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Sample records for fe-containing zeolite catalysts

  1. 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.

  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. 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.

  4. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

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

    1987-01-01

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

  5. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

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

    1987-03-31

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

  6. Pf/Zeolite Catalyst for Tritium Stripping

    SciTech Connect

    Hsu, R.H.

    2001-03-26

    This report described promising hydrogen (protium and tritium) stripping results obtained with a Pd/zeolite catalyst at ambient temperature. Preliminary results show 90-99+ percent tritium stripping efficiency may be obtained, with even better performance expected as bed configuration and operating conditions are optimized. These results suggest that portable units with single beds of the Pd/zeolite catalyst may be utilized as ''catalytic absorbers'' to clean up both tritium gas and tritiated water. A cart-mounted prototype stripper utilizing this catalyst has been constructed for testing. This portable stripper has potential applications in maintenance-type jobs such as tritium line breaks. This catalyst can also potentially be utilized in an emergency stripper for the Replacement Tritium Facility.

  7. Characterization of active sites in zeolite catalysts

    SciTech Connect

    Eckert, J.; Bug, A.; Nicol, J.M.

    1997-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Atomic-level details of the interaction of adsorbed molecules with active sites in catalysts are urgently needed to facilitate development of more effective and/or environmentally benign catalysts. To this end the authors have carried out neutron scattering studies combined with theoretical calculations of the dynamics of small molecules inside the cavities of zeolite catalysts. The authors have developed the use of H{sub 2} as a probe of adsorption sites by observing the hindered rotations of the adsorbed H{sub 2} molecule, and they were able to show that an area near the four-rings is the most likely adsorption site for H{sub 2} in zeolite A while adsorption of H{sub 2} near cations located on six-ring sites decreases in strength as Ni {approximately} Co > Ca > Zn {approximately} Na. Vibrational and rotational motions of ethylene and cyclopropane adsorption complexes were used as a measure for zeolite-adsorbate interactions. Preliminary studies of the binding of water, ammonia, and methylamines were carried out in a number of related guest-host materials.

  8. Chemical interactions in multimetal/zeolite catalysts

    SciTech Connect

    Sachtler, W.M.H.

    1992-02-07

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

  9. Magnesia-alumina-aluminum phosphate-zeolite catalyst

    SciTech Connect

    Reynolds, E.H.; Stanulonis, J.J.; Swift, H.E.

    1980-09-16

    A catalyst for cracking gasoline feedstock with superior selectivity to gasoline production and greater metals tolerance comprises a magnesia-alumina-aluminum phosphate matrix composited with a zeolite having cracking activity.

  10. Formulation of cracking catalyst based on zeolite and natural clays

    SciTech Connect

    Aliev, R.R.; Lupina, M.I.

    1995-11-01

    Domestically manufactured cracking catalysts are based on a synthetic amorphous aluminosilicate matrix and Y zeolite. A multistage {open_quotes}gel{close_quotes} technology is used in manufacturing the catalysts. The process includes mixing solutions of sodium silicate and acidic aluminum sulfate, forming, syneresis, and activation of the beaded gel. In the manufacture of bead catalysts, the next steps in the process are washing, drying, and calcining; in the manufacture of microbead catalysts, the next steps are dispersion and formation of a hydrogel slurry, spray-drying, and calcining. The Y zeolite is either introduced into the alumina-silica sol in the stage of forming the beads, or introduced in the dispersion stage. With the aim of developing an active and selective cracking catalyst based on Y zeolite and natural clays, with improved physicomechanical properties, the authors carried out a series of studies, obtaining results that are set forth in the present article.

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

    PubMed

    Nowicki, Janusz; Mokrzycki, Łukasz; Sulikowski, Bogdan

    2015-01-01

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

  12. Advanced NMR characterization of zeolite catalysts

    NASA Astrophysics Data System (ADS)

    Welsh, L. B.

    1985-04-01

    The program discussed in this report is a two-year two-phase joint UOP-University of Illinois study of the application of improved high resolution solid state nuclear magnetic resonance (NMR) techniques to the characterization of zeolite catalysts. During the first phase of this program very pure, and in some cases isotopically enriched faujasites will be prepared and studied by magic angle sample spinning NMR (MASS NMR) and variable engine sample spinning NMR (VASS NMR) on 500 and 360 MHz (proton frequency) NMR spectrometers. The NMR techniques that will be emphasized are the measurement and analysis of the (17)O NMR properties, (27)Al NMR intensity quantitation, and (27)Al and (29)Si NMR relaxation rates. During the second phase of this program these NMR techniques will be used to study the effects of impurity concentration, dealumination treatments and cation exchange on the NMR properties of faujasites. The initial emphasis of this program during Phase I is on the preparation and measurement of the NMR properties of (17)O enriched Na-Y faujasties.

  13. Catalytic Fast Pyrolysis of Cellulose Using Nano Zeolite and Zeolite/Matrix Catalysts in a GC/Micro-Pyrolyzer.

    PubMed

    Lee, Kyong-Hwan

    2016-05-01

    Cellulose, as a model compound of biomass, was catalyzed over zeolite (HY,.HZSM-5) and zeolite/matrix (HY/Clay, HM/Clay) in a GC/micro-pyrolyzer at 500 degrees C, to produce the valuable products. The catalysts used were pure zeolite and zeolite/matrix including 20 wt% matrix content, which were prepared into different particle sizes (average size; 0.1 mm, 1.6 mm) to study the effect of the particle size of the catalyst for the distribution of product yields. Catalytic pyrolysis had much more volatile products as light components and less content of sugars than pyrolysis only. This phenomenon was strongly influenced by the particle size of the catalyst in catalytic fast pyrolysis. Also, in zeolite and zeolite/matrix catalysts the zeolite type gave the dominant impact on the distribution of product yields. PMID:27483802

  14. Catalytic Fast Pyrolysis of Cellulose Using Nano Zeolite and Zeolite/Matrix Catalysts in a GC/Micro-Pyrolyzer.

    PubMed

    Lee, Kyong-Hwan

    2016-05-01

    Cellulose, as a model compound of biomass, was catalyzed over zeolite (HY,.HZSM-5) and zeolite/matrix (HY/Clay, HM/Clay) in a GC/micro-pyrolyzer at 500 degrees C, to produce the valuable products. The catalysts used were pure zeolite and zeolite/matrix including 20 wt% matrix content, which were prepared into different particle sizes (average size; 0.1 mm, 1.6 mm) to study the effect of the particle size of the catalyst for the distribution of product yields. Catalytic pyrolysis had much more volatile products as light components and less content of sugars than pyrolysis only. This phenomenon was strongly influenced by the particle size of the catalyst in catalytic fast pyrolysis. Also, in zeolite and zeolite/matrix catalysts the zeolite type gave the dominant impact on the distribution of product yields.

  15. Microcalorimetric study of silica- and zeolite-supported platinum catalysts

    SciTech Connect

    Sharma, S.B.; Dumesic, J.A. ); Miller, J.T. )

    1994-07-01

    Microcalorimetric measurements of the differential heats of hydrogen and carbon monoxide adsorption versus adsorbate coverate were made at 403 K for platinum supported on silica, magnesia/alumina, L-zeolite, Y-zeolite, and ZSM-5. The differential heats at zero coverage for hydrogen and carbon monoxide adsorption were 90 and 140 kJ/mol, respectively, for platinum supported on silica and nonacidic zeolites. The differential heats were large by approximately 20 kJ/mol for hydrogen and carbon monoxide adsorption on platinum particles supported on basis supports such as potassium/silica, magnesia/alumina, and zeolites containing basic cations (K[sup +], Ba[sup 2+]) exchanged in excess of the zeolite framework aluminum content. The microcalorimetric results suggest that the high paraffin aromatization activity and selectivity observed for L-zeolite-supported platinum catalysts do not appear to be caused solely by changes in the adsorptive properties of the cluster-size platinum particles located within the zeolite. 35 refs., 10 figs., 2 tabs.

  16. Chemical interactions in multimetal/zeolite catalysts

    SciTech Connect

    Sachtler, W.M.H.

    1992-02-07

    This report treats four subject areas: PtCu/NaY and Pd/Cu/NaY catalysts; reducibility of Ni in PdNi/NaY catalysts; CO hydrogenation over PdNi/NaY catalysts; and PdFe/NaY, Ga/H-ZSM5 and PtGa/H-ZSM5 catalysts.

  17. Synthesis H-Zeolite catalyst by impregnation KI/KIO3 and performance test catalyst for biodiesel production

    NASA Astrophysics Data System (ADS)

    Widayat, W.; Rizky Wicaksono, Adit; Hakim Firdaus, Lukman; Okvitarini, Ndaru

    2016-02-01

    The objective of this research is to produce H-catalyst catalyst that was impregnated with KI/KIO3. The catalyst was analyzed about surface area, X-Ray Diffraction (XRD) and performance test of catalyst for biodiesel production. An H-Zeolite catalyst was synthesized from natural zeolite with chemical treatment processing, impregnation KI/KIO3 and physical treatment. The results shows that the surface area of the catalyst by 27.236 m2/g at a concentration of 5% KI. XRD analysis shows peak 2-θ at 23.627o indicating that KI was impregnated on H-zeolite catalyst. The catalyst was tested in production of biodiesel using palm oil with conventional methods for 3 hour at temperature of 70-80 oC. The result for conversion Fatty Acid Methyl Ester (FAME) reached maximum value on 87.91% under production process using catalyst 5% KIO3-H zeolite.

  18. Metal resistance of zeolitic cracking catalysts

    SciTech Connect

    Chester, A.W.

    1981-03-01

    The impregnation-cracking technique of metal poisoning provides a rapid method for determining the metal resistance of a series of cracking catalysts. The method is useful for determining the effects of changes in a closely related series of catalysts or in evaluating a wide spectrum of commercially available catalysts. Containment-yields parameters allow determination of metal resistance independently of other catalyst properties. Actual catalyst performance, as indicated by the adjusted yields, is determined by both metal resistance characteristics and inherent selectivity. The results obtained in these tests are, however, relative and are not quantitatively translatable to commercial performance. Further, the impregnation-cracking technique allows detailed examination of some of the fundamental phenomena involved in metal poisoning. The overall validity of the method for qualitatively rating metal resistance can be - and has been - verified by comparing the behavior of the same catalysts in commercial units. The effect of antimony on metal poisons in commercial units has been reported and is successfully mimicked by the laboratory method. Relative metal activities, synergistic effects and metal dependences are readily determined for catalysts of particular interest. The different relative metal (Ni and V) activities for coke and hydrogen production is of importance in unit design for high metal feedstocks. In commercial FCC units, conversion or throughput is limited by either coke or hydrogen yields. Thus, units designed for increased contaminant yields based on a Ni/V activity ratio of 4 may well be underdesigned for coke. A knowledge of catalyst metal resistance, as determined here, coupled with feedstock properties, should allow more efficient designs for cracking processes for high-metal residual feedstocks.

  19. Heterogeneities of the nanostructure of platinum/zeolite y catalysts revealed by electron tomography.

    PubMed

    Zečević, Jovana; van der Eerden, Ad M J; Friedrich, Heiner; de Jongh, Petra E; de Jong, Krijn P

    2013-04-23

    To develop structure-performance relationships for important catalysts, a detailed characterization of their morphology is essential. Using electron tomography, we determined in three dimensions the structure of Pt/zeolite Y bifunctional catalysts. Optimum experimental conditions enabled for the first time high-resolution 3D imaging of Pt particles as small as 1 nm located inside zeolite micropores. Semiautomated image analysis of 3D reconstructions provided an efficient study of numbers, size distributions, and interparticle distances of thousands of Pt particles within individual zeolite crystals. Upon extending this approach to a number of zeolite crystals of one batch of Pt/zeolite Y catalyst, heterogeneities were revealed. The Pt loading, an important parameter for catalyst performance, varied between zeolite crystals up to a factor of 35. This discovery calls for re-evaluation of catalyst preparation methods and suggests potential for lowering the nominal loading with noble metals.

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

    NASA Astrophysics Data System (ADS)

    Campen, Adam

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

  1. Catalyst Activity Comparison of Alcohols over Zeolites

    SciTech Connect

    Ramasamy, Karthikeyan K.; Wang, Yong

    2013-01-01

    Alcohol transformation to transportation fuel range hydrocarbon on HZSM-5 (SiO2 / Al2O3 = 30) catalyst was studied at 360oC and 300psig. Product distributions and catalyst life were compared using methanol, ethanol, 1-propanol or 1-butanol as a feed. The catalyst life for 1-propanol and 1-butanol was more than double compared to that for methanol and ethanol. For all the alcohols studied, the product distributions (classified to paraffin, olefin, napthene, aromatic and naphthalene compounds) varied with time on stream (TOS). At 24 hours TOS, liquid product from 1-propanol and 1-butanol transformation primarily contains higher olefin compounds. The alcohol transformation process to higher hydrocarbon involves a complex set of reaction pathways such as dehydration, oligomerization, dehydrocyclization, and hydrogenation. Compared to ethylene generated from methanol and ethanol, oligomerization of propylene and butylene has a lower activation energy and can readily take place on weaker acidic sites. On the other hand, dehydrocyclization of propylene and butylene to form the cyclic compounds requires the sits with stronger acid strength. Combination of the above mentioned reasons are the primary reasons for olefin rich product generated in the later stage of the time on stream and for the extended catalyst life time for 1 propanol and 1 butanol compared to methanol and ethanol conversion over HZSM-5.

  2. Mechanochemical approach for selective deactivation of external surface acidity of ZSM-5 zeolite catalyst.

    PubMed

    Inagaki, Satoshi; Sato, Koki; Hayashi, Shunsuke; Tatami, Junichi; Kubota, Yoshihiro; Wakihara, Toru

    2015-03-01

    The acid sites associated with the external surface of zeolite particles are responsible for undesirable consecutive reactions, such as isomerization, alkylation, and oligomerization, resulting in a lower selectivity to a target product; therefore, the selective modification (deactivation) of the external surface of zeolite particles has been an important issue in zeolite science. Here, a new method for surface deactivation of zeolite catalyst was tested via a mechanochemical approach using powder composer. Postsynthetic mechanochemical treatment of ZSM-5 zeolite causes a selective deactivation of catalytically active sites existing only on the external surface, as a potentially useful catalyst for highly selective production of p-xylene.

  3. Novel zeolite-supported rhodium catalysts for ethanol steam reforming

    NASA Astrophysics Data System (ADS)

    Campos-Skrobot, Fabiana C.; Rizzo-Domingues, Roberta C. P.; Fernandes-Machado, Nádia R. C.; Cantão, Mauricio P.

    Renewable bioethanol is an interesting hydrogen source for fuel cells through steam reforming, but its C-C bond promotes parallel reactions, mainly coke and by-products formation. In this way, good ethanol reforming catalysts are still needed, which explains current research and development efforts around the world. Most catalysts proposed for ethanol reforming are based on oxide-supported noble metals with surface area below 100 m 2 g -1 and reaction temperatures above 500 °C. Novel Rh and Rh-K catalysts supported on NaY zeolite with surface area above 440 m 2 g -1 are presented in this work. Reaction temperature was fixed at 300 °C and H 2O/EtOH molar ratio and reagent flow were varied. Ethanol conversion varied from 50 to 99%, with average increase of 50% due to K promoter, and hydrogen production yield achieved 68%.

  4. In Situ Observation of Active Oxygen Species in Fe-Containing Ni-Based Oxygen Evolution Catalysts: The Effect of pH on Electrochemical Activity.

    PubMed

    Trześniewski, Bartek J; Diaz-Morales, Oscar; Vermaas, David A; Longo, Alessandro; Bras, Wim; Koper, Marc T M; Smith, Wilson A

    2015-12-01

    Ni-based oxygen evolution catalysts (OECs) are cost-effective and very active materials that can be potentially used for efficient solar-to-fuel conversion process toward sustainable energy generation. We present a systematic spectroelectrochemical characterization of two Fe-containing Ni-based OECs, namely nickel borate (Ni(Fe)-B(i)) and nickel oxyhydroxide (Ni(Fe)OOH). Our Raman and X-ray absorption spectroscopy results show that both OECs are chemically similar, and that the borate anions do not play an apparent role in the catalytic process at pH 13. Furthermore, we show spectroscopic evidence for the generation of negatively charged sites in both OECs (NiOO(-)), which can be described as adsorbed "active oxygen". Our data conclusively links the OER activity of the Ni-based OECs with the generation of those sites on the surface of the OECs. The OER activity of both OECs is strongly pH dependent, which can be attributed to a deprotonation process of the Ni-based OECs, leading to the formation of the negatively charged surface sites that act as OER precursors. This work emphasizes the relevance of the electrolyte effect to obtain catalytically active phases in Ni-based OECs, in addition to the key role of the Fe impurities. This effect should be carefully considered in the development of Ni-based compounds meant to catalyze the OER at moderate pHs. Complementarily, UV-vis spectroscopy measurements show strong darkening of those catalysts in the catalytically active state. This coloration effect is directly related to the oxidation of nickel and can be an important factor limiting the efficiency of solar-driven devices utilizing Ni-based OECs.

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

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2007-09-30

    The objective of this project is to synthesize nanocrystals of highly acidic zeolite Y nanoclusters, 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. In comparison to conventionally-used zeolite Y catalysts of micron size particles, the nanocrystals (< 100 nm particle size) which contain shorter path lengths, are expected to allow faster diffusion of large hydrocarbon substrates and the catalysis products within and out of the zeolite's channels and cages (<1 nm size). This is expected to significantly reduce deactivation of the catalyst and to prolong their period of reactivity. Encapsulating zeolite Y nanocrystals within the nanoporous materials is expected to protect its external surfaces and pore entrances from being blocked by large hydrocarbon substrates, since these substrates will initially be converted to small molecules by the nanoporous host (a catalyst in its own right). The project consisted of four major tasks as follows: (1) synthesis of the nanoparticles of zeolite Y (of various chemical compositions) using various techniques such as the addition of organic additives to conventional zeolite Y synthesis mixtures to suppress zeolite Y crystal growth; (2) synthesis of nanoporous silicate host materials of up to 30 nm pore diameter, using poly (alkylene oxide) copolymers which when removed will yield a mesoporous material; (3) synthesis of zeolite Y/Nanoporous Host composite materials as potential catalysts; and (4) evaluation of the catalyst for the upgrading of heavy petroleum feedstocks.

  6. Scandium(III)-zeolites as new heterogeneous catalysts for imino-Diels-Alder reactions.

    PubMed

    Olmos, Andrea; Louis, Benoit; Pale, Patrick

    2012-04-16

    This study demonstrates the first zeolite-catalyzed synthesis of piperidine derivatives, including peptidomimetics and indoloquinolizidine alkaloids. The approach developed utilizes a highly effective one-pot reaction cascade, through imine formation and imino-Diels-Alder reactions, promoted by scandium-loaded zeolites as a heterogeneous catalyst. The methodology described benefits from very low catalyst loadings (≤5 mol % of Sc(III) ), commercially and readily available starting materials, and mild reaction conditions. Furthermore, the Sc(III) -zeolite catalyst can be readily reused more than 10 times without any loss in efficiency.

  7. Selective Ring Opening of 1-Methylnaphthalene Over NiW-Supported Catalyst Using Dealuminated Beta Zeolite.

    PubMed

    Kim, Eun-Sang; Lee, You-Jin; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

    2016-02-01

    Nanoporous Beta zeolite was dealuminated by weak acid treatment for reducing the acidity. Bi-functional catalysts were prepared using commercial Beta zeolites and the dealuminated zeolites for acidic function, NiW for metallic function. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction has been investigated using the prepared bi-functional catalysts with different acidity in fixed bed reaction system. The dealuminated Beta zeolites, which crystal structure and nanoporosity were maintained, showed the higher SiO2/Al2O3 ratio and smaller acidity than their original zeolite. NiW-supported catalyst using the dealuminated Beta zeolite with SiO2/Al203 mole ratio of 55 showed the highest performance for the selective ring opening. The acidity of catalyst seemed to play an important role as active sites for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. The acidity of Beta zeolite could be controlled by the acid treatment and the catalyst with the optimum acidity for the selective ring opening could be prepared.

  8. Selective Ring Opening of 1-Methylnaphthalene Over NiW-Supported Catalyst Using Dealuminated Beta Zeolite.

    PubMed

    Kim, Eun-Sang; Lee, You-Jin; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

    2016-02-01

    Nanoporous Beta zeolite was dealuminated by weak acid treatment for reducing the acidity. Bi-functional catalysts were prepared using commercial Beta zeolites and the dealuminated zeolites for acidic function, NiW for metallic function. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction has been investigated using the prepared bi-functional catalysts with different acidity in fixed bed reaction system. The dealuminated Beta zeolites, which crystal structure and nanoporosity were maintained, showed the higher SiO2/Al2O3 ratio and smaller acidity than their original zeolite. NiW-supported catalyst using the dealuminated Beta zeolite with SiO2/Al203 mole ratio of 55 showed the highest performance for the selective ring opening. The acidity of catalyst seemed to play an important role as active sites for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. The acidity of Beta zeolite could be controlled by the acid treatment and the catalyst with the optimum acidity for the selective ring opening could be prepared. PMID:27433655

  9. Influence of zeolite content and nature of matrix on properties of cracking catalysts

    SciTech Connect

    Klaptsov, V.F.; Khlebnikova, M.A.; Maslova, A.A.; Nefedov, B.K.

    1986-07-01

    This paper reports on an investigation of the bulk density, attrition resistance, and catalytic activity of cracking catalysts synthesized by mechanical mixing of components (zeolite, pseudoboehmite, a silica sol, clay, and kaolin). The data presented demonstrate the feasibility of commercial preparation of a microbead cracking catalyst using a low-waste technology, the catalyst having satisfactory agreement between the properties of the milled catalyst and the microbead catalyst. This indicated good reproductibility of the laboratory results under near-commercial conditions.

  10. Nanocrystalline SSZ-39 zeolite as an efficient catalyst for the methanol-to-olefin (MTO) process.

    PubMed

    Martín, Nuria; Li, Zhibin; Martínez-Triguero, Joaquín; Yu, Jihong; Moliner, Manuel; Corma, Avelino

    2016-04-26

    The synthesis of nanosized SSZ-39 zeolite has been achieved using a high silica FAU zeolite as the Si and Al source and tetraethylphosphonium (TEP) cations as OSDAs. The obtained SSZ-39 material shows a remarkably high catalyst lifetime compared to conventional SSZ-13 and SSZ-39 materials. PMID:26947336

  11. Catalytic conversion of palm oil to hydrocarbons: Performance of various zeolite catalysts

    SciTech Connect

    Twaiq, F.A.; Zabidi, N.A.M.; Bhatia, S.

    1999-09-01

    The catalytic cracking of palm oil to fuels was studied in a fixed bed microreactor operated at atmospheric pressure, a reaction temperature of 350--450 C and weight hourly space velocities (WHSVs) of 1--4 h{sup {minus}1}. HZSM-5, zeolite {beta}, and ultrastable Y (USY) zeolites with different pore sizes were used to study the effects of reaction temperature and WHSV on the conversion of palm oil and yields of gasoline. The performances of HZSM-5-USY and HZSM-5-zeolite {beta} hybrid catalysts containing 10, 20, and 30 wt % HZSM-5 were investigated. Potassium-impregnated K-HZSM-5 catalysts with different potassium loadings were used to study the effect of acidity on the selectivity for gasoline formation. The major products obtained were organic liquid product (OLP), hydrocarbon gases, and water. HZSM-5 catalyst gave conversion of 99 wt % and a gasoline yield of 28 wt % at a reaction temperature of 350 C and WHSV of 1 h{sup {minus}1} and was the best among the three zeolites tested. The HZSM-5-USY hybrid catalyst performed better than USY catalyst as it resulted in a higher gasoline yield, whereas HZSM-5-zeolite {beta} hybrid catalyst gave lower conversion compared to that of zeolite {beta}. The selectivity for gasoline decreased from 45 to 10 wt % with an increase in potassium concentration from 0 to 1.5 wt %.

  12. Development of advanced zeolite catalysts for the vapor phase Beckmann rearrangement of cyclohexanone oxime

    NASA Astrophysics Data System (ADS)

    Dai, Lian-Xin; Iwaki, Yoshihide; Koyama, Katsuyuki; Tatsumi, Takashi

    1997-11-01

    The vapor phase Beckmann rearrangement of cyclohexanone oxime to ɛ-caprolactam catalyzed by various zeolites was studied. The catalytic performance was greatly affected by both the zeolite structure and diluent solvent. When 1-hexanol was used in place of benzene, the catalytic performance of all catalysts except silicalite-1 was greatly improved. In particular, the selectivity and stability of H-LTL and H-OFF-ERI zeolites remarkably increased; both catalysts exhibited ca. 100% oxime conversion and ɛ-caprolactam selectivity of >95% for 6 h.

  13. Transformation of phenol and its ethers in conditions of hydrogenation on bifunctional zeolite catalysts

    SciTech Connect

    Marchenko, L.S.; Levin, D.Z.; Plakhotnik, V.A.; Mortikov, E.S.

    1986-07-10

    The reaction of hydrodimerization of phenol, anisole, and phenetole on bifunctional zeolite catalysts and the products and mechanism of the reaction were investigated. 2-Cyclohexylcyclohexanone is the basic product of the hydrodimerization of phenol, anisole, and phenetole in the presence of bifunctional zeolite catalysts containing palladium, nickel, rhodium, calcium, and lanthanum. The activity of the catalysts is a function of the type of cations added. Hydrodimerization of phenol and its ethers takes place through the stage of hydrogenation of the starting substances to cyclohexanone on metallic sites with subsequent condensation to 2-cyclohexylidenecyclohexane on acid sites and hydrogenation of the latter to 2-cyclohexylcyclohexanone.

  14. The Different Impacts of SO2 and SO3 on Cu/zeolite SCR Catalysts

    SciTech Connect

    Cheng, Y.; Lambert, C; Kim, D; Kwak, J; Cho, S; Peden, C

    2010-01-01

    The different impacts of SO{sub 2} and SO{sub 3} on Cu/zeolite SCR catalysts were investigated by SCR performance tests and multiple characterization techniques including temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS). The results indicate that a larger amount of highly dispersed CuSO{sub 4} formed in the zeolite catalysts (Z-CuSO{sub 4}) upon SO{sub 3} poisoning, explaining the much more significant deactivation of the Cu/zeolite catalysts that were exposed to SO{sub 3} compared to poisoning by SO{sub 2}. This paper provides the first demonstration that active sites of Cu/zeolite SCR catalysts involved in the storage and removal of sulfur can react with SO{sub 2} and SO{sub 3} in very different ways. In particular, the significant differences in the extent of sulfur uptake account for the considerably different impacts of SO{sub 2} and SO{sub 3} poisoning on the performance of Cu/zeolite SCR catalysts.

  15. The Different Impacts of SO2 and SO3 on Cu/Zeolite SCR Catalysts

    SciTech Connect

    Cheng, Yisun; Lambert, Christine; Kim, Do Heui; Kwak, Ja Hun; Cho, Sung June; Peden, Charles HF

    2010-06-19

    The different impacts of SO2 and SO3 on Cu/zeolite SCR catalysts were investigated by SCR performance tests and multiple characterization techniques including temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS). The results indicate that a larger amount of highly dispersed CuSO4 formed in the zeolite catalysts (Z-CuSO4) upon SO3 poisoning, explaining the much more significant deactivation of the Cu/zeolite catalysts that were exposed to SO3 compared to poisoning by SO2. This paper provides the first demonstration that active sites of Cu/zeolite SCR catalysts involved in the storage and removal of sulfur can react with SO2 and SO3 in very different ways. In particular, the significant differences in the extent of sulfur uptake account for the considerably different impacts of SO2 and SO3 poisoning on the performance of Cu/zeolite SCR catalysts.

  16. Palladium-Zeolite nanofiber as an effective recyclable catalyst membrane for water treatment.

    PubMed

    Choi, Jungsu; Chan, Sophia; Yip, Garriott; Joo, Hyunjong; Yang, Heejae; Ko, Frank K

    2016-09-15

    Zeolite is an exciting natural material due to its unique capability of ammonium nitrogen (NH3N) adsorption in water. In this study, multifunctional hybrid composites of zeolite/palladium (Ze/Pd) on polymer nanofiber membranes were fabricated and explored for sustainable contaminant removal. SEM and XRD demonstrated that zeolite and palladium nanoparticles were uniformly distributed and deposited on the nanofibers. NH3N recovery rate was increased from 23 to 92% when palladium coated zeolite was embedded on the nanofiber. Multifunctional nanofibers of Ze/Pd membranes were able to adsorb NH3N on the zeolites placed on the surface of fibers and palladium catalysts were capable of selective oxidation of NH3N to N2 gas. The cycling of NH3N adsorption-oxidation, high flux, hydrophilicity, and flexibility of the membrane makes it a strong candidate for water treatment. PMID:27253639

  17. Zeolite-based SCR catalysts and their use in diesel engine emission treatment

    DOEpatents

    Narula, Chaitanya K; Yang, Xiaofan

    2015-03-24

    A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

  18. Zeolite-based SCR catalysts and their use in diesel engine emission treatment

    DOEpatents

    Narula, Chaitanya K.; Yang, Xiaofan

    2016-08-02

    A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

  19. HDS activity and characterization of zeolite-supported nickel sulfide catalysts

    SciTech Connect

    Welters, W.J.J.; Vorbeck, G.; Haan, J.W. de; Beer, V.H.J. de; Santen, R.A. van; Zandbergen, H.W.

    1994-11-01

    Catalysts of nickel sulfide supported on zeolite Y have been prepared (by impregnation or ion exchange) and characterized by means of thiophene hydrodesulfurization (HDS), sulfur analysis, temperature-programmed sulfiding, {sup 129}Xe-NMR, HREM and dynamic oxygen chemisorption. The catalysts show large differences in catalytic behavior dependent on the preparation method (impregnation vs ion exchange) and the pretreatment conditions (method of sulfidation). Especially the ion-exchanged catalysts show a high initial activity, but due to the presence of acid sites deactivation is very strong. The initial activity of these catalysts can be improved significantly by drying prior to sulfidation. In all cases sulfidation results in quantitative formation of nickel sulfide, with Ni{sub 3}S{sub 2} being the main product. Occasionally, also some NiS appears to be present. The major part of the nickel sulfide phase is invariably located on the outside of the zeolite particles. The fraction of nickel sulfide in the zeolite pores depends on the preparation method and the pretreatment conditions. The differences in catalytic activity are ascribed not only to variations in overall nickel sulfide dispersion but also to the acidity of the support, and the presence of very active small nickel sulfide clusters in the pores of the zeolite can have a strong influence on the thiophene HDS activity. 40 refs., 13 figs., 3 tabs.

  20. Catalytic cracking with zeolite-containing silica-alumina hydrogel catalyst

    SciTech Connect

    Kuehl, G.H.; Sherry, H.S.

    1980-08-26

    A specially prepared zeolite-containing silica-alumina hydrogel gives a catalyst that is attrition resistant, more active catalytically, more selective and more stable. The hydrogel is prepared by steps including nozzle mixing of reactants to form a hydrogel, ion exchanging with ammonium, aluminum and rare earth ions, washing, drying and impregnating with rare earths.

  1. Evaluation of photocatalytic activities of supported catalysts on NaX zeolite or activated charcoal.

    PubMed

    de Brites-Nóbrega, Fernanda F; Polo, Aldino N B; Benedetti, Angélica M; Leão, Mônica M D; Slusarski-Santana, Veronice; Fernandes-Machado, Nádia R C

    2013-12-15

    This study aimed to evaluate the photocatalytic activity of ZnO and Nb2O5 catalysts, both supported on NaX zeolite and activated charcoal (AC). The synergistic effect between oxide and support and the influence of solution pH (3, 7 and 9) on photocatalytic degradation of reactive blue 5G (C.I. 222) were analyzed. The catalysts Nb2O5/NaX, Nb2O5/AC and ZnO/NaX, ZnO/AC with 5 and 10% (wt%) were prepared by wet impregnation. The results showed that the catalysts exhibit quite different structural and textural properties. The synergic effect between ZnO and NaX support was higher than that with the activated charcoal, showing that these catalysts were more efficient. The most photoactive catalyst was 10% ZnO/NaX which showed 100% discoloration of the dye solution at pH 3, 7 and 9 after 0.5, 5 and 2h of irradiation, respectively. The hydrolytic nature of zeolite favored the formation of surface hydroxyl radicals, which increased the activity of the photocatalyst. Thus, catalysts supported on NaX zeolite are promising for use in photocatalysis.

  2. Evaluation of some new zeolite-supported metal catalysts for synthesis gas conversion

    SciTech Connect

    Melson, G.A.; Crawford, J.E.; Crites, J.W.; Mbadcam, K.J.; Rao, V.U.S.; Stencel, J.M.

    1982-03-01

    The use of bifunctional zeolite-based catalysts for the conversion of synthesis gas (carbon monoxide and hydrogen) to gasoline range hydrocarbons has recently attracted much attention. For example, the combination of metal oxides with the medium pore (about 6A) zeolite ZSM-5 and the use of a metal nitrate impregnated ZSM-5 catalyst have been shown to produce gasoline range hydrocarbons containing a high percentage of aromatics from synthesis gas. The production of gasoline range hydrocarbons which have a high olefin content has also been reported by using iron or cobalt impregnated ZSM-5 catalysts. The efficiency and selectivity of supported metal heterogeneous catalysts is closely related to the dispersion and particle size of the metal component and to the nature of the interaction between the metal and the support. For a particular metal, catalytic activity may be varied by changing the metal dispersion and the support, thus, the method of synthesis and any pre-treatment of the catalyst is important in the overall process of catalyst evaluation. Supported metal catalysts have traditionally been prepared by impregnation techniques that involve treatment of a support with an aqueous solution of a metal salt followed by calcination. In the Fe/ZSM-5, system, the decomposition of the iron nitrate during calcination usually produces iron oxides of relatively large crystallite size. This work was initiated in an attempt to produce highly dispersed, thermally stable supported metal catalysts which may be effective for synthesis gas conversion.

  3. Possible Origin of Improved High Temperature Performance of Hydrothermally Aged Cu/Beta Zeolite Catalysts

    SciTech Connect

    Peden, Charles HF; Kwak, Ja Hun; Burton, Sarah D.; Tonkyn, Russell G.; Kim, Do Heui; Lee, Jong H.; Jen, H. W.; Cavattaio, Giovanni; Cheng, Yisun; Lambert, Christine

    2012-04-30

    The hydrothermal stability of Cu/beta NH3 SCR catalysts are explored here. In particular, this paper focuses on the interesting ability of this catalyst to maintain and even enhance high-temperature performance for the "standard" SCR reaction after modest (900 °C, 2 hours) hydrothermal aging. Characterization of the fresh and aged catalysts was performed with an aim to identify possible catalytic phases responsible for the enhanced high temperature performance. XRD, TEM and 27Al NMR all showed that the hydrothermally aging conditions used here resulted in almost complete loss of the beta zeolite structure between 1 and 2 hours aging. While the 27Al NMR spectra of 2 and 10 hour hydrothermally-aged catalysts showed significant loss of a peak associated with tetrahedrally-coordinated Al species, no new spectral features were evident. Two model catalysts, suggested by these characterization data as possible mimics of the catalytic phase formed during hydrothermal aging of Cu/beta, were prepared and tested for their performance in the "standard" SCR and NH3 oxidation reactions. The similarity in their reactivity compared to the 2 hour hydrothermally-aged Cu/beta catalyst suggests possible routes for preparing multi-component catalysts that may have wider temperature windows for optimum performance than those provided by current Cu/zeolite catalysts.

  4. NMR Studies of Cu/zeolite SCR Catalysts Hydrothermally Aged with Urea

    SciTech Connect

    Cheng, Yisun; Hoard, John; Lambert, Christine; Kwak, Ja Hun; Peden, Charles HF

    2008-06-26

    The effects of hydrothermal aging of Cu/zeolite urea-SCR catalysts on their reactivity and material properties was assessed by performance tests and multiple characterization techniques that included 27Al NMR and XRD. Three aging protocols were used that consisted of varying temperature during hydrothermal aging with or without exposure to aqueous urea solution. Differences in behavior were even found for samples hydrothermally aged immediately following exposure to the urea solution or if the sample was dried overnight before hydrothermal aging. The combination of urea and high temperature exposure increased the deactivation of Cu/zeolite SCR catalysts beyond that observed by hydrothermal aging alone, with an immediate high temperature exposure following wetting of the catalyst core with aqueous urea causing the most significant deterioration in performance. The impact of urea on SCR catalyst durability was also found to increase with the aging temperature. NMR analysis suggested that aging with urea resulted in relatively more dealumination of the zeolite for the SCR catalysts in this study.

  5. Studies on the metal poisoning and metal resistance of zeolitic cracking catalysts

    SciTech Connect

    Chester, A.W.

    1987-05-01

    The effects of metal poisons (Ni, V) on zeolitic cracking catalyst have been investigated with the goal of developing a method for determining the inherent metal resistance of different catalyst compositions in the laboratory. Metal resistance is evaluated by determining activity and selectivity both before and after a synthetic poisoning procedure so that ''contaminant yields'' - the excess coke and hydrogen produced by metals during cracking - could be calculated. After several methods are compared, that chosen involves impregnation of steam-deactivated catalysts with a gas oil doped with metal naphthenates, followed by high-temperature cracking and regeneration.

  6. Metalloenzyme-Like Zeolites as Lewis Acid Catalysts for C-C Bond Formation.

    PubMed

    Van de Vyver, Stijn; Román-Leshkov, Yuriy

    2015-10-19

    The use of metalloenzyme-like zeolites as Lewis acid catalysts for C-C bond formation reactions has received increasing attention over the past few years. In particular, the observation of direct aldol condensation reactions enabled by hydrophobic zeolites with isolated framework metal sites has encouraged the development of catalytic approaches for producing chemicals from biomass-derived compounds. The discovery of new Diels-Alder cycloaddition/dehydration routes and experimental and computational studies of Lewis acid catalyzed carbonyl-ene reactions have given a further boost to this rapidly evolving field. PMID:26465652

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

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2006-09-30

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

  8. Zealous zeolites

    SciTech Connect

    Hairston, D.W.

    1996-07-01

    Zeolites have made significant inroads in fluid cracking catalysts for gasoline and have pushed phosphates out of laundry detergents. But these crystalline aluminosilicate structures are just beginning to make their mark in chemical processes and environmental applications. Ideally suited for work as molecular sieves and catalysts, zeolites sport uniform surface pores and channels that are receptive only to molecules of a specific size and shape. This high selectivity makes zeolites a good alterative to some of the conventional products used for chemical reaction and filtration. One of the most potentially lucrative markets for zeolites is chemical catalyst replacements for liquid acids, such as hydrofluoric acid and sulfuric acid, and aluminum chloride in a number of alkylation and acrylation reactions. Zeolites are also being considered for oligomerization,isomerization, amination and condensation processes for the manufacture of chemical intermediates. The paper discusses the market and manufacturers of zeolites, justifying the cost of converting to zeolite catalysts, and natural zeolites.

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

    PubMed

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

    2011-11-01

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

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

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2006-06-20

    Al-SBA-15 mesoporous catalysts with strong Broensted acid sites and Al stabilized in a totally tetrahedral coordination was synthesized from the addition of hydrothermally aged zeolite Y precursor to SBA-15 synthesis mixture under mildly acidic condition of pH 5.5. The materials possessed surface areas between 690 and 850 m{sup 2}/g, pore sizes ranging from 5.6 to 7.5 nm and pore volumes up 1.03 cm{sup 3}, which were comparable to parent SBA-15 synthesized under similar conditions. Up to 2 wt. % Al was present in the most aluminated sample that was investigated, and the Al remained stable in totally tetrahedral coordination, even after calcination at 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. The catalyst's activity was not affected by the aging time of the precursor for up to the 24 hr aging time investigated. This method of introducing Al and maintaining it in a total tetrahedral coordination is very effective, in comparison to other direct and post synthesis alumination methods reported. The catalytic performance of the zeolite Y/SBA-15 composite materials will be compared with that of pure SBA-15. The catalysts will then be evaluated for the conversion of heavy petroleum feedstocks.

  11. Hydrocracking of n-decane over zeolite-supported metal sulfide catalysts. 2: Zeolite Y-supported Ni and Ni-Mo sulfides

    SciTech Connect

    Welters, W.J.J.; Waerden, O.H. van der; Beer, V.H.J. de; Santen, R.A. van

    1995-04-01

    For zeolite Y-supported nickel sulfide catalysts the influence of the metal sulfide dispersion on the hydrocracking properties for n-decane is examined. In order to obtain different nickel sulfide distributions (inside or outside the zeolite structure) and dispersions, the preparation method (impregnation of CaY or ion exchange of NaY), sulfidation procedure (direct sulfidation or sulfidation after drying), and metal loading are varied. A higher nickel sulfide surface (as measured by dynamic oxygen chemisorption) results in a strong increase of the n-decane conversion, but this is not accompanied by an improvement of the catalytic properties toward ideal hydrocracking. Additionally, some zeolite Y-supported Ni-Mo sulfide catalysts (varying in preparation method and sulfidation procedure) are tested for the hydroconversion of it-decane. However, no promoter effect could be observed. The activity of the bimetallic sulfide catalysts is always almost equal to that of the most active monometallic sulfide constituent.

