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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

    SciTech Connect

    Nicholas, Christopher P; Boldingh, Edwin P

    2013-12-17

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

  3. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    SciTech Connect

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-10-07

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

  4. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    SciTech Connect

    Nicholas, Christpher P; Boldingh, Edwin P

    2013-12-17

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

  5. 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

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

    PubMed

    Muraoka, Koki; Chaikittisilp, Watcharop; Okubo, Tatsuya

    2016-05-18

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

  7. Destructive hydroisomerization of naphtha cuts over zeolitic nickel aluminosilicate catalyst

    SciTech Connect

    Abad-zade, K.I.; Rustamov, M.I.

    1987-05-01

    The authors discuss a process developed for hydroisomerization of low-octane naphtha cuts with the aim of obtaining light isoparaffinic hydrocarbons. A zeolitic Ni-Al-Si catalyst with highly dispersed nickel was synthesized. The characteristics of the naphtha cuts used are provided. Data is given on the influence of temperature on destructive hydroisomerization of the 85-195/sup 0/C cut. It is found that the zeolitic Ni-Al-Si catalyst is adequate in activity so that the naphtha cut can be subjected to thorough destructive hydroisomerization through an ionic mechanism with little formation of C/sub 1/ and C/sub 2/ hydrocarbons.

  8. 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

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

    SciTech Connect

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

    2000-12-01

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

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

    PubMed

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

    2014-02-12

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

  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

  12. Ordered hexagonal mesoporous aluminosilicates synthesized using zeolite as precursor and the wall-thickness tuned by pH control

    NASA Astrophysics Data System (ADS)

    Wang, Chunlei; Zhu, Guangshang; Shang, Tiecun; Cai, Xiaohui; Liu, Chengzhan; Li, Nan; Wei, Yuhong; Li, Jian; Zhang, Weiwei; Qiu, Shilun

    2005-07-01

    High aluminium content mesoporous aluminosilicates MAS-X1 and MAS-X3 have been successfully synthesized using zeolite FAU-X as precursors and triblock copolymer pluronic P123 as structure directing agent. Samples have been characterized by XRD, TEM, nitrogen adsorption/desorption, 27Al MAS NMR, and ICP element analysis techniques. The salt, NaCl, which was introduced by dissolving the zeolite FAU-X, played an important role in the synthesis of high order sample. The secondary growth of the wall was considered to occur after the pH value had been increased up to five.

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

    PubMed

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

    2016-03-14

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

  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. 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.

  16. Quantifying defects in zeolites and zeolite membranes

    NASA Astrophysics Data System (ADS)

    Hammond, Karl Daniel

    Zeolites are crystalline aluminosilicates that are frequently used as catalysts to transform chemical feedstocks into more useful materials in a size- or shape-selective fashion; they are one of the earliest forms of nanotechnology. Zeolites can also be used, especially in the form of zeolite membranes (layers of zeolite on a support), to separate mixtures based on the size of the molecules. Recent advances have also created the possibility of using zeolites as alkaline catalysts, in addition to their traditional applications as acid catalysts and catalytic supports. Transport and catalysis in zeolites are greatly affected by physical and chemical defects. Such defects can be undesirable (in the case of zeolite membranes), or desirable (in the case of nitrogen-doped alkaline zeolites). Studying zeolites at the relevant length scales requires indirect experimental methods such as vapor adsorption or atomic-scale modeling such as electronic structure calculations. This dissertation explores both experimental and theoretical characterization of zeolites and zeolite membranes. Physical defects, important in membrane permeation, are studied using physical adsorption experiments and models of membrane transport. The results indicate that zeolite membranes can be modeled as a zeolite powder on top of a support---a "supported powder," so to speak---for the purposes of adsorption. Mesoporosity that might be expected based on permeation and confocal microscopy measurements is not observed. Chemical defects---substitutions of nitrogen for oxygen---are studied using quantum mechanical models that predict spectroscopic properties. These models provide a method for simulating the 29Si NMR spectra of nitrogendefected zeolites. They also demonstrate that nitrogen substitutes into the zeolite framework (not just on the surface) under the proper reaction conditions. The results of these studies will be valuable to experimentalists and theorists alike in our efforts to understand the

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

    NASA Astrophysics Data System (ADS)

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

    2011-07-01

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

  18. 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

  19. 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

  20. 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.

  1. 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.

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

    PubMed

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

    2001-11-16

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

  3. Influence of starting zeolite on synthesis of RUT type zeolite by interzeolite conversion method

    NASA Astrophysics Data System (ADS)

    Itakura, Masaya; Ota, Kai; Shibata, Shohei; Inoue, Takayuki; Ide, Yusuke; Sadakane, Masahiro; Sano, Tsuneji

    2011-01-01

    In this study, hydrothermal conversions of *BEA and FAU type zeolites using various structure-directing agents were carried out. Highly crystalline and pure RUT type zeolites were obtained from both zeolites in the presence of tetramethylammonium hydroxide. There were no major differences between the characteristics of the RUT type zeolites obtained from the two starting zeolites. However, the Si/Al ratio and the crystallization rate of the RUT type zeolites were strongly dependent on both the framework structure and the Si/Al ratio of the starting zeolite. That is, the crystallization rate of the RUT type zeolite from the *BEA type zeolite did not depend on the Si/Al ratio of the starting *BEA type zeolite, whereas the crystallization rate of the RUT type zeolite from the FAU type zeolite was dependent on the Si/Al ratio of the starting FAU type zeolite. This suggests that the chemical structure and the concentration of locally ordered aluminosilicate species produced by the decomposition/dissolution of the starting zeolite can be altered by changing the framework structure of the zeolite.

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

    SciTech Connect

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

    2014-11-15

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

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

    PubMed

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

    2014-11-01

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

  6. 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…

  7. 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

  8. Crystalline-like molecularly ordered mesoporous aluminosilicates derived from aluminosilica-surfactant mesophases via benign template removal.

    PubMed

    Xia, Yongde; Mokaya, Robert

    2006-05-11

    We report the preparation of mesoporous aluminosilicate materials that exhibit molecular-scale ordering in their pore wall framework. The materials were derived from mesoporous aluminosilica-surfactant mesophases via benign template removal methods, which allowed the retention of molecular ordering in surfactant-free materials. The molecularly ordered aluminosilica-surfactant mesophases were obtained from hydrothermal crystallization of cetyltrimethylammonium hydroxide/Al,Si/H2O systems at 135 degrees C for 12 days. Benign template removal via H2O2-mediated oxidation of the surfactant at room temperature was found to be the most effective method in generating surfactant-free materials with molecular ordering, high textural properties (depending on Al content), and high acidity. The Al in the resulting aluminosilicates was entirely incorporated in framework (tetrahedrally coordinated) sites. Template extraction in acidified ethanol also generated molecularly ordered materials but compromised the Al content and acidity. Template removal via conventional calcination generated porous materials with high textural properties but which exhibited only limited molecular ordering and had relatively low acidity and significant amounts of nonframework Al. This work demonstrates that molecular ordering in mesoporous silicate-surfactant mesophases is due to crystallographic ordering within inorganic frameworks rather than the arrangement/packing of surfactant molecules. PMID:16671724

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

    PubMed

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

    2016-03-22

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

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  12. Beryllosilicate frameworks and zeolites.

    PubMed

    Armstrong, Jennifer A; Weller, Mark T

    2010-11-10

    Using inspiration derived from studying naturally occurring minerals, a series of framework beryllosilicates have been synthesized under hydrothermal conditions. These include two new zeolite topologies, a unique layered beryllosilicate, and beryllosilicate analogues of numerous aluminosilicate zeolites. Materials with the structure of the rare zeolite mineral nabesite have been synthesized for the first time, including both sodium and potassium derivatives. The structural chemistry of these beryllosilicates frameworks is discussed with reference to the networks of linked tetrahedra, which include the first instance of pentagonal, two-dimensional Cairo-tiling of silicate tetrahedra in one of the new zeolite topologies, their porosity, and their thermal stability. PMID:20949941

  13. Synthesis strategies in the search for hierarchical zeolites.

    PubMed

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

    2013-05-01

    Great interest has arisen in the past years in the development of hierarchical zeolites, having at least two levels of porosities. Hierarchical zeolites show an enhanced accessibility, leading to improved catalytic activity in reactions suffering from steric and/or diffusional limitations. Moreover, the secondary porosity offers an ideal space for the deposition of additional active phases and for functionalization with organic moieties. However, the secondary surface represents a discontinuity of the crystalline framework, with a low connectivity and a high concentration of silanols. Consequently, hierarchical zeolites exhibit a less "zeolitic behaviour" than conventional ones in terms of acidity, hydrophobic/hydrophilic character, confinement effects, shape-selectivity and hydrothermal stability. Nevertheless, this secondary surface is far from being amorphous, which provides hierarchical zeolites with a set of novel features. A wide variety of innovative strategies have been developed for generating a secondary porosity in zeolites. In the present review, the different synthetic routes leading to hierarchical zeolites have been classified into five categories: removal of framework atoms, surfactant-assisted procedures, hard-templating, zeolitization of preformed solids and organosilane-based methods. Significant advances have been achieved recently in several of these alternatives. These include desilication, due to its versatility, dual templating with polyquaternary ammonium surfactants and framework reorganization by treatment with surfactant-containing basic solutions. In the last two cases, the materials so prepared show both mesoscopic ordering and zeolitic lattice planes. Likewise, interesting results have been obtained with the incorporation of different types of organosilanes into the zeolite crystallization gels, taking advantage of their high affinity for silicate and aluminosilicate species. Crystallization of organofunctionalized species favours the

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

    PubMed

    Hui, K S; Chao, C Y H

    2006-09-01

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

  15. X‐ray Excited Optical Fluorescence and Diffraction Imaging of Reactivity and Crystallinity in a Zeolite Crystal: Crystallography and Molecular Spectroscopy in One

    PubMed Central

    Ristanović, Zoran; Hofmann, Jan P.; Richard, Marie‐Ingrid; Jiang, Tao; Chahine, Gilbert A.; Schülli, Tobias U.; Meirer, Florian

    2016-01-01

    Abstract Structure–activity relationships in heterogeneous catalysis are challenging to be measured on a single‐particle level. For the first time, one X‐ray beam is used to determine the crystallographic structure and reactivity of a single zeolite crystal. The method generates μm‐resolved X‐ray diffraction (μ‐XRD) and X‐ray excited optical fluorescence (μ‐XEOF) maps of the crystallinity and Brønsted reactivity of a zeolite crystal previously reacted with a styrene probe molecule. The local gradients in chemical reactivity (derived from μ‐XEOF) were correlated with local crystallinity and framework Al content, determined by μ‐XRD. Two distinctly different types of fluorescent species formed selectively, depending on the local zeolite crystallinity. The results illustrate the potential of this approach to resolve the crystallographic structure of a porous material and its reactivity in one experiment via X‐ray induced fluorescence of organic molecules formed at the reactive centers. PMID:27145171

  16. X‐ray Excited Optical Fluorescence and Diffraction Imaging of Reactivity and Crystallinity in a Zeolite Crystal: Crystallography and Molecular Spectroscopy in One

    PubMed Central

    Ristanović, Zoran; Hofmann, Jan P.; Richard, Marie‐Ingrid; Jiang, Tao; Chahine, Gilbert A.; Schülli, Tobias U.; Meirer, Florian

    2016-01-01

    Abstract Structure–activity relationships in heterogeneous catalysis are challenging to be measured on a single‐particle level. For the first time, one X‐ray beam is used to determine the crystallographic structure and reactivity of a single zeolite crystal. The method generates μm‐resolved X‐ray diffraction (μ‐XRD) and X‐ray excited optical fluorescence (μ‐XEOF) maps of the crystallinity and Brønsted reactivity of a zeolite crystal previously reacted with a styrene probe molecule. The local gradients in chemical reactivity (derived from μ‐XEOF) were correlated with local crystallinity and framework Al content, determined by μ‐XRD. Two distinctly different types of fluorescent species formed selectively, depending on the local zeolite crystallinity. The results illustrate the potential of this approach to resolve the crystallographic structure of a porous material and its reactivity in one experiment via X‐ray induced fluorescence of organic molecules formed at the reactive centers. PMID:27478278

  17. X-ray Excited Optical Fluorescence and Diffraction Imaging of Reactivity and Crystallinity in a Zeolite Crystal: Crystallography and Molecular Spectroscopy in One.

    PubMed

    Ristanović, Zoran; Hofmann, Jan P; Richard, Marie-Ingrid; Jiang, Tao; Chahine, Gilbert A; Schülli, Tobias U; Meirer, Florian; Weckhuysen, Bert M

    2016-06-20

    Structure-activity relationships in heterogeneous catalysis are challenging to be measured on a single-particle level. For the first time, one X-ray beam is used to determine the crystallographic structure and reactivity of a single zeolite crystal. The method generates μm-resolved X-ray diffraction (μ-XRD) and X-ray excited optical fluorescence (μ-XEOF) maps of the crystallinity and Brønsted reactivity of a zeolite crystal previously reacted with a styrene probe molecule. The local gradients in chemical reactivity (derived from μ-XEOF) were correlated with local crystallinity and framework Al content, determined by μ-XRD. Two distinctly different types of fluorescent species formed selectively, depending on the local zeolite crystallinity. The results illustrate the potential of this approach to resolve the crystallographic structure of a porous material and its reactivity in one experiment via X-ray induced fluorescence of organic molecules formed at the reactive centers. PMID:27145171

  18. Nanoscale encapsulation: the structure of cations in hydrophobic microporous aluminosilicates

    SciTech Connect

    Wasserman, S.R.; Yuchs, S.E.; Giaquinta, D.; Soderholm, L.; Song, Kang

    1996-10-01

    Hydrophobic microporous aluminosilicates, created by organic surface modification of inherently hydrophilic materials such as zeolites and clays, are currently being investigated as storage media for hazardous cations. Use of organic monolayers to modify the surface of an aluminosilicate after introducing an ion into the zeolite/clay reduces the interaction of water with the material. Resulting systems are about 20 times more resistant to leaching of stored ion. XAS spectra from the encapsulated ion demonstrate that byproducts from the organic modifier can complex with the stored cation. This complexation can result in a decreased affinity of the cation for the aluminosilicate matrix. Changing the organic modifier eliminates this problem. XAS spectra also indicate that the reactivity and speciation of the encapsulated ion may change upon application of the hydrophobic layer.

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

    SciTech Connect

    Raman, S.

    1993-12-01

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

  20. Calibration analysis of zeolites by laser induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  1. Rapid synthesis of beta zeolites

    SciTech Connect

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

    2015-08-18

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

  2. Tailored crystalline microporous materials by post-synthesis modification.

    PubMed

    Valtchev, Valentin; Majano, Gerardo; Mintova, Svetlana; Pérez-Ramírez, Javier

    2013-01-01

    Crystalline microporous solids are an important class of inorganic materials with uses in different areas impacting our everyday lives, namely as catalysts, adsorbents, and ion exchangers. Advancements in synthesis have been invaluable in expanding the classical aluminosilicate zeolites to new unique framework types and compositions, motivating innovative developments. However, the inexhaustible post-synthetic options to tailor zeolite properties have been and will continue to be indispensable to realize emerging and to improve conventional applications. Starting from the routine drying and template removal processes that every zeolite must experience prior to use, a wide spectrum of treatments exists to alter individual or collective characteristics of these materials for optimal performance. This review documents the toolbox of post-synthetic strategies available to tune the properties of zeolitic materials for specific functions. The categorisation is based on the scale at which the alteration is aimed at, including the atomic structure (e.g. the introduction, dislodgment, or replacement of framework atoms), the micropore level (e.g. template removal and functionalisation by inorganic and organic species), and the crystal and particle levels (e.g. the introduction of auxiliary porosity). Through examples in the recent literature, it is shown that the combination of post-synthetic methods enables rational zeolite design, extending the characteristics of these materials way beyond those imposed by the synthesis conditions. PMID:22996351

  3. Zeolite synthesis: an energetic perspective.

    PubMed

    Zwijnenburg, Martijn A; Bromley, Stefan T

    2010-11-21

    Taking |D(H(2)O)(x)|[AlSiO(4)] based materials (where D is Li, Na, K, Rb or Cs) as an archetypal aluminosilicate system, we use accurate density functional theory calculations to demonstrate how the substitution of silicon cations in silica, with pairs of aluminium and (alkali metal) cations, changes the energetic ordering of different competing structure-types. For large alkali metal cations we further show that the formation of porous aluminosilicate structures, the so-called zeolites, is energetically favored. These findings unequivocally demonstrate that zeolites can be energetic preferred reaction products, rather than being kinetically determined, and that the size of the (hydrated) cations in the pore, be it inorganic or organic, is critical for directing zeolite synthesis. PMID:20938518

  4. Microprobes aluminosilicate ceramic membranes

    DOEpatents

    Anderson, Marc A.; Sheng, Guangyao

    1993-01-01

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

  5. 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''.

  6. Synthesis of MCM-22 zeolite by an ultrasonic-assisted aging procedure.

    PubMed

    Wang, Baoyu; Wu, Jianmei; Yuan, Zhong-Yong; Li, Niu; Xiang, Shouhe

    2008-04-01

    The synthesis of MCM-22 zeolite under hydrothermal crystallization conditions has been performed by an ultrasonic-assisted aging procedure. The ultrasonic-assisted aging of the initial aluminosilicate gel can shorten the crystallization time of MCM-22, decrease the amount of hexamethyleneimine (HMI) used, and broaden the range of SiO(2)/Al(2)O(3) ratios. By using the ultrasonic aging, pure phase of high-silica MCM-22 products with SiO(2)/Al(2)O(3)>100 can be obtained. When SiO(2)/Al(2)O(3) crystalline MCM-22 zeolites with the reduced average crystal sizes can be made even with low HMI/SiO(2) ratio of 0.05 under static crystallization conditions. The acoustic cavitation of the ultrasonic is believed to be responsible for these positive results due to its cracking the crystal seeds and improving the solubility of silicate species. PMID:17845863

  7. On the Mesoporogen-Free Synthesis of Single-Crystalline Hierarchically Structured ZSM-5 Zeolites in a Quasi-Solid-State System.

    PubMed

    Ge, Tongguang; Hua, Zile; He, Xiaoyun; Lv, Jian; Chen, Hangrong; Zhang, Lingxia; Yao, Heliang; Liu, Ziwei; Lin, Chucheng; Shi, Jianlin

    2016-06-01

    Hierarchically structured zeolites (HSZs) have gained much academic and industrial interest owing to their multiscale pore structures and consequent excellent performances in varied chemical processes. Although a number of synthetic strategies have been developed in recent years, the scalable production of HSZs single crystals with penetrating and three-dimensionally (3-D) interconnected mesopore systems but without using a mesoscale template is still a great challenge. Herein, based on a steam-assisted crystallization (SAC) method, we report a facile and scalable strategy for the synthesis of single-crystalline ZSM-5 HSZs by using only a small amount of micropore-structure-directing agents (i.e., tetrapropylammonium hydroxide). The synthesized materials exhibited high crystallinity, a large specific surface area of 468 m(2)  g(-1) , and a pore volume of 0.43 cm(3)  g(-1) without sacrificing the microporosity (≈0.11 cm(3)  g(-1) ) in a product batch up to 11.7 g. Further, a kinetically controlled nucleation-growth mechanism is proposed for the successful synthesis of single-crystalline ZSM-5 HSZs with this novel process. As expected, compared with the conventional microporous ZSM-5 and amorphous mesoporous Al-MCM-41 counterparts, the synthesized HSZs exhibited significantly enhanced activity and stability and prolonged lifetime in model reactions, especially when bulky molecules were involved. PMID:27106662

  8. 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

  9. Accelerated crystallization of zeolites via hydroxyl free radicals.

    PubMed

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

    2016-03-11

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

  10. 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

  11. 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.

  12. Properties and applications of zeolites.

    PubMed

    Rhodes, Christopher J

    2010-01-01

    Zeolites are aluminosilicate solids bearing a negatively charged honeycomb framework of micropores into which molecules may be adsorbed for environmental decontamination, and to catalyse chemical reactions. They are central to green-chemistry since the necessity for organic solvents is minimised. Proton-exchanged (H) zeolites are extensively employed in the petrochemical industry for cracking crude oil fractions into fuels and chemical feedstocks for other industrial processes. Due to their ability to perform cation-exchange, in which the cations that are originally present to counterbalance the framework negative charge may be exchanged out of the zeolite by cations present in aqueous solution, zeolites are useful as industrial water-softeners, in the removal of radioactive Cs+ and Sr2+ cations from liquid nuclear waste and in the removal of toxic heavy metal cations from groundwaters and run-off waters. Surfactant-modified zeolites (SMZ) find particular application in the co-removal of both toxic anions and organic pollutants. Toxic anions such as arsenite, arsenate, chromate, cyanide and radioactive iodide can also be removed by adsorption into zeolites that have been previously loaded with co-precipitating metal cations such as Ag+ and Pb2+ which form practically insoluble complexes that are contained within the zeolite matrix. PMID:21047018

  13. 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.

  14. Cracking process with catalyst of combined zeolites

    SciTech Connect

    Gladrow, E. M.; Winter, W. E.

    1981-09-01

    A hydrocarbon cracking catalyst comprises an ultrastable y-type crystalline zeolite, a small pore crystalline zeolite such as mordenite, an inorganic oxide matrix and, optionally, a porous inert component. The cracking catalyst has a high activity and selectivity for the production of high octane naphtha fractions from higher boiling point hydrocarbonaceous oils. Catalytic cracking processes utilizing the catalyst are also provided.

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

    PubMed

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

    2015-02-01

    C-dots obtained in the homogeneous phase may exhibit a broad particle size distribution. The formation of C-dots within nanometric reaction cavities could be a methodology to gain control on their size distribution. Among the various possibilities, in the present work, the cavities of small pore size zeolites have been used to confine C-dots generated by the pyrolysis of the organic structure directing agent present in the synthesis of these crystalline aluminosilicates. To explore this methodology, ITQ-29 zeolite having a Linde type A (LTA) structure was prepared as pure silica with 4-methyl-2,3,6,7-tetrahydro-1H,5H-pyrido[3.2.1-ij]quinolinium as the organic structure directing agent. Pyrolysis under an inert atmosphere at 550 °C of a pure-silica ITQ-29 sample (cubic particles of 4 μm edge) renders a highly fluorescent zeolite containing about 15 wt% of the carbonised residue. While another small pore zeolite, ITQ-12 (ITW), also renders photoluminescent C-dots under similar conditions, medium or large pore zeolites, such as silicalite (MFI) or pure silica Beta (BEA), failed to produce fluorescent powders under analogous thermal treatment and only decomposition and complete removal of the corresponding quaternary ammonium ion templates was observed for these zeolites. The dissolution of the pyrolysed ITQ-29 zeolite framework and the extraction of the carbon residue with ethyl acetate have allowed the characterisation of C-dots with particle sizes between 5 and 12 nm and a photoluminescence quantum yield of 0.4 upon excitation at 350 nm that is among the highest reported for non-surface functionalized C-dots. Photoluminescence varies with the excitation wavelength and is quenched by oxygen. Pyrolysed ITQ-29 powders can act as fluorescent oxygen sensors. PMID:25516465

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  17. Uranium and Aluminosilicate Surface Precipitation Tests

    SciTech Connect

    Hu, M.Z.

    2002-11-27

    The 2H evaporator at the Savannah River Site has been used to treat an aluminum-rich waste stream from canyon operations and a silicon-rich waste stream from the Defense Waste Processing Facility. The formation of aluminosilicate scale in the evaporator has caused significant operational problems. Because uranium has been found to accumulate in the aluminosilicate solids, the scale deposition has introduced criticality concerns as well. The objective of the tests described in this report is to determine possible causes of the uranium incorporation in the evaporator scale materials. The scope of this task is to perform laboratory experiments with simulant solutions to determine if (1) uranium can be deposited on the surfaces of various sodium aluminosilicate (NAS) forms and (2) aluminosilicates can form on the surfaces of uranium-containing solids. Batch experiments with simulant solutions of three types were conducted: (1) contact of uranium solutions/sols with NAS coatings on stainless steel surfaces, (2) contact of uranium solutions with NAS particles, and (3) contact of precipitated uranium-containing particles with solutions containing aluminum and silicon. The results show that uranium can be incorporated in NAS solids through encapsulation in bulk agglomerated NAS particles of different phases (amorphous, zeolite A, sodalite, and cancrinite) as well as through heterogeneous deposition on the surfaces of NAS coatings (amorphous and cancrinite) grown on stainless steel. The results also indicate that NAS particles can grow on the surfaces of precipitated uranium solids. Particularly notable for evaporator operations is the finding that uranium solids can form on existing NAS scale, including cancrinite solids. If NAS scale is present, and uranium is in sufficient concentration in solution to precipitate, a portion of the uranium can be expected to become associated with the scale. The data obtained to date on uranium-NAS affinity are qualitative. A necessary

  18. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

    Lead (Pb) is a hazardous pollutant commonly found in aquatic ecosystems. Among several methods available, the addition of sorbent amendments to soils or sediments is attractive, since its application is relatively simple, while it can also be cost effective when a low cost and re-usable sorbent is used; e.g. natural zeolites. Zeolites are crystalline aluminosilicates with a three-dimensional structure composed of a set of cavities occupied by large ions and water molecules. Zeolites can accommodate a wide variety of cations, such as Na+, K+, Ca2+, Mg2+, which are rather loosely held and can readily be exchanged for others in an aqueous solution. Natural zeolites are capable of removing cations, such as lead, from aqueous solutions by ion exchange. There is a wide variation in the cation exchange capacity (CEC) of natural zeolites because of the different nature of various zeolites cage structures, natural structural defects, adsorbed ions, and their associated gangue minerals. Naturally occurring zeolites are rarely pure and are contaminated to varying degrees by other minerals, such as clays and feldspars, metals, quartz, or other zeolites as well. These impurities affect the CEC even for samples originated from the same region but from a different source. CEC of the material increases with decreasing impurity content. Potentially exchangeable ions in such impurities do not necessarily participate in ion exchange mechanism, while, in some cases, impurities may additionally block the access to active sites. For zeoliferous rocks having the same percentage of a zeolitic phase, the CEC increases with decreasing Si/Al ratio, as the more Si ions are substituted by Al ions, the more negative the valence of the matrix becomes. Sodium seems to be the most effective exchangeable ion for lead. On the contrary, it is unlikely that the potassium content of the zeolite would be substituted. A pretreatment with high concentration solutions of Na, such as 2 M NaCl, can

  20. Synthesis of ‘unfeasible’ zeolites

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  1. Modeling the local structure and energetics of protozeolitic nanoclusters in hydrothermally stable aluminosilicate mesostructures.

    PubMed

    Li, Hong; Mahanti, S D; Pinnavaia, Thomas J

    2005-02-24

    The density functional theory (DFT) method is used to investigate the structure and bonding of silica and aluminosilicate nanoclusters containing five- and six-membered oxygen rings. The clusters, which are derived from the BEA zeolite structure, are considered as models of the protozeolitic clusters that are incorporated into the pore walls of steam stable aluminosilicate mesostructures assembled from zeolite seeds. Two locally different Brønsted acid sites in the aluminosilicate structure are identified for the adsorption of a water molecule. The sterically more open acid site is favored for water binding. The stability of the aluminosilicate structure in the presence of H2O molecule is studied by breaking an Al-O bond and inserting a water molecule into the five-membered ring structure. We find that an excitation energy at least 18 times larger than the room-temperature thermal energy is needed to break the stable five-membered ring structure, implying a high hydrothermal stability and acidity for this aluminosilicate structure. PMID:16851274

  2. 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

  3. Synthesis of Giant Zeolite Crystals by a Bulk-Material Dissolution Technique.

    PubMed

    Shimizu; Hamada

    1999-09-01

    Using a quartz glass tube as a bulk silica source under aqueous hydrothermal conditions afforded giant crystals of MFI zeolite about 3 mm in size (see photo). Similar procedures were successfully applied to bulk aluminosilicate ceramics to synthesize large crystals of other zeolites, such as ANA, JBW, CAN, and SOD. PMID:10508361

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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....

  9. 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....

  10. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

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

  11. 21 CFR 182.2727 - Sodium aluminosilicate.

    Code of Federal Regulations, 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....

  12. 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....

  13. 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....

  14. 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....

  15. 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...

  16. 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....

  17. 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....

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

    PubMed

    Vinh-Thang, Hoang; Huang, Qinglin; Ungureanu, Adrian; Eić, 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

  19. Dry-gel synthesis of shaped binderless zeolites composed of nanosized ZSM-5

    NASA Astrophysics Data System (ADS)

    Yue, Ming Bo; Yang, Na; Jiao, Wen Qian; Wang, Yi Meng; He, Ming-Yuan

    2013-06-01

    Shaped binderless ZSM-5 zeolites are prepared via a dry-gel conversion (DGC) technique from aluminosilicate extrudates, where the addition of seed gels not only provides crystal nuclei for rapid crystallization of zeolite but also controls the size of ZSM-5 crystal. Furthermore, the introduction of amine into the steam favors the formation of nanosized ZSM-5 zeolite. Especially, the morphology of these aluminosilicate extrudates well kept in the crystallization process. The obtained shaped zeolites are characterized by X-ray diffraction (XRD), nitrogen adsorption analysis, and scanning electron micrographs (SEM). The shaped zeolites show hierarchical structure with high mesopore volume (0.22 cm3 g-1) and demonstrate similar activity as commercial ZSM-5 samples in the transformation of i-propanol to hydrocarbons reaction.

  20. Hydrocarbon cracking with mixture of zeolites y and zsm-5

    SciTech Connect

    Gladrow, E.M.; Winter, W.E.

    1981-09-15

    A hydrocarbon cracking catalyst comprises an ultrastable y-type crystalline zeolite, a small pore crystalline zsm-type zeolite, an inorganic oxide matrix and, optionally, a porous inert component. The cracking catalyst has a high activity and selectivity for the production of high octane naphtha fractions from higher boiling point hydrocarbonaceous oils. Catalytic cracking processes utilizing the catalyst are also provided.

  1. Amorphous and nanostructured silica and aluminosilicate spray-dried microspheres

    NASA Astrophysics Data System (ADS)

    Todea, M.; Turcu, R. V. F.; Frentiu, B.; Tamasan, M.; Mocuta, H.; Ponta, O.; Simon, S.

    2011-08-01

    Amorphous silica and aluminosilicate microspheres with diameters in the 0.1-20 μm range were produced by spray drying method. SEM, TEM and AFM images showed the spherical shape of the obtained particles. Based on thermal analysis data, several heat treatments have been applied on the as-prepared samples in order to check the amorphous state stability of the microspheres and to develop nanosized crystalline phases. As-prepared microspheres remain amorphous up to 1400 °C. By calcination at 1400 °C, cristobalite type nanocrystals are developed on silica sample, while in aluminosilicate sample first are developed mullite type nanocrystals and only after prolonged treatment are developed also cristobalite type nanocrystals. 29Si and 27Al MAS NMR results show that the local order around aluminum and silicon atoms strongly depend on the thermal history of the microspheres.

  2. Conventional hydrothermal synthesis of Na-A zeolite from cupola slag and aluminum sludge.

    PubMed

    Anuwattana, Rewadee; Khummongkol, Pojanie

    2009-07-15

    Na-A type zeolites were prepared from two industrial wastes: the solid by-product of cupola slag and aluminum sludge from an aluminum plating plant. Two preparation methods using the same starting material compositions were carried out. In the first method, alkaline fusion was introduced, followed by the hydrothermal treatment to obtain sodium aluminosilicate which was then crystallized in NaOH solution under the condition of 90+/-3 degrees C for 1-9h with different H(2)O/SiO2 ratios. The result shows that higher H(2)O/SiO2 ratio increases the rate of crystallization. The largest amount of crystallinity for Na-A was found at 3h. In the second method, alkaline hydrothermal treatment without fusion was carried out in the same condition as the first method. No Na-A zeolite was obtained by this method. The changes of the dissolved amounts of Si(4+) and Al(3+) in 3M NaOH were investigated during the hydrothermal reaction. PMID:19111982

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

    NASA Technical Reports Server (NTRS)

    Wiesner, Valerie L.; Bansal, Narottam P.

    2015-01-01

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

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

    PubMed

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

    2015-05-28

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

  5. Synthesis and characterization of a new zeolite of the offretite type

    SciTech Connect

    Occelli, M.L.; Perrotta, A.J.

    1982-03-01

    Offretite is an hexagonal zeolite first discovered by Professor Gonnard in 1890 in amygdaloidal basalt at Mount Semiouse near Montbreson, France. Offretite has been synthesized by Rubin and Aiello and Barrer from aluminosilicate hydrogels in a TMA (tetramethylammonium)-KOH-NaOH mixed base system. Aiello and Barrer noted that this zeolite can be grown from gels in the presence of KOH-TMAOH but not in the presence of NaOH-TMAOH. Sand has shown that offretite can be synthesized without TMA-OH from NaOH-KOH solutions. The synthesis of offretite crystals always included the presence of potassium ions until fairly recently when Barrer and Sieber were able to crystallize this zeolite from a LiOH-CsOH-TMAOH containing hydrogel. It is the purpose of this paper to describe the Perrotta synthesis of a new zeolite of the offretite type crystallized from a potassium free, aluminosilicate hydrogel in the presence of Rb-TMA ions.

  6. Mesoporous aluminosilicates with ordered hexagonal structure, strong acidity, and extraordinary hydrothermal stability at high temperatures.

    PubMed

    Zhang, Z; Han, Y; Xiao, F S; Qiu, S; Zhu, L; Wang, R; Yu, Y; Zhang, Z; Zou, B; Wang, Y; Sun, H; Zhao, D; Wei, Y

    2001-05-30

    Highly ordered hexagonal mesoporous aluminosilicates (MAS-5) with uniform pore sizes have been successfully synthesized from assembly of preformed aluminosilcate precursors with cetyltrimethylammonium bromide (CTAB) surfactant. The aluminosilicate precursors were obtained by heating, at 100--140 degrees C for 2--10 h, aluminasilica gels at the Al(2)O(3)/SiO(2)/TEAOH/H(2)O molar ratios of 1.0/7.0--350/10.0--33.0/500--2000. Mesoporous MAS-5 shows extraordinary stability both in boiling water (over 300 h) and in steam (800 degrees C for 2 h). Temperature-programmed desorption of ammonia shows that the acidic strength of MAS-5 is much higher than that of MCM-41 and is comparable to that of microporous Beta zeolite. In catalytic cracking of 1,3,5-triisopropylbenzene and alkylation of isobutane with butene, MAS-5 exhibits greater catalytic activity and selectivity, as compared with MCM-41 and HZSM-5. The MAS-5 samples were characterized with infrared, UV--Raman, and NMR spectroscopy and numerous other techniques. The results suggest that MAS-5 consists of both mesopores and micropores and that the pore walls of MAS-5 contain primary and secondary structural building units, similar to those of microporous zeolites. Such unique structural features might be responsible for the observed strong acidity and high thermal stability of the mesoporous aluminosilicates with well-ordered hexagonal symmetry. PMID:11457329

  7. A new approach to the determination of atomic-architecture of amorphous zeolite precursors by high-energy X-ray diffraction technique.

    PubMed

    Wakihara, Toru; Kohara, Shinji; Sankar, Gopinathan; Saito, Seijiro; Sanchez-Sanchez, Manuel; Overweg, Arian R; Fan, Wei; Ogura, Masaru; Okubo, Tatsuya

    2006-01-14

    The structure of amorphous precursor species formed under hydrothermal conditions, prior to the onset of crystallization of microporous aluminosilicate zeolites, is determined employing high-energy X-ray diffraction (HEXRD). The investigation, combined with the use of reverse Monte Carlo modelling suggests that even numbered rings, especially 4R (R: ring) and 6R, which are the dominant aluminosilicate rings in zeolite A, have already been produced in the precursor. The model implies that the formation of double 4Rs occurs at the final step of the crystallization of zeolite A. PMID:16482264

  8. [Raman active vibrations of aluminosilicates].

    PubMed

    Pan, Feng; Yu, Xue-hui; Mo, Xuan-xue; You, Jing-lin; Wang, Chen; Chen, Hui; Jiang, Guo-chang

    2006-10-01

    Raman spectra of aluminosilicate minerals, namely kyanite, andalusite, and sillimanite and K2O-Al2O3-SiO2 glasses were recorded. Four alumino-silicon tetrahedral model clusters were calculated by self-consistent (SCF) molecular orbital ab-ini-tio calculation of the quantum chem (QC) method. The result shows a decrease tendency in Raman frequencies in the 800-1200 cm(-1) frequency region with increase in four-coordinated Al content, which is assigned to the Si--Onb symmetry stretching vibrations. The Raman spectra in the 700-800 cm(-1) frequency region is attributed to Al-Onb symmetry stretching vibrations. PMID:17205741

  9. 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.

  10. 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.

  11. Synthesis of NaY zeolite on preformed kaolinite spheres. Evolution of zeolite content and textural properties with the reaction time

    SciTech Connect

    Basaldella, E.I.; Bonetto, R.; Tara, J.C. )

    1993-04-01

    The synthesis of NaY zeolite was carried out on fired kaolinite microspheres. Changes in porosity, chemical composition, and crystallinity of the solid show zeolite growth on both internal and external microsphere surfaces. It was also observed that, as a consequence of the alkaline treatment, the SiO[sub 2]/Al[sub 2]O[sub 3] ratio in the solid diminishes prior to the appearance of the zeolite, but increases when the zeolite begins to crystallize.

  12. 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

  13. Effect of ultrasound on the synthesis of low-modulus zeolites from a metakaolin.

    PubMed

    Gordina, Natalya E; Prokof'ev, Valery Yu; Kul'pina, Yuliya N; Petuhova, Nina V; Gazahova, Sevil I; Hmylova, Olga E

    2016-11-01

    It was studied the effect of ultrasonic processing (22kHz) of the aqueous suspension of metakaolin, sodium hydroxide and alumina with a molar ratio 2Al2Si2O7:12NaOH:2Al2O3 on the low-modulus zeolite synthesis processes. To investigate the XRD, SEM, IR, EDS had been used. It was shown that after ultrasonic processing, sodium aluminates are formed, what leads to a change in process of further synthesis. It was found that without ultrasonic processing on the stage of thermal treatment at 650°C, SOD zeolite (|Na6|[Al6Si6O24]) and sodium aluminosilicate (Na6Al4Si4O17) are synthesized. In the sample after ultrasound during thermal treatment, only sodium aluminosilicates of cubic syngony (Na6Al4Si4O17 and Na8Al4Si4O18) are formed. It was demonstrated that sodium aluminosilicates are precursors for the formation of LTA zeolite (|Na12|[Al12Si12O48]). As a result zeolitization of sodium aluminosilicates after the hydrothermal crystallization in alkaline solution, the sonicated sample contained 97wt% LTA. Without ultrasonic processing, the product of synthesis contained 50wt% SOD and 40wt% LTA. PMID:27245972

  14. Molecular simulations and experimental studies of zeolites

    NASA Astrophysics Data System (ADS)

    Moloy, Eric C.

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

  15. Zeolites: Can they be synthesized by design

    SciTech Connect

    Davis, M.E. )

    1994-09-01

    Zeolites and zeolite-like molecular sieves are crystalline oxides that have high surface-to-volume ratios and are able to recognize, discriminate, and organize molecules with differences of < 1 [angstrom]. The close connection between the atomic structure and macroscopic properties of these materials has led to uses in molecular recognition. For example, zeolites and zeolite-like molecular sieves can reveal marvelous molecular recognition specificity and sensitivity that can be applied to catalysis, separations technology, and chemical sensing. Additionally, they can serve as hosts to organize guest atoms and molecules that endow composite materials with optoelectric and electrochemical properties. Because of the high level of structural control necessary to create high-performance materials with zeolites or zeolite-like molecular sieves, the design and synthesis of these solids with specific architectures and properties are highly desired. Although this lofty goal is still elusive, advances have been made to allow the serious consideration of designing molecular sieves. Here, the author covers two aspects of this ongoing effort. First, he discusses the feasibility of designing pore architectures through the use of organic structure-directing agents. Second, he explores the possibility of creating zeolites through ''Lego chemistry.''

  16. Dissolution and Separation of Aluminum and Aluminosilicates

    DOE PAGESBeta

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

    2015-12-19

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

  17. Dissolution and Separation of Aluminum and Aluminosilicates

    SciTech Connect

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

    2015-12-19

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

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

    PubMed

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

    2015-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

  20. Rapid synthesis of an aluminum-rich MSE-type zeolite by the hydrothermal conversion of an FAU-type zeolite.

    PubMed

    Inagaki, Satoshi; Tsuboi, Yasuyuki; Nishita, Yuji; Syahylah, Tuan; Wakihara, Toru; Kubota, Yoshihiro

    2013-06-10

    An aluminum-rich MSE-type zeolite (Si/Al is as small as 7) has been successfully synthesized in a remarkably short crystallization period of only 3 days by the hydrothermal conversion of an FAU-type zeolite, presumably by the assembly of four-membered-ring (4-R) aluminosilicate oligomers supplied by the double 6-R (D6R) components of the FAU framework with the aid of the structure-directing agents and seed crystals. The dealuminated version of the aluminum-rich MSE-type zeolite showed a high level of coke durability in addition to a significant yield of propylene, which indicates that this novel zeolitic material is suitable for industrial applications as a highly selective and long-lived catalyst. PMID:23606200

  1. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

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

  2. 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...

  3. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

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

  4. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

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

  5. 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...

  6. 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-β 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

  7. 40 CFR 721.633 - Aluminosilicates, phospho-.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... reporting. (1) The chemical substance identified as Aluminosilicates, phospho- (PMN P-98-1275; CAS No... in § 721.125 (a), (b), (c), (d), (f), (g), (h), and (i) are applicable to manufacturers, importers... Section 721.633 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC...

  8. 40 CFR 721.633 - Aluminosilicates, phospho-.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... reporting. (1) The chemical substance identified as Aluminosilicates, phospho- (PMN P-98-1275; CAS No... in § 721.125 (a), (b), (c), (d), (f), (g), (h), and (i) are applicable to manufacturers, importers... Section 721.633 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC...

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

    PubMed

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

    2016-07-01

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

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

    PubMed

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

    2016-06-01

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

  11. 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...

  12. Synthesis and characterization of nitrogen substituted zeolites

    NASA Astrophysics Data System (ADS)

    Dogan, Fulya

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

  13. Zeolite-like liquid crystals

    PubMed Central

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

    2015-01-01

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

  14. 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 π-conjugated rod-like molecules form pentagonal channels, encircling larger octagonal channels, a structural motif also found in some zeolites. Additional bundles of coaxial molecules penetrate the centres of the larger channels, unreachable by chains attached to the honeycomb framework. This creates a unique fluid hybrid structure combining positive and negative anisotropies, providing the potential for tuning the directionality of anisotropic optical, electrical and magnetic properties. This work also demonstrates a new approach to complex soft-matter self-assembly, by using frustration between space filling and the entropic penalty of chain extension.

  15. Zeolite-like liquid crystals.

    PubMed

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

    2015-01-01

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

  16. 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

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

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

    Crystals grown from liquid solutions have important industrial applications. Zeolites, for instance, a class of crystalline aluminosilicate materials, form the backbone of the chemical process industry worldwide, as they are used as adsorbents and catalysts. Many of the phenomena associated with crystal growth processes are not well understood due to complex microscopic and macroscopic interactions. Microgravity could help elucidate these phenomena and allow the control of defect locations, concentration, as well as size of crystals. Microgravity in an orbiting spacecraft could help isolate the possible effects of natural convection (which affects defect formation) and minimize sedimentation. In addition, crystals will stay essentially suspended in the nutrient pool under a diffusion-limited growth condition. This is expected to promote larger crystals by allowing a longer residence time in a high-concentration nutrient field. Among other factors, the crystal size distribution depends on the nucleation rate and crystallization. These two are also related to the "gel" polymerization/depolymerization rate. Macroscopic bulk mass and flow transport and especially gravity, force the crystals down to the bottom of the reactor, thus forming a sedimentation layer. In this layer, the growth rate of the crystals slows down as crystals compete for a limited amount of nutrients. The macroscopic transport phenomena under certain conditions can, however, enhance the nutrient supply and therefore, accelerate crystal growth. Several zeolite experiments have been performed in space with mixed results. The results from our laboratory have indicated an enhancement in size of 30 to 70 percent compared to the best ground based controls, and a reduction of lattice defects in many of the space grown crystals. Such experiments are difficult to interpret, and cannot be easily used to derive empirical or other laws since many physical parameters are simultaneously involved in the process

  18. Zeolite catalysis: technology

    SciTech Connect

    Heinemann, H.

    1980-07-01

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

  19. 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.

  20. 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.

  1. 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.

  2. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks

    PubMed Central

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

    2006-01-01

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

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

    PubMed

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

    2016-03-14

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

  4. The effects of surface modification on the speciation of metal ions intercalated into aluminosilicates

    SciTech Connect

    Wasserman, S.R.; Giaquinta, D.M.; Yuchs, S.E.; Soderholm, L.

    1996-12-31

    Microporous aluminosilicates, including clay minerals and zeolites, are ion-exchange materials. In their most common forms, they have the ability to incorporate cationic species within their matrices. Because of this property, microporous aluminosilicates have been proposed as storage media for hazardous waste. In this paper the authors use X-ray absorption spectroscopy (XAS) to examine the structure of cations held within smectite clay minerals and to determine how modification of the surface of the clay using an organic monolayer affects the coordination of the stored cation. The effects of hydrothermal and thermal processing on the coordination of the ions contained within these systems are also investigated. The presence of the monolayer changes the surface of the clay from hydrophilic to hydrophobic. It inhibits the interlayer ions from exchanging freely into environmental water and reduces the leach rate of cations out of the clay by approximately a factor of 20. Significant changes are observed when these coated samples are treated under hydrothermal and thermal conditions. Reductions of uranium (VI), in the form of uranyl, and cupric ions occur. In addition, the uranium aggregates, forming small particles that appear similar to UO{sub 2}. Comparable conglomeration occurs with lead cations and with the reduced copper species.

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

    NASA Astrophysics Data System (ADS)

    Nosrati, Rahimeh; Olad, Ali

    2015-12-01

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

  6. 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.

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

    PubMed

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

    2010-02-16

    Zeolites are a class of crystalline oxides that have uniform and molecular-sized pores (3-12 A in diameter). Although natural zeolites were first discovered in 1756, significant commercial development did not begin until the 1950s when synthetic zeolites with high purity and controlled chemical composition became available. Since then, major commercial applications of zeolites have been limited to catalysis, adsorption, and ion exchange, all using zeolites in powder form. Although researchers have widely investigated zeolite thin films within the last 15 years, most of these studies were motivated by the potential application of these materials as separation membranes and membrane reactors. In the last decade, we have recognized and demonstrated that zeolite thin films can have new, diverse, and economically significant applications that others had not previously considered. In this Account, we highlight our work on the development of zeolite thin films as low-dielectric constant (low-k) insulators for future generation computer chips, environmentally benign corrosion-resistant coatings for aerospace alloys, and hydrophilic and microbiocidal coatings for gravity-independent water separation in space stations. Although these three applications might not seem directly related, they all rely on the ability to fine-tune important macroscopic properties of zeolites by changing their ratio of silicon to aluminum. For example, pure-silica zeolites (PSZs, Si/Al = infinity) are hydrophobic, acid stable, and have no ion exchange capacity, while low-silica zeolites (LSZs, Si/Al < 2) are hydrophilic, acid soluble, and have a high ion exchange capacity. These new thin films also take advantage of some unique properties of zeolites that have not been exploited before, such as a higher elastic modulus, hardness, and heat conductivity than those of amorphous porous silicas, and microbiocidal capabilities derived from their ion exchange capacities. Finally, we briefly discuss our

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

    PubMed Central

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

    2013-01-01

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

  9. 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.

  10. 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.

  11. 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

  12. 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.

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

    SciTech Connect

    Carrado, K.A.

    1986-01-01

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

  14. Wet gringing of zeolite in stirred media mill

    NASA Astrophysics Data System (ADS)

    Mucsi, G.; Bohács, K.

    2016-04-01

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

  15. 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.

  16. 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; Palčić, 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

  17. Direct hydrothermal synthesis of hierarchically porous siliceous zeolite by using alkoxysilylated nonionic surfactant.

    PubMed

    Mukti, Rino R; Hirahara, Hirotomo; Sugawara, Ayae; Shimojima, Atsushi; Okubo, Tatsuya

    2010-02-16

    A hierarchically porous siliceous MFI zeolite (silicalite-1) with narrow mesoporosity has been hydrothermally synthesized by using trialkoxysilylated alkyl poly(oxyethylene ether) as mesopore-directing agent. A mesostructured silica-surfactant composite was formed at the early stage of the reaction, and zeolite crystallization proceeded during subsequent hydrothermal treatment. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations of the crystallized products showed that micro- and mesopores were hierarchically assembled in unique particle morphology with rugged surfaces. Solid-state (29)Si and (13)C NMR revealed that the covalent bonds between the zeolite framework and mesopore-directing agent were present in the products before calcination. The use of nonsilylated alkyl poly(oxyethylene ether) or a silylated alkytrimethyl-ammonium-type cationic surfactant for the synthesis of silicalite-1 resulted in a mixture of mesoporous silica and zeolite as the final product, which suggests that the covalent interaction and nonelectrostatic charge matching interaction favor the formation of hierarchically mesoporous siliceous zeolite. This alkoxysilylated nonionic surfactant can also be extended to synthesize aluminosilicate MFI zeolite (ZSM-5). PMID:19817366

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

    NASA Astrophysics Data System (ADS)

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

    2007-02-01

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

  19. 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

  20. 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

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. Composite zeolite membranes

    DOEpatents

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

    2002-01-01

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

  6. Synthesis of colloidal suspensions of zeolite ZSM-2

    SciTech Connect

    Schoeman, B.J.; Sterte, J.; Otterstedt, J.E.

    1995-03-15

    Discrete colloidal particles of zeolite ZSM-2 with crystal sizes less than 100 nm, in the form of aqueous suspensions, have been synthesized in tetramethylammonium (TMA)-aluminosilicate solutions in the presence of either lithium or a combination of lithium and sodium hydroxide. The well-crystallized ZSM-2 has a specific surface area of 781 m{sup 2}/g after purification and removal of the organic base by calcination. Synthesis times (t) are as short as 3 < t < 12 h and in certain cases, less than 3 h, less than those previously reported in the literature. Prolonged hydrothermal treatment of sols in the presence of sodium cations (>12 h) results in the phase transformation of ZSM-2 to the nitrogeneous edingtonite zeolite (Li,Na)-E. The synthesis of nitrogeneous (Li,Na)-E is also favored by a high TMA content in conjunction with sodium, whereas synthesis of zeolite N-A is favored by a high sodium content. Furthermore, it is shown that colloidal suspensions of TMA sodalite with crystal sizes less than 40 nm are synthesized in the absence of alkali cations.

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

    PubMed

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

    2014-03-12

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

  8. 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

  9. Synthesis of nanoporous material from zeolite USY and catalytic application to bio-oil conversion.

    PubMed

    Park, Hyun Ju; Jeon, Jong-Ki; Kim, Ji Man; Lee, Hyung Ik; Yim, Jin-Heong; Park, Junhong; Park, Young-Kwon

    2008-10-01

    A highly ordered nanoporous aluminosilicate (MMZ(USY)) was synthesized using commercially available zeolite USY as the framework source and cetyltrimethylammonium bromide as the template. The aluminosilicate was characterized by XRD, N2 adsorption, ICP-AES and TPD. The catalytic performance of the MMZ(USY) material in the conversion of bio-oil was compared with that of Al-MCM-41, which was synthesized using a direct sol-gel method. The highly accessible nanopores, hydrothermal stability and the intermediate acidic properties of MMZ(USY) correlated with the catalytic performance in the conversion of the bio-oil. The MMZ(USY) used in this study showed excellent activity, selectivity and stability for the production of desirable organic compounds, such as phenolics, with a high degree of deoxygenation. PMID:19198472

  10. 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

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

    SciTech Connect

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

    2015-02-15

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

  12. 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.

  13. Preparation of functionalized zeolitic frameworks

    DOEpatents

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

    2012-11-20

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

  14. 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.

  15. 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.

  16. 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

  17. 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

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

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2004-06-30

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

  19. 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.

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

    PubMed

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

    2016-05-23

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

  1. 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

  2. Influence of aluminum speciation on the stability of aluminosilicate glasses against crystallization

    NASA Astrophysics Data System (ADS)

    Zheng, Qiuju; Smedskjaer, Morten M.; Youngman, Randall E.; Potuzak, Marcel; Mauro, John C.; Yue, Yuanzheng

    2012-07-01

    In this letter, we investigate the correlation between glass microstructure and glass stability (GS) in soda lime aluminosilicates. We find a loss of GS (i.e., an onset of crystallization) in the glasses above a critical concentration of Al2O3 when heating at the standard rate of 20 K/min. This loss in GS may be attributed to formation of five-fold coordinated Al species when [Al2O3]/[Na2O] > 1. The primary crystalline phase is identified as nepheline, in which Al exists in four-fold coordination. This implies that the five-fold coordinated Al is energetically less stable compared to Al in a tetrahedral environment.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  4. 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.

  5. 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

  6. 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

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

    PubMed

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

    2009-06-15

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

  8. 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

  9. 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.

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

    SciTech Connect

    Schneider, E.

    1985-11-01

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

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

    PubMed

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

    2015-05-20

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

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

    NASA Astrophysics Data System (ADS)

    Sarkar, Madhuchhanda; Dana, Kausik; Das, Sukhen

    2015-10-01

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

  13. Mesostructured silica and aluminosilicate carriers for oxytetracycline delivery systems.

    PubMed

    Berger, D; Nastase, S; Mitran, R A; Petrescu, M; Vasile, E; Matei, C; Negreanu-Pirjol, T

    2016-08-30

    Oxytetracycline delivery systems containing various MCM-type silica and aluminosilicate with different antibiotic content were developed in order to establish the influence of the support structural and textural properties and aluminum content on the drug release profile. The antibiotic molecules were loaded into the support mesochannels by incipient wetness impregnation method using a drug concentrated aqueous solution. The carriers and drug-loaded materials were investigated by small- and wide-angle XRD, FTIR spectroscopy, TEM and N2 adsorption-desorption isotherms. Faster release kinetics of oxytetracycline from uncalcined silica and aluminosilicate supports was observed, whereas higher drug content led to lower delivery rate. The presence of aluminum into the silica network also slowed down the release rate. The antimicrobial assays performed on Staphylococcus aureus clinical isolates showed that the oxytetracycline-loaded materials containing MCM-41-type mesoporous silica or aluminosilicate carriers inhibited the bacterial development. PMID:26861688

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

    PubMed

    Franus, Wojciech; Wdowin, Magdalena; Franus, Małgorzata

    2014-09-01

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

  15. 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

  16. Lactic acid production on liquid distillery stillage by Lactobacillus rhamnosus immobilized onto zeolite.

    PubMed

    Djukić-Vuković, Aleksandra P; Mojović, Ljiljana V; Jokić, Bojan M; Nikolić, Svetlana B; Pejin, Jelena D

    2013-05-01

    In this study, lactic acid and biomass production on liquid distillery stillage from bioethanol production with Lactobacillus rhamnosus ATCC 7469 was studied. The cells were immobilized onto zeolite, a microporous aluminosilicate mineral and the lactic acid production with free and immobilized cells was compared. The immobilization allowed simple cell separation from the fermentation media and their reuse in repeated batch cycles. A number of viable cells of over 10(10) CFU g(-1) of zeolite was achieved at the end of fourth fermentation cycle. A maximal process productivity of 1.69 g L(-1), maximal lactic acid concentration of 42.19 g L(-1) and average yield coefficient of 0.96 g g(-1) were achieved in repeated batch fermentation on the liquid stillage without mineral or nitrogen supplementation. PMID:23186681

  17. Formation of ZSM-22 zeolite catalytic particles by fusion of elementary nanorods.

    PubMed

    Hayasaka, Kazuaki; Liang, Duoduo; Huybrechts, Ward; De Waele, Bart R; Houthoofd, Kristof J; Eloy, Pierre; Gaigneaux, Eric M; van Tendeloo, Gustaaf; Thybaut, Joris W; Marin, Guy B; Denayer, Joeri F M; Baron, Gino V; Jacobs, Pierre A; Kirschhock, Christine E A; Martens, Johan A

    2007-01-01

    An ZSM-22 aluminosilicate zeolite was synthesized using the hydrothermal gel method at 150 degrees C. Products obtained after different synthesis times were characterized using various techniques and catalytic testing. Massive formation of ZSM-22 nanocrystals occurs after only a short synthesis time, appearing as isolated rods with a cross section of 12+/-4 nm. Nanorods have aluminum enriched at their external surface. Later in the crystallization process nanorods align and fuse sideways, whereby the external surface is systematically converted into an internal micropore surface. The formation of aluminum bearing micropores by the joining of nanorod surfaces is responsible for the enhanced catalytic activity. For this, the zeolite synthesis of nanoscale crystallites is ineffective for enhancing catalytic activity. PMID:17868172

  18. 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.

  19. 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.

  20. 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.

  1. Luminescent properties of bismuth centres in aluminosilicate optical fibres

    SciTech Connect

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

    2010-02-28

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

  2. 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

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

    NASA Astrophysics Data System (ADS)

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

    1988-01-01

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

  4. Pioneering In Situ Recrystallization during Bead Milling: A Top-down Approach to Prepare Zeolite A Nanocrystals.

    PubMed

    Anand, Chokkalingam; Yamaguchi, Yudai; Liu, Zhendong; Ibe, Sayoko; Elangovan, Shanmugam P; Ishii, Toshihiro; Ishikawa, Tsuyoshi; Endo, Akira; Okubo, Tatsuya; Wakihara, Toru

    2016-01-01

    Top-down approach has been viewed as an efficient and straightforward method to prepare nanosized zeolites. Yet, the mechanical breaking of zeolite causes amorphization, which usually requires a post-milling recrystallization to obtain fully crystalline nanoparticles. Herein we present a facile methodology to prepare zeolite nanocrystals, where milling and recrystallization can be performed in situ. A milling apparatus specially designed to work under conditions of high alkalinity and temperature enables the in situ recrystallization during milling. Taking zeolite A as an example, we demonstrate its size reduction from ~3 μm to 66 nm in 30 min, which is quite faster than previous methods reported. Three functions, viz., miniaturization, amorphization and recrystallization were found to take effect concurrently during this one-pot process. The dynamic balance between these three functions was achieved by adjusting the milling period and temperature, which lead to the tuning of zeolite A particle size. Particle size and crystallinity of the zeolite A nanocrystals were confirmed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and water adsorption-desorption. This work presents a pioneering advancement in this field of nanosized zeolites, and will facilitate the mass production as well as boost the wide applications of nanosized zeolites. PMID:27378145

  5. Pioneering In Situ Recrystallization during Bead Milling: A Top-down Approach to Prepare Zeolite A Nanocrystals

    PubMed Central

    Anand, Chokkalingam; Yamaguchi, Yudai; Liu, Zhendong; Ibe, Sayoko; Elangovan, Shanmugam P.; Ishii, Toshihiro; Ishikawa, Tsuyoshi; Endo, Akira; Okubo, Tatsuya; Wakihara, Toru

    2016-01-01

    Top-down approach has been viewed as an efficient and straightforward method to prepare nanosized zeolites. Yet, the mechanical breaking of zeolite causes amorphization, which usually requires a post-milling recrystallization to obtain fully crystalline nanoparticles. Herein we present a facile methodology to prepare zeolite nanocrystals, where milling and recrystallization can be performed in situ. A milling apparatus specially designed to work under conditions of high alkalinity and temperature enables the in situ recrystallization during milling. Taking zeolite A as an example, we demonstrate its size reduction from ~3 μm to 66 nm in 30 min, which is quite faster than previous methods reported. Three functions, viz., miniaturization, amorphization and recrystallization were found to take effect concurrently during this one-pot process. The dynamic balance between these three functions was achieved by adjusting the milling period and temperature, which lead to the tuning of zeolite A particle size. Particle size and crystallinity of the zeolite A nanocrystals were confirmed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and water adsorption-desorption. This work presents a pioneering advancement in this field of nanosized zeolites, and will facilitate the mass production as well as boost the wide applications of nanosized zeolites. PMID:27378145

  6. Pioneering In Situ Recrystallization during Bead Milling: A Top-down Approach to Prepare Zeolite A Nanocrystals

    NASA Astrophysics Data System (ADS)

    Anand, Chokkalingam; Yamaguchi, Yudai; Liu, Zhendong; Ibe, Sayoko; Elangovan, Shanmugam P.; Ishii, Toshihiro; Ishikawa, Tsuyoshi; Endo, Akira; Okubo, Tatsuya; Wakihara, Toru

    2016-07-01

    Top-down approach has been viewed as an efficient and straightforward method to prepare nanosized zeolites. Yet, the mechanical breaking of zeolite causes amorphization, which usually requires a post-milling recrystallization to obtain fully crystalline nanoparticles. Herein we present a facile methodology to prepare zeolite nanocrystals, where milling and recrystallization can be performed in situ. A milling apparatus specially designed to work under conditions of high alkalinity and temperature enables the in situ recrystallization during milling. Taking zeolite A as an example, we demonstrate its size reduction from ~3 μm to 66 nm in 30 min, which is quite faster than previous methods reported. Three functions, viz., miniaturization, amorphization and recrystallization were found to take effect concurrently during this one-pot process. The dynamic balance between these three functions was achieved by adjusting the milling period and temperature, which lead to the tuning of zeolite A particle size. Particle size and crystallinity of the zeolite A nanocrystals were confirmed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and water adsorption-desorption. This work presents a pioneering advancement in this field of nanosized zeolites, and will facilitate the mass production as well as boost the wide applications of nanosized zeolites.

  7. Ionic liquids and eutectic mixtures as solvent and template in synthesis of zeolite analogues.

    PubMed

    Cooper, Emily R; Andrews, Christopher D; Wheatley, Paul S; Webb, Paul B; Wormald, Philip; Morris, Russell E

    2004-08-26

    The challenges associated with synthesizing porous materials mean that new classes of zeolites (zeotypes)-such as aluminosilicate zeolites and zeolite analogues-together with new methods of preparing known zeotypes, continue to be of great importance. Normally these materials are prepared hydrothermally with water as the solvent in a sealed autoclave under autogenous pressure. The reaction mixture usually includes an organic template or 'structure-directing agent' that guides the synthesis pathway towards particular structures. Here we report the preparation of aluminophosphate zeolite analogues by using ionic liquids and eutectic mixtures. An imidazolium-based ionic liquid acts as both solvent and template, leading to four zeotype frameworks under different experimental conditions. The structural characteristics of the materials can be traced back to the solvent chemistry used. Because of the vanishingly low vapour pressure of ionic liquids, synthesis takes place at ambient pressure, eliminating safety concerns associated with high hydrothermal pressures. The ionic liquid can also be recycled for further use. A choline chloride/urea eutectic mixture is also used in the preparation of a new zeotype framework. PMID:15329717

  8. Disilane-modified mordenite zeolites

    SciTech Connect

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

    1990-03-22

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

  9. Zeolite exposure and associated pneumoconiosis

    SciTech Connect

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

    1985-06-01

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

  10. SO2 REMOVAL FROM FLUE GASES USING UTILITY SYNTHESIZED ZEOLITES

    SciTech Connect

    Michael Grutzeck

    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.

  11. 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.

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

    PubMed

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

    2015-02-01

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

  13. Improved zeolitic isocracking catalysts

    SciTech Connect

    Dahlberg, A.J.; Habib, M.M.; Moore, R.O.; Law, D.V.; Convery, L.J.

    1995-09-01

    Chevron Research Company introduced the first low pressure, low temperature catalytic hydrocracking process--ISOCRACKING--in 1959. Within the last four years, Chevron has developed and commercialized three new zeolitic ISOCRACKING catalysts. ICR 209 is Chevron`s latest noble metal ISOCRACKING catalyst. It offers improved liquid yield stability, longer life, and superior polynuclear aromatics control compared to its predecessor. ICR 209`s high hydrogenation activity generates the highest yields of superior quality jet fuel of any zeolitic ISOCRACKING catalyst. The second new ISOCRACKING catalyst, ICR 208, is a base metal catalyst which combines high liquid selectivity and high light naphtha octane in hydrocrackers operating for maximum naphtha production. ICR 210 is another new base metal catalyst which offers higher liquid yields and longer life than ICR 208 by virtue of a higher hydrogenation-to-acidity ratio. Both ICR 208 and ICR 210 have been formulated to provide higher liquid yield throughout the cycle and longer cycle length than conventional base metal/zeolite catalysts. This paper will discuss the pilot plant and commercial performances of these new ISOCRACKING catalysts.

  14. Zeolite vitrification demonstration program: characterization of radioactive vitrified zeolite materials

    SciTech Connect

    Barner, J O; Daniel, J L; Marshall, R K

    1984-01-01

    The leach behavior of radioactive vitrified zeolite material was studied as part of the Three Mile Island (TMI) Zeolite Vitrification Program conducted by Pacific Northwest Laboratory (PNL). Experimental procedures, test results, and discussions of the results are presented. The leach behavior of material from three canisters of vitrified zeolite is discussed in terms of the normalized weight loss of the glass-formers and the normalized activity loss of the fission products cesium and strontium. The leach behavior of the radioactive vitrified zeolite material is also compared to the leach behavior of MCC 76-68 reference glass. The effects of changes in the surface microstructure of the vitrified zeolite that occurred during leaching are also presented. 3 references, 23 figures, 10 tables.

  15. 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

  16. Abu Zenima synthetic zeolite for removing iron and manganese from Assiut governorate groundwater, Egypt

    NASA Astrophysics Data System (ADS)

    Farrag, Abd El Hay Ali; Abdel Moghny, Th.; Mohamed, Atef Mohamed Gad; Saleem, Saleem Sayed; Fathy, Mahmoud

    2016-06-01

    Groundwater in Upper Egypt especially in Assiut Governorate is considered the second source of fresh water and used for drinking, agriculture, domestic and industrial purposes. Unfortunately, it is characterized by high concentrations of iron and manganese ions. The study aimed at synthesizing zeolite-4A from kaolinite for removing the excess iron and manganese ions from Assiut Governorate groundwater wells. Therefor, the kaolinite was hydrothermally treated through the metakaolinization and zeolitization processes to produce crystalline zeolite-4A. The chemical composition of crystalline zeolite-4A and its morphology were then characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Then the column experiments were conducted to study the performance of crystalline salt-4A as ion exchange and investigate their operating parameters and regeneration conditions. Thomas and Yoon-Nelson models were applied to predict adsorption capacity and the time required for 50 % breakthrough curves. The effects of initial concentrations of 600 and 1000 mg L-1 for Fe2+ and Mn2+, feed flow rate of 10-30 ml/min, and height range of 0.4-1.5 cm on the breakthrough behavior of the adsorption system were determined. The obtained results indicated that the synthesized zeolite-A4 can remove iron and manganese ions from groundwater to the permissible limit according to the standards drinking water law.

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

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

  19. ZSM-5 zeolite single crystals with b-axis-aligned mesoporous channels as an efficient catalyst for conversion of bulky organic molecules.

    PubMed

    Liu, Fujian; Willhammar, Tom; Wang, Liang; Zhu, Longfeng; Sun, Qi; Meng, Xiangju; Carrillo-Cabrera, Wilder; Zou, Xiaodong; Xiao, Feng-Shou

    2012-03-14

    The relatively small and sole micropores in zeolite catalysts strongly influence the mass transfer and catalytic conversion of bulky molecules. We report here aluminosilicate zeolite ZSM-5 single crystals with b-axis-aligned mesopores, synthesized using a designed cationicamphiphilic copolymer as a mesoscale template. This sample exhibits excellent hydrothermal stability. The orientation of the mesopores was confirmed by scanning and transmission electron microscopy. More importantly, the b-axis-aligned mesoporous ZSM-5 shows much higher catalytic activities for bulky substrate conversion than conventional ZSM-5 and ZSM-5 with randomly oriented mesopores. The combination of good hydrothermal stability with high activities is important for design of novel zeolite catalysts. The b-axis-aligned mesoporous ZSM-5 reported here shows great potential for industrial applications. PMID:22380406

  20. Adamantanes from petroleum, with zeolites

    SciTech Connect

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

    1995-12-31

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

  1. Tailoring ZSM-5 Zeolites for the Fast Pyrolysis of Biomass to Aromatic Hydrocarbons.

    PubMed

    Hoff, Thomas C; Gardner, David W; Thilakaratne, Rajeeva; Wang, Kaige; Hansen, Thomas W; Brown, Robert C; Tessonnier, Jean-Philippe

    2016-06-22

    The production of aromatic hydrocarbons from cellulose by zeolite-catalyzed fast pyrolysis involves a complex reaction network sensitive to the zeolite structure, crystallinity, elemental composition, porosity, and acidity. The interplay of these parameters under the reaction conditions represents a major roadblock that has hampered significant improvement in catalyst design for over a decade. Here, we studied commercial and laboratory-synthesized ZSM-5 zeolites and combined data from 10 complementary characterization techniques in an attempt to identify parameters common to high-performance catalysts. Crystallinity and framework aluminum site accessibility were found to be critical to achieve high aromatic yields. These findings enabled us to synthesize a ZSM-5 catalyst with enhanced activity, which offers the highest aromatic hydrocarbon yield reported to date. PMID:27167613

  2. 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.

  3. 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.

  4. Inelastic neutron scattering from tetramethylammonium cations occluded within zeolites

    SciTech Connect

    Brun, T.O.; Curtiss, L.A.; Iton, L.E.; Kleb, R.; Newsam, J.M.; Beyerlein, R.A.; Vaughan, D.E.W.

    1987-06-24

    The use of organic bases, for example, tetraalklylammonium hydroxides, and other organic reagents has greatly enhanced the scope of gel/solution synthesis routes to crystalline microporous materials such as zeolites. The role of these organic components, however, continues to be the topic of considerable debate. The organic components first modify the gel structural chemistry. The presence of tetramethylammonium (TMA) hydroxide, for example, promotes the formation of double four-ring units in silicate solutions. Occlusion of organic gel components in zeolite crystal structures, however, leads also to the concept of a templating effect in which the organic component provides a basis around which the developing zeolite cages form. The mechanism of this templating process remains somewhat ill defined and must, at least, be of variable specificity. The authors describe here the use of inelastic neutron scattering (INS) to measure TMA template torsional vibrations, vibrations that provide to be sensitive to the strength of the interaction between the template cation and the enclosing zeolite cage.

  5. Zeolites X and A crystallization compared by simultaneous UV/VIS-Raman and X-ray diffraction.

    PubMed

    Depla, Anouschka; Verheyen, Elke; Veyfeyken, An; Gobechiya, Elena; Hartmann, Thomas; Schaefer, Reinhold; Martens, Johan A; Kirschhock, Christine E A

    2011-08-14

    The hydrothermal crystallizations of two zeolite topologies (FAU and LTA) have been studied by simultaneous UV-Raman spectroscopy and X-ray diffraction in a home built setup. A wide angle X-ray diffractometer has been redesigned and combined with Raman components. The results revealed, despite similar structures of the starting gels, different aluminosilicate species evolved in the two systems, prior to emerging Bragg scattering. Based on this the sodalite cage could be ruled out as a common building unit for both frameworks. PMID:21720615

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

    PubMed

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

    2016-05-17

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

  7. 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.

  8. Oxygen and hydrogen isotope geochemistry of zeolites

    NASA Technical Reports Server (NTRS)

    Karlsson, Haraldur R.; Clayton, Robert N.

    1990-01-01

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

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

    PubMed

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

    2015-11-25

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

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

    DOEpatents

    Clough, Roger L.; Gill, John T.; Hawkins, Daniel B.; Renschler, Clifford L.; Shepodd, Timothy J.; Smith, Henry M.

    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.

  11. Barium aluminosilicate reinforced in situ with silicon nitride

    SciTech Connect

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

    1995-10-01

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

  12. Alteration of biophysical activity of pulmonary surfactant by aluminosilicate nanoparticles.

    PubMed

    Kondej, Dorota; Sosnowski, Tomasz R

    2013-02-01

    The influence of five different types of aluminosilicate nanoparticles (NPs) on the dynamic surface activity of model pulmonary surfactant (PS) (Survanta) was studied experimentally using oscillating bubble tensiometry. Bentonite, halloysite and montmorillonite (MM) NPs, which are used as fillers of polymer composites, were characterized regarding the size distribution, morphology and surface area. Particle doses applied in the studies were estimated based on the inhalation rate and duration, taking into account the expected aerosol concentration and deposition efficiency after penetration of NPs into the alveolar region. The results indicate that aluminosilicate NPs at concentrations in the pulmonary liquid above 0.1 mg cm(-3) are capable of promoting alterations of the original dynamic biophysical activity of the PS. This effect is indicated by deviation of the minimum surface tension, stability index and the size of surface tension hysteresis. Such response is dependent on the type of NPs present in the system and is stronger when particle concentration increases. It is suggested that interactions between NPs and the PS must be related to the surfactant adsorption on the suspended particles, while in the case of surface-modified clay NPs the additional washout of surface-active components may be expected. It is speculated that observed changes in surface properties of the surfactant may be associated with undesired health effects following extensive inhalation of aluminosilicate NPs in the workplace. PMID:23363039

  13. 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.

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

    PubMed

    Tang, Yuanyuan; Shih, Kaimin

    2015-01-01

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

  15. 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.

  16. Removal of radionuclides using zeolites

    SciTech Connect

    Reddy, R.G.; Cai, Z.

    1996-10-01

    Adsorption of uranium(VI) from aqueous solutions on natural zeolites, i.e., chabazite, clinoptilolite, erionite and mordenite, was investigated. The influence of time and pH of the solution were studied. The results showed that uranium(VI) species are strongly adsorbed on the zeolites between pH 6 to 9. The amount of uranium adsorption is strongly dependent on pH and, to some extent, on the type of zeolites. For pH {ge} 6 and at 25 C, more than 92% of uranium from solution was removed in 10 minutes. Adsorption mechanism of uranium is discussed.

  17. 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.

  18. Synthesis of NaP zeolite at room temperature and short crystallization time by sonochemical method.

    PubMed

    Pal, Pameli; Das, Jugal K; Das, Nandini; Bandyopadhyay, Sibdas

    2013-01-01

    NaP zeolite nano crystals were synthesized by sonochemical method at room temperature with crystallization time of 3h. For comparison, to insure the effect of sonochemical method, the hydrothermal method at conventional synthesis condition, with same initial sol composition was studied. NaP zeolites are directly formed by ultrasonic treatment without the application of autogenous pressure and also hydrothermal treatment. The effect of ultrasonic energy and irradiation time showed that with increasing sonication energy, the crystallinity of the powders decreased but phase purity remain unchanged. The synthesized powders were characterized by XRD, IR, DTA TGA, FESEM, and TEM analysis. FESEM images revealed that 50 nm zeolite crystals were formed at room temperature by using sonochemical method. However, agglomerated particles having cactus/cabbage like structure was obtained by sonochemical method followed by hydrothermal treatment. In sonochemical process, formation of cavitation and the collapsing of bubbles produced huge energy which is sufficient for crystallization of zeolite compared to that supplied by hydrothermal process for conventional synthesis. With increasing irradiation energy and time, the crystallinity of the synthesized zeolite samples increased slightly. PMID:22922038

  19. Phase transitions in natural zeolites and the importance of P H2O

    NASA Astrophysics Data System (ADS)

    Bish, David L.; Wang, Hsiu-Wen

    2010-06-01

    Zeolites are low-density silicates with structures consisting of a negatively charged aluminosilicate framework that creates a system of uniform linked channels and cavities. Variable amounts of extraframework cations and H2O molecules occupy the channel system, and the H2O molecules are very responsive to changes in temperature, pressure and partial pressure of water (i.e. P H2O or relative humidity, RH). As the H2O molecules occupy much of the volume of the extraframework sites, a gain or loss of H2O molecules has a direct effect on the extraframework cations and an indirect effect on the framework. Temperature or RH-induced changes can result in both first- and second-order phase transitions, the latter resulting from continuous, minor changes in hydration state and cation position, and the former resulting from discrete changes in hydration state, which can cause similar shifts in cation position. Second-order transitions are typically reversible with no hysteresis, but first-order transitions exhibit considerable hysteresis. As H2O molecules are crucial in determining zeolite behavior, it is important that any study of thermal behavior involve control of not only temperature but also of relative humidity. Stabilization of a zeolite's hydrated phase to higher temperatures under higher RH conditions can cause some phase transitions to be missed, as is the case with natrolite.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  1. Copper-containing zeolite catalysts

    DOEpatents

    Price, Geoffrey L.; Kanazirev, Vladislav

    1996-01-01

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

  2. 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.

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

    SciTech Connect

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

    2008-01-01

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

  4. 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.

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

    SciTech Connect

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

    2014-06-24

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

  6. Radiation damage of a glass-bonded zeolite waste form using ion irradiation.

    SciTech Connect

    Allen, T. R.; Storey, B. G.

    1997-12-05

    Glass-bonded zeolite is being considered as a candidate ceramic waste form for storing radioactive isotopes separated from spent nuclear fuel in the electrorefining process. To determine the stability of glass-bonded zeolite under irradiation, transmission electron microscope samples were irradiated using high energy helium, lead, and krypton. The major crystalline phase of the waste form, which retains alkaline and alkaline earth fission products, loses its long range order under both helium and krypton irradiation. The dose at which the long range crystalline structure is lost is about 0.4 dpa for helium and 0.1 dpa for krypton. Because the damage from lead is localized in such a small region of the sample, damage could not be recognized even at a peak damage of 50 dpa. Because the crystalline phase loses its long range structure due to irradiation, the effect on retention capacity needs to be further evaluated.

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

    PubMed Central

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

    2013-01-01

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

  8. 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.

  9. Analysis of paramagnetic centers for threevalent iron in aluminosilicates

    NASA Astrophysics Data System (ADS)

    Apushkinskaya, D.; Apushkinskiy, E.; Popov, B.; Romanov, V. N.; Saveliev, V.; Sobolevskiy, V.

    2015-09-01

    We present the results of investigation of the defects in fluorine aluminosilicates from the Volyn-field Al2 [SiO4][F,OH]2 by the Electron Paramagnetic Resonance (EPR) method. The studies were carried out on the spectrometer Bruker ER 220D. Three types of EPR spectra of single centers were obtained. Their angular dependence was also investigated. The obtained EPR spectra correspond to the paramagnetic ion Fe3+ in the high-spin state S = 5/2. Three types of paramagnetic centers were found: one with cubic-symmetry and two with orthorhombic- symmetries.

  10. Cesium adsorption on composite ferrocyanide-aluminosilicate adsorbents

    SciTech Connect

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

    1995-11-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  12. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  14. Electron microscopy study of zeolite ZK-14; a synthetic chabazite

    NASA Astrophysics Data System (ADS)

    Cartlidge, S.; Wessicken, R.; Nissen, H.-U.

    1983-03-01

    The defect structure of zeolite (K+, TMA+) — ZK-14, a synthetic chabazite, has been studied using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SEM together with TEM bright field (BF) and dark field (DF) micrographs indicate that the hexagonal, platelet ZK-14 crystals are built up of crystalline blocks joined by twinning along (00.1). High resolution transmission electron microscopy (HRTEM) reveals faulting of the ideal AABBCC single 6-ring stacking sequence of ZK-14. This is consistent with an observed line broadening in its X-ray powder diffraction profile. Channel apertures are imaged, even for thick specimens.

  15. Probing zeolite syntheses to determine natural occurances of zeolites

    NASA Astrophysics Data System (ADS)

    Chen, H.; Song, S.; Fang, J.

    2003-12-01

    In this study, zeolites were synthesized from different glasses to probe the occurrence of zeolites in nature. The experiments were carried out with synthetic glass systems of Na2O.Al2O3.nSiO2, CaO.Al2O3.nSiO2, xNa2O.(1-x)CaO.Al2O3.nSiO2 and xNa2O.(1-x)K2O.Al2O3.6SiO2 in alkaline solutions of NaOH, KOH, Na2CO3, NH4OH, NaOH (+) NaCl and NaOH (+) KOH at temperatures ranging from 110›J to 210›J and with autogeneous pressures in the autoclaves. Synthetic products were examined by an X-ray powder diffractometer, a scanning electron microscopy with an energy dispersive spectrometer, and an electron microprobe. The minerals synthesized included zeolites, i.e., thomsonite, gismondine, amicite, garronite, gobbinsite, analcime, phillipsite, merlinoite, chabazite and mordenite; artificial synthetic zeolites, and feldspars. Chemical analyses indicated that the composition of synthetic zeolites is profoundly influenced by the composition of the initial glasses, especially the SiO2/Al2O3 ratios and cations. On the other hand, the influence of Na+ and K+ have over the formation of zeolites in solution, other ions, such as CO32- were involved in the preventing of the formation of Ca-zeolites. Comparing the experimental results with natural occurrences suggests that thomsonite, gismondine and amicite are usually found in ultrabasic and basic rocks; garronite and gobbinsite in basic to intermediate rocks; analcime, phillipsite, and chabazite in basic to acid rocks; merlinoite in high-potassium rocks; and mordenite in acid rocks. In addition, Ca-zeolites including thomsonite, gismondine and garronite are favored in fresh water environments, and alkali zeolites including gobbinsite, phillipsite, and analcime are most abundant in saline lake and deep sea conditions.

  16. 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

  17. 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

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

    NASA Astrophysics Data System (ADS)

    Clayden, Nigel J.; Esposito, Serena; Ferone, Claudio; Pansini, Michele

    2006-07-01

    The thermal transformation of Ba exchanged zeolite X to celsian has been studied by 27Al and 29Si MAS NMR spectroscopy. Evidence for the degradation of the zeolite framework is present in the 29Si NMR spectra after thermal treatment at 850 °C. Confirmation is provided by the 29Si NMR data that synthesis of celsian via the decomposition of Ba exchanged zeolite leads to a single defect phase. Clustering of the isomorphous replacement of aluminium by silicon must occur to explain the observed 29Si chemical shifts. The 27Al NMR data show distorted aluminium co-ordination sites upon the thermal transformation of Ba exchanged zeolite X. The distortions present in the amorphous matrix are greater than those present in the monoclinic and hexagonal crystalline phases of celsian.

  19. 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

  20. Magnetic self-assembled zeolite clusters for sensitive detection and rapid removal of mercury(II).

    PubMed

    Yin, Meili; Li, Zhenhua; Liu, Zhen; Yang, Xinjian; Ren, Jinsong

    2012-01-01

    We reported here the fabrication of a hierarchical mesoporous zeolite nanocomposite using 20 nm crystalline domins of zeolite L as building "bricks" by a simple and general one-step synthetic approach. By taking advantages of the large pore volumes, superparamagnetic iron oxide nanocrystals could be encapsulated into the nanocomposite conveniently for further facilitate separation and detection. In addition, by covalent coupling of fluorescent receptor (rhodamine-hydrazine), the combination of well-defined inorganic nanomaterials and organic receptors could be applied to selective detection of Hg(2+). Importantly, the unique adsorption capacity enabled by the hierarchical mesoporous zeolite and the efficient removal ability form complex multiphase systems by the magnetic characteristic made this multifunctional nanomaterial an excellent probe for detection, adsorption, and removal of Hg(2+) from waste aqueous solution. PMID:22126125

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  2. 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

  3. 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

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

    PubMed

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

    2005-06-30

    Hydrothermally stable and structrurally ordered mesoporous and microporous aluminosilicates with different pore sizes have been synthesized to immobilize cytochrome c (cyt c): MAS-9 (pore size 90 A), MCM-48-S (27 A), MCM-41-S (25 A), and Y zeolites (7.4 A). The amount of cyt c adsorption could be increased by the introduction of aluminum into the framework of pure silica materials. Among these mesoprous silicas (MPS), MAS-9 showed the highest loading capacity due to its large pore size. However, cyt c immobilized in MAS-9 could undergo facile unfolding during hydrothermal treatments. MCM-41-S and MCM-48-S have the pore sizes that match well the size of cyt c (25 x 25 x 37 A). Hence the adsorbed cyt c in these two medium pore size MPS have the highest hydrothermal stability and overall catalytic activity. On the other hand, the pore size of NaY zeolite is so small that cyt c is mostly adsorbed only on the outer surface and loses its enzymatic activity rapidly. The improved stability and high catalytic activity of cyt c immobilized in MPS are attributed to the electrostatic attraction between the pore surface and cyt c and the confinement provided by nanochannels. We further observed that cyt c immobilized in MPS exists in both high and low spin states, as inferred from the ESR and UV-vis studies. This is different from the native cyt c, which shows primarily the low spin state. The high spin state arises from the replacement of Met-80 ligands of heme Fe (III) by water or silanol group on silica surface, which could open up the heme groove for easy access of oxidants and substrates to iron center and facilitate the catalytic activity. In the catalytic study, MAS-9-cyt c showed the highest specific activity toward the oxidation of polycyclic aromatic hydrocarbons (PAHs), which arises from the fast mass transfer rate of reaction substrate due to its large pore size. For pinacyanol (a hydrophilic substrate), MCM-41-S-cyt c and MCM-48-S-cyt c showed higher specific

  5. Metal immobilization in soils using synthetic zeolites.

    PubMed

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

    2002-01-01

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

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  8. Bonding Preferences of Non-Bridging Oxygens in Calcium Aluminosilicate Glass: Evidence from O-17 MAS and 3QMAS NMR on Calcium Aluminate Glass

    NASA Astrophysics Data System (ADS)

    Allwardt, J. R.; Lee, S.; Stebbins, J.

    2001-12-01

    Non-bridging oxygens (NBO's) play a significant role in the thermodynamic and transport properties in glasses and silicate melts. Previous oxygen-17 (O-17) triple quantum magic angle spinning (3QMAS NMR) data have shown the presence of NBO's in several calcium aluminosilicate (CAS) glasses on the CaAl2O4-SiO2 join (Stebbins and Xu 1997). The observed chemical shifts of these glasses are similar to those for the NBO in calcium silicate glasses (Stebbins et al. 1997 and Stebbins et al 1999); however, a recent O-17 MAS NMR study of crystalline CaAl2O4 showed that the NBO peak in an associated impurity phase is shifted to a higher frequency by 30 to 40 ppm from that of CAS and Ca-silicate glasses (Stebbins et al. in press). This finding suggests that Si is the preferred network cation for NBO's in aluminosilicate glasses and melts at the glass transition temperature. The preference for Si over that of Al as the network cation host for NBO's has also been suggested by Raman and other spectroscopic techniques (Mysen 1988). To investigate this apparent preference for Si-NBO, O-17 3QMAS and MAS experiments were conducted to examine the location of the NBO peak in the spectra of a calcium aluminate glass. Since the CaAl2O4 glass is difficult to make by conventional cooling methods, the binary eutectic composition (63CaO-37Al2O3) was chosen. The resulting O-17 MAS spectrum shows an intense, relatively narrow peak centered at 72 ppm, which nearly coincides with the peak location and width of the Al-O-Al peak in the crystalline Ca-aluminates (Stebbins et al. in press.) (70 ppm). There is a broader, less intense peak centered at 155 ppm that is assigned to the Al-NBO peak. This peak is in approximately the same location as that for a Ca-aluminate phase reported by Stebbins et al. (in press) (137 ppm). In addition, our 3QMAS data show that the peak maximum of the NBO in the Ca-aluminate (-85 and 150 ppm in isotropic and MAS dimensions, respectively) differs significantly from

  9. 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.

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

    SciTech Connect

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

    2015-09-15

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