{sub 3} to the glass composition increases the environmental durability of the glass. The objective of this study is to examine the ability of the soda-lime-aluminosilicate glass as an alternative vitrification tool for the disposal of radioactive waste and to investigate the sensitivity of product chemical durability to variations in composition.

  7. Fictive temperature-independent density and minimum indentation size effect in calcium aluminosilicate glass

    SciTech Connect

    Gross, T. M.; Tomozawa, M.

    2008-09-15

    Using the calcium aluminosilicate system a glass was developed that exhibits fictive temperature-independent density by creating an intermediate glass between normal and anomalous glasses. Normal glass, such as soda-lime silicate glass, exhibits decreasing density with increasing fictive temperature while anomalous glass, such as silica glass, exhibits increasing density with increasing fictive temperature. This intermediate glass composition was found to exhibit the minimum indentation size effect during indentation hardness testing. It appears that the indentation size effect is correlated with a deformation-induced fictive temperature increase, which is accompanied by a density change and hardness change in the vicinity of the indentation. It is suggested from these observations that indentation size effect originates from the energy required to create interfaces and defects such as shear bands, subsurface cracks, and point defects near the indenter-specimen boundary, which accompany the volume change.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Synthesis and characterization of inorganic polymers from the alkali activation of an aluminosilicate

    NASA Astrophysics Data System (ADS)

    Gonzlez, C. P.; Montao, A. M.; Gonzlez, A. K.; Ros, C. A.

    2014-06-01

    This paper presents the results of the synthesis and characterization of inorganic polymers (IP) from aluminosilicates: bentonite (BT) and pumice (PP). The synthesis of IP, was carried out by two methods involving alkaline activation, at room temperature and 80 5 C, using as activating agent sodium silicate both commercial and analytical (Na2SiO3). Sodium hydroxide (NaOH) at 3 M, 7 M and 12 M was added. A lower degree of polymerization was obtained by using analytical precursors subjected to room temperature and 80 5C. Replacement of heating by the use of the commercial activating agent with greater alkalinity allows the formation of a 3D network. The materials were structurally characterized by FTIR spectroscopy with Attenuated Reflectance (ATR), Scanning Electron Microscope (SEM) and X -ray diffraction (DRX).

  14. 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.

  15. Synthesis and characterization of ionic liquid-functionalized alumino-silicate MCM-41 hybrid mesoporous materials

    NASA Astrophysics Data System (ADS)

    Cai, Chao; Wang, Hua; Han, Jinyu

    2011-09-01

    Ionic liquid-functionalized alumino-silicate MCM-41 hybrid mesoporous materials have been synthesized with two-step approach, by means of in situ skeleton doping with aluminium and post surface grafting with N-methylimidazole ionic liquid groups. The samples were characterized by X-ray diffraction (XRD), high resolution transmission electron microscope (HRTEM), N2 adsorption-desorption, Fourier transform infrared (FTIR) spectra, 27Al and 13C MAS NMR spectra and temperature-programmed desorption (TPD) of NH3. The results indicated that the bifunctionalized MCM-41 possessed ordered mesostructure. Aluminium was efficiently introduced into the framework of the mesostructure, generating Lewis and Brnsted acid sites. N-methylimidazole ionic liquid groups were covalently grafted onto the surface of mesoporous materials. The as-synthesized bifunctional MCM-41 showed good catalytic performance in the coupling reaction of CO2 and propylene oxide.

  16. Raman response of network modifier cations in alumino-silicate glasses.

    PubMed

    Hehlen, B; Neuville, D R

    2015-03-12

    Raman scattering is performed in three sets of aluminosilicate glasses with light cations and concentrations varying from peralcaline to peraluminate domain. The depolarized spectra highlight two cation modes below ?400 cm(-1). Comparison with infrared data reveals very stringent selection rules providing as much additional information for a vibrational analysis. The latter suggests in-phase (network-coupled) and out-of-phase (network-decoupled) displacements of the cations relative to their adjacent negatively charged structures. The low frequency vibration involves all cations whatever their role in the glass, network modifiers or charge compensators. Very interestingly, the second mode originates mostly from cations at modifier's places, providing thereby a new support for structural and chemical analysis of silicate glasses using Raman scattering. PMID:25710130

  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. 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.

  19. 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

  20. 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)