  12. Characterization of Na+- beta-Zeolite Supported Pd and Pd Ag Bimetallic Catalysts using EXAFS, TEM and Flow Reactor

    SciTech Connect

    Huang,W.; Lobo, R.; Chen, J.

    2008-01-01

    Flow reactor studies of the selective hydrogenation of acetylene in the presence of ethylene have been performed on Na+ exchanged {beta}-zeolite supported Pd, Ag and PdAg catalysts, as an extension of our previous batch reactor studies [W. Huang, J.R. McCormick, R.F. Lobo, J.G. Chen, J. Catal. 246 (2007) 40-51]. Results from flow reactor studies show that the PdAg/Na+-{beta}-zeolite bimetallic catalyst has lower activity than Pd/Na+-{beta}-zeolite monometallic catalyst, while Ag/Na+-{beta}-zeolite does not show any activity for acetylene hydrogenation. However, the selectivity for the PdAg bimetallic catalyst is much higher than that for either the Pd catalyst or Ag catalyst. The selectivity to byproduct (ethane) is greatly inhibited on the PdAg bimetallic catalyst as well. The results from the current flow reactor studies confirmed the pervious results from batch reactor studies [W. Huang, J.R. McCormick, R.F. Lobo, J.G. Chen, J. Catal. 246 (2007) 40-51]. In addition, we used transmission electron microscope (TEM), extended X-ray absorption fine structure (EXAFS), and FTIR of CO adsorption to confirm the formation of Pd-Ag bimetallic alloy in the PdAg/Na+-{beta}-zeolite catalyst.

  13. 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

  14. Deactivation of Accelerated Engine-Aged and Field-Aged Fe-Zeolite SCR Catalysts

    SciTech Connect

    Toops, Todd J; Nguyen, Ke; Foster, Adam; Bunting, Bruce G; Hagaman, Edward {Ed} W; Jiao, Jian

    2010-01-01

    A single-cylinder diesel engine with an emissions control system - diesel oxidation catalyst (DOC), Fe-zeolite selective catalytic reduction (SCR) catalyst, and diesel particulate filter (DPF) - was used to perform accelerated thermal aging of the SCR catalyst. Cyclic aging is performed at SCR inlet temperatures of 650, 750 and 850 degrees C for up to 50 aging cycles. To assess the validity of the implemented accelerated thermal aging protocol, a field-aged SCR catalyst of similar formulation was also evaluated. The monoliths were cut into sections and evaluated for NO{sub x} performance in a bench-flow reactor. While the rear section of both the field-aged and the accelerated engine-aged SCR catalysts maintained high NO{sub x}conversion, 75-80% at 400 degrees C, the front section exhibited a drastic decrease to only 20-35% at 400 degrees C. This two-tiered deactivation was also observed for field-aged samples that were analyzed in this study. To understand the observed performance changes, thorough materials characterization was performed which revealed two primary degradation mechanisms. The first mechanism is a general Fe-zeolite deterioration which led to surface area losses, dealumination of the zeolite, and Fe{sub 2}O{sub 3} crystal growth. This degradation accelerated above 750 degrees C, and the effects were generally more severe in the front of the catalyst. The second deactivation mechanism is linked to trace levels of Pt that are suspected to be volatizing from the DOC and depositing on the front section of the SCR catalyst. Chemical evidence of this can be seen in the high levels of NH{sub 3} oxidation (80% conversion at 400 degrees C), which coincides with the decrease in performance.

  15. DIRECT DECOMPOSITION OF METHANE TO HYDROGEN ON METAL LOADED ZEOLITE CATALYST

    SciTech Connect

    Lucia M. Petkovic; Daniel M. Ginosar; Kyle C. Burch; Harry W. Rollins

    2005-08-01

    The manufacture of hydrogen from natural gas is essential for the production of ultra clean transportation fuels. Not only is hydrogen necessary to upgrade low quality crude oils to high-quality, low sulfur ultra clean transportation fuels, hydrogen could eventually replace gasoline and diesel as the ultra clean transportation fuel of the future. Currently, refinery hydrogen is produced through the steam reforming of natural gas. Although efficient, the process is responsible for a significant portion of refinery CO2 emissions. This project is examining the direct catalytic decomposition of methane as an alternative to steam reforming. The energy required to produce one mole of hydrogen is slightly lower and the process does not require water-gas-shift or pressure-swing adsorption units. The decomposition process does not produce CO2 emissions and the product is not contaminated with CO -- a poison for PEM fuel cells. In this work we examined the direct catalytic decomposition of methane over a metal modified zeolite catalyst and the recovery of catalyst activity by calcination. A favorable production of hydrogen was obtained, when compared with previously reported nickel-zeolite supported catalysts. Reaction temperature had a strong influence on catalyst activity and on the type of carbon deposits. The catalyst utilized at 873 and 973 K could be regenerated without any significant loss of activity, however the catalyst utilized at 1073 K showed some loss of activity after regeneration.

  16. Using High-Voltage Direct Current in Removing Coke from a Zeolite Catalyst Grain

    NASA Astrophysics Data System (ADS)

    Aljalal, Abdulaziz

    2009-03-01

    Zeolite catalysts are commonly used in petroleum refining processes. Over a period of time, these catalysts lose their activity due to gradual deposition of carbonaceous materials, called coke. The coked catalysts are usually reactivated by combusting the coke at elevated temperatures in presence of an oxygen-enriched gas. But the elevated temperatures cause damages to the structure of the catalyst which result in reduced activity. Normally, the catalyst is reactivated 3 or 4 times before it must be returned to the manufacturer for reclamation of the valuable platinum and/or rhenium content. This study is an attempt to come up with a new procedure to remove coke from a zeolite catalyst grain using high-voltage direct current. It is found that the process is self-terminated due to the loss of electrical conductivity of the grain. In addition, it is found that there an optimum current range for which up to 90% of the coke can be removed. Higher or lower currents result in much smaller removal of the coke.

  17. Catalytic wet peroxide oxidation of azo dye (Congo red) using modified Y zeolite as catalyst.

    PubMed

    Kondru, Arun Kumar; Kumar, Pradeep; Chand, Shri

    2009-07-15

    The present study explores the degradation of azo dye (Congo red) by catalytic wet peroxide oxidation using Fe exchanged commercial Y zeolite as a catalyst. The effects of various operating parameters like temperature, initial pH, hydrogen peroxide concentration and catalyst loading on the removal of dye, color and COD from an aqueous solution were studied at atmospheric pressure. The percent removals of dye, color and COD at optimum pH(0) 7, 90 degrees C using 0.6 ml H(2)O(2)/350 ml solution and 1g/l catalyst was 97% (in 4h), 100% (in 45 min) and 58% (in 4h), respectively. The % dye removal has been found to be less in comparison to % color removal at all conditions, e.g. dye removal in 45 min and at above conditions was 82%, whereas the color removal was 100%. The results indicate that the Fe exchanged Y zeolite is a promising catalyst for dye removal. Fe exchanged catalyst is characterized using XRD, SEM/EDAX, surface area analyzer and FTIR. Though the dye, color and COD removals were maximum at pH(0) 2 but as the leaching of Fe from the catalyst was more in acidic pH range, pH(0) 7 was taken as operating pH due to almost comparable removals as of pH(0) 2 and no leaching of Fe ions. PMID:19135790

  18. 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.

  19. XAFS Study of HY Zeolite Supported Pt Nanoparticle Catalysts Prepared With Different Methods

    NASA Astrophysics Data System (ADS)

    Li, Zhongrui; Yan, Wensheng; Wei, Shiqiang

    2007-02-01

    The electronic and geometric effects induced by preparation methods on small platinum particles supported on high surface-area zeolite HY were studied by X-ray absorption fine structure (XAFS) spectroscopy. Pt/HY catalysts were prepared by a variety of techniques, including incipient wetness impregnation (IWI) and vapor-phase impregnation (VPI). Results of EXAFS for series of equal loadings of Pt prepared by IWI and VPI showed that the Pt clusters resulting from the VPI preparation had lower Pt—Pt coordination and higher coordination to the zeolite lattice oxygen. The electronic properties and structures of Pt/HY catalysts prepared with IWI approach can be altered by using different Pt precursor solutions.

  20. XAFS Study of HY Zeolite Supported Pt Nanoparticle Catalysts Prepared With Different Methods

    SciTech Connect

    Li Zhongrui; Yan Wensheng; Wei Shiqiang

    2007-02-02

    The electronic and geometric effects induced by preparation methods on small platinum particles supported on high surface-area zeolite HY were studied by X-ray absorption fine structure (XAFS) spectroscopy. Pt/HY catalysts were prepared by a variety of techniques, including incipient wetness impregnation (IWI) and vapor-phase impregnation (VPI). Results of EXAFS for series of equal loadings of Pt prepared by IWI and VPI showed that the Pt clusters resulting from the VPI preparation had lower Pt--Pt coordination and higher coordination to the zeolite lattice oxygen. The electronic properties and structures of Pt/HY catalysts prepared with IWI approach can be altered by using different Pt precursor solutions.

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

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2007-03-31

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

  2. Ring Opening of Naphthenic Molecules Over Metal Containing Mesoporous Y Zeolite Catalyst.

    PubMed

    Lee, You-Jin; Kim, Eun Sang; Kim, Tae-Wan; Kim, Chul-Ung; Jeong, Kwang-Eun; Lee, Chang-Ha; Jeong, Soon-Yong

    2015-07-01

    Mesoporous Y zeolite (Meso-Y) with a uniform mesopore was synthesized via pseudomorphic syn- thesis. The Meso-Y supported Ni-W catalyst (NiW/Meso-Y) was introduced as a catalyst for the selective ring opening of naphthenic rings. The catalytic test for the ring opening of naphthalene as a model compound of multi-ring aromatics was performed using a batch-type reaction system with both sulfided 20 wt% NiW/Meso-Y and NiW/Y catalysts under different reaction conditions. The catalytic results reveal that the Meso-Y supported NiW catalyst experiences a naphthalene conversion similar to the NiW/Y catalyst, but the NiW/Meso-Y catalyst has higher product yields for BTEX (benzene, toluene, ethyl benzene, and xylene) and the middle distillate than those of the NiW/Y catalyst at a low reaction temperature. These results suggest that the mesoporosity of the NiW/Meso-Y catalyst is more advantageous for the ring opening reaction of multi-ring aromatics due to the easier access for the bulky molecules compared to the NiW/Y catalyst.

  3. Selective Transformation of Various Nitrogen-Containing Exhaust Gases toward N2 over Zeolite Catalysts.

    PubMed

    Zhang, Runduo; Liu, Ning; Lei, Zhigang; Chen, Biaohua

    2016-03-23

    In this review we focus on the catalytic removal of a series of N-containing exhaust gases with various valences, including nitriles (HCN, CH3CN, and C2H3CN), ammonia (NH3), nitrous oxide (N2O), and nitric oxides (NO(x)), which can cause some serious environmental problems, such as acid rain, haze weather, global warming, and even death. The zeolite catalysts with high internal surface areas, uniform pore systems, considerable ion-exchange capabilities, and satisfactory thermal stabilities are herein addressed for the corresponding depollution processes. The sources and toxicities of these pollutants are introduced. The important physicochemical properties of zeolite catalysts, including shape selectivity, surface area, acidity, and redox ability, are described in detail. The catalytic combustion of nitriles and ammonia, the direct catalytic decomposition of N2O, and the selective catalytic reduction and direct catalytic decomposition of NO are systematically discussed, involving the catalytic behaviors as well as mechanism studies based on spectroscopic and kinetic approaches and molecular simulations. Finally, concluding remarks and perspectives are given. In the present work, emphasis is placed on the structure-performance relationship with an aim to design an ideal zeolite-based catalyst for the effective elimination of harmful N-containing compounds. PMID:26889565

  4. Selective Transformation of Various Nitrogen-Containing Exhaust Gases toward N2 over Zeolite Catalysts.

    PubMed

    Zhang, Runduo; Liu, Ning; Lei, Zhigang; Chen, Biaohua

    2016-03-23

    In this review we focus on the catalytic removal of a series of N-containing exhaust gases with various valences, including nitriles (HCN, CH3CN, and C2H3CN), ammonia (NH3), nitrous oxide (N2O), and nitric oxides (NO(x)), which can cause some serious environmental problems, such as acid rain, haze weather, global warming, and even death. The zeolite catalysts with high internal surface areas, uniform pore systems, considerable ion-exchange capabilities, and satisfactory thermal stabilities are herein addressed for the corresponding depollution processes. The sources and toxicities of these pollutants are introduced. The important physicochemical properties of zeolite catalysts, including shape selectivity, surface area, acidity, and redox ability, are described in detail. The catalytic combustion of nitriles and ammonia, the direct catalytic decomposition of N2O, and the selective catalytic reduction and direct catalytic decomposition of NO are systematically discussed, involving the catalytic behaviors as well as mechanism studies based on spectroscopic and kinetic approaches and molecular simulations. Finally, concluding remarks and perspectives are given. In the present work, emphasis is placed on the structure-performance relationship with an aim to design an ideal zeolite-based catalyst for the effective elimination of harmful N-containing compounds.

  5. Effect of Unburned Methyl Esters on the NOx Conversion of Fe-Zeolite SCR Catalyst

    SciTech Connect

    Williams, A.; Ratcliff, M.; Pedersen, D.; McCormick, R.; Cavataio, G.; Ura, J.

    2010-03-01

    Engine and flow reactor experiments were conducted to determine the impact of biodiesel relative to ultra-low-sulfur diesel (ULSD) on inhibition of the selective catalytic reduction (SCR) reaction over an Fe-zeolite catalyst. Fe-zeolite SCR catalysts have the ability to adsorb and store unburned hydrocarbons (HC) at temperatures below 300 C. These stored HCs inhibit or block NO{sub x}-ammonia reaction sites at low temperatures. Although biodiesel is not a hydrocarbon, similar effects are anticipated for unburned biodiesel and its organic combustion products. Flow reactor experiments indicate that in the absence of exposure to HC or B100, NO{sub x} conversion begins at between 100 and 200 C. When exposure to unburned fuel occurs at higher temperatures (250-400 C), the catalyst is able to adsorb a greater mass of biodiesel than of ULSD. Experiments show that when the catalyst is masked with ULSD, NO{sub x} conversion is inhibited until it is heated to 400 C. However, when masked with biodiesel, NO{sub x} conversion is observed to begin at temperatures as low as 200 C. Engine test results also show low-temperature recovery from HC storage. Engine tests indicate that, overall, the SCR system has a faster recovery from HC masking with biodiesel. This is at least partially due to a reduction in exhaust HCs, and thus total HC exposure with biodiesel.

  6. Zeolites

    NASA Technical Reports Server (NTRS)

    1992-01-01

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

  7. Zeolite supported iron-cobalt catalysts for the Fischer-Tropsch synthesis

    SciTech Connect

    Lin, T.

    1984-01-01

    A series of Fe, Co, FeCo catalysts on Y and ZSM-5 supports, prepared by impregnation and ion exchange, has been investigated. Characterization methods utilized were x-ray diffraction, H{sub 2}/CO chemisorption, Moessbauer spectroscopy, and atomic absorption. A differential reactor and as chromatographs were also employed to analyze the reaction activity and product selectivity. (i) Y supported catalysts: The oxidation, reduction, and carburization behavior of the iron-containing catalysts were observed via Moessbauer spectra. The reversibility of FeY (ion exchange) in oxidation-reduction cycles was confirmed in this experiment. Furthermore, ion exchange catalysts (FeY, FeCoY) do not show any iron metal, alloy or carbide phase after reduction or carburization. In contrast to silica supported catalysts, FeCo/HY (impregnated) reveals a Moessbauer spectra similar to Fe/HY. A 1/1 (CO/H{sub 2}) feed was used to investigate the Fischer-Tropsch reaction at 1 atm, 250{degree}C. (ii) ZSM-5 supported catalysts: Moessbauer results indicate similar patterns for impregnated and ion-exchanged catalysts, and reaction studies reveal similar catalytic behavior for the two preparation methods. This is in contrast to the rather widely different properties of these metals resulting from impregnation or ion exchange on Y zeolite. In generation, the ZSM-5 supported metals produce higher activity and selectivity for high molecular weight materials, and are particularly identified with significant aromatic content in the production distribution.

  8. Selective synthesis and chain growth of linear hydrocarbons in the Fischer-Tropsch synthesis over zeolite-entrapped cobalt catalysts

    SciTech Connect

    Koh, D.J.; Chung, J.S.; Kim, Y.G.

    1995-06-01

    The impregnation of NaOH solution into the pores of cobalt-exchanged zeolite promoted the conventional reduction of cobalt ions with hydrogen gas. The method yielded catalysts that had high degrees of reduction and small cobalt clusters located inside zeolite pores. In the Fischer-Tropsch synthesis these catalysts showed a chain-extension effect, producing hydrocarbons higher than C{sub 10} in appreciable amounts, and an enhanced production of linear hydrocarbons such as 1-olefins and n-paraffins. The formation of long-chain hydrocarbons is attributed to an increased chance of the chain growth owing to a hold-up effect of reaction intermediates, especially 1-olefins, which are accumulated inside zeolite pores during the reaction. Hydrocarbon isomers are produced over acidic sites of zeolite by secondary reactions (isomerization and cracking), which result in a chain shortening of the long-chain hydrocarbons.

  9. Local ammonia storage and ammonia inhibition in a monolithic copper-beta zeolite SCR catalyst

    SciTech Connect

    Auvray, Xavier P; Partridge Jr, William P; Choi, Jae-Soon; Pihl, Josh A; Yezerets, Alex; Kamasamudram, Krishna; Currier, Neal; Olsson, Louise

    2012-01-01

    Selective catalytic reduction of NO with NH{sub 3} was studied on a Cu-beta zeolite catalyst, with specific focus on the distributed NH{sub 3} capacity utilization and inhibition. In addition, several other relevant catalyst parameter distributions were quantified including the SCR zone, or catalyst region where SCR occurs, and NO and NH{sub 3} oxidation. We show that the full NH{sub 3} capacity (100% coverage) is used within the SCR zone for a range of temperatures. By corollary, unused NH{sub 3} capacity exists downstream of the SCR zone. Consequently, the unused capacity relative to the total capacity is indicative of the portion of the catalyst unused for SCR. Dynamic NH{sub 3} inhibition distributions, which create local transient conversion inflections, are measured. Dynamic inhibition is observed where the gas phase NH{sub 3} and NO concentrations are high, driving rapid NH{sub 3} coverage buildup and SCR. Accordingly, we observe dynamic inhibition at low temperatures and in hydrothermally aged states, but predict its existence very near the catalyst front in higher conversion conditions where we did not specifically monitor its impact. While this paper addresses some general distributed SCR performance parameters including Oxidation and SCR zone, our major new contributions are associated with the NH{sub 3} capacity saturation within the SCR zone and dynamic inhibition distributions and the associated observations. These new insights are relevant to developing accurate models, designs and control strategies for automotive SCR catalyst applications.

  10. Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water

    SciTech Connect

    Moliner, Manuel; Roman-Leshkov, Yuriy; Davis, Mark E.

    2010-04-06

    The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containing a catalytic amount of Sn-Beta (1:50 Sn:glucose molar ratio) gives product yields of approximately 46% (wt/wt) glucose, 31% (wt/wt) fructose, and 9% (wt/wt) mannose after 30 min and 12 min of reaction at 383 K and 413 K, respectively. This reactivity is achieved also when a 45 wt% glucose solution is used. The properties of the large-pore zeolite greatly influence the reaction behavior because the reaction does not proceed with a medium-pore zeolite, and the isomerization activity is considerably lower when the metal centers are incorporated in ordered mesoporous silica (MCM-41). The Sn-Beta catalyst can be used for multiple cycles, and the reaction stops when the solid is removed, clearly indicating that the catalysis is occurring heterogeneously. Most importantly, the Sn-Beta catalyst is able to perform the isomerization reaction in highly acidic, aqueous environments with equivalent activity and product distribution as in media without added acid. This enables Sn-Beta to couple isomerizations with other acid-catalyzed reactions, including hydrolysis/isomerization or isomerization/dehydration reaction sequences [starch to fructose and glucose to 5-hydroxymethylfurfural (HMF) demonstrated here].

  11. 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.

  12. Production of alkyl-aromatics from light oxygenates over zeolite catalysts for bio-oil refining

    NASA Astrophysics Data System (ADS)

    Hoang, Trung Q.

    Upgrading of light oxygenates derived from biomass conversion, such as propanal and glycerol, to more valuable aromatics for biofuels has been demonstrated on zeolite catalysts. Aromatics with a high ratio of C 9/(C8+C7) and little benzene are produced at much higher yield from oxygenates than from olefins at mild conditions over HZSM-5. It is proposed that C9 aromatics are predominantly produced via acid-catalyzed aldol condensation. This reaction pathway is different from the pathway of propylene and other hydrocarbon aromatization that occurs via a hydrocarbon pool at more severe conditions with major aromatic products C6 and C7. In fact, investigation on the effect of crystallite size HZSM-5 has shown a higher ratio of C9/(C8+C 7) aromatics on small crystallite. This is due to faster removal of products from the shorter diffusion path length. As a result, a longer catalyst lifetime, less isomerization, and less cracking were observed on small crystallites. Beside crystallite size, pore geometry of zeolites was also found to significantly affect aromatic production for both conversion of propanal and glycerol. It is shown that the structure of the HZSM-22, with a one-dimensional and narrower channel system, restricts the formation of aromatics. In contrast, a higher yield of aromatic products is observed over HZSM-5 with its three-dimensional channel system. By increasing channel dimension and connectivity of the channels, increasing catalyst activity was also observed due to more accessible acid sites. It was also found that glycerol is highly active for dehydration on zeolites to produce high yields of acrolein (propenal), a high value chemical. To maximize aromatics from glycerol conversion, HZSM-5 and HY were found to be effective. A two-bed reactor of Pd/ZnO and HZSM-5 was used to first deoxygenate/hydrogenate glycerol over Pd/ZnO to intermediate oxygenates that can further aromatize on HZSM-5. The end results are very promising with significant improvement

  13. Highly-basic large-pore zeolite catalysts for NOx reduction at low temperatures

    DOEpatents

    Penetrante, Bernardino M.; Brusasco, Raymond M.; Merritt, Bernard T.; Vogtlin, George E.

    2004-02-03

    A high-surface-area (greater than 600 m2/g), large-pore (pore size diameter greater than 6.5 angstroms), basic zeolite having a structure such as an alkali metal cation-exchanged Y-zeolite is employed to convert NO.sub.x contained in an oxygen-rich engine exhaust to N.sub.2 and O.sub.2. Preferably, the invention relates to a two-stage method and apparatus for NO.sub.x reduction in an oxygen-rich engine exhaust such as diesel engine exhaust that includes a plasma oxidative stage and a selective reduction stage. The first stage employs a non-thermal plasma treatment of NO.sub.x gases in an oxygen-rich exhaust and is intended to convert NO to NO.sub.2 in the presence of O.sub.2 and added hydrocarbons. The second stage employs a lean-NO.sub.x catalyst including the basic zeolite at relatively low temperatures to convert such NO.sub.2 to environmentally benign gases that include N.sub.2, CO.sub.2, and H.sub.2 O.

  14. Hollow zeolitic imidazolate framework nanospheres as highly efficient cooperative catalysts for [3+3] cycloaddition reactions.

    PubMed

    Zhang, Fang; Wei, Yongyi; Wu, Xiaotao; Jiang, Huangyong; Wang, Wei; Li, Hexing

    2014-10-01

    Herein we describe a novel, hollow-structured zeolitic imidazolate framework (ZIF-8-H) nanosphere as a highly efficient catalyst for [3+3] cycloaddition reactions. The programmed installation of acidic Zn(2+) species and basic imidazolate moieties creates a synergistic catalytic system. Appropriate positioning of these functionalities in the catalytic system makes it possible to bring two substrates into close proximity and activate them cooperatively. Moreover, the flexible shell and the surface mesopores of ZIF-8-H provide the capacity for favorable binding of various sized substrates, stabilizing intermediates via their multiple force networks and the increased accessibility of the active sites. These features render ZIF-8-H a more highly active promoter than its homogeneous precursors, bulk ZIF-8 and ZIF-8-N nanoparticles. Finally, the robust catalyst can be easily recovered and reused 10 times without loss of catalytic activity.

  15. Zr-zeolite beta: a new heterogeneous catalyst system for the highly selective cascade transformation of citral to (+/-)-menthol.

    PubMed

    Nie, Yuntong; Jaenicke, Stephan; Chuah, Gaik-Khuan

    2009-01-01

    The transformation of citral to menthols involves hydrogenation steps as well as cyclisation of the intermediate, citronellal. The ability of Zr-zeolite beta to catalyse the cyclisation with high diastereoselectivity to (+/-)-isopulegol is the critical step in this cascade transformation. Bifunctional catalysts containing nickel or rhodium supported on Zr-zeolite beta gave menthols in yields of 87-89% and an excellent diastereoselectivity of 94% for the desired (+/-)-menthol. Dual catalyst systems of Zr-zeolite beta and nano-dispersed Ni on an MCM-41 support were equally effective and have the added advantage that the rates of the acid- and hydrogenation-catalysed steps can be independently varied. By applying a pressure ramp of 0.2-2 MPa, the yield of menthols could be increased to 95%, with 94% diastereoselectivity for (+/-)-menthol. The low initial pressure minimises the rates of competing hydrogenation reactions to byproducts such as citronellol and 3,7-dimethyloctanol. PMID:19132702

  16. Ultraviolet Raman spectroscopy of catalysts: Adsorption and coke formation in zeolites and vibrational spectra of supported metal oxides

    NASA Astrophysics Data System (ADS)

    Chua, Yek Tann

    2001-10-01

    The primary goal of this dissertation is to study the physicochemical and catalytic properties of zeolites and supported metal oxide catalysts using UV Raman spectroscopy. In order to reduce the thermal degradation and possible photodecomposition of adsorbates by UV radiation, we have developed a novel fluidized bed method for measuring the UV Raman spectra of catalysts and adsorbates. The UV Raman spectra of various organic compounds adsorbed in zeolites H-USY and H-ZSM-5 are recorded. When measurements are performed on stationary and spinning samples, the Raman spectra show the presence of coke, a typical end product of heat and photochemistry. In contrast, the Raman peaks of the unreacted adsorbates dominate the spectra measured using the fluidized bed method. These results indicate that the fluidized bed technique is a good method for measuring UV Raman spectra of catalysts and adsorbates. The formation of coke in the methanol-to-gasoline conversion over zeolite H-ZSM-5 causes deactivation of the catalyst. To gain insight into the formation of coke, we have studied this reaction using UV Raman spectroscopy. The Raman spectral changes suggest coke is produced from conjugated olefins via cyclopentadiene intermediates. Aromatic compounds in gasoline may also be produced from cyclopentadienes. The adsorbate-induced structural changes of zeolites may alter the molecular sieving characteristics of these materials which ultimately affect their performance as catalysts and adsorbents. We have quantified the adsorbate-induced structural changes of zeolite H-RHO using UV Raman spectroscopy. The Raman spectra of the zeolite after the adsorption of water, methanol or acetonitrile are consistent with an increase in the average T-O-T angle of the zeolite of 5-8°. The adsorption of ammonia, on the other hand, decreases the average T-O-T angle by 5°. Because of certain advantages of UV Raman spectroscopy over visible Raman spectroscopy, recently there is a strong interest in

  17. Constructing a polyfunctional zeolite-encaged metal catalyst for the multistage oxidation of ethanol into ethyl acetate

    SciTech Connect

    Shakhtakhtinskii, T.N.; Aliev, A.M.; Kuliev, A.R.

    1995-08-01

    To construct an efficient polyfunctional catalyst for the given multistage reaction, the authors previously studied the catalysts HNaY, clinosorb, H-clinoptilolite, and H-mordenite in the reaction of esterification of ethanol with acetic acid; CuH-clinoptilolite, Cu-clinosorb, CuH-mordenite, and CuHNaY in the reaction of oxidative dehydration of ethanol; PdH-clinoptilolite, Pd-clinosorb, PdH-mordenite, and PdHNaY in the oxidation of ethanol; and CuPdH-clinoptilolite in the oxidative transformation of ethanol into ethyl acetate. The catalytic activity of these zeolites and other Pd- and Cu-containing zeolite catalysts, which the authors synthesized by the ion-exchange technique, was studied in a flow-circulating set-up.

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

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2005-11-15

    Composite materials of SBA-15/zeolite Y were synthesized from zeolite Y precursor and a synthesis mixture of mesoporous silicate SBA-15 via a hydrothermal process in the presence of a slightly acidic media of pH 4-6 with 2M H{sub 2}SO{sub 4}. The SBA-15/ZY composites showed Type IV adsorption isotherms, narrow BJH average pore size distribution of 4.9 nm, surface areas up to 800 m{sup 2}2/g and pore volumes 1.03 cm{sup 3}, all comparable to pure SBA-15 synthesized under similar conditions. Chemical analysis revealed Si/Al ratio down to 8.5 in the most aluminated sample, and {sup 27}AlSS MAS NMR confirmed aluminum was in tetrahedral coordination. This method of introduction of Al in pure T{sub d} coordination is effective in comparison to other direct and post synthesis alumination methods. Bronsted acid sites were evident from a pyridinium peak at 1544 cm-1 in the FTIR spectrum after pyridine adsorption, and from NH{sub 3} -TPD experiments. SBA-15/ZY composites showed significant catalytic activities for the dealkylation of isopropylbenzene to benzene and propene, similar to those of commercial zeolite Y. It was observed that higher conversion for catalysts synthesized with high amount of ZY precursor mixture added to the SBA-15. Over all the composites has shown good catalytic activity. Further studies will be focused on gaining a better understand the nature of the precursor, and to characterize and to locate the acid sites in the composite material. The composite will also be evaluated for heavy oil conversion to naphtha and middle distillates.

  19. Tip Growth Of Carbon Nanotubes Obtained By Pyrolyzation Of Camphor Oil With Zeolite Embedded With Fe/Ni/Mn Catalyst

    NASA Astrophysics Data System (ADS)

    Azira, A. A.; Zainal, N. F. A.; Nik, S. F.; Rusop, M.

    2009-06-01

    Highly efficient synthesis of carbon nanotubes (CNTs) have been synthesized by thermal decomposition of camphor oil, on a zeolite support impregnated with Fe/Ni/Mn (molar ratio of Fe:Ni:Mn = 1:1:1) catalyst in the temperature range from 550-950° C by the thermal CVD method. Besides the surface fluidization of the catalyst nanoparticles themselves, assistance of the metal oxides embedded in zeolite supports is supposed to be responsible for high activity and selectivity of the Fe/Ni/Mn catalyst over which carbon source (camphor oil) successfully decomposes. The CNT yield was higher at 850° C and can be considered as the optimum deposition temperature. This result demonstrates that zeolite impregnated with the catalyst Fe/Ni/Mn is a suitable support for effective formation of CNTs. The morphological studies support `tip growth mechanism' for the growth of the CNT's in our case. The as-grown CNTs were characterized by FESEM and FTIR spectroscopy.

  20. Ordered Silicon Vacancies in the Framework Structure of the Zeolite Catalyst SSZ-74

    SciTech Connect

    Baerlocher,C.; Xie, D.; McCusker, L.; Hwang, S.; Chan, I.; Ong, K.; Burton, A.; Zones, S.

    2008-01-01

    Physico-chemical characterization of the high-silica zeolite catalyst SSZ-74 (ref. 1) suggested that it, like the related materials TNU-9 (ref. 2) and IM-5 (ref. 3), has a multidimensional 10-ring channel system4. Such pore systems are ideal for many petrochemical applications, and indeed SSZ-74 has been shown to be a good catalyst for a wide variety of reactions1. The elucidation of its framework structure, however, proved to be difficult. Comparable problems were encountered with TNU-9 and IM-5, which were synthesized with related structure-directing agents. Their framework structures, which are the two most complex ones known, both have 24 Si atoms in the asymmetric unit, and were finally solved by combining high-resolution powder diffraction data with information derived from high-resolution electron microscopy images5, 6. Therefore, a similar approach, using the powder charge-flipping algorithm7 to combine the two types of data and molecular modelling to help to locate the structure-directing agent, was applied to SSZ-74. This procedure eventually revealed a most unusual 23-Si-atom framework structure (|(C16H34N2)4|[Si92square4O184(OH)8]) with ordered Si vacancies.

  1. Isomerization and hydrocracking of heptane over bimetallic bifunctional PtPd/H-Beta and PtPd/USY zeolite catalysts

    SciTech Connect

    Blomsma, E.; Martens, J.A.; Jacobs, P.A.

    1997-01-15

    Bifunctional catalysts are prepared by loading NH{sub 4}-Beta zeolites with platinum, palladium, and platinum-palladium metal combinations via cation exchange and incipient wetness impregnation with Pt(NH{sub 3}){sub 4}Cl{sub 2} and Pd(NH{sub 3}){sub 4}Cl{sub 2} complexes, followed by calcination and reduction. In comparison to the Pt and Pd loaded acid zeolites, the bimetallic Pd-Pt zeolites are found to be more active and selective in the isomerization of heptane. The noble metal phases are characterized with temperature programmed reduction and hydrogen chemisorption. The dispersion of platinum is significantly improved in presence of as little as 20 mole% of palladium. The improved Pt dispersion leads to a better intimacy and balance of the acid and hydrogenation-dehydrogenation functions in these bi-functional catalysts and suppression of undesirable hydrogenolysis and dimerization-cracking activity. On Pt/USY zeolite, the addition of palladium has similar beneficial effects on the catalytic performances. 34 refs., 4 figs., 3 tabs.

  2. Preferential catalytic oxidation of carbon monoxide in presence of hydrogen over bimetallic AuPt supported on zeolite catalysts

    NASA Astrophysics Data System (ADS)

    Naknam, Pattarasuda; Luengnaruemitchai, Apanee; Wongkasemjit, Sujitra; Osuwan, Somchai

    A series of AuPt/A zeolite and Pt/A zeolite catalysts prepared by incipient wetness impregnation are investigated for the preferential oxidation (PROX) of carbon monoxide in the presence of hydrogen over the temperature range of 50-310 °C under atmospheric pressure. The results indicate that when a small amount of gold is added to the Pt/A zeolite catalyst, the CO selectivity is improved at low temperatures, and 1% AuPt/A zeolite (at a weight ratio of Au:Pt = 1:2) gives the best performance, which provides a high CO conversion in combination with a high CO selectivity. In more realistic simulated reformate gases containing 10% CO 2 and 10% H 2O, there is not much difference between those in the presence and the absence of CO 2 and H 2O. Transmission electron microscopic and X-ray diffraction studies show that the two metals, Au and Pt, appear to be severely phase separated, which is confirmed by energy dispersive investigations.

  3. Elucidation of Diels-Alder Reaction Network of 2,5-Dimethylfuran and Ethylene on HY Zeolite Catalyst

    SciTech Connect

    Do, Phuong T. M.; McAtee, Jesse R.; Watson, Donald A.; Lobo, Raul F.

    2012-12-12

    The reaction of 2,5-dimethylfuran and ethylene to produce p-xylene represents a potentially important route for the conversion of biomass to high-value organic chemicals. Current preparation methods suffer from low selectivity and produce a number of byproducts. Using modern separation and analytical techniques, the structures of many of the byproducts produced in this reaction when HY zeolite is employed as a catalyst have been identified. From these data, a detailed reaction network is proposed, demonstrating that hydrolysis and electrophilic alkylation reactions compete with the desired Diels–Alder/dehydration sequence. This information will allow the rational identification of more selective catalysts and more selective reaction conditions.

  4. Bayberry-like ZnO/MFI zeolite as high performance methanol-to-aromatics catalyst.

    PubMed

    Wang, Ning; Qian, Weizhong; Shen, Kui; Su, Chang; Wei, Fei

    2016-02-01

    Unique bayberry-like MFI zeolites are synthesized through a quasi-solid-state crystallization approach. This hierarchical zeolite structure has a relatively thick shell, densely grown nanocrystals with an ordered packed channel, high mechanical stability, high surface area and a low Si/Al ratio. Its catalytic efficiency for methanol-to-aromatics is significantly higher than that of conventional MFI zeolites.

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

    SciTech Connect

    Rolllins, Harry W.; Petkovic, Lucia M.; Ginosar, Daniel M.

    2012-07-24

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

  6. Activity of double wash-coat monolith catalyst with noble metals and zeolites in selective catalytic reduction of NO(x) with C3H6.

    PubMed

    Lee, Jung-Dae; Kim, Ki-Joong; Kim, Yong-Hwa; Jeon, Gyung-Soo; Choi, Young-Key; Ahn, Ho-Geun

    2008-10-01

    The selective catalytic reduction (SCR) of NO(x) with C3H6 was studied in the presence of oxygen. The double wash-coat monolith catalysts for SCR comprised a lower layer of Au (or Pt)/Al2O3 and a upper layer of zeolites. The catalytic performance of the double wash-coated catalyst was remarkably improved to broaden the temperature window. The Au and Pt particles were dispersed uniformly on the monolith with particle sizes range of 3 approximately 5 nm and 5 approximately 10 nm, respectively. The catalyst binders used were colloidal silica, potassium silicate and tetraethyl orthosilicate, and the best catalyst activity was achieved with using colloidal silica as a binder. The zeolites used for the catalyst upper layer were MCM-41, FER, Y5.3-Zeolite and ZSM5, among which the NH4-ZSM5-coated catalyst showed the highest activity. The experimental results confirmed the promising potential of the double wash-coat, monolith catalyst for SCR of NO(x) with C3H6 due to the effective combination of noble metal monolith catalyst with zeolite for the removal of NO(x) by SCR with hydrocarbons.

  7. Degradation of a textile dye, Rhodamine 6G (Rh6G), by heterogeneous sonophotoFenton process in the presence of Fe-containing TiO2 catalysts.

    PubMed

    Demir, Nazlı; Gündüz, Gönül; Dükkancı, Meral

    2015-03-01

    In this study, degradation of Rhodamine 6G (Rh6G) was investigated with ultrasound-assisted heterogeneous photoFenton process by iron-containing TiO2 catalysts. The catalysts were prepared by incipient wetness impregnation method and characterized by XRD, SEM, FT-IR, nitrogen adsorption, and ICP-AES measurements. Almost complete color removal (99.9 %) was achieved after a reaction time of 90 min while chemical oxygen demand (COD) could be removed by 24 % only with the 1 wt% iron-containing TiO2 catalyst. Initial color removal after 15 min of reaction and total COD abatement after 90 min of reaction decreased with increasing calcination temperature of the catalyst from 573 to 973 K. This indicated that the catalytic activity of the catalyst depend on the percentage of anatase phase in the TiO2, which was decreased with increasing calcination temperature.

  8. Degradation of a textile dye, Rhodamine 6G (Rh6G), by heterogeneous sonophotoFenton process in the presence of Fe-containing TiO2 catalysts.

    PubMed

    Demir, Nazlı; Gündüz, Gönül; Dükkancı, Meral

    2015-03-01

    In this study, degradation of Rhodamine 6G (Rh6G) was investigated with ultrasound-assisted heterogeneous photoFenton process by iron-containing TiO2 catalysts. The catalysts were prepared by incipient wetness impregnation method and characterized by XRD, SEM, FT-IR, nitrogen adsorption, and ICP-AES measurements. Almost complete color removal (99.9 %) was achieved after a reaction time of 90 min while chemical oxygen demand (COD) could be removed by 24 % only with the 1 wt% iron-containing TiO2 catalyst. Initial color removal after 15 min of reaction and total COD abatement after 90 min of reaction decreased with increasing calcination temperature of the catalyst from 573 to 973 K. This indicated that the catalytic activity of the catalyst depend on the percentage of anatase phase in the TiO2, which was decreased with increasing calcination temperature. PMID:24756679

  9. Preparation, catalysis, and characterization of highly dispersed molybdenum sulfide catalysts supported on a NaY zeolite

    SciTech Connect

    Okamoto, Yasuaki; Katsuyama, Hiromoto

    1996-06-01

    The structure and dispersion of the molybdenum sulfides supported on a NaY zeolite were studied using XAFS techniques. It was found that molybdenum sulfide species prepared by sulfiding vapor deposited Mo(CO){sub 6} or by sulfiding molybdenum oxide dimer species encaged in the zeolite are highly dispersed and thermally stabilized against sintering or restructuring. These molybdenum species are formed via molybdenum sulfide dimer species as an intermediate. On the other hand, with the molybdenum sulfide catalysts prepared by an impregnation method, the sulfidation of molybdenum oxides was incomplete. The molybdenum oxide species are suggested to be mainly located in the zeolite cavities after calcination, forming isolated molybdenum oxides in tetrahedral configurations. The molybdenum sulfide species prepared from Mo(CO){sub 6} showed much higher catalytic activities for thiophene hydrodesulfurization and butadiene hydrogenation than the molybdenum sulfides prepared by the impregnation, in conformity with a higher dispersion and higher fraction of the molybdenum sulfide species. It is demonstrated that in combination with metal carbonyl techniques, zeolite supports are very suitable for the preparation of highly dispersed molybdenum sulfides at a high Mo loading.

  10. Heteropoly acid encapsulated into zeolite imidazolate framework (ZIF-67) cage as an efficient heterogeneous catalyst for Friedel-Crafts acylation

    NASA Astrophysics Data System (ADS)

    Ammar, Muhammad; Jiang, Sai; Ji, Shengfu

    2016-01-01

    A new strategy has been developed for the encapsulation of the phosphotungstic heteropoly acid (H3PW12O40 denoted as PTA) into zeolite imidazolate framework (ZIF-67) cage and the PTA@ZIF-67(ec) catalysts with different PTA content were prepared. The structure of the catalysts was characterized by XRD, BET, SEM, FT-IR, ICP-AES and TG. The catalytic activity and recovery properties of the catalysts for the Friedel-Crafts acylation of anisole with benzoyl chloride were evaluated. The results showed that 14.6-31.7 wt% PTA were encapsulated in the ZIF-67 cage. The PTA@ZIF-67(ec) catalysts had good catalytic activity for Friedel-Crafts acylation. The conversion of anisole can reach ~100% and the selectivity of the production can reach ~94% over 26.5 wt% PTA@ZIF-67(ec) catalyst under the reaction condition of 120 °C and 6 h. After reaction, the catalyst can be easily separated from the reaction mixture by the centrifugation. The recovered catalyst can be reused five times and the selectivity can be kept over 90%.

  11. Natrolite zeolite supported copper nanoparticles as an efficient heterogeneous catalyst for the 1,3-diploar cycloaddition and cyanation of aryl iodides under ligand-free conditions.

    PubMed

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Khalaj, Mehdi

    2015-09-01

    In this paper, we report the preparation of Natrolite zeolite supported copper nanoparticles as a heterogeneous catalyst for 1,3-diploar cycloaddition and synthesis aryl nitriles from aryl iodides under ligand-free conditions. The catalyst was characterized using XRD, SEM, TEM, EDS and TG-DTA. The experimental procedure is simple, the products are formed in high yields and the catalyst can be recycled and reused several times without any significant loss of catalytic activity.

  12. Kinetics and Mechanism of Deoxygenation Reactions over Proton-Form and Molybdenum-Modified Zeolite Catalysts

    NASA Astrophysics Data System (ADS)

    Bedard, Jeremy William

    .04-0.10, HCOOH/CH 4 = 0.01-0.03, CO2/CH4 = 0.01-0.03) on Mo/H-ZSM-5 formulations at 950 K and atmospheric pressure in an effort to couple deoxygenation and dehydrogenation reaction sequences results instead in a two-zone, stratified bed reactor configuration consisting of upstream oxygenate/CH4 reforming and downstream CH4 dehydroaromatization. X-ray absorption spectroscopy and chemical transient experiments show that molybdenum carbide is formed inside zeolite micropores during CH4 reactions. The addition of an oxygenate co-feed causes oxidation of the active molybdenum carbide catalyst while producing CO and H2 until completely converted. Forward rates of C6H6 synthesis are unperturbed by the introduction of an oxygenate co-feed after rigorously accounting for the thermodynamic reversibility caused by the H2 produced in oxygenate reforming reactions and the fraction of the active catalyst deemed unavailable for CH 4 dehydroaromatization. All effects of co-processing C1-2 oxygenates and molecular H2 with CH4 can be interpreted in terms of an approach to equilibrium. Co-processing H2O, CO2, or light (C1-2, C/Heff < 0.25) oxygenates with CH4 at 950 K over Mo/H-ZSM-5 catalysts results in complete fragmentation of the oxygenate and CO as the sole oxygen-containing product. The C/Heff accounts for removal of O as CO and describes the net C6H6 and total hydrocarbon synthesis rates at varying (0.0-0.10) C1-2 oxygenate and H2 to CH4 co-feed ratios. Co-processing larger (C 3-5, C/Heff ≥ 0.25) oxygenates with CH4 results in incomplete fragmentation of the co-fed oxygenate and preferential pathways of C6H6 synthesis that exclude CH4 incorporation. This results in greater net C6H6 synthesis rates than would be predicted from observations made when co-processing C1-2 oxygenates. Catalytic technologies have served a crucial role in processing petroleum feedstocks and are faced with new challenges as the feedstock shifts to chemically diverse but renewable biomass sources. This research

  13. Hydrocarbon Effect on a Fe-zeolite Urea-SCR Catalyst: An Experimental and Modeling Study

    SciTech Connect

    Devarakonda, Maruthi N.; Tonkyn, Russell G.; Herling, Darrell R.

    2010-04-14

    Synergies between various catalytic converters such as SCR and DPF are vital to the success of an integrated aftertreatment system for simultaneous NOx and particulate matter control in diesel engines. Several issues such as hydrocarbon poisoning, thermal aging and other coupled aftertreatment dynamics need to be addressed to develop an effective emission control system. This paper reports an experimental and modeling study to understand the effect of hydrocarbons on a Fe-zeolite urea-SCR bench reactor. Several bench-reactor tests to understand the inhibition of NOx oxidation, to characterize hydrocarbon storage and to investigate the impact of hydrocarbons on SCR reactions were conducted. Toluene was chosen as a representative hydrocarbon in diesel exhaust and various tests using toluene reveal its inhibition of NO oxidation at low temperatures and its oxidation to CO and CO2 at high temperatures. Surface isotherm tests were conducted to characterize the adsorption-desorption equilibrium of toluene through Langmuir isotherms. Using the rate parameters, a toluene storage model was developed and validated in simulation. With toluene in the stream, controlled SCR tests were run on the reactor and performance metrics such as NOx conversion and NH3 slip were compared to a set of previously run tests with no toluene in the stream. Tests indicate a significant effect of toluene on NOx and NH3 conversion efficiencies even at temperatures greater than 300oC. A kinetic model to address the toluene inhibition during NO oxidation reaction was developed and is reported in the paper. This work is significant especially in an integrated DPF-SCR aftertreatment scenario where the SCR catalyst on the filter substrate is exposed to un-burnt diesel hydrocarbons during active regeneration of the particulate filter.

  14. 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...

  15. Acidic and basic properties of zeolite-containing cracking catalyst in the process of butene-1 isomerization

    NASA Astrophysics Data System (ADS)

    Mursalova, L. A.; Guseinova, E. A.; Adzhamov, K. Yu.

    2016-08-01

    The process of butene-1 isomerization in the presence of two groups of samples of zeolite-containing catalyst (ZCC) that earlier participated in the traditional and oxidative catalytic cracking of vacuum gasoil is investigated. It is established that the nature of the reaction mixture and conditions of the cracking process are key factors in forming the acidic and basic properties of the catalyst. It is shown that the highest activity in the butene-1 isomerization into cis-/ trans-butene-2 is demonstrated by ZCC samples that participated in the oxidative catalytic cracking (oxycracking). It is suggested that the enhanced catalytic activity of this group of ZCC samples was related to the availability of acid-base centers in the form of radical-like oxygen along with protic- and aprotic-type acidic centers in the structure of the oxidative compaction products.

  16. Elucidation of Diels-Alder Reaction Network of 2,5-Dimethylfuran and Ethylene on HY Zeolite Catalyst.

    PubMed

    Do, Phuong T M; McAtee, Jesse R; Watson, Donald A; Lobo, Raul F

    2013-01-01

    The reaction of 2,5-dimethylfuran and ethylene to produce p-xylene represents a potentially important route for the conversion of biomass to high-value organic chemicals. Current preparation methods suffer from low selectivity and produce a number of byproducts. Using modern separation and analytical techniques, the structure of many of the byproducts produced in this reaction when HY zeolite is employed as a catalyst has been identified. From these data, a detailed reaction network is proposed demonstrating that hydrolysis and electrophilic alkylation reactions compete with the desired Diels-Alder/dehydration sequence. This information will allow the rational identification of more selective catalysts and more selective reaction conditions. PMID:23316419

  17. Elucidation of Diels-Alder Reaction Network of 2,5-Dimethylfuran and Ethylene on HY Zeolite Catalyst

    PubMed Central

    Do, Phuong T.M.; McAtee, Jesse R.; Watson, Donald A.; Lobo, Raul F.

    2012-01-01

    The reaction of 2,5-dimethylfuran and ethylene to produce p-xylene represents a potentially important route for the conversion of biomass to high-value organic chemicals. Current preparation methods suffer from low selectivity and produce a number of byproducts. Using modern separation and analytical techniques, the structure of many of the byproducts produced in this reaction when HY zeolite is employed as a catalyst has been identified. From these data, a detailed reaction network is proposed demonstrating that hydrolysis and electrophilic alkylation reactions compete with the desired Diels-Alder/dehydration sequence. This information will allow the rational identification of more selective catalysts and more selective reaction conditions. PMID:23316419

  18. Capture and isotopic exchange method for water and hydrogen isotopes on zeolite catalysts up to technical scale for pre-study of processing highly tritiated water

    SciTech Connect

    Michling, R.; Braun, A.; Cristescu, I.; Dittrich, H.; Gramlich, N.; Lohr, N.; Glugla, M.; Shu, W.; Willms, S.

    2015-03-15

    Highly tritiated water (HTW) may be generated at ITER by various processes and, due to the excessive radio toxicity, the self-radiolysis and the exceedingly corrosive property of HTW, a potential hazard is associated with its storage and process. Therefore, the capture and exchange method for HTW utilizing Molecular Sieve Beds (MSB) was investigated in view of adsorption capacity, isotopic exchange performance and process parameters. For the MSB, different types of zeolite were selected. All zeolite materials were additionally coated with platinum. The following work comprised the selection of the most efficient zeolite candidate based on detailed parametric studies during the H{sub 2}/D{sub 2}O laboratory scale exchange experiments (about 25 g zeolite per bed) at the Tritium Laboratory Karlsruhe (TLK). For the zeolite, characterization analytical techniques such as Infrared Spectroscopy, Thermogravimetry and online mass spectrometry were implemented. Followed by further investigation of the selected zeolite catalyst under full technical operation, a MSB (about 22 kg zeolite) was processed with hydrogen flow rates up to 60 mol*h{sup -1} and deuterated water loads up to 1.6 kg in view of later ITER processing of arising HTW. (authors)

  19. CHARACTERIZATION OF H-Y AND CR-Y ZEOLITE CATALYSTS DURING THE OXIDATIVE DESTRUCTION OF CFC11 AND CFC12

    EPA Science Inventory

    The long term stability-deactivation characteristics of two Y zeolite catalysts, namely H-Y and cation exchanged Cr-Y, were studied during the oxidative destruction of CFC11 and CFC12 feeds. Experiments were carried out at 300 degrees C and 500 h-1 space velocity. Properties of...

  20. 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.

  1. 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.

  2. Conversion of waste cooking oil to jet biofuel with nickel-based mesoporous zeolite Y catalyst.

    PubMed

    Li, Tao; Cheng, Jun; Huang, Rui; Zhou, Junhu; Cen, Kefa

    2015-12-01

    Three types of zeolites (Meso-Y, SAPO-34, and HY) loaded with nickel were used to convert waste cooking oil to jet biofuel. Mesoporous zeolite Y exhibited a high jet range alkane selectivity of 53% and a proper jet range aromatic hydrocarbon selectivity of 13.4% in liquid fuel products. Reaction temperature was optimized to produce quality jet biofuel. Zeolite Meso-Y exhibited a high jet range alkane yield of 40.5% and a low jet range aromatic hydrocarbon yield of 11.3% from waste cooking oil at 400°C. The reaction pathway for converting waste cooking oil to jet biofuel was proposed. Experimental results showed that waste cooking oil mainly deoxygenated to heptadecane (C17H36) and pentadecane (C15H30) through the decarbonylation pathway for the first 3h. Long chain alkanes cracked into jet range alkanes (C8-C16). Cycloalkanes and aromatic hydrocarbons were produced through cyclization and dehydrogenation pathways.

  3. The Effect of Time dealumination and Solvent Concentration in Synthesis of Zeolite Catalyst and Catalytic Test for DiEthyl Ether Production Process

    NASA Astrophysics Data System (ADS)

    Widayat, Widayat; Roesyadi, A.; Rachimoellah, M.

    2009-09-01

    Ethanol is an alternative energy, but its has three distinct disadvantages as a transportation fuel. Its availability is currently limited, and it has a lower volumetric heating value and a lower Reid vapour pressure (RVP) than gasoline. This paper focuses for this disadvantages and to solve this problem can do with converts ethanol to DiEthyl Ether product. This research produced DiEthyl Ether by ethanol dehydration process with zeolite as catalyst. The catalyst synthesis from natural material from District Gunung Kidul, Indonesia. The catalyst produced with dealumination, neutralization, drying and calcination processes. The zeolite catalyst was analysed of Si/Al, X-ray Diffraction and specific surface area. The catalyst product then used for ethanol dehydration to produce DiEthyl Ether. The results shown the biggest surface area is 184,52 m 2 / gram at catalyst production at 10 hours for time dealumination. The crystallite of catalyst product is similar like shown at diffractogram of XRD analysis. The ratio Si/Al biggest is 313.7 that obtaining at catalyst production with 7 hours for time dealumination. The catalytic test use fixed bed reactor with 1 inci diameter and ethanol fermentation borth as feed. The operation condition is 150° C at temperature and atmosphere pressure. The compounds product in liquid phase are diethyl ether, methanol and water.

  4. One-Pot Template-Free Synthesis of Cu-MOR Zeolite toward Efficient Catalyst Support for Aerobic Oxidation of 5-Hydroxymethylfurfural under Ambient Pressure.

    PubMed

    Zhang, Wei; Xie, Jingyan; Hou, Wei; Liu, Yangqing; Zhou, Yu; Wang, Jun

    2016-09-01

    Supported catalysts are widely studied, and exploring new promising supports is significant to access more applications. In this work, novel copper-containing MOR-type zeolites Cu-MOR were synthesized in a one-pot template-free route and served as efficient supports for vanadium oxide. In the heterogeneous oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) with molecular oxygen (O2) under ambient pressure, the obtained catalyst demonstrated high yield (91.5%) and good reusability. Even under the ambient air pressure, it gave a DFF yield of 72.1%. Structure-activity relationship analysis indicated that the strong interaction between the framework Cu species and the guest V sites accounted for the remarkable performance. This work reveals that the Cu-MOR zeolite uniquely acts as the robust support toward well-performed non-noble metal heterogeneous catalyst for biomass conversion. PMID:27523255

  5. Investigation of PCDD/F emissions from mobile source diesel engines: impact of copper zeolite SCR catalysts and exhaust aftertreatment configurations.

    PubMed

    Liu, Z Gerald; Wall, John C; Barge, Patrick; Dettmann, Melissa E; Ottinger, Nathan A

    2011-04-01

    This study investigated the impact of copper zeolite selective catalytic reduction (SCR) catalysts and exhaust aftertreatment configurations on the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from mobile source diesel engines. Emissions of PCDD/Fs, reported as the weighted sum of 17 congeners called the toxic equivalency quotient (TEQ), were measured using a modified EPA Method 0023A in the absence and presence of exhaust aftertreatment. Engine-out emissions were measured as a reference, while aftertreatment configurations included various combinations of diesel oxidation catalyst (DOC), diesel particulate filter (DPF), Cu-zeolite SCR, Fe-zeolite SCR, ammonia oxidation catalyst (AMOX), and aqueous urea dosing. In addition, different chlorine concentrations were evaluated. Results showed that all aftertreatment configurations reduced PCDD/F emissions in comparison to the engine-out reference, consistent with reduction mechanisms such as thermal decomposition or combined trapping and hydrogenolysis reported in the literature. Similarly low PCDD/F emissions from the DOC-DPF and the DOC-DPF-SCR configurations indicated that PCDD/F reduction primarily occurred in the DOC-DPF with no noticeable contribution from either the Cu- or Fe-zeolite SCR systems. Furthermore, experiments performed with high chlorine concentration provided no evidence that chlorine content has an impact on the catalytic synthesis of PCDD/Fs for the chlorine levels investigated in this study.

  6. The Effect of K and Acidity of NiW-Loaded HY Zeolite Catalyst for Selective Ring Opening of 1-Methylnaphthalene.

    PubMed

    Lee, You-Jin; Kim, Eun-Sang; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

    2016-05-01

    Bi-functional catalysts were prepared using HY zeolites with various SiO2/Al2O3 ratios for acidic function, NiW for metallic function, and K for acidity control. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction was investigated using the prepared bi-functional catalysts with different levels of acidity in a fixed bed reactor system. In NiW/HY catalysts without K addition, the acidity decreased with the SiO2/Al2O3 mole ratio of the HY zeolite. Ni1.1W1.1/HY(12) catalyst showed the highest acidity but slightly lower yields for the selective ring opening than Ni1.1W1.1/HY(30) catalyst. The acidity of the catalyst seemed to play an important role as the active site for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. Catalyst acidity could be controlled between Ni1.1W1.1/HY(12) and Ni1.1W1.1/HY(30) by adding a moderate amount of K to Ni1.1W1.1/HY(12) catalyst. K0.3Ni1.1W1.1/HY(12) catalyst should have the optimum acidity for the selective ring opening. The addition of a moderate amount of K to the NiW/HY catalyst must improve the catalytic performance due to the optimization of catalyst acidity. PMID:27483754

  7. The Effect of K and Acidity of NiW-Loaded HY Zeolite Catalyst for Selective Ring Opening of 1-Methylnaphthalene.

    PubMed

    Lee, You-Jin; Kim, Eun-Sang; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

    2016-05-01

    Bi-functional catalysts were prepared using HY zeolites with various SiO2/Al2O3 ratios for acidic function, NiW for metallic function, and K for acidity control. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction was investigated using the prepared bi-functional catalysts with different levels of acidity in a fixed bed reactor system. In NiW/HY catalysts without K addition, the acidity decreased with the SiO2/Al2O3 mole ratio of the HY zeolite. Ni1.1W1.1/HY(12) catalyst showed the highest acidity but slightly lower yields for the selective ring opening than Ni1.1W1.1/HY(30) catalyst. The acidity of the catalyst seemed to play an important role as the active site for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. Catalyst acidity could be controlled between Ni1.1W1.1/HY(12) and Ni1.1W1.1/HY(30) by adding a moderate amount of K to Ni1.1W1.1/HY(12) catalyst. K0.3Ni1.1W1.1/HY(12) catalyst should have the optimum acidity for the selective ring opening. The addition of a moderate amount of K to the NiW/HY catalyst must improve the catalytic performance due to the optimization of catalyst acidity.

  8. A Single-Site Platinum CO Oxidation Catalyst in Zeolite KLTL: Microscopic and Spectroscopic Determination of the Locations of the Platinum Atoms

    SciTech Connect

    Kistler, Joseph D.; Chotigkrai, Nutchapon; Xu, Pinghong; Enderle, Bryan; Praserthdam, Piyasan; Chen, Cong-Yan; Browning, Nigel D.; Gates, Bruce C.

    2014-07-01

    A stable site-isolated mononuclear platinum catalyst with a well-defined structure is presented. Platinum complexes supported in zeolite KLTL were synthesized from [Pt(NH3)4](NO3)2, oxidized at 633 K, and used to catalyze CO oxidation. Finally, IR and X-ray absorption spectra and electron micrographs determine the structures and locations of the platinum complexes in the zeolite pores, demonstrate the platinum-support bonding, and show that the platinum remained site isolated after oxidation and catalysis.

  9. 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.

  10. Control of carbon monoxide (CO) from automobile exhaust by a dealuminated zeolite supported regenerative MnCo2O4 catalyst.

    PubMed

    Arun, P S; Ranjith, B P; Shibli, S M A

    2013-03-19

    We synthesized MnCo(2)O(4) catalyst with very high porosity on the surface of dealuminated zeolite molecular sieves (DAZMS) for CO oxidation under actual automobile conditions. The MnCo(2)O(4) catalyst was selected on the basis of preliminary DFT study using the software ADF BAND. The MnCo(2)O(4) catalyst had comparatively higher CO adsorption energy and very low oxygen vacancy formation energy. The synthesized MnCo(2)O(4)/DAZMS catalyst was characterized by XRD, XRF, BET, SEM, and Confocal Microscopy. The Confocal microscopic analysis revealed that porosity of the dealuminated zeolite surface was significantly enhanced after the catalyst loading process. The completely precious metal free and DAZMS-supported catalyst exhibited excellent CO oxidation ability with renewed activity for seven months under actual automobile conditions with reference to normal and cold start conditions. The synthesized MnCo(2)O(4)/DAZMS not only exhibited surprisingly high catalytic activity for CO oxidation at a temperature resembling a cold start period but was also sufficiently stable/active under actual automobile conditions and ambient conditions containing large amounts of CO,H(2)O,CO(2), and NO(x) at 155-715 °C. These significant results revealed the flexible use of the present catalyst system for a wide variety of automobiles from a small gasoline-fuelled vehicle to a large diesel-fuelled vehicle that may produce high CO-content exhaust. PMID:23406461

  11. HERFD-XANES and XES as complementary operando tools for monitoring the structure of Cu-based zeolite catalysts during NOx-removal by ammonia SCR

    NASA Astrophysics Data System (ADS)

    Günter, T.; Doronkin, D. E.; Carvalho, H. W. P.; Casapu, M.; Grunwaldt, J.-D.

    2016-05-01

    In this article, we demonstrate the potential of hard X-ray techniques to characterize catalysts under working conditions. Operando high energy resolution fluorescence detected (HERFD) XANES and valence to core (vtc) X-ray emission spectroscopy (XES) have been used in a spatially-resolved manner to study Cu-zeolite catalysts during the standard-SCR reaction and related model conditions. The results show a gradient in Cu oxidation state and coordination along the catalyst bed as the reactants are consumed. Vtc-XES gives complementary information on the direct adsorption of ammonia at the Cu sites. The structural information on the catalyst shows the suitability of X-ray techniques to understand catalytic reactions and to facilitate catalyst optimization.

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

    PubMed

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

    2013-05-01

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

  13. Chromium removal by zeolite-rich materials obtained from an exhausted FCC catalyst: Influence of chromium incorporation on the sorbent structure.

    PubMed

    Gonzalez, Maximiliano R; Pereyra, Andrea M; Torres Sánchez, Rosa M; Basaldella, Elena I

    2013-10-15

    A spent FCC catalyst was converted into a zeolitic mixture, and the product obtained was afterward used as trapping material for Cr(III) species frequently found in aqueous solutions. Eventual changes in the sorbent structure produced by Cr incorporation were studied by different characterization techniques such as point of zero charge determinations (PZC), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and infrared absorption (FTIR). The XRD and FTIR analyses indicated that chromium incorporation produces an amorphization of the material, and PZC measurements show no surface adsorption of charged chromium species. SEM and EDX analyses clearly show that after chromium sorption, the initial microspheroidal catalyst morphology was maintained, and the presence of chromium species was mainly detected in the outer microsphere surface, where the zeolite crystals were hydrothermally grown.

  14. XAFS Study on Nano-Sized Pd Metal Catalyst Deposited on Ti-Containing Zeolite by a Photo-Assisted Deposition (PAD) Method

    SciTech Connect

    Yamashita, Hiromi; Miura, Yuki; Tomonari, Masanori; Masui, Yosuke; Mori, Kohsuke

    2007-02-02

    The nano-sized Pd metal catalyst can be highly deposited on Ti-containing silicalite zeolite (TS-1) under UV-light irradiation (PAD-Pd/TS-1) using a photo-assisted deposition (PAD) method. The nano-sized Pd metal was deposited having the direct interaction with the photo-excited tetrahedrally coordinated titanium oxide moieties of TS-1. Under a flow of H2 and O2 in water, H2O2 could be synthesized efficiently on this nano-sized Pd metal catalyst.

  15. Process for combining the regeneratorless operation of tandem super-dense riser and fluid-bed oligomerization reactors containing a zeolite oligomerization catalyst

    SciTech Connect

    Harandi, M.N.; Owen, H.

    1990-05-15

    This patent describes a catalytic process for upgrading a C{sub 2}{sup +} olefin feedstream to a heavier product stream rich in C{sub 10}{sup +} aliphatic hydrocarbons in first and second oligomerization zones. It comprises: contacting the olefin feedstream in the first zone with a finely divided medium pore size zeolite metallosilicate catalyst having a silica:alumina ratio grater than 12, and a constraint index in the range from about 1 to about 12, at a weight hourly space velocity (WHSV) sufficient to maintain a transport zone, and, then with essentially the same catalyst maintained as a fluid bed, the first zone containing riser catalyst having a higher coke content than that of catalyst in the second zone maintained in a turbulent regime.

  16. 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.

  17. 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.

  18. Transient Spectroscopic Characterization of the Genesis of a Ruthenium Complex Catalyst Supported on Zeolite Y

    SciTech Connect

    Ogino, Isao; Gates, Bruce C.

    2010-01-12

    A mononuclear ruthenium complex anchored to dealuminated zeolite HY, Ru(acac)(C{sub 2}H{sub 4}){sup 2+} (acac = acetylacetonate, C{sub 5}H{sub 7}O{sup 2}{sup -}), was characterized in flow reactors by transient infrared (IR) spectroscopy and Ru K edge X-ray absorption spectroscopy. The combined results show how the supported complex was converted into a form that catalyzes ethene conversion to butene. The formation of these species resulted from the removal of acac ligands from the ruthenium (as shown by IR and extended X-ray absorption fine structure (EXAFS) spectra) and the simultaneous decrease in the symmetry of the ruthenium complex, with the ruthenium remaining mononuclear and its oxidation state remaining essentially unchanged (as shown by EXAFS and X-ray absorption near-edge structure spectra). The removal of anionic acac ligands from the ruthenium was evidently compensated by the bonding of other anionic ligands, such as hydride from H2 in the feed stream, to form species suggested to be Ru(H)(C{sub 2}H{sub 4}){sub 2}{sup +}, which is coordinatively unsaturated and inferred to react with ethene, leading to the observed formation of butene in a catalytic process.

  19. Template-synthesized porous silicon carbide as an effective host for zeolite catalysts.

    PubMed

    Gu, Lijun; Ma, Ding; Yao, Songdong; Liu, Xiumei; Han, Xiuwen; Shen, Wenjie; Bao, Xinhe

    2009-12-14

    A facile method has been developed for the fabrication of porous silicon carbide (SiC) by means of sintering a mixture of SiC powder and carbon pellets at a relatively lower temperature, that is, 1450 degrees C, in air. The pore density and the total pore volume of the resulting porous SiC could be tuned by changing the initial SiC/C weight ratio. The structure evolution and the associated property changes during the preparation were examined through X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, (29)Si magic-angle spinning (MAS) NMR spectroscopy, and mercury-intrusion porosimetry analyses. Silica and SiO(x)C(y) ceramics formed in situ during the calcination process acted as binders of the porous SiC grains. The porous SiC can be used as a host for the growth of ZSM-5 zeolite crystals to form the ZSM-5/porous-SiC composite material. After loading another catalytic active component of molybdenum, a novel catalytic material, Mo-ZSM-5/porous-SiC, was obtained, which exhibited improved catalytic activity in the methane dehydroaromatization reaction.

  20. A Comparative Study of N2O Formation during the Selective Catalytic Reduction of NOx with NH3 on Zeolite Supported Cu Catalysts

    SciTech Connect

    Chen, Hai-Ying; Wei, Zhehao; Kollar, Marton; Gao, Feng; Wang, Yilin; Szanyi, Janos; Peden, Charles HF

    2015-09-01

    A comparative study was carried out on a small-pore CHA.Cu and a large-pore BEA.Cu zeolite catalyst to understand the lower N2O formation on small-pore zeolite supported Cu catalysts in the selective catalytic reduction (SCR) of NOx with NH3. On both catalysts, the N2O yield increases with an increase in the NO2/NOx ratios of the feed gas, suggesting N2O formation via the decomposition of NH4NO3. Temperature-programmed desorption experiments reveal that NH4NO3 is more stable on CHA.Cu than on BEA.Cu. In situ FTIR spectra following stepwise (NO2 + O2) and (15NO + NH3 + O2) adsorption and reaction, and product distribution analysis using isotope-labelled reactants, unambiguously prove that surface nitrate groups are essential for the formation of NH4NO3. Furthermore, CHA.Cu is shown to be considerably less active than BEA.Cu in catalyzing NO oxidation and the subsequent formation of surface nitrate groups. Both factors, i.e., (1) the higher thermal stability of NH4NO3 on CHA.Cu, and (2) the lower activity for this catalyst to catalyze NO oxidation and the subsequent formation of surface nitrates, likely contribute to the higher SCR selectivity with less N2O formation on this catalyst as compared to BEA.Cu. The latter is determined as the primary reason since surface nitrates are the source that leads to the formation of NH4NO3 on the catalysts.

  1. Enhancement of Treatment Efficiency of Recalcitrant Wastewater Containing Textile Dyes Using a Newly Developed Iron Zeolite Socony Mobil-5 Heterogeneous Catalyst.

    PubMed

    Ahmad, Mushtaq; Asghar, Anam; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

    2015-01-01

    Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption.

  2. Enhancement of Treatment Efficiency of Recalcitrant Wastewater Containing Textile Dyes Using a Newly Developed Iron Zeolite Socony Mobil-5 Heterogeneous Catalyst

    PubMed Central

    Ahmad, Mushtaq; Asghar, Anam; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

    2015-01-01

    Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption. PMID:26517827

  3. I. Synthesis, characterization, and base catalysis of novel zeolite supported super-basic materials II. Oxidative dehydrogenation of ethane over reduced heteropolyanion catalysts

    NASA Astrophysics Data System (ADS)

    Galownia, Jonathan M.

    reliable precursor for the formation of zeolite supported super-basic materials. The second part of this thesis describes the oxidative dehydrogenation of ethane over partially reduced heteropolyanions. Niobium and pyridine exchanged salts of phosphomolybdic (NbPMo12Pyr) and phosphovanadomolybdic (NbPMo11VPyr) acids are investigated as catalyst precursors to prepare materials for catalyzing the oxidative dehydrogenation of ethane to ethylene and acetic acid at atmospheric pressure. The effects of feed composition, steam flow, temperature, and precursor composition on catalytic activity and selectivity are presented for both ethane and ethylene oxidation. Production of ethylene and acetic acid from ethane using the catalytic materials exceeds that reported in the literature for Mo-V-Nb-Ox systems under atmospheric or elevated pressure. Production of acetic acid from ethylene is also greater than that observed for Mo-V-Nb-Ox systems. Addition of vanadium reduces catalytic activity and selectivity to both ethylene and acetic acid while niobium is essential for the formation of acetic acid from ethane. Other metals such as antimony, iron, and gallium do not provide the same beneficial effect as niobium. Molybdenum in close proximity to niobium is the active site for ethane activation while niobium is directly involved in the transformation of ethylene to acetic acid. A balance of niobium and protonated pyridine is required to produce an active catalyst. Water is found to aid in desorption of acetic acid, thereby limiting deep oxidation to carbon oxides. A reaction scheme is proposed for the production of acetic acid from ethane over the catalytic materials.

  4. Investigation of the possibility of intermediate formation of allyl alcohol in the process of oxidative acetoxylation of propylene on a palladium-copper zeolite catalyst

    SciTech Connect

    Minachev, K.M.; Chizhov, O.S.; Kadentsev, V.I.; Kharlamov, V.V.; Nefedov, O.M.; Rodin, A.N.

    1985-12-10

    The formation of allyl acetate in reactions of oxidative acetoxylation of propylene by labeled acetic acid and esterification of labeled acetic acid by allyl alcohol on a Pd, Cu-zeolite catalyst occur with complete conservation of the labeled oxygen of the original labeled acetic acid in the reaction product. The authors propose a reaction scheme for the oxidative acetoxylation of propylene, providing for the formation of allyl alcohol as an intermediate compound, present in a chemisorbed state in the form of a complex with a Pd atom. The gas-phase oxidative acetoxylation of propylene is an industrial method of producing allyl acetate.

  5. Cracking and aromatization of C{sub 6}-C{sub 10} n-alkanes and n-alkenes on a zeolite-containing catalyst

    SciTech Connect

    Gairbekov, T.M.; Takaeva, M.I.; Khadzhiev, S.N.; Manovyan, A.K.

    1992-05-10

    Despite the extensive studies on catalysis on zeolites, the question of the mechanism of the reactions of cracking and aromatization of hydrocarbons is still debated. The classic Whitmore theory hypothesizes that cracking of alkanes and alkenes takes place through the formation of the same intermediate trivalent carbenium ions of the (C{sub n}H{sub 2n+1}){sup +} type. Ola`s protolytic mechanism hypothesizes nonclassic five- (four-)coordinated ions of the (C{sub n}H{sub 2n+3}){sup +} type for cracking of alkanes and classic carbenium ions for alkenes. When the classic mechanism occurs on zeolites, an analogous effect on the rate of the reactions of alkanes and alkenes with the molecular weight of the starting hydrocarbons and similar compositions of the products obtained should be predicted. The authors investigated the transformation of individual n-alkanes and n-1-alkenes of C{sub 6}-C{sub 10} composition in the presence of a catalyst synthesized by addition of 30 wt.% decationized ultrahigh-silicon zeolite of the ZSM type (Si/Al - 16) modified with 1 wt.% zinc on {gamma}-Al{sub 2}O{sub 3}. The experiment was conducted on a flow-type laboratory setup at 425{degrees}C in conditions of the minimum effect of diffusion factors with the method described in detail previously. 13 refs., 4 figs., 1 tab.

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

    PubMed

    Shamzhy, Mariya; Opanasenko, Maksym; Shvets, Oleksiy; Cejka, 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

    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 BEA 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)BEA < (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)BEA 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.

  9. SSZ-52, a zeolite with an 18-layer aluminosilicate framework structure related to that of the DeNOx catalyst Cu-SSZ-13.

    PubMed

    Xie, Dan; McCusker, Lynne B; Baerlocher, Christian; Zones, Stacey I; Wan, Wei; Zou, Xiaodong

    2013-07-17

    A new zeolite (SSZ-52, |(C14H28N)6Na6(H2O)18|[Al12Si96O216]), related to the DeNOx catalyst Cu-SSZ-13 (CHA framework type), has been synthesized using an unusual polycyclic quaternary ammonium cation as the structure-directing agent. By combining X-ray powder diffraction (XPD), high-resolution transmission electron microscopy (HRTEM) and molecular modeling techniques, its porous aluminosilicate framework structure (R3m, a = 13.6373(1) Å, c = 44.7311(4) Å), which can be viewed as an 18-layer stacking sequence of hexagonally arranged (Si,Al)6O6 rings (6-rings), has been elucidated. The structure has a three-dimensional 8-ring channel system and is a member of the ABC-6 family of zeolites (those that can be described in terms of 6-ring stacking sequences) like SSZ-13, but it has cavities that are twice as large. The code SFW has been assigned to this new framework type. The large cavities contain pairs of the bulky organic cations. HRTEM and XPD simulations show that stacking faults do occur, but only at the 5-10% level. SSZ-52 has considerable potential as a catalyst in the areas of gas conversion and sequestration.

  10. SSZ-52, a zeolite with an 18-layer aluminosilicate framework structure related to that of the DeNOx catalyst Cu-SSZ-13.

    PubMed

    Xie, Dan; McCusker, Lynne B; Baerlocher, Christian; Zones, Stacey I; Wan, Wei; Zou, Xiaodong

    2013-07-17

    A new zeolite (SSZ-52, |(C14H28N)6Na6(H2O)18|[Al12Si96O216]), related to the DeNOx catalyst Cu-SSZ-13 (CHA framework type), has been synthesized using an unusual polycyclic quaternary ammonium cation as the structure-directing agent. By combining X-ray powder diffraction (XPD), high-resolution transmission electron microscopy (HRTEM) and molecular modeling techniques, its porous aluminosilicate framework structure (R3m, a = 13.6373(1) Å, c = 44.7311(4) Å), which can be viewed as an 18-layer stacking sequence of hexagonally arranged (Si,Al)6O6 rings (6-rings), has been elucidated. The structure has a three-dimensional 8-ring channel system and is a member of the ABC-6 family of zeolites (those that can be described in terms of 6-ring stacking sequences) like SSZ-13, but it has cavities that are twice as large. The code SFW has been assigned to this new framework type. The large cavities contain pairs of the bulky organic cations. HRTEM and XPD simulations show that stacking faults do occur, but only at the 5-10% level. SSZ-52 has considerable potential as a catalyst in the areas of gas conversion and sequestration. PMID:23782259

  11. Chemical Imaging of Catalyst Deactivation during the Conversion of Renewables at the Single Particle Level: The Etherification of Biomass-based Polyols with Alkenes over H-Beta Zeolites

    SciTech Connect

    A Parvulescu; D Mores; E Stavitski; C Teodorescu; P Bruijnicx; R Klein Gebbing; B Weckhuysen

    2011-12-31

    The etherification of biomass-based alcohols with various linear {alpha}-olefins under solvent-free conditions was followed in a space- and time-resolved manner on 9 {micro}m large H-Beta zeolite crystals by confocal fluorescence microscopy. This allowed us to visualize the interaction with the substrate and distribution of the coke products into the catalyst at the level of an individual zeolite crystal during the etherification process. The spectroscopic information obtained on the micrometer-scale zeolite was in line with the results obtained with bulk characterization techniques and further confirmed by the catalytic results obtained both for micrometer-scale and nanoscale zeolites. This allowed us to explain the influence of the substrate type (glycerol, glycols, and alkenes) and zeolite properties (Si/Al ratio and particle size) on the etherification activity. The etherification of the biomass-based alcohols takes place mainly on the external surface of the zeolite particles. The gradual blockage of the external surface of the zeolite results in a partial or total loss of etherification activity. The deactivation could be attributed to olefin oligomerization. The high conversions obtained in the etherification of 1,2-propylene glycol with long linear alkenes (up to 80%) and the pronounced deactivation of the zeolite observed in the etherification of glycerol with long linear alkenes (max. 20% conversion) were explained by the spectroscopic measurements and is due to differences in the adsorption, i.e., in the center of the zeolite particle for glycerol and on the external surface in the case of glycols.

  12. Transition metal sulfide loaded catalyst

    DOEpatents

    Maroni, V.A.; Iton, L.E.; Pasterczyk, J.W.; Winterer, M.; Krause, T.R.

    1994-04-26

    A zeolite-based catalyst is described for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C[sub 2]+ hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

  13. Transition metal sulfide loaded catalyst

    DOEpatents

    Maroni, Victor A.; Iton, Lennox E.; Pasterczyk, James W.; Winterer, Markus; Krause, Theodore R.

    1994-01-01

    A zeolite based catalyst for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C.sub.2 + hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

  14. Hexane cracking over steamed phosphated zeolite H-ZSM-5: promotional effect on catalyst performance and stability.

    PubMed

    van der Bij, Hendrik E; Meirer, Florian; Kalirai, Sam; Wang, Jian; Weckhuysen, Bert M

    2014-12-15

    The nature behind the promotional effect of phosphorus on the catalytic performance and hydrothermal stability of zeolite H-ZSM-5 has been studied using a combination of (27) Al and (31) P MAS NMR spectroscopy, soft X-ray absorption tomography and n-hexane catalytic cracking, complemented with NH3 temperature-programmed desorption and N2 physisorption. Phosphated H-ZSM-5 retains more acid sites and catalytic cracking activity after steam treatment than its non-phosphated counterpart, while the selectivity towards propylene is improved. It was established that the stabilization effect is twofold. First, the local framework silico-aluminophosphate (SAPO) interfaces, which form after phosphatation, are not affected by steam and hold aluminum atoms fixed in the zeolite lattice, preserving the pore structure of zeolite H-ZSM-5. Second, the four-coordinate framework aluminum can be forced into a reversible sixfold coordination by phosphate. These species remain stationary in the framework under hydrothermal conditions as well. Removal of physically coordinated phosphate after steam-treatment leads to an increase in the number of strong acid sites and increased catalytic activity. We propose that the improved selectivity towards propylene during catalytic cracking can be attributed to local SAPO interfaces located at channel intersections, where they act as impediments in the formation of bulky carbenium ions and therefore suppress the bimolecular cracking mechanism.

  15. A mechanistic model for hydrogen activation, spillover, and its chemical reaction in a zeolite-encapsulated Pt catalyst.

    PubMed

    Shin, Hyeyoung; Choi, Minkee; Kim, Hyungjun

    2016-03-14

    The hydrogen (H) spillover phenomenon has attracted considerable attention in the catalysis field. Many researchers have focused on the phenomenon itself, as well as its applications for advanced catalytic systems. In particular, H spillover on non-reducible materials, such as alumina, silica, and zeolites, is a controversial issue owing to the lack of understanding regarding its mechanistic properties. In this study, we use density functional theory calculations to propose the entire mechanism of H spillover from H2 activation on a platinum to its participation in chemical reactions on the external surface of a zeolite. We determined that surface hydroxyl groups of the zeolites, such as Brønsted acid sites, play a role in initiating H spillover, and the Lewis acid sites facilitate the entire process by allowing H to be transferred as a H(+)/e(-) charge pair, as well as providing good binding sites for organic reactants. Theoretical results explain the key experimental features, and we expect that this work will help to elucidate the H spillover phenomenon on non-reducible support materials and to utilize it for catalytic systems. PMID:26735140

  16. Molecular models of site-isolated cobalt, rhodium, and iridium catalysts supported on zeolites: Ligand bond dissociation energies

    DOE PAGESBeta

    Chen, Mingyang; Serna, Pedro; Lu, Jing; Gates, Bruce C.; Dixon, David A.

    2015-09-28

    The chemistry of zeolite-supported site-isolated cobalt, rhodium, and iridium complexes that are essentially molecular was investigated with density functional theory (DFT) and the results compared with experimentally determined spectra characterizing rhodium and iridium species formed by the reactions of Rh(C2H4)2(acac) and Ir(C2H4)2(acac) (acac = acetylacetonate) with acidic zeolites such as dealuminated HY zeolite. The experimental results characterize ligand exchange reactions and catalytic reactions of adsorbed ligands, including olefin hydrogenation and dimerization. Two molecular models were used to characterize various binding sites of the metal complexes in the zeolites, and the agreement between experimental and calculated infrared frequencies and metal-ligand distancesmore » determined by extended X-ray absorption fine structure spectroscopy was generally very good. The calculated structures and energies indicate a metal-support-oxygen (M(I)-O) coordination number of two for most of the supported complexes and a value of three when the ligands include the radicals C2H5 or H. The results characterizing various isomers of the supported metal complexes incorporating hydrocarbon ligands indicate that some carbene and carbyne ligands could form. Ligand bond dissociation energies (LDEs) are reported to explain the observed reactivity trends. The experimental observations of a stronger M-CO bond than M-(C2H4) bond for both Ir and Rh match the calculated LDEs, which show that the single-ligand LDEs of the mono and dual-ligand complexes for CO are similar to 12 and similar to 15 kcal/mol higher in energy (when the metal is Rh) and similar to 17 and similar to 20 kcal/mol higher (when the metal is Ir) than the single-ligand LDEs of the mono and dual ligand complexes for C2H4, respectively. The results provide a foundation for the prediction of the catalytic properties of numerous supported metal complexes, as summarized in detail here.« less

  17. Molecular models of site-isolated cobalt, rhodium, and iridium catalysts supported on zeolites: Ligand bond dissociation energies

    SciTech Connect

    Chen, Mingyang; Serna, Pedro; Lu, Jing; Gates, Bruce C.; Dixon, David A.

    2015-09-28

    The chemistry of zeolite-supported site-isolated cobalt, rhodium, and iridium complexes that are essentially molecular was investigated with density functional theory (DFT) and the results compared with experimentally determined spectra characterizing rhodium and iridium species formed by the reactions of Rh(C2H4)2(acac) and Ir(C2H4)2(acac) (acac = acetylacetonate) with acidic zeolites such as dealuminated HY zeolite. The experimental results characterize ligand exchange reactions and catalytic reactions of adsorbed ligands, including olefin hydrogenation and dimerization. Two molecular models were used to characterize various binding sites of the metal complexes in the zeolites, and the agreement between experimental and calculated infrared frequencies and metal-ligand distances determined by extended X-ray absorption fine structure spectroscopy was generally very good. The calculated structures and energies indicate a metal-support-oxygen (M(I)-O) coordination number of two for most of the supported complexes and a value of three when the ligands include the radicals C2H5 or H. The results characterizing various isomers of the supported metal complexes incorporating hydrocarbon ligands indicate that some carbene and carbyne ligands could form. Ligand bond dissociation energies (LDEs) are reported to explain the observed reactivity trends. The experimental observations of a stronger M-CO bond than M-(C2H4) bond for both Ir and Rh match the calculated LDEs, which show that the single-ligand LDEs of the mono and dual-ligand complexes for CO are similar to 12 and similar to 15 kcal/mol higher in energy (when the metal is Rh) and similar to 17 and similar to 20 kcal/mol higher (when the metal is Ir) than the single-ligand LDEs of the mono and dual ligand complexes for C2H4, respectively. The results provide a foundation for the prediction

  18. The effect of soot on ammonium nitrate species and NO2 selective catalytic reduction over Cu-zeolite catalyst-coated particulate filter.

    PubMed

    Mihai, Oana; Tamm, Stefanie; Stenfeldt, Marie; Olsson, Louise

    2016-02-28

    interacting with the ammonium nitrate species on the CuxOy or other copper species on the surface of the zeolite particles, which reduces the ammonium nitrate blocking of the catalyst and thereby results in higher NO2 SCR activity.

  19. The effect of soot on ammonium nitrate species and NO2 selective catalytic reduction over Cu-zeolite catalyst-coated particulate filter.

    PubMed

    Mihai, Oana; Tamm, Stefanie; Stenfeldt, Marie; Olsson, Louise

    2016-02-28

    interacting with the ammonium nitrate species on the CuxOy or other copper species on the surface of the zeolite particles, which reduces the ammonium nitrate blocking of the catalyst and thereby results in higher NO2 SCR activity. PMID:26755757

  20. 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

  1. Technico-economic assessment of groundwater treatment by palladium-on-zeolite-catalyst in comparison to GAC fixed bed adsorbers.

    PubMed

    Bayer, P; Schüth, C

    2010-01-01

    A technico-economic comparison between palladium-on-zeolite (Pd/Y), and granular activated carbon (GAC) based methods of groundwater clean-up is presented. The treatment concepts are assessed by means of process-based cost functions that can be applied to a broad range of case-specific conditions. The analysis accounts for variability in cost and performance parameters and reduces the interplay of multiple factors to expressive indifference curves that can be used for identifying a favorable technology. The findings for the treatment of halogenated hydrocarbons reveal that the Pd/Y offers advantages compared to GAC use in case of high contaminant concentrations and for the treatment of lower halogenated compounds such as cis-Dichloroethene.

  2. NO{sub X} REDUCTION BEHAVIOR OF ALUMINA AND ZEOLITE CATALYSTS IN COMBINATION WITH NON-THERMAL PLASMA

    SciTech Connect

    Panov, A.G.

    2000-08-20

    Lean burn gasoline and diesel engines provide improved fuel economy when compared to engines operating under stoichiometric fuel/air conditions. At the same time, lean burn and diesel engines present a problem for emission control. Because they operate under oxidizing conditions, the conventional three-way catalyst is not effective in NOx reduction [1,2]. In addition, the wide temperature range of automobile exhaust gases present a challenge for catalyst design. The temperature of exhaust gases from a light duty diesel engine can vary from 150 to 500 C, depending on the operating conditions. To date, a catalyst that operates with high NOx conversion efficiency over the entire operating range has not been found. Non-thermal plasma assisted catalysis has been shown to be a promising technology for NOx reduction in lean burn and diesel exhaust gases [3,4]. The approach exploited in this paper is to use a plasma in combination with several catalysts, each of which are active over unique temperature ranges. It was reported in the literature, that the one of the essential roles of plasma treatment is to oxidize NO to easier reducible NO2 [7]. In this contribution, the other important function of plasma treatment, namely partial oxidation of propylene, will be demonstrated.

  3. UV-vis spectroscopy of iodine adsorbed on alkali-metal-modified zeolite catalysts for addition of carbon dioxide to ethylene oxide

    SciTech Connect

    Doskocil, E.J.; Bordawekar, S.V.; Kaye, B.G.; Davis, R.J.

    1999-07-29

    The basicity of alkali-metal-exchange (Na, K, Cs) zeolites X and Y was probed by UV-vis diffuse reflectance spectroscopy of adsorbed iodine. The observed blue shift in the visible absorption spectrum of adsorbed iodine, compared to gaseous iodine, correlated well with the negative charge on the framework oxygen atoms calculated from the Sanderson electronegativity equalization principle. The blue shifts associated with iodine adsorbed on classical catalytic supports like silica, alumina, and magnesia suggest that the iodine adsorption technique for probing basicity is applicable to a wide variety of solids. Iodine was also adsorbed on X and Y zeolites containing occluded cesium oxide formed by decomposition of impregnated cesium acetate. However, the iodine appeared to irreversibly react on these strongly basic samples, possibly forming an adsorbed triiodide ions. As a complement to the adsorption studies, the activity of alkali-metal-containing zeolites for the base-catalyzed formation of ethylene carbonate from ethylene oxide and carbon dioxide was investigated. Among the ion-exchanged zeolites, the cesium form of zeolite X exhibited the highest activity for ethylene carbonate formation. The catalytic activity of a zeolite containing occluded cesium was even higher than that of a cesium-exchanged zeolite. The presence of water adsorbed in zeolite pores promoted the rate of ethylene carbonate formation for both cesium-exchanged and cesium-impregnated zeolite X.

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

    NASA Astrophysics Data System (ADS)

    Lindquist, David A.; Smoot, Alison L.

    1997-05-01

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

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

    PubMed

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

    2016-02-21

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

  6. Cracking vegetable oil from Callophylluminnophyllum L. seeds to bio-gasoline by Ni-Mo/Al2O3 and Ni-Mo/Zeolite as micro-porous catalysts

    NASA Astrophysics Data System (ADS)

    Savitri, Effendi, R.; Tursiloadi, S.

    2016-02-01

    Natural minerals such as zeolite are local natural resources in the various regions in Indonesia. Studies on the application of natural mineral currently carried out by national research institutions, among others, as a filler, bleaching agent, or dehydration agent. However, not many studies that utilize these natural minerals as green catalysts material which has high performance for biomass conversion processes and ready to be applied directly by the bio-fuel industry. The trend movement of green and sustainable chemistry research that designing environmentally friendly chemical processes from renewable raw materials to produce innovative products derived biomass for bio-fuel. Callophylluminnophyllum L. seeds can be used as raw material for bio-energy because of its high oil content. Fatty acid and triglyceride compounds from this oil can be cracked into bio-gasoline, which does not contain oxygen in the hydrocarbon structure. Bio-gasoline commonly is referred to as drop-in biofuel because it can be directly used as a substitute fuel. This paper focused on the preparation and formulation of the catalyst NiMo/H-Zeolite and Ni-Mo/Al2O3 which were used in hydro-cracking process of oil from Callophylluminnophyllum L. seeds to produce bio-gasoline. The catalysts were analyzed using XRD, BET and IR-adsorbed pyridine method. The results of hydro-cracking products mostly were paraffin (C10-C19) straight chain, with 59.5 % peak area based on GC-MS analysis.

  7. Identification of the iron oxidation state and coordination geometry in iron oxide- and zeolite-based catalysts using pre-edge XAS analysis.

    PubMed

    Boubnov, Alexey; Lichtenberg, Henning; Mangold, Stefan; Grunwaldt, Jan Dierk

    2015-03-01

    Analysis of the oxidation state and coordination geometry using pre-edge analysis is attractive for heterogeneous catalysis and materials science, especially for in situ and time-resolved studies or highly diluted systems. In the present study, focus is laid on iron-based catalysts. First a systematic investigation of the pre-edge region of the Fe K-edge using staurolite, FePO4, FeO and α-Fe2O3 as reference compounds for tetrahedral Fe(2+), tetrahedral Fe(3+), octahedral Fe(2+) and octahedral Fe(3+), respectively, is reported. In particular, high-resolution and conventional X-ray absorption spectra are compared, considering that in heterogeneous catalysis and material science a compromise between high-quality spectroscopic data acquisition and simultaneous analysis of functional properties is required. Results, which were obtained from reference spectra acquired with different resolution and quality, demonstrate that this analysis is also applicable to conventionally recorded pre-edge data. For this purpose, subtraction of the edge onset is preferentially carried out using an arctangent and a first-degree polynomial, independent of the resolution and quality of the data. For both standard and high-resolution data, multiplet analysis of pre-edge features has limitations due to weak transitions that cannot be identified. On the other hand, an arbitrary empirical peak fitting assists the analysis in that non-local transitions can be isolated. The analysis of the oxidation state and coordination geometry of the Fe sites using a variogram-based method is shown to be effective for standard-resolution data and leads to the same results as for high-resolution spectra. This method, validated by analysing spectra of reference compounds and their well defined mixtures, is finally applied to track structural changes in a 1% Fe/Al2O3 and a 0.5% Fe/BEA zeolite catalyst during reduction in 5% H2/He. The results, hardly accessible by other techniques, show that Fe(3+) is

  8. Towards a full understanding of the nature of Ni(II) species and hydroxyl groups over highly siliceous HZSM-5 zeolite supported nickel catalysts prepared by a deposition-precipitation method.

    PubMed

    Chen, Bao-Hui; Chao, Zi-Sheng; He, Hao; Huang, Chen; Liu, Ya-Juan; Yi, Wen-Jun; Wei, Xue-Ling; An, Jun-Fang

    2016-02-14

    Highly siliceous HZSM-5 zeolite supported nickel catalysts prepared by a deposition-precipitation (D-P) method were characterized by Fourier transform infrared (FT-IR), hydrogen temperature programmed reduction (H2-TPR), X-ray diffraction (XRD), N2-absorption/desorption, field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), and (27)Al magic-angle nuclear magnetic resonance (MAS NMR) techniques. The results showed that the D-P of nickel species occurred predominantly on the internal surface of highly siliceous HZSM-5 zeolite, in which the internal silanol groups located on the hydroxylated mesopores or nanocavities played a key role. During the D-P process, nickel hydroxide was first deposited-precipitated via olation/polymerization of neutral hydroxoaqua nickel species over the HZSM-5 zeolite. With the progress of the D-P process, 1 : 1 nickel phyllosilicate was formed over the HZSM-5 via the hetero-condensation/polymerization between charged hydroxoaqua nickel species and monomer silicic species generated due to the partial dissolution of the HZSM-5 framework. The 1 : 1 nickel phyllosilicate could also be generated via the hydrolytic adsorption of hydroxoaqua nickel species and their subsequent olation condensation. After calcination, the deposited-precipitated nickel hydroxide was decomposed into nickel oxide, while the 1 : 1 nickel phyllosilicate was transformed into 2 : 1 nickel phyllosilicate. According to the above mechanism, Ni(ii) species were present both in the form of nickel oxide and 2 : 1 nickel phyllosilicate, which were mutually separated from each other, being highly dispersed over HZSM-5 zeolite.

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

    SciTech Connect

    Dutta, Prabir K.

    2001-09-30

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

  10. Functionalization of zeolitic cavities: grafting NH2 groups in framework T sites of B-SSZ-13--a way to obtain basic solids catalysts?

    PubMed

    Regli, Laura; Bordiga, Silvia; Busco, Claudia; Prestipino, Carmelo; Ugliengo, Piero; Zecchina, Adriano; Lamberti, Carlo

    2007-10-10

    Insertion of B atoms into an Al-free zeolitic framework with CHA topology results in the formation of B-SSZ-13 zeotype with Si/B = 11. B K-edge NEXAFS testifies that B forms [B(OSi)4] units in a Td-like geometry (sp3-hybridized B atoms). According to B K-edge NEXAFS and IR, template burning results in the formation of [B(OSi)3] units in a D3h-like geometry (sp2-hybridized B atoms) with a break of a B-O-Si bond and the formation of a Si-OH group. The activated material contains B(III) Lewis acid centers able to specifically coordinate bases like NH3. Such [B(OSi)3] units are reactive toward ammonia, resulting in the formation of B-NH2 surface functionality inside the pores of B-SSZ-13 already under mild conditions, i.e., 35 mbar of NH3 at 373 K for 30 min and without crystallinity degradation. A minor fraction of Si-NH2 cannot be excluded owing to the presence of two IR doublets at 3500 and 3430 cm-1 and at 1600 and 1550 cm-1. Ab initio B3LYP/6-31+G(d,p) calculations on a cluster model, supported by a single-point MP2 on B3LYP/6-31+G(D,P) optimized structures, found the break by NH3 of a B-O-Si bond of the [B(OSi)3] unit with formation of [SiOH] and [H2N-B(OSi)2] species to be energetically favored. Comparison between experimental and computed frequency shifts shows them to be in semiquantitative agreement. The high stability of the B-NH2 surface functionality is probed by N K-edge NEXAFS spectra collected under UHV conditions. These findings can open a new route in the preparation of shape selective solid basic catalysts. PMID:17867687

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

    SciTech Connect

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

    2014-02-22

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

  12. Nanostructured Basic Catalysts: Opportunities for Renewable Fuels

    SciTech Connect

    Conner, William C; Huber, George; Auerbach, Scott

    2009-06-30

    This research studied and developed novel basic catalysts for production of renewable chemicals and fuels from biomass. We focused on the development of unique porous structural-base catalysts zeolites. These catalysts were compared to conventional solid base materials for aldol condensation, that were being commercialized for production of fuels from biomass and would be pivotal in future biomass conversion to fuels and chemicals. Specifically, we had studied the aldolpyrolysis over zeolites and the trans-esterification of vegetable oil with methanol over mixed oxide catalysts. Our research has indicated that the base strength of framework nitrogen in nitrogen substituted zeolites (NH-zeolites) is nearly twice as strong as in standard zeolites. Nitrogen substituted catalysts have been synthesized from several zeolites (including FAU, MFI, BEA, and LTL) using NH3 treatment.

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

    NASA Astrophysics Data System (ADS)

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

    1999-10-01

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

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

    PubMed

    Boranić, M

    2000-01-01

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

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

    ERIC Educational Resources Information Center

    Smoot, Alison L.; Lindquist, David A.

    1997-01-01

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

  16. Zeolites Remove Sulfur From Fuels

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E.; Sharma, Pramod K.

    1991-01-01

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

  17. Characterization of a zeolite membrane for catalytic membrane reactor application

    SciTech Connect

    Giroir-Fendler, A.; Peureux, J.; Mozzanega, H.; Dalmon, J.A.

    1996-12-31

    This paper describes the morphological and transport properties of a composite zeolite (silicalite) - alumina membrane. Some advantages obtained in combining the membrane with a conventional fixed-bed catalyst are also reported.

  18. Removal of ethylene from air stream by adsorption and plasma-catalytic oxidation using silver-based bimetallic catalysts supported on zeolite.

    PubMed

    Trinh, Quang Hung; Lee, Sang Baek; Mok, Young Sun

    2015-03-21

    Dynamic adsorption of ethylene on 13X zeolite-supported Ag and Ag-M(x)O(y) (M: Co, Cu, Mn, and Fe), and plasma-catalytic oxidation of the adsorbed ethylene were investigated. The experimental results showed that the incorporation of Ag into zeolite afforded a marked enhancement in the adsorptivity for ethylene. The addition of transition metal oxides was found to have a positive influence on the ethylene adsorption, except Fe(x)O(y). The presence of the additional metal oxides, however, appeared to somewhat interrupt the diffusion of ozone into the zeolite micro-pores, leading to a decrease in the plasma-catalytic oxidation efficiency of the ethylene adsorbed there. Among the second additional metal oxides, Fe(x)O(y) was able to reduce the emission of ozone during the plasma-catalytic oxidation stage while keeping a high effectiveness for the oxidative removal of the adsorbed ethylene. The periodical treatment consisting of adsorption followed by plasma-catalytic oxidation may be a promising energy-efficient ethylene abatement method.

  19. Enhanced Activity of Nanocrystalline Beta Zeolite for Acylation of Veratrole with Acetic Anhydride.

    PubMed

    Aisha Mahmood Abdulkareem, Al-Turkustani; Selvin, Rosilda

    2016-04-01

    Friedel-Craft acylation of veratrole using homogeneous acid catalysts such as AlCl3, FeCl3, ZnCl2, and HF etc. produces acetoveratrone, (3',4'-dimethoxyacetophenone), which is the intermediate for synthesis of papavarine alkaloids. The problems associated with these homogeneous catalysts can be overcome by using heterogeneous solid catalysts. Since acetoveratrone is a larger molecule, large pore Beta zeolites with smaller particle sizes are beneficial for the liquid-phase acylation of veratrole, for easy diffusion of reactants and products. The present study aims in the acylation of veratrole with acetic anhydride using nanocrystalline Beta Zeolite catalyst. A systematic investigation of the effects of various reaction parameters was done. The catalysts were characterized for their structural features by using XRD, TEM and DLS analyses. The catalytic activity of nanocrystalline Beta zeolite was compared with commercial Beta zeolite for the acylation and was found that nanocrystalline Beta zeolite possessed superior activity.

  20. Enhanced Activity of Nanocrystalline Beta Zeolite for Acylation of Veratrole with Acetic Anhydride.

    PubMed

    Aisha Mahmood Abdulkareem, Al-Turkustani; Selvin, Rosilda

    2016-04-01

    Friedel-Craft acylation of veratrole using homogeneous acid catalysts such as AlCl3, FeCl3, ZnCl2, and HF etc. produces acetoveratrone, (3',4'-dimethoxyacetophenone), which is the intermediate for synthesis of papavarine alkaloids. The problems associated with these homogeneous catalysts can be overcome by using heterogeneous solid catalysts. Since acetoveratrone is a larger molecule, large pore Beta zeolites with smaller particle sizes are beneficial for the liquid-phase acylation of veratrole, for easy diffusion of reactants and products. The present study aims in the acylation of veratrole with acetic anhydride using nanocrystalline Beta Zeolite catalyst. A systematic investigation of the effects of various reaction parameters was done. The catalysts were characterized for their structural features by using XRD, TEM and DLS analyses. The catalytic activity of nanocrystalline Beta zeolite was compared with commercial Beta zeolite for the acylation and was found that nanocrystalline Beta zeolite possessed superior activity. PMID:27451793

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

    PubMed

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

    2013-01-01

    Zeolites have potential application as ion-exchangers, catalysts and molecular sieves. Zeolites are once again drawing attention in Japan as stable adsorbents and solidification materials of fission products, such as (137)Cs(+) from damaged nuclear-power plants. Although there is a long history of scientific studies on the crystal structures and ion-exchange properties of zeolites for practical application, there are still open questions, at the atomic-level, on the physical and chemical origins of selective ion-exchange abilities of different cations and detailed atomic structures of exchanged cations inside the nanoscale cavities of zeolites. Here, the precise locations of Cs(+) ions captured within A-type zeolite were analyzed using high-resolution electron microscopy. Together with theoretical calculations, the stable positions of absorbed Cs(+) ions in the nanocavities are identified, and the bonding environment within the zeolitic framework is revealed to be a key factor that influences the locations of absorbed cations.

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

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

    Zeolites have potential application as ion-exchangers, catalysts and molecular sieves. Zeolites are once again drawing attention in Japan as stable adsorbents and solidification materials of fission products, such as 137Cs+ from damaged nuclear-power plants. Although there is a long history of scientific studies on the crystal structures and ion-exchange properties of zeolites for practical application, there are still open questions, at the atomic-level, on the physical and chemical origins of selective ion-exchange abilities of different cations and detailed atomic structures of exchanged cations inside the nanoscale cavities of zeolites. Here, the precise locations of Cs+ ions captured within A-type zeolite were analyzed using high-resolution electron microscopy. Together with theoretical calculations, the stable positions of absorbed Cs+ ions in the nanocavities are identified, and the bonding environment within the zeolitic framework is revealed to be a key factor that influences the locations of absorbed cations.

  3. Zeolite catalysis in conversion of cellulosics. Annual report

    SciTech Connect

    Tsao, G.T.

    1994-02-01

    The authors have studied the kinetics of oxylose/xylulose isomerization in significant detail over a variety of zeolites and obtained the pseudo-first order reaction rate constants. The authors have found that HY zeolite is still the best material and zeolites are more selective than homogeneous acid catalysts where decomposition of the sugar compounds is much faster. They have completed, as described in the Year 2 Work Plan, the study of cellobiose hydrolysis with an ion exchange resin. The kinetics of the solid-catalyzed reaction is qualitatively similar to that for catalysis by homogeneous acids. The planned program of NMR studies has revealed the dynamics of sugar molecules within the zeolite cavities. Two chemisorbed and a physisorbed state have been identified in HY zeolite. A new state, accounting for as much as a half of the sugar, has been found in ZSM-5 zeolite.

  4. [Zeolite catalysis in conversion of cellulosics

    SciTech Connect

    Tsao, G.T.

    1992-01-01

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

  5. [Zeolite catalysis in conversion of cellulosics

    SciTech Connect

    Tsao, G.T.

    1992-12-31

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

  6. Preparation of zeolites for TEM (Transmission Electron Microscopy) using microtomy

    SciTech Connect

    Csencsits, R.; Gronsky, R.

    1987-12-01

    The application of microtomy to Transmission Electron Microscopy (TEM) specimen preparation of zeolite catalysts is explained. Using a new acrylic resin (LR White) thin sections (less than or equal to60 nm) may be cut with relative ease. Although the details described are specific to catalysts, microtomy and the use of the acrylic resin are applicable to any hard ceramic powder sample. 3 figs.

  7. Highly active and highly selective aromatization catalyst

    SciTech Connect

    Santilli, D.S.; Long, J.J.; Lewis, R.T.

    1987-10-06

    This patent describes a reforming catalyst comprising an L zeolite containing platinum metal and at least one promoter metal selected from the group consisting of iron, cobalt, titanium, and rare earth metal. The catalyst has a platinum to promoter metal mole ratio of less than 10:1. The patent also includes a method of preparing the reforming catalyst of claim 1, comprising steps of: (a) forming an aqueous solution of alkali hydroxide, aluminum hydroxide, and ferric salt; (b) combining the solution with an aqueous solution of silica to form a thickening gel in a mother liquor; (c) heating the thickening gel to form an L zeolite; (d) cooling the gel containing the L zeolite; (e) decanting the mother liquor from the gel; (f) filtering the L zeolite from the gel; (g) washing the filtered L zeolite; (h) drying the washed L zeolite; (i) adding platinum to the dried L zeolite to form a catalyst; (j) drying the catalyst; and (k) calcining the dried catalyst.

  8. Synthesis and catalytic applications of combined zeolitic/mesoporous materials

    PubMed Central

    Vernimmen, Jarian; Cool, Pegie

    2011-01-01

    Summary In the last decade, research concerning nanoporous siliceous materials has been focused on mesoporous materials with intrinsic zeolitic features. These materials are thought to be superior, because they are able to combine (i) the enhanced diffusion and accessibility for larger molecules and viscous fluids typical of mesoporous materials with (ii) the remarkable stability, catalytic activity and selectivity of zeolites. This review gives an overview of the state of the art concerning combined zeolitic/mesoporous materials. Focus is put on the synthesis and the applications of the combined zeolitic/mesoporous materials. The different synthesis approaches and formation mechanisms leading to these materials are comprehensively discussed and compared. Moreover, Ti-containing nanoporous materials as redox catalysts are discussed to illustrate a potential implementation of combined zeolitic/mesoporous materials. PMID:22259762

  9. Towards a sustainable manufacture of hierarchical zeolites.

    PubMed

    Verboekend, Danny; Pérez-Ramírez, Javier

    2014-03-01

    Hierarchical zeolites have been established as a superior type of aluminosilicate catalysts compared to their conventional (purely microporous) counterparts. An impressive array of bottom-up and top-down approaches has been developed during the last decade to design and subsequently exploit these exciting materials catalytically. However, the sustainability of the developed synthetic methods has rarely been addressed. This paper highlights important criteria to ensure the ecological and economic viability of the manufacture of hierarchical zeolites. Moreover, by using base leaching as a promising case study, we verify a variety of approaches to increase reactor productivity, recycle waste streams, prevent the combustion of organic compounds, and minimize separation efforts. By reducing their synthetic footprint, hierarchical zeolites are positioned as an integral part of sustainable chemistry.

  10. Distribution of metal and adsorbed guest species in zeolites

    SciTech Connect

    Chmelka, B.F.

    1989-12-01

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

  11. Octane boosting catalyst

    SciTech Connect

    Miller, J.G.; Pellet, R.J.; Shamshoun, E.S.; Rabo, J.A

    1989-02-07

    The invention provides petroleum cracking and octane boosting catalysts containing a composite of an intermediate pore NZMS in combination with another non-zeolitic molecular sieve having the same framework structure, and processes for cracking of petroleum for the purpose of enhancing the octane rating of the gasoline produced.

  12. Controlled synthesis of mixed-valent Fe-containing metal organic frameworks for the degradation of phenol under mild conditions.

    PubMed

    Sun, Qiao; Liu, Min; Li, Keyan; Han, Yitong; Zuo, Yi; Wang, Junhu; Song, Chunshan; Zhang, Guoliang; Guo, Xinwen

    2016-05-10

    A series of MIL-53(Fe)-type materials, Fe(BDC)(DMF,F), were prepared by using different ratios of n(FeCl3)/n(FeCl2), which have varied amounts of Fe(2+) in their frameworks. From FeCl3 to FeCl2, the structures of the synthesized samples transform from MIL-53(Fe) to Fe(BDC)(DMF,F). Along with this structure transformation, the crystal morphology goes through a striking change from a small irregular shape to a big triangular prism. This phenomenon indicates that the addition of FeCl2 is beneficial for the formation of a Fe(BDC)(DMF,F) structure. The catalytic activity of these iron-containing MOFs was tested in phenol degradation with hydrogen peroxide as an oxidant at near neutral pH and 35 °C. The degradation efficiency of these samples increases gradually from MIL-53(Fe) to Fe(BDC)(DMF,F). (57)Fe Mössbauer spectra reveal that Fe(2+) and Fe(3+) coexist in the Fe(BDC)(DMF,F) framework, and the highest amount of Fe(2+) in the sample prepared with mixed FeCl3 and FeCl2 is 26.0%. The result illustrates that the amount of Fe(2+) in the samples can be controlled using varied n(FeCl3)/n(FeCl2) in the feed. The diverse amount of Fe(2+) in this series of FeMOF materials exactly explains the distinction of reaction efficiency. The iron leaching tests, structures of the fresh and used catalysts, and the data of the recycling runs show that the Fe-containing MOFs are stable in this liquid-phase reaction. PMID:26862863

  13. Catalysts and process for liquid hydrocarbon fuel production

    SciTech Connect

    White, Mark G; Liu, Shetian

    2014-12-09

    The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality gasoline components, aromatic compounds, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion, as well as a novel rhenium-zeolite catalyst in place of the molybdenum-zeolite catalyst, and provides for use of the novel catalysts in the process and system of the invention.

  14. Lithium modified zeolite synthesis for conversion of biodiesel-derived glycerol to polyglycerol

    SciTech Connect

    Ayoub, Muhammad; Abdullah, Ahmad Zuhairi; Inayat, Abrar

    2014-10-24

    Basic zeolite has received significant attention in the catalysis community. These zeolites modified with alkaline are the potential replacement for existing zeolite catalysts due to its unique features with added advantages. The present paper covers the preparation of lithium modified zeolite Y (Li-ZeY) and its activity for solvent free conversion of biodiesel-derived glycerol to polyglycerol via etherification process. The modified zeolite was well characterized by X-ray diffraction (XRD), Scanning Electron Microscope (SEM) and Nitrogen Adsorption. The SEM images showed that there was no change in morphology of modified zeolite structure after lithium modification. XRD patterns showed that the structure of zeolite was sustained after lithium modification. The surface properties of parent and modified zeolite was also observed N{sub 2} adsortion-desorption technique and found some changes in surface area and pore size. In addition, the basic strength of prepared materials was measured by Hammet indicators and found that basic strength of Li-ZeY was highly improved. This modified zeolite was found highly thermal stable and active heterogamous basic catalyst for conversion of solvent free glycerol to polyglycerol. This reaction was conducted at different temperatures and 260 °C was found most active temperature for this process for reaction time from 6 to 12 h over this basic catalyst in the absence of solvent.

  15. Development of GREET Catalyst Module

    SciTech Connect

    Wang, Zhichao; Benavides, Pahola T.; Dunn, Jennifer B.; Cronauer, Donald C.

    2015-09-01

    In this report, we develop energy and material flows for the production of five different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5], Mo/Co/ γ-Al2O3, and Pt/ γ-Al2O3) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module.

  16. Zeolite membranes from kaolin

    SciTech Connect

    Karle, B.G.; Brinker, C.J. |; Phillips, M.L.F.

    1996-07-01

    Zeolite films are sought as components of molecular sieve membranes. Different routes used to prepare zeolite composite membranes include growing zeolite layers from gels on porous supports, depositing oriented zeolites on supports, and dispersing zeolites in polymeric membranes. In most cases, it is very difficult to control and avoid the formation of cracks and/or pinholes. The approach to membrane synthesis is based on hydrothermally converting films of layered aluminosilicates into zeolite films. The authors have demonstrated this concept by preparing zeolite A membranes on alumina supports from kaolin films. The authors have optimized the process parameters not only for desired bulk properties, but also for preparing thin (ca. 5 {micro}m), continuous zeolite A films. Scanning electron microscopy shows highly intergrown zeolite A crystals over most of the surface area of the membrane, but gas permeation experiments indicate existence of mesoporous defects and/or intercrystalline gaps. It has been demonstrated that the thickness of the final zeolite A membrane can be controlled by limiting the amount of precursor kaolin present in the membrane.

  17. 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

  18. Intercalated clay catalysts

    SciTech Connect

    Pinnavaia, T.J.

    1983-04-22

    Recent advances in the intercalation of metal complex cations in smectite clay minerals are leading to the development of new classes of selective heterogeneous catalysts. The selectivity of both metal-catalyzed and proton-catalyzed chemical conversions in clay intercalates can often be regulated by controlling surface chemical equilibria, interlamellar swelling, or reactant pair proximity in the interlayer regions. Also, the intercalation of polynuclear hydroxy metal cations and metal cluster cations in smectites affords new pillared clay catalysts with pore sizes that can be made larger than those of conventional zeolite catalysts.

  19. Intercalated Clay Catalysts

    NASA Astrophysics Data System (ADS)

    Pinnavaia, Thomas J.

    1983-04-01

    Recent advances in the intercalation of metal complex cations in smectite clay minerals are leading to the development of new classes of selective heterogeneous catalysts. The selectivity of both metal-catalyzed and proton-catalyzed chemical conversions in clay intercalates can often be regulated by controlling surface chemical equilibria, interlamellar swelling, or reactant pair proximity in the interlayer regions. Also, the intercalation of polynuclear hydroxy metal cations and metal cluster cations in smectites affords new pillared clay catalysts with pore sizes that can be made larger than those of conventional zeolite catalysts.

  20. Production of hydroxyl radicals from Fe-containing fine particles in Guangzhou, China

    NASA Astrophysics Data System (ADS)

    Ma, Shexia; Ren, Ke; Liu, Xiaowen; Chen, Laiguo; Li, Mei; Li, Xiaoying; Yang, Jian; Huang, Bo; Zheng, Mei; Xu, Zhencheng

    2015-12-01

    Reactive oxygen species (ROS) production from ambient fine particles has been correlated with the soluble transition metal content of PM2.5, which also has clear association with particle-mediated cardiopulmonary toxicity. Hydroxyl radical (rad OH) is the most harmful ROS species through chemical reactions of redox-active particle components. Atmospheric Fe, as the dominant species of the transition metals in the atmosphere, is associated with rad OH generation in ambient particle extracts. Our results revealed that Fe-containing particles (18,730 in total number) contributed approximately 3.7% on average to all detected particles throughout the summer and winter sampling period in Guangzhou, which was clustered into four distinct particle classes, including Fe-rich, Metal-rich, NaK-rich and Dust-rich. Fe-rich class was the dominant one with a fraction of 61%, followed by Dust-rich (14%), Metal-rich (13%). and NaK-rich (12%). The iron oxide was enriched in the Fe-rich class. rad OH generation induced by Fe-containing fine particles collected in Guangzhou (GZ) was quantified in a surrogate lung fluid (SLF), and it was found that Fe-containing fine particles were generally much reactive in generating rad OH in the presence of four antioxidants (200 μM ascorbate, 300 μM citrate, 100 μM reduced L-glutathione, and 100 μM uric acid). The annual average rad OH amount produced in our samples was 132.98 ± 27.43 nmol rad OH mg-1 PM2.5. rad OH production had a clear seasonal pattern with higher amount in summer and lower in winter. By measuring the amount of total and SLF-soluble metal in our PM2.5 samples using ICP-MS, we found that ROS activities were associated with the ionizable Fe through Fenton type reactions in the Guangzhou PM2.5. Expected burdens of PM2.5 derived rad OH in human lung lining fluid suggests that typical daily particulate matter exposure in Guangzhou is already a concern, and it could produce much higher levels of rad OH, leading to higher

  1. 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

  2. The Influence of Zeolites on Radical Formation During Lignin Pyrolysis.

    PubMed

    Bährle, Christian; Custodis, Victoria; Jeschke, Gunnar; van Bokhoven, Jeroen A; Vogel, Frédéric

    2016-09-01

    Lignin from lignocellulosic biomass is a promising source of energy, fuels, and chemicals. The conversion of the polymeric lignin to fuels and chemicals can be achieved by catalytic and noncatalytic pyrolysis. The influence of nonporous silica and zeolite catalysts, such as silicalite, HZSM5, and HUSY, on the radical and volatile product formation during lignin pyrolysis was studied by in situ high-temperature electron paramagnetic resonance spectroscopy (HTEPR) as well as GC-MS. Higher radical concentrations were observed in the samples containing zeolite compared to the sample containing only lignin, which suggests that there is a stabilizing effect by the inorganic surfaces on the formed radical fragments. This effect was observed for nonporous silica as well as for HUSY, HZSM5, and silicalite zeolite catalysts. However, the effect is far larger for the zeolites owing to their higher specific surface area. The zeolites also showed an effect on the volatile product yield and the product distribution within the volatile phase. Although silicalite showed no effect on the product selectivity, the acidic zeolites such as HZSM5 or HUSY increased the formation of deoxygenated products such as benzene, toluene, xylene (BTX), and naphthalene.

  3. The Influence of Zeolites on Radical Formation During Lignin Pyrolysis.

    PubMed

    Bährle, Christian; Custodis, Victoria; Jeschke, Gunnar; van Bokhoven, Jeroen A; Vogel, Frédéric

    2016-09-01

    Lignin from lignocellulosic biomass is a promising source of energy, fuels, and chemicals. The conversion of the polymeric lignin to fuels and chemicals can be achieved by catalytic and noncatalytic pyrolysis. The influence of nonporous silica and zeolite catalysts, such as silicalite, HZSM5, and HUSY, on the radical and volatile product formation during lignin pyrolysis was studied by in situ high-temperature electron paramagnetic resonance spectroscopy (HTEPR) as well as GC-MS. Higher radical concentrations were observed in the samples containing zeolite compared to the sample containing only lignin, which suggests that there is a stabilizing effect by the inorganic surfaces on the formed radical fragments. This effect was observed for nonporous silica as well as for HUSY, HZSM5, and silicalite zeolite catalysts. However, the effect is far larger for the zeolites owing to their higher specific surface area. The zeolites also showed an effect on the volatile product yield and the product distribution within the volatile phase. Although silicalite showed no effect on the product selectivity, the acidic zeolites such as HZSM5 or HUSY increased the formation of deoxygenated products such as benzene, toluene, xylene (BTX), and naphthalene. PMID:27486717

  4. Fluidized catalyst process for production and hydration of olefins

    SciTech Connect

    Harandi, M.N.

    1993-08-03

    A continuous multi-stage process is described for increasing octane quality and yield of liquid hydrocarbons from an integrated fluidized catalytic cracking unit and hydration reaction zone comprising: contacting heavy hydrocarbon feedstock in a primary fluidized bed reaction stage with cracking catalyst comprising particulate solid large pore acid aluminosilicate zeolite catalyst at conversion conditions to produce a hydrocarbon effluent comprising gas containing C2-C6 olefins, intermediate hydrocarbons in the gasoline and distillate range, and cracked bottoms; regenerating primary stage zeolite cracking catalyst in a primary stage regeneration zone and returning at least a portion of regenerated zeolite cracking catalyst to the primary reaction stage; reacting an olefinic stream containing at least one iso-olefin with water in a secondary fluidized bed hydration reactor stage in contact with a closed fluidized bed of acid zeolite catalyst particles comprising solid acid zeolite under hydration reaction conditions to effectively convert said isoolefin to alkyl alkanol; adding fresh acid zeolite particles to the secondary stage reactor in an amount sufficient to maintain average equilibrium catalyst particle activity for effective alkanol synthesis reaction without regeneration of the secondary catalyst bed; withdrawing a portion of equilibrium catalyst from the secondary fluidized bed reactor stage; and passing said withdrawn catalyst portion to the primary fluidized bed reaction stage for contact with the petroleum feedstock.

  5. Effect of hierarchical porosity and phosphorus modification on the catalytic properties of zeolite Y

    NASA Astrophysics Data System (ADS)

    Li, Wenlin; Zheng, Jinyu; Luo, Yibin; Da, Zhijian

    2016-09-01

    The zeolite Y is considered as a leading catalyst for FCC industry. The acidity and porosity modification play important roles in determining the final catalytic properties of zeolite Y. The alkaline treatment of zeolite Y by dealumination and alkaline treatment with NaOH and NaOH&TBPH was investigated. The zeolites were characterized by X-ray diffraction, low-temperature adsorption of nitrogen, transmission electron microscope, NMR, NH3-TPD and IR study of acidity. Accordingly, the hierarchical porosity and acidity property were discussed systematically. Finally, the catalytic performance of the zeolites Y was evaluated in the cracking of 1,3,5-TIPB. It was found that desilication with NaOH&TBPH ensured the more uniform intracrystalline mesoporosity with higher microporosity, while preserving higher B/L ratio and moderate Brønsted acidities resulting in catalysts with the most appropriated acidity and then with better catalytic performance.

  6. The stability of copper oxo species in zeolite frameworks

    DOE PAGESBeta

    Vilella, Laia; Studt, Felix

    2016-03-07

    Cu-exchanged zeolites are promising heterogeneous catalysts, as they provide a confined environment to carry out highly selective reactions. Furthermore, the knowledge of how the zeolite framework and the location of Al atoms therein affect the adsorption of copper species is still not well understood. In this work, DFT was used to investigate the adsorption of potential Cu oxo active species suggested in the literature [Cu(η2-O2), Cu(µ-O)Cu, and Cu2O2] into zeolites with different pore sizes and shapes (AFI, CHA, TON, MOR, and MFI). The calculations revealed that both monomeric and dimeric Cu oxo species bind strongly to the O atoms ofmore » the lattice. For the monometallic species similar adsorption energies are obtained with the different zeolite frameworks, whereas an optimum Al–Al distance is required for the dimeric species.« less

  7. Hierarchical zeolites overcome all obstacles: next stop industrial implementation.

    PubMed

    Verboekend, Danny; Mitchell, Sharon; Pérez-Ramírez, Javier

    2013-01-01

    This review emphasizes key recent accomplishments towards the industrial exploitation of hierarchically structured zeolites in catalytic processes. A major milestone comprises the demonstration that affordable post-synthetic modifications enable the transformation of any conventional zeolite into hierarchical analogues with tunable porosity and functionality. Through specific examples, belonging to the transformation of fossil fuel and renewable feedstocks, we quantitatively illustrate the spectacular benefits attained upon application of hierarchical zeolite catalysts due to improved accessibility or modification of the type and distribution of active sites. A crucial step for these exciting lab-designed materials to be implemented in industrial processes is to shape them into technical forms. Accordingly, we studied the synthesis, characterization, and catalytic evaluation of millimeter-sized hierarchical zeolite bodies, enriching the fundamental understanding on scale-up and representing an additional solid step towards the commercial application of these materials.

  8. Fluid catalytic cracking catalyst for reformulated gasolines: Kinetic modeling

    SciTech Connect

    Gianetto, A. ); Farag, H.I. . Dept. of Chemical Engineering); Blasetti, A.P. . Dept. de Procesos); Lasa, H.I. de . Faculty of Engineering Science)

    1994-12-01

    Changes of the relative importance of intradiffusion on USY zeolite crystals were studied as a way of affecting selectivity of catalytic cracking reactions. Zeolite crystals were synthesized (Si/Al = 2.4), activated and stabilized using ion exchange and steam calcination to obtain USSY (Ultra Stable Submicron Y) zeolites. After the activation the zeolites were pelletized (45--60 [mu]m particles). USSYs were tested in a novel Riser Simulator. Results obtained show that total aromatics (BTX), benzene, C[sub 4] olefins, and coke were significantly affected with the change of zeolite crystal sizes. Gasolines produced with USSY zeolites contain less aromatics and particularly lower benzene levels. Experimental results were analyzed with a model including several lumps: unconverted gas oil, gasoline, light gases, and coke. This model also accounts for catalyst deactivation as a function of coke on catalyst. Various kinetic parameters were determined with their corresponding spans for the 95% level of confidence.

  9. Facile synthesis of hollow zeolite microspheres through dissolution–recrystallization procedure in the presence of organosilanes

    SciTech Connect

    Tao, Haixiang; Ren, Jiawen; Liu, Xiaohui; Wang, Yanqin; Lu, Guanzhong

    2013-04-15

    Hollow zeolite microspheres have been hydrothermally synthesized in the presence of organosilanes via a dissolution–recrystallization procedure. In the presence of organosilanes, zeolite particles with a core/shell structure formed at the first stage of hydrothermal treatment, then the core was consumed and recrystallized into zeolite framework to form the hollow structure during the second hydrothermal process. The influence of organosilanes was discussed, and a related dissolution–recrystallization mechanism was proposed. In addition, the hollow zeolite microspheres exhibited an obvious advantage in catalytic reactions compared to conventional ZSM-5 catalysts, such as in the alkylation of toluene with benzyl chloride. - Graphical abstract: Hollow zeolite spheres with aggregated zeolite nanocrystals were synthesized via a dissolution–recrystallization procedure in the presence of organosiline. Highlights: ► Hollow zeolite spheres with aggregated zeolite nanocrystals were synthesized via a dissolution–recrystallization procedure. ► Organosilane influences both the morphology and hollow structure of zeolite spheres. ► Hollow zeolite spheres showed an excellent catalytic performance in alkylation of toluene with benzyl chloride.

  10. Metallocene supported core@LDH catalysts for slurry phase ethylene polymerisation.

    PubMed

    Buffet, Jean-Charles; Byles, Coral F H; Felton, Ryan; Chen, Chunping; O'Hare, Dermot

    2016-03-14

    We report the synthesis of solid catalysts based on a zirconocene supported on either silica@AMO-LDH or zeolite@AMO-LDH for the slurry phase polymerisation of ethylene. The hybrid catalysts demonstrate synergistic effects in which the polymerisation activity is up to three times higher than the zirconocene supported on analogous single phase silica or zeolite supports.

  11. An Overview of Recent Development in Composite Catalysts from Porous Materials for Various Reactions and Processes

    PubMed Central

    Xie, Zaiku; Liu, Zhicheng; Wang, Yangdong; Yang, Qihua; Xu, Longya; Ding, Weiping

    2010-01-01

    Catalysts are important to the chemical industry and environmental remediation due to their effective conversion of one chemical into another. Among them, composite catalysts have attracted continuous attention during the past decades. Nowadays, composite catalysts are being used more and more to meet the practical catalytic performance requirements in the chemical industry of high activity, high selectivity and good stability. In this paper, we reviewed our recent work on development of composite catalysts, mainly focusing on the composite catalysts obtained from porous materials such as zeolites, mesoporous materials, carbon nanotubes (CNT), etc. Six types of porous composite catalysts are discussed, including amorphous oxide modified zeolite composite catalysts, zeolite composites prepared by co-crystallization or overgrowth, hierarchical porous catalysts, host-guest porous composites, inorganic and organic mesoporous composite catalysts, and polymer/CNT composite catalysts. PMID:20559508

  12. An overview of recent development in composite catalysts from porous materials for various reactions and processes.

    PubMed

    Xie, Zaiku; Liu, Zhicheng; Wang, Yangdong; Yang, Qihua; Xu, Longya; Ding, Weiping

    2010-01-01

    Catalysts are important to the chemical industry and environmental remediation due to their effective conversion of one chemical into another. Among them, composite catalysts have attracted continuous attention during the past decades. Nowadays, composite catalysts are being used more and more to meet the practical catalytic performance requirements in the chemical industry of high activity, high selectivity and good stability. In this paper, we reviewed our recent work on development of composite catalysts, mainly focusing on the composite catalysts obtained from porous materials such as zeolites, mesoporous materials, carbon nanotubes (CNT), etc. Six types of porous composite catalysts are discussed, including amorphous oxide modified zeolite composite catalysts, zeolite composites prepared by co-crystallization or overgrowth, hierarchical porous catalysts, host-guest porous composites, inorganic and organic mesoporous composite catalysts, and polymer/CNT composite catalysts. PMID:20559508

  13. Cluster formula of Fe-containing Monel alloys with high corrosion-resistance

    SciTech Connect

    Li Baozeng; Gu Junjie; Wang Qing; Ji Chunjun; Wang Yingmin; Qiang Jianbing; Dong Chuang

    2012-06-15

    The cluster-plus-glue-atom model is applied in the composition interpretation of Monel alloys. This model considers ideal atomic nearest neighbor configurations among the constituent elements and has been used in understanding compositions of complex alloys like quasicrystals, amorphous alloys, and cupronickels. According to this model, any structure can be expressed by cluster formula [cluster](glue atom){sub x}, x denoting the number of glue atoms matching one cluster. According to this model, two groups of experimental composition series [Fe{sub 1}Ni{sub 12}]Cu{sub x} and [Fe{sub y}Ni{sub 12}]Cu{sub 5} were designed which fell close to conventional Fe-containing Monel alloys. The designed alloys after solution treatment plus water quenching, are monolithic FCC Ni-based solid solutions. Among them, the [Fe{sub 1}Ni{sub 12}]Cu{sub 5} alloy has the highest corrosion resistance in simulated sea water, and its performance is superior to that of industrial Monel 400 alloy. - Highlights: Black-Right-Pointing-Pointer A stable solid solution model is proposed using our 'cluster-plus-glue-atom model'. Black-Right-Pointing-Pointer This model is used to develop Monel corrosion resistant alloys. Black-Right-Pointing-Pointer Single FCC structure is easily retained. Black-Right-Pointing-Pointer The alloys show good corrosion properties. Black-Right-Pointing-Pointer This work contributes to the general understanding of engineering alloys.

  14. Enhanced catalyst for conversion of syngas to liquid motor fuels

    DOEpatents

    Coughlin, P.K.; Rabo, J.A.

    1985-12-03

    Synthesis gas comprising carbon monoxide and hydrogen is converted to C[sub 5][sup +] hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising a SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

  15. Enhanced catalyst for conversion of syngas to liquid motor fuels

    DOEpatents

    Coughlin, Peter K.; Rabo, Jule A.

    1985-01-01

    Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

  16. Dual template synthesis of a highly mesoporous SSZ-13 zeolite with improved stability in the methanol-to-olefins reaction.

    PubMed

    Wu, Leilei; Degirmenci, Volkan; Magusin, Pieter C M M; Szyja, Bartłomiej M; Hensen, Emiel J M

    2012-10-01

    The dual template synthesis of zeolite SSZ-13 by use of trimethyl-adamantanammonium hydroxide and a diquaternary-ammonium mesoporogen induces considerable mesoporosity without impeding zeolite microporosity. The strongly improved accessibility of Brønsted sites in mesoporous SSZ-13 increases its stability during application as an acid catalyst in the methanol-to-olefins reaction. PMID:22896837

  17. Hydrogenation properties of ruthenium sulfide clusters in acidic zeolites

    SciTech Connect

    Breysse, M.; Cattenot, M.; Kougionas, V.

    1997-06-01

    Catalysts of ruthenium sulfide, dispersed in a series of Y zeolites with various acidic properties, were prepared by ion exchange and subsequent sulfidation. The activities for the reactions of hydrogenation of tetralin and toluene, carried out in the presence of H{sub 2}S (1.9%), vary widely according to the nature of the zeolites. Ruthenium sulfide catalysts are much more active when using acidic zeolite, HY and HYd (dealuminated), and a partially potassium-exchanged KHYd sample, than when using the KY support. The acidic properties of the sulfided RuY catalysts were determined in situ using infrared spectroscopy and the conversion of isooctane. Both methods gave similar rankings of catalyst acidity. The electronic properties of the ruthenium sulfide phase were examined by means of the infrared study of the adsorption of CO. A low-frequency shift of 15 cm{sup -1} was observed for CO adsorbed on RuKY by reference to CO adsorbed on all other samples. The increase in activity for the hydrogenation of aromatics is related to the electron- deficient character of the sulfide particles in the acidic zeolites; as has been proposed, in the literature, for metal catalysts. A superimposed influence of the acidic sites on the adsorption of the aromatic molecule may also occur which could explain the amplitude of the effect (difference of activity between the most and less active catalysts {approximately}200 times) and the variations of activity observed within the series of the acidic catalysts. 33 refs., 10 figs., 7 tabs.

  18. Catalytic pyrolysis of wheat bran for hydrocarbons production in the presence of zeolites and noble-metals by using TGA-FTIR method.

    PubMed

    Lazdovica, K; Liepina, L; Kampars, V

    2016-05-01

    Pyrolysis of wheat bran with or without catalysts was investigated using TGA-FTIR method in order to determine the influence of zeolite and noble metal catalysts on the evolution profile and relative yield of the volatile compounds. The addition of all catalysts decreased the volatile matter of wheat bran from 76.3% to 75.9%, 73.9%, 73.5%, 69.7% and increased the solid residue from 18.0% to 18.4%, 20.4%, 20.8%, 24.6% under the catalyst of ZSM-5, 5% Pd/C, MCM-41, and 5% Pt/C. Noble-metal catalysts had higher activity for deoxygenation of compounds containing carbonyl, carboxyl, and hydroxyl groups than zeolites. Degradation of nitrogen containing compounds atom proceeded better in presence of zeolites. Noble-metal catalysts promoted formation of aromatics and changed the profiles of evolved compounds whereas zeolites advanced formation of aliphatics and olefins.

  19. Pyrolysis of scrap tyres with zeolite USY.

    PubMed

    Shen, Boxiong; Wu, Chunfei; Wang, Rui; Guo, Binbin; Liang, Cai

    2006-09-21

    A zeolite catalyst of ultrastable Y-type (USY) was investigated in the research of two staged pyrolysis-catalysis of scrap tyres. Scrap tyres were pyrolysed in a fixed bed reactor and the evolved pyrolysis gases were passed through a secondary catalytic reactor. The main objective of this paper was to investigate the effect of zeolite USY on the yield of products and the composition of derived oil. The influences of several parameters such as pyrolysis temperature, catalytic temperature, catalyst/tyre ratio, heating rate, etc. on the yield of the derived oil, char and gas were investigated. It showed that the increase of catalytic temperature and catalyst/tyre ratio resulted in high yield of gas at the expense of the oil yield. For example, when the catalyst/tyre ratio increased from 0.25 to 1.0, the yield of gas increased from 30.5 to 49.9 wt.%, and the oil yield decreased nearly two-fold from 31.6 to 12.7 wt.%. The concentration of light naphtha (boiling point < 160 degrees C) was also investigated in this study. And the high catalyst/tyre ratio favored to increase the concentration of light naphtha (< 160 degrees C) in oil. In order to study the composition of derived oil, a distilled fraction (< 280 degrees C), which was 92.5 wt.% of the oil obtained from catalytic pyrolysis of scrap tyre at a pyrolysis temperature, catalytic temperature and catalyst/tyre ratio of 500, 400 degrees C and 0.5, respectively, was analyzed with gas chromatography/mass spectrometry (GC/MS). The distillate was found to contain 1.23 wt.% benzene, 9.35 wt.% toluene, 3.68 wt.% ethylbenzene, 12.64 wt.% xylenes, 1.81 wt.% limonene and 13.89 wt.% PAHs, etc., where the single ring aromatics represented a significant potential use as chemicals.

  20. 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

  1. Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template

    NASA Astrophysics Data System (ADS)

    Kim, Kyoungsoo; Lee, Taekyoung; Kwon, Yonghyun; Seo, Yongbeom; Song, Jongchan; Park, Jung Ki; Lee, Hyunsoo; Park, Jeong Young; Ihee, Hyotcherl; Cho, Sung June; Ryoo, Ryong

    2016-07-01

    Three-dimensional graphene architectures with periodic nanopores—reminiscent of zeolite frameworks—are of topical interest because of the possibility of combining the characteristics of graphene with a three-dimensional porous structure. Lately, the synthesis of such carbons has been approached by using zeolites as templates and small hydrocarbon molecules that can enter the narrow pore apertures. However, pyrolytic carbonization of the hydrocarbons (a necessary step in generating pure carbon) requires high temperatures and results in non-selective carbon deposition outside the pores. Here, we demonstrate that lanthanum ions embedded in zeolite pores can lower the temperature required for the carbonization of ethylene or acetylene. In this way, a graphene-like carbon structure can be selectively formed inside the zeolite template, without carbon being deposited at the external surfaces. X-ray diffraction data from zeolite single crystals after carbonization indicate that electron densities corresponding to carbon atoms are generated along the walls of the zeolite pores. After the zeolite template is removed, the carbon framework exhibits an electrical conductivity that is two orders of magnitude higher than that of amorphous mesoporous carbon. Lanthanum catalysis allows a carbon framework to form in zeolite pores with diameters of less than 1 nanometre; as such, microporous carbon nanostructures can be reproduced with various topologies corresponding to different zeolite pore sizes and shapes. We demonstrate carbon synthesis for large-pore zeolites (FAU, EMT and beta), a one-dimensional medium-pore zeolite (LTL), and even small-pore zeolites (MFI and LTA). The catalytic effect is a common feature of lanthanum, yttrium and calcium, which are all carbide-forming metal elements. We also show that the synthesis can be readily scaled up, which will be important for practical applications such as the production of lithium-ion batteries and zeolite-like catalyst

  2. Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template.

    PubMed

    Kim, Kyoungsoo; Lee, Taekyoung; Kwon, Yonghyun; Seo, Yongbeom; Song, Jongchan; Park, Jung Ki; Lee, Hyunsoo; Park, Jeong Young; Ihee, Hyotcherl; Cho, Sung June; Ryoo, Ryong

    2016-07-01

    Three-dimensional graphene architectures with periodic nanopores—reminiscent of zeolite frameworks—are of topical interest because of the possibility of combining the characteristics of graphene with a three-dimensional porous structure. Lately, the synthesis of such carbons has been approached by using zeolites as templates and small hydrocarbon molecules that can enter the narrow pore apertures. However, pyrolytic carbonization of the hydrocarbons (a necessary step in generating pure carbon) requires high temperatures and results in non-selective carbon deposition outside the pores. Here, we demonstrate that lanthanum ions embedded in zeolite pores can lower the temperature required for the carbonization of ethylene or acetylene. In this way, a graphene-like carbon structure can be selectively formed inside the zeolite template, without carbon being deposited at the external surfaces. X-ray diffraction data from zeolite single crystals after carbonization indicate that electron densities corresponding to carbon atoms are generated along the walls of the zeolite pores. After the zeolite template is removed, the carbon framework exhibits an electrical conductivity that is two orders of magnitude higher than that of amorphous mesoporous carbon. Lanthanum catalysis allows a carbon framework to form in zeolite pores with diameters of less than 1 nanometre; as such, microporous carbon nanostructures can be reproduced with various topologies corresponding to different zeolite pore sizes and shapes. We demonstrate carbon synthesis for large-pore zeolites (FAU, EMT and beta), a one-dimensional medium-pore zeolite (LTL), and even small-pore zeolites (MFI and LTA). The catalytic effect is a common feature of lanthanum, yttrium and calcium, which are all carbide-forming metal elements. We also show that the synthesis can be readily scaled up, which will be important for practical applications such as the production of lithium-ion batteries and zeolite-like catalyst

  3. Lanthanum-catalysed synthesis of microporous 3D graphene-like carbons in a zeolite template.

    PubMed

    Kim, Kyoungsoo; Lee, Taekyoung; Kwon, Yonghyun; Seo, Yongbeom; Song, Jongchan; Park, Jung Ki; Lee, Hyunsoo; Park, Jeong Young; Ihee, Hyotcherl; Cho, Sung June; Ryoo, Ryong

    2016-07-01

    Three-dimensional graphene architectures with periodic nanopores—reminiscent of zeolite frameworks—are of topical interest because of the possibility of combining the characteristics of graphene with a three-dimensional porous structure. Lately, the synthesis of such carbons has been approached by using zeolites as templates and small hydrocarbon molecules that can enter the narrow pore apertures. However, pyrolytic carbonization of the hydrocarbons (a necessary step in generating pure carbon) requires high temperatures and results in non-selective carbon deposition outside the pores. Here, we demonstrate that lanthanum ions embedded in zeolite pores can lower the temperature required for the carbonization of ethylene or acetylene. In this way, a graphene-like carbon structure can be selectively formed inside the zeolite template, without carbon being deposited at the external surfaces. X-ray diffraction data from zeolite single crystals after carbonization indicate that electron densities corresponding to carbon atoms are generated along the walls of the zeolite pores. After the zeolite template is removed, the carbon framework exhibits an electrical conductivity that is two orders of magnitude higher than that of amorphous mesoporous carbon. Lanthanum catalysis allows a carbon framework to form in zeolite pores with diameters of less than 1 nanometre; as such, microporous carbon nanostructures can be reproduced with various topologies corresponding to different zeolite pore sizes and shapes. We demonstrate carbon synthesis for large-pore zeolites (FAU, EMT and beta), a one-dimensional medium-pore zeolite (LTL), and even small-pore zeolites (MFI and LTA). The catalytic effect is a common feature of lanthanum, yttrium and calcium, which are all carbide-forming metal elements. We also show that the synthesis can be readily scaled up, which will be important for practical applications such as the production of lithium-ion batteries and zeolite-like catalyst

  4. Zeolite Membrane Reactor for Water Gas Shift Reaction for Hydrogen Production

    SciTech Connect

    Lin, Jerry Y.S.

    2013-01-29

    Gasification of biomass or heavy feedstock to produce hydrogen fuel gas using current technology is costly and energy-intensive. The technology includes water gas shift reaction in two or more reactor stages with inter-cooling to maximize conversion for a given catalyst volume. This project is focused on developing a membrane reactor for efficient conversion of water gas shift reaction to produce a hydrogen stream as a fuel and a carbon dioxide stream suitable for sequestration. The project was focused on synthesizing stable, hydrogen perm-selective MFI zeolite membranes for high temperature hydrogen separation; fabricating tubular MFI zeolite membrane reactor and stable water gas shift catalyst for membrane reactor applications, and identifying experimental conditions for water gas shift reaction in the zeolite membrane reactor that will produce a high purity hydrogen stream. The project has improved understanding of zeolite membrane synthesis, high temperature gas diffusion and separation mechanisms for zeolite membranes, synthesis and properties of sulfur resistant catalysts, fabrication and structure optimization of membrane supports, and fundamentals of coupling reaction with separation in zeolite membrane reactor for water gas shift reaction. Through the fundamental study, the research teams have developed MFI zeolite membranes with good perm-selectivity for hydrogen over carbon dioxide, carbon monoxide and water vapor, and high stability for operation in syngas mixture containing 500 part per million hydrogen sulfide at high temperatures around 500°C. The research teams also developed a sulfur resistant catalyst for water gas shift reaction. Modeling and experimental studies on the zeolite membrane reactor for water gas shift reaction have demonstrated the effective use of the zeolite membrane reactor for production of high purity hydrogen stream.

  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. FCCU operating changes optimize octane catalyst use

    SciTech Connect

    Desai, P.H.

    1986-09-01

    The use of octane-enhancing catalysts in a fluid catalytic cracking unit (FCCU) requires changes in the operation of the unit to derive maximum benefits from the octane catalyst. In addition to the impressive octane gain achieved by the octane catalyst, the catalyst also affects the yield structure, the unit heat balance, and the product slate by reducing hydrogen transfer reactions. Catalyst manufacturers have introduced new product lines based upon ultrastable Y type (USY) zeolites which can result in 2 to 3 research octane number (RON) gains over the more traditional rare earth exchanged Y type (REY) zeolites. Here are some operating techniques for the FCCU and associated processes that will allow maximum benefits from octane catalyst use.

  7. Evaporation Mechanism of Cu from Liquid Fe Containing C and S

    NASA Astrophysics Data System (ADS)

    Jung, Sung-Hoon; Kang, Youn-Bae

    2016-08-01

    A number of liquid-gas experiments were carried out in order to elucidate evaporation mechanism of Cu from liquid Fe containing C and S. Rate of Cu evaporation in liquid Fe droplets at 1873 K (1600 °C) was determined using electromagnetic levitation equipment. Evaporation rate of the Cu under various conditions (flow rate of gas mixtures, initial C, and S concentrations) was examined. It was found from a series of kinetic analyses of the experimental data that Cu evaporates in forms of Cu(g) and CuS(g). As was reported for the Sn evaporation from liquid iron (Jung et al. Met. Mater. Trans. 46B, 250-258, 2014), S plays two roles for the evaporation of Cu: accelerating the rate by forming CuS(g) and decelerating the rate by blocking evaporation sites. As a result of these combinatorial effects, the evaporation of Cu is decelerated at low S content, but is accelerated at high S content. Based on the elucidated mechanism, an evaporation model equation for Cu was developed in the present study, which takes into account (1) evaporation of Cu in the two forms (Cu(g) and CuS(g)), (2) surface blocking by S using ideal Langmuir adsorption, and (3) effect of C. The obtained rate constant of a reaction Cu i + S i = CuS i (g), k CuS R , is 1.37 × 10-9 m4 mol-1 s-1, and the residual rate constant, k CuS r , is 4.11 × 10-10 m4 mol-1 s-1 at 1873 K (1600 °C). Both of them were found to be one order lower than those for Sn evaporation.

  8. Synthesis and characterization of nanocrystalline and mesoporous zeolites

    NASA Astrophysics Data System (ADS)

    Petushkov, Anton

    2011-12-01

    Mesoporous aggregates of nanocrystalline zeolites with MFI and BEA frameworks have been synthesized using a one-pot and single structure directing agent. The effect of different reaction conditions, such as temperature, time, pH and water content, on the particle size, surface area and mesopore volume has been studied. Nanocrystalline and mesoporous ZSM-5, beta and Y zeolites were modified with different transition metals and the resulting single- and double metal containing catalyst materials were characterized. Nanocrystalline Silicalite-1 zeolite samples with varying particle size were functionalized with different organosilane groups and the cytotoxic activity of the zeolite nanocrystals was studied as a function of particle size, concentration, organic functional group type, as well as the type of cell line. Framework stability of nanocrystalline NaY zeolite was tested under different pH conditions. The synthesized zeolites used in this work were characterized using a variety of physico-chemical methods, including powder X-ray diffraction, Solid State NMR, nitrogen sorption, electron microscopy, Inductively Coupled Plasma -- Optical Emission Spectroscopy and X-ray Photoelectron Spectroscopy.

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

    SciTech Connect

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

    2008-01-01

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

  10. Increasing the hydrogenation activity of commercial catalysts for selective hydrocracking

    SciTech Connect

    Khashagul`gova, N.S.; Freiman, L.L.; Zelentsov, Yu.N.

    1994-07-01

    The catalysts generally used in hydrodewaxing or selective hydrocracking of n-paraffins are zeolites with the pentasil structure: TsVK, TsVM, TsVN, and Ultrasil. For use in the production of high-quality transformer oils from paraffinic feedstocks, these catalysts have not only a high cracking activity but also an adequate hydrogenating activity. Catalysts containing a nickel-molybdenum complex (or nickel molybdate synthesized by a specific method) are higher in hydrogenating activity in comparison with catalysts in which the metals are introduced by coextrusion or impregnation. Precipitation of a nickel-molybdenum complex on a solid support (aluminosilicate or zeolite) tends to increase its hydrogenating activity, so that the content of the hydrogenating metals in the catalyst can be reduced. This report describes studies on catalysts based on TsVM and TsVN high-silica zeolites.

  11. Visualizing Dealumination of a Single Zeolite Domain in a Real-Life Catalytic Cracking Particle.

    PubMed

    Kalirai, Sam; Paalanen, Pasi P; Wang, Jian; Meirer, Florian; Weckhuysen, Bert M

    2016-09-01

    Fluid catalytic cracking (FCC) catalysts play a central role in the chemical conversion of crude oil fractions. Using scanning transmission X-ray microscopy (STXM) we investigate the chemistry of one fresh and two industrially deactivated (ECAT) FCC catalysts at the single zeolite domain level. Spectro-microscopic data at the Fe L3 , La M5 , and Al K X-ray absorption edges reveal differing levels of deposited Fe on the ECAT catalysts corresponding with an overall loss in tetrahedral Al within the zeolite domains. Using La as a localization marker, we have developed a novel methodology to map the changing Al distribution of single zeolite domains within real-life FCC catalysts. It was found that significant changes in the zeolite domain size distributions as well as the loss of Al from the zeolite framework occur. Furthermore, inter- and intraparticle heterogeneities in the dealumination process were observed, revealing the complex interplay between metal-mediated pore accessibility loss and zeolite dealumination.

  12. Recent advances of pore system construction in zeolite-catalyzed chemical industry processes.

    PubMed

    Shi, Jing; Wang, Yangdong; Yang, Weimin; Tang, Yi; Xie, Zaiku

    2015-12-21

    The kaleidoscopic applications of zeolite catalysts (zeo-catalysts) in petrochemical processes has been considered as one of the major accomplishments in recent decades. About twenty types of zeolite have been industrially applied so far, and their versatile porous architectures have contributed their most essential features to affect the catalytic efficiency. This review depicts the evolution of pore models in zeolite catalysts accompanied by the increase in industrial and environmental demands. The indispensable roles of modulating pore models are outlined for zeo-catalysts for the enhancement of their catalytic performances in various industrial processes. The zeolites and related industrial processes discussed range from the uni-modal micropore system of zeolite Y (12-ring micropore, 12-R) in fluid catalytic cracking (FCC), zeolite ZSM-5 (10-R) in xylene isomerization and SAPO-34 (8-R) in olefin production to the multi-modal micropore system of MCM-22 (10-R and 12-R pocket) in aromatic alkylation and the hierarchical pores in FCC and catalytic cracking of C4 olefins. The rational construction of pore models, especially hierarchical features, is highlighted with a careful classification from an industrial perspective accompanied by a detailed analysis of the theoretical mechanisms.

  13. Gallium Zeolites for Light Paraffin Aromatization

    SciTech Connect

    Price, G.L.; Dooley, K.M.

    1999-02-10

    The primary original goal of this project was to investigate the active state of gallium-containing MFI catalysts for light paraffin aromatization, in particular the state of gallium in the active material. Our original hypothesis was that the most active and selective materials were those which contained gallium zeolitic cations, and that previously reported conditions for the activation of gallium-containing catalysts served to create these active centers. We believed that in high silica materials such as MFI, ion-exchange is most effectively accomplished with metals in their 1+ oxidation state, both because of the sparsity of the anionic ion-exchange sites associated with the zeolite, and because the large hydration shells associated with aqueous 3+ cations hinder transport. Metals such as Ga which commonly exist in higher oxidation states need to be reduced to promote ion-exchange and this is the reason that reduction of gallium-containing catalysts for light paraffin aromatization often yields a dramatic enhancement in catalytic activity. We have effectively combined reduction with ion-exchange and we term this combined process ''reductive solid-state ion-exchange''. Our hypothesis has largely been proven true, and a number of the papers we have published directly address this hypothesis.

  14. Bifunctional Nanostructured Base Catalysts: Opportunities for BioFuels

    SciTech Connect

    Connor, William

    2010-12-30

    ABSTRACT This research studied and develop novel basic catalysts for production of renewable chemicals and fuels from biomass. We will focus on the development of unique porous structural-base catalysts formed by two techniques: from (mixed) metal-oxide bases and by nitrogen substitution for oxygen in zeolites. These catalysts will be compared to conventional solid base materials for aldol condensation, catalytic fast pyrolysis, and transesterification reactions. These reactions are important in processes that are currently being commercialized for production of fuels from biomass and will be pivotal in future biomass conversion to fuels and chemicals. Specifically, we have studied the aldol-condensation of acetone with furfural over oxides and zeolites, the conversion of sugars by rapid pyrolysis over zeolites and the trans-esterification of vegetable oil with methanol over mixed oxide catalysts. Our previous research has indicated that the base strength of framework nitrogen in nitrogen-substituted zeolites (NH-zeolites) is nearly twice as strong as in standard zeolites. Nitrogen substituted catalysts have been synthesized from several zeolites (including FAU, MFI, BEA, and LTL) using NH3 treatment.

  15. Mobil/Badger to market zeolite-based cumene technology

    SciTech Connect

    Rotman, D.

    1993-02-24

    Badger (Cambridge, MA) and Mobil (Fairfax, VA) are ready to jointly license a new cumene technology that they say achieves higher yields and product purity than existing processes. The zeolite-based technology is scheduled to be introduced at next month's DeWitt Petrochemical Review in Houston. The Mobil/Badger technology aims to challenge the dominant position of UOP's (Des Plaines, IL) solid phosphoric acid (SPA) catalyst process - which accounts for 80%-90% of the world's cumene production. In addition, Monsanto/Kellogg's aluminum chloride-based technology has gained significant momentum since its introduction in the 1980s. And late last year, ABB Lummus Crest (Bloomfield, NJ) also began marketing a zeolite-based cumene technology. While all the technologies make cumene via the alkylation of benzene with propylene, the Mobil/Badger process uses a zeolite-containing catalyst designed by Mobil to selectively catalyze the benzene/propylene reaction, avoiding unwanted propylene oligomerization. Because the olefin reactions are so fast, says Frank A. Demers, Badger's v.p./technology development and marketing, other zeolite technologies are forced to use complex reactor arrangements to stop the propylene-propylene reactions. However, he says, Mobil has designed a catalyst that wants to react benzene with propylene to make cumene.'

  16. Improvement of microbead cracking catalyst manufacture

    SciTech Connect

    Mirskii, Ya.B.; Kosolapova, A.P.; Meged, N.F.

    1986-11-01

    In order to improve the manufacturing process for KMTsR microbead catalyst for use in new cracking units, the authors consider the method of increasing the content of aluminum oxide in its amorphous part. A microbead catalyst of zeolite, containing rare-earth elements of the KMTsR type was obtained by spray-drying a slurry prepared by mechanical dispersion of hydrogel beads, with the subsequent molding and processing operations the same as in the production of bead catalyst.

  17. Hydraulic conductivity of compacted zeolites.

    PubMed

    Oren, A Hakan; Ozdamar, Tuğçe

    2013-06-01

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

  18. Bifunctional conversion of cyclooctane. A suitable reaction to test shape-selective effects in high-silica zeolites

    SciTech Connect

    Jacobs, P.A.; Mielen, M.; Hernandez, R.S.

    1983-01-01

    A study was made of the conversion of cyclooctane on various zeolite catalysts that were platinum loaded. Three zeolites of identical chemical analysis but differing structures were used: FAU, MFI, and MEL. It was determined that acid sites of intermediate strength were necessary, and that the relative activities of the zeolites were MEL > MFI > FAU. It was concluded that the transformation of cyclooctane will depend mainly upon the dimensions and structure of the zeolite pores. Five illustrations of reaction kinetics data were also included.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Discovery of optimal zeolites for challenging separations and chemical transformations using predictive materials modeling

    NASA Astrophysics Data System (ADS)

    Bai, Peng; Jeon, Mi Young; Ren, Limin; Knight, Chris; Deem, Michael W.; Tsapatsis, Michael; Siepmann, J. Ilja

    2015-01-01

    Zeolites play numerous important roles in modern petroleum refineries and have the potential to advance the production of fuels and chemical feedstocks from renewable resources. The performance of a zeolite as separation medium and catalyst depends on its framework structure. To date, 213 framework types have been synthesized and >330,000 thermodynamically accessible zeolite structures have been predicted. Hence, identification of optimal zeolites for a given application from the large pool of candidate structures is attractive for accelerating the pace of materials discovery. Here we identify, through a large-scale, multi-step computational screening process, promising zeolite structures for two energy-related applications: the purification of ethanol from fermentation broths and the hydroisomerization of alkanes with 18-30 carbon atoms encountered in petroleum refining. These results demonstrate that predictive modelling and data-driven science can now be applied to solve some of the most challenging separation problems involving highly non-ideal mixtures and highly articulated compounds.

  5. Discovery of optimal zeolites for challenging separations and chemical transformations using predictive materials modeling.

    PubMed

    Bai, Peng; Jeon, Mi Young; Ren, Limin; Knight, Chris; Deem, Michael W; Tsapatsis, Michael; Siepmann, J Ilja

    2015-01-21

    Zeolites play numerous important roles in modern petroleum refineries and have the potential to advance the production of fuels and chemical feedstocks from renewable resources. The performance of a zeolite as separation medium and catalyst depends on its framework structure. To date, 213 framework types have been synthesized and >330,000 thermodynamically accessible zeolite structures have been predicted. Hence, identification of optimal zeolites for a given application from the large pool of candidate structures is attractive for accelerating the pace of materials discovery. Here we identify, through a large-scale, multi-step computational screening process, promising zeolite structures for two energy-related applications: the purification of ethanol from fermentation broths and the hydroisomerization of alkanes with 18-30 carbon atoms encountered in petroleum refining. These results demonstrate that predictive modelling and data-driven science can now be applied to solve some of the most challenging separation problems involving highly non-ideal mixtures and highly articulated compounds.

  6. Catalyst regeneration with flue gas

    SciTech Connect

    Harandi, M.N.; Owen, H.

    1989-09-19

    This patent describes an integrated once through reactor system for regenerating acidic medium pore zeolite olefin or oxygenate feedstock conversion catalyst with flue gas. It comprises in combination: fluid catalytic cracking catalyst regenerator means for providing the flue gas containing oxygen; at least two fixed bed reactor means for containing the zeolite catalyst, the reactor means receivably connected to the regenerator means for alternately receiving the flue gas therefrom; feedstock conduit means connected to the reactor means for alternately transferring the feedstock thereto; conversion product conduit means receivably connected to the reactor means for alternately transferring the product therefrom; flue gas conduit means receivably connected to the reactor means for alternately transferring flue gas therefrom.

  7. Acid-Base Pairs in Lewis Acidic Zeolites Promote Direct Aldol Reactions by Soft Enolization.

    PubMed

    Lewis, Jennifer D; Van de Vyver, Stijn; Román-Leshkov, Yuriy

    2015-08-17

    Hf-, Sn-, and Zr-Beta zeolites catalyze the cross-aldol condensation of aromatic aldehydes with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled molecules confirm that acid-base pairs in the Si-O-M framework ensemble promote soft enolization through α-proton abstraction. The Lewis acidic zeolites maintain activity in the presence of water and, unlike traditional base catalysts, in acidic solutions.

  8. Synthetic Zeolites and Other Microporous Oxide Molecular Sieves

    NASA Astrophysics Data System (ADS)

    Sherman, John D.

    1999-03-01

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

  9. Synthetic zeolites and other microporous oxide molecular sieves.

    PubMed

    Sherman, J D

    1999-03-30

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

  10. Mechanistic proposal for the zeolite catalyzed methylation of aromatic compounds.

    PubMed

    Svelle, Stian; Bjørgen, Morten

    2010-12-01

    Alkylation and methylation reactions are important reactions in petrochemical production and form part of the reaction mechanism of many hydrocarbon transformation processes. Here, a new reaction mechanism is explored for the zeolite catalyzed methylation of arenes using quantum chemical calculations. It is proposed that the most substituted methylbenzenes, which will reside predominantly on the protonated form when adsorbed in a zeolite, can react directly with a neutral methanol molecule in the vicinity, thereby initiating the methylation reaction without having to return a proton to the zeolite surface. The calculated barriers are quite low, indicating that the suggested mechanism is plausible. This route might explain how the most substituted methylbenzenes can function as efficient reaction intermediates in the methanol to hydrocarbons reaction without themselves acting as catalyst poisons as a consequence of their high proton affinities. PMID:21049891

  11. Process for magnetic beneficiating petroleum cracking catalyst

    DOEpatents

    Doctor, R.D.

    1993-10-05

    A process is described for beneficiating a particulate zeolite petroleum cracking catalyst having metal values in excess of 1000 ppm nickel equivalents. The particulate catalyst is passed through a magnetic field in the range of from about 2 Tesla to about 5 Tesla generated by a superconducting quadrupole open-gradient magnetic system for a time sufficient to effect separation of said catalyst into a plurality of zones having different nickel equivalent concentrations. A first zone has nickel equivalents of about 6,000 ppm and greater, a second zone has nickel equivalents in the range of from about 2000 ppm to about 6000 ppm, and a third zone has nickel equivalents of about 2000 ppm and less. The zones of catalyst are separated and the second zone material is recycled to a fluidized bed of zeolite petroleum cracking catalyst. The low nickel equivalent zone is treated while the high nickel equivalent zone is discarded. 1 figures.

  12. Process for magnetic beneficiating petroleum cracking catalyst

    DOEpatents

    Doctor, Richard D.

    1993-01-01

    A process for beneficiating a particulate zeolite petroleum cracking catalyst having metal values in excess of 1000 ppm nickel equivalents. The particulate catalyst is passed through a magnetic field in the range of from about 2 Tesla to about 5 Tesla generated by a superconducting quadrupole open-gradient magnetic system for a time sufficient to effect separation of said catalyst into a plurality of zones having different nickel equivalent concentrations. A first zone has nickel equivalents of about 6,000 ppm and greater, a second zone has nickel equivalents in the range of from about 2000 ppm to about 6000 ppm, and a third zone has nickel equivalents of about 2000 ppm and less. The zones of catalyst are separated and the second zone material is recycled to a fluidized bed of zeolite petroleum cracking catalyst. The low nickel equivalent zone is treated while the high nickel equivalent zone is discarded.

  13. Conversion of biomass to ethanol: Isomerization of xylose over HY zeolite

    SciTech Connect

    Lee, C.Y.; Wen, J.; Thomas, S.

    1995-12-31

    Xylose, a pentose indigestible to most yeasts, was converted to ethanol by a two-step isomerization and fermentation. HY zeolite was used to catalyze the isomerization of xylose, and the xylulose produced was directly used as the carbon source in ethanol fermentation. Zeolite catalysts offer pH compatibility with yeast fermentation and the ability to carry out isomerization at higher temperature where equilibrium xylulose concentration is higher. Initial rate studies indicate that xylose consumption follows pseudo-first-order kinetics, with a specific rate constant of 6.2 x 10{sup -4} L/solution/g zeolite/h.

  14. Orthophosphoric acid interactions with ultrastable zeolite Y: Infrared and NMR studies

    SciTech Connect

    Corma, A.; Fornes, V.; Kolodziejski, W.; Martinez-Triguero, L.J. )

    1994-01-01

    Zeolite Y is the active component of most commercial cracking catalysts. Interaction of H[sub 3]PO[sub 4] with extraframework aluminum of ultra-stable zeolite (USY) leads to the formation of different types of aluminum phosphates, while there is no indication of the formation of SAPO zeotype structures. The total acidity of USY slightly decreases upon the H[sub 3]PO[sub 4] treatment, while the maximum in the distribution of acid strength is shifted to milder acidities. Dealumination of the zeolite and creation of POH sites associated with AIPO[sub 4] are responsible for the modifications observed. 37 refs., 8 figs., 3 tabs.

  15. Potential of sustainable hierarchical zeolites in the valorization of α-pinene.

    PubMed

    Nuttens, Nicolas; Verboekend, Danny; Deneyer, Aron; Van Aelst, Joost; Sels, Bert F

    2015-04-13

    In the valorization of α-pinene, which is an important biomass intermediate derived from turpentine oil, hierarchical (mesoporous) zeolites represent a superior class of catalysts. Hierarchical USY, ZSM-5, and beta zeolites have been prepared, characterized, and catalytically evaluated, with the aim of combining the highest catalytic performance with the most sustainable synthetic protocol. These zeolites are prepared by alkaline treatment in aqueous solutions of NH4 OH, NaOH, diethylamine, and NaOH complemented with tetrapropylammonium bromide. The hierarchical USY zeolite is the most attractive catalyst of the tested series, and is able to combine an overall organic-free synthesis with an up to sixfold activity enhancement and comparable selectivity over the conventional USY zeolite. This superior performance relates to a threefold greater activity than that of the commercial standard, namely, H2 SO4 /TiO2 . Correlation of the obtained benefits to the amount of solid lost during the postsynthetic modifications highlights that the highest activity gains are obtained with minor leaching. Furthermore, a highly zeolitic character, as determined by bulk XRD, is beneficial, but not crucial, in the conversion of α-pinene. The alkaline treatments not only result in a higher overall activity, but also a more functional external surface area, attaining up to four times the pinene conversions per square nanometer. The efficiency of the hierarchical USY zeolite is concomitantly demonstrated in the conversion of limonene and turpentine oil, which emphasizes its industrial potential. PMID:25736719

  16. Potential of sustainable hierarchical zeolites in the valorization of α-pinene.

    PubMed

    Nuttens, Nicolas; Verboekend, Danny; Deneyer, Aron; Van Aelst, Joost; Sels, Bert F

    2015-04-13

    In the valorization of α-pinene, which is an important biomass intermediate derived from turpentine oil, hierarchical (mesoporous) zeolites represent a superior class of catalysts. Hierarchical USY, ZSM-5, and beta zeolites have been prepared, characterized, and catalytically evaluated, with the aim of combining the highest catalytic performance with the most sustainable synthetic protocol. These zeolites are prepared by alkaline treatment in aqueous solutions of NH4 OH, NaOH, diethylamine, and NaOH complemented with tetrapropylammonium bromide. The hierarchical USY zeolite is the most attractive catalyst of the tested series, and is able to combine an overall organic-free synthesis with an up to sixfold activity enhancement and comparable selectivity over the conventional USY zeolite. This superior performance relates to a threefold greater activity than that of the commercial standard, namely, H2 SO4 /TiO2 . Correlation of the obtained benefits to the amount of solid lost during the postsynthetic modifications highlights that the highest activity gains are obtained with minor leaching. Furthermore, a highly zeolitic character, as determined by bulk XRD, is beneficial, but not crucial, in the conversion of α-pinene. The alkaline treatments not only result in a higher overall activity, but also a more functional external surface area, attaining up to four times the pinene conversions per square nanometer. The efficiency of the hierarchical USY zeolite is concomitantly demonstrated in the conversion of limonene and turpentine oil, which emphasizes its industrial potential.

  17. Glycerol upgrading over zeolites by batch-reactor liquid-phase oligomerization: heterogeneous versus homogeneous reaction.

    PubMed

    Krisnandi, Yuni K; Eckelt, Reinhard; Schneider, Matthias; Martin, Andreas; Richter, Manfred

    2008-01-01

    Glycerol upgrading to diglycerols in the presence of basic (Na+ or Cs+) ion-exchanged (FAU or BEA) zeolite catalysts was studied in a liquid-phase batch rector at 260 degrees C under normal pressure. Homogeneous NaHCO3 and CsHCO3 catalysts were studied for comparison. All the catalysts, including NaHCO3 and CsHCO3, displayed the same conversion-selectivity relationship. The selectivity to linear diglycerols decreased at higher conversions/reaction times owing to the consecutive formation of higher oligomers, with preferential further conversion of alpha,alpha'-diglycerol. The maximum yield of linear diglycerols was limited to about 30 %. The activities of the zeolites followed the order X>Y>Beta, independent of the alkali ion present. Catalysis by the zeolites starts with an induction period attributed to a slow leaching of alkaline cations from the zeolite. Thereafter, the reaction is characterized by a progressive loss of the microporous structure of the zeolite and increasing overlap of heterogeneous and homogeneous catalysis, where, primarily, the activity depends on the cation content of the zeolite.

  18. Catalytic activities of zeolite compounds for decomposing aqueous ozone.

    PubMed

    Kusuda, Ai; Kitayama, Mikito; Ohta, Yoshio

    2013-12-01

    The advanced oxidation process (AOP), chemical oxidation using aqueous ozone in the presence of appropriate catalysts to generate highly reactive oxygen species, offers an attractive option for removing poorly biodegradable pollutants. Using the commercial zeolite powders with various Si/Al ratios and crystal structures, their catalytic activities for decomposing aqueous ozone were evaluated by continuously flowing ozone to water containing the zeolite powders. The hydrophilic zeolites (low Si/Al ratio) with alkali cations in the crystal structures were found to possess high catalytic activity for decomposing aqueous ozone. The hydrophobic zeolite compounds (high Si/Al ratio) were found to absorb ozone very well, but to have no catalytic activity for decomposing aqueous ozone. Their catalytic activities were also evaluated by using the fixed bed column method. When alkali cations were removed by acid rinsing or substituted by alkali-earth cations, the catalytic activities was significantly deteriorated. These results suggest that the metal cations on the crystal surface of the hydrophilic zeolite would play a key role for catalytic activity for decomposing aqueous ozone.

  19. Catalytic activities of zeolite compounds for decomposing aqueous ozone.

    PubMed

    Kusuda, Ai; Kitayama, Mikito; Ohta, Yoshio

    2013-12-01

    The advanced oxidation process (AOP), chemical oxidation using aqueous ozone in the presence of appropriate catalysts to generate highly reactive oxygen species, offers an attractive option for removing poorly biodegradable pollutants. Using the commercial zeolite powders with various Si/Al ratios and crystal structures, their catalytic activities for decomposing aqueous ozone were evaluated by continuously flowing ozone to water containing the zeolite powders. The hydrophilic zeolites (low Si/Al ratio) with alkali cations in the crystal structures were found to possess high catalytic activity for decomposing aqueous ozone. The hydrophobic zeolite compounds (high Si/Al ratio) were found to absorb ozone very well, but to have no catalytic activity for decomposing aqueous ozone. Their catalytic activities were also evaluated by using the fixed bed column method. When alkali cations were removed by acid rinsing or substituted by alkali-earth cations, the catalytic activities was significantly deteriorated. These results suggest that the metal cations on the crystal surface of the hydrophilic zeolite would play a key role for catalytic activity for decomposing aqueous ozone. PMID:25078817

  20. Synthesis of Zeolites Using the ADOR (Assembly-Disassembly-Organization-Reassembly) Route

    PubMed Central

    Wheatley, Paul S.; Čejka, Jiří; Morris, Russell E.

    2016-01-01

    Zeolites are an important class of materials that have wide ranging applications such as heterogeneous catalysts and adsorbents which are dependent on their framework topology. For new applications or improvements to existing ones, new zeolites with novel pore systems are desirable. We demonstrate a method for the synthesis of novel zeolites using the ADOR route. ADOR is an acronym for Assembly, Disassembly, Organization and Reassembly. This synthetic route takes advantage of the assembly of a relatively poorly stable that which can be selectively disassembled into a layered material. The resulting layered intermediate can then be organized in different manners by careful chemical manipulation and then reassembled into zeolites with new topologies. By carefully controlling the organization step of the synthetic pathway, new zeolites with never before seen topologies are capable of being synthesized. The structures of these new zeolites are confirmed using powder X-ray diffraction and further characterized by nitrogen adsorption and scanning electron microscopy. This new synthetic pathway for zeolites demonstrates its capability to produce novel frameworks that have never been prepared by traditional zeolite synthesis techniques. PMID:27078165

  1. Ru complexes of Hoveyda-Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions.

    PubMed

    Balcar, Hynek; Žilková, Naděžda; Kubů, Martin; Mazur, Michal; Bastl, Zdeněk; Čejka, Jiří

    2015-01-01

    Hoveyda-Grubbs type catalysts with cationic tags on NHC ligands were linker-free immobilized on the surface of lamellar zeolitic supports (MCM-22, MCM-56, MCM-36) and on mesoporous molecular sieves SBA-15. The activity of prepared hybrid catalysts was tested in olefin metathesis reactions: the activity in ring-closing metathesis of citronellene and N,N-diallyltrifluoroacetamide decreased in the order of support MCM-22 ≈ MCM-56 > SBA-15 > MCM-36; the hybrid catalyst based on SBA-15 was found the most active in self-metathesis of methyl oleate. All catalysts were reusable and exhibited low Ru leaching (<1% of Ru content). XPS analysis revealed that during immobilization ion exchange between Hoveyda-Grubbs type catalyst and zeolitic support occurred in the case of Cl(-) counter anion; in contrast, PF6 (-) counter anion underwent partial decomposition.

  2. Ru complexes of Hoveyda–Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions

    PubMed Central

    Žilková, Naděžda; Kubů, Martin; Mazur, Michal; Bastl, Zdeněk; Čejka, Jiří

    2015-01-01

    Summary Hoveyda–Grubbs type catalysts with cationic tags on NHC ligands were linker-free immobilized on the surface of lamellar zeolitic supports (MCM-22, MCM-56, MCM-36) and on mesoporous molecular sieves SBA-15. The activity of prepared hybrid catalysts was tested in olefin metathesis reactions: the activity in ring-closing metathesis of citronellene and N,N-diallyltrifluoroacetamide decreased in the order of support MCM-22 ≈ MCM-56 > SBA-15 > MCM-36; the hybrid catalyst based on SBA-15 was found the most active in self-metathesis of methyl oleate. All catalysts were reusable and exhibited low Ru leaching (<1% of Ru content). XPS analysis revealed that during immobilization ion exchange between Hoveyda–Grubbs type catalyst and zeolitic support occurred in the case of Cl− counter anion; in contrast, PF6 − counter anion underwent partial decomposition. PMID:26664629

  3. Ru complexes of Hoveyda-Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions.

    PubMed

    Balcar, Hynek; Žilková, Naděžda; Kubů, Martin; Mazur, Michal; Bastl, Zdeněk; Čejka, Jiří

    2015-01-01

    Hoveyda-Grubbs type catalysts with cationic tags on NHC ligands were linker-free immobilized on the surface of lamellar zeolitic supports (MCM-22, MCM-56, MCM-36) and on mesoporous molecular sieves SBA-15. The activity of prepared hybrid catalysts was tested in olefin metathesis reactions: the activity in ring-closing metathesis of citronellene and N,N-diallyltrifluoroacetamide decreased in the order of support MCM-22 ≈ MCM-56 > SBA-15 > MCM-36; the hybrid catalyst based on SBA-15 was found the most active in self-metathesis of methyl oleate. All catalysts were reusable and exhibited low Ru leaching (<1% of Ru content). XPS analysis revealed that during immobilization ion exchange between Hoveyda-Grubbs type catalyst and zeolitic support occurred in the case of Cl(-) counter anion; in contrast, PF6 (-) counter anion underwent partial decomposition. PMID:26664629

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

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

    Zeolites are a class of crystalline aluminosilicate materials that form the backbone of the chemical process industry worldwide. They are used primarily as adsorbents and catalysts and support to a significant extent the positive balance of trade realized by the chemical industry in the United States (around $19 billion in 1991). The magnitude of their efforts can be appreciated when one realizes that since their introduction as 'cracking catalysts' in the early 1960's, they have saved the equivalent of 60 percent of the total oil production from Alaska's North Slope. Thus the performance of zeolite catalysts can have a profound effect on the U.S. economy. It is estimated that a 1 percent increase in yield of the gasoline fraction per barrel of oil would represent a savings of 22 million barrels of crude oil per year, representing a reduction of $400 million in the United States' balance of payments. Thus any activity that results in improvement in zeolite catalyst performance is of significant scientific and industrial interest. In addition, due to their 'stability,' uniformity, and, within limits, their 'engineerable' structures, zeolites are being tested as potential adsorbents to purify gases and liquids at the parts-per-billion levels needed in today's electronic, biomedical, and biotechnology industries and for the environment. Other exotic applications, such as host materials for quantum-confined semiconductor atomic arrays, are also being investigated. Because of the importance of this class of material, extensive efforts have been made to characterize their structures and to understand their nucleation and growth mechanisms, so as to be able to custom-make zeolites for a desired application. To date, both the nucleation mechanics and chemistry (such as what are the 'key' nutrients) are, as yet, still unknown for many, if not all, systems. The problem is compounded because there is usually a 'gel' phase present that is assumed to control the degree of

  5. Fabrication and catalytic tests of MCM-22/silicon carbide structured catalysts.

    PubMed

    Gu, Lijun; Ma, Ding; Hu, Gang; Wu, Jingjing; Wang, Hongxia; Sun, Changyong; Yao, Songdong; Shen, Wenjie; Bao, Xinhe

    2010-10-28

    The structured catalyst of zeolite MCM-22/silicon carbide (SiC) was prepared for the first time through the in situ hydrothermal synthesis approach. The zeolite loading of the structured catalyst could be tuned by changing the synthesis time and applying alkali pre-treatment of SiC substrate. An additional silica layer formed on SiC substrate after the precalcination treatment facilitated the crystallization of MCM-22 zeolite on the SiC substrate. The MCM-22/SiC structured catalyst thus prepared exhibited good catalytic performance in the methane dehydroaromatization reaction.

  6. One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters.

    PubMed

    Kim, Seok-Jhin; Tan, Shuai; Taborga Claure, Micaela; Briones Gil, Laura; More, Karren L; Liu, Yujun; Moore, Jason S; Dixit, Ravindra S; Pendergast, John G; Sholl, David S; Jones, Christopher W; Nair, Sankar

    2016-09-21

    Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal clusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5-2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal clusters. To characterize the properties of the hybrid (zeolite/metal) membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 °C and 1 atm. The results indicate that Pt metal clusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction along with H2 removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. The hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanoclusters and reduced catalyst deactivation. PMID:27574979

  7. One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters.

    PubMed

    Kim, Seok-Jhin; Tan, Shuai; Taborga Claure, Micaela; Briones Gil, Laura; More, Karren L; Liu, Yujun; Moore, Jason S; Dixit, Ravindra S; Pendergast, John G; Sholl, David S; Jones, Christopher W; Nair, Sankar

    2016-09-21

    Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal clusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5-2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal clusters. To characterize the properties of the hybrid (zeolite/metal) membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 °C and 1 atm. The results indicate that Pt metal clusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction along with H2 removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. The hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanoclusters and reduced catalyst deactivation.

  8. Process for catalyst regeneration with flue gas

    SciTech Connect

    Harandi, M.N.; Owen, H.

    1991-03-26

    This paper discusses a continuous, once through process using a hot flue gas stream from a fluid catalytic cracking catalyst regenerator to regenerate deactivated zeolite catalysts having carbonaceous deposits thereon in catalytic conversion processes employing multiple fixed bed reactors operatively connected for sequential conversion and catalyst regeneration. It comprises withdrawing a first portion of the hot flue gas stream to provide an oxidizing flue gas stream containing a substantial amount of water; partially cooling the oxidizing flue gas stream by indirect heat exchange to preheat the catalytic conversion process feedstock stream; contacting the heated feedstock with active zeolite catalyst under conversion conditions in a first fixed bed reactor to produce hydrocarbon products; separating the hydrocarbon products; contacting a particulate free first portion of partially cooled, oxidizing flue gas stream containing a substantial amount of water at a temperature between about 700{degrees} to 100{degrees}F and a pressure of between about 15 to 35 psig with deactivated zeolite catalyst having carboneous deposits thereon in a second fixed bed reactor under catalyst oxidative regenerating conditions at a temperature substantially lower than the fluid catalytic cracking catalyst regenerator; cooling the consolidated streams comprising the effluent gas streams from the second reactor, the remaining portion of partially cooled oxidizing flue gas stream and the remaining portion of hot flue gas stream; and discharging the cooled consolidated streams without recycling.

  9. Zeolite catalysis in the synthesis of isobutylene from hydrous ethanol

    NASA Astrophysics Data System (ADS)

    Phillips, Cory Bernard

    1999-11-01

    containing Pd are the most efficient catalysts for the dimerization reaction. Characterization results from x-ray diffraction (XRD), electron paramagnetic resonance (EPR) spectroscopy, and CTPAD suggest a stable, Pd species with a low oxidation state as part of the active site in Pd-exchanged zeolites. Isobutylene was present in the C4 fraction at reasonable quantities for most of the catalyst candidates, especially those containing an alkali metal co-cation.

  10. Zeolite crystal growth in space

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  11. Transversal spin freezing and re-entrant spin glass phases in chemically disordered Fe-containing perovskite multiferroics.

    PubMed

    Stephanovich, V A; Laguta, V V

    2016-03-14

    We propose experimental verification and theoretical explanation of magnetic anomalies in the complex Fe-containing perovskite multiferroics like PbFe1/2Nb1/2O3 and PbFe1/2Ta1/2O3. The theoretical part is based on our model of coexistence of the long-range magnetic order and spin glass in the above compounds. In our model, the exchange interaction is anisotropic, coupling antiferromagnetically z spin components of Fe(3+) ions. At the same time, the xy components are coupled by much weaker exchange interaction of ferromagnetic sign. In the system with spatial disorder (half of the corresponding lattice sites are occupied by spinless Nb(5+) ions) such frustrating interaction results in the fact that the antiferromagnetic order is formed by the z projection of the spins, while their xy components contribute to spin glass behaviour. Our theoretical findings are supported by the experimental evidence of such a coexistence of antiferromagnetic and spin glass phases in chemically disordered Fe-containing complex perovskite multiferroics. PMID:26890550

  12. 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.

  13. Squaraines inside Zeolites: Preparation, Stability, and Photophysical Properties.

    PubMed

    Cano, María Luz; Cozens, Frances L.; Esteves, María A.; Márquez, Francisco; García, Hermenegildo

    1997-10-17

    A series of four symmetrical squaraines (ditoylyl, di-m-xylyl, dianisyl, and diresorcinyl) incorporated inside zeolites Y, mordenite, and ZSM-5 have been obtained by treating squaric acid and the corresponding arene in the presence of acid zeolites. Acid sites and high reaction temperatures (150 degrees C) were found to be crucial for the success of the preparation procedure. Surprisingly, this method failed for the preparation of the squaraine derived from N,N-dimethylaniline, which is known to be readily formed from squaric acid in homogeneous phase without a catalyst. The solid samples containing squaraines were characterized by diffuse reflectance and Raman spectroscopies and by thermogravimetry-differential scanning calorimetry. Among the hosts, mordenite was found to be the most general and convenient zeolite for the preparation of the squaraines, while in the other solids either the organic content adsorbed was comparatively smaller (ZSM-5) or some squaraines were not very stable (Y zeolite for ditolyl and dixylyl squaraines). The absorption spectra of the samples correspond to the J-aggregation state of the squaraines, except for some ZSM-5 samples, where simultaneous observation of the bands due to both monomers and aggregates occurs. Aggregation also changes with the water content of the samples. Treatment of the zeolite-bound diresorcinyl squaraine with basic aqueous solutions leads to remarkable variations in the diffuse reflectance and Raman spectra. These changes in the Raman spectrum of the diresorcinyl squaraine were found to be reversible by basic or acid washings. Laser flash photolysis using the 355- or 532-nm output of a Nd-YAG laser (<10 ns pulses; zeolite host. On the basis of the similarity of the UV-vis absorption spectra obtained in solution, these transients have been identified as the radical cation (HY) and the triplet excited

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

    SciTech Connect

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

    2006-11-01

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

  15. Metal nanoparticles as a conductive catalyst

    SciTech Connect

    Coker, Eric N.

    2010-08-03

    A metal nanocluster composite material for use as a conductive catalyst. The metal nanocluster composite material has metal nanoclusters on a carbon substrate formed within a porous zeolitic material, forming stable metal nanoclusters with a size distribution between 0.6-10 nm and, more particularly, nanoclusters with a size distribution in a range as low as 0.6-0.9 nm.

  16. Development of a stable cobalt-ruthenium Fisher-Tropsch catalyst. Final report

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1995-02-01

    The reverse micelle catalyst preparation method has been used to prepare catalysts on four supports: magnesium oxide, carbon, alumina- titania and steamed Y zeolite. These catalysts were not as active as a reference catalyst prepared during previous contracts to Union Carbide Corp. This catalyst was supported on steamed Y zerolite support and was impregnated by a pore-filling method using a nonaqueous solvent. Additional catalysts were prepared via pore- filling impregnation of steamed Y zeolites. These catalysts had levels of cobalt two to three and a half times as high as the original Union Carbide catalyst. On a catalyst volume basis they were much more active than the previous catalyst; on an atom by atom basis the cobalt was about of the same activity, i.e., the high cobalt catalysts` cobalt atoms were not extensively covered over and deactivated by other cobalt atoms. The new, high activity, Y zerolite catalysts were not as stable as the earlier Union Carbide catalyst. However, stability enhancement of these catalysts should be possible, for instance, through adjustment of the quantity and/or type of trace metals present. A primary objective of this work was determination whether small amounts of ruthenium could enhance the activity of the cobalt F-T catalyst. The reverse micelle catalysts were not activated by ruthenium, indeed scanning transmission electronic microscopy (STEM) analysis provided some evidence that ruthenium was not present in the cobalt crystallites. Ruthenium did not seem to activate the high cobalt Y zeolite catalyst either, but additional experiments with Y zeolite-supported catalysts are required. Should ruthenium prove not to be an effective promoter under the simple catalyst activation procedure used in this work, more complex activation procedures have been reported which are claimed to enhance the cobalt/ruthenium interaction and result in activity promotion by ruthenium.

  17. Ammonia synthesis catalyzed by ruthenium supported on basic zeolites

    SciTech Connect

    Fishel, C.T.; Davis, R.J.; Garces, J.M.

    1996-09-15

    Ammonia synthesis was catalyzed by ruthenium metal clusters, promoted by alkali and alkaline earth elements, supported on zeolite X, magnesia, and pure silica MCM-41. At atmospheric total pressure and temperatures ranging from 623 to 723 K, the turnover frequencies of ammonia synthesis on Ru/KX varied significantly with Fu cluster size, demonstrating the known structure sensitivity of the reaction. Therefore, zeolite and magnesia catalysts were prepared with similar Ru cluster sizes, about 1 nm in diameter, in order to properly evaluate the effect of promoters. The same high degree of metal dispersion could not be obtained with Ru/MCM-41 catalysts. The turnover frequency for ammonia synthesis over Ru/CsX exceeded that over Ru/KX, consistent with the rank of promoter basicity. However, alkaline earth metals were more effective promoters than alkali metals for Ru supported on both zeolite X and MCM-41. Since alkaline earth metals are less basic; this promotional effect was unexpected. In addition, the turnover frequency for ammonia synthesis on Ru/BaX exceeded that of Ru/MgO, a nonzeolitic material. Pore volumes for Ru/BaX and Ru/KX measured by N{sub 2} adsorption were essentially identical, suggesting that pore blockage by ions within the zeolites does not account for the differences in reaction rates. The kinetics of ammonia synthesis over ruthenium differed considerably from what has been reported for industrial iron catalysts. Most significantly, the order of reaction in H{sub 2} was negative over Ru but is positive over Fe. A likely cause of this change in reaction order is that dissociated hydrogen atoms cover a greater fraction of the Ru clusters compared to Fe under reaction conditions. 49 refs., 8 figs., 10 tabs.

  18. Adsorption and photocatalytic degradation of pharmaceuticals and pesticides by carbon doped-TiO2 coated on zeolites under solar light irradiation.

    PubMed

    An, Ye; de Ridder, David Johannes; Zhao, Chun; Schoutteten, Klaas; Bussche, Julie Vanden; Zheng, Huaili; Chen, Gang; Vanhaecke, Lynn

    2016-01-01

    To evaluate the performance of zeolite-supported carbon-doped TiO(2) composite catalysts toward target pollutants under solar light irradiation, the adsorption and photocatalytic degradation of 18 pharmaceuticals and pesticides with distinguishing features (molecular size and volume, and photolysis) were investigated using mordenite zeolites with SiO(2)/Al(2)O(3) ratios of 18 and 240. Different quantities of carbon-doped TiO(2) were coated on the zeolites, and then the finished composite catalysts were tested in demineralized, surface, and hospital wastewater samples, respectively. The composite photocatalysts were characterized by X-ray diffraction, field emission scanning electron microscopy, and surface area and porosity analyses. Results showed that a dispersed layer of carbon-doped TiO(2) is formed on the zeolite surface; this layer blocks the micropores of zeolites and reduces their surface area. However, these reductions did not significantly affect adsorption onto the zeolites. Our results demonstrated that zeolite-supported carbon-doped TiO(2) systems can effectively degrade 18 pharmaceuticals and pesticides in demineralized water under natural and simulated solar light irradiation. In surface and hospital wastewaters, zeolite-supported carbon-doped TiO(2) systems present excellent anti-interference capability against radical scavengers and competitive organics for pollutants removal, and higher pollutants adsorption on zeolites evidently enhances the removal rate of target pollutants in surface and hospital wastewater samples with a complicated matrix.

  19. Adsorption and photocatalytic degradation of pharmaceuticals and pesticides by carbon doped-TiO2 coated on zeolites under solar light irradiation.

    PubMed

    An, Ye; de Ridder, David Johannes; Zhao, Chun; Schoutteten, Klaas; Bussche, Julie Vanden; Zheng, Huaili; Chen, Gang; Vanhaecke, Lynn

    2016-01-01

    To evaluate the performance of zeolite-supported carbon-doped TiO(2) composite catalysts toward target pollutants under solar light irradiation, the adsorption and photocatalytic degradation of 18 pharmaceuticals and pesticides with distinguishing features (molecular size and volume, and photolysis) were investigated using mordenite zeolites with SiO(2)/Al(2)O(3) ratios of 18 and 240. Different quantities of carbon-doped TiO(2) were coated on the zeolites, and then the finished composite catalysts were tested in demineralized, surface, and hospital wastewater samples, respectively. The composite photocatalysts were characterized by X-ray diffraction, field emission scanning electron microscopy, and surface area and porosity analyses. Results showed that a dispersed layer of carbon-doped TiO(2) is formed on the zeolite surface; this layer blocks the micropores of zeolites and reduces their surface area. However, these reductions did not significantly affect adsorption onto the zeolites. Our results demonstrated that zeolite-supported carbon-doped TiO(2) systems can effectively degrade 18 pharmaceuticals and pesticides in demineralized water under natural and simulated solar light irradiation. In surface and hospital wastewaters, zeolite-supported carbon-doped TiO(2) systems present excellent anti-interference capability against radical scavengers and competitive organics for pollutants removal, and higher pollutants adsorption on zeolites evidently enhances the removal rate of target pollutants in surface and hospital wastewater samples with a complicated matrix. PMID:27332831

  20. Hierarchical Macro-meso-microporous ZSM-5 Zeolite Hollow Fibers With Highly Efficient Catalytic Cracking Capability

    PubMed Central

    Liu, Jia; Jiang, Guiyuan; Liu, Ying; Di, Jiancheng; Wang, Yajun; Zhao, Zhen; Sun, Qianyao; Xu, Chunming; Gao, Jinsen; Duan, Aijun; Liu, Jian; Wei, Yuechang; Zhao, Yong; Jiang, Lei

    2014-01-01

    Zeolite fibers have attracted growing interest for a range of new applications because of their structural particularity while maintaining the intrinsic performances of the building blocks of zeolites. The fabrication of uniform zeolite fibers with tunable hierarchical porosity and further exploration of their catalytic potential are of great importance. Here, we present a versatile and facile method for the fabrication of hierarchical ZSM-5 zeolite fibers with macro-meso-microporosity by coaxial electrospinning. Due to the synergistic integration of the suitable acidity and the hierarchical porosity, high yield of propylene and excellent anti-coking stability were demonstrated on the as-prepared ZSM-5 hollow fibers in the catalytic cracking reaction of iso-butane. This work may also provide good model catalysts with uniform wall thickness and tunable porosity for studying a series of important catalytic reactions. PMID:25450726

  1. Fluorescence labelling as tool for zeolite particle tracking in nanoremediation approaches.

    PubMed

    Gillies, Glenn; Mackenzie, Katrin; Kopinke, Frank-Dieter; Georgi, Anett

    2016-04-15

    Colloidal Fe-zeolites such as Fe-BEA-35 are currently under study as new adsorbent and catalyst materials for in-situ chemical oxidation with H2O2. As for nanoremediation in general, the availability of suitable particle detection methods is a requirement for successful process development and particle tracing. Detection and distinguishing between natural colloids and introduced particles with a similar composition are a challenge. By means of fluorescence labelling, a highly specific detection option for Fe-BEA-35 was developed. 'Ship-in-a-bottle' synthesis of fluorescein within the zeolite pores, which was applied for the first time for a BEA type zeolite, provides a product with stable and non-extractable fluorescence. When the fluorescent labelled zeolite is added at a concentration of 1wt.% referring to the total zeolite mass, a very low detection limit of 1mg/L of total zeolite is obtained. Compared to commonly applied turbidity measurements, detection via fluorescence labelling is much more specific and sensitive. Fluorescence is only marginally affected by carboxymethyl cellulose, which is frequently applied as stabilizer in application suspensions but will be depleted upon contact with H2O2. Transport properties of fluorescent labelled and non-labelled Fe-zeolite particles are in agreement as determined in a column study with quartz sand and synthetic groundwater (classified as very hard).

  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-44 aluminosilicate zeolite

    SciTech Connect

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-04-29

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

  4. Quantitatively Probing the Al Distribution in Zeolites

    SciTech Connect

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

    2014-06-11

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

  5. Improved zeolite regeneration processes for preparing saturated branched-chain fatty acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ferrierite zeolite solid is an excellent catalyst for the skeletal isomerization of unsaturated linear-chain fatty acids (i.e., oleic acid) to unsaturated branched-chain fatty acids (i.e., iso-oleic acid) follow by hydrogenation to give saturated branched-chain fatty acids (i.e., isostearic acid). ...

  6. Ir/KLTL zeolites: Structural characterization and catalysis on n-hexane reforming

    SciTech Connect

    Triantafillou, N.D.; Gates, B.C.

    1996-03-01

    Ir/KLTL zeolite catalysts were prepared by incipient wetness impregnation of LTL zeolites with [Ir(NH{sub 3}){sub 5}Cl]Cl{sub 2}. The catalysts were characterized by extended X-ray absorption fine structure (EX-AFS) spectroscopy, infrared spectroscopy, and H{sub 2} chemisorption. EXAFS data show that the average Ir cluster size (after treatment at 300{degrees}C in H{sub 2}) increased from about 7 to 20 {Angstrom} as the zeolite K:Al atomic ratio increased from 0.34 to 1.56. Infrared spectra of adsorbed CO show that the electron donation to the Ir increased as the K:Al ratio increased. In contrast to the performance reported for Pt/KLTL zeolites with metal clusters as small as those observed in the present experiments, the Ir/KLTL catalyst has a low selectivity for dehydrocyclization of n-hexane at 440-480{degrees}C and 1 atm with a H{sub 2}: n-hexane feed molar ratio of 6. Instead, the catalysts are selective for hydrogenolysis. The selectivity is insensitive to the K:Al ratio, but the activity for dehydrocyclization is a maximum at a K:Al atomic ratio of about 1. The results show that even the smallest Ir clusters to which electron donation is significant still behave essentially like metallic Ir in the catalytic reactions. 49 refs., 4 figs., 7 tabs.

  7. Core-shell strain structure of zeolite microcrystals.

    PubMed

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

    2013-08-01

    Zeolites are crystalline aluminosilicate minerals featuring a network of 0.3-1.5-nm-wide pores, used in industry as catalysts for hydrocarbon interconversion, ion exchangers, molecular sieves and adsorbents. For improved applications, it is highly useful to study the distribution of internal local strains because they sensitively affect the rates of adsorption and diffusion of guest molecules within zeolites. Here, we report the observation of an unusual triangular deformation field distribution in ZSM-5 zeolites by coherent X-ray diffraction imaging, showing the presence of a strain within the crystal arising from the heterogeneous core-shell structure, which is supported by finite element model calculation and confirmed by fluorescence measurement. The shell is composed of H-ZSM-5 with intrinsic negative thermal expansion whereas the core exhibits a different thermal expansion behaviour due to the presence of organic template residues, which usually remain when the starting materials are insufficiently calcined. Engineering such strain effects could have a major impact on the design of future catalysts. PMID:23832126

  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. Catalysts for conversion of syngas to liquid motor fuels

    DOEpatents

    Rabo, Jule A.; Coughlin, Peter K.

    1987-01-01

    Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst composition capable of ensuring the production of only relatively minor amounts of heavy products boiling beyond the diesel oil range. The catalyst composition, having desirable stability during continuous production operation, employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component. The latter component is a steam-stabilized zeolite Y catalyst of hydrophobic character, desirably in acid-extracted form.

  10. Reactive molecular simulations of protonation of water clusters and depletion of acidity in H-ZSM-5 zeolite.

    PubMed

    Joshi, Kaushik L; Psofogiannakis, George; van Duin, Adri C T; Raman, Sumathy

    2014-09-14

    Using reactive molecular dynamics (RMD), we present an atomistic insight into the interaction between water molecules and acidic centers of H-ZSM-5 zeolite. The reactive force field method, ReaxFF, was used to evaluate the adsorption and diffusion of water as well as to study the protonation of water molecules inside zeolite channels. The existing Si/Al/O/H parameters were refitted against DFT calculations to improve the ReaxFF description of interaction between water molecules and the acidic sites of zeolites. The diffusion coefficient of water in the zeolite obtained from refitted parameters is in excellent agreement with experimental results. The molecular dynamics (MD) simulations indicate that protonation of water molecules and acidity of the zeolite catalyst depend on water loadings and temperature and the observed trends compare favorably with existing experimental and theoretical studies. At higher water loadings, protonation of water molecules is more frequent leading to formation and growth of protonated water clusters inside zeolite channels. From the analysis of various reaction channels that were observed during the simulations, we found that such water clusters have relatively short life due to frequent interchange of protons and water molecules among the water clusters. Such proton hopping events play a key role in moving the protons between different acidic centers of zeolite. These simulations show the capability of ReaxFF in providing atomistic details of complex chemical interactions between the water phase and solid acid zeolites.

  11. Synthesis and characterization of mesoporous hydrocracking catalysts

    NASA Astrophysics Data System (ADS)

    Munir, D.; Usman, M. R.

    2016-08-01

    Mesoporous catalysts have shown great prospective for catalytic reactions due to their high surface area that aids better distribution of impregnated metal. They have been found to contain more adsorption sites and controlled pore diameter. Hydrocracking, in the presence of mesoporous catalyst is considered more efficient and higher conversion of larger molecules is observed as compared to the cracking reactions in smaller microporous cavities of traditional zeolites. In the present study, a number of silica-alumina based mesoporous catalysts are synthesized in the laboratory. The concentration and type of surfactants and quantities of silica and alumina sources are the variables studied in the preparation of catalyst supports. The supports prepared are well characterized using SEM, EDX, and N2-BET techniques. Finally, the catalysts are tested in a high pressure autoclave reactor to study the activity and selectivity of the catalysts for the hydrocracking of a model mixture of plastics comprising of LDPE, HDPE, PP, and PS.

  12. The dual role of palladium in enhancing the photocatalytic activity of CdS dispersed on NaY-zeolite.

    PubMed

    Sasikala, R; Gaikwad, A P; Sudarsan, V; Rao, R; Jagannath; Viswanadh, B; Bharadwaj, S R

    2015-03-14

    A stable photocatalyst, CdS dispersed on zeolite with Pd as both the dopant and the co-catalyst, has been developed. Enhancement of photocatalytic activity for hydrogen generation is observed for CdS when doped with palladium and dispersed on NaY-zeolite (CdPdS-Z). A further increase in the photocatalytic activity of CdPdS-Z is observed when palladium is added as a co-catalyst (Pd-CdPdS-Z). Cd0.95Pd0.05S-Z is synthesized via a facile soft chemical route and the Pd co-catalyst is loaded onto the composite using a wet impregnation method. This composite catalyst exists as two phases consisting of CdPdS and zeolite and CdPdS exists as a highly dispersed phase on zeolite as revealed by TEM studies. The Pd doped CdS-zeolite composite exhibits increased visible light absorption indicating the alteration of the band structure of CdS as a result of doping. Time resolved fluorescence studies reveal that the lifetime of the charge carriers is higher in the composites than in pure CdS. A detailed characterization using XRD, Raman and X-ray photoelectron spectroscopy indicates that Pd has substituted for Cd in the CdS lattice and Pd exists in the Pd(2+) oxidation state. Solid state MAS NMR studies indicate that an interaction exists between CdS (or CdPdS) and zeolite at the interface and Cd selectively interacts with Al of the zeolite framework. The photocatalytic activity of the Pd-CdPdS-Z catalyst remains unchanged with repeated cycles. Characterization of the used catalyst indicates that it is stable under the present experimental conditions. The enhanced photocatalytic activity of Pd-CdPdS-Z is attributed to the enhanced visible light absorption arising due to Pd doping and increased lifetime of the photogenerated charge carriers assisted by zeolite and the Pd co-catalyst. This study highlights the multiple roles played by palladium in enhancing the photocatalytic activity of the CdS-zeolite composite.

  13. Deactivation and regeneration of ZSM-5 zeolite in catalytic pyrolysis of plastic wastes

    SciTech Connect

    Lopez, A.

    2011-08-15

    Highlights: > Pyrolysis transforms plastic wastes in valuable liquids and gases useful as fuels or source of chemicals. > The use of ZSM-5 zeolite in pyrolysis favours the production of gases and of lighter and more aromatic liquids. > ZSM-5 zeolite is almost completely deactivated after one plastics pyrolysis experiment. > ZSM-5 zeolite used in plastic wastes pyrolysis can be regenerated by burning the deposited coke in an air stream. > Regenerated ZSM-5 recovers its activity and produces liquids and gases equivalent to those obtained with fresh catalyst. - Abstract: In this work, a study of the regeneration and reuse of ZSM-5 zeolite in the pyrolysis of a plastic mixture has been carried out in a semi-batch reactor at 440 deg. C. The results have been compared with those obtained with fresh-catalyst and in non-catalytic experiments with the same conditions. The use of fresh catalyst produces a significant change in both the pyrolysis yields and the properties of the liquids and gases obtained. Gases more rich in C3-C4 and H{sub 2} are produced, as well as lower quantities of aromatic liquids if compared with those obtained in thermal decomposition. The authors have proved that after one pyrolysis experiment the zeolite loses quite a lot of its activity, which is reflected in both the yields and the products quality; however, this deactivation was found to be reversible since after regeneration heating at 550 deg. C in oxygen atmosphere, this catalyst recovered its initial activity, generating similar products and in equivalent proportions as those obtained with fresh catalyst.

  14. Rapid determination of particle size distribution of microbead catalysts

    SciTech Connect

    Mirshii, Y.V.; Goos, T.V.; Kaviev, V.M.; Kazahov, G.I.; Klimov, A.V.; Nesmeyanova, T.S.

    1986-05-01

    The authors have developed a rapid method for the determination of the particle size distribution of microbead catalysts by a photosedimentation method. This method is based on a determination of the settling velocity of the particles according to the change in optical density of the suspension as the particles settle. The design of the instrument was modified for application to the analysis of microbead cracking catalysts and microbead zeolites; it was originally developed for studies of particle size distribution in other materials. The measuring part of the AFS-2M photosedimentograph is shown schematically. For the high-zeolite catalysts, the results obtained by photosedimenation analysis are somewhat different from those obtained by the pipette method. The photosedimentation method can also be used in the analysis of microbead zeolites that are intended for use in the fluid-bed recovery of liquid paraffins.

  15. GREEN CHEMISTRY. Shape-selective zeolite catalysis for bioplastics production.

    PubMed

    Dusselier, Michiel; Van Wouwe, Pieter; Dewaele, Annelies; Jacobs, Pierre A; Sels, Bert F

    2015-07-01

    Biodegradable and renewable polymers, such as polylactic acid, are benign alternatives for petrochemical-based plastics. Current production of polylactic acid via its key building block lactide, the cyclic dimer of lactic acid, is inefficient in terms of energy, time, and feedstock use. We present a direct zeolite-based catalytic process, which converts lactic acid into lactide. The shape-selective properties of zeolites are essential to attain record lactide yields, outperforming those of the current multistep process by avoiding both racemization and side-product formation. The highly productive process is strengthened by facile recovery and practical reactivation of the catalyst, which remains structurally fit during at least six consecutive reactions, and by the ease of solvent and side-product recycling. PMID:26138977

  16. Shape-selective zeolite catalysis for bioplastics production

    NASA Astrophysics Data System (ADS)

    Dusselier, Michiel; Van Wouwe, Pieter; Dewaele, Annelies; Jacobs, Pierre A.; Sels, Bert F.

    2015-07-01

    Biodegradable and renewable polymers, such as polylactic acid, are benign alternatives for petrochemical-based plastics. Current production of polylactic acid via its key building block lactide, the cyclic dimer of lactic acid, is inefficient in terms of energy, time, and feedstock use. We present a direct zeolite-based catalytic process, which converts lactic acid into lactide. The shape-selective properties of zeolites are essential to attain record lactide yields, outperforming those of the current multistep process by avoiding both racemization and side-product formation. The highly productive process is strengthened by facile recovery and practical reactivation of the catalyst, which remains structurally fit during at least six consecutive reactions, and by the ease of solvent and side-product recycling.

  17. GREEN CHEMISTRY. Shape-selective zeolite catalysis for bioplastics production.

    PubMed

    Dusselier, Michiel; Van Wouwe, Pieter; Dewaele, Annelies; Jacobs, Pierre A; Sels, Bert F

    2015-07-01

    Biodegradable and renewable polymers, such as polylactic acid, are benign alternatives for petrochemical-based plastics. Current production of polylactic acid via its key building block lactide, the cyclic dimer of lactic acid, is inefficient in terms of energy, time, and feedstock use. We present a direct zeolite-based catalytic process, which converts lactic acid into lactide. The shape-selective properties of zeolites are essential to attain record lactide yields, outperforming those of the current multistep process by avoiding both racemization and side-product formation. The highly productive process is strengthened by facile recovery and practical reactivation of the catalyst, which remains structurally fit during at least six consecutive reactions, and by the ease of solvent and side-product recycling.

  18. Hierarchical zeolites and their catalytic performance in selective oxidative processes.

    PubMed

    Ojeda, Manuel; Grau-Atienza, Aida; Campos, Rafael; Romero, Antonio A; Serrano, Elena; Maria Marinas, Jose; García Martínez, Javier; Luque, Rafael

    2015-04-24

    Hierarchical ZSM-5 zeolites prepared using a simple alkali treatment and subsequent HCl washing are found to exhibit unprecedented catalytic activities in selective oxidation of benzyl alcohol under microwave irradiation. The metal-free zeolites promote the microwave-assisted oxidation of benzyl alcohol with hydrogen peroxide in yields ranging from 45-35 % after 5 min of reaction under mild reaction conditions as well as the epoxidation of cyclohexene to valuable products (40-60 % conversion). The hierarchically porous systems also exhibited an interesting catalytic activity in the dehydration of N,N-dimethylformamide (25-30 % conversion), representing the first example of transition-metal free catalysts in this reaction.

  19. Synergistic removal of nitrogen monoxide by non-thermal plasma and catalyst simultaneously.

    PubMed

    Yu, Gang; Yu, Qi; Zeng, Ke-si; Zhai, Xiao-dong

    2005-01-01

    An experimental system of De-NO with plasma-catalyst(Cu zeolite) was established to investigate the differences between De-NO with plasma-catalyst and De-NO only with plasma, to provide the instruction for selecting appropriate catalyst and operating condition. The characteristics of De-NO with plasma and De-NO with plasma-catalyst were investigated comparatively by experiments. The experimental results show that De-NO with plasma-catalyst has high NO removal rate; Cu zeolite is an effective catalyst which can promote NO removal rate in plasma remarkably; De-NO with plasma-catalyst should be operated at low temperature and the temperature has opposite effects on the function of catalyst and plasma; water vapor and O2 can increase the NO removal rate.

  20. Studying Two-Dimensional Zeolites with the Tools of Surface Science: MFI Nanosheets on Au(111)

    DOE PAGESBeta

    J. D. Kestell; Zhong, J. Q.; Shete, M.; Waluyo, I.; Sadowski, J. T.; Stacchiola, D. J.; Tsapatsis, M.; Boscoboinik, J. A.

    2016-07-26

    While surface science has provided fundamental insights into a variety a materials, the most used catalysts in the industry, namely zeolites, still remain a challenge. The recent preparation of two-dimensional versions of MFI zeolite frameworks and the possibility of their deposition on electrically conductive supports provides for the first time a viable strategy to perform detailed studies on industrially relevant zeolites using the vast toolkit of surface science. In this work we demonstrate the use of infrared reflection absorption spectroscopy (IRRAS) and synchrotron-based x-ray photoelectron spectroscopy (XPS) to study these materials. Furthermore, polarization modulation IRRAS is used to study themore » adsorption of methanol and its effect in phonon vibrations of the zeolite framework. The possibility of using surface science methods, in particular under ambient pressure conditions, for the study of well-defined zeolites and other microporous structures opens new avenues to understand structural and mechanistic aspects of these materials as catalysts, adsorbents and molecular sieves.« less

  1. 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

  2. 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.

  3. 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.

  4. Single Molecule Nanospectroscopy Visualizes Proton-Transfer Processes within a Zeolite Crystal

    PubMed Central

    2016-01-01

    Visualizing proton-transfer processes at the nanoscale is essential for understanding the reactivity of zeolite-based catalyst materials. In this work, the Brønsted-acid-catalyzed oligomerization of styrene derivatives was used for the first time as a single molecule probe reaction to study the reactivity of individual zeolite H-ZSM-5 crystals in different zeolite framework, reactant and solvent environments. This was accomplished via the formation of distinct dimeric and trimeric fluorescent carbocations, characterized by their different photostability, as detected by single molecule fluorescence microscopy. The oligomerization kinetics turned out to be very sensitive to the reaction conditions and the presence of the local structural defects in zeolite H-ZSM-5 crystals. The remarkably photostable trimeric carbocations were found to be formed predominantly near defect-rich crystalline regions. This spectroscopic marker offers clear prospects for nanoscale quality control of zeolite-based materials. Interestingly, replacing n-heptane with 1-butanol as a solvent led to a reactivity decrease of several orders and shorter survival times of fluorescent products due to the strong chemisorption of 1-butanol onto the Brønsted acid sites. A similar effect was achieved by changing the electrophilic character of the para-substituent of the styrene moiety. Based on the measured turnover rates we have established a quantitative, single turnover approach to evaluate substituent and solvent effects on the reactivity of individual zeolite H-ZSM-5 crystals. PMID:27709925

  5. Oxidation of benzyl alcohol by K2FeO4 to benzaldehyde over zeolites

    NASA Astrophysics Data System (ADS)

    Wang, Yuan-Yuan; Song, Hua; Song, Hua-Lin; Jin, Zai-Shun

    2016-10-01

    A novel and green procedure for benzaldehyde synthesis by potassium ferrate oxidation of benzyl alcohol employing zeolite catalysts was studied. The prepared oxidant was characterized by SEM and XRD. The catalytic activity of various solid catalysts was studied using benzyl alcohol as a model compound. USY was found to be a very efficient catalyst for this particular oxidation process. Benzaldehyde yields up to 96.0% could be obtained at the following optimal conditions: 0.2 mL of benzyl alcohol, 4 mmol of K2FeO4, 0.5 g of USY zeolite; 20 mL of cyclohexene, 0.3 mL of acetic acid (36 wt %), 30°C temperature, 4 h reaction time.

  6. Oxidation catalyst

    DOEpatents

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

    The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

  7. Conversion of Methanol, Ethanol and Propanol over Zeolites

    SciTech Connect

    Ramasamy, Karthikeyan K.; Wang, Yong

    2013-06-04

    Renewable fuel from lignocellulosic biomass has recently attracted more attention due to its environmental and the potential economic benefits over the crude oil [1]. In particular the production of fuel range hydrocarbon (HC) from alcohol generated lots of interest since the alcohol can be produced from biomass via thermochemical [2] (mixed alcohol from gasification derived synthesis gas) as well as the biochemical routes [3] (alcohol fermentation). Along with the development of ZSM5 synthesis and the discovery of methanol-to-gasoline (MTG) process by Mobil in 1970’s triggered lots of interest in research and development arena to understand the reaction mechanisms of alcohols over zeolites in particular ZSM5 [4]. More detailed research on methanol conversion was extensively reported [5] and in recent times the research work can be found on ethanol [6] and other alcohols as well but comprehensive comparison of catalyst activity and the deactivation mechanism of the conversion of various alcohols over zeolites has not been reported. The experiments were conducted on smaller alcohols such as methanol, ethanol and 1-propanol over HZSM5. The experimental results on the catalyst activity and the catalyst deactivation mechanism will be discussed.

  8. 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.

  9. 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.

  10. Highly selective Lewis acid sites in desilicated MFI zeolites for dihydroxyacetone isomerization to lactic acid.

    PubMed

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

    2013-05-01

    Desilication of commercial MFI-type (ZSM-5) zeolites in solutions of alkali metal hydroxides is demonstrated to generate highly selective heterogeneous catalysts for the aqueous-phase isomerization of biobased dihydroxyacetone (DHA) to lactic acid (LA). The best hierarchical ZSM-5 sample attains a LA selectivity exceeding 90 %, which is comparable to that of the state-of-the-art catalyst (i.e., the Sn-beta zeolite); this optimized hierarchical catalyst is recyclable over three runs. The Lewis acid sites, which are created through desilication along with the introduction of mesoporosity, are shown to play a crucial role in the formation of the desired product; these cannot be achieved by using other post-synthetic methods, such as steaming or impregnation of aluminum species. Desilication of other metallosilicates, such as Ga-MFI, also leads to high LA selectivity. In the presence of a soluble aluminum source, such as aluminum nitrate, alkaline-assisted alumination can introduce these unique Lewis acid centers in all-silica MFI zeolites. These findings highlight the potential of zeolites in the field of biomass-to-chemical conversion, and expand the applicability of desilication for the generation of selective catalytic centers. PMID:23554234

  11. Site activities of zeolite-support Ru for CO hydrogenation. Final report

    SciTech Connect

    Goodwin, J.G. Jr.

    1983-10-01

    The work supported by this grant can be grouped under three headings: a comprehensive study of RuY, Ru supported on zeolites having a range of Si/Al values, and alkali promotion of Ru. NaY-supported Ru catalysts have been prepared by incipient-wetness (I.W.) (using RuCl/sub 3/), ion-exchange (I.E.) (using Ru(NH/sub 3/)/sub 6/Cl/sub 3/), and vapor-impregnation (V.I.) (using Ru/sub 3/(CO)/sub 12/). The resulting catalysts were extensively studied by chemisorption, atomic absorption, IR, ESCA, and catalytic reaction (especially F-T). Significant differences were found depending on the method of preparation. These differences were exhibited in both the physical and chemical characteristics of the catalysts. By variation of the preparation method and Si/Al ratio of the zeolite it is possible to develop a better understanding of how metal particle size and location, metal-zeolite interactions, neutralizing cation type and concentration, and the presence of zeolite acid sites can influence the catalytic properties of the supported metal. Ten papers are included in this final report and are grouped under the following headings: (1) chemisorption characteristics; (2) electronic state of Ru; (3) hydrogenolysis properties of NaY-supported Ru; and (4) Fischer-Tropsch synthesis. All papers have been processed for inclusion in the Energy Data Base.

  12. In-situ imaging of reacting single-particle zeolites by non-linear optical microscopy

    NASA Astrophysics Data System (ADS)

    Wrzesinski, Paul J.; Slipchenko, Mikhail N.; Zaman, Taslima A.; Rioux, Robert M.; Gord, James R.; Roy, Sukesh

    2015-03-01

    Zeolite catalysis has been exploited by the petrochemical industry since the 1940's for catalytic cracking reactions of long chain hydrocarbons. The selectivity of zeolites strongly depends on a pore size, which is controlled by the chosen structure-directing agent (SDA) and by the SDA decomposition/removal process. Although zeolites are composed of micron-sized crystals, studies of zeolite materials typically focus on bulk (i.e., ensemble) measurements to elucidate structure-function information or to optimize catalysts and/or process parameters. To examine these phenomena on the microscale, non-linear optical microscopy is used to provide real-time imaging of chemical reactions in zeolites at temperatures exceeding 400°C. The template decomposition mechanism is studied, as elucidation of the mechanism is critical to understanding the relationship between the decomposition chemistry and the nanoscale features of the zeolite (topology, Si/Al ratio, added dopants). Forward stimulated Raman scattering (SRS), forward coherent anti-Stokes Raman scattering (CARS) and epi two-photon fluorescence (TPF) modalities are acquired simultaneously providing video-rate structural and chemical information. A high-temperature cell with gas inlet system is used for the study of reactions under various temperatures and gas environments. Examining the decomposition process with single-particle resolution enables access to ensemble-level and spatially-resolved behavior. Parallel experiments on bulk zeolite powders are conducted to enable comparison of ensemble and single-particle behavior during template decomposition. Our multi-technique approach has high potential for gaining insight into the link between nanoscale structure and catalytic activity and selectivity of zeolitic materials.

  13. European Microgravity Facilities for ZEOLITE Experiments on the International Space Station

    NASA Astrophysics Data System (ADS)

    Pletser, V.; Minster, O.; Kremer, S.; Kirschhock, C.; Martens, J.; Jacobs, P.

    2002-01-01

    Synthetic zeolites are complex porous silicates. Zeolites are applied as catalysts, adsorbents and sensors. Whereas the traditional applications are situated in the petrochemical area, zeolite catalysis and related zeolite-based technologies have a growing impact on the economics and sustainability of products and processes in a growing number of industrial sectors, including environmental protection and nanotechnology. A Sounding Rocket microgravity experiment led to significant insight in the physical aggregation patterns of zeolitic nanoscopic particles and the occurrence of self-organisation phenomena when undisturbed by convection. The opportunity of performing longer microgravity duration experiments on zeolite structures was recently offered in the frame of a Taxi-Flight to the ISS in November 2002 organized by Belgium and ESA. Two facilities are currently under development for this flight. One of them will use the Microgravity Science Glovebox (MSG) in the US Lab. Destiny to achieve thermal induced self-organization of different types of Zeosil nanoslabs by heating and cooling. The other facility will be flown on the ISS Russian segment and will allow to form Zeogrids at ambient temperature. On the other hand, the European Space Agency (ESA) is studying the possibility of developing a dedicated insert for zeolite experiments to be used with the optical and diagnostic platform of the Protein Crystallisation Diagnostic Facility (PCDF), that will fly integrated in the European Drawer Rack on the Columbus Laboratory starting in 2004. This paper will present the approach followed by ESA to prepare and support zeolite investigations in microgravity and will present the design concept of these three facilities.

  14. Vapor-phase esterification catalyzed by decationized Y zeolites

    SciTech Connect

    Santacesaria, E.; Gelosa, D.; Danise, P.; Carra, S.

    1983-04-01

    The kinetics of acetic acid esterification with ethyl alcohol, in vapor phase, have been studied in the presence of decationized Y zeolite catalysts. Two kinetic models have been considered: a Rideal model and a bimolecular surface reaction model. Both of these models satisfactorily fit the experimental data. The choice of the better model has been made on the basis of the physical significance of the parameters obtained by nonlinear regression analysis of the data. Suggestions are given on the mechanism of the reaction, which appears to be similar to that occurring under homogeneous liquid-phase conditions.

  15. Leaching of petroleum catalysts with cyanide for palladium recovery

    SciTech Connect

    Sibrell, P.L.; Atkinson, G.B.

    1995-12-31

    The US Bureau of Mines has tested cyanide leaching for recovery of palladium (Pd) from spent petroleum processing catalysts. Three different catalyst samples were supplied by a spent-catalyst processor. These catalysts consisted of a zeolite base and contained 0.4 to 0.7 pct Pd. During alkaline cyanide leaching, the catalysts exhibited ion-exchange properties due to their zeolite matrices. Hydrogen ions were released from the zeolite in exchange for sodium ions in solution, resulting in a significant decrease in solution pH. This could present a safety hazard because of the potential for release of toxic hydrogen cyanide gas. A pretreatment step where the catalysts were contacted with a 1.OM sodium hydroxide solution was found to prevent the pH shift from occurring. Following the sodium hydroxide pretreatment, two stages of leaching at 160 C with solution containing 1 pct sodium cyanide and 0.1M sodium hydroxide gave at least 75 and up to 95 pct Pd recovery. The Pd was quantitatively recovered from the leach solution by thermal decomposition in an autoclave at 250 C for 1 h. The Pd content of the precipitate was over 50 pct. Thermal decomposition also decreased the total cyanide content of the barren solution to less than 0.2 mg/L. The catalyst leach residues passed the Federal Toxicity Characteristic Leaching Procedure and the California Waste Extraction Test, indicating that landfill disposal of the leach residues would be acceptable.

  16. Leaching of petroleum catalysts with cyanide for palladium recovery

    SciTech Connect

    Sibrell, P.L.; Atkinson, G.B.

    1995-06-01

    The US Bureau of Mines has tested cyanide leaching for recovery of palladium (Pd) from spent petroleum processing catalysts. Three different catalyst samples were supplied by a spent-catalyst processor. These catalysts consisted of a zeolite base and contained 0.4 to 0.7% Pd. During alkaline cyanide leaching, the catalysts exhibited ion-exchange properties due to their zeolite matrices. Hydrogen ions were released from the zeolite in exchange for sodium ions in solution, resulting in a significant decrease in solution pH. This could present a safety hazard because of the potential for release of toxic hydrogen cyanide gas. A pretreatment step where the catalysts were contacted with a 1.0 M sodium hydroxide was found to prevent the pH shift from occurring. Following the sodium hydroxide pretreatment, two stages of leaching at 160 C with solution containing 1% sodium cyanide and 0.1 M sodium hydroxide gave at least 75 and up to 95% Pd recovery. The Pd was quantitatively recovered from the leach solution by thermal decomposition in an autoclave at 250 C for 1 h. The Pd content of the precipitate was over 50%. Thermal decomposition also decreased the total cyanide content of the barren solution to less than 0.2 mg/L. The catalyst leach residues passed the Federal Toxicity Characteristic Leaching Procedure and the California Waste Extraction Test, indicating that landfill disposal of the leach residues would be acceptable.

  17. Nano Catalysts for Diesel Engine Emission Remediation

    SciTech Connect

    Narula, Chaitanya Kumar; Yang, Xiaofan; Debusk, Melanie Moses; Mullins, David R; Mahurin, Shannon Mark; Wu, Zili

    2012-06-01

    The objective of this project was to develop durable zeolite nanocatalysts with broader operating temperature windows to treat diesel engine emissions to enable diesel engine based equipment and vehicles to meet future regulatory requirements. A second objective was to improve hydrothermal durability of zeolite catalysts to at least 675 C. The results presented in this report show that we have successfully achieved both objectives. Since it is accepted that the first step in NO{sub x} conversion under SCR (selective catalytic reduction) conditions involves NO oxidation to NO{sub 2}, we reasoned that catalyst modification that can enhance NO oxidation at low-temperatures should facilitate NO{sub x} reduction at low temperatures. Considering that Cu-ZSM-5 is a more efficient catalyst than Fe-ZSM-5 at low-temperature, we chose to modify Cu-ZSM-5. It is important to point out that the poor low-temperature efficiency of Fe-ZSM-5 has been shown to be due to selective absorption of NH{sub 3} at low-temperatures rather than poor NO oxidation activity. In view of this, we also reasoned that an increased electron density on copper in Cu-ZSM-5 would inhibit any bonding with NH{sub 3} at low-temperatures. In addition to modified Cu-ZSM-5, we synthesized a series of new heterobimetallic zeolites, by incorporating a secondary metal cation M (Sc{sup 3+}, Fe{sup 3+}, In{sup 3+}, and La{sup 3+}) in Cu exchanged ZSM-5, zeolite-beta, and SSZ-13 zeolites under carefully controlled experimental conditions. Characterization by diffuse-reflectance ultra-violet-visible spectroscopy (UV-Vis), X-ray powder diffraction (XRD), extended X-ray absorption fine structure spectroscopy (EXAFS) and electron paramagnetic resonance spectroscopy (EPR) does not permit conclusive structural determination but supports the proposal that M{sup 3+} has been incorporated in the vicinity of Cu(II). The protocols for degreening catalysts, testing under various operating conditions, and accelerated aging

  18. Time- and space-resolved high energy operando X-ray diffraction for monitoring the methanol to hydrocarbons reaction over H-ZSM-22 zeolite catalyst in different conditions

    NASA Astrophysics Data System (ADS)

    del Campo, Pablo; Slawinski, Wojciech Andrzej; Henry, Reynald; Erichsen, Marius Westgård; Svelle, Stian; Beato, Pablo; Wragg, David; Olsbye, Unni

    2016-06-01

    The conversion of methanol to hydrocarbons (MTH) over H-ZSM-22 was studied by operando time- and space-resolved X-ray diffraction (XRD) at 370-385 °C and WHSV = 2 g/g h at the Swiss-Norwegian Beamline at ESRF. The performance of a commercial H-ZSM-22 sample was compared before and after acid-base treatment, and with and without propanol co-feed, respectively. N2 adsorption, Scanning Electron Microscopy and propyl amine desorption experiments showed that acid-base treatment led to enhanced accessibility of acid sites, mainly due to the formation of mesopores between agglomerated H-ZSM-22 crystals. The catalytic set-up allowed us to simultaneously observe the catalyst activity and unit cell volume variations by time- and space-resolved HXRD in operando conditions. The expansion of the unit cell and final flattening at different positions in the catalytic bed matched very nicely with the catalytic activity gradients. Different scenarios provided different behaviors and gave insights in the effect of morphology and co-feed process on the activity in the MTH process. This technique is the only one which has so far been able to provide direct evidence of the behavior of the species inside the catalytic reactor.

  19. Exploring the reactivity of framework vanadium, niobium, and tantalum sites in zeolitic materials using DFT reactivity descriptors.

    PubMed

    Tielens, Frederik

    2009-09-01

    The acid-base properties of zeolites with group 5 transition metal framework sites are investigated, and a first step into the understanding of their acid/base and redox properties is undertaken using DFT reactivity descriptors. It is evidenced, using sodalite as model system, that zeolites with vanadium framework sites are more nucleophilic than zeolites with niobium and tantalum framework sites. It is predicted that the formation of carbonates would be favorable in zeolites with Ta framework sites compared with V framework sites, whereas the basicity of the bridging oxygens is predicted to interact preferentially with a soft nucleophile. In this context, the poisoning of the deNO(x) catalysts in the presence of SO2 is discussed.

  20. High-resolution single-molecule fluorescence imaging of zeolite aggregates within real-life fluid catalytic cracking particles.

    PubMed

    Ristanović, Zoran; Kerssens, Marleen M; Kubarev, Alexey V; Hendriks, Frank C; Dedecker, Peter; Hofkens, Johan; Roeffaers, Maarten B J; Weckhuysen, Bert M

    2015-02-01

    Fluid catalytic cracking (FCC) is a major process in oil refineries to produce gasoline and base chemicals from crude oil fractions. The spatial distribution and acidity of zeolite aggregates embedded within the 50-150 μm-sized FCC spheres heavily influence their catalytic performance. Single-molecule fluorescence-based imaging methods, namely nanometer accuracy by stochastic chemical reactions (NASCA) and super-resolution optical fluctuation imaging (SOFI) were used to study the catalytic activity of sub-micrometer zeolite ZSM-5 domains within real-life FCC catalyst particles. The formation of fluorescent product molecules taking place at Brønsted acid sites was monitored with single turnover sensitivity and high spatiotemporal resolution, providing detailed insight in dispersion and catalytic activity of zeolite ZSM-5 aggregates. The results point towards substantial differences in turnover frequencies between the zeolite aggregates, revealing significant intraparticle heterogeneities in Brønsted reactivity.

  1. Zeolites as nanoporous, gas-sensitive materials for in situ monitoring of DeNO(x)-SCR.

    PubMed

    Simons, Thomas; Simon, Ulrich

    2012-01-01

    In a proof-of-concept study we demonstrate in situ reaction monitoring of DeNO(x)-SCR on proton-conducting zeolites serving as catalyst and gas sensor at the same time. By means of temperature-dependent impedance spectroscopy we found that the thermally induced NH(3) desorption in H-form and in Fe-loaded zeolite H-ZSM-5 follow the same process, while a remarkable difference under DeNO(x)-SCR reaction conditions was found. The Fe-loaded catalyst shows a significantly lower onset temperature, and time-dependent measurements suggest different SCR reaction mechanisms for the two catalysts tested. These results may help in the development of catalysts for the reduction of NO(x) emissions and ammonia consumption, and provide insight into the elementary catalytic process promoting a full description of the NH(3)-SCR reaction system.

  2. Effect of Hydrocarbon Emissions From PCCI-Type Combustion on the Performance of Selective Catalytic Reduction Catalysts

    SciTech Connect

    Prikhodko, Vitaly Y; Pihl, Josh A; Lewis Sr, Samuel Arthur; Parks, II, James E

    2011-01-01

    Core samples cut from full size commercial Fe- and Cu-zeolite SCR catalysts were exposed to a slipstream of raw engine exhaust from a 1.9-liter 4-cylinder diesel engine operating in conventional and PCCI combustion modes. Subsequently, the NOx reduction performance of the exposed catalysts was evaluated on a laboratory bench-reactor fed with simulated exhaust. The Fe-zeolite NOx conversion efficiency was significantly degraded, especially at low temperatures (<250 C), after the catalyst was exposed to the engine exhaust. The degradation of the Fe-zeolite performance was similar for both combustion modes. The Cu-zeolite was much more resistant to HC fouling than the Fe-zeolite catalyst. In the case of the Cu-zeolite, PCCI exhaust had a more significant impact than the exhaust from conventional combustion on the NOx conversion efficiency. For all cases, the clean catalyst performance was recovered after heating to 600 C. GC-MS analysis of the HCs adsorbed to the catalyst surface provided insights into the observed NOx reduction performance trends.

  3. Effect of Hydrocarbon Emissions From PCCI-Type Combustion On The Performance of Selective Catalytic Reduction Catalysts

    SciTech Connect

    Prikhodko, Vitaly Y; Pihl, Josh A; Lewis Sr, Samuel Arthur; Parks, II, James E

    2011-01-01

    Core samples cut from full size commercial Fe-and Cu-zeolite SCR catalysts were exposed to a slipstream of raw engine exhaust from a 1.9-liter 4-cylinder diesel engine operating in conventional and PCCI combustion modes. Subsequently, the NOx reduction performance of the exposed catalysts was evaluated on a laboratory bench- reactor fed with simulated exhaust. The Fe-zeolite NOx conversion efficiency was significantly degraded, especially at low temperatures (<250 C), after the catalyst was exposed to the engine exhaust. The degradation of the Fe-zeolite performance was similar for both combustion modes. The Cu-zeolite was much more resistant to HC fouling than the Fe-zeolite catalyst. In the case of the Cu-zeolite, PCCI exhaust had a more significant impact than the exhaust from conventional combustion on the NOx conversion efficiency. For all cases, the clean catalyst performance was recovered after heating to 600 C. GC-MS analysis of the HCs adsorbed to the catalyst surface provided insights into the observed NOx reduction performance trends.

  4. Effect of Hydrocarbon Emissions from PCCI-type Combustion on the Performance of Selective Catalytic Reduction Catalysts

    SciTech Connect

    Prikhodko, Vitaly Y; Pihl, Josh A; Lewis Sr, Samuel Arthur; Parks, II, James E

    2012-01-01

    Core samples cut from full size commercial Fe- and Cu-zeolite selective catalytic reduction catalysts were exposed to a slipstream of raw engine exhaust from a 1.9-liter 4-cylinder diesel engine operating in conventional and premixed charge compression ignition (PCCI) combustion modes. Subsequently, the NO{sub x} reduction performance of the exposed catalysts was evaluated on a laboratory bench-reactor fed with simulated exhaust. The Fe-zeolite NO{sub x} conversion efficiency was significantly degraded, especially at low temperatures (<250 C), after the catalyst was exposed to the engine exhaust. The degradation of the Fe-zeolite performance was similar for both combustion modes. The Cu-zeolite was much more resistant to hydrocarbon (HC) fouling than the Fe-zeolite catalyst. In the case of the Cu-zeolite, PCCI exhaust had a more significant impact than the exhaust from conventional combustion on the NO{sub x} conversion efficiency. For all cases, the clean catalyst performance was recovered after heating to 600 C. Gas chromatography mass spectrometry analysis of the HCs adsorbed to the catalyst surface provided insights into the observed NO{sub x} reduction performance trends.

  5. Regeneration of Hydrotreating and FCC Catalysts

    SciTech Connect

    CM Wai; JG Frye; JL Fulton; LE Bowman; LJ Silva; MA Gerber

    1999-09-30

    Y zeolite in a silica-alumina matrix. X-ray fluorescence analyses showed that the rare earths used in preparing the catalysts were a mixture of lanthanum and cerium. Antimony found in the spent catalyst was added during operation of the FCC unit as a way to suppress the adverse effects of deposited nickel. The fresh HDS samples consisted of sulfided nickel and molybdenum on an alumina support. The spent catalyst showed nearly 10% vanadium on the catalyst and a modest increase in nickel and sulfur on the catalyst as a result of operations. Hydrocracking catalysts were not available for this study.

  6. Catalytic reactions of cyclooctane and ethylcyclohexane on HY zeolite

    SciTech Connect

    Abbot, J.; Wojciechowski, B.W.

    1987-10-01

    Few systematic studies of the reactions of cycloparaffins on zeolites have been reported, considering their importance as a component of commercial crude feedstocks. Studies of small ring (C/sub 3/, C/sub 4/) cycloparaffins have shown that the primary reaction product is the corresponding olefin. It has not been established, however, that the corresponding olefin is produced as an initial product of the cracking of medium-sized (C/sub 5/, C/sub 6/) rings. Studies of cycloparaffin cracking on silica-alumina catalysts report that the degree of saturation of low-molecular-weight products is much greater than that observed in comparable n-paraffin cracking. Reactions of methylcyclohexane on HY zeolite at 450/sup 0/C have shown that dehydrogenation, isomerization, and cracking are all primary processes. Here the authors report product distributions in the cracking of ethylcyclohexane and cyclooctane on HY zeolite at 400/sup 0/C and compare product distributions for these cycloparaffins. 19 references.

  7. Synthetic zeolites and other microporous oxide molecular sieves

    PubMed Central

    Sherman, John D.

    1999-01-01

    Use of synthetic zeolites and other microporous oxides since 1950 has improved insulated windows, automobile air-conditioning, refrigerators, air brakes on trucks, laundry detergents, etc. Their large internal pore volumes, molecular-size pores, regularity of crystal structures, and the diverse framework chemical compositions allow “tailoring” of structure and properties. Thus, highly active and selective catalysts as well as adsorbents and ion exchangers with high capacities and selectivities were developed. In the petroleum refining and petrochemical industries, zeolites have made possible cheaper and lead-free gasoline, higher performance and lower-cost synthetic fibers and plastics, and many improvements in process efficiency and quality and in performance. Zeolites also help protect the environment by improving energy efficiency, reducing automobile exhaust and other emissions, cleaning up hazardous wastes (including the Three Mile Island nuclear power plant and other radioactive wastes), and, as specially tailored desiccants, facilitating the substitution of new refrigerants for the ozone-depleting chlorofluorocarbons banned by the Montreal Protocol. PMID:10097059

  8. Zeolites on Mars: Possible environmental indicators in soils and sediments

    NASA Technical Reports Server (NTRS)

    Ming, D. W.; Gooding, J. L.

    1988-01-01

    Weathering products should serve as indicators of weathering environments and may provide the best evidence of the nature of climate change on Mars. No direct mineralogical measurements of Martian regolith were performed by the Viking missions, but the biology and X-ray fluorescence experiments provided some information on the physiochemical properties of Martian regolith. Most post-Viking studies of candidate weathering products have emphasized phyllosilicates and Fe-oxides; zeolites are potentially important, but overlooked, candidate Martian minerals. Zeolites would be important on Mars for three different reasons. First, they are major sinks of atmospheric gases and, per unit mass, are stronger and more efficient sorbents than are phyllosilicates. Secondly, they can be virtually unique sorbents and shelters for organic compounds and possible catalysts for organic-based reactions. Finally, their exchangeable ions are good indicators of the chemical properties of solutions with which they have communicated. Accordingly, the search for information on past compositions of the Martian atmosphere and hydrosphere should find zeolites to be rich repositories.

  9. Synthetic zeolites and other microporous oxide molecular sieves.

    PubMed

    Sherman, J D

    1999-03-30

    Use of synthetic zeolites and other microporous oxides since 1950 has improved insulated windows, automobile air-conditioning, refrigerators, air brakes on trucks, laundry detergents, etc. Their large internal pore volumes, molecular-size pores, regularity of crystal structures, and the diverse framework chemical compositions allow "tailoring" of structure and properties. Thus, highly active and selective catalysts as well as adsorbents and ion exchangers with high capacities and selectivities were developed. In the petroleum refining and petrochemical industries, zeolites have made possible cheaper and lead-free gasoline, higher performance and lower-cost synthetic fibers and plastics, and many improvements in process efficiency and quality and in performance. Zeolites also help protect the environment by improving energy efficiency, reducing automobile exhaust and other emissions, cleaning up hazardous wastes (including the Three Mile Island nuclear power plant and other radioactive wastes), and, as specially tailored desiccants, facilitating the substitution of new refrigerants for the ozone-depleting chlorofluorocarbons banned by the Montreal Protocol. PMID:10097059

  10. Hydrothermally stable, low-temperature NO.sub.x reduction NH.sub.3-SCR catalyst

    DOEpatents

    Narula, Chaitanya K.; Yang, Xiaofan

    2016-10-25

    A catalyst composition includes a heterobimetallic zeolite characterized by a chabazite structure loaded with copper ions and at least one trivalent metal ion other than Al.sup.3+. The catalyst composition decreases NO.sub.x emissions in diesel exhaust and is suitable for operation in a catalytic converter.

  11. Hydrothermally stable, low-temperature NO.sub.x reduction NH.sub.3-SCR catalyst

    DOEpatents

    Narula, Chaitanya K; Yang, Xiaofan

    2015-03-24

    A catalyst composition includes a heterobimetallic zeolite characterized by a chabazite structure loaded with copper ions and at least one trivalent metal ion other than Al.sup.3+. The catalyst composition decreases NO.sub.x emissions in diesel exhaust and is suitable for operation in a catalytic converter.

  12. 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.

  13. 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.

  14. Catalyst and process for the hydrogenitrogenation and hydrocracking of high-nitrogen feeds

    SciTech Connect

    Tait, A. M.; Hensley, A. L. Jr.; Nevitt, T. D.

    1984-10-09

    There is disclosed a catalyst, which catalyst comprises a hydrogenation component comprising chromium, molybdenum, and at least one metal of Group VIII, a crystalline molecular sieve zeolite, and a porous refractory inorganic oxide. Suitable molecular sieve zeolites are those having pore diameters of at least 5 A (0.5 nm) and containing exchangeable cations, for example, faujasite crystalline aluminosilicates, mordenite crystalline aluminosilicates, ZSM crystalline aluminosilicates, and AMS crystalline metallosilicates. There are also disclosed processes for the hydrodenitrogenation and hydrocracking of a hydrocarbon stream containing a substantial amount of nitrogen compounds, which processes comprise contacting said stream under suitable conditions and in the presence of hydrogen with the aforesaid catalyst.

  15. Combination of ozone with nano TiO2 supported by zeolite for the decontamination of raw water from Songhua River

    NASA Astrophysics Data System (ADS)

    Yang, Yi-Xin; Ma, Jun; Wang, Sheng-jun; Zhang, Jing

    2013-03-01

    In the present paper, nanosized TiO2 supported by zeolite was used in the ozonation of Songhua River as catalyst. The catalytic activity of TiO2/Zeolite for ozonation was testified by nitrobenzene removal, which is one kind of representatively resistant organic contaminant. And the removal of some organic and inorganic compounds existing in the Songhua River by TiO2/Zeolite catalyzed ozonation was investigated. GC-MS analysis showed that the Songhua River was obviously polluted by organic contaminants. Catalytic ozonation can remove about 30 kinds of organic matters from water and reduce the total organic peak area of feed water by 62.5%.

  16. Catalyst for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C.

    2010-04-06

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

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

    SciTech Connect

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

    2015-06-15

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

  18. 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.

  19. 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

  20. Development of catalyst production facilities at Ufa Oil Refinery

    SciTech Connect

    Propkopyuk, S.G.; Rozenbaum, B.L.; Putilin, N.Ye.; Amirkhanov, K.Sh.; Morozov, B.F.; Britenkova, T.G.

    1982-08-03

    The Ufa Order of Lenin Oil Refinery is one of the USSR's largest facilities for production of catalysts for oil refining and petrochemistry, as well as for the food industry. Nine types of catalysts are produced for cracking, selective hydrogenation and oligomerization. A plant for production of NaY zeolite catalysts by the ash method has been remodeled. The production of nickel catalysts on kieselgur is growing rapidly. The facility for producing copper-chromium type MKhB catalyst is to be remodeled during the 11th Five-Year Plan. Production of cracking catalysts will be basically redesigned, increasing the capacity by 50% and significantly improving the operating characteristics of microspherical catalysts.

  1. STRONTIUM AS AN EFFICIENT PROMOTER FOR SUPPORTED PALLADIUM HYDROGENATION CATALYSTS

    EPA Science Inventory

    The effect of strontium promotion is studied for a series of supported palladium catalysts such as Pd/zeolite-β, Pd/Al2O3, Pd/SiO2, Pd/hydrotalcite and Pd/MgO. Strontium is found to be an effective promoter for enhancing the metal area, perce...

  2. Enhanced selectivity of zeolites by controlled carbon deposition

    DOEpatents

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

    2006-05-09

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

  3. Xylose isomerization with zeolites in a two-step alcohol-water process.

    PubMed

    Paniagua, Marta; Saravanamurugan, Shunmugavel; Melian-Rodriguez, Mayra; Melero, Juan A; Riisager, Anders

    2015-03-01

    Isomerization of xylose to xylulose was efficiently catalyzed by large-pore zeolites in a two-step methanol-water process that enhanced the product yield significantly. The reaction pathway involves xylose isomerization to xylulose, which, in part, subsequently reacts with methanol to form methyl xyluloside (step 1) followed by hydrolysis after water addition to form additional xylulose (step 2). NMR spectroscopy studies performed with (13) C-labeled xylose confirmed the proposed reaction pathway. The most active catalyst examined was zeolite Y, which proved more active than zeolite beta, ZSM-5, and mordenite. The yield of xylulose obtained over H-USY (Si/Al=6) after 1 h of reaction at 100 °C was 39%. After water hydrolysis in the second reaction step, the yield increased to 47%. Results obtained from pyridine adsorption studies confirm that H-USY (6) is a catalyst that combines Brønsted and Lewis acid sites, and isomerizes xylose in alcohol media to form xylulose at low temperature. The applied zeolites are commercially available; do not contain any auxiliary tetravalent metals, for example, tin, titanium, or zirconium; isomerize xylose efficiently; are easy to regenerate; and are prone to recycling.

  4. Xylose isomerization with zeolites in a two-step alcohol-water process.

    PubMed

    Paniagua, Marta; Saravanamurugan, Shunmugavel; Melian-Rodriguez, Mayra; Melero, Juan A; Riisager, Anders

    2015-03-01

    Isomerization of xylose to xylulose was efficiently catalyzed by large-pore zeolites in a two-step methanol-water process that enhanced the product yield significantly. The reaction pathway involves xylose isomerization to xylulose, which, in part, subsequently reacts with methanol to form methyl xyluloside (step 1) followed by hydrolysis after water addition to form additional xylulose (step 2). NMR spectroscopy studies performed with (13) C-labeled xylose confirmed the proposed reaction pathway. The most active catalyst examined was zeolite Y, which proved more active than zeolite beta, ZSM-5, and mordenite. The yield of xylulose obtained over H-USY (Si/Al=6) after 1 h of reaction at 100 °C was 39%. After water hydrolysis in the second reaction step, the yield increased to 47%. Results obtained from pyridine adsorption studies confirm that H-USY (6) is a catalyst that combines Brønsted and Lewis acid sites, and isomerizes xylose in alcohol media to form xylulose at low temperature. The applied zeolites are commercially available; do not contain any auxiliary tetravalent metals, for example, tin, titanium, or zirconium; isomerize xylose efficiently; are easy to regenerate; and are prone to recycling. PMID:25703506

  5. Discovery of optimal zeolites for challenging separations and chemical conversions through predictive materials modeling

    NASA Astrophysics Data System (ADS)

    Siepmann, J. Ilja; Bai, Peng; Tsapatsis, Michael; Knight, Chris; Deem, Michael W.

    2015-03-01

    Zeolites play numerous important roles in modern petroleum refineries and have the potential to advance the production of fuels and chemical feedstocks from renewable resources. The performance of a zeolite as separation medium and catalyst depends on its framework structure and the type or location of active sites. To date, 213 framework types have been synthesized and >330000 thermodynamically accessible zeolite structures have been predicted. Hence, identification of optimal zeolites for a given application from the large pool of candidate structures is attractive for accelerating the pace of materials discovery. Here we identify, through a large-scale, multi-step computational screening process, promising zeolite structures for two energy-related applications: the purification of ethanol beyond the ethanol/water azeotropic concentration in a single separation step from fermentation broths and the hydroisomerization of alkanes with 18-30 carbon atoms encountered in petroleum refining. These results demonstrate that predictive modeling and data-driven science can now be applied to solve some of the most challenging separation problems involving highly non-ideal mixtures and highly articulated compounds. Financial support from the Department of Energy Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Award DE-FG02-12ER16362 is gratefully acknowledged.

  6. Sulfonated hierarchical H-USY zeolite for efficient hydrolysis of hemicellulose/cellulose.

    PubMed

    Zhou, Lipeng; Liu, Zhen; Shi, Meiting; Du, Shanshan; Su, Yunlai; Yang, Xiaomei; Xu, Jie

    2013-10-15

    Sulfonated hierarchical H-USY zeolite was prepared and characterized by X-ray diffraction, N2 physisorption, Fourier transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, temperature-programmed desorption of ammonia, and acid-base titration. It was proved that sulfonic group was successfully anchored onto the hierarchical H-USY zeolite. The acidity of the hierarchical H-USY was remarkably improved. Sulfonated hierarchical H-USY zeolite was efficient for the hydrolysis of hemicellulose and cellulose. The yield of TRS for hydrolysis of hemicellulose reached 78.0% at 140 °C for 9h. For hydrolysis of α-cellulose, 60.8% conversion with 22.4% yield of glucose was obtained. Even for microcrystalline cellulose, 43.7% conversion with 15.1% yield of glucose can be obtained. These results are much higher than those obtained over hierarchical H-USY zeolite, indicating that both the acidity and the pore structure determine the activity of zeolite as catalyst in the hydrolysis of biomass. PMID:23987328

  7. Bubbling Reactor Technology for Rapid Synthesis of Uniform, Small MFI-Type Zeolite Crystals

    SciTech Connect

    Liu, Wei; Rao, Yuxiang; Wan, Haiying; Karkamkar, Abhijeet J.; Liu, Jun; Wang, Li Q.

    2011-06-27

    MFI-type zeolite is an important family of materials used in today’s industries as catalysts and adsorbents. Preparation of this type of zeolite material as uniform and pure crystals of sizes from tens of nanometer to hundreds of nanometer are not only desired by current catalytic and adsorption processes for enhanced reaction kinetics and/or selectivity, but also much needed by some new applications, such as CO2 capture adsorbents and composite materials. However, it has been a major challenge in the zeolite synthesis field to prepare small crystals of MFI-type zeolite over a range of Si/Al ratio with very high throughput. In this work, a gas-bubbling flow reactor is used to conduct hydrothermal growth of the zeolite crystals with controllable Si/Al ratio and crystal sizes. Distinctive, uniform ZSM-5 crystals are successfully synthesized within two hours of reaction time, exceptionally short compared to the conventional synthesis process. The crystals are small enough to form a stable milk-like suspension in water. The Si/Al ratio can be controlled by adjusting the growth solution composition and reaction conditions over a range from about 9 to infinity. Characterization by SEM/EDS, XRD, TEM, N2 adsorption/desorption, and NMR confirms ZSM-5 crystal structures and reveals presence of meso-porosity in the resulting crystals.

  8. The effect of alkali metal on the surface properties of potassium doped Au-Beta zeolites

    SciTech Connect

    Sobczak, Izabela; Rydz, Michal; Ziolek, Maria

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► Interaction of gold with K leads to the change of electronic state and redox properties of gold. ► The amount of potassium incorporated into Au-zeolites determines the size of gold particles. ► K(0.2 wt.%)/Au-Beta exhibits the best performance in decomposition of N{sub 2}O and removal of Bu{sub 2}S. -- Abstract: Beta zeolite was applied as support for gold introduced by gold-precipitation method and potassium added by impregnation or adsorption. The effect of zeolite composition and the amount of potassium introduced on the surface properties of the final materials was considered. Moreover, the interaction of gold and potassium species was found to be related to the adsorptive and catalytic behaviour of zeolites in NO reduction with propene and deodorization. K/Au-Beta(Impregnated) exhibits the best performance in the above mentioned processes because of the small gold particles (between 2 and 5 nm) and interaction of gold with potassium species leading to the change of electronic properties of the surface (the appearance of cationic gold species). Potassium added as a promoter improves the catalytic properties of Au-zeolite in N{sub 2}O decomposition and also in deodorization (increase of the ability to dibutyl sulphide oxidation). The catalysts prepared were characterized by XRD, XPS, UV–vis, TEM, pyridine adsorption combined with FTIR and test reaction (2-propanol transformation).

  9. Enhanced Activity of Nanocrystalline Zeolites for Selective Catalytic Reduction of NOx

    SciTech Connect

    Sarah C. Larson; Vicki H. Grassian

    2006-12-31

    Nanocrystalline zeolites with discrete crystal sizes of less than 100 nm have different properties relative to zeolites with larger crystal sizes. Nanocrystalline zeolites have improved mass transfer properties and very large internal and external surface areas that can be exploited for many different applications. The additional external surface active sites and the improved mass transfer properties of nanocrystalline zeolites offer significant advantages for selective catalytic reduction (SCR) catalysis with ammonia as a reductant in coal-fired power plants relative to current zeolite based SCR catalysts. Nanocrystalline NaY was synthesized with a crystal size of 15-20 nm and was thoroughly characterized using x-ray diffraction, electron paramagnetic resonance spectroscopy, nitrogen adsorption isotherms and Fourier Transform Infrared (FT-IR) spectroscopy. Copper ions were exchanged into nanocrystalline NaY to increase the catalytic activity. The reactions of nitrogen dioxides (NO{sub x}) and ammonia (NH{sub 3}) on nanocrystalline NaY and CuY were investigated using FT-IR spectroscopy. Significant conversion of NO{sub 2} was observed at room temperature in the presence of NH{sub 3} as monitored by FT-IR spectroscopy. Copper-exchanged nanocrystalline NaY was more active for NO{sub 2} reduction with NH{sub 3} relative to nanocrystalline NaY.

  10. Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature.

    PubMed

    Narsimhan, Karthik; Iyoki, Kenta; Dinh, Kimberly; Román-Leshkov, Yuriy

    2016-06-22

    The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C-H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483-498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions. PMID:27413787

  11. Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature

    PubMed Central

    2016-01-01

    The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C–H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483–498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions. PMID:27413787

  12. Simultaneous SO{sub 2}/NO{sub x} abatement using zeolite-supported copper. Progress report, April 1--June 30, 1995

    SciTech Connect

    Mitchell, M.B.; White, M.G.

    1995-12-31

    Several catalysts for NO decomposition have been reported in the literature to include the following: Cu/ZSM-5; Cu/Zeolite-Y; Cu/mordenite; Cu/{beta} zeolite; Cu/alumina; and Cu/silica which have been studied less than Cu/ZSM-5. The catalytic properties for NO conversion are found to be different on these samples with the ZSM-5 supported catalysts showing the highest activity in a dry environment free from sulfur oxides. One of the goals of this study is to have a better fundamental understanding on the different roles of Cu and the support in the catalytic reaction. The authors use stable, cationic metal complexes in non-aqueous solvents as sources of the Cu ions in producing model catalysts for which the fate of the source molecule is known and is controlled during the ion exchange/impregnation. Molecular models of these systems can be used to identify the possible configurations of the metal complexes within the zeolite support. The authors compare the performance of the model catalysts to one prepared by aqueous impregnation of ZSM-5 zeolite. The performance of the dinuclear metal complex on silica is compared to the same complex in ZSM-5 and Y-zeolites.

  13. Thermal Durability of Cu-CHA NH3-SCR Catalysts for Diesel NOx Reduction

    SciTech Connect

    Schmieg, Steven J.; Oh, Se H.; Kim, Chang H.; Brown, David B.; Lee, Jong H.; Peden, Charles HF; Kim, Do Heui

    2012-04-30

    Multiple catalytic functions (NOx conversion, NO and NH3 oxidation, NH3 storage) of a commercial Cu-zeolite urea/NH3-SCR catalyst were assessed in a laboratory fixed-bed flow reactor system after differing degrees of hydrothermal aging. Catalysts were characterized by using x-ray diffraction (XRD), 27Al solid state nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM) / energy dispersive X-ray (EDX) spectroscopy to develop an understanding of the degradation mechanisms during catalyst aging. The catalytic reaction measurements of laboratory-aged catalysts were performed, which allows us to obtain a universal curve for predicting the degree of catalyst performance deterioration as a function of time at each aging temperature. Results show that as the aging temperature becomes higher, the zeolite structure collapses in a shorter period of time after an induction period. The decrease in SCR performance was explained by zeolite structure destruction and/or Cu agglomeration, as detected by XRD/27Al NMR and by TEM/EDX, respectively. Destruction of the zeolite structure and agglomeration of the active phase also results in a decrease in the NO/NH3 oxidation activity and the NH3 storage capacity of the catalyst. Selected laboratory aging conditions (16 h at 800oC) compare well with a 135,000 mile vehicle-aged catalyst for both performance and characterization criteria.

  14. Lewis Acid Zeolites for Biomass Conversion: Perspectives and Challenges on Reactivity, Synthesis, and Stability.

    PubMed

    Luo, Helen Y; Lewis, Jennifer D; Román-Leshkov, Yuriy

    2016-06-01

    Zeolites containing Sn, Ti, Zr, Hf, Nb, or Ta heteroatoms are versatile catalysts for the activation and conversion of oxygenated molecules owing to the unique Lewis acid character of their tetrahedral metal sites. Through fluoride-mediated synthesis, hydrophobic Lewis acid zeolites can behave as water-tolerant catalysts, which has resulted in a recent surge of experimental and computational studies in the field of biomass conversion. However, many open questions still surround these materials, especially relating to the nature of their active sites. This lack of fundamental understanding is exemplified by the many dissonant results that have been described in recent literature reports. In this review, we use a molecular-based approach to provide insight into the relationship between the structure of the metal center and its reactivity toward different substrates, with the ultimate goal of providing a robust framework to understand the properties that have the strongest influence on catalytic performance for the conversion of oxygenates. PMID:27146555

  15. Selection of new catalysts for single-stage hydrogenation of phenol to cyclohexanone

    SciTech Connect

    Areshidze, K.I.; Chivadze, G.O.; Tsereteli, B.S.

    1983-03-10

    Catalysts studied for the single-stage hydrogenation of phenol to cyclohexanone were palladium deposited on a native zeolite and Cu and Ni on a native aluminosilicate. The catalyst samples were investigated by x-ray photoelectron spectroscopy. The mixed Cu and Ni catalyst on the aluminosilicate modified with 3% KOH solution and containing 6% Cu and 2% Ni was found to be most selective for the hydrogenation of phenol. 1 figure, 3 tables.

  16. Hydrogen Selective Exfoliated Zeolite Membranes

    SciTech Connect

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

    2015-04-06

    The objective of this project was to develop and evaluate an innovative membrane technology at process conditions that would be representative of Integrated Gasification Combined Cycle (IGCC) advanced power generation with pre-combustion capture of carbon dioxide (CO2). This research focused on hydrogen (H2)-selective zeolite membranes that could be utilized to separate conditioned syngas into H2-rich and CO2-rich components. Both experiments and process design and optimization calculations were performed to evaluate the concept of ultra-thin membranes made from zeolites nanosheets. In this work, efforts in the laboratory were made to tackle two fundamental challenges in application of zeolite membranes in harsh industrial environments, namely, membrane thickness and membrane stability. Conventional zeolite membranes have thicknesses in the micron range, limiting their performance. In this research, we developed a method for fabrication of ultimately thin zeolite membranes based on zeolite nanosheets. A range of layered zeolites (MWW, RWR, NSI structure types) suitable for hydrogen separation was successfully exfoliated to their constituent nanosheets. Further, membranes were made from one of these zeolites, MWW, to demonstrate the potential of this group of materials. Moreover, long-term steam stability of these zeolites (up to 6 months) was investigated in high concentrations of steam (35 mol% and 95 mole%), high pressure (10 barg), and high temperatures (350 °C and 600 °C) relevant to conditions of water-gas-shift and steam methane reforming reactions. It was found that certain nanosheets are stable, and that stability depends on the concentration of structural defects. Additionally, models that represent a water-gas-shift (WGS) membrane reactor equipped with the zeolite membrane were developed for systems studies. These studies had the aim of analyzing the effect of the membrane reactor integration into IGCC plants

  17. Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons.

    PubMed

    Zečević, Jovana; Vanbutsele, Gina; de Jong, Krijn P; Martens, Johan A

    2015-12-10

    The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts. Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called intimacy criterion has dictated the maximum distance between the two types of site, beyond which catalytic activity decreases. A lack of synthesis and material-characterization methods with nanometre precision has long prevented in-depth exploration of the intimacy criterion, which has often been interpreted simply as 'the closer the better' for positioning metal and acid sites. Here we show for a bifunctional catalyst--comprising an intimate mixture of zeolite Y and alumina binder, and with platinum metal controllably deposited on either the zeolite or the binder--that closest proximity between metal and zeolite acid sites can be detrimental. Specifically, the selectivity when cracking large hydrocarbon feedstock molecules for high-quality diesel production is optimized with the catalyst that contains platinum on the binder, that is, with a nanoscale rather than closest intimacy of the metal and acid sites. Thus, cracking of the large and complex hydrocarbon molecules that are typically derived from alternative sources, such as gas-to-liquid technology, vegetable oil or algal oil, should benefit especially from bifunctional catalysts that avoid locating platinum on the zeolite (the traditionally assumed optimal location). More generally, we anticipate that the ability demonstrated here to spatially organize different active sites at the nanoscale will benefit the further development and optimization of the emerging generation of multifunctional catalysts.

  18. Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons

    PubMed Central

    Zečević, Jovana; Vanbutsele, Gina; de Jong, Krijn P.; Martens, Johan A.

    2016-01-01

    The ability to precisely control nanoscale features is increasingly exploited to develop and improve monofunctional catalysts1–4. Striking effects might also be expected in the case of bifunctional catalysts, which play an important role in hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel5–7. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called ‘intimacy criterion’8 has dictated the maximum distance between the two site types beyond which catalytic activity decreases. The lack of synthesis and material characterization methods with nanometer precision has long prevented in-depth exploration of the criterion, which has often been interpreted simply as ‘the closer the better’ for positioning metal and acid sites8–11. Here we show for a bifunctional catalyst, comprised of an intimate mixture of zeolite Y and alumina binder and with platinum (Pt) metal controllably deposited20,21 on either the zeolite or the binder, that close proximity between metal and zeolite acid sites can be detrimental: the selectivity when cracking large hydrocarbon feedstock molecules for high-quality diesel production is optimized with the catalyst that contains Pt on the binder, i.e. with a larger distance between metal and acid sites. Cracking of the large and complex hydrocarbon molecules typically derived from alternative sources such as gas-to-liquid technology, vegetable oil or algal oil6–7 should thus benefit especially from bifunctional catalysts that avoid locating Pt on the zeolite as the traditionally assumed optimal location. More generally, we anticipate that the ability to spatially organize different active sites at the nanoscale demonstrated here will benefit the further development and optimization of the newly emerging generation of multifunctional catalysts12–15. PMID:26659185

  19. UTILITY OF ZEOLITES IN HAZARDOUS METAL REMOVAL FROM WATER

    EPA Science Inventory

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

  20. Tailored zeolites for the removal of metal oxyanions: overcoming intrinsic limitations of zeolites.

    PubMed

    Figueiredo, Hugo; Quintelas, Cristina

    2014-06-15

    This review aims to present a global view of the efforts conducted to convert zeolites into efficient supports for the removal of heavy metal oxyanions. Despite lacking affinity for these species, due to inherent charge repulsion between zeolite framework and anionic species, zeolites have still received considerable attention from the scientific community, since their versatility allowed tailoring them to answer specific requirements. Different processes for the removal and recovery of toxic metals based on zeolites have been presented. These processes resort to modification of the zeolite surface to allow direct adsorption of oxyanions, or by combination with reducing agents for oxyanions that allow ion-exchange with the converted species by the zeolite itself. In order to testify zeolite versatility, as well as covering the wide array of physicochemical constraints that oxyanions offer, chromium and arsenic oxyanions were selected as model compounds for a review of treatment/remediation strategies, based on zeolite modification.

  1. Uniform Catalytic Site in Sn-beta Zeolite Determined using X-ray Absorption Fine Structure

    SciTech Connect

    Bare,S.; Kelly, S.; Sinkler, W.; Low, J.; Modica, F.; Valencia, S.; Corma, A.; Nemeth, L.

    2005-01-01

    The Sn silicate zeolite, Sn-{beta}, has been shown to be an efficient, selective heterogeneous catalyst for Baeyer-Villiger oxidations. Using primarily a multishell fit to extended X-ray absorption fine structure (EXAFS) data, we show that the Sn does not randomly insert into the {beta}-zeolite structure but rather occupies identical, specific, crystallographic sites. These sites are the T5/T6 sites in the six-membered rings. Moreover, the Sn is substituted in pairs on opposite sides of these six-membered rings. We believe that it is the specific, uniform crystallographic location of the Sn in the crystal structure that leads to sites with uniform catalytic activity, and consequently to the high chemical selectivity demonstrated for this catalyst. This manifests itself in the almost enzyme-like selectivity of this catalyst in Baeyer-Villiger oxidations. This uniform site distribution of the Sn suggests that there is likely a symbiotic relationship between the structure-directing agent in the zeolite synthesis and the Sn heteroatoms during the framework formation.

  2. Ag-Promoted ZrBEA Zeolites Obtained by Post-Synthetic Modification for Conversion of Ethanol to Butadiene.

    PubMed

    Sushkevich, Vitaly L; Ivanova, Irina I

    2016-08-23

    1,3-Butadiene was synthesized from ethanol using zirconium-containing zeolite beta (ZrBEA) catalysts doped with 1 wt % silver. The Zr was planted using post-synthesis modification by dealumination of the parent zeolite followed by treatment with ZrOCl2 in a DMSO solution. FTIR and NMR spectroscopy were used to investigate the planting process by preparing materials with different Si/Al ratios and crystal sizes. The results showed preferential grafting of Zr to the terminal silanols present on the external surface of the zeolite crystals instead of incorporation of Zr into silanol nests. The grafting yielded highly accessible Zr(OSi)3 OH open sites with high Lewis acidity, as confirmed by FTIR spectroscopy of adsorbed CO. These sites are shown to be extremely active for the conversion of ethanol to butadiene. Ag/ZrBEA catalysts prepared using the post-synthesis method showed significant advantages compared with Ag/ZrBEA catalysts synthesized using a conventional hydrothermal procedure. The best catalyst performance in terms of butadiene formation rate (3 μmol g(-1)  s(-1) ) was observed over Ag/Zr(3.5)BEA(75) (containing 3.5 wt % Zr), which had the smallest crystal size and the highest content of Zr open sites of the prepared catalysts. PMID:27467567

  3. Effect of preparation methods on the catalytic properties of zeolite-supported ruthenium in the Fischer-Tropsch synthesis

    SciTech Connect

    Chen, Y.W.; Wang, H.T.; Goodwin, J.G. Jr.

    1983-10-01

    Three preparation techniques (incipient wetness using a solution of ruthenium chloride (RuCl/sub 3/), vapor impregnation by the ruthenium carbonyl (Ru/sub 3/(CO)/sub 12/), and ion exchange with Ru(NH/sub 3/)/sub 6/Cl/sub 3/) have been used to prepare sodium (Na)Y zeolite-supported ruthenium catalysts. The effect of these preparation methods on the activity and product selectivity of the Ru catalysts in the Fischer-Tropsch synthesis was examined at temperatures in the range of 220 to 320/sup 0/C, a pressure of 1 atm, a CO/H/sub 2/ ratio of 1, and flow rates in the range GHSV = 1800 to 3600 h/sup -1/. It was found that there is a good inverse correlation of turnover numbers for CO conversion to the CO/H adsorption ratio, suggesting that the relative availability of adsorbed H/sub 2/ and CO determines catalyst activity during reaction. Selectivity in the Fischer-Tropsch synthesis was greatly influenced by the preparation method and metal loading. Catalysts prepared by incipient wetness produced mainly methane. Catalysts prepared by vapor impregnation had the best selectivities for higher hydrocarbons and olefins even though they had the smallest average Ru particle sizes. The observed changes in adsorption, activity, and selectivity with preparation method appear to result from differences produced in metal location in/on the zeolite, metal particle size, and zeolite-metal interactions. 12 figures, 2 tables.

  4. New Claus and FCC catalyst production capacity on line

    SciTech Connect

    Not Available

    1983-07-01

    Two new, major catalyst manufacturing plants have recently gone into commercial operation in the U.S. In Louisiana, Aluminum Co. of America (Alcoa) last month put an activated alumina plant in production at Vidalia, La., on the Mississippi River near Natchez, Miss. Activated alumina after processing serves as, among other things, the catalyst in Claus sulfur recovery plants. In Georgia, Katalistiks International Inc. put its fluid catalytic cracking catalyst plant on stream in June, with an expected output of 60,000/80,000 tons/year of FFC catalyst. Alcoa says its Vidalia plant will have the capacity to make 20 million lb/year of either Claus catalyst or adsorbants, catalyst substrates, or combinations of such products. Management says it hopes to develop the catalyst plant's processing flexibility to make products for special and new applications. For the moment, the Vidalia plant will not make zeolites for fluid catalytic catalyst manufacturing though it has that capability. However, production of combinations of mixtures of alumina and zeolites is planned.

  5. Mesoporous MFI zeolites by microwave induced assembly between sulfonic acid functionalized MFI zeolite nanoparticles and alkyltrimethylammonium cationic surfactants.

    PubMed

    Jin, Hailian; Ansari, Mohd Bismillah; Park, Sang-Eon

    2011-07-14

    Mesoporous MFI zeolites (ZSM-5, TS-1, S-1) having intracrystalline mesoporosity within zeolite crystals were synthesized by microwave induced assembly through the ionic interaction between the sulfonic acid functionalized MFI zeolite nanoparticles and alkyltrimethylammonium cationic surfactants.

  6. Efficient photocatalytic degradation of organics present in gas and liquid phases using Pt-TiO2/Zeolite (H-ZSM).

    PubMed

    Neppolian, B; Mine, Shinya; Horiuchi, Yu; Bianchi, C L; Matsuoka, M; Dionysiou, D D; Anpo, M

    2016-06-01

    TiO2-encapsulated H-ZSM photocatalysts were prepared by physical mixing of TiO2 and zeolites. Pt was immobilized on the surface of the TiO2-encapsulated zeolite (H-ZSM) catalysts by a simple photochemical reduction method. Different weight ratios of both TiO2 and Pt were hybridized with H-ZSM and the catalytic performance of the prepared catalysts was investigated for 2-propanol oxidation in liquid phase and acetaldehyde in gas phase reaction. Around 5-10 wt% TiO2-encapsulated H-ZSM catalysts was found to be optimal amount for the effective oxidation of the organics. Prior to light irradiation, Pt-TiO2-H-ZSM showed considerable amount of catalytic degradation of 2-propanol in the dark, forming acetone as an intermediate. In this study, Pt has played a major and important role on the total oxidation of 2-propanol as well as acetaldehyde. As a result, no residual organics were present in the pores of the zeolites. The catalysts could be reused more than three times without losing their catalytic activity in both phases. The Pt-TiO2-H-ZSM photocatalysts could overcome the problem of strong adsorption of organics in the zeolite pores (after the reaction). Thus, Pt-TiO2-H-ZSM can be used as a potential catalyst for both liquid and gas phase oxidation of organic pollutants.

  7. Method for regeneration and activity improvement of syngas conversion catalyst

    DOEpatents

    Lucki, Stanley J.; Brennan, James A.

    1980-01-01

    A method is disclosed for the treatment of single particle iron-containing syngas (synthes.s gas) conversion catalysts comprising iron, a crystalline acidic aluminosilicate zeolite having a silica to alumina ratio of at least 12, a pore size greater than about 5 Angstrom units and a constraint index of about 1-12 and a matrix. The catalyst does not contain promoters and the treatment is applicable to either the regeneration of said spent single particle iron-containing catalyst or for the initial activation of fresh catalyst. The treatment involves air oxidation, hydrogen reduction, followed by a second air oxidation and contact of the iron-containing single particle catalyst with syngas prior to its use for the catalytic conversion of said syngas. The single particle iron-containing catalysts are prepared from a water insoluble organic iron compound.

  8. Conversion of straight-run gas-condensate benzenes into high- octane gasolines based on modified ZSM-5 zeolites

    NASA Astrophysics Data System (ADS)

    Erofeev, V.; Reschetilowski, V.; Tatarkina, A.; Khomajakov, I.; Egorova, L.; Volgina, T.

    2014-08-01

    This paper describes the conversion of straight-run benzene of gas condensate into high-octane gasoline based on zeolite catalyst ZSM-5, modified in binary system oxide- based Sn (III) and Bi (III). It was defined that the introduction of the binary system oxide-based Sn(III) and Bi (III) into the basic zeolite results in the 2-fold increase of its catalytic activity.High-octane gasoline converted from straight-run benzene is characterized by a low benzol content in comparison to the high-octane benzenes produced during the catalytic reforming.

  9. Propene poisoning on three typical Fe-zeolites for SCR of NOχ with NH₃: from mechanism study to coating modified architecture.

    PubMed

    Ma, Lei; Li, Junhua; Cheng, Yisun; Lambert, Christine K; Fu, Lixin

    2012-02-01

    Application of Fe-zeolites for urea-SCR of NO(x) in diesel engine is limited by catalyst deactivation with hydrocarbons (HCs). In this work, a series of Fe-zeolite catalysts (Fe-MOR, Fe-ZSM-5, and Fe-BEA) was prepared by ion exchange method, and their catalytic activity with or without propene for selective catalytic reduction of NO(x) with ammonia (NH(3)-SCR) was investigated. Results showed that these Fe-zeolites were relatively active without propene in the test temperature range (150-550 °C); however, all of the catalytic activity was suppressed in the presence of propene. Fe-MOR kept relatively higher activity with almost 80% NO(x) conversion even after propene coking at 350 °C, and 38% for Fe-BEA and 24% for Fe-ZSM-5 at 350 °C, respectively. It was found that the pore structures of Fe-zeolite catalysts were one of the main factors for coke formation. As compared to ZSM-5 and HBEA, MOR zeolite has a one-dimensional structure for propene diffusion, relatively lower acidity, and is not susceptible to deactivation. Nitrogenated organic compounds (e.g., isocyanate) were observed on the Fe-zeolite catalyst surface. The site blockage was mainly on Fe(3+) sites, on which NO was activated and oxidized. Furthermore, a novel fully formulated Fe-BEA monolith catalyst coating modified with MOR was designed and tested, the deactivation due to propene poisoning was clearly reduced, and the NO(x) conversion reached 90% after 700 ppm C(3)H(6) exposure at 500 °C.

  10. 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.

  11. Increased thermal conductivity monolithic zeolite structures

    DOEpatents

    Klett, James; Klett, Lynn; Kaufman, Jonathan

    2008-11-25

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

  12. NO.sub.x catalyst and method of suppressing sulfate formation in an exhaust purification system

    DOEpatents

    Balmer-Millar, Mari Lou; Park, Paul W.; Panov, Alexander G.

    2007-06-26

    The activity and durability of a zeolite lean-burn NOx catalyst can be increased by loading metal cations on the outer surface of the zeolite. However, the metal loadings can also oxidize sulfur dioxide to cause sulfate formation in the exhaust. The present invention is a method of suppressing sulfate formation in an exhaust purification system including a NO.sub.x catalyst. The NO.sub.x catalyst includes a zeolite loaded with at least one metal. The metal is selected from among an alkali metal, an alkaline earth metal, a lanthanide metal, a noble metal, and a transition metal. In order to suppress sulfate formation, at least a portion of the loaded metal is complexed with at least one of sulfate, phosphate, and carbonate.

  13. NO.sub.x catalyst and method of suppressing sulfate formation in an exhaust purification system

    DOEpatents

    Balmer-Millar, Mari Lou; Park, Paul W.; Panov, Alexander G.

    2006-08-22

    The activity and durability of a zeolite lean-bum NOx catalyst can be increased by loading metal cations on the outer surface of the zeolite. However, the metal loadings can also oxidize sulfur dioxide to cause sulfate formation in the exhaust. The present invention is a method of suppressing sulfate formation in an exhaust purification system including a NO.sub.x catalyst. The NO.sub.x catalyst includes a zeolite loaded with at least one metal. The metal is selected from among an alkali metal, an alkaline earth metal, a lanthanide metal, a noble metal, and a transition metal. In order to suppress sulfate formation, at least a portion of the loaded metal is complexed with at least one of sulfate, phosphate, and carbonate.

  14. Conversion of synthesis gas with iron-containing catalyst

    SciTech Connect

    Butter, S.A.; Chester, A.W.

    1981-03-10

    A method is disclosed for the conversion of synthesis gas to a liquid hydrocarbon product having a boiling range of less than 400* F. at a 90% overhead utilizing a novel catalyst prepared from a water-insoluble organic iron compound. The novel method involves contacting synthesis gas with a single particle catalyst containing iron, a crystalline acidic aluminosilicate zeolite having a silica-to-alumina ratio of at least 12, a pore size greater than about 5 angstrom units, and a constraint index of about 1 to 12, and a matrix. The catalyst does not contain promoters.

  15. Sulfuric acid dissolution of 4A and Na-Y synthetic zeolites and effects on Na-Y surface and particle properties

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoyu; Wang, Kunping; Plackowski, Chris A.; Nguyen, Anh V.

    2016-03-01

    Sodium rich synthetic zeolites 4A and Na-Y have different silicon-to-aluminium (Si/Al) ratios and are widely used as molecular sieves, catalysts and adsorbents. This study investigates the changes in 4A and Na-Y synthetic zeolites treated by H2SO4 at room temperature. Both zeolite types are examined before and after treatment by following the dissolution and re-crystallisation processes, and Na-Y by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and particle size analysis. Na-Y zeolite (high Si/Al ratio) has stronger acid-resistivity than 4A zeolite (low Si/Al ratio) and can be treated with H2SO4 up to 5 M without complete dissolution, whereas 4A zeolite is completely dissolved by 0.5 M acid. For both zeolites, the treatment generates dissolution (of both Si and Al) of first order fast kinetics, followed by re-crystallization. XRD studies of Na-Y zeolite indicate that acid treatment leads to structural changes where cations are removed and as dissolution progresses de-alumination takes place, thereby altering the main tetrahedral structure. XPS analysis shows the Si/Al atomic ratio for Na-Y zeolite increases from 2.94 at 0 M to 8.18 at 0.1 M, and a significant binding energy (BE) shift of Si and O occurs even at a high Si/Al ratio. The acid treatment increases the surface intermediate electronegativity of Na-Y zeolite, and the BE of each main structural element changes in the same way as the electronegativity ratio (element electronegativity to total surface electronegativity) as the acid concentration increases. Particle size analysis indicates that a recrystallization process occurs during acid treatment, as shown by a shift of the coarse particle distribution peak size to progressively smaller sizes with increasing acid concentration.

  16. Structural and catalytic properties of zeolite EMT containing NiMo sulfide

    SciTech Connect

    Becue, T.; Manoli, J.M.; Potvin, C.; Leglise, J.; Cornet, D.

    1998-10-01

    This work examines bifunctional catalysts made of an acidic EMT zeolite into which Ni and Mo ions were introduced, and then sulfided. Their structure and catalytic properties were compared to those of analogous NiMo/HY. Ni and Mo were loaded onto the HEMT by wet treatment, and the solids were characterized in the calcined and sulfided state by means of XRD, porosimetry, and TEM coupled with EDX analysis. When the oxidic NiMo/EMT was sulfided, the zeolite crystals fractured in a few planar directions, and the fissures appeared to be filled with MoS{sub 2} particles promoted with Ni. This is very different to the HY zeolite in which the sulfide slabs were scattered into the mesopores. With both supports, however, about half of the NiMo is present outside the zeolite as incompletely sulfided particles. The catalytic properties of the sulfided NiMo/EMT were examined by measuring the conversion of an n-heptane and benzene mixture in a flow reactor under 8 MPa hydrogen pressure. With the EMT as well as with the HY support, the rate of benzene hydrogenation varied in accordance with the amount of internal Mo. The intrinsic activity of the internal Mo matched that of a commercial NiMo/Al{sub 2}O{sub 3}. The NiMo/zeolites exhibited high activity for the conversion of heptane, but the cracked products exceeded by far the heptane isomers. Differences in selectivity between EMT and HY catalysts are interpreted on the basis of the balance between acidic and hydrogenation functions.

  17. Conversion of methyl halides to hydrocarbons on basic zeolites. A discovery by in situ NMR

    SciTech Connect

    Murray, D.K.; Chang, J.W.; Haw, J.F. )

    1993-06-02

    It is shown that methyl halides (I, Br, Cl) react to form ethylene and other hydrocarbons on basic, alkali metal-exchanged zeolites at low temperatures. For example, methyl iodide is converted to ethylene on CsX zeolite at ca. 500 K. The order of reactivity of various catalyst/adsorbate combinations is consistent with the predictions of elementary chemical principles. The order of reactivity of the methyl halides follows the expected leaving-group trend. The activity of the catalyst framework correlates with its basicity (or nucleophilicity). All reactions were performed in a batch mode in sealed magic angle spinning (MAS) rotors while the contents were continuously monitored by in situ [sup 13]C NMR. Methyl iodide reacts on CsX below room temperature to form a framework-bound methoxy species in high yield. An analogous ethoxy species readily formed from ethyliodide. These species were characterized in detail. The ethoxy species was quantitatively converted to ethylene below 500 K. [sup 133]Cs MAS NMR was used to characterize the interactions of methyl iodide and other adsorbates with the cation in zeolite CsZSM-5. Solvation of the alkali metal cation was reflected in large, loading-dependent chemical shifts for [sup 133]Cs. Interactions between the cation and adsorbates were also reflected in the [sup 13]C shifts of the alkyl halides and ethylene. The cumulative evidence suggests a mechanism for carbon-carbon bond formation analogous to one proposed by Chang and co-workers for methanol-to-gasoline chemistry on acidic zeolites (J. Chem. Soc., Chem. Commun, 1987, 1320) that involves framework-bound methoxy and ethoxy species. The mechanism for methyl halide conversion is proposed to include roles for the basicity of the zeolite framework as well as the Lewis acidity of the cation. 68 refs., 18 figs., 2 tabs.

  18. Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons

    NASA Astrophysics Data System (ADS)

    Zecevic, Jovana; Vanbutsele, Gina; de Jong, Krijn P.; Martens, Johan A.

    2015-12-01

    The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts. Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called intimacy criterion has dictated the maximum distance between the two types of site, beyond which catalytic activity decreases. A lack of synthesis and material-characterization methods with nanometre precision has long prevented in-depth exploration of the intimacy criterion, which has often been interpreted simply as ‘the closer the better’ for positioning metal and acid sites. Here we show for a bifunctional catalyst—comprising an intimate mixture of zeolite Y and alumina binder, and with platinum metal controllably deposited on either the zeolite or the binder—that closest proximity between metal and zeolite acid sites can be detrimental. Specifically, the selectivity when cracking large hydrocarbon feedstock molecules for high-quality diesel production is optimized with the catalyst that contains platinum on the binder, that is, with a nanoscale rather than closest intimacy of the metal and acid sites. Thus, cracking of the large and complex hydrocarbon molecules that are typically derived from alternative sources, such as gas-to-liquid technology, vegetable oil or algal oil, should benefit especially from bifunctional catalysts that avoid locating platinum on the zeolite (the traditionally assumed optimal location). More generally, we anticipate that the ability demonstrated here to spatially organize different active sites at the nanoscale will benefit the further development and optimization of the emerging generation of multifunctional catalysts.

  19. Catalyst for cracking of paraffinic feedstocks. [Tetradecane

    SciTech Connect

    Chapman, D.M.

    1993-08-17

    A zeolite catalyst is described for improved hydrocarbon cracking comprising a crystalline aluminosilicate MFI or MEL zeolite in its protic form having a SiO[sub 2]/Al[sub 2]O[sub 3] ratio greater than 5, containing nickel in an amount of from about 0.1 wt % Ni to about 10 wt % of the total weight of the zeolite and having been subjected to severe hydrothermal treatment under controlled conditions of temperature, time or steam partial pressure and at a temperature of at least 500 C so as (a) to effect an increase in the relative surface concentrations of nickel and aluminum in the zeolite; (b) to transform the Ni 2p x-ray photoelectron spectral feature from one with a line shape and binding energy similar to those of NiO to one with a line shape and binding energy similar to those of NiAl[sub 2]O[sub 4]; and (c) to effect in the cracking of tetradecane at 500 C, atmospheric pressure and 55% conversion an n-paraffin selectivity in the C5-C12 fraction of the products which is less than 29 wt. %.

  20. 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

  1. Comparison of real waste (MSW and MPW) pyrolysis in batch reactor over different catalysts. Part II: contaminants, char and pyrolysis oil properties.

    PubMed

    Miskolczi, Norbert; Ateş, Funda; Borsodi, Nikolett

    2013-09-01

    Pyrolysis of real wastes (MPW and MSW) has been investigated at 500°C, 550°C and 600°C using Y-zeolite, β-zeolite, equilibrium FCC, MoO3, Ni-Mo-catalyst, HZSM-5 and Al(OH)3 as catalysts. The viscosity of pyrolysis oils could be decreased by the using of catalysts, especially by β-zeolite and MoO3. Both carbon frame and double bound isomerization was found in case of thermo-catalytic pyrolysