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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. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    DOEpatents

    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.

  4. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    DOEpatents

    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. 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.

  6. 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

  7. 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

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

    SciTech Connect

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

    1993-11-01

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

  9. 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

  10. 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

  11. 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

  12. 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.

  13. Metal-supported aluminosilicate ultrathin films as a versatile tool for studying the surface chemistry of zeolites.

    PubMed

    Shaikhutdinov, Shamil; Freund, Hans-Joachim

    2013-01-14

    The application of a variety of "surface-science" techniques to elucidate surface structures and mechanisms of chemical reactions at zeolite surfaces has long been considered as almost impossible because of the poor electrical and thermal conductivity of those materials. Here, we show that the growth of a thin aluminosilicate film on a metal single crystal under controlled conditions results in adequate and well-defined model systems for zeolite surfaces. In principle, silicate films that contain metals other than Al (e.g. Ti, Fe, etc) may be prepared in a similar way. We believe that this approach opens up a new playground for experimental and theoretical modeling of zeolites, aimed at a fundamental understanding of structure-reactivity relationships in such materials. PMID:23143912

  14. 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

  15. First-principles molecular modeling of structure-property relationships and reactivity in the zeolite chabazite

    E-print Network

    Lo, Cynthia

    2005-01-01

    Zeolites are crystalline, porous aluminosilicates; while a pure silicate structure is charge-neutral, the substitution of A1³? for Si?? creates in the framework a negative charge, which can be compensated by a proton that ...

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

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

    SciTech Connect

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

    2014-07-08

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

  3. 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).

  4. Dehydration of n-butanol on zeolite H-ZSM-5 and amorphous aluminosilicate: Detailed mechanistic study and the effect of pore confinement

    SciTech Connect

    Makarova, M.A.; Paukshtis, E.A.; Zamaraev, K.I.

    1994-09-01

    This study of the catalytic dehydration of n-butanol on zeolite H-ZSM-5 and amorphous aluminosilicate confirms the reaction scheme proposed earlier by the authors for isobutanol dehydration. The rate constant for n-butanol dehydration on H-ZSM-5 (determined from in situ FTIR kinetic studies by monitoring the growth of the water deformation peak at 1640 cm{sup -1}) is shown to be the true dehydration rate constant (1.7 x 10{sup -4}s{sup -1} at 100{degrees}C). On the other hand, the rate constants determined from GC steady-state kinetic studies (temperature interval 105-185{degrees}C) are effective ones, giving activation energies of 22{+-}2 kcal/mol and 33{+-}2 kcal/mol for complete dehydration and dehydration to butene only, respectively. By studying the dehydration reaction under different conditions (flow and static reactors, steady-state and non-steady-state regimes) and on samples with rather similar acid strengths but different porous systems (H-ZSM-5-microporous channels with diameter {approximately}5.5 {angstrom}, and amorphous aluminosilicate-pores of average diameter {approximately}50 {angstrom}), it was shown that depending on the concentration of butanol in the immediate vicinity of the active alkoxide intermediate {exists}-OC{sub 4}H{sub 9}, different reaction paths are utilized. High concentrations of alcohol favor ether formation, whereas low ones favour butene. This also explains the so-called {open_quotes}stop effect{close_quotes} observed in GC experiments, where an increase in the rate of butene formation occurs when the flow of alcohol is stopped and replaced with a flow of pure helium. Here, decreasing the concentration of alcohol in the micropores results in more of the alkoxide intermediate transforming to butene rather than to ether (which was the case at steady state). 28 refs., 17 figs., 3 tabs.

  5. 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…

  6. Photochemical processes in zeolites: new developments Prabir K. Dutta *, Yanghee Kim

    E-print Network

    Dutta, Prabir K.

    , the triplet state, radical cation, and radical anion of biphenyl was formed. At low light fluence, the triplet framework, extra-framework cations and the unique solvent nature of the zeolite all have profound influence crystalline aluminosilicates with structural features that make them attractive hosts for photochemical

  7. Chemical Zeolites Combinatorial . . .

    E-print Network

    Servatius, Brigitte

    . Chemical Zeolites · crystalline solid · units: Si + 4O Si O O O O · two covalent bonds per oxygen #12Chemical Zeolites Combinatorial . . . Realization 2d Zeolites Finite Zeolites The Layer . . . Holes University (Brigitte Servatius -- WPI) #12;Chemical Zeolites Combinatorial . . . Realization 2d Zeolites

  8. Structural, compositional and acidic characteristics of nanosized amorphous or partially crystalline

    E-print Network

    Trikalitis, Pantelis N.

    -ray amorphous aluminosilicates possessed tetrahedral aluminum atoms which were more zeolitic in character; received in revised form 23 June 2004; accepted 13 July 2004 Available online 11 September 2004 Abstract. The particle/crystal size and microporosity of the partially crystalline materials increased with increasing

  9. 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

  10. [What a physician should know about zeolites].

    PubMed

    Borani?, M

    2000-01-01

    Zeolites are natural and synthetic hydrated crystalline aluminosilicates endowed with absorptive and ion exchange properties. They have found numerous and multifarous applications--in industry as catalysts and absorbents, in water sanitation for the removal of ammonia and heavy metals, in agriculture as fertilizers, and in animal husbandry as the absorbents of excreted material and as food additives. Medical applications have included the use in filtration systems for anesthesia or dialysis and as the contrast materials in NMR imaging. Recently, zeolite powders for external use have found application as deodorants, antimycotic agents and wound dressings. Peroral use of encapsulated zeolite powders enriched with vitamins, oligoelements or other ingredients has been claimed to exert beneficial medical effects. Ingestion of zeolites may be considered analogous to the clay eating (geophagia), considered in traditional medicine as a remedy for various illnesses. Being amphoteric, zeolites are partly soluble in acid or alkaline media, but within the physiological pH range the solubility is generally low. Minimal amounts of free aluminium or silicium from the ingested zeolites are resorbed from the gut. The bulk of ingested zeolite probably remains undissolved in the gut. In view of the ion exchange properties, zeolites may be expected to change the ionic content, pH and buffering capacity of the gastrointestinal secretions and to affect the transport through the intestinal epithelium. In addition, zeolites could affect the bacterial flora and the resorption of bacterial products, vitamins and oligoelements. The contact of zeolite particles with gastrointestinal mucosa may elicit the secretion of cytokines with local and systemic actions. Reactive silicium ions might react with biomolecules of the intestinal epithelium, and if resorbed, do so in other cells. Mutagenic and carcinogenic effects of zeolite particles have been described, resembling such effects of asbestos fibers. Thus, local and systemic effects of zeolites may be complex and interrelated, and an objective assessment requires appropriate experimental models. PMID:11291273

  11. Flexibility mechanisms in ideal zeolite frameworks.

    PubMed

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

    2014-02-13

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

  12. 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

  13. 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

  14. Cesium incorporation and diffusion in cancrinite, sodalite, zeolite, and allophane

    E-print Network

    Flury, Markus

    Cesium incorporation and diffusion in cancrinite, sodalite, zeolite, and allophane Jarai Mon of silicate minerals and precipitation of new aluminosilicate minerals. Cancrinite, sodalite, LTA zeolite in sodalite and cancrinite was far more difficult to replace than that in LTA zeolite or allophane. Most

  15. 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.

  16. Rapid synthesis of beta zeolites

    DOEpatents

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

    2015-08-18

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

  17. 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''.

  18. 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.

  19. Zeolite Crystal Growth

    NASA Astrophysics Data System (ADS)

    2002-12-01

    Zeolites are as hard as rocks but work like sponges. They have a rigid crystalline structure with a network of interconnected tunnels and cages, similar to honeycomb. These tunnels can store chemicals, like fuels, and then release them when the zeolites are heated. The Center for Advanced Microgravity Materials Processing (CAMMP) - one of 17 NASA sponsored Commercial Space Centers - is working to improve zeolite materials for storing hydrogen fuel. The center is also applying zeolite research to detergents, optical cables, gas and vapor detection for environmental monitoring and control, and chemical production techniques that significantly reduce hazardous by-products.

  20. 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

  1. Core-shell strain structure of zeolite microcrystals

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

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

  2. 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

  3. 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.

  4. 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...

  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. 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.

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

    SciTech Connect

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

    2010-01-19

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

  8. 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)

  9. Salt-occluded zeolite waste forms: Crystal structures and transformability

    SciTech Connect

    Richardson, J.W. Jr.

    1996-12-31

    Neutron diffraction studies of salt-occluded zeolite and zeolite/glass composite samples, simulating nuclear waste forms loaded with fission products, have revealed complex structures, with cations assuming the dual roles of charge compensation and occlusion (cluster formation). These clusters roughly fill the 6--8 {angstrom} diameter pores of the zeolites. Samples are prepared by equilibrating zeolite-A with complex molten Li, K, Cs, Sr, Ba, Y chloride salts, with compositions representative of anticipated waste systems. Samples prepared using zeolite 4A (which contains exclusively sodium cations) as starting material are observed to transform to sodalite, a denser aluminosilicate framework structure, while those prepared using zeolite 5A (sodium and calcium ions) more readily retain the zeolite-A structure. Because the sodalite framework pores are much smaller than those of zeolite-A, clusters are smaller and more rigorously confined, with a correspondingly lower capacity for waste containment. Details of the sodalite structures resulting from transformation of zeolite-A depend upon the precise composition of the original mixture. The enhanced resistance of salt-occluded zeolites prepared from zeolite 5A to sodalite transformation is thought to be related to differences in the complex chloride clusters present in these zeolite mixtures. Data relating processing conditions to resulting zeolite composition and structure can be used in the selection of processing parameters which lead to optimal waste forms.

  10. 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.

  11. 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.

  12. 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

  13. Constructing Hierarchical Porous Zeolites via Kinetic Regulation.

    PubMed

    Ding, Kunlun; Corma, Avelino; Maciá-Agulló, Juan Antonio; Hu, Jerry G; Krämer, 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

  14. 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.

  15. 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.

  16. 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

  17. 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

  18. 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....

  19. 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....

  20. 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...

  1. 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....

  2. 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....

  3. 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....

  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, 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....

  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 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....

  8. Topologically ordered amorphous silica obtained from the collapsed siliceous zeolite, silicalite-1-F: a step toward "perfect" glasses.

    PubMed

    Haines, Julien; Levelut, Claire; Isambert, Aude; Hébert, Philippe; Kohara, Shinji; Keen, David A; Hammouda, Tahar; Andrault, Denis

    2009-09-01

    A dense amorphous form of silica was prepared at high pressure from the highly compressible, siliceous zeolite, silicalite-1-F. Reverse Monte Carlo modeling of total X-ray scattering data shows that the structure of this novel amorphous form of SiO(2) recovered under ambient conditions is distinct from vitreous SiO(2) and retains the basic framework topology (i.e., chemical bonds) of the starting crystalline zeolite. This material is, however, amorphous over the different length scales probed by Raman and X-ray scattering due to strong geometrical distortions. This is thus an example of new topologically ordered, amorphous material with a different intermediate-range structure, a lower entropy with respect to a standard glass, and distinct physical and mechanical properties, eventually approaching those of an "ordered" or "perfect" glass. The same process in more complex aluminosilicate zeolites will, in addition, lead to an amorphous material which conserves the framework topology and chemical order of the crystal. The large volume collapse in this material may also be of considerable interest for new applications in shock wave absorption. PMID:19705916

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

    USGS Publications Warehouse

    Virta, R.

    2008-01-01

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

  10. Dietary supplementation with the tribomechanically activated zeolite clinoptilolite in immunodeficiency: effects on the immune system.

    PubMed

    Ivkovic, Slavko; Deutsch, Ulrich; Silberbach, Angelika; Walraph, Erwin; Mannel, Marcus

    2004-01-01

    Natural zeolites are crystalline aluminosilicates with unique adsorption, cation-exchange, and catalytic properties that have multiple uses in industry and agriculture. TMAZ, a natural zeolite clinoptilolite with enhanced physicochemical properties, is the basis of the dietary supplements Megamin and Lycopenomin, which have demonstrated antioxidant activity in humans. The aim of this prospective, open, and controlled parallel-group study was to investigate the effects of supplementation with TMAZ on the cellular immune system in patients undergoing treatment for immunodeficiency disorder. A total of 61 patients were administered daily TMAZ doses of 1.2 g (Lycopenomin) and 3.6 g (Megamin) for 6 to 8 weeks, during which the patients' primary medical therapy was continued unchanged. Blood and lymphocyte counts were performed at baseline and at the end of the study. Blood count parameters were not relevantly affected in either of the two treatment groups. Megamin administration resulted in significantly increased CD4+, CD19+, and HLA-DR+ lymphocyte counts and a significantly decreased CD56+ cell count. Lycopenomin was associated with an increased CD3+ cell count and a decreased CD56+ lymphocyte count. No adverse reactions to the treatments were observed. PMID:15310086

  11. 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.

  12. 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

  13. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...2014-04-01 2014-04-01 false Sodium calcium aluminosilicate, hydrated... Anticaking Agents § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium...

  14. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...2011-04-01 2011-04-01 false Sodium calcium aluminosilicate, hydrated... Anticaking Agents § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium...

  15. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...2010-04-01 2010-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729...Anticaking Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium...

  16. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...2014-04-01 2014-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729...Anticaking Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium...

  17. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...2011-04-01 2011-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729...Anticaking Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium...

  18. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...2013-04-01 2013-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729...Anticaking Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium...

  19. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...2010-04-01 2009-04-01 true Sodium calcium aluminosilicate, hydrated... Anticaking Agents § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium...

  20. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...2012-04-01 2012-04-01 false Hydrated sodium calcium aluminosilicate. 582.2729...Anticaking Agents § 582.2729 Hydrated sodium calcium aluminosilicate. (a) Product. Hydrated sodium calcium aluminosilicate (sodium...

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

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...2013-04-01 2013-04-01 false Sodium calcium aluminosilicate, hydrated... Anticaking Agents § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium...

  2. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...2012-04-01 2012-04-01 false Sodium calcium aluminosilicate, hydrated... Anticaking Agents § 182.2729 Sodium calcium aluminosilicate, hydrated. (a) Product. Hydrated sodium calcium aluminosilicate (sodium...

  3. 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%.

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

    SciTech Connect

    Grutzeck, Michael W.

    2004-06-10

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

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. Acidity of two-dimensional zeolites.

    PubMed

    Rybicki, Marcin; Sauer, Joachim

    2015-10-14

    Hybrid quantum mechanics:molecular mechanics (QM/MM) calculations of absolute deprotonation energies are performed with periodic boundary conditions for Brønsted 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

  10. Computational studies of water adsorption in zeolites

    SciTech Connect

    Zygmunt, S.A.; Curtiss, L.A.; Iton, L.E.

    1995-05-01

    We have performed high-level ab initio calculations using Hartree-Fock (HF) theory, Moller-Plesset perturbation theory (MP2), and density-functional theory (DFT) to study the geometry and energetics of the adsorption complex involving H{sub 2}O and the Bronsted acid site in the zeolite H-ZSM-5. These calculations use aluminosilicate cluster models for the zeolite framework with as many as 28 T atoms (T=Si, Al). We included geometry optimization in the local vicinity of the acid site at the MP2 and DFT levels of theory for the smallest cluster, while in the larger clusters this was done at the HF/6-31G(d) level of theory. We have also calculated corrections for zero-point energies, extensions to higher basis sets, and higher levels of electron correlation. Results for the adsorption energy and geometry of this complex are reported and compared with previous theoretical and experimental values.

  11. Single and Multiple Heteroatom Incorporation in MFI Zeolites 

    E-print Network

    Garcia Vargas, Nataly

    2012-11-05

    Zeolites are crystalline inorganic solids that are industrially used for adsorption, ion exchange and catalysis. As catalysts, they have been particularly successful in the hydrocarbon processing industry due to their ...

  12. 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 ?-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

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

    PubMed

    Vai?iukynien?, Danut?; Kantautas, Aras; Vaitkevi?ius, Vitoldas; Jakevi?ius, Leonas; Rudžionis, Žymantas; Paškevi?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

  14. 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...

  15. 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...

  16. 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...

  17. 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

  18. 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 Brønsted 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

  19. 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 Brönsted 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

  20. 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.

  1. 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

  2. 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 ?-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

  3. 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...

  4. 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

  5. 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.

  6. 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.

  7. Computational studies of Bronsted acid sites in zeolites

    SciTech Connect

    Curtiss, L.A.; Iton, L.E.; Zygmunt, S.A.

    1995-01-01

    The authors have performed high-level ab initio calculations using both Hartree-Fock (HF) and Moller-Plesset perturbation theory (MP2) to study the geometry and energetics of the adsorption complex involving H{sub 2}O and the Bronsted acid site in the zeolite H-ZSM-5. In these calculations, which use aluminosilicate cluster models for the zeolite framework with as many a 28 T atoms (T = Si, Al), we included geometry optimization in the local vicinity of the acid site at the HF/6-31G(d) level of theory, and have calculated corrections for zero-point energies, extensions for zero-point energies, extensions to higher basis sets, and the influence of electron correlation. Results for the adsorption energy and geometry of this complex are reported and compared with previous theoretical and experimental values.

  8. 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

  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. Association of Indigo with Zeolites for Improved Color Stabilization

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

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

  11. Association of indigo with zeolites for improved color stabilization.

    PubMed

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

    2010-10-01

    The durability of an organic color 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 oxidizing conditions, using Raman and ultraviolet-visible (UV-Vis) spectrometric techniques. Blending indigo with MFI is shown to yield the most stable composite in all of our artificial indigo pigments. In the 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 color 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. PMID:20925983

  12. 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.

  13. 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

  14. 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 150°C 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.

  15. 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.

  16. 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.

  17. 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.

  18. 3D Study of the Morphology and Dynamics of Zeolite Nucleation.

    PubMed

    Melinte, Georgian; Georgieva, Veselina; Springuel-Huet, Marie-Anne; Nossov, Andreï; 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

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

    PubMed

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

    2010-09-15

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

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

    SciTech Connect

    Rossin, J.A.

    1986-01-01

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

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. The roles of entropy and enthalpy in stabilizing ion-pairs at transition states in zeolite acid catalysis.

    PubMed

    Gounder, Rajamani; Iglesia, Enrique

    2012-02-21

    Acidic zeolites are indispensable catalysts in the petrochemical industry because they select reactants and their chemical pathways based on size and shape. Voids of molecular dimensions confine reactive intermediates and transition states that mediate chemical reactions, stabilizing them by van der Waals interactions. This behavior is reminiscent of the solvation effects prevalent within enzyme pockets and has analogous consequences for catalytic specificity. Voids provide the "right fit" for certain transition states, reflected in their lower free energies, thus extending the catalytic diversity of zeolites well beyond simple size discrimination. This catalytic diversity is even more remarkable because acid strength is essentially unaffected by confinement among known crystalline aluminosilicates. In this Account, we discuss factors that determine the "right fit" for a specific chemical reaction, exploring predictive criteria that extend the prevailing discourse based on size and shape. We link the structures of reactants, transition states, and confining voids to chemical reactivity and selectivity. Confinement mediates enthalpy-entropy compromises that determine the Gibbs free energies of transition states and relevant reactants; these activation free energies determine turnover rates via transition state theory. At low temperatures (400-500 K), dimethyl ether carbonylation occurs with high specificity within small eight-membered ring (8-MR) voids in FER and MOR zeolite structures, but at undetectable rates within larger voids (MFI, BEA, FAU, and SiO(2)-Al(2)O(3)). More effective van der Waals stabilization within 8-MR voids leads to lower ion-pair enthalpies but also lower entropies; taken together, carbonylation activation free energies are lower within 8-MR voids. The "right fit" is a "tight fit" at low temperatures, a consequence of how temperature appears in the defining equation for Gibbs free energy. In contrast, entropy effects dominate in high-temperature alkane activation (700-800 K), for which the "right fit" becomes a "loose fit". Alkane activation turnovers are still faster on 8-MR MOR protons because these transition states are confined only partially within shallow 8-MR pockets; they retain higher entropies than ion-pairs fully confined within 12-MR channels at the expense of enthalpic stability. Selectivities for n-alkane dehydrogenation (relative to cracking) and isoalkane cracking (relative to dehydrogenation) are higher on 8-MR than 12-MR sites because partial confinement preferentially stabilizes looser ion-pair structures; these structures occur later along reaction coordinates and are higher in energy, consistent with Marcus theory for charge-transfer reactions. Enthalpy differences between cracking and dehydrogenation ion-pairs for a given reactant are independent of zeolite structure (FAU, FER, MFI, or MOR) and predominantly reflect the different gas-phase proton affinities of alkane C-C and C-H bonds, as expected from Born-Haber thermochemical cycles. These thermochemical relations, together with statistical mechanics-based treatments, predict that rotational entropy differences between intact reactants and ion-pair transition states cause intrinsic cracking rates to increase with n-alkane size. Through these illustrative examples, we highlight the effects of reactant and catalyst structures on ion-pair transition state enthalpies and entropies. Our discussion underscores the role of temperature in mediating enthalpic and entropic contributions to free energies and, in turn, to rates and selectivities in zeolite acid catalysis. PMID:21870839

  7. Composite zeolite membranes

    DOEpatents

    Nenoff, Tina M. (Albuquerque, NM); Thoma, Steven G. (Albuquerque, NM); Ashley, Carol S. (Albuquerque, NM); Reed, Scott T. (Albuquerque, NM)

    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.

  8. 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.

  9. 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.

  10. Crystalline Silica

    Cancer.gov

    An abundant natural material, crystalline silica is found in stone, soil, and sand. It is also found in concrete, brick, mortar, and other construction materials. Crystalline silica comes in several forms, with quartz being the most common. Quartz dust is respirable crystalline silica, which means it can be taken in by breathing.

  11. 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

  12. Structural analysis of hierarchically organized zeolites

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  13. Structural analysis of hierarchically organized zeolites.

    PubMed

    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

  14. 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

  15. 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.

  16. 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.

  17. Preparation of functionalized zeolitic frameworks

    SciTech Connect

    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.

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

    NASA Astrophysics Data System (ADS)

    Sarkar, Madhuchhanda; Dana, Kausik; Das, Sukhen

    2015-10-01

    This work aims to investigate the microstructural and phase evolution of alkali activated metakaolin products with different activators and added aluminosilicate filler phases. The added filler phases have different reactivity to the alkali activated metakaolin system. Microstructural evolution in the alkali activated products has been investigated by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Field Emission Scanning Electron Microscope (FESEM). Variation in strength development in alkali activated metakaolin products was followed by compressive strength measurement test. Microstructural study shows that in case of metakaolin with NaOH activator crystalline sodalite formed in all the product samples irrespective of the added filler phases. The microstructure of these NaOH activated products investigated by FESEM showed crystalline and inhomogeneous morphology. Mixed activator containing both NaOH and sodium silicate in a fixed mass ratio formed predominantly amorphous phase. Microstructure of these samples showed more homogeneity than that of NaOH activated metakaolin products. The study further shows that addition of ?-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.

  19. Intraframework migration of tetrahedral atoms in a zeolite.

    PubMed

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

    2014-08-18

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

  1. 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

  2. ZSM-5 zeolite nanosheets with improved catalytic activity synthesized using a new class of structure-directing agents.

    PubMed

    Kore, Rajkumar; Srivastava, Rajendra; Satpati, Biswarup

    2014-09-01

    A new series of multiquaternary ammonium structure-directing agents, based on 1,4-diazabicyclo[2.2.2]octane, was prepared. ZSM-5 zeolites with nanosheet morphology (10?nm crystal thickness) were synthesized under hydrothermal conditions using multiquaternary ammonium surfactants as the zeolite structure-generating agents. Both wide-angle and small-angle diffraction patterns were obtained using only a suitable structure-directing agent under a specific zeolite synthesis composition. A mechanism of zeolite formation is proposed based on the results obtained from various physicochemical characterizations. ZSM-5 materials were investigated in catalytic reactions requiring medium to strong acidity, which are important for the synthesis of a wide range of industrially important fine and specialty chemicals. The catalytic activity of ZSM-5 materials was compared with that of the conventional ZSM-5 and amorphous mesoporous aluminosilicate Al-MCM-41. The synthesis strategy of the present investigation using the new series of structure-directing agents could be extended for the synthesis of other related zeolites or other porous materials in the future. Zeolite with a structural feature as small as the size of a unit cell (5-10?nm) with hierarchically ordered porous structure would be very promising for catalysis. PMID:25056112

  3. 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

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

    PubMed

    van der Bij, Hendrik E; Weckhuysen, Bert M

    2015-10-21

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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

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

    SciTech Connect

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

    2011-03-15

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

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

    PubMed

    Franus, Wojciech; Wdowin, Magdalena; Franus, Ma?gorzata

    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

  11. 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.

  12. ALUMINOSILICATE-COATED SILICA SAND FOR REACTIVE TRANSPORT EXPERIMENTS

    E-print Network

    Flury, Markus

    oxides have been used as well, mainly in form of iron-oxide-coated silica sand. Clay minerals, however of reactive chemicals in the subsurface. Most commonly, silica sand is used as the model porous medium. IronALUMINOSILICATE-COATED SILICA SAND FOR REACTIVE TRANSPORT EXPERIMENTS By JORGE ANTONIO JEREZ

  13. 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.

  14. Fiber-optic exhaust-gas sensor based on the fluorescence characteristics of Cu containing zeolites

    NASA Astrophysics Data System (ADS)

    Remillard, Jeffrey

    2000-03-01

    A single catalyst in the exhaust system can reduce the concentration of toxic gases emitted by automobiles if the engine is operated close to the stoichiometric air-fuel ratio. This is accomplished through the use of an electrochemical oxygen sensor in the exhaust stream. Near the stoichiometric point, this sensor produces a step-function response when the exhaust gas transitions from an oxygen-poor to an oxygen-rich condition. This talk describes a different kind of sensor based on the use of copper-containing zeolites that produces a proportional output. Zeolites are a class of aluminosilicate materials that have an open 3D structure containing channels and cavities. The Al sites are negatively charged and are generally compensated by cations present during formation of the zeolite. Our experiments use a zeolite designated Cu-ZSM-5, which has the protons originally present in the ZSM-5 material replaced with cupric (Cu^+2) ions. Exposure of this zeolite to a reducing gas results in the conversion of some cupric ions to cuprous (Cu^+1) ions. Subsequent exposure of the zeolite to an oxidizing gas reverses this reaction. The use of this material as a gas sensor is based on the observation that cuprous ions produce a green fluorescent emission when exposed to blue light, whereas no fluorescence is observed from cupric ions. Monitoring the fluorescence of Cu-ZSM-5 placed in a gas stream can thus provide information on the gas's reductant-to-oxidant ratio. We present the results of high temperature in-situ fluorescence spectra, intensity, and reponse-time measurements performed on samples of Cu-ZSM-5 exposed to various O_2-reductant combinations and also discuss data obtained from a single-fiber prototype sensor fabricated using a sol-gel processing technique.(J.T. Remillard et al.), Appl. Opt. 38 5306 (1999).

  15. 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

  16. 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.

  17. SO2 REMOVAL FROM FLUE GASES USING UTILITY SYNTHESIZED ZEOLITES

    SciTech Connect

    MICHAEL GRUTZECK

    1998-10-31

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

  18. SO2 REMOVAL FROM FLUE GASES USING UTILITY SYNTHESIZED ZEOLITES

    SciTech Connect

    Michael Grutzeck

    1999-04-30

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

  19. EMM-23: a stable high-silica multidimensional zeolite with extra-large trilobe-shaped channels.

    PubMed

    Willhammar, Tom; Burton, Allen W; Yun, Yifeng; Sun, Junliang; Afeworki, Mobae; Strohmaier, Karl G; Vroman, Hilda; Zou, Xiaodong

    2014-10-01

    Stable, multidimensional, and extra-large pore zeolites are desirable by industry for catalysis and separation of bulky molecules. Here we report EMM-23, the first stable, three-dimensional extra-large pore aluminosilicate zeolite. The structure of EMM-23 was determined from submicron-sized crystals by combining electron crystallography, solid-state nuclear magnetic resonance (NMR), and powder X-ray diffraction. The framework contains highly unusual trilobe-shaped pores that are bound by 21-24 tetrahedral atoms. These extra-large pores are intersected perpendicularly by a two-dimensional 10-ring channel system. Unlike most ideal zeolite frameworks that have tetrahedral sites with four next-nearest tetrahedral neighbors (Q(4) species), this unusual zeolite possesses a high density of Q(2) and Q(3) silicon species. It is the first zeolite prepared directly with Q(2) species that are intrinsic to the framework. EMM-23 is stable after calcination at 540 °C. The formation of this highly interrupted structure is facilitated by the high density of extra framework positive charge introduced by the dicationic structure directing agent. PMID:25198917

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  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. 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.

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

    PubMed

    Myers, Rupert J; L'Hôpital, 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. 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.

  9. 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

  10. Zeolite Salt Occlusion: A Potential Route for the Immobilisation of Iodine-129? Neil C. Hyatt,1*

    E-print Network

    Sheffield, University of

    decomposes to produce a single crystalline phase at 800o C prior to further decomposition at 850o C to a mixture of nepheline and elemental silver. INTRODUCTION The long term immobilisation of iodine-129 arising. The occlusion of a metal (iodide) salt into a suitable zeolite host affords a nano-composite material in which

  11. 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.

  12. 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

  13. 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.

  14. Thermal behavior of natural zeolites

    SciTech Connect

    Bish, D.L.

    1993-09-01

    Thermal behavior of natural zeolites impacts their application and identification and varies significantly from zeolite to zeolite. Zeolites evolve H{sub 2}0 upon heating, but recent data show that distinct ``types`` of water (e.g., loosely bound or tightly bound zeolitic water) do not exist. Rather water is bound primarily to extra-framework cations with a continuum of energies, giving rise to pseudocontinuous loss of water accompanied by a dynamic interaction between remaining H{sub 2}0 molecules and extra-framework cations. These interactions in the channels of zeolites give rise to dehydration dependent on the extra-framework cation, in addition to temperature and water vapor pressure. The dehydration reaction and the extra-framework cation also affect the thermal expansion/contraction. Most zeolites undergo dehydration-induced contractions that may be anisotropic, although minor thermal expansion can be seen with some zeolites. Such contractions can be partially or completely irreversible if they involve modifications of the tetrahedral framework and/or if rehydration is sluggish. Thermally induced structural modifications are also driven initially by dehydration and the concomitant contraction and migration of extra-framework cations. Contraction is accommodated by rotations of structural units and tetrahedral cation-oxygen linkages may break. Thermal reactions that involve breaking of tetrahedral cation-oxygen bonds markedly irreversible and may be kinetically limited, producing large differences between short- and long-term heating.

  15. 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.

  16. 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

  17. 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

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

    SciTech Connect

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

    2012-01-01

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

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

    PubMed

    Tang, Yuanyuan; Shih, Kaimin

    2015-12-01

    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, ?-Al2O3 and quartz were further used as precursors to observe ZnAl2O4 and Zn2SiO4 formations. 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 ZnAl2O4 and Zn2SiO4 in the system. In addition, with a competitive formation between ZnAl2O4 and Zn2SiO4, the ZnAl2O4 spinel 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 Zn2SiO4 product phases. The zinc concentrations in ZnO and Zn2SiO4 leachates were about two orders of magnitude higher than that of ZnAl2O4 leachate at the end of the experiment, indicating that ZnAl2O4 formation is the preferred stabilization mechanism for incorporating zinc in ceramic products. PMID:25399963

  20. 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.

  1. 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.

  2. 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

    2014-08-07

    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.

  3. 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.

  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 -?Sm(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?í

    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. 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.

  7. The aluminum ordering in aluminosilicates: a dipolar 27Al NMR spectroscopy study.

    PubMed

    Gee, Becky A

    2004-01-01

    The spatial ordering of aluminum atoms in CsAl(SiO3)2 and 3Al2O3.2SiO2 was probed by 27Al dipolar solid-state NMR spectroscopy. The 27Al response to a Hahn spin-echo pulse sequence in a series of aluminum-containing model crystalline compounds demonstrates that quantitative 27Al homonuclear dipolar second moments can be obtained to within +/-20% of the theoretical values, if evaluation of the spin-echo response curve is limited to short evolution periods (2t1 < or = 0.10 ms). Additionally, selective excitation of the central transition m = 1/2 --> -1/2 is necessary in order to ensure quantitative results. Restriction of spin exchange affecting the dephasing of the magnetization may decelerate the spin-echo decay at longer evolution periods. Considering these restraints, the method was used to probe the spatial distribution of aluminum atoms among the tetrahedral sites in two aluminosilicate materials. Experimental 27Al spin-echo response data for the aluminosilicates CsAl(SiO3)2 (synthetic pollucite) and 3Al2O3.2SiO2 (mullite) are compared with theoretical data based on (I) various degrees of aluminum-oxygen-aluminum bond formation among tetrahedrally coordinated aluminum atoms (Al(T(d) )-O-Al(T(d) )) and (II) the maximum avoidance of Al(T(d) )-O-Al(T(d) ) bonding. Analysis of the second moment values and resulting echo decay responses suggests that partial suppression of spin exchange among aluminum atoms in crystallographically distinct sites may contribute to the 27Al spin echo decay in 3Al2O3.2SiO2, thus complicating quantitative analysis of the data. Silicon-29 and aluminum-27 magic angle spinning (MAS) NMR spectra of 3Al2O3.2SiO2 are consistent with those previously reported. The experimental 27Al spin-echo response behavior of CsAl(SiO3)2 differs from the theoretical response behavior based on the maximum avoidance of Al-O-Al bonding between tetrahedral aluminum sites in CsAl(SiO3)2. A single unresolved resonance is observed in both the silicon-29 and aluminum-27 MAS spectra of CsAl(SiO3)2. PMID:14745814

  8. 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 Brønsted 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

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. 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

  14. 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

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

    PubMed

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

    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

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

    PubMed

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

    2015-10-19

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

  17. Experimental proof for resonant diffusion of normal alkanes in LTL and ZSM-12 zeolites

    E-print Network

    Yoo, K; Smirniotis, P G

    2015-01-01

    The intra-crystalline diffusion of normal alkanes in LTL and ZSM-12 zeolite was experimentally studied via gravimetric measurements performed at different temperatures. A periodic dependence of the diffusion coefficient on the number of carbon atoms in alkane was detected, which is an experimental proof for resonant diffusion. The present observations were described on the base of the existing theory of the resonant diffusion and several important parameters of the alkane-zeolite interaction and zeolite vibrations were obtained. In the considered temperature region the diffusion coefficient follows the Arrhenius law with periodic dependences of the pre-exponential factor and activation energy on the number of carbon atoms in alkanes. A compensation effect of simultaneous increases of the pre-exponential factor and the activation energy was also established.

  18. 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.

  19. 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.

  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. Structure-Directing Roles and Interactions of Fluoride and Organocations with Siliceous Zeolite Frameworks

    SciTech Connect

    Shayib, Ramzy M.; George, Nathan C.; Seshadri, Ram; Burton, Allen W.; Zones, Stacey I.; Chmelka, Bradley F.

    2012-02-06

    Interactions of fluoride anions and organocations with crystalline silicate frameworks are shown to depend subtly on the architectures of the organic species, which significantly influence the crystalline structures that result. One- and two-dimensional (2D) {sup 1}H, {sup 19}F, and {sup 29}Si nuclear magnetic resonance (NMR) spectroscopy measurements establish distinct intermolecular interactions among F{sup -} anions, imidazolium structure-directing agents (SDA{sup +}), and crystalline silicate frameworks for as-synthesized siliceous zeolites ITW and MTT. Different types and positions of hydrophobic alkyl ligands on the imidazolium SDA{sup +} species under otherwise identical zeolite synthesis compositions and conditions lead to significantly different interactions between the F{sup -} and SDA{sup +} ions and the respective silicate frameworks. For as-synthesized zeolite ITW, F{sup -} anions are established to reside in the double-four-ring (D4R) cages and interact strongly and selectively with D4R silicate framework sites, as manifested by their strong {sup 19}F{sup 29}Si dipolar couplings. By comparison, for as-synthesized zeolite MTT, F{sup -} anions reside within the 10-ring channels and interact relatively weakly with the silicate framework as ion pairs with the SDA{sup +} ions. Such differences manifest the importance of interactions between the imidazolium and F{sup -} ions, which account for their structure-directing influences on the topologies of the resulting silicate frameworks. Furthermore, 2D {sup 29}Si{l_brace}{sup 29}Si{r_brace} double-quantum NMR measurements establish {sup 29}Si-O-{sup 29}Si site connectivities within the as-synthesized zeolites ITW and MTT that, in conjunction with synchrotron X-ray diffraction analyses, establish insights on complicated order and disorder within their framework structures.

  3. 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

  4. 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.

  5. 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.

  6. 2.5 Zeolites 2.5.1 Introduction

    E-print Network

    58 2.5 Zeolites 2.5.1 Introduction Zeolites are a well-established technology used in a range of processes and industries. Zeolites are not new materials--they have been investigated for over two in agriculture (St. Cloud 2007, BRZ Zeolite 2007, Zeolite Australia 2007), horticulture (ZeoPro 2007), gas

  7. Surfactants as Promising Media for the Preparation of Crystalline Inorganic Materials.

    PubMed

    Xiong, Wei-Wei; Zhang, Qichun

    2015-09-28

    Given that surfactants can control the shape and size of micro-/nanoparticles, they should be able to direct the growth of bulk crystals. This Minireview summarizes recent developments in the application of surfactants for the preparation of new crystalline inorganic materials, including chalcogenides, metal-organic frameworks, and zeolite analogues. The roles of surfactants in different reaction systems are discussed. PMID:26266458

  8. 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.

  9. 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...

  10. 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; ?ejka, Ji?í

    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 ?-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 ?-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

  11. 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.

  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. Adsorption of unsaturated hydrocarbons on zeolites: the eects of the zeolite framework on adsorption

    E-print Network

    Truong, Thanh N.

    Adsorption of unsaturated hydrocarbons on zeolites: the eects of the zeolite framework industrially important reactions, namely the polymerization and hydrocarbon cracking processes [9 as a starting point for a more comprehensive study on hydrocarbon cracking and ethylene epoxidation reactions

  14. 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.

  15. 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.

  16. 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.

  17. SODIUM ALUMINOSILICATE SOLIDS AFFINITY FOR CESIUM AND ACTINIDES

    SciTech Connect

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

    2007-07-31

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

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

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

    PubMed

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

    2014-07-21

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

  5. 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.

  6. 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.

  7. 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.

  8. On the multiplicity of Bismuth active centres in germano-aluminosilicate preform

    NASA Astrophysics Data System (ADS)

    Razdobreev, Igor; Bigot, Laurent

    2011-04-01

    Spatially resolved optical spectroscopy of Bismuth-doped germano-aluminosilicate fibre preform prepared by modified chemical vapor deposition (MCVD) reveals the existence of two subnetworks accommodating the active centres connected to Bismuth doping: a pure silica subnetwork and an aluminosilicate one. Even at low Bismuth doping level for which laser generation in the fibre has been demonstrated, two kinds of optical centres in a silica subnetwork can be identified. At least one of these centres is able to inhibit the laser generation in aluminosilicate fibres at high Bismuth doping levels. We discuss the technological issues for improving the efficiency of Bi-doped fibre lasers in the spectral range of 1150-1500 nm.

  9. 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/m×K 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.

  10. 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...

  11. Durability of Hydrophilic and Antimicrobial Zeolite Coatings under Water Immersion

    E-print Network

    Chen, Wilfred

    Durability of Hydrophilic and Antimicrobial Zeolite Coatings under Water Immersion Cory O-exchanged zeolite A (Ag-ZA) coatings have been shown to have excellent hydrophilicity and are highly antimicrobial Keywords: zeolite coating, zeolite A, hydrophilic, antimicrobial, gravity Introduction Condensing heat

  12. 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...

  13. Visible emission from Ag+ exchanged SOD zeolites

    NASA Astrophysics Data System (ADS)

    Lin, H.; Imakita, K.; Fujii, M.; Prokof'ev, V. Yu.; Gordina, N. E.; Saïd, B.; Galarneau, A.

    2015-09-01

    Broad visible emissions dominant at green or red have been observed for the thermally-treated Ag+ exchanged SOD zeolites, determined by the Ag+ loading contents and the excitation wavelengths. Contrary to the notable reversible green/red dominant emission evolution in the Ag+ exchanged LTA zeolites upon hydration/dehydration in air (or water vapor)/vacuum, emission spectra of the Ag+ exchanged SOD zeolites are insensitive to the environmental change. This is most probably due to the difficult H2O permeation in SOD zeolites in comparison with LTA zeolites. By combining the environment dependent emission spectra of the Ag+ exchanged LTA and SOD zeolites, we proposed the following emission mechanisms for Ag+ exchanged LTA and SOD zeolites: the green emission is due to the transition from ligand-to-metal (framework O2- --> Ag+) charge transfer state to the ground state and the red emission is due to the transition from the metal-metal (Ag+-Ag+) charge transfer state to the ground state. The insensitive environment dependent emission characteristics of Ag+ exchanged SOD zeolites may have potential applications as robust phosphors.

  14. Visible emission from Ag(+) exchanged SOD zeolites.

    PubMed

    Lin, H; Imakita, K; Fujii, M; Prokof'ev, V Yu; Gordina, N E; Saïd, B; Galarneau, A

    2015-10-14

    Broad visible emissions dominant at green or red have been observed for the thermally-treated Ag(+) exchanged SOD zeolites, determined by the Ag(+) loading contents and the excitation wavelengths. Contrary to the notable reversible green/red dominant emission evolution in the Ag(+) exchanged LTA zeolites upon hydration/dehydration in air (or water vapor)/vacuum, emission spectra of the Ag(+) exchanged SOD zeolites are insensitive to the environmental change. This is most probably due to the difficult H2O permeation in SOD zeolites in comparison with LTA zeolites. By combining the environment dependent emission spectra of the Ag(+) exchanged LTA and SOD zeolites, we proposed the following emission mechanisms for Ag(+) exchanged LTA and SOD zeolites: the green emission is due to the transition from ligand-to-metal (framework O(2-)? Ag(+)) charge transfer state to the ground state and the red emission is due to the transition from the metal-metal (Ag(+)-Ag(+)) charge transfer state to the ground state. The insensitive environment dependent emission characteristics of Ag(+) exchanged SOD zeolites may have potential applications as robust phosphors. PMID:26349525

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

    PubMed

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

    2015-01-01

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

  16. 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

  17. 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.

  18. Water nanodroplets confined in zeolite pores.

    PubMed

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

    2009-01-01

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

  19. 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...

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

    PubMed

    Léonard, 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

  1. 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.

  2. 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

  3. 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.

  4. 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

  5. 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.

  6. Selective anisotropic growth of zeolite crystals 

    E-print Network

    Desai, Tasha April

    2013-02-22

    -1 Selective Anisotropic Growth of Zeolite Crystals A Senior Honors Thesis by TASHA APRIL DESAI Submitted to the Office of Honors Programs & Academic Scholarships Texas A&M University in partial fulfillment of the requirements of the UNIVERSITY... UNDERGRADUATE RESEARCH FELLOWS Apri I 2003 Group: Engineering & Physics 3 Selective Anisotropic Growth of Zeolite Crystals A Senior Honors Thesis by TASFIA APRIL DESAI Submitted to the Office of Honors Programs k Academic Scholarships Texas A...

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Probing zeolites by vibrational spectroscopies.

    PubMed

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

    2015-10-21

    This review addresses the most relevant aspects of vibrational spectroscopies (IR, Raman and INS) applied to zeolites and zeotype materials. Surface Brønsted 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

  13. 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.

  14. The catalytic diversity of zeolites: confinement and solvation effects within voids of molecular dimensions.

    PubMed

    Gounder, Rajamani; Iglesia, Enrique

    2013-05-01

    The ability of molecular sieves to control the access and egress of certain reactants and products and to preferentially contain certain transition states while excluding others based on size were captured as shape selectivity concepts early in the history of zeolite catalysis. The marked consequences for reactivity and selectivity, specifically in acid catalysis, have since inspired and sustained many discoveries of novel silicate frameworks and driven the engineering of hierarchical structures and void size to influence catalysis. The catalytic diversity of microporous voids is explored and extended here in the context of their solvating environments, wherein voids act as hosts and stabilize guests, whether reactive intermediates or transition states, by van der Waals forces. We use specific examples from acid catalysis, including activation of C-C and C-H bonds in alkanes, alkylation and hydrogenation of alkenes, carbonylation of dimethyl ether, and elimination and homologation reactions of alkanols and ethers, which involve transition states and adsorbed precursors of varying size and composition. Mechanistic interpretations of measured turnover rates enable us to assign precise chemical origins to kinetic and thermodynamic constants in rate equations and, in turn, to identify specific steps and intermediates that determine the free energy differences responsible for chemical reactivity and selectivity. These free energy differences reflect the stabilization of transition states and their relevant precursors via electrostatic interactions that depend on acid strength and van der Waals interactions that depend on confinement within voids. Their respective contributions to activation free energies are examined by Born-Haber thermochemical cycles by considering plausible transition states and the relevant precursors. These examples show that zeolite voids solvate transition states and precursors differently, and markedly so for guest moieties of different size and chemical composition, thus enabling voids of a given size and shape to provide the "right fit" for a given elementary step, defined as that which minimizes Gibbs free energies of activation. Tighter confinement is preferred at low temperatures because enthalpic gains prevail over concomitant entropic losses, while looser fits are favored at high temperatures because entropy gains offset losses in enthalpic stabilization. Confinement and solvation by van der Waals forces are not directly involved in the making or breaking of strong chemical bonds; yet, they confer remarkable diversity to zeolites, in spite of their structural rigidity and their common aluminosilicate composition. A single zeolite can itself contain a range of local void environments, each with distinct reactivity and selectivity; as a result, varying the distribution of protons among these locations within a given framework or modifying a given location by partial occlusion of the void space can extend the range of catalytic opportunities for zeolites. Taken together with theoretical tools that accurately describe van der Waals interactions between zeolite voids and confined guests and with synthetic protocols that place protons or space-filling moieties at specific locations, these concepts promise to broaden the significant impact and catalytic diversity already shown by microporous solids. PMID:23507832

  15. 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

  16. Formation processes and main properties of hollow aluminosilicate microspheres in fly ash from thermal power stations

    SciTech Connect

    V.S. Drozhzhin; M.Ya. Shpirt; L.D. Danilin; M.D. Kuvaev; I.V. Pikulin; G.A. Potemkin; S.A. Redyushev

    2008-04-15

    The main parameters of aluminosilicate microspheres formed at thermal power stations in Russia were studied. These parameters are responsible for the prospective industrial application of these microspheres. A comparative analysis of the properties of mineral coal components, the conditions of coal combustion, and the effects of chemical and phase-mineralogical compositions of mineral impurities in coals from almost all of the main coal deposits on the formation of microspheres was performed. The effects of thermal treatment conditions on gas evolution processes in mineral particles and on the fraction of aluminosilicate microspheres in fly ash were considered. It was found that the yield of microspheres was higher in pulverized coal combustion in furnaces with liquid slag removal, all other factors being equal. The regularities of microsphere formation were analyzed, and the mechanism of microsphere formation in fly ash during the combustion of solid fuels was considered.

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

    PubMed

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

    2014-01-01

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

  18. 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 Brønsted acids, are crucial for utilizing the catalytic functions of hydrogen spillover on the aluminosilicate surface. The catalysts with optimized nanostructure show remarkable activities in hydro-/dehydrogenation, but virtually no activity for hydrogenolysis. This distinct chemoselectivity may be beneficial in industrially important hydroconversions such as propane dehydrogenation to propylene because the undesired hydrogenolysis pathway producing light hydrocarbons of low value (methane and ethane) is greatly suppressed.

  19. 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.

  20. 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)

  1. Linearly polarized ytterbium-doped fiber laser in a pedestal design with aluminosilicate inner cladding

    NASA Astrophysics Data System (ADS)

    Yoo, S.; Webb, A. S.; Boyland, A. J.; Standish, R. J.; Dhar, A.; Sahu, J. K.

    2011-06-01

    Ytterbium-doped polarization-maintaining fiber in a pedestal geometry is demonstrated using MCVD and a novel in-situ doping technique. The aluminosilicate pedestal layers minimize the thermal expansion mismatch against the silica outer cladding and permits complete freedom of location for the stress-applying parts in the fiber. A birefringence of 2.4×10-4 is experimentally determined. The fiber delivers linearly polarized laser exhibiting 79% slope efficiency with a polarization extinction ratio of 12 dB.

  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. 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

  4. 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 ?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. 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.

  5. 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.

  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. Crystalline color superconductivity

    SciTech Connect

    Alford, Mark; Bowers, Jeffrey A.; Rajagopal, Krishna

    2001-04-01

    In any context in which color superconductivity arises in nature, it is likely to involve pairing between species of quarks with differing chemical potentials. For suitable values of the differences between chemical potentials, Cooper pairs with nonzero total momentum are favored, as was first realized by Larkin, Ovchinnikov, Fulde, and Ferrell (LOFF). Condensates of this sort spontaneously break translational and rotational invariance, leading to gaps which vary periodically in a crystalline pattern. Unlike the original LOFF state, these crystalline quark matter condensates include both spin-zero and spin-one Cooper pairs. We explore the range of parameters for which crystalline color superconductivity arises in the QCD phase diagram. If in some shell within the quark matter core of a neutron star (or within a strange quark star) the quark number densities are such that crystalline color superconductivity arises, rotational vortices may be pinned in this shell, making it a locus for glitch phenomena.

  8. 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.

  9. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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.

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

    PubMed Central

    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

  12. 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

  13. Molecular recognition in cation-exchanged zeolites

    NASA Astrophysics Data System (ADS)

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

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

  14. 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.

  15. Zeolite-templated Pt/C electrocatalysts

    SciTech Connect

    Coker, Eric N.; Steen, William A.; Miller, James E.

    2008-06-16

    In an effort to reduce the amount of platinum required in low temperature fuel cells, we have prepared electrocatalysts of platinum nanoparticles-on-carbon through zeolite-templating methods. Several different zeolite structure-types, as well as clays and mesoporous silicas were investigated as hosts for the preparation of small Pt clusters through thermal decomposition of ion exchanged (NH{sub 3}){sub 4}Pt{sup 2+}. Several factors relating to cluster confinement and mobility influence cluster size, and clusters below 1 nm with narrow size distribution have been prepared. To enable electrochemical application, the pores of the Pt cluster-containing zeolite were filled with electrically conductive carbon via infiltration with carbon precursors, polymerization, and pyrolysis. The zeolite host was then removed by acid digestion, to leave a micro-/mesoporous Pt/C electrocatalyst possessing Pt clusters of controlled size. Preliminary electrochemical evaluation of these catalysts is reported. The energetics of thermal decomposition of (NH{sub 3}){sub 4}Pt{sup 2+} to form Pt clusters in zeolite X have been investigated through Differential Scanning Calorimetry, and apparent activation energies calculated. The relationship between (NH{sub 3}){sub 4}Pt{sup 2+} decomposition and conditions of calcination has been explored in an effort to better control Pt cluster sizes.

  16. 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.

  17. Zeolite, a versatile air pollutant adsorber. Technical bulletin (final)

    SciTech Connect

    Not Available

    1999-05-01

    The purpose of this document is to make people aware of zeolite, what it is, and what other used it has had. Zeolite is a relatively new medium for adsorption, but has a long history in other uses. Synthetic zeolite has an important role to play in controlling volatile organic compound (VOC) emissions. This document describes what synthetic zeolite is, and what it can do. Also shown are a number of other instances in which the unique properties of zeolite have been used to advantage.

  18. 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.

  19. Photocatalytic activity of undoped and Ag-doped TiO{sub 2}-supported zeolite for humic acid degradation and mineralization

    SciTech Connect

    Lazau, C.; Ratiu, C.; National Institute for Research and Development in Microtechnologies, Erou Iancu Nicolae Street, 077190 Bucharest ; Orha, C.; Pode, R.; Manea, F.

    2011-11-15

    Highlights: {yields} Hybrid materials based on natural zeolite and TiO{sub 2} obtained by solid-state reaction. {yields} XRD proved the presence of anatase form of undoped and Ag-doped TiO{sub 2} onto zeolite. {yields} FT-IR spectra evidenced the presence on TiO{sub 2} bounded at the zeolite network. {yields} Ag-doped TiO{sub 2} onto zeolitic matrix exhibited an enhanced photocatalytic activity. -- Abstract: The hybrid materials based on natural zeolite and undoped and Ag-doped TiO{sub 2}, i.e., Z-Na-TiO{sub 2} and Z-Na-TiO{sub 2}-Ag, were successfully synthesized by solid-state reaction in microwave-assisted hydrothermal conditions. Undoped TiO{sub 2} and Ag-doped TiO{sub 2} nanocrystals were previously synthesized by sol-gel method. The surface characterization of undoped TiO{sub 2}/Ag-doped TiO{sub 2} and natural zeolite hybrid materials has been investigated by X-ray diffraction, DRUV-VIS spectroscopy, FT-IR spectroscopy, BET analysis, SEM microscopy and EDX analysis. The results indicated that anatase TiO{sub 2} is the dominant crystalline type as spherical form onto zeolitic matrix. The presence of Ag into Z-Na-TiO{sub 2}-Ag was confirmed by EDX analysis. The DRUV-VIS spectra showed that Z-Na-TiO{sub 2}-Ag exhibited absorption within the range of 400-500 nm in comparison with Z-Na-TiO{sub 2} catalyst. The enhanced photocatalytic activity of Z-Na-TiO{sub 2}-Ag catalyst is proved through the degradation and mineralization of humic acid under ultraviolet and visible irradiation.

  20. 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.

  1. 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.

  2. 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

  3. Studies of anions sorption on natural zeolites.

    PubMed

    Barczyk, K; Mozgawa, W; Król, 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

  4. 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

  5. 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.

  6. Structural studies of ?-crystallin

    PubMed Central

    Waley, S. G.

    1965-01-01

    1. ?-Crystallin has been isolated from the cortex of ox lens by isoelectric precipitation followed by chromatography on DEAE-cellulose. The amino acid composition is in agreement with that reported for ?-crystallin prepared by a different method. There is one thiol group/20000g. of protein (20000 is the order of magnitude of the sub-unit molecular weight), and disulphide bonds are absent. 2. The thiol group has been alkylated with radioactive iodoacetate in the presence of urea. 3. Partial acid hydrolysis of the alkylated protein gives, according to the conditions, mainly three radioactive peptides or nearly exclusively one radioactive dipeptide. The dipeptide is N-seryl-(S-carboxymethyl)cysteine, Ser-CMCys. The two other peptides are probably the tripeptides related to Ser-CMCys. 4. The simplest interpretation of these results is that the sequence around the cysteine residue is a common structural feature of the sub-units of ?-crystallin. PMID:5862412

  7. 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 Brønsted 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 Brønsted 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 Brønsted 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 Brønsted acid sites. Sites are hypothesized to be blocked due to reprecipitation of silica dissolved during framework hydrolysis in the aging procedure. PMID:26237038

  8. 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.

  9. 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.

  10. 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

  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 200-600 °C. 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. 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...

  13. 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…

  14. 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 ...

  15. 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.

  16. 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...

  17. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

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

    1987-03-31

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

  18. 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.

  19. 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...

  20. 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

  1. Hydrothermal stability of high silica zeolites 

    E-print Network

    Young, David

    1988-01-01

    This thesis concerns the hydrothermal stability of two zeolite molecular sieves with the MFI structure, ZSM-5 and its 'aluminium free' form silicalite. Silicalite was synthesised from low pH alkali metal free aqueous gels at 95°C and characterised...

  2. 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

  3. 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.

  4. 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

  5. Conversion of Fly Ash into Mesoporous Aluminosilicate Hsiao-Lan Chang, Chang-Min Chun, Ilhan A. Aksay, and Wei-Heng Shih*,

    E-print Network

    Aksay, Ilhan A.

    and aluminum sources. Fly ash, which is a byproduct of coal burning, contains mostly aluminosilicates. RecentlyConversion of Fly Ash into Mesoporous Aluminosilicate Hsiao-Lan Chang, Chang-Min Chun, Ilhan A been synthesized from fused fly ash solutions and cationic cetyltrimethylammonium bromide (CTAB

  6. 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.

  7. 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.

  8. First Principles Simulations of Hydrocarbon Conversion Processes in Functionalized Zeolitic Materials

    NASA Astrophysics Data System (ADS)

    Mazar, Mark Nickolaus

    With increasing demand for chemicals and fuels, and finite traditional crude oil resources, there is a growing need to invent, establish, or optimize chemical processes that convert gasifiable carbon-based feedstocks (e.g., coal, natural gas, oil sands, or biomass) into the needed final products. Catalysis is central to almost every industrial chemical process, including alkane metathesis (AM) and the methanol-to-hydrocarbons (MTH) process, which represent final steps in a sequence of hydrocarbon conversion reactions. An in depth understanding of AM and MTH is essential to the selective production of the desired end products. In this dissertation, ab initio density functional theory simulations provide unique mechanistic and thermodynamic insight of specific elementary steps involved in AM and MTH as performed on zeolite supports. Zeolites have been employed throughout the petroleum industry because of their ability to perform acid-catalyzed reactions (e.g., cracking or MTH). The crystalline structure of zeolites imparts regular microporous networks and, in turn, the selective passage of molecules based on shape and functionality. Many different elements can be grafted onto or substituted into zeolites, resulting in a broad range of catalytic behavior. However, due to the variety of competing and secondary reactions that occur at experimental conditions, it is often difficult to extract quantitative information regarding individual elementary steps. ab initio calculations can be particularly useful for this purpose. Alkane metathesis (i.e., the molecular redistribution or chain length averaging of alkanes) is typically performed by transition metal hydrides on amorphous alumina or silica supports. In Chapter 3, the feasibility of AM in zeolites is assessed by using a grafted Ta-hydride complex to explore the full catalytic cycle in the self-metathesis of ethane. The decomposition of a Ta-metallacyclobutane reaction intermediate that forms during olefin metathesis is responsible for the largest activation energy of the catalytic cycle. This assessment is similar to the findings of alkane metathesis studies on alumina/silica supports and indicates that the entire AM cycle can be performed in zeolites by isolated single-atom transition metal hydrides. Performed over acid form zeolites, MTH is used in the conversion of methanol into a broad range of hydrocarbons, including alkenes, alkanes, and aromatics. For reasons that are not yet rigorously quantified, product selectivities vary dramatically based on the choice of catalyst and reaction conditions. The methylation of species containing double bonds (i.e., co-catalysts) is central to the overall process. Distinct structure-function relationships were found with respect to the elementary steps in the methylation and beta-scission of olefins. In Chapter 4, the role of zeolite topology in the step-wise methylation of ethene by surface methoxides is investigated. Elementary steps are studied across multiple frameworks (i.e., BEA, CHA, FER, MFI, and MOR) constituting a wide variety of confinement environments. The reaction of surface methoxides with ethene is found to require a transition state containing a primary carbocation. The barrier height is found to decrease nearly monotonically with respect to the degree of dispersion interactions stabilizing the primary carbocationic species in the transition state. In addition, quantification of the ``local'' dispersion energy indicates that confinement effects can not be simply correlated to pore size. The beta-scission of olefins plays an important role in the product selectivities of many important chemical processes, including MTH. In Chapter 5, beta-scission modes involving C6 and C8 isomers are investigated at a single, isolated Bronsted acid site within H-ZSM-5. We find that the relative enthalpic barriers of beta-scission elementary steps can be rationalized by the substitution order of the two different carbocationic carbon atoms that are present in the reactant (C+) and transition states (betaC). In fact, the increase in c

  9. 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, C

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

    PubMed

    Jaworski, Aleksander; Stevensson, Baltzar; Edén, 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

  11. 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.

  12. Seeding of Porous Alumina Substrate with MFI Zeolite Nanocrystals using Spin-coating Technique

    E-print Network

    Baroud, T.

    Zeolite membranes offer a great potential for applications in many challenging separation processes. Controlled thickness of zeolite membrane allows high flux and excellent selectivity commercially available; producing ...

  13. 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

  14. 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.

  15. 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.

  16. Atomic sites and stability of Cs+ captured within zeolitic nanocavities.

    PubMed

    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 (137)Cs(+) 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

  17. Atomic sites and stability of Cs+ captured within zeolitic nanocavities

    NASA Astrophysics Data System (ADS)

    Yoshida, Kaname; Toyoura, Kazuaki; Matsunaga, Katsuyuki; Nakahira, Atsushi; Kurata, Hiroki; Ikuhara, Yumi H.; Sasaki, Yukichi

    2013-08-01

    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.

  18. Elution of cesium from zeolite IE-96 using oxalic acid

    SciTech Connect

    Sills, J.A.; Russell, R.L.; Patello, G.K.

    1996-12-31

    The West Valley Demonstration Project (WVDP) is preparing to begin vitrification at the site in West Valley, NY. The wastes to be vitrified include high-level radioactive waste (HLW) generated as a result of the former reprocessing operations and cesium-loaded zeolite, a high-activity waste, generated from WVDP pretreatment operations. These pretreatment operations used zeolite in an ion-exchange process designed to remove radioactive cesium from liquid HLW. Zeolite transfer operations, in which the majority of the cesium-loaded zeolite is transferred to a tank containing HLW, are currently being performed in preparation for vitrification. Due to operating constraints and tank design, a portion of the zeolite will remain in the tank after the transfer occurs. The use of oxalic acid to elute the radioactive cesium from the zeolite to decrease the radioactivity remaining in the tank is being evaluated.

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

    PubMed

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

    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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Barrier properties of hydrogenated acrylonitrile-butadiene rubber composites containing modified layered aluminosilicates

    NASA Astrophysics Data System (ADS)

    Krzemi?ska, S.; Rzymski, W. M.

    2011-12-01

    The resistance to permeation by the selected solvents of flat membranes made of cured hydrogenated acrylonitrile-butadiene rubber (HNBR) materials without any fillers and containing 5 phr of layered aluminosilicate nanofiller (bentonite), modified with various types of ammonium salts or N330 type carbon black, was investigated. The barrier properties were assessed on the basis of the breakthrough time of a liquid with low (cyclohexane) or average (butyl acetate) thermodynamic affinity to HNBR, determined according to EN 6529:2001, through a cured elastomer sample. The addition of bentonite, irrespectively of the method of modification of its particles, was found to increase the cured HNBR breakthrough time by 20 - 35 % in the case of slowly permeating non-polar cyclohexane, and by 50 - 130 % in the case of polar butyl acetate permeating more rapidly, in comparison with the barrier material containing no filler. The layered aluminosilicate nanofillers increased the breakthrough time of the material sample for both the tested solvents. In particular, the breakthrough time for polar butyl acetate was even longer than for conventional carbon black. Additionally, the increase of the breakthrough time was observed to depend on the modifier of bentonite particle surface.

  6. 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.

  7. 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.

  8. 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

  9. 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

  10. 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

  11. 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.

  12. Cellular morphology of organic-inorganic hybrid foams based on alkali alumino-silicate matrix

    SciTech Connect

    Verdolotti, Letizia; Capasso, Ilaria; Lavorgna, Marino; Liguori, Barbara; Caputo, Domenico; Iannace, Salvatore

    2014-05-15

    Organic-inorganic hybrid foams based on an alkali alumino-silicate matrix were prepared by using different foaming methods. Initially, the synthesis of an inorganic matrix by using aluminosilicate particles, activated through a sodium silicate solution, was performed at room temperature. Subsequently the viscous paste was foamed by using three different methods. In the first method, gaseous hydrogen produced by the oxidization of Si powder in an alkaline media, was used as blowing agent to generate gas bubbles in the paste. In the second method, the porous structure was generated by mixing the paste with a “meringue” type of foam previously prepared by whipping, under vigorous stirring, a water solution containing vegetal proteins as surfactants. In the third method, a combination of these two methods was employed. The foamed systems were consolidated for 24 hours at 40°C and then characterized by FTIR, X-Ray diffraction, scanning electron microscopy (SEM) and compression tests. Low density foams (?500 Kg/m{sup 3}) with good cellular structure and mechanical properties were obtained by combining the “meringue” approach with the use of the chemical blowing agent based on Si.

  13. 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

  14. 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.

  15. 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

  16. Development of low-cost integrated zeolite collector

    NASA Astrophysics Data System (ADS)

    Tchernev, D. I.

    1981-07-01

    The optimum zeolite loading and the best zeolite for this purpose were determined by careful mathematical analysis, followed by experimental test, to confirm the theoretical results. The integrated collector design was then completed and the collector was constructed. After sealing and vacuum testing the zeolite panels and heat exchanges, the collector was coated with flat black paint and provided with double glazing, aluminum frame and insulation. Preliminary testing indicates close agreement with theoretical predictions of its performance.

  17. Layered Topological Crystalline Insulators.

    PubMed

    Kim, Youngkuk; Kane, C L; Mele, E J; Rappe, Andrew M

    2015-08-21

    Topological crystalline insulators (TCIs) are insulating materials whose topological property relies on generic crystalline symmetries. Based on first-principles calculations, we study a three-dimensional (3D) crystal constructed by stacking two-dimensional TCI layers. Depending on the interlayer interaction, the layered crystal can realize diverse 3D topological phases characterized by two mirror Chern numbers (MCNs) (?1,?2) defined on inequivalent mirror-invariant planes in the Brillouin zone. As an example, we demonstrate that new TCI phases can be realized in layered materials such as a PbSe (001) monolayer/h-BN heterostructure and can be tuned by mechanical strain. Our results shed light on the role of the MCNs on inequivalent mirror-symmetric planes in reciprocal space and open new possibilities for finding new topological materials. PMID:26340198

  18. 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) (?1,?2 ) 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.

  19. 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

  20. 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.

  1. Method for the recovery of silver from silver zeolite

    DOEpatents

    Reimann, George A. (Idaho Falls, ID)

    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.

  2. 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.

  3. Crystalline titanate catalyst supports

    DOEpatents

    Anthony, Rayford G. (Bryan, TX); Dosch, Robert G. (Albuquerque, NM)

    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.

  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. 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.

  6. 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.

  7. Reduction of nitrogen oxides with catalytic acid resistant aluminosilicate molecular sieves and ammonia

    DOEpatents

    Pence, Dallas T. (Idaho Falls, ID); Thomas, Thomas R. (Idaho Falls, ID)

    1980-01-01

    Noxious nitrogen oxides in a waste gas stream such as the stack gas from a fossil-fuel-fired power generation plant or other industrial plant off-gas stream is catalytically reduced to elemental nitrogen and/or innocuous nitrogen oxides employing ammonia as reductant in the presence of a zeolite catalyst in the hydrogen or sodium form having pore openings of about 3 to 10 A.

  8. 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. 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.

  10. CIT-7, a crystalline, molecular sieve with pores bounded by 8 and 10-membered rings

    DOE PAGESBeta

    Schmidt, Joel E.; Xie, Dan; Rea, Thomas; Davis, Mark E.

    2015-01-23

    A new crystalline molecular sieve, denoted CIT-7, is synthesized using an imidazolium-based diquaternary organic structure directing agent (OSDA). The framework structure is determined from a combination of rotation electron diffraction and synchrotron X-ray powder diffraction data. The structure has 10 crystallographically unique tetrahedral atoms (T-atoms) in the unit cell, and can be described as an ordered arrangement of the [425462] mtw building unit and a previously unreported [4452] building unit. The framework contains a 2-dimensional pore system that is bounded by 10 T-atom rings (10-ring, 5.1 Å × 6.2 Å opening) that are connected with oval 8-rings (2.9 Å ×more »5.5 Å opening) through medium-sized cavities (~7.9 Å) at the channel intersections. CIT-7 can be synthesized over a broad range of compositions including pure-silica and heteroatom, e.g., aluminosilicate and titanosilicate, containing variants.« less

  11. Design of composite photocatalyst of TiO2 and Y-zeolite for degradation of 2-propanol in the gas phase under UV and visible light irradiation.

    PubMed

    Kamegawa, Takashi; Ishiguro, Yasushi; Kido, Ryota; Yamashita, Hiromi

    2014-01-01

    Hydrophobic Y-zeolite (SiO2/Al2O3 = 810) and TiO2 composite photocatalysts were designed by using two different types of TiO2 precursors, i.e., titanium ammonium oxalate and ammonium hexafluorotitanate. The porous structure, surface property and state of TiO2 were investigated by various characterization techniques. By using an ammonium hexafluorotitanate as a precursor, hydrophobic modification of the Y-zeolite surface and realizing visible light sensitivity was successfully achieved at the same time after calcination at 773 K in the air. The prepared sample still maintained the porous structure of Y-zeolite and a large surface area. Highly crystalline anatase TiO2 was also formed on the Y-zeolite surface by the role of fluorine in the precursor. The usages of ammonium hexafluorotitanate were effective for the improvement of the photocatalytic performance of the composite in the degradation of 2-propanol in the gas phase under UV and visible light (? > 420 nm) irradiation. PMID:25314607

  12. Design of Lewis-acid centres in zeolitic matrices for the conversion of renewables.

    PubMed

    Dapsens, Pierre Y; Mondelli, Cecilia; Pérez-Ramírez, Javier

    2015-10-21

    The catalytic conversion of renewable feedstocks into chemicals is pursued as a means to sustainably fulfil future societal needs. Due to the oxygen-rich nature of bio-derived substrates, isomerisation, transfer-hydrogenation and retro-aldol reactions have emerged as relevant transformations to produce commodity chemicals and polymer building blocks. In this context, porous materials containing Lewis-acid metals (e.g., Al, Ga, Sn, Ti, Zr) play an important role. Among these, tin-containing zeolites have demonstrated superior catalytic properties which have mainly been attributed to their hydrophobicity and crystallinity. This review evaluates the versatility and the scalability of bottom-up and top-down approaches to introduce Lewis-acid functionalities in zeolitic matrices. A precise characterisation is shown to be crucial to determine the structure, acidity and environment of the sites introduced. In this regard, we highlight the limitations of conventional techniques and the advantages of analytical and modelling tools recently applied to gain an improved understanding of these solids. Thereafter, property-performance relations and important aspects for the industrial amenability of new synthetic routes are exemplified through case studies. Finally, we put forward the need for gathering deeper knowledge of the site location, surface properties and stability to aid the design of next-generation Lewis-acid catalysts. PMID:25917850

  13. 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

  14. 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.

  15. 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

  16. Zeolites in Eocene basaltic pillow lavas of the Siletz River Volcanics, Central Coast Range, Oregon.

    USGS Publications Warehouse

    Keith, T.E.C.; Staples, L.W.

    1985-01-01

    Zeolites and associated minerals occur in a tholeiitic basaltic pillow lava sequence. Although the zeolite assemblages are similar to those found in other major zeolite occurrences in basaltic pillow lavas, regional zoning of the zeolite assemblages is not apparent. The formation of the different assemblages is discussed.-D.F.B.

  17. Oxygen transport in zeolite Y measured by quenching of encapsulated tris(bipyridyl)ruthenium

    E-print Network

    Dutta, Prabir K.

    Oxygen transport in zeolite Y measured by quenching of encapsulated tris(bipyridyl)ruthenium Abstract This study deals with emission quenching of zeolite encapsulated trisbipyridyl ruthenium (II) (Ru the migration of O2 within zeolites using the emis- sion quenching of zeolite encapsulated ruthenium

  18. Photochemical template removal and spatial patterning of zeolite MFI thin films using UV/ozone treatment

    E-print Network

    Parikh, Atul N.

    Photochemical template removal and spatial patterning of zeolite MFI thin films using UV of thin films of microporous or zeolite materials. We prepared thin-films of a high silica zeolite leads to complete removal of template (structure-direc- ting-agent) from zeolite films comparable

  19. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz (Berkeley, CA); Blatter, Fritz (Basel, CH); Sun, Hai (Saint Charles, MO)

    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.

  20. Selective thermal oxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz (Berkeley, CA); Blatter, Fritz (Basel, CH); Sun, Hai (Saint Charles, MO)

    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.

  1. 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...

  2. 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.

  3. 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 ...

  4. 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.

  5. Preferential orientations of structure directing agents in zeolites.

    PubMed

    Dib, Eddy; Gimenez, Antoine; Mineva, Tzonka; Alonso, Bruno

    2015-10-14

    The local structure of as-synthesised silicalite-1 zeolites is modified using asymmetric R(Pr)3N(+) structure directing agents. Using multi-nuclear NMR ((1)H, (13)C, (14)N, (19)F, (29)Si), we show for the first time the ability of these cations to adopt preferential orientations at the zeolite channels' crossing. PMID:26346931

  6. Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz (Berkeley, CA); Blatter, Fritz (Basel, CH); Sun, Hai (Saint Charles, MO)

    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.

  7. 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%.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

    González, C. P.; Montaño, A. M.; González, A. K.; Ríos, 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 ± 5°C. 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).

  13. 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.

  14. Oxidation behavior of a Si-C-O-fiber-reinforced magnesium aluminosilicate

    SciTech Connect

    Kumar, A.; Knowles, K.M.

    1996-09-01

    The oxidation behavior of a Si-C-O-fiber-reinforced magnesium aluminosilicate has been investigated in the temperature range 1,000--1,200 C. Parabolic weight gain, together with other experimental observations, has suggested that the oxidation process was controlled by the outward diffusion of carbon monoxide gas. The matrix and fibers reacted to form enstatite and forsterite. During the initial stages of oxidation, an interlayer containing a mixture of silica and turbostratic carbon was formed. This interlayer was modified progressively over time to create interface morphologies near the surface and near the center of the oxidized samples that were different from one another. A mechanism explaining the morphological evolution of the fiber-matrix interfaces has been proposed.

  15. Optical spectroscopy and waveguide fabrication in Sm3+/Tb3+ doped zinc-sodium-aluminosilicate glasses

    NASA Astrophysics Data System (ADS)

    Caldiño, U.; Speghini, A.; Berneschi, S.; Bettinelli, M.; Brenci, M.; Pelli, S.; Righini, G. C.

    2012-05-01

    A spectroscopic investigation of sodium-zinc-aluminosilicate glasses activated with Sm3+ and Tb3+/Sm3+ ions is performed through their luminescence spectra and decay times. Yellowish-green light emission, with x = 0.37 and y = 0.58 CIE chromaticity coordinates, is obtained in the Tb3+/Sm3+ codoped glass excited at 318 nm. Such yellowish-green emission is generated by the simultaneous emission of Tb3+ and Sm3+ ions, samarium being sensitized by the terbium through a non-radiative energy transfer. From spectroscopic data it is inferred that this energy transfer takes place between Tb3+ and Sm3+ clusters through a short-range interaction mechanism. Optical waveguides are also effectively produced in the glasses by Ag+-Na+ ion exchange.

  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. Structure and properties of sodium aluminosilicate glasses from molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Xiang, Ye; Du, Jincheng; Smedskjaer, Morten M.; Mauro, John C.

    2013-07-01

    Addition of alumina to sodium silicate glasses considerably improves the mechanical properties and chemical durability and changes other properties such as ionic conductivity and melt viscosity. As a result, aluminosilicate glasses find wide industrial and technological applications including the recent Corning® Gorilla® Glass. In this paper, the structures of sodium aluminosilicate glasses with a wide range of Al/Na ratios (from 1.5 to 0.6) have been studied using classical molecular dynamics simulations in a system containing around 3000 atoms, with the aim to understand the structural role of aluminum as a function of chemical composition in these glasses. The short- and medium-range structures such as aluminum coordination, bond angle distribution around cations, Qn distribution (n bridging oxygen per network forming tetrahedron), and ring size distribution have been systematically studied. In addition, the mechanical properties including bulk, shear, and Young's moduli have been calculated and compared with experimental data. It is found that aluminum ions are mainly four-fold coordinated in peralkaline compositions (Al/Na < 1) and form an integral part of the rigid silicon-oxygen glass network. In peraluminous compositions (Al/Na > 1), small amounts of five-fold coordinated aluminum ions are present while the concentration of six-fold coordinated aluminum is negligible. Oxygen triclusters are also found to be present in peraluminous compositions, and their concentration increases with increasing Al/Na ratio. The calculated bulk, shear, and Young's moduli were found to increase with increasing Al/Na ratio, in good agreement with experimental data.

  18. Prospects and challenges of iron pyroelectrolysis in magnesium aluminosilicate melts near minimum liquidus temperature.

    PubMed

    Ferreira, N M; Kovalevsky, A V; Mikhalev, S M; Costa, F M; Frade, J R

    2015-04-14

    Although steel production by molten oxide electrolysis offers potential economic and environmental advantages over classic extractive metallurgy, its feasibility is far from being convincingly demonstrated, mainly due to inherent experimental difficulties exerted by harsh conditions and lack of knowledge regarding relevant mechanisms and physico-chemical processes in the melts. The present work was intended to demonstrate the concept of pyroelectrolysis at very high temperature near the minimum liquidus point of magnesium aluminosilicate, being conducted under electron-blocking conditions using yttria-stabilized zirconia cells, and to provide a new insight into electrochemistry behind this process. Significant current yields are possible for pyroelectrolysis performed in electron-blocking mode using a solid electrolyte membrane to separate the anode and the molten electrolyte. Parasitic electrochemical processes rise gradually as the concentration of iron oxide dissolved in the molten electrolytes is depleted, impairing faradaic efficiency. Reduction of silica to metallic silicon was identified as a significant contribution to those parasitic currents, among other plausible processes. Direct pyroelectrolysis without electron blocking was found much less plausible, due to major limitations on faradaic efficiency imposed by electronic leakage and insufficient ionic conductivity of the aluminosilicate melt. Ohmic losses may consume an excessive fraction of the applied voltage, thus failing to sustain the Nernst potential required for reduction to metallic iron. The results suggest the need for further optimization of the molten electrolyte composition to promote ionic conductivity and to suppress electronic transport contribution, possibly, by tuning the Al/Si ratio and altering the network-forming/modifying behaviour of the iron cations. PMID:25760633

  19. Preparation of a Versatile Bifunctional Zeolite for Targeted Imaging Applications

    PubMed Central

    Ndiege, Nicholas; Raidoo, Renugan; Schultz, Michael K.; Larsen, Sarah

    2011-01-01

    Bifunctional zeolite Y was prepared for use in targeted in vivo molecular imaging applications. The strategy involved functionalization of the external surface of zeolite Y with chloropropyltriethoxysilane followed by reaction with sodium azide to form azide-functionalized NaY, which is amenable to copper(1) catalyzed click chemistry. In this study, a model alkyne (4-pentyn-1-ol) was attached to the azide-terminated surface via click chemistry to demonstrate feasibility for attachment of molecular targeting vectors (e.g., peptides, aptamers) to the zeolite surface. The modified particle efficiently incorporates the imaging radioisotope gallium-68 (68Ga) into the pores of the azide-functionalized NaY zeolite to form a stable bifunctional molecular targeting vector. The result is a versatile “clickable” zeolite platform that can be tailored for future in vivo molecular targeting and imaging modalities. PMID:21306141

  20. Potential and actual uses of zeolites in crop protection.

    PubMed

    De Smedt, Caroline; Someus, Edward; Spanoghe, Pieter

    2015-10-01

    In this review, it is demonstrated that zeolites have a potential to be used as crop protection agents. Similarly to kaolin, zeolites can be applied as particle films against pests and diseases. Their honeycomb framework, together with their carbon dioxide sorption capacity and their heat stress reduction capacity, makes them suitable as a leaf coating product. Furthermore, their water sorption capacity and their smaller particle sizes make them effective against fungal diseases and insect pests. Finally, these properties also ensure that zeolites can act as carriers of different active substances, which makes it possible to use zeolites for slow-release applications. Based on the literature, a general overview is provided of the different basic properties of zeolites as promising products in crop protection. PMID:25727795

  1. A pair distribution function analysis of zeolite beta

    SciTech Connect

    Martinez-Inesta, M.M.; Peral, I.; Proffen, T.; Lobo, R.F.

    2010-07-20

    We describe the structural refinement of zeolite beta using the local structure obtained with the pair distribution function (PDF) method. A high quality synchrotron and two neutron scattering datasets were obtained on two samples of siliceous zeolite beta. The two polytypes that make up zeolite beta have the same local structure; therefore refinement of the two structures was possible using the same experimental PDF. Optimized structures of polytypes A and B were used to refine the structures using the program PDFfit. Refinements using only the synchrotron or the neutron datasets gave results inconsistent with each other but a cyclic refinement with the two datasets gave a good fit to both PDFs. The results show that the PDF method is a viable technique to analyze the local structure of disordered zeolites. However, given the complexity of most zeolite frameworks, the use of both X-ray and neutron radiation and high-resolution patterns is essential to obtain reliable refinements.

  2. Oxidative regeneration of toluene-saturated natural zeolite by gaseous ozone: the influence of zeolite chemical surface characteristics.

    PubMed

    Alejandro, Serguei; Valdés, Héctor; Manéro, Marie-Hélène; Zaror, Claudio A

    2014-06-15

    In this study, the effect of zeolite chemical surface characteristics on the oxidative regeneration of toluene saturated-zeolite samples is investigated. A Chilean natural zeolite (53% clinoptilolite, 40% mordenite and 7% quartz) was chemically modified by acid treatment with hydrochloric acid and by ion-exchange with ammonium sulphate. Thermal pre-treatments at 623 and 823K were applied and six zeolite samples with different chemical surface characteristics were generated. Chemical modification of natural zeolite followed by thermal out-gassing allows distinguishing the role of acidic surface sites on the regeneration of exhausted zeolites. An increase in Brønsted acid sites on zeolite surface is observed as a result of ammonium-exchange treatment followed by thermal treatment at 623K, thus increasing the adsorption capacity toward toluene. High ozone consumption could be associated to a high content of Lewis acid sites, since these could decompose ozone into atomic active oxygen species. Then, surface oxidation reactions could take part among adsorbed toluene at Brønsted acid sites and surface atomic oxygen species, reducing the amount of adsorbed toluene after the regenerative oxidation with ozone. Experimental results show that the presence of adsorbed oxidation by-products has a negative impact on the recovery of zeolite adsorption capacity. PMID:24794812

  3. Influence of NaA Zeolite Crystal Expansion/Contraction on Zeolite Membrane Separations

    SciTech Connect

    Sorenson, Stephanie G; Payzant, E Andrew; Gibbons, Will T; Soydas, Belma; Kita, Hidetoshi; Noble, Richard D; Falconer, John L.

    2011-01-01

    In-situ powder XRD measurements showed that the NaA zeolite unit cell contracts and expands upon adsorption, and these changes in zeolite crystal size correlate with permeation changes through NaA zeolite membranes. These membranes had high pervaporation selectivities, even though gas permeation was mainly through defects, as indicated by Knudsen selectivities for gases. At 300 K and a thermodynamic activity of 0.03, water contracted the NaA crystals by 0.22 vol%, and this contraction increased the helium flux through two NaA membranes by approximately 80%. Crystal contraction also increased the fluxes of i-butane during vapor permeation and i-propanol (IPA) during pervaporation (~ 0.03 wt% water). At activities above 0.07, water expanded NaA crystals and correspondingly decreased the membrane fluxes of helium, i-butane, and IPA. Similarly, methanol contracted NaA crystals by 0.05 vol% at an activity of 0.02, and this contraction slightly increased the helium and i-butane fluxes through a NaA membrane. Above an activity of 0.06, methanol expanded the crystals, and the fluxes of helium and i-butane through a NaA membrane decreased. The adsorbate-induced changes explain some pervaporation behavior reported by others, and they indicate that crystal expansion and contraction may increase or decrease zeolite NaA membrane selectivity by changing the defect sizes.

  4. Probing zeolites with organic molecules: Supercages of X and Y zeolites are superpolar

    SciTech Connect

    Uppili, S.; Thomas, K.J.; Crompton, E.M.; Ramamurthy, V.

    2000-01-11

    Supercages of Li{sup +}- and Na{sup +}-exchanged X and Y zeolites are much more polar than even water. The extent of polarity depends on the nature and the number of cations present within a supercage. The polarity of Li{sup +}- and Na{sup +}-exchanged X and Y zeolites decreases in the presence of water. In presence of water the contribution of cations toward polarity is much smaller than water itself. In this study polarity has been monitored with organic probe molecules, Nile red, pyrene 1-carboxaldehyde and coumarin-500. A connection between polarity and electric field within a cage has also been established. Since the supercages are much more polar than all organic solvents, they can be characterized as superpolar. Because of this one may be able to achieve excited-state switching of carbonyl compounds within a zeolite while such may not be possible in organic solvents. The n{pi}*-{pi}{pi}* state switching of acetophenones is easily achieved within a zeolite while such does not occur in polar solvent methanol-ethanol mixture.

  5. Novel long-term immobilization method for radioactive iodine-129 using a zeolite/apatite composite sintered body.

    PubMed

    Watanabe, Yujiro; Ikoma, Toshiyuki; Yamada, Hirohisa; Suetsugu, Yasushi; Komatsu, Yu; Stevens, Geoffrey W; Moriyoshi, Yusuke; Tanaka, Junzo

    2009-07-01

    The amount of radioactive iodine generated from nuclear power plants is expected to increase with the proliferation of nuclear energy production, and long-term immobilization methods for such radioactive elements need to be developed to make nuclear energy sustainable. The standard immobilization method of radioactive elements, vitrification, is not very effective for radioactive iodine-129 because of the low solubility of iodine in silicate melts, its very high volatility at standard vitrification process temperatures, and its instability in the alkaline environment of deep geological layers below 300 m. We have developed a novel three-phase ceramic composite produced by a sintering process. Iodine adsorbed onto Ca-type zeolite A was covered with a hydroxyapatite nanolayer through the exchange reaction of ammonium with calcium. Clusters of iodine of 30 nm within the zeolite structure were found to be thermally stable up to 1253 K because of the partial blockage of the alpha-cage apertures by ammonium ions and the partial change from a crystalline phase to an amorphous phase at 473 K. No gasification of iodine molecules was found to occur during the sintering process. The outer phase was highly crystalline hydroxyfluorapatite in which the hydroxyapatite nanolayer plays an important role for successful sintering. The elution of iodine in low-dioxygen water, similar to that found within the Earth's crust, was investigated and was found to occur only in the surface layer of the sintered body. PMID:20355964

  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. A Novel Conversion Process for Waste Slag: The Preparation of Aluminosilicate Glass with Evaluation of the Dielectric Properties from Blast Furnace Slag

    NASA Astrophysics Data System (ADS)

    Li, Sheng; Huang, Sanxi; Liu, Hongting; Wu, Fengnian; Chang, Ziyuan; Yue, Yunlong

    2015-09-01

    In this paper, aluminosilicate glass was prepared from blast furnace slag and quartz sand. Fourier transform infrared, differential scanning calorimetry and density measurements were carried out to investigate the effects of SiO2 on the aluminosilicate glass network rigidity. The results indicate that glass structure would be enhanced if more SiO2 was introduced into the glass system. Meanwhile, both the glass transition temperature (T g) and the glass crystallization temperature (T c) increase slightly; the increase in density of the glass being further evidence of the enhancement in glass network rigidity. Dielectric measurements show that the dielectric constant and dielectric loss decrease with more SiO2. The properties of the prepared aluminosilicate glasses are comparable to those of E glass, indicating that blast furnace slags are suitable for producing aluminosilicate glass with low dielectric constant and dielectric loss.

  8. A Novel Conversion Process for Waste Slag: The Preparation of Aluminosilicate Glass with Evaluation of the Dielectric Properties from Blast Furnace Slag

    NASA Astrophysics Data System (ADS)

    Li, Sheng; Huang, Sanxi; Liu, Hongting; Wu, Fengnian; Chang, Ziyuan; Yue, Yunlong

    2015-11-01

    In this paper, aluminosilicate glass was prepared from blast furnace slag and quartz sand. Fourier transform infrared, differential scanning calorimetry and density measurements were carried out to investigate the effects of SiO2 on the aluminosilicate glass network rigidity. The results indicate that glass structure would be enhanced if more SiO2 was introduced into the glass system. Meanwhile, both the glass transition temperature ( T g) and the glass crystallization temperature ( T c) increase slightly; the increase in density of the glass being further evidence of the enhancement in glass network rigidity. Dielectric measurements show that the dielectric constant and dielectric loss decrease with more SiO2. The properties of the prepared aluminosilicate glasses are comparable to those of E glass, indicating that blast furnace slags are suitable for producing aluminosilicate glass with low dielectric constant and dielectric loss.

  9. Fault zone architecture and fluid flow in interlayered basaltic volcaniclastic-crystalline sequences

    NASA Astrophysics Data System (ADS)

    Walker, R. J.; Holdsworth, R. E.; Imber, J.; Faulkner, D. R.; Armitage, P. J.

    2013-06-01

    Faults in continental flood basalt sequences potentially control subsurface fluid flow. We present field and microstructural observations from fault zones cutting interlayered basaltic volcaniclastic-crystalline sequences within the North Atlantic Igneous Province. Fractures likely initiate within lava units, before linking through the volcaniclastic units. Through-going faults show refraction, with subvertical faults in the lavas joined to variably inclined faults in the volcaniclastic layers. At >1.0 m displacement, volcaniclastic units are progressively dragged into the fault plane forming a smear. Volcaniclastic sandstones deform by flow. Claystones fracture, and are incorporated into smears as breccia. Experimentally measured host and fault rock sample permeabilities, at aquifer to reservoir pressures (i.e., 10-90 MPa; ˜0.3-3.0 km depth) show fault rocks from low displacement faults have relatively low permeability (10-17-10-20 m2); fault rocks from higher displacement structures have comparatively high permeability (10-15-10-17 m2). Our observations suggest that permeability is determined by the opposing influences of clay mineralization, which decreases permeability, versus the development of interconnected, higher permeability zeolite veins. Brecciation and the formation of zeolite vein networks within claystone smears results in high permeability. Zeolite veins in volcaniclastic units form poorly-connected, spaced sets, parallel to the slip plane, hence sequence permeability remains low.

  10. 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.

  11. Crystalline amorphous semiconductor superlattice.

    PubMed

    Chong, T C; Shi, L P; Wei, X Q; Zhao, R; Lee, H K; Yang, P; Du, A Y

    2008-04-01

    A new class of superlattice, crystalline amorphous superlattice (CASL), by alternatively depositing two semiconductor materials, is proposed. CASL displays three states depending on the component materials' phase: both polycrystalline phases, both amorphous phases, and one polycrystalline phase while another amorphous phase. Using materials capable of reversible phase transition, CASL can demonstrate reversibility among three states. GeTe/Sb(2)Te(3) CASL has been synthesized and proved by x-ray reflectometry and TEM results. The reversible transition among three states induced by electrical and laser pulse was observed. The changes in the optical absorption edge, electrical resistivity, thermal conductivity, and crystallization temperature as a function of layer thickness are interpreted as quantum or nanoeffects. The unique properties of CASL enable the design of materials with specific properties. PMID:18517969

  12. High pressure synthesis of novel, zeolite based nano-composite materials

    NASA Astrophysics Data System (ADS)

    Santoro, Mario

    2013-06-01

    Meso/micro-porous solids such as zeolites are complex materials exhibiting an impressive range of applications, including molecular sieve, gas storage, catalysis, electronics and photonics. We used these materials, particularly non catalytic zeolites in an entirely different fashion. In fact, we performed high pressure (0.5-30 GPa) chemical reactions of simple molecules on a sub-nanometer scale in the channels of a pure SiO2 zeolite, silicalite to obtain unique nano-composite materials with drastically modified physical and chemical properties. Our material investigations are based on a combination of X-ray diffraction and optical spectroscopy techniques in the diamond anvil cell. I will first briefly show how silicalite can be easily filled by simple molecules such as Ar, CO2 and C2H4 among others from the fluid phase at high pressures, and how this efficient filling removes the well known pressure induced amorphization of the silica framework (Haines et al., JACS 2010). I will then present on a silicon carbonate crystalline phase synthesized by reacting silicalite and molecular CO2 that fills the nano-pores, at 18-26 GPa and 600-980 K; after the synthesis the compound is temperature quenched and it results to be slightly metastable at room conditions (Santoro et al., PNAS 2011). On the other hand, a stable at room condition spectacular crystalline nano-composite is obtained by photo-polymerizing ethylene at 0.5-1.5 GPa under UV (351-364 nm) irradiation in the channels of silicalite (Santoro et al., Nat. Commun, in press 2013). For this composite we obtained a structure with single polyethylene chains adapting very well to the confining channels, which results in significant increases in bulk modulus and density, and the thermal expansion coefficient changes sign from negative to positive with respect to the original silicalite host. Mechanical properties may thus be tuned by varying the amount of polymerized ethylene. We then think our findings could allow the high pressure, catalyst free synthesis of a unique generation of technological, functional materials based on simple hydrocarbons polymerized in confining meso/micro-porous solids.

  13. One-step DGC assembly and structural characterization of a hairy particle zeolite-like organic-inorganic hybrid as an efficient modifiable catalytic material.

    PubMed

    Zhou, Dan; Xu, Jun; Deng, Jiejie; Wei, Xianlong; Lu, Xinhuan; Chu, Xing; Deng, Feng; Xia, Qinghua

    2015-09-01

    Organic-inorganic hybrid microporous crystalline molecular sieves, extending the application of conventional zeolites in the fields of selective catalysis and adsorption, have aroused great interest in chemists. However, the complicated and difficult synthesis of organic-inorganic hybrid microporous molecular sieves by using a conventional hydrothermal method has hindered the rapid development of this field. The present work describes the recent progress in the synthesis of a hairy particle zeolite-like organic-inorganic hybrid with the high organic group content by one-step dry-gel conversion (DGC) assembly of organic Si, inorganic Si and other inorganic species without any organic template, which is proven to be efficient, economical, simple, and controllable. Thus-synthesized hybrid materials, as we know, with the highest organic group content reported in the literature, can be bestowed with modifiable catalytic activities by different treatments. This study will be applicable for the development of organic-inorganic hybrid catalytic materials. PMID:26218297

  14. [Zeolite catalysis in conversion of cellulosics

    SciTech Connect

    Tsao, G.T.

    1992-12-31

    To transform biomass into fermentable substrate for yeast, we are using zeolites instead of enzymes to catalyze the two bottleneck reactions in biomass conversion, xylose isomerization and ceuobiose hydrolysis. The experimental results on these reactions carried out over various zeolites and other catalysts are presented herein. The advantages and disadvantages of using these catalysts over enzymes are also discussed. Heterogeneous solid catalysts other than zeolites has been employed for cellobiose-to-glucose hydrolysis. The size and shape selectivity that makes zeoutes unique for some reactions can add diffusional hindrance. We have spent some time screening various known solid acidic catalysts. We report that a class of cationic ion exchange resins in the acidified form (e.g. Amberlite) has worked well as an acidic catalyst in hydrolyzing cellobiose to glucose. Our experimental results, together with those obtained from a homogeneous acid catalyst (e.g. sulfuric acid) for comparison are provided. Having succeeded in finding an alternative solid acid catalyst for hydrolysis, we explored other solid resin or other homogeneous but non-enzyme catalyst to carry out the xylose-to-xylulose isomerization. A fairly extensive search has been made. We explored the use of sodium aluminates in the homogeneous phase isomerization of glucose to fructose and obtained a very high conversion of glucose to fructose with the final mixture containing 85% of fructose instead of the common 45%. Fructose apparently complexes with aluminates, and its equilibrium concentration is shifted to considerably higher values than permitted by simple glucose/fructose equilibrium. We have recently found a number of catalysts capable of promoting isomerization between aldoses and ketoses. One solid resin, known as polyvinyl pyridine (PVP), is able to convert xylose to xylulose at a pH below 7. Our usage of alternative isomerization catalysts, including PVP, are described.

  15. [Zeolite catalysis in conversion of cellulosics

    SciTech Connect

    Tsao, G.T.

    1992-01-01

    To transform biomass into fermentable substrate for yeast, we are using zeolites instead of enzymes to catalyze the two bottleneck reactions in biomass conversion, xylose isomerization and ceuobiose hydrolysis. The experimental results on these reactions carried out over various zeolites and other catalysts are presented herein. The advantages and disadvantages of using these catalysts over enzymes are also discussed. Heterogeneous solid catalysts other than zeolites has been employed for cellobiose-to-glucose hydrolysis. The size and shape selectivity that makes zeoutes unique for some reactions can add diffusional hindrance. We have spent some time screening various known solid acidic catalysts. We report that a class of cationic ion exchange resins in the acidified form (e.g. Amberlite) has worked well as an acidic catalyst in hydrolyzing cellobiose to glucose. Our experimental results, together with those obtained from a homogeneous acid catalyst (e.g. sulfuric acid) for comparison are provided. Having succeeded in finding an alternative solid acid catalyst for hydrolysis, we explored other solid resin or other homogeneous but non-enzyme catalyst to carry out the xylose-to-xylulose isomerization. A fairly extensive search has been made. We explored the use of sodium aluminates in the homogeneous phase isomerization of glucose to fructose and obtained a very high conversion of glucose to fructose with the final mixture containing 85% of fructose instead of the common 45%. Fructose apparently complexes with aluminates, and its equilibrium concentration is shifted to considerably higher values than permitted by simple glucose/fructose equilibrium. We have recently found a number of catalysts capable of promoting isomerization between aldoses and ketoses. One solid resin, known as polyvinyl pyridine (PVP), is able to convert xylose to xylulose at a pH below 7. Our usage of alternative isomerization catalysts, including PVP, are described.

  16. Growth of large zeolite crystals in space

    NASA Technical Reports Server (NTRS)

    Sacco, A., Jr.; Dixon, A.; Thompson, R.; Scott, G.; Ditr, J.

    1988-01-01

    Synthesis studies performed using close analogs of triethanolamine (TEA) have shown that all three hydroxyl groups and the amine group in this molecule are necessary to provide nucleation suppression. Studies using C-13 nuclear magnetic resonance (NMR) revealed that the hydroxyl ions and the amine group are involved in the formation of an aluminum complex. It was also shown that silicate species fo not interact this way with TEA in an alkaline solution. These results suggest that successful aluminum complexation leads to nucleation in zeolite-A crystallization.

  17. Distribution of metal and adsorbed guest species in zeolites

    SciTech Connect

    Chmelka, B.F.

    1989-12-01

    Because of their high internal surface areas and molecular-size cavity dimensions, zeolites are used widely as catalysts, shape- selective supports, or adsorbents in a variety of important chemical processes. For metal-catalyzed reactions, active metal species must be dispersed to sites within the zeolite pores that are accessible to diffusing reactant molecules. The distribution of the metal, together with transport and adsorption of reactant molecules in zeolite powders, are crucial to ultimate catalyst performance. The nature of the metal or adsorbed guest distribution is known, however, to be dramatically dependent upon preparatory conditions. Our objective is to understand, at the molecular level, how preparatory treatments influence the distribution of guest species in zeolites, in order that macroscopic adsorption and reaction properties of these materials may be better understood. The sensitivity of xenon to its adsorption environment makes {sup 129}Xe NMR spectroscopy an important diagnostic probe of metal clustering and adsorbate distribution processes in zeolites. The utility of {sup 129}Xe NMR depends on the mobility of the xenon atoms within the zeolite-guest system, together with the length scale of the sample heterogeneity being studied. In large pore zeolites containing dispersed guest species, such as Pt--NaY, {sup 129}Xe NMR is insensitive to fine structural details at room temperature.

  18. Zeolite Crystal Growth (ZCG) Flight on USML-2

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.; Bac, Nurcan; Warzywoda, Juliusz; Guray, Ipek; Marceau, Michelle; Sacco, Teran L.; Whalen, Leah M.

    1997-01-01

    The extensive use of zeolites and their impact on the world's economy has resulted in many efforts to characterize their structure, and improve the knowledge base for nucleation and growth of these crystals. The zeolite crystal growth (ZCG) experiment on USML-2 aimed to enhance the understanding of nucleation and growth of zeolite crystals, while attempting to provide a means of controlling the defect concentration in microgravity. Zeolites A, X, Beta, and Silicalite were grown during the 16 day - USML-2 mission. The solutions where the nucleation event was controlled yielded larger and more uniform crystals of better morphology and purity than their terrestrial/control counterparts. The external surfaces of zeolite A, X, and Silicalite crystals grown in microgravity were smoother (lower surface roughness) than their terrestrial controls. Catalytic studies with zeolite Beta indicate that crystals grown in space exhibit a lower number of Lewis acid sites located in micropores. This suggests fewer structural defects for crystals grown in microgravity. Transmission electron micrographs (TEM) of zeolite Beta crystals also show that crystals grown in microgravity were free of line defects while terrestrial/controls had substantial defects.

  19. Charge-transfer state excitation as the main mechanism of the photodarkening process in ytterbium-doped aluminosilicate fibres

    SciTech Connect

    Bobkov, K K; Rybaltovsky, A A; Vel'miskin, V V; Likhachev, M E; Bubnov, M M; Dianov, E M; Umnikov, A A; Gur'yanov, A N; Vechkanov, N N; Shestakova, I A

    2014-12-31

    We have studied photodarkening in ytterbium-doped fibre preforms with an aluminosilicate glass core. Analysis of their absorption and luminescence spectra indicates the formation of stable Yb{sup 2+} ions in the glass network under IR laser pumping at a wavelength ? = 915 nm and under UV irradiation with an excimer laser (? = 193 nm). We have performed comparative studies of the luminescence spectra of the preforms and crystals under excitation at a wavelength of 193 nm. The mechanism behind the formation of Yb{sup 2+} ions and aluminium – oxygen hole centres (Al-OHCs), common to ytterbium-doped YAG crystals and aluminosilicate glass, has been identified: photoinduced Yb{sup 3+} charge-transfer state excitation. (optical fibres)

  20. The evolution of strength and crystalline phases for alkali-activated ground blast furnace slag and fly ash-based geopolymers

    SciTech Connect

    Oh, Jae Eun; Monteiro, Paulo J.M.; Jun, Ssang Sun; Choi, Sejin; Clark, Simon M.

    2010-02-15

    The increase in strength and evolution of crystalline phases in inorganic polymer cement, made by the alkali activation of slag, Class C and Class F fly ashes, was followed using compressive strength test and synchrotron X-ray diffraction. In order to increase the crystallinity of the product the reactions were carried out at 80 deg. C. We found that hydrotalcite formed in both the alkali-activated slag cements and the fly ash-based geopolymers. Hydroxycancrinite, one member of the ABC-6 family of zeolites, was found only in the fly ash geopolymers. Assuming that the predominantly amorphous geopolymer formed under ambient conditions relates to the crystalline phases found when the mixture is cured at high temperature, we propose that the structure of this zeolitic precursor formed in Na-based high alkaline environment can be regarded as a disordered form of the basic building unit of the ABC-6 group of zeolites which includes poly-types such as hydroxycancrinite, hydroxysodalite and chabazite-Na.

  1. Zeolite crystal growth in space - What has been learned

    NASA Technical Reports Server (NTRS)

    Sacco, A., Jr.; Thompson, R. W.; Dixon, A. G.

    1993-01-01

    Three zeolite crystal growth experiments developed at WPI have been performed in space in last twelve months. One experiment, GAS-1, illustrated that to grow large, crystallographically uniform crystals in space, the precursor solutions should be mixed in microgravity. Another experiment evaluated the optimum mixing protocol for solutions that chemically interact ('gel') on contact. These results were utilized in setting the protocol for mixing nineteen zeolite solutions that were then processed and yielded zeolites A, X and mordenite. All solutions in which the nucleation event was influenced produced larger, more 'uniform' crystals than did identical solutions processed on earth.

  2. Method of preparing sodalite from chloride salt occluded zeolite

    DOEpatents

    Lewis, Michele A. (Naperville, IL); Pereira, Candido (Lisle, IL)

    1997-01-01

    A method for immobilizing waste chloride salts containing radionuclides and hazardous nuclear material for permanent disposal starting with a substantially dry zeolite and sufficient glass to form leach resistant sodalite with occluded radionuclides and hazardous nuclear material. The zeolite and glass are heated to a temperature up to about 1000.degree. K. to convert the zeolite to sodalite and thereafter maintained at a pressure and temperature sufficient to form a sodalite product near theoretical density. Pressure is used on the formed sodalite to produce the required density.

  3. Method of preparing sodalite from chloride salt occluded zeolite

    DOEpatents

    Lewis, M.A.; Pereira, C.

    1997-03-18

    A method is described for immobilizing waste chloride salts containing radionuclides and hazardous nuclear material for permanent disposal starting with a substantially dry zeolite and sufficient glass to form leach resistant sodalite with occluded radionuclides and hazardous nuclear material. The zeolite and glass are heated to a temperature up to about 1000 K to convert the zeolite to sodalite and thereafter maintained at a pressure and temperature sufficient to form a sodalite product near theoretical density. Pressure is used on the formed sodalite to produce the required density.

  4. Method of preparing sodalite from chloride salt occluded zeolite A

    SciTech Connect

    Lewis, M.A.; Pereira, C.

    1995-12-31

    A method is described for immobilizing waste chloride salts containing radionuclides and hazardous nuclear material for permanent disposal starting with a substantially dry zeolite and sufficient glass to form leach resistance sodalite with occluded radionuclides and hazardous nuclear material. The zeolite and glass are heated to a temperature up to about 1,000 K to convert the zeolite to sodalite and thereafter maintained at a pressure and temperature sufficient to form a sodalite product near theoretical density. Pressure is used on the formed sodalite to produce the required density.

  5. The selective adsorption of tellurium in the aluminosilicate regions of AFI- and MOR-type microporous crystals.

    PubMed

    Kodaira, Tetsuya; Ikeda, Takuji

    2014-10-01

    Attempts have been made to load tellurium (Te) atoms into the one-dimensional nano-channels of microporous crystals of aluminophosphate AlPO4-5 and of aluminosilicate mordenites of the Na(+) form (Na-MOR) and the H(+)-form (H-MOR) at 673 K. The density of the atoms adsorbed was in the sequence 0 ? AlPO4-5 ? H-MOR < Na-MOR. AlPO4-5 provides a shallow potential of periodical charge fluctuation for Te atoms, from the alternate ordering of Al and P atoms through O atoms. Mordenite offers a sufficiently strong potential for Te adsorption, but the magnitude varies with the type of cation. Dipoles between framework AlO2(-) anion sites and their Na(+) counter-ions in Na-MOR provide a stronger potential than the Brønsted acid points in H-MOR. The adsorption of Te atoms in the silico-aluminophosphate SAPO-5 was between that of AlPO4-5 and H-MOR, leading us to suspect that Te atoms are selectively adsorbed in the aluminosilicate regions accompanying the Brønsted acid points distributed in the major aluminophosphate network. The aluminosilicate regions in SAPO-5 are below 500 nm in size and are distributed throughout a single crystal. PMID:25117797

  6. Quantitatively Probing the Al Distribution in Zeolites

    SciTech Connect

    Vjunov, Aleksei; Fulton, John L.; Huthwelker, Thomas; Pin, Sonia; Mei, Donghai; Schenter, Gregory K.; Govind, Niranjan; Camaioni, Donald M.; Hu, Jian Z.; Lercher, Johannes A.

    2014-06-11

    The degree of substitution of Si4+ by Al3+ in the oxygen-terminated tetrahedra (Al T-sites) of zeolites determines the concentration of ion-exchange and Brønsted acid sites. As the location of the tetrahedra and the associated subtle variations in bond angles influence the acid strength, quantitative information about Al T-sites in the framework is critical to rationalize catalytic properties and to design new catalysts. A quantitative analysis is reported that uses a combination of extended X-ray absorption fine structure (EXAFS) analysis and 27Al MAS NMR spectroscopy supported by DFT-based molecular dynamics simulations. To discriminate individual Al atoms, sets of ab initio EXAFS spectra for various T-sites are generated from DFT-based molecular dynamics simulations allowing quantitative treatment of the EXAFS single- and multiple-photoelectron scattering processes out to 3-4 atom shells surrounding the Al absorption center. It is observed that identical zeolite types show dramatically different Al-distributions. A preference of Al for T-sites that are part of one or more 4-member rings in the framework over those T-sites that are part of only 5- and 6-member rings in the HBEA150 sample has been determined from a combination of these methods. This work was supported by the U. S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences.

  7. Topological Crystalline Insulators

    NASA Astrophysics Data System (ADS)

    Hsieh, Timothy

    2015-03-01

    Topological crystalline insulators (TCI) are new phases of matter in which nontrivial band topology and crystal symmetry unite to protect metallic states on the boundary. Remarkably, TCIs have been predicted and observed in the conveniently simple rocksalt SnTe class of IV-VI semiconductors. Despite the simple crystal structure, the interplay between topology and crystal symmetry in these materials have led to a rich variety of new phenomena, including the coexistence of massless and massive Dirac fermions arising from ferroelectric distortion and strain-induced flat band superconductivity. These new physical mechanisms are not only of intrinsic interest but may also find application in new transistor devices. After discussing the topological nature and potential uses of IV-VI family TCIs, I will present recent predictions of TCIs in several anti-perovskite materials. The origin of TCI in this new class of materials is strikingly different and involves the band inversion of two J = 3/2 quartets of Dirac fermions, which together form a ``Dirac octet.'' As interactions play a significant role in many anti-perovskites, this prediction serves as first step toward realizing TCIs in strongly correlated systems. This work is supported by NSF Graduate Research Fellowship No. 0645960 and DOE Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award DE-SC0010526.

  8. Aluminosilicate melts and glasses at 1 to 3 GPa: temperature and pressure effects on recovered structural and density changes

    NASA Astrophysics Data System (ADS)

    Bista, S.; Stebbins, J. F.; Hankins, B.; Sisson, T. W.

    2013-12-01

    The effects of pressure on aluminosilicate melt and glass structure have been studied by both in-situ methods and by quenching and recovering glasses from high pressure and temperature. Significant increases in the coordination number of Al are now well known from the pressure range of 6-10 GPa. New results show that even at shallower mantle pressures of 1-3 GPa, typical aluminosilicate melts have significant concentrations of aluminum cations with coordination numbers greater than 4, with up to 10's of percents of AlO5 and AlO6. Here, we compare the densities and Al coordinations of glass samples recovered from piston-cylinder experiments carried out at 1 to 3 GPa and different temperatures. Samples of two different compositions (Ca3Al2Si6O18 and Na2Si3O7 with 0.5% Al2O3) were compressed and held at temperatures ranging from near to their ambient glass transitions (Tg) up to temperatures above the liquidus. Our 2 GPa sodium aluminosilicate and calcium aluminosilicate glasses quenched from near to Tg show about 5 and 6 percent recovered densification, respectively. In both compositions, samples that were quenched from above the melting point showed substantially lower recovered density and lower Al coordination number compared to the samples that were held near to Tg. For example, sodium aluminosilicate glass quenched from 510°C (near to Tg) had 70% more AlO5 than samples from 1200°C. Based on the measurement of actual cooling rates, fictive temperature differences for the glasses from these two extreme temperatures are not large enough to account for this apparent loss in density and Al-coordination during quench. The most likely cause for these differences is therefore probably the pressure drop during cooling from temperatures above liquidus, as the pressure medium does not respond quickly enough to the thermal contraction of the liquid and furnace parts to remain isobaric. Results from previous high T and P quenching studies thus give only minimum estimates of pressure effects on melt structure. Samples were made in a piston-cylinder apparatus in 5mm platinum capsules, with 1 inch diameter calcium fluorite assemblies and graphite heaters. Structure was examined by Al-27 and Na-23 MAS NMR at 14.4 and 18.8 Tesla fields, and glass densities determined by high-precision sink-float methods.

  9. Investigation of Zeolite Nucleation and Growth Using NMR Spectroscopy 

    E-print Network

    Rivas Cardona, Alejandra

    2012-02-14

    Zeolite nucleation and growth is a complex problem that has been widely investigated but still not completely understood. However, a full understanding of this process is required in order to develop predictive models for ...

  10. Oxidation of bioethanol using zeolite-encapsulated gold nanoparticles.

    PubMed

    Mielby, Jerrik; Abildstrøm, Jacob Oskar; Wang, Feng; Kasama, Takeshi; Weidenthaler, Claudia; Kegnaes, Søren

    2014-11-10

    With the ongoing developments in biomass conversion, the oxidation of bioethanol to acetaldehyde may become a favorable and green alternative to the preparation from ethylene. Here, a simple and effective method to encapsulate gold nanoparticles in zeolite silicalite-1 is reported and their high activity and selectivity for the catalytic gas-phase oxidation of ethanol are demonstrated. The zeolites are modified by a recrystallization process, which creates intraparticle voids and mesopores that facilitate the formation of small and disperse nanoparticles upon simple impregnation. The individual zeolite crystals comprise a broad range of mesopores and contain up to several hundred gold nanoparticles with a diameter of 2-3?nm that are distributed inside the zeolites rather than on the outer surface. The encapsulated nanoparticles have good stability and result in 50?% conversion of ethanol with 98?% selectivity toward acetaldehyde at 200?°C, which (under the given reaction conditions) corresponds to 606?mol?acetaldehyde/mol?Au?hour(-1) . PMID:25196739

  11. 12. INTERIOR OF BUILDING 2, ORIGINAL ZEOLITE PLANT, AT WEYMOUTH ...

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

    12. INTERIOR OF BUILDING 2, ORIGINAL ZEOLITE PLANT, AT WEYMOUTH LOOKING WEST TO FOUNTAIN. STAIRWAY RUNS DOWN TO FILTRATION BAYS. - F. E. Weymouth Filtration Plant, 700 North Moreno Avenue, La Verne, Los Angeles County, CA

  12. Iba of Zeolites Exchanged with Lithium for Co2 Retention

    NASA Astrophysics Data System (ADS)

    Andrade, E.; Alfaro, S.; Valenzuela, M. A.; Solis, C.; Zaval, E. P.; Rocha, M. F.; Cruz, J.; Pfeiffer, H.; Bosch, P.; Contreras, C.; Baptiste, J.

    2009-03-01

    A great concern on the global climatic change, partially due to industry CO2 expelled to the atmosphere, has motivated the search of new materials able to retain this gas. Clays, perovskites, zeolites and membranes have been utilized to trap the CO2. Zeolites are widely used as molecular sieves in different industrial processes related to gas purification or gas separation. Synthetic zeolites exchanged with lithium were prepared as potential material for CO2 retention. A NRA method using the 7Li (p,?)4He was performed in order to measure the the Li contents. With SEM-EDS the atomic concentrations of elements as C, Na, Si, Al, K, Ca, Fe, etc. were determined. Zeolites were also characterized by XRD.

  13. Synthesis and characterization of zeolite-type materials: Germanates and zirconogermanates

    NASA Astrophysics Data System (ADS)

    Smith, Rebeca

    The great importance that zeolites have in the industry accounting for 40 billion US dollars a year to the petroleum cracking industry alone has attracted the interest of synthesizing and developing new crystalline microstructures. This work presents the unique structural properties of germanates, zeolite-type materials, by first reviewing five unique structure building units (SBUs) that include: 4=1 units, D4R units and large clusters with 7-, 9-, and 10-germanium atoms. Then, the work of the syntheses and characterization of different germanate structures is presented. The synthesis and characterization of four zirconogermanates constructed from the same cluster consisting of five tetrahedral germanium atoms and one zirconium atom in octahedral coordination is presented. The structures were prepared using different amines as structure directing agents (SDA); ASU-23 (using 1,4-bis(3-aminopropyl) consists of one layered structure, ASU-24 (using hexamethylenediamine) is a pillared layered structure with exceptionally low framework density (FD=8.48 metal atoms per nanometer cubed), ASU-25 and ASU-26 (using 1,3-diaminopropane and ethylenediamine respectively) have 3-dimensional (3D) frameworks. The layer germanate (ASU-22) is built from 7-germanium clusters. X-ray structural analysis [P6(3)cm, a =28.794(2), c=20.603(4), V=14793(3) (unit cell parameters are in angstroms, volume in angstroms cubed)] revealed that the framework exhibits the kagome (kgm) topology. The extensive series of syntheses demonstrated the key role played by HF in the condensation of the 7-germanium clusters (these clusters have not been synthesized without HF). The zirconogermanate, ASU-17, in the 1,4-diaminobutane-HF system, was synthesized as crystalline powder and identified in the cubic crystals system with space group Ia-3d and unit cell parameter a =51.3 (angstroms) and corresponds to the SU-M structure reported by a group in Sweden. Exploratory work leading to the discovery this 3D cubic framework built from 10-germanium clusters showing pore size reaching the mesoporous range is presented. The synthesis and characterization of ASU-21, a crystalline germanate displaying large rigid cylinders, was also synthesized in the presence of hexamethylenediamine. The single crystal X-ray analysis [Ibam, a=49.257(10), b=28.439(6), c=14.866(3), V=20825(7) (unit cell parameters in angstroms and volume in angtrom cubed)] revealed the novel open-framework built form the same 10-germanium clusters found in ASU-17.

  14. Fabrication of large diameter alumino-silicate K{sup +} sources

    SciTech Connect

    Baca, D.; Chacon-Golcher, E.; Kwan, J.W.; Wu, J.K.

    2003-02-20

    Alumino-silicate K{sup +} sources have been used in HIF experiments for many years. For example the Neutralized Transport Expt. (NTX) and the High Current Transport Expt. (HCX) are now using this type of ion source with diameters of 2.54 cm and 10 cm respectively. These sources have demonstrated ion currents of 80 mA and 700 mA, for typical HIF pulse lengths of 5-10 {micro}s. The corresponding current density is {approx} 10-15 mA/cm{sup 2}, but much higher current density has been observed using smaller size sources. Recently we have improved our fabrication techniques and, therefore, are able to reliably produce large diameter ion sources with high quality emitter surface without defects. This note provides a detailed description of the procedures employed in the fabrication process. The variables in the processing steps affecting surface quality, such as substrate porosity, powder size distribution, coating technique on large area concave surfaces, drying, and heat firing temperature have been investigated.

  15. Relationships among the structural topology, bond strength, and mechanical properties of single-walled aluminosilicate nanotubes.

    PubMed

    Liou, Kai-Hsin; Tsou, Nien-Ti; Kang, Dun-Yen

    2015-10-21

    Carbon nanotubes (CNTs) are regarded as small but strong due to their nanoscale microstructure and high mechanical strength (Young's modulus exceeds 1000 GPa). A longstanding question has been whether there exist other nanotube materials with mechanical properties as good as those of CNTs. In this study, we investigated the mechanical properties of single-walled aluminosilicate nanotubes (AlSiNTs) using a multiscale computational method and then conducted a comparison with single-walled carbon nanotubes (SWCNTs). By comparing the potential energy estimated from molecular and macroscopic material mechanics, we were able to model the chemical bonds as beam elements for the nanoscale continuum modeling. This method allowed for simulated mechanical tests (tensile, bending, and torsion) with minimum computational resources for deducing their Young's modulus and shear modulus. The proposed approach also enabled the creation of hypothetical nanotubes to elucidate the relative contributions of bond strength and nanotube structural topology to overall nanotube mechanical strength. Our results indicated that it is the structural topology rather than bond strength that dominates the mechanical properties of the nanotubes. Finally, we investigated the relationship between the structural topology and the mechanical properties by analyzing the von Mises stress distribution in the nanotubes. The proposed methodology proved effective in rationalizing differences in the mechanical properties of AlSiNTs and SWCNTs. Furthermore, this approach could be applied to the exploration of new high-strength nanotube materials. PMID:26204559

  16. Molecular Dynamics Simulations of Uranyl and Uranyl Carbonate Adsorption at Alumino-silicate Surfaces

    SciTech Connect

    Kerisit, Sebastien N.; Liu, Chongxuan

    2014-03-03

    Adsorption at mineral surfaces is a critical factor controlling the mobility of uranium(VI) in aqueous environments. Therefore, molecular dynamics (MD) simulations were performed to investigate uranyl(VI) adsorption onto two neutral alumino-silicate surfaces, namely the orthoclase (001) surface and the octahedral aluminum sheet of the kaolinite (001) surface. Although uranyl preferentially adsorbed as a bi-dentate innersphere complex on both surfaces, the free energy of adsorption at the orthoclase surface (-15 kcal mol-1) was significantly more favorable than that at the kaolinite surface (-3 kcal mol-1), which was attributed to differences in surface functional groups and to the ability of the orthoclase surface to dissolve a surface potassium ion upon uranyl adsorption. The structures of the adsorbed complexes compared favorably with X-ray absorption spectroscopy results. Simulations of the adsorption of uranyl complexes with up to three carbonate ligands revealed that uranyl complexes coordinated to up to 2 carbonate ions are stable on the orthoclase surface whereas uranyl carbonate surface complexes are unfavored at the kaolinite surface. Combining the MD-derived equilibrium adsorption constants for orthoclase with aqueous equilibrium constants for uranyl carbonate species indicates the presence of adsorbed uranium complexes with one or two carbonates in alkaline conditions, in support of current uranium(VI) surface complexation models.

  17. Alkaline solution/binder ratio as a determining factor in the alkaline activation of aluminosilicates

    SciTech Connect

    Ruiz-Santaquiteria, C.; Fernandez-Jimenez, A.; Palomo, A.

    2012-09-15

    This study investigates the effect of the alkaline solution/binder (S/B) ratio on the composition and nanostructure of the reaction products generated in the alkaline activation of aluminosilicates. The experiments used two mixtures of fly ash and dehydroxylated white clay and for each of these, varying proportions of the solution components. The alkali activator was an 8 M NaOH solution (with and without sodium silicate) used at three S/B ratios: 0.50, 0.75 and 1.25. The {sup 29}Si, {sup 27}Al MAS NMR and XRD characterisation of the reaction products reveal that for ratios nearest the value delivering suitable paste workability, the reaction-product composition and structure depend primarily on the nature and composition of the starting materials and the alkaline activator used. However, when an excess alkaline activator is present in the system, the reaction products tend to exhibit SiO{sub 2}/Al{sub 2}O{sub 3} ratios of approximately 1, irrespective of the composition of the starting binder or the alkaline activator.

  18. Structure and mechanical properties of aluminosilicate geopolymer composites with Portland cement and its constituent minerals

    SciTech Connect

    Tailby, Jonathan; MacKenzie, Kenneth J.D.

    2010-05-15

    The compressive strengths and structures of composites of aluminosilicate geopolymer with the synthetic cement minerals C{sub 3}S, beta-C{sub 2}S, C{sub 3}A and commercial OPC were investigated. All the composites showed lower strengths than the geopolymer and OPC paste alone. X-ray diffraction, {sup 29}Si and {sup 27}Al MAS NMR and SEM/EDS observations indicate that hydration of the cement minerals and OPC is hindered in the presence of geopolymer, even though sufficient water was present in the mix for hydration to occur. In the absence of SEM evidence for the formation of an impervious layer around the cement mineral grains, the poor strength development is suggested to be due to the retarded development of C-S-H because of the preferential removal from the system of available Si because geopolymer formation is more rapid than the hydration of the cement minerals. This possibility is supported by experiments in which the rate of geopolymer formation is retarded by the substitution of potassium for sodium, by the reduction of the alkali content of the geopolymer paste or by the addition of borate. In all these cases the strength of the OPC-geopolymer composite was increased, particularly by the combination of the borate additive with the potassium geopolymer, producing an OPC-geopolymer composite stronger than hydrated OPC paste alone.

  19. Chemical and mechanical consequences of environmental barrier coating exposure to calcium-magnesium-aluminosilicate.

    SciTech Connect

    Harder, B.; Ramirez-Rico, J.; Almer, J. D.; Kang, L.; Faber, K.

    2011-06-01

    The success of Si-based ceramics as high-temperature structural materials for gas turbine applications relies on the use of environmental barrier coatings (EBCs) with low silica activity, such as Ba{sub 1-x}Sr{sub x}Al{sub 2}Si{sub 2}O{sub 8} (BSAS), which protect the underlying components from oxidation and corrosion in combustion environments containing water vapor. One of the current challenges concerning EBC lifetime is the effect of sandy deposits of calcium-magnesium-aluminosilicate (CMAS) glass that melt during engine operation and react with the EBC, changing both its composition and stress state. In this work, we study the effect of CMAS exposure at 1300 C on the residual stress state and composition in BSAS-mullite-Si-SiC multilayers. Residual stresses were measured in BSAS multilayers exposed to CMAS for different times using high-energy X-ray diffraction. Their microstructure was studied using a combination of scanning electron microscopy and transmission electron microscopy techniques. Our results show that CMAS dissolves the BSAS topcoat preferentially through the grain boundaries, dislodging the grains and changing the residual stress state in the topcoat to a nonuniform and increasingly compressive stress state with increasing exposure time. The presence of CMAS accelerates the hexacelsian-to-celsian phase transformation kinetics in BSAS, which reacts with the glass by a solution-reprecipitation mechanism. Precipitates have crystallographic structures consistent with Ca-doped celsian and Ba-doped anorthite.

  20. Chemical Compatibility of Barium-Calcium-Aluminosilicate Based Sealing Glasses with Heat Resistant Alloys

    SciTech Connect

    Yang, Z Gary; Weil, K. Scott; Meinhardt, Kerry D.; Stevenson, Jeffry W.; Paxton, Dean M.; Xia, Gordon; Kim, Dong-Sang

    2003-09-15

    Over the past several years, advances in the design and fabrication of planar SOFCs have led to a steady reduction in the temperatures necessary for their operation. Consequently, it appears more realistic now to use low cost heat resistant alloys for interconnect sub-components in the SOFC stack. Considering these materials requirements, heat resistant alloys, which overall demonstrate oxidation resistance at elevated temperatures, could be potential candidates. Overall, the heat resistant alloys of interest may include superalloys and the stainless steels. Depending whether a chromia or alumina scale forms on the alloy surface for protection, these heat resistant alloys can be also classified into chromia or alumina formers, repetitively. To help screening alloys and understanding the interface of sealing glass, a couple of alloy compositions have been carefully chosen as a reprehensive of different groups of alloys for the study on their chemical compatibility with a barium-aluminosilicate base glass. These alloys selected are AL 29-4, Nicrofer 6025, and Fecralloy, representing chromia forming stainless steels, superalloys and alumina formers, respectively. Results of chemical and microstructural analyses on sealing glass interfaces with different alloys will be presented, and accordingly, the applicability of alloys in terms of sealing glass chemical compatibility will be discussed. Possible means of modification on alloys for an improved applicability will be elaborated as well.

  1. Synthesis of hydrothermally stable, hierarchically mesoporous aluminosilicate Al-SBA-1 and their catalytic properties

    NASA Astrophysics Data System (ADS)

    Li, Na; Wang, Jin-Gui; Xu, Jian-Xiong; Liu, Jin-Yu; Zhou, Hui-Jing; Sun, Ping-Chuan; Chen, Tie-Hong

    2012-03-01

    Hydrothermally stable mesoporous aluminosilicates Al-SBA-1 with hierarchical pore structure have been successfully synthesized under alkaline condition at 120 °C by employing organic mesomorphous complexes of polyelectrolyte (poly(acrylic acid) (PAA)) and cationic surfactant (hexadecyl pyridinium chloride (CPC)) as template. The Si/Al ratio could be as high as 5 and the incorporation of Al into the silica framework did not disturb the well-ordered cubic Pm3&cmb.macr;n mesostructure. Meanwhile, the incorporation of Al could greatly increase the specific surface area and pore volume of the samples. The Al-SBA-1 materials exhibited a high hydrothermal stability and remained stable even after being treated in boiling water for 10 days. The catalytic activity of the Al-SBA-1 materials was investigated by employing the Friedel-Crafts alkylation of toluene with benzyl alcohol as a model reaction and they exhibited excellent catalytic property due to the incorporated acid sites and the hierarchically mesoporous structure.

  2. Monodisperse Aluminosilicate Spheres with Tunable Al/Si Ratio and Hierarchical Macro-Meso-Microporous Structure.

    PubMed

    Sheng, Yuan; Zeng, Hua Chun

    2015-06-24

    While tremendous success has been seen in the development of ordered mesoporous silica by soft-templated methods, synthesis of hierarchical structures with controllable multiscale pore networks has remained a challenging topic. On the other hand, introduction of heteroatoms as an effective method of chemically functionalizing silica leads to difficulties in morphological control of the product, and multistep synthesis has been necessary for functionalized silica particles with hierarchical pore structure and uniform size. The present work demonstrates that the conflict between morphological control and heteroatom incorporation can be resolved in a CTAB-stabilized toluene-water-ethanol microemulsion system. For the first time, monodisperse macro-meso-microporous aluminosilicate spheres (MASS) are synthesized in one step at room temperature. Simultaneous tuning of Al/Si ratio (0-0.35) and the hierarchical pore structure is realized by Hofmeister anion effects of the Al source itself, [Al(OH)4](-), which change the geometry of CTAB micelles and giant vesicles. The Al is incorporated purely in a tetrahedrally coordinated status, and preliminary results from catalytic experiments show improved acidity of MASS as a catalyst support. PMID:26035078

  3. Single-molecule studies of acidity distributions in mesoporous aluminosilicate thin films.

    PubMed

    Sun, Xiaojiao; Xie, Jingyi; Xu, Jiayi; Higgins, Daniel A; Hohn, Keith L

    2015-05-26

    Solid acid catalysts are important for many petrochemical processes. The ensemble methods most often employed to characterize acid site properties in catalyst materials provide limited insights into their heterogeneity. Single-molecule (SM) fluorescence spectroscopic methods provide a valuable route to probing the properties of individual microenvironments. In this work, dual-color SM methods are adopted to study acidity distributions in mesoporous aluminosilicate (Al-Si) films prepared by the sol-gel method. The highly fluorescent pH-sensitive dye C-SNARF-1 was employed as a probe. The ratio of C-SNARF-1 emission in two bands centered at 580 and 640 nm provides an effective means to sense the pH of bulk solutions. In mesoporous thin films, SM emission data provide a measure of the effective pH of the microenvironment in which each molecule resides. SM emission data were obtained from mesoporous Al-Si films as a function of Al2O3 content for films ranging from 0% to 30% alumina. Histograms of the emission ratio reveal a broad distribution of acidity properties, with the film microenvironments becoming more acidic, on average, as the alumina content of the films increases. This work provides new insights into the distribution of Brønsted acidity in solid acids that cannot be obtained by conventional means. PMID:25941900

  4. Preparation of bioinorganic fertilizing media by adsorption of humates on glassy aluminosilicates.

    PubMed

    Chassapis, Konstantinos; Roulia, Maria; Vrettou, Evangelia; Parassiris, Anastassios

    2010-11-01

    Surface-modified expanded perlite was synthesized using humic substances from the Megalopolis peaty lignite. Adsorption is efficient and increases at higher temperatures and lower pHs. The preparation can be carried out under mild conditions leading to an eco-friendly, bioinorganic material useful as soil conditioner and biofertilizer. Six adsorption models were applied; the Klotz, Freundlich and Redlich-Peterson isotherms fit more successfully to the experimental data. The obeying of the theoretical models was correlated with the heterogeneity and non-uniform distribution of the adsorption sites, host-guest attraction forces as well as the formation of self-assembled aggregates and self-organized multilayers of humic substances onto the aluminosilicate adsorbent, consistent with changes in micromorphology. Thermodynamic quantities revealing distinct physicochemical characteristics of the adsorption phenomena, i.e., enthalpy, entropy and free energy change, were calculated. Desorption experiments and cultivation of microorganisms demonstrated that perlite may act successfully as host material for microbial populations upgrading the humic-loaded perlite for soil applications. PMID:20692818

  5. Synthesis and Properties of a Barium Aluminosilicate Solid Oxide Fuel Cell Glass-Ceramic Sealant

    SciTech Connect

    Meinhardt, Kerry D.; Kim, Dong-Sang; Chou, Y. S.; Weil, K. Scott

    2008-07-15

    A series of barium aluminosilicate glasses modified with CaO and B2O3, were prepared and evaluated with respect to their suitability in sealing planar solid oxide fuel cells (SOFCs). At a target operating temperature of 750ºC, the long-term CTE of one particular composition (35 mol% BaO, 15 mol% CaO, 10 mol% B2O3, 5 mol% Al2O3, bal. SiO2) was found to be particularly stable, due to devitrification to a mixture of glass and ceramic phases. This sealant composition exhibits minimal chemical interaction with the yttria-stabilized zirconia electrolyte, yet forms a strong bond with this material. Interactions with metal components were found to be more extensive and depended on the composition of the metal oxide scale that formed during sealing. Generally alumina-scale formers exhibited a more compact reaction zone with the glass than chromia-scale forming alloys. Mechanical measurements conducted on the bulk glass-ceramic and on seals formed using these materials indicate that the sealant is anticipated to display adequate long-term strength for most conventional stationary SOFC applications.

  6. Commander Bowersox Tends to Zeolite Crystal Samples Aboard Space Station

    NASA Technical Reports Server (NTRS)

    2003-01-01

    Expedition Six Commander Ken Bowersox spins Zeolite Crystal Growth sample tubes to eliminate bubbles that could affect crystal formation in preparation of a 15 day experiment aboard the International Space Station (ISS). Zeolites are hard as rock, yet are able to absorb liquids and gases like a sponge. By using the ISS microgravity environment to grow better, larger crystals, NASA and its commercial partners hope to improve petroleum manufacturing and other processes.

  7. Metal Oxide/Zeolite Combination Absorbs H2S

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E.; Sharma, Pramod K.

    1989-01-01

    Mixed copper and molybdenum oxides supported in pores of zeolite found to remove H2S from mixture of gases rich in hydrogen and steam, at temperatures from 256 to 538 degree C. Absorber of H2S needed to clean up gas streams from fuel processors that incorporate high-temperature steam reformers or hydrodesulfurizing units. Zeolites chosen as supporting materials because of their high porosity, rigidity, alumina content, and variety of both composition and form.

  8. Achievement of Bulky Homochirality in Zeolitic Imidazolate-Related Frameworks.

    PubMed

    Wang, Fei; Tang, Yu-Huan; Zhang, Jian

    2015-12-01

    Before this work, adding chiral C centers into zeolitic imidazolate frameworks (ZIFs) has never been realized. Presented here are the first examples on achieving bulky homochirality in ZIF systems, and three homochiral zeolitic imidazolate-related frameworks with sodalite and dia topologies are successfully synthesized by employing enantiopure imidazolate derivatives. The results open a new blueprint on the synthetic design of homochiral ZIFs for future applications. PMID:26558292

  9. Characterization of Chemical Properties, Unit Cell Parameters and Particle Size Distribution of Three Zeolite Reference Materials: RM 8850 - Zeolite Y, RM 8851 - Zeolite A and RM 8852 - Ammonium ZSM-5 Zeolite

    SciTech Connect

    Turner,S.; Sieber, J.; Vetter, T.; Zeisler, R.; Marlow, A.; Moreno-Ramirez, M.; Davis, M.; Kennedy, G.; Borghard, W.; et al

    2008-01-01

    Zeolites have important industrial applications including use as catalysts, molecular sieves and ion exchange materials. In this study, three zeolite materials have been characterized by the National Institute of Standards and Technology (NIST) as reference materials (RMs): zeolite Y (RM 8850), zeolite A (RM 8851) and ZSM-5 zeolite (RM 8852). They have been characterized by a variety of chemical and physical measurement methods: X-ray fluorescence (XRF), gravimetry, instrumental neutron activation analysis (INAA), nuclear magnetic resonance (NMR), calorimetry, synchrotron X-ray diffraction, neutron diffraction, laser light extinction, laser light scattering, electric sensing zone, X-ray sedimentation, scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM) and optical microscopy. The chemical homogeneity of the materials has been characterized. Reference values are given for the major components (major elements, loss on ignition [LOI] and loss on fusion [LOF]), trace elements and Si/Al and Na/Al ratios. Information values are given for enthalpies of formation, unit cell parameters, particle size distributions, refractive indices and variation of mass with variation in relative humidity (RH). Comparisons are made to literature unit cell parameters. The RMs are expected to provide a basis for intercomparison studies of these zeolite materials.

  10. Nanocellulose-Zeolite Composite Films for Odor Elimination.

    PubMed

    Keshavarzi, Neda; Mashayekhy Rad, Farshid; Mace, Amber; Ansari, Farhan; Akhtar, Farid; Nilsson, Ulrika; Berglund, Lars; Bergström, Lennart

    2015-07-01

    Free standing and strong odor-removing composite films of cellulose nanofibrils (CNF) with a high content of nanoporous zeolite adsorbents have been colloidally processed. Thermogravimetric desorption analysis (TGA) and infrared spectroscopy combined with computational simulations showed that commercially available silicalite-1 and ZSM-5 have a high affinity and uptake of volatile odors like ethanethiol and propanethiol, also in the presence of water. The simulations showed that propanethiol has a higher affinity, up to 16%, to the two zeolites compared with ethanethiol. Highly flexible and strong free-standing zeolite-CNF films with an adsorbent loading of 89 w/w% have been produced by Ca-induced gelation and vacuum filtration. The CNF-network controls the strength of the composite films and 100 ?m thick zeolite-CNF films with a CNF content of less than 10 vol % displayed a tensile strength approaching 10 MPa. Headspace solid phase microextraction (SPME) coupled to gas chromatography-mass spectroscopy (GC/MS) analysis showed that the CNF-zeolite films can eliminate the volatile thiol-based odors to concentrations below the detection ability of the human olfactory system. Odor removing zeolite-cellulose nanofibril films could enable improved transport and storage of fruits and vegetables rich in odors, for example, onion and the tasty but foul-smelling South-East Asian Durian fruit. PMID:26061093

  11. An analysis of commerical zeolite catalysts by multinuclear NMR

    SciTech Connect

    Flanagan, L.

    1990-09-21

    This work involves studying two commercial hydrocracking catalysts by solid state multinuclear NMR silicon 29 and aluminum 27 with the goal of developing a method of determining the fraction zeolite in the catalysts. The zeolite fraction is known to be one of the faujasite zeolites type X or Y. The clay matrix of the catalyst is assumed to be kaolinite. Fresh, air-exposed commercial hydrocracking catalysts were provided by Phillips Petroleum. Sample 33351-86 was known to be a physical mixture of a Y zeolite and a clay matrix. The other catalyst, 33351-20, was composed of a faujasite zeolite grown within a clay matrix. Both were suspected of being about 20 wt % zeolite. Nothing is known about the state of pretreatment or cation exchange. A portion of each catalyst was calcined in a porcelain crucible in air at 500{degree}C for two hours with a hour heating ramp preceding and a two hour cooling ramp following calcination. 64 refs., 21 figs., 8 tabs.

  12. Inhibition of palm oil oxidation by zeolite nanocrystals.

    PubMed

    Tan, Kok-Hou; Awala, Hussein; Mukti, Rino R; Wong, Ka-Lun; Rigaud, Baptiste; Ling, Tau Chuan; Aleksandrov, Hristiyan A; Koleva, Iskra Z; Vayssilov, Georgi N; Mintova, Svetlana; Ng, Eng-Poh

    2015-05-13

    The efficiency of zeolite X nanocrystals (FAU-type framework structure) containing different extra-framework cations (Li(+), Na(+), K(+), and Ca(2+)) in slowing the thermal oxidation of palm oil is reported. The oxidation study of palm oil is conducted in the presence of zeolite nanocrystals (0.5 wt %) at 150 °C. Several characterization techniques such as visual analysis, colorimetry, rheometry, total acid number (TAN), FT-IR spectroscopy, (1)H NMR spectroscopy, and Karl Fischer analyses are applied to follow the oxidative evolution of the oil. It was found that zeolite nanocrystals decelerate the oxidation of palm oil through stabilization of hydroperoxides, which are the primary oxidation product, and concurrently via adsorption of the secondary oxidation products (alcohols, aldehydes, ketones, carboxylic acids, and esters). In addition to the experimental results, periodic density functional theory (DFT) calculations are performed to elucidate further the oxidation process of the palm oil in the presence of zeolite nanocrystals. The DFT calculations show that the metal complexes formed with peroxides are more stable than the complexes with alkenes with the same ions. The peroxides captured in the zeolite X nanocrystals consequently decelerate further oxidation toward formation of acids. Unlike the monovalent alkali metal cations in the zeolite X nanocrystals (K(+), Na(+), and Li(+)), Ca(2+) reduced the acidity of the oil by neutralizing the acidic carboxylate compounds to COO(-)(Ca(2+))1/2 species. PMID:25897618

  13. Nanosized zeolites as a perspective material for conductometric biosensors creation

    NASA Astrophysics Data System (ADS)

    Kucherenko, Ivan; Soldatkin, Oleksandr; Kasap, Berna Ozansoy; Kirdeciler, Salih Kaan; Kurc, Burcu Akata; Jaffrezic-Renault, Nicole; Soldatkin, Alexei; Lagarde, Florence; Dzyadevych, Sergei

    2015-05-01

    In this work, the method of enzyme adsorption on different zeolites and mesoporous silica spheres (MSS) was investigated for the creation of conductometric biosensors. The conductometric transducers consisted of gold interdigitated electrodes were placed on the ceramic support. The transducers were modified with zeolites and MSS, and then the enzymes were adsorbed on the transducer surface. Different methods of zeolite attachment to the transducer surface were used; drop coating with heating to 200°C turned out to be the best one. Nanozeolites beta and L, zeolite L, MSS, and silicalite-1 (80 to 450 nm) were tested as the adsorbents for enzyme urease. The biosensors with all tested particles except zeolite L had good analytical characteristics. Silicalite-1 (450 nm) was also used for adsorption of glucose oxidase, acetylcholinesterase, and butyrylcholinesterase. The glucose and acetylcholine biosensors were successfully created, whereas butyrylcholinesterase was not adsorbed on silicalite-1. The enzyme adsorption on zeolites and MSS is simple, quick, well reproducible, does not require use of toxic compounds, and therefore can be recommended for the development of biosensors when these advantages are especially important.

  14. Tailoring and visualizing the pore architecture of hierarchical zeolites.

    PubMed

    Wei, Ying; Parmentier, Tanja E; de Jong, Krijn P; Ze?evi?, Jovana

    2015-10-21

    Recently the concept of hierarchical zeolites invoked more explicit attention to enhanced accessibility of zeolites. By realizing additional meso-/macroporosity with the intrinsic microporosity of zeolites, a hierarchical pore system arises which facilitates mass transport while maintaining the zeolite shape selectivity. A great number of synthesis strategies have been developed for tailoring the pore architecture of hierarchical zeolites. In this review, we give a general overview of different synthesis methods for introduction of additional porosity. Advantages and limitations of these different synthesis approaches are addressed. The assessment of pore structure is essential to build the link between the zeolite pore structure and its functionality. A variety of 2D and 3D microscopy techniques are crucial to visualize the hierarchical pore structure, providing unique and comprehensive information that, however, should be linked to the results of bulk characterization techniques as much as possible. The microscopy techniques are classified and discussed according to the different probes used, such as optical light, X-rays and electrons. Representative work is reviewed to elucidate the capability of each technique and their drawbacks. PMID:26007224

  15. Removal of ammonium from municipal landfill leachate using natural zeolites.

    PubMed

    Ye, Zhihong; Wang, Jiawen; Sun, Lingyu; Zhang, Daobin; Zhang, Hui

    2015-12-01

    Ammonium ion-exchange performance of the natural zeolite was investigated in both batch and column studies. The effects of zeolite dosage, contact time, stirring speed and pH on ammonium removal were investigated in batch experiments. The result showed that ammonium removal efficiency increased with an increase in zeolite dosage from 25 to 150 g/L, and an increase in stirring speed from 200 to 250 r/min. But further increase in zeolite dosage and stirring speed would result in an unpronounced increase of ammonium removal. The optimal pH for the removal of ammonium was found as 7.1. In the column studies, the effect of flow rate was investigated, and the total ammonium removal percentage during 180 min operation time decreased with the flow rate though the ion-exchange capacity varied to a very small extent with the flow rate ranging from 4 to 9 mL/min. The spent zeolite was regenerated by sodium chloride solution and the ammonia removal capacity of zeolite changed little or even increased after three regeneration cycles. PMID:26510611

  16. Zeolite synthesis from fly ash and cement kiln dust

    SciTech Connect

    Grutzeck, M.W.

    1996-12-31

    Zeolites added to portland cement paste normally undergo a pozzolanic reaction. However, if the composition of the cement is modified by blending it with fly ash, the calcium silicate hydrate (C-S-H) that forms has a low CaO/SiO{sub 2} ratio which allows it to coexist with a zeolite. In fact, if one adds alkali to the system, it then becomes possible to nucleate and grow a zeolitic phase with C-S-H. Normally zeolites that form from fly ash and NaOH include NaP-1 and analcime. But when the fly ash and NaOH are mixed with cement kiln dust, cancrinite-like phases and tobermorite form instead. This implies that a zeolite-containing monolith could be produced that would exhibit both the cation-exchange and adsorptive properties of zeolites while retaining the characteristic strength and ease of use attributable to cement based materials. These composites show promise as a new class of inexpensive cation exchange and/or chemical adsorbents that can be used for large scale applications.

  17. Solvent Evaporation Assisted Preparation of Oriented Nanocrystalline Mesoporous MFI Zeolites

    SciTech Connect

    Zhu, Kake; Sun, Junming; Liu, Jun; Wang, Li Q.; Wan, Haiying; Hu, Jian Z.; Wang, Yong; Peden, Charles HF; Nie, Zimin

    2011-07-01

    A solvent evaporation route to produce hierarchically porous zeolites with an oriented MFI nanocrystalline structure has been developed, and the method is scalable and productive. In this method, hexadecyltrimethoxysilane is added to an ethanol solution containing zeolitic precursors. A hard gel is formed during the evaporation process. Subsequent hydrothermal treatments produce the hierarchically porous zeolite. High resolution transmission electron microscopy (HRTEM) studies suggest that misoriented zeolite nuclei are produced in the very early stages of the hydrothermal treatment, but further reactions lead to single crystal-like aggregates composed of intergrowth nanocrystals with a mean interparticle pore diameter of 12 nm. All Al atoms exist in tetrahedral sites, as confirmed by 27Al magic angle spinning nuclear magnetic resonance (MAS NMR). Variable temperature hyperpolarized (HP) 129Xe NMR spectroscopy suggest a fast molecular diffusion process from the interconnection between micro- and mesopores. Catalytic conversion of acetone to the isobutene reactions show comparable (with respect to conventional zeolites) selectivity to isobutene. However, hierarchically porous zeolites display enhanced activity and durability because of the more accessible acidic sites in the hierarchically porous structures.

  18. Alkali metal crystalline polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Zhang, Chuhong; Gamble, Stephen; Ainsworth, David; Slawin, Alexandra M. Z.; Andreev, Yuri G.; Bruce, Peter G.

    2009-07-01

    Polymer electrolytes have been studied extensively because uniquely they combine ionic conductivity with solid yet flexible mechanical properties, rendering them important for all-solid-state devices including batteries, electrochromic displays and smart windows. For some 30 years, ionic conductivity in polymers was considered to occur only in the amorphous state above Tg. Crystalline polymers were believed to be insulators. This changed with the discovery of Li+ conductivity in crystalline poly(ethylene oxide)6:LiAsF6 (refs 4, 5). However, new crystalline polymer electrolytes have proved elusive, questioning whether the 6:1 complex has particular structural features making it a unique exception to the rule that only amorphous polymers conduct. Here, we demonstrate that ionic conductivity in crystalline polymers is not unique to the 6:1 complex by reporting several new crystalline polymer electrolytes containing different alkali metal salts (Na+, K+ and Rb+), including the best conductor poly(ethylene oxide)8:NaAsF6 discovered so far, with a conductivity 1.5 orders of magnitude higher than poly(ethylene oxide)6:LiAsF6. These are the first crystalline polymer electrolytes with a different composition and structures to that of the 6:1 Li+ complex.

  19. Preparation of zeolite NaA for CO2 capture from nickel laterite residue

    NASA Astrophysics Data System (ADS)

    Du, Tao; Liu, Li-ying; Xiao, Penny; Che, Shuai; Wang, He-ming

    2014-08-01

    Zeolite NaA was successfully prepared from nickel laterite residue for the first time via a fusion-hydrothermal procedure. The structure and morphology of the as-synthesized zeolite NaA were characterized with a range of experimental techniques, such as X-ray diffraction, scanning electronic microscopy, and infrared spectroscopy. It was revealed that the structures of the produced zeolites were dependent on the molar ratios of the reactants and hydrothermal reaction conditions, so the synthesis conditions were optimized to obtain pure zeolite NaA. Adsorption of nitrogen and carbon dioxide on the prepared zeolite NaA was also measured and analyzed. The results showed that zeolite NaA could be prepared with reasonable purity, it had physicochemical properties comparable with zeolite NaA made from other methods, and it had excellent gas adsorption properties, thus demonstrating that zeolite NaA could be prepared from nickel laterite residue.

  20. Study of pure-silica Zeolite Nucleation and Growth from Solution 

    E-print Network

    Li, Xiang

    2011-10-21

    and direct zeolite nuclei. Unlike many studies performed analyzing the inorganic phase (silica) present in synthesis mixtures, this study quantified the organocation-silica particle interaction and its ultimate effect on zeolite growth mainly through probing...

  1. Interaction of Dimethylmethylphosphonate with Zeolite Y: Impedance-Based Sensor for Detecting Nerve Agent Simulants

    E-print Network

    Dutta, Prabir K.

    sensors.6 At temperatures less than 110 °C, a change in the conductivity of hydrated zeolites is induced control. There are also reports on utilization of zeolites as ionic electrolytes for hydrocarbon sensors

  2. Adsorption and isothermal models of atrazine by zeolite prepared from Egyptian kaolin

    NASA Astrophysics Data System (ADS)

    Jamil, Tarek S.; Gad-Allah, Tarek A.; Ibrahim, Hanan S.; Saleh, Tamer S.

    2011-01-01

    The adsorption behavior of Atrazine on zeolites, prepared from Egyptian kaolin, has been studied in order to consider the application of these types of zeolites in water purification. The batch mode has been employed, using atrazine solution of concentration ranging from 2 to 10 mg /l. The adsorption capacity and distribution coefficients ( Kd) were determined for the adsorption system as a function of sorbate concentration. It was found that, under the studies concentrations, the percent of adsorbed atrazine on both zeolites match to Langmuir and Freundlich adsorption models. The constants of each model were calculated to assess the adsorption behavior of atrazine on each type of zeolite. According to the equilibrium studies, adsorption of atrazine on zeolite X at lower concentrations is much better than that on zeolite A. The application of Dublin-Kaganer-Radushkevich model revealed physisorption endothermic adsorption process for both zeolites. These results show that natural zeolites hold great potential to remove hazardous materials such as atrazine from water.

  3. Nanostructures having crystalline and amorphous phases

    DOEpatents

    Mao, Samuel S; Chen, Xiaobo

    2015-04-28

    The present invention includes a nanostructure, a method of making thereof, and a method of photocatalysis. In one embodiment, the nanostructure includes a crystalline phase and an amorphous phase in contact with the crystalline phase. Each of the crystalline and amorphous phases has at least one dimension on a nanometer scale. In another embodiment, the nanostructure includes a nanoparticle comprising a crystalline phase and an amorphous phase. The amorphous phase is in a selected amount. In another embodiment, the nanostructure includes crystalline titanium dioxide and amorphous titanium dioxide in contact with the crystalline titanium dioxide. Each of the crystalline and amorphous titanium dioxide has at least one dimension on a nanometer scale.

  4. Relationships among the structural topology, bond strength, and mechanical properties of single-walled aluminosilicate nanotubes

    NASA Astrophysics Data System (ADS)

    Liou, Kai-Hsin; Tsou, Nien-Ti; Kang, Dun-Yen

    2015-10-01

    Carbon nanotubes (CNTs) are regarded as small but strong due to their nanoscale microstructure and high mechanical strength (Young's modulus exceeds 1000 GPa). A longstanding question has been whether there exist other nanotube materials with mechanical properties as good as those of CNTs. In this study, we investigated the mechanical properties of single-walled aluminosilicate nanotubes (AlSiNTs) using a multiscale computational method and then conducted a comparison with single-walled carbon nanotubes (SWCNTs). By comparing the potential energy estimated from molecular and macroscopic material mechanics, we were able to model the chemical bonds as beam elements for the nanoscale continuum modeling. This method allowed for simulated mechanical tests (tensile, bending, and torsion) with minimum computational resources for deducing their Young's modulus and shear modulus. The proposed approach also enabled the creation of hypothetical nanotubes to elucidate the relative contributions of bond strength and nanotube structural topology to overall nanotube mechanical strength. Our results indicated that it is the structural topology rather than bond strength that dominates the mechanical properties of the nanotubes. Finally, we investigated the relationship between the structural topology and the mechanical properties by analyzing the von Mises stress distribution in the nanotubes. The proposed methodology proved effective in rationalizing differences in the mechanical properties of AlSiNTs and SWCNTs. Furthermore, this approach could be applied to the exploration of new high-strength nanotube materials.Carbon nanotubes (CNTs) are regarded as small but strong due to their nanoscale microstructure and high mechanical strength (Young's modulus exceeds 1000 GPa). A longstanding question has been whether there exist other nanotube materials with mechanical properties as good as those of CNTs. In this study, we investigated the mechanical properties of single-walled aluminosilicate nanotubes (AlSiNTs) using a multiscale computational method and then conducted a comparison with single-walled carbon nanotubes (SWCNTs). By comparing the potential energy estimated from molecular and macroscopic material mechanics, we were able to model the chemical bonds as beam elements for the nanoscale continuum modeling. This method allowed for simulated mechanical tests (tensile, bending, and torsion) with minimum computational resources for deducing their Young's modulus and shear modulus. The proposed approach also enabled the creation of hypothetical nanotubes to elucidate the relative contributions of bond strength and nanotube structural topology to overall nanotube mechanical strength. Our results indicated that it is the structural topology rather than bond strength that dominates the mechanical properties of the nanotubes. Finally, we investigated the relationship between the structural topology and the mechanical properties by analyzing the von Mises stress distribution in the nanotubes. The proposed methodology proved effective in rationalizing differences in the mechanical properties of AlSiNTs and SWCNTs. Furthermore, this approach could be applied to the exploration of new high-strength nanotube materials. Electronic supplementary information (ESI) available: The convergence test used in DFT calculation and the validation of the assumption of negligible Poisson effects can be found in the ESI, along with illustrations of total strain energy and the reaction force response of carbon-carbon, Al-O, and Si-O beam elements, von Mises stress and ? distributions of AlSiNT14 and 16, potential energy types, and boundary conditions in the simulations. The mol files of AlSiNT models with various diameters are also appended. See DOI: 10.1039/c5nr03365a

  5. The Roles of Temperature and Composition in High-Pressure Structural Changes in Aluminosilicate Melts

    NASA Astrophysics Data System (ADS)

    Stebbins, J. F.

    2009-12-01

    Extensive recent NMR studies show large effects of composition on the extent of structural change in aluminosilicate glasses quenched from melts at high pressure, which correlate with observed, recovered density increases. Although such results will eventually need to be complemented by quantitative, in situ spectroscopic and scattering measurements, they already provide important constraints on the types of models necessary to capture the complexity of structure-property relationships for multicomponent natural magmas. For example, smaller and/or higher charged network modifier/charge compensator cations (e.g. Mg2+ vs. Ca2+, Ca2+ vs. K+) generally promote greater densification as well as increased conversion of four-coordinated to five- and six-coordinated Al (Al-27 NMR), but such effects may be non-linear in mixed-cation systems. At the same time, simple calculations with estimates of changes in partial molar volumes suggest that much of the observed density increases must be due to compression of “soft” sites in the structure and to the accompanying narrowing of inter-tetrahedral network bond angles (e.g. Si-O-Si). These can in turn be detected as reductions in mean Na-O distances (Na-23 NMR) and shifts in Si-29 spectra. As the field strength of the modifier cation increases farther (e.g. from Ca2+ to La3+), this pattern shifts: such “intermediate” cations can react to pressure increases by increasing their own coordinations and M-O distances (La K-edge XAS), reducing effects on network cation coordination. An extreme example of this can be seen as the Al/Si ratio changes: only at low Al contents are increases in Si coordination large enough to be detected by Si-29 NMR. Numerous recent studies of high-pressure glasses by O-17 NMR (e.g. S.K. Lee et al.) have emphasized the role of non-bridging oxygens (NBO) in increases of Si and Al coordination with pressure, as well as the critical importance of this species to melt properties. It is likely that modifier cation field strength has an important effect on this process as well: it is now well-known from borosilicate analog systems that higher field-strength modifiers (e.g. Ca2+ vs. Na+) stabilize local concentrations of negative charge as on NBO. This competing effect may again complicate models of density vs. composition. At best, quenched and decompressed glasses sample the melt structure only at the high P glass transition temperature. Given that the solidus temperatures of greatest interest to geological processes generally increase with pressure, changes in melt structure with temperature become even more important. The still poorly-known effects of ambient T decompression on glass structure also need to be resolved by future studies of the kinetics of this process and key in-situ measurements. Simple estimates of density changes during quench from a high P/T melt and subsequent decompression suggest that there is not a great deal of “room” for inelastic structural relaxation in typical aluminosilicate glasses, unless the high pressure thermal expansivity has a much larger structural contribution (Si coordination shift with T?) than is known from ambient P.

  6. Solution properties of ?-crystallins: Hydration of fish and mammal ?-crystallins

    PubMed Central

    Zhao, Huaying; Chen, Yingwei; Rezabkova, Lenka; Wu, Zhengrong; Wistow, Graeme; Schuck, Peter

    2014-01-01

    Lens ? crystallins are found at the highest protein concentration of any tissue, ranging from 300 mg/mL in some mammals to over 1000 mg/mL in fish. Such high concentrations are necessary for the refraction of light, but impose extreme requirements for protein stability and solubility. ?-crystallins, small stable monomeric proteins, are particularly associated with the lowest hydration regions of the lens. Here, we examine the solvation of selected ?-crystallins from mammals (human ?D and mouse ?S) and fish (zebrafish ?M2b and ?M7). The thermodynamic water binding coefficient B1 could be probed by sucrose expulsion, and the hydrodynamic hydration shell of tightly bound water was probed by translational diffusion and structure-based hydrodynamic boundary element modeling. While the amount of tightly bound water of human ?D was consistent with that of average proteins, the water binding of mouse ?S was found to be relatively low. ?M2b and ?M7 crystallins were found to exhibit extremely low degrees hydration, consistent with their role in the fish lens. ?M crystallins have a very high methionine content, in some species up to 15%. Structure-based modeling of hydration in ?M7 crystallin suggests low hydration is associated with the large number of surface methionine residues, likely in adaptation to the extremely high concentration and low hydration environment in fish lenses. Overall, the degree of hydration appears to balance stability and tissue density requirements required to produce and maintain the optical properties of the lens in different vertebrate species. PMID:24282025

  7. A new titanium-bearing calcium aluminosilicate phase. 1: Meteoritic occurrences and formation in synthetic systems

    NASA Technical Reports Server (NTRS)

    Paque, Julie M.; Beckett, John R.; Barber, David J.; Stolper, Edward M.

    1994-01-01

    A new titanium-bearing calcium aluminosilicate mineral has been identified in coarse-grained calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrites. The formula for this phase, which we have temporarily termed 'UNK,' is Ca3Ti(Al,Ti)2(Si,Al)3O14, and it is present in at least 8 of the 20 coarse-grained CAIs from the Allende CV3 chondrite examined as part of this project. The phase occurs in Types A and B1 inclusions as small tabular crystal oriented along two mutually perpendicular planes in melilite. UNK crystallizes from melts in dynamic crystallization experiments conducted in air from four bulk compositions modeled after Types A, B1, B2 and C inclusions. Cooling rates resulting in crystallization of UNK ranged from 0.5 to 200 C/h from maximum (initial) temperatures of 1375 to 1580 C. Only below 1190 C does UNK itself begin to crystallize. To first order, the presence or absence of UNK from individual experiments can be understood in terms of the compositions of residual melts and nucleation probabilities. Compositions of synthetic and meteoritic UNK are very similar in terms of major oxides, differing only in the small amounts of trivalent Ti(7-13% of total Ti) in meteoritic samples. UNK crystallized from the Type A analog is similar texturally to that found in CAIs, although glass, which is typically associated with synthetic UNK, is not observed in the meteoritic occurrences. A low Ti end-member of UNK ('Si-UNK') with a composition near that of Ca3Al2Si4O14 was produced in a few samples from the Type B1 analog. This phase has not been found in the meteoritic inclusions.

  8. A New Titanium-Bearing Calcium Aluminosilicate Phase. 1; Meteoritic Occurrences and Formation in Synthetic Systems

    NASA Technical Reports Server (NTRS)

    Paque, Julie M.; Beckett, John R.; Barber, David J.; Stolper, Edward M.

    1994-01-01

    A new titanium-bearing calcium aluminosilicate mineral has been identified in coarse-grained calcium-aluminum-rich inclusions (CAIs) from carbonaceous chondrites. The formula for this phase, which we have temporarily termed "UNK," is Ca3Ti(AlTi)2(Si,Al)3O14, and it is present in at least 8 of the 20 coarse-grained CAIs from the Allende CV3 chondrite examined as part of this project. The phase occurs in Types A and B1 inclusions as small tabular crystals oriented along two mutually perpendicular planes in melilite. UNK crystallizes from melts in dynamic crystallization experiments conducted in air from four bulk compositions modeled after Types A, B1, B2 and C inclusions. Cooling rates resulting in crystallization of UNK ranged from 0.5 to 200 C/h from maximum (initial) temperatures of 1375 to 1580 C. Only below 1190 C does UNK itself begin to crystallize. To first order, the presence or absence of UNK from individual experiments can be understood in terms of the compositions of residual melts and nucleation probabilities. Compositions of synthetic and meteoritic LINK are very similar in terms of major oxides, differing only in the small amounts of trivalent Ti (7-13% of total Ti) in meteoritic samples. UNK crystallized from the Type A analog is similar texturally to that found in CAls, although glass, which is typically associated with synthetic UN& is not observed in meteoritic occurrences. A low Ti end-member of UNK ("Si-UNK") with a composition new that of Ca3Al2Si4O14 was produced in a few samples from the Type B1 analog. This phase has not been found in the meteoritic inclusions.

  9. Correlation of the changes in the framework and active Cu sites for typical Cu/CHA zeolites (SSZ-13 and SAPO-34) during hydrothermal aging.

    PubMed

    Su, Wenkang; Li, Zhenguo; Peng, Yue; Li, Junhua

    2015-10-28

    The relative framework stability of Cu/CHA zeolites (SAPO-34 and SSZ-13) was studied during hydrothermal aging at 800 °C, and the fundamental mechanism for the framework change was investigated. Additionally, the relationship between the variation in the framework and active SCR reaction sites was established. SAPO-34 showed stronger stability during hydrothermal aging than SSZ-13. The results showed that dealumination occurred in the SSZ-13 zeolite, leading to the loss of crystallinity and a severe decrease of the Brönsted acid sites. Simultaneously, the detached Al(OH)3 species deactivated the Cu species by the transformation of isolated Cu(2+) ions to CuAlOx species. While the vacancy in the SAPO-34 framework caused by desilication could be healed with the migration of extra-framework Al and P atoms to the defects. And the Cu species showed a certain degree of aggregation with the improved redox ability of the aged Cu/SAPO-34 zeolite and the acidic properties were well maintained. PMID:26462874

  10. Highly dispersed metal atoms in zeolites. Progress report. [Hydroformylation

    SciTech Connect

    Suib, S.L.

    1985-04-15

    Our studies this past year have involved work in the following areas: preparation of highly dispersed metal atoms in molecular sieves via microwave discharge methods, hydroformylation of l-pentene with rhodium zeolites and Rutherford backscattering studies of zeolites. The microwave discharge method has been developed by us to provide a synthetic route to produce highly dispersed iron and cobalt atom clusters in several molecular sieves such as zeolites, aluminophosphates, pillared clays and clays. We have done ferromagnetic resonance, infrared, Mossbauer and scanning electron microscopy experiments on these materials. Generalizations that can be made so far are that these particles are extremely small, reactive and their formation is governed by the type of support. They are all active in Fischer-Tropsch reactions although cobalt materials are more selective and stable than iron materials. Superparamagnetic iron clusters have been observed for the incorporation of iron into zeolites, ALPO's and pillared clays. These results are unique in that iron (0) is usually oxidized in a zeolite environment. The second project deals with Wilkinson's catalyst and the preparation of phosphine rhodium zeolite catalysts. These catalysts are selective towards aldehyde formation and the normal to branched aldehyde ratio can be controlled. EXAFS, Fourier transform infrared and x-ray powder diffraction experiments have been carried out on these catalysts. The third project deals with Rutherford backscattering studies of zeolites. We have shown that Rutherford backscattering methods can be used to distinguish metal ions on the surface of a porous support from internal metal ions exchanged into the pores of the support.

  11. Synthesis of mesoporous zeolite single crystals with cheap porogens

    SciTech Connect

    Tao Haixiang; Li Changlin; Ren Jiawen; Wang Yanqin; Lu Guanzhong

    2011-07-15

    Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals have been successfully synthesized by adding soluble starch or sodium carboxymethyl cellulose (CMC) to a conventional zeolite synthesis system. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption analysis, {sup 27}Al magic angle spinning nuclear magnetic resonance ({sup 27}Al MAS NMR), temperature-programmed desorption of ammonia (NH{sub 3}-TPD) and ultraviolet-visible spectroscopy (UV-vis). The SEM images clearly show that all zeolite crystals possess the similar morphology with particle size of about 300 nm, the TEM images reveal that irregular intracrystal pores are randomly distributed in the whole crystal. {sup 27}Al MAS NMR spectra indicate that nearly all of the Al atoms are in tetrahedral co-ordination in ZSM-5, UV-vis spectra confirm that nearly all of titanium atoms are incorporated into the framework of TS-1. The catalytic activity of meso-ZSM-5 in acetalization of cyclohexanone and meso-TS-1 in hydroxylation of phenol was also studied. The synthesis method reported in this paper is cost-effective and environmental friendly, can be easily expended to prepare other hierarchical structured zeolites. - Graphical abstract: Mesoporous zeolite single crystals were synthesized by using cheap porogens as template. Highlights: > Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals were synthesized. > Soluble starch or sodium carboxymethyl cellulose (CMC) was used as porogens. > The mesoporous zeolites had connected mesopores although closed pores existed. > Higher catalytic activities were obtained.

  12. Molecular composites from liquid crystalline polymers and liquid crystalline thermosets

    SciTech Connect

    Benicewicz, B.C.; Douglas, E.P.; Hjelm, R.P. Jr.

    1993-07-01

    We propose a new approach to molecular composites. This approach uses a mixture of a liquid crystalline polymer and a liquid crystalline thermoset to enhance the miscibility. Preliminary neutron scattering data is presented on a system of short and long rod aromatic amides. The data is interpreted using the interpenetrating phase model of Debye and Bueche. The analysis indicates that the scattering is consistent with this model and shows a characteristic length scale in the range of 70 to 80 A. The intensity of the scattering is lower than calculated for the strong segregation limit, suggesting that there is some intermixing of the components.

  13. Lens Aging: Effects of Crystallins

    PubMed Central

    Sharma, K. Krishna; Santhoshkumar, Puttur

    2009-01-01

    The primary function of the eye lens is to focus light on the retina. The major proteins in the lens—a, b, and g-crystallins—are constantly subjected to age-related changes such as oxidation, deamidation, truncation, glycation, and methylation. Such age-related modifications are cumulative and affect crystallin structure and function. With time, the modified crystallins aggregate, causing the lens to increasingly scatter light on the retina instead of focusing light on it and causing the lens to lose its transparency gradually and become opaque. Age-related lens opacity, or cataract, is the major cause of blindness worldwide. We review deamidation, and glycation that occur in the lenses during aging keeping in mind the structural and functional changes that these modifications bring about in the proteins. In addition, we review proteolysis and discuss recent observations on how crystallin fragments generated in vivo, through their anti-chaperone activity may cause crystallin aggregation in aging lenses. We also review hyperbaric oxygen treatment induced guinea pig and ‘humanized’ ascorbate transporting mouse models as suitable options for studies on age-related changes in lens proteins. PMID:19463898

  14. Diverse topics in crystalline beams

    SciTech Connect

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

    1995-11-27

    Equations of motion are presented, appropriate to interacting charged particles of diverse charge and mass, subject to the external forces produced by various kinds of magnetic fields and radio-frequency (rf) electric fields in storage rings. These equations are employed in the molecular dynamics simulations to study the properties of crystalline beams. The two necessary conditions for the formation and maintenance of crystalline beams are summarized. The transition from ID to 2D, and from 2D to 3D is explored, and the scaling behavior of the heating rates is discussed especially in the high temperature limit. The effectiveness of various cooling techniques in achieving crystalline states has been investigated. Crystalline beams made of two different species of ions via sympathetic cooling are presented, as well as circulating ``crystal balls`` bunched in all directions by magnetic focusing and rf field. By numerically reconstructing the original experimental conditions of the NAP-M ring, it is found that only at extremely low beam intensities, outside of the range of the original measurement, proton particles can form occasionally-passing disks. The proposed New ASTRID ring is shown to be suitable for the formation and maintenance of crystalline beams of all dimensions.

  15. Rotationally Molded Liquid Crystalline Polymers

    NASA Technical Reports Server (NTRS)

    Rogers, Martin; Scribben, Eric; Baird, Donald; Hulcher, Bruce

    2002-01-01

    Rotational molding is a unique process for producing hollow plastic parts. Rotational molding offers low cost tooling and can produce very large parts with complicated shapes. Products made by rotational molding include water tanks with capacities up to 20,000 gallons, truck bed liners, playground equipment, air ducts, Nylon fuel tanks, pipes, toys, stretchers, kayaks, pallets, and many others. Thermotropic liquid crystalline polymers are an important class of engineering resins employed in a wide variety of applications. Thermotropic liquid crystalline polymers resins are composed of semirigid, nearly linear polymeric chains resulting in an ordered mesomorphic phase between the crystalline solid and the isotropic liquid. Ordering of the rigid rod-like polymers in the melt phase yields microfibrous, self-reinforcing polymer structures with outstanding mechanical and thermal properties. Rotational molding of liquid crystalline polymer resins results in high strength and high temperature hollow structures useful in a variety of applications. Various fillers and reinforcements can potentially be added to improve properties of the hollow structures. This paper focuses on the process and properties of rotationally molded liquid crystalline polymers. This paper will also highlight the interactions between academia and small businesses in developing new products and processes.

  16. Rotationally Molded Liquid Crystalline Polymers

    NASA Technical Reports Server (NTRS)

    Rogers, Martin; Stevenson, Paige; Scribben, Eric; Baird, Donald; Hulcher, Bruce

    2002-01-01

    Rotational molding is a unique process for producing hollow plastic parts. Rotational molding offers advantages of low cost tooling and can produce very large parts with complicated shapes. Products made by rotational molding include water tanks with capacities up to 20,000 gallons, truck bed liners, playground equipment, air ducts, Nylon fuel tanks, pipes, toys, stretchers, kayaks, pallets, and many others. Thermotropic liquid crystalline polymers are an important class of engineering resins employed in a wide variety of applications. Thermotropic liquid crystalline polymers resins are composed of semi-rigid, nearly linear polymeric chains resulting in an ordered mesomorphic phase between the crystalline solid and the isotropic liquid. Ordering of the rigid rod-like polymers in the melt phase yields microfibrous, self-reinforcing polymer structures with outstanding mechanical and thermal properties. Rotational molding of liquid crystalline polymer resins results in high strength and high temperature hollow structures useful in a variety of applications. Various fillers and reinforcements can potentially be added to improve properties of the hollow structures. This paper focuses on the process and properties of rotationally molded liquid crystalline polymers.

  17. Toward a Database of Hypothetical Zeolite Structures David J. Earl, and Michael W. Deem*,

    E-print Network

    Earl, David J.

    Toward a Database of Hypothetical Zeolite Structures David J. Earl, and Michael W. Deem the sampling. We discuss construction of a database of hypothetical zeolite frameworks with this approach and discuss how the database may be used to search for new zeolite structures with specific material

  18. Ion exchange of zeolite membranes by a vacuum `flow-through' Seok-Jhin Kim a

    E-print Network

    Nair, Sankar

    Ion exchange of zeolite membranes by a vacuum `flow-through' technique Seok-Jhin Kim October 2014 Keywords: Ion exchange Zeolite membrane Flow-through technique Separation Catalysis a b s t r a c t Ion exchange of nanoporous (e.g., zeolite) membranes is of increasing importance

  19. Molecular simulations of hydrogen and methane permeation through pore mouth modified zeolite Sang Eun Jeea

    E-print Network

    McGaughey, Alan

    Molecular simulations of hydrogen and methane permeation through pore mouth modified zeolite zeolite membranes whose pore mouths have been chemically modified. An important challenge for materials the hydrogen flux possible with an unmodified zeolite membrane. Motivated by this, the effect of the pore mouth

  20. Framework Stabilization of Si-Rich LTA Zeolite Prepared in Organic-Free Media

    SciTech Connect

    Conato, Marlon T.; Oleksiak, Matthew D.; McGrail, B. Peter; Motkuri, Radha K.; Rimer, Jeffrey D.

    2014-10-16

    Zeolite HOU-2 (LTA type) is prepared with the highest silica content (Si/Al = 2.1) reported for Na-LTA zeolites without the use of an organic structure-directing agent. The rational design of Si-rich zeolites has the potential to improve their thermal stability for applications in catalysis, gas storage, and selective separations.

  1. UTILITY OF SYNTHETIC ZEOLITES IN REMOVAL OF INORGANIC AND ORGANIC WATER POLLUTANTS

    EPA Science Inventory

    Zeolites are well known for their ion exchange and adsorption properties. Different inorganic and organic pollutants have been removed from water at room temperature using various zeolites. Synthetic zeolites like ZSM-5, Ferrierite, Beta and Faujasite Y have been used to remove i...

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

    ERIC Educational Resources Information Center

    Smoot, Alison L.; Lindquist, David A.

    1997-01-01

    Presents experiments that introduce students to the myriad properties of zeolites using the sodium form of zeolite A (Na-A) from laundry detergent. Experiments include extracting Na-A from detergent, water softening properties, desiccant properties, ion-exchange properties, and Zeolite HA as a dehydration catalyst. (JRH)

  3. Zeolite-Mediated Photochemical Charge Separation Using a Surface-Entrapped Ruthenium-Polypyridyl Complex

    E-print Network

    Dutta, Prabir K.

    Zeolite-Mediated Photochemical Charge Separation Using a Surface-Entrapped Ruthenium)ethenyl]benzene (L), a polypyridyl complex of ruthenium(II) was tethered on the surface of zeolite Y. Electrochemical photolysis of the ruthenium-zeolite solid ion-exchanged with diquat and suspended in a propyl viologen

  4. ZEOLITE PERFORMANCE AS AN ANION EXCHANGER FOR ARSENIC SEQUESTRATION IN WATER

    EPA Science Inventory

    Zeolites are well known for their use in ion exchange and acid catalysis reactions. The use of zeolites in anion or ligand exchange reactions is less studied. The NH4+ form of zeolite Y (NY6, Faujasite) has been tested in this work to evaluate its performance for arsenic removal...

  5. Algebraic Description of Coordination Sequences and Exact Topological Densities for Zeolites

    E-print Network

    Sloane, Neil J. A.

    Algebraic Description of Coordination Sequences and Exact Topological Densities for Zeolites R. Although it was known that for many zeolites the terms of the CS grow quadratically with k, no systematic investigation had been carried out. Up to 2000 terms have now been calculated for all the zeolites tabulated

  6. Algebraic Description of Coordination Sequences and Exact Topological Densities for Zeolites

    E-print Network

    Sloane, Neil J. A.

    Algebraic Description of Coordination Sequences and Exact Topological Densities for Zeolites R- dimensional sphere packings. Although was known that for many zeolites the terms the CS grow quadratically with systematic investigation had been carried out. 2000 terms have now been calculated for the zeolites tabulated

  7. Locating stationary points of sorbate-zeolite potential energy surfaces using interval analysis

    E-print Network

    Stadtherr, Mark A.

    Locating stationary points of sorbate-zeolite potential energy surfaces using interval analysis in a zeolite can be studied using transition-state theory. In this application, and other applications points, transition states, zeolites, diffusion, interval-Newton method Author to whom all correspondence

  8. Materials Chemistry and Physics 83 (2004) 8995 Microwave preparation of Li-zeolite directly from

    E-print Network

    Gulari, Erdogan

    2004-01-01

    Materials Chemistry and Physics 83 (2004) 89­95 Microwave preparation of Li-zeolite directly from in revised form 3 September 2003; accepted 12 September 2003 Abstract Li-zeolites were successfully and lithium hydroxide as the hydrolytic agent. Many types of Li-zeolites were obtained by controlling

  9. Researchers are developing novel zeolite-based materials with 1-D nanopores for automotive applications.

    E-print Network

    Bustamante, Fabián E.

    Researchers are developing novel zeolite-based materials with 1-D nanopores for automotive its optimal temperature. The HC trap is based upon a special class of zeolites with non with the team led by Dr. Broadbelt in conducting theoretical modeling of zeolites in an effort to improve

  10. Crystalline 'Genes' in Metallic Liquids

    E-print Network

    Sun, Yang; Ye, Zhuo; Fang, Xiaowei; Ding, Zejun; Wang, Cai-Zhuang; Mendelev, Mikhail I; Ott, Ryan T; Kramer, M J; Ho, Kai-Ming

    2014-01-01

    The underlying structural order that transcends the liquid, glass and crystalline states is identified using an efficient genetic algorithm (GA). GA identifies the most common energetically favorable packing motif in crystalline structures close to the alloy's Al-10 at.% Sm composition. These motifs are in turn compared to the observed packing motifs in the actual liquid structures using a cluster-alignment method which reveals the average topology. Conventional descriptions of the short-range order, such as Voronoi tessellation, are too rigid in their analysis of the configurational poly-types when describing the chemical and topological ordering during transition from undercooled metallic liquids to crystalline phases or glass. Our approach here brings new insight into describing mesoscopic order-disorder transitions in condensed matter physics.

  11. Synthesis of nanosized ZSM-5 zeolite using extracted silica from rice husk without adding any alumina source

    NASA Astrophysics Data System (ADS)

    Sari, Zahra Ghasemi Laleh Vajheh; Younesi, Habibollah; Kazemian, Hossein

    2015-08-01

    The synthesis of analcime and nanosized ZSM-5 zeolites was carried out by a hydrothermal method with silica extracted from rice husk, available as an inexpensive local biowaste, and without the use of an extra alumina source. Amorphous silica (with 88 wt% of SiO2) was extracted from rice husk ash by a suitable alkali solution. The effects of crystallization temperature, time and SiO2/Al2O3 ratio of the initial system on the properties of final products were investigated. For the characterization of the synthesized product, X-ray diffraction, scanning electron microscope, energy dispersive X-ray techniques, Fourier transform infrared and Brunauer-Emmett-Teller method were applied. Crystallinity percentages of analcime and nanosized ZSM-5 were 95.86 and 89.56, respectively, with specific surface area of 353.5 m2 g-1 for ZSM-5. The experimental results revealed that the synthesis of analcime and nanosized ZSM-5 zeolites was more practical with using silica extracted from inexpensive raw materials, while the whole crystallization process was accomplished without adding any alumina source during.

  12. Molecular Models of the Structure and Hydration of Sodalite and Laumontite Zeolites

    NASA Astrophysics Data System (ADS)

    Moloy, E. C.; Cygan, R. T.; Teter, D. M.; Navrotsky, A.

    2001-12-01

    An energy forcefield for the simulation of hydrated aluminosilicate zeolites has been developed to examine the structure and dynamics of water in nanoporous materials. Radial distribution functions for O-O, Na-O, and Ca-O in solvated ion systems, as well as unit cell volumes for hydrated sodalite (Na6Al6Si6O24”8H2O), fully dehydrated sodalite, hydrated laumontite (Ca4Al8Si16O48”18H2O), and partially dehydrated laumontite (12 and 14 H2O/unit cell) have been used to validate and apply this forcefield. Molecular dynamics simulations (NVT canonical ensembles) were run for the water-cation systems, each comprised of 216 water molecules, a single cation, and with a density of ~1 g/cm3 at 300 K. The theoretical RDFs for the first hydration spheres of O-O, Na-O, Ca-O are 2.78 +/- 0.02 A, 2.36 +/- 0.02 A, and 2.48 +/- 0.02 A, respectively. These results compare favorably to average observed values of 2.90 A (-4.1%), 2.43 A (-2.9%), and 2.42 A (+1.8%), respectively. Energy minimization and molecular dynamics simulations for the various hydration states of sodalite suggest complex interactions between the water molecules and the zeolitic framework. In particular, water oxygens prefer to coordinate with the extra-framework cations, while the water hydrogens associate with other water molecules, and to a lesser extent, framework oxygens. Energy minimizations (at constant pressure) provide unit cell volumes of 732.0 A3 and 759.7 A3 for the two sodalite endmember structures, and these values compare well to average observed values of 693.4 A3 (+5.6%) and 756.9 A3 (+0.4%), respectively. Note the smaller unit cell volume for the fully hydrated structure, obtained from both simulation and experimental techniques. Theoretical hydration curves for sodalite, incorporating intermediate water contents, support the observed trend in unit cell volumes. A similar approach has also been used to examine the natural hydration states of laumontite, to evaluate the mechanisms of hydration, and to help interpret experimental hydration curves. In contrast to sodalite, energy minimization models of laumontite illustrate a more direct relationship between unit cell volume and water content. The unit cell volumes for partially and fully hydrated laumontite are 1402.8 A3, 1424.9 A3, and 1425.1 A3, comparing well to average observed values of 1341.0 A3 (+4.6%), 1366.0 A3 (+4.3%), and 1380.6 A3 (+3.2%), respectively. Finally, we use plane-wave pseudopotential density functional calculations to validate our potential-based simulation models. In the case of fully dehydrated sodalite, our DFT simulations suggest that the sodium ions occupy the centers of the six-membered rings, in agreement with our forcefield results. This configuration is in contrast to the results of a recent DFT study, which suggests that the sodium ions are significantly offset from the planes of the six-membered rings.

  13. Fabrication of zeolite/polymer multilayer composite membranes for carbon dioxide capture: Deposition of zeolite particles on polymer supports.

    PubMed

    Ramasubramanian, Kartik; Severance, Michael A; Dutta, Prabir K; Ho, W S Winston

    2015-08-15

    Membranes, due to their smaller footprint and potentially lower energy consumption than the amine process, offer a promising route for post-combustion CO2 capture. Zeolite Y based inorganic selective layers offer a favorable combination of CO2 permeance and CO2/N2 selectivity, membrane properties crucial to the economics. For economic viability on large scale, we propose to use flexible and scalable polymer supports for inorganic selective layers. The work described in this paper developed a detailed protocol for depositing thin zeolite Y seed layers on polymer supports, the first step in the synthesis of a polycrystalline zeolite Y membrane. We also studied the effects of support surface morphology (pore size and surface porosity) on the quality of deposition and identified favorable supports for the deposition. Two different zeolite Y particles with nominal sizes of 200 nm and 40 nm were investigated. To obtain a complete coverage of zeolite particles on the support surface with minimum defects and in a reproducible manner, a vacuum-assisted dip-coating technique was developed. Images obtained using both digital camera and optical microscope showed the presence of color patterns on the deposited surface which suggested that the coverage was complete. Electron microscopy revealed that the particle packing was dense with some drying cracks. Layer thickness with the larger zeolite Y particles was close to 1 ?m while that with the smaller particles was reduced to less than 0.5 ?m. In order to reduce drying cracks for layers with smaller zeolite Y particles, thickness was reduced by lowering the dispersion concentration. Transport measurement was used as an additional technique to characterize these layers. PMID:25950846

  14. Single crystalline mesoporous silicon nanowires

    SciTech Connect

    Hochbaum, Allon; Dargas, Daniel; Hwang, Yun Jeong; Yang, Peidong

    2009-08-18

    Herein we demonstrate a novel electroless etching synthesis of monolithic, single-crystalline, mesoporous silicon nanowire arrays with a high surface area and luminescent properties consistent with conventional porous silicon materials. The photoluminescence of these nanowires suggest they are composed of crystalline silicon with small enough dimensions such that these arrays may be useful as photocatalytic substrates or active components of nanoscale optoelectronic devices. A better understanding of this electroless route to mesoporous silicon could lead to facile and general syntheses of different narrow bandgap semiconductor nanostructures for various applications.

  15. Single crystalline mesoporous silicon nanowires

    SciTech Connect

    Hochbaum, A.I.; Gargas, Daniel; Jeong Hwang, Yun; Yang, Peidong

    2009-08-04

    Herein we demonstrate a novel electroless etching synthesis of monolithic, single-crystalline, mesoporous silicon nanowire arrays with a high surface area and luminescent properties consistent with conventional porous silicon materials. These porous nanowires also retain the crystallographic orientation of the wafer from which they are etched. Electron microscopy and diffraction confirm their single-crystallinity and reveal the silicon surrounding the pores is as thin as several nanometers. Confocal fluorescence microscopy showed that the photoluminescence (PL) of these arrays emanate from the nanowires themselves, and their PL spectrum suggests that these arrays may be useful as photocatalytic substrates or active components of nanoscale optoelectronic devices.

  16. Zeolites for the selective adsorption of sulfur hexafluoride.

    PubMed

    Matito-Martos, I; Álvarez-Ossorio, J; Gutiérrez-Sevillano, J J; Doblaré, M; Martin-Calvo, A; Calero, S

    2015-07-21

    Molecular simulations have been used to investigate at the molecular level the suitability of zeolites with different topology on the adsorption, diffusion and separation of a nitrogen-sulfur hexafluoride mixture containing the latter at low concentration. This mixture represents the best alternative for the sulfur hexafluoride in industry since it reduces the use of this powerful greenhouse gas. A variety of zeolites are tested with the aim to identify the best structure for the recycling of sulfur hexafluoride in order to avoid its emission to the atmosphere and to overcome the experimental difficulties of its handling. Even though all zeolites show preferential adsorption of sulfur hexafluoride, we identified local structural features that reduce the affinity for sulfur hexafluoride in zeolites such as MOR and EON, providing exclusive adsorption sites for nitrogen. Structures such as ASV and FER were initially considered as good candidates based on their adsorption features. However, they were further discarded based on their diffusion properties. Regarding operation conditions for separation, the range of pressure that spans from 3 × 10(2) to 3 × 10(3) kPa was identified as the optimal to obtain the highest adsorption loading and the largest SF6/N2 selectivity. Based on these findings, zeolites BEC, ITR, IWW, and SFG were selected as the most promising materials for this particular separation. PMID:26099734

  17. Cadmium adsorption on vermiculite, zeolite and pumice: batch experimental studies.

    PubMed

    Panuccio, Maria Rosaria; Sorgonà, Agostino; Rizzo, Marcella; Cacco, Giovanni

    2009-01-01

    Batch experiments were performed to evaluate the combined effects of ionic activity, pH, and contact time on the cadmium sorption in three different minerals, vermiculite, zeolite, and pumice, commonly employed as substrata in nurseries and recently considered for their potential use in remediation methods. The extent of cadmium sorption was vermiculite>zeolite>pumice, as shown by the Langmuir and Freundlich parameters, and it was highly dependent on mineral characteristics. The percentage of cadmium sorption in zeolite and vermiculite did not depend on cadmium concentration, while in pumice this percentage was positively correlated to the initial cadmium concentration. At low cadmium concentrations (30-120 microM), the metal sorbed on zeolite was mainly present in the nonexchangeable form (70%) at levels much higher than those found for vermiculite and pumice. The primary variable responsible for determination of cadmium mobility in these minerals was confirmed to be pH. The ionic concentrations of Hoagland nutrient solution were significantly modified by both pH and mineral composition, while the presence of cadmium caused no changes. With vermiculite and zeolite, the time-course of cadmium sorption was related to mineral composition to a greater extent than to cadmium concentration. While with pumice, the percentage of cadmium sorbed after 6 weeks was lower than with the other two minerals, and it was inversely correlated to the initial cadmium concentration. PMID:18082309

  18. Phenol removal from wastewater by adsorption on zeolitic composite.

    PubMed

    Bizerea Spiridon, Otilia; Preda, Elena; Botez, Alexandru; Pitulice, Laura

    2013-09-01

    It is well known that adsorption is an efficient method of removal of various pollutants from wastewater. The present study examines the phenol removal from water by adsorption on a new material, based on zeolitic volcanic tuff. This compound contains zeolitic tuff and cellulose, another known adsorbent, in a mass ratio of 4 to 1. The performances of the new adsorbent composite were compared with those of a widely used adsorbent material, zeolitic volcanic tuff. The adsorbent properties were tested on batch synthetic solutions containing 1-10 mg L(-1) (1-10 ppm) phenol, at room temperature without pH adjustment. The influence of the adsorbent dose, pH and contact time on the removal degree of phenol from water was investigated. The experimental data were modeled using the Langmuir, Freundlich, and Temkin adsorption isotherms. The Langmuir model was found to best represent our data revealing a monolayer adsorption with a maximum adsorption capacity between 0.12 and 0.53 mg g(-1) at 25 °C, for 2.00 g of adsorbent, depending on the initial phenol concentration. The adsorption kinetic study was performed using a pseudo-first- and pseudo-second-order kinetic models illustrating that phenol adsorption on zeolite composite is well described by pseudo-first kinetic equations. Our results indicated that phenol adsorption on the new adsorbent composite is superior to that on the classic zeolite. PMID:23589237

  19. Risk assessment for the transportation of radioactive zeolite liners

    SciTech Connect

    Not Available

    1982-01-01

    The risk is estimated for the shipment of radioactive zeolite liners in support of the Zeolite Vitrification Demonstration Program currently underway at Pacific Northwest Laboratory under the sponsorship of the US Department of Energy. This program will establish the feasibility of zeolite vitrification as an effective means of immobilizing high-specific-activity wastes. In this risk assessment, it is assumed that two zeolite liners, each loaded around July 1, 1981 to 60,000 Ci, will be shipped by truck around January 1, 1982. However, to provide a measure of conservatism, each liner is assumed to initially hole 70,000 Ci, with the major radioisotopes as follow: /sup 90/Sr = 3000 Ci, /sup 134/Cs = 7000 Ci, /sup 137/Cs = 60,000 Ci. Should shipment take place with essentially no delay after initial loading (regardless of loading date), the shipment loading would be only 2.7% higher than that for the assumed six-month delay. This would negligibly affect the overall risk. As a result of this risk assessment, it is concluded that the transport of the radioactive zeolite liners from TMI to PNL by truck can be conducted at an insignificant level of risk to the public.

  20. One-step hydrothermal synthesis of manganese-containing MFI-type zeolite, Mn-ZSM-5, characterization, and catalytic oxidation of hydrocarbons.

    PubMed

    Meng, Yongtao; Genuino, Homer C; Kuo, Chung-Hao; Huang, Hui; Chen, Sheng-Yu; Zhang, Lichun; Rossi, Angelo; Suib, Steven L

    2013-06-12

    Manganese-containing MFI-type Mn-ZSM-5 zeolite was synthesized by a facile one-step hydrothermal method using tetrapropylammonium hydroxide (TPAOH) and manganese(III)-acetylacetonate as organic template and manganese salts, respectively. A highly crystalline MFI zeolite structure was formed under pH = 11 in 2 days, without the need for additional alkali metal cations. Direct evidence of the incorporation of Mn in the zeolite framework sites was observed by performing structure parameter refinements, supported by data collected from other characterization techniques such as IR, Raman, UV-vis, TGA, N2-adsorption, SEM, TEM, EDAX, and XPS. UV-vis spectra from the unique optical properties of Mn-ZSM-5 show two absorption peaks at 250 and 500 nm. The absorption varies in different atmospheres accompanied by a color change of the materials due to oxygen evolution. Raman spectra show a significant and gradual red shift from 383 cm(-1) to 372 cm(-1) when the doping amount of Mn is increased from 0 to 2 wt %. This suggests a weakened zeolite structural unit induced by the Mn substitution. The catalytic activity was studied in both gas-phase benzyl alcohol oxidation and toluene oxidation reactions with remarkable oxidative activity presented for the first time. These reactions result in a 55% yield of benzaldehyde, and 65% total conversion of toluene to carbon dioxide for the 2% Mn-ZSM-5. Temperature programmed reduction (TPR) using CO in He demonstrates two reduction peaks: one between 300 and 500 °C and the other between 500 and 800 °C. The first reduction peak, due to manganese-activated oxidation sites shifted from higher temperature to lower temperature, and the peak intensity of CO2 rises when the dopant amount increases. For the first time, calculated photophysical properties of a model Mn(O-SiH3)4(-) compound, an Mn-embedded zeolite cluster, and model Mn oxides help to explain and interpret the diffuse reflectance spectroscopy of Mn-ZSM-5 zeolites. PMID:23679582

  1. Zeolite thin film-coated fiber sensors based on Fabry-Perot interferometer for detection of chemical vapors

    NASA Astrophysics Data System (ADS)

    Ning, Xiangping; Zhao, Chunliu; Shi, Feifei; Kang, Juan

    2015-06-01

    A novel zeolite-coated fiber sensors for detection of volatile organic compounds (VOCs) based on the Fabry-Perot interferometer was proposed and demonstrated. The sensor comprised a polycrystalline silicalite thin film grown up on the cleaved end face of a standard single-mode fiber. The inline Fabry-Perot cavity was composed by the end face of the single-mode fiber and the thin film. The sensor device operated by measuring the interference signal, which was a function of the amount of chemical vapor adsorption in its crystalline micro porous structure. Experimental results showed that the proposed VOC sensor worked well and the sensitivities were 2.78×10-3 dB/ppm when the concentration ranged from 350 ppm to 2100 ppm and 1.23×10-3 dB/ppm when the concentration ranged from 2100 ppm to 5250 ppm.

  2. Synthesis of chiral polymorph A-enriched zeolite Beta with an extremely concentrated fluoride route

    PubMed Central

    Tong, Mingquan; Zhang, Daliang; Fan, Weibin; Xu, Jun; Zhu, Liangkui; Guo, Wen; Yan, Wenfu; Yu, Jihong; Qiu, Shilun; Wang, Jianguo; Deng, Feng; Xu, Ruren

    2015-01-01

    Chiral zeolitic materials with intrinsically chiral frameworks are highly desired because they can combine both shape selectivity and enantioselectivity. In the field of zeolite, the synthesis of chiral polymorph A of zeolite Beta or chiral polymorph A-enriched zeolite Beta is one of the biggest challenges. We demonstrate here a generalized extremely concentrated fluoride route for the synthesis of chiral polymorph A-enriched zeolite Beta in the presence of five achiral organic structure-directing agents. The polymorph A-enriched Ti-Beta shows a higher enantioselectivity for the asymmetric epoxidation of alkenes than the normal Ti-Beta. PMID:26096214

  3. Synthesis of chiral polymorph A-enriched zeolite Beta with an extremely concentrated fluoride route

    NASA Astrophysics Data System (ADS)

    Tong, Mingquan; Zhang, Daliang; Fan, Weibin; Xu, Jun; Zhu, Liangkui; Guo, Wen; Yan, Wenfu; Yu, Jihong; Qiu, Shilun; Wang, Jianguo; Deng, Feng; Xu, Ruren

    2015-06-01

    Chiral zeolitic materials with intrinsically chiral frameworks are highly desired because they can combine both shape selectivity and enantioselectivity. In the field of zeolite, the synthesis of chiral polymorph A of zeolite Beta or chiral polymorph A-enriched zeolite Beta is one of the biggest challenges. We demonstrate here a generalized extremely concentrated fluoride route for the synthesis of chiral polymorph A-enriched zeolite Beta in the presence of five achiral organic structure-directing agents. The polymorph A-enriched Ti-Beta shows a higher enantioselectivity for the asymmetric epoxidation of alkenes than the normal Ti-Beta.

  4. Nondestructive depth profiling of rare-earth and actinide zeolites via Rutherford backscattering methods

    SciTech Connect

    Baumann, S.A.; Strathman, M.D.; Suib, S.L.

    1988-05-15

    Rutherford backscattering (RBS) methods have been used to study rare-earth and actinide-ion-exchanged small pore (A) and large pore (Y) zeolites. A theoretical discussion of the RBS method and a novel method of data treatment are given. Experimental data for zeolites have been simulated and theoretical depth profiles have been determined. Both experimental and theoretical data suggest that uranyl-exchanged A zeolite has a large uranium to oxygen surface ratio while the corresponding Y zeolite has a large uranium to oxygen bulk ratio. Relative atomic fractions of all zeolite elements are also given.

  5. Selective sensing of alcohols in water influenced by chemically Zeolite coatings on optical fiber sensors

    NASA Astrophysics Data System (ADS)

    Nazari, Marziyeh; Hill, Matthew R.; Duke, Mikel; Sidiroglou, Fotios; Collins, Stephen F.

    2014-05-01

    The application of a MFI type zeolite coating on the end of an optical fiber is presented. Zeolite coatings were directly grown on the freshly cleaved endface of optical fibers. It was found that the produced integrated zeolite-fiber sensors exhibit specific chemical sensitivity towards certain chemicals. The molecular adsorption induced change of zeolite refractive index was studied to understand the sensing mechanisms of the developed sensor system. This work can lead to a new class of portable zeolite thin film enabled miniaturized fiber optic sensors.

  6. Glycation precedes lens crystallin aggregation

    SciTech Connect

    Swamy, M.S.; Perry, R.E.; Abraham, E.C.

    1987-05-01

    Non-enzymatic glycosylation (glycation) seems to have the potential to alter the structure of crystallins and make them susceptible to thiol oxidation leading to disulfide-linked high molecular weight (HMW) aggregate formation. They used streptozotocin diabetic rats during precataract and cataract stages and long-term cell-free glycation of bovine lens crystallins to study the relationship between glycation and lens crystallin aggregation. HMW aggregates and other protein components of the water-soluble (WS) and urea-soluble (US) fractions were separated by molecular sieve high performance liquid chromatography. Glycation was estimated by both (/sup 3/H)NaBH/sub 4/ reduction and phenylboronate agarose affinity chromatography. Levels of total glycated protein (GP) in the US fractions were about 2-fold higher than in the WS fractions and there was a linear increase in GP in both WS and US fractions. This increase was parallelled by a corresponding increase in HMW aggregates. Total GP extracted by the affinity method from the US fraction showed a predominance of HMW aggregates and vice versa. Cell-free glycation studies with bovine crystallins confirmed the results of the animals studies. Increasing glycation caused a corresponding increase in protein insolubilization and the insoluble fraction thus formed also contained more glycated protein. It appears that lens protein glycation, HMW aggregate formation, and protein insolubilization are interrelated.

  7. Ductile crystalline–amorphous nanolaminates

    PubMed Central

    Wang, Yinmin; Li, Ju; Hamza, Alex V.; Barbee, Troy W.

    2007-01-01

    It is known that the room-temperature plastic deformation of bulk metallic glasses is compromised by strain softening and shear localization, resulting in near-zero tensile ductility. The incorporation of metallic glasses into engineering materials, therefore, is often accompanied by complete brittleness or an apparent loss of useful tensile ductility. Here we report the observation of an exceptional tensile ductility in crystalline copper/copper–zirconium glass nanolaminates. These nanocrystalline–amorphous nanolaminates exhibit a high flow stress of 1.09 ± 0.02 GPa, a nearly elastic-perfectly plastic behavior without necking, and a tensile elongation to failure of 13.8 ± 1.7%, which is six to eight times higher than that typically observed in conventional crystalline–crystalline nanolaminates (<2%) and most other nanocrystalline materials. Transmission electron microscopy and atomistic simulations demonstrate that shear banding instability no longer afflicts the 5- to 10-nm-thick nanolaminate glassy layers during tensile deformation, which also act as high-capacity sinks for dislocations, enabling absorption of free volume and free energy transported by the dislocations; the amorphous–crystal interfaces exhibit unique inelastic shear (slip) transfer characteristics, fundamentally different from those of grain boundaries. Nanoscale metallic glass layers therefore may offer great benefits in engineering the plasticity of crystalline materials and opening new avenues for improving their strength and ductility. PMID:17592136

  8. Synthetic Zeolites and Other Microporous Oxide Molecular Sieves

    NASA Astrophysics Data System (ADS)

    Sherman, John D.

    1999-03-01

    Use of synthetic zeolites and other microporous oxides since 1950 has improved insulated windows, automobile air-conditioning, refrigerators, air brakes on trucks, laundry detergents, etc. Their large internal pore volumes, molecular-size pores, regularity of crystal structures, and the diverse framework chemical compositions allow "tailoring" of structure and properties. Thus, highly active and selective catalysts as well as adsorbents and ion exchangers with high capacities and selectivities were developed. In the petroleum refining and petrochemical industries, zeolites have made possible cheaper and lead-free gasoline, higher performance and lower-cost synthetic fibers and plastics, and many improvements in process efficiency and quality and in performance. Zeolites also help protect the environment by improving energy efficiency, reducing automobile exhaust and other emissions, cleaning up hazardous wastes (including the Three Mile Island nuclear power plant and other radioactive wastes), and, as specially tailored desiccants, facilitating the substitution of new refrigerants for the ozone-depleting chlorofluorocarbons banned by the Montreal Protocol.

  9. Aluminum Redistribution during the Preparation of Hierarchical Zeolites by Desilication.

    PubMed

    Mitchell, Sharon; Milina, Maria; Verel, René; Hernández-Rodríguez, Manuel; Pinar, Ana B; McCusker, Lynne B; Pérez-Ramírez, Javier

    2015-09-28

    A literature survey reveals a prominent reduction in the concentration of Brønsted acid sites in hierarchically organized zeolites with increasing mesoporous or external surface area independent of the framework type or synthesis route; this suggests a common fundamental explanation. To determine the cause, nature, and impact of the underlying changes in aluminum speciation, this study combines a multitechnique analysis that integrates basic characterization, a detailed synchrotron XRD and multiple-quantum NMR spectroscopy assessment, and catalytic tests to correlate evolution of the properties with performance during successive steps in the preparation of hierarchical MFI-type zeolites by desilication. The findings, subsequently generalized to FAU- and BEA-type materials, identify the crucial impact of calcination on the protonic form, which is an integral step in the synthesis and regeneration of zeolite catalysts; on aluminum coordination; and the associated acidity trends. PMID:26268428

  10. Direct Dual-Template Synthesis of MWW Zeolite Monolayers.

    PubMed

    Margarit, Vicente J; Martínez-Armero, Marta E; Navarro, M Teresa; Martínez, Cristina; Corma, Avelino

    2015-11-01

    A two-dimensional zeolite with the topology of MWW sheets has been obtained by direct synthesis with a combination of two organic structure-directing agents. The resultant material consists of approximately 70?% single and double layers and displays a well-structured external surface area of about 300?m(2) ?g(-1) . The delaminated zeolite prepared by means of this single-step synthetic route has a high delamination degree, and the structural integrity of the MWW layers is well preserved. The new zeolite material displayed excellent activity, selectivity, and stability when used as a catalyst for the alkylation of benzene with propylene and found to be superior to the catalysts that are currently used for producing cumene. PMID:26381669

  11. The removal of bacteria by modified natural zeolites.

    PubMed

    Milán, Z; de Las Pozas, C; Cruz, M; Borja, R; Sánchez, E; Ilangovan, K; Espinosa, Y; Luna, B

    2001-01-01

    The removal effect of natural and modified zeolites containing different heavy metals (Ni2+, Zn2+, Fe3+ and Cu2+) on pure cultures of Escherichia coli and Staphylococcus aureus in a solid medium was evaluated in this work. These experiments were carried out in a continuous mode treating municipal wastewater. Faecal coliform species and Pseudomonas aeruginosa were identified. The rate constants of heavy metal lixiviation were determined using a first order kinetic model. The removal effect of modified natural zeolites in both a solid medium and in continuous mode showed an increased elimination of the bacterial population. The results established a decreasing order of the removal effect as follows: Cu2+ > Fe3+ > Zn2+ > Ni2+. The best performance of columns was obtained for inlet bacterial concentrations below 10(6) cells/100 ml. Most of the identified bacterial species were affected by copper modified zeolites, although Serratia marcescens presented the highest sensitivity and Klebsiella pneumoniae the greatest resistance. PMID:11501306

  12. Heterogeneous radiolysis of CO 2 in the presence of zeolites

    NASA Astrophysics Data System (ADS)

    Garibov, A. A.; Velibekova, G. Z.; Agayev, T. N.

    Radiation catalytic activity of different zeolites Ca A, Na X, Na Y, LiNa Y, Ba M in CO 2 radiolysis has been investigated. This has led to studies in the catalyst porosity, the number of adsorbed CO 2 molecules and adsorption forces on their surface on the yield of CO 2 radiolysis products. A mechanism has been suggested for the observed CO 2 radiolysis processes over different zeolites. One of the possible ways to increase CO yield in radiolytic processes of CO 2 decomposition is to use various types of catalyst. (1-3) Therefore, the development of a scientific basis for appropriate catalyst selection is becoming of particular interest. For this purpose, heterogeneous CO 2 radiolysis in the presence of high-silica zeolites has been studied in this paper.

  13. Organic zeolites from a diolefinic monomer.

    PubMed

    Guney-Altay, Ozge; Pestov, Dmitry; Tepper, Gary

    2007-11-14

    Submicrometer particles of diethyl p-phenylenediacrylate (EPA) with tunable molecular adsorption characteristics were produced by solid-state photopolymerization in the presence of template molecules. EPA monomer particles were produced by rapid expansion of supercritical solutions (RESS), and deposited directly onto surface acoustic wave (SAW) resonators. The EPA particles were photopolymerized directly on the SAW devices in the presence of molecular templates, and dynamic sorption isotherms of C1- through C9-alkanes were studied to characterize the particle-vapor interaction. The mass increase due to vapor uptake into the particulate coatings was measured by monitoring the SAW resonance frequency during vapor sorption. The vapor selectivity and molecular porosity of the particulate coatings were studied in situ on the piezoelectric substrate by measuring sorption isotherms. A gradual exclusion of smaller alkane molecules from the molecularly imprinted particulate coatings was observed with decreasing template molecule size. The observed selective and reversible adsorption of alkane analytes with different molecular sizes suggest that these imprinted polymers may be categorized as organic analogues of zeolites. PMID:17948997

  14. Formation of hollow and mesoporous structures in single-crystalline microcrystals of metal-organic frameworks via double-solvent mediated overgrowth.

    PubMed

    Chou, Lien-Yang; Hu, Pan; Zhuang, Jia; Morabito, Joseph V; Ng, Ka Chon; Kao, Ya-Chuan; Wang, Shao-Chun; Shieh, Fa-Kuen; Kuo, Chun-Hong; Tsung, Chia-Kuang

    2015-11-19

    The creation of hierarchical porosity in metal-organic frameworks (MOFs) could benefit various applications of MOFs such as gas storage and separation. Having single-crystalline microcrystals instead of poly-crystalline composites is critical for these potential applications of MOFs with hierarchical porosity. We developed a room temperature synthetic method to generate uniform hollow and mesoporous zeolitic imidazolate framework-8 (ZIF-8) microcrystals with a single-crystalline structure via overgrowing a ZIF-8 shell in methanol solution on a ZIF-8 core with water adsorbed in the pores. The cavities formed as a result of the different solvent micro-environment. This double-solvent mediated overgrowth method could be applied to prepare other MOFs with hierarchical porosity. PMID:26538214

  15. Variation in performance of surfactant loading and resulting nitrate removal among four selected natural zeolites.

    PubMed

    Guan, Huade; Bestland, Erick; Zhu, Chuanyu; Zhu, Honglin; Albertsdottir, Dora; Hutson, John; Simmons, Craig T; Ginic-Markovic, Milena; Tao, Xian; Ellis, Amanda V

    2010-11-15

    Surfactant modified zeolites (SMZs) have the capacity to target various types of water contaminants at relatively low cost and thus are being increasingly considered for use in improving water quality. It is important to know the surfactant loading performance of a zeolite before it is put into application. In this work we compare the loading capacity of a surfactant, hexadecyltrimethylammonium bromide (HDTMA-Br), onto four natural zeolites obtained from specific locations in the USA, Croatia, China, and Australia. The surfactant loading is examined using thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, and Raman spectroscopy. We then compare the resulting SMZs performance in removing nitrate from water. Results show that TGA is useful to determine the HDTMA loading capacity on natural zeolites. It is also useful to distinguish between a HDTMA bi-layer and a HDTMA mono-layer on the SMZ surface, which has not been previously reported in the literature. TGA results infer that HDTMA (bi-layer) loading decreases in the order of US zeolite>Croatian zeolite>Chinese zeolite>Australian zeolite. This order of loading explains variation in performance of nitrate removal between the four SMZs. The SMZs remove 8-18 times more nitrate than the raw zeolites. SMZs prepared from the selected US and Croatian zeolites were more efficient in nitrate removal than the two zeolites commercially obtained from Australia and China. PMID:20709446

  16. Monodispersed Ultrafine Zeolite Crystal Particles by Microwave Hydrothermal Synthesis

    SciTech Connect

    Hu, Michael Z.; Harris, Michael Tyrone; Khatri, Lubna

    2008-01-01

    Microwave hydrothermal synthesis of zeolites is reviewed. Monodispersed ultrafine crystal particles of zeolite (Silicalite-1) have been synthesized in batch reactor vessels by microwave irradiation heating of aqueous basic silicate precursor solutions with tetra propyl ammonium hydroxide as the templating molecule. The effects of major process parameters (such as synthesis temperature, microwave heating rate, volume ratio (i.e., the volume of the initial synthesis solution over the total volume of the reactor vessel), and synthesis time on the zeolite particle characteristics are studied using a computer-controlled microwave reactor system that allows real-time monitoring and control of reaction medium temperature. The changes in the morphology, size and crystal structure of the particles are investigated using scanning electron microscope, dynamic light scattering, X-ray diffraction, and BET surface analysis. We have found that the synthesis temperature, volume ratio, and heating rate play a significant role in controlling the particle size, uniformity, and morphology. Microwave processing has generated new morphologies of zeolite particles (i.e., uniform block-shaped particles that contain mixed gel-nanocrystallites and agglomerated crystal particles) that could not be made by a conventional hydrothermal process. At higher synthesis temperature and lower volume ratio, irregular block-shaped particles were produced, whereas increasing the volume ratio promoted the formation of monodispersed single-crystal particles with uniform shape. Our results clearly demonstrate that faster microwave heating is advantageous to enhance the zeolite crystallization kinetics and produces larger-size crystal particles in shorter time. In addition, zeolite crystallization mechanisms, depending on the microwave heating rate, were also discussed.

  17. Novel modified zeolites for energy-efficient hydrocarbon separations.

    SciTech Connect

    Arruebo, Manuel; Dong, Junhang; Anderson, Thomas (Burns and McDonnell, Kansas City, MO); Gu, Xuehong; Gray, Gary (Goodyear Chemical Company, Akron, OH); Bennett, Ron (Goodyear Chemical Company, Akron, OH); Nenoff, Tina Maria; Kartin, Mutlu; Johnson, Kaylynn (Goodyear Chemical Company, Akron, OH); Falconer, John; Noble, Richard

    2006-11-01

    We present synthesis, characterization and testing results of our applied research project, which focuses on the effects of surface and skeletal modification of zeolites for significant enhancements in current hydrocarbon (HC) separations. Zeolites are commonly used by the chemical and petroleum industries as catalysts and ion-exchangers. They have high potential for separations owing to their unique pore structures and adsorption properties and their thermal, mechanical and chemical properties. Because of zeolites separation properties, low cost, and robustness in industrial process, they are natural choice for use as industrial adsorbents. This is a multidisciplinary effort to research, design, develop, engineer, and test new and improved materials for the separation of branched vs. linear organic molecules found in commercially important HC streams via adsorption based separations. The focus of this project was the surface and framework modification of the commercially available zeolites, while tuning the adsorption properties and the selectivities of the bulk and membrane separations. In particular, we are interested with our partners at Goodyear Chemical, on how to apply the modified zeolites to feedstock isoprene purification. For the characterization and the property measurements of the new and improved materials powder X-ray diffraction (PXRD), Residual Gas Analyzer-Mass Spectroscopy (RGA-MS), Electron Microscopy (SEM/EDAX), temperature programmed desorption (TPD) and surface area techniques were utilized. In-situ carbonization of MFI zeolite membranes allowed for the maximum separation of isoprene from n-pentane, with a 4.1% enrichment of the binary stream with n-pentane. In four component streams, a modified MFI membrane had high selectivities for n-pentane and 1-3-pentadiene over isoprene but virtually no separation for the 2-methyl-2-butene/isoprene pair.

  18. Influence of Crystal Expansion/Contraction on Zeolite Membrane Permeation

    SciTech Connect

    Sorenson, Stephanie G; Payzant, E Andrew; Noble, Richard D; Falconer, John L.

    2010-01-01

    X-ray diffraction was used to measure the unit cell parameters of B-ZSM-5, SAPO-34, and NaA zeolite powders as a function of adsorbate loading at 303 K, and in one case, at elevated temperatures. Most adsorbates expanded the zeolite crystals below saturation loading at 303 K: n-hexane and SF6 in B-ZSM-5, methanol and CO2 in SAPO-34, and methanol in NaA zeolite. As the loadings increased, the crystals expanded more. Changes in the unit cell volumes of B-ZSM-5 and SAPO-34 zeolite powders correlated with changes in permeation through zeolite membranes defects. When the zeolite crystals expanded or contracted upon adsorption, the defect sizes decreased or increased. In B-ZSM-5 membranes, the fluxes through defects decreased dramatically when n-hexane or SF6 adsorbed. In contrast, i-butane adsorption at 303 K contracted B-ZSM-5 crystals at low loadings and expanded them at higher loadings. Correspondingly, the flux through B-ZSM-5 membrane defects increased at low i-butane loadings and decreased at high loading because the defects increased in size at low loading and decreased at high loadings. At 398 K and 473 K, n-hexane expanded the B-ZSM-5 unit cell more as the temperature increased from 303 to 473 K. The silicalite-1 and B-ZSM-5 unit cell volumes expanded similarly upon n-hexane adsorption at 303 K; boron substitution had little effect on volume expansion.

  19. Experiments with Zeolites at the Secondary School Level: Experience from The Netherlands

    NASA Astrophysics Data System (ADS)

    Coker, Eric N.; Davis, Pamela J.; Kerkstra, Aonne; van Bekkum, Herman

    1999-10-01

    This article describes a number of experiments that involve zeolites and are suitable for secondary-school chemistry laboratories. The experiments have been introduced successfully into secondary schools in The Netherlands. Zeolites are used in enormous quantities as builders (water softeners) in laundry detergents; they account for 15-30 wt % of most laundry detergents currently on the European market. In a series of experiments, students test the hardness of tap water before and after treatment with some zeolite and perform tests with a range of commercial laundry detergents containing zeolites. Zeolites are also used as catalysts in numerous industrial processes; another experiment described here highlights the use of zeolites as recyclable catalysts in an esterification reaction. A duplicate reaction is carried out in parallel, but using the conventional sulfuric acid catalyst instead of the zeolite. This experiment provides a good example of the benefit of a recyclable, heterogeneous catalyst over the conventional homogeneous one that is discarded as waste material.

  20. Systems including catalysts in porous zeolite materials within a reactor for use in synthesizing hydrocarbons

    DOEpatents

    Rolllins, Harry W. (Idaho Falls, ID); Petkovic, Lucia M. (Idaho Falls, ID); Ginosar, Daniel M. (Idaho Falls, ID)

    2012-07-24

    Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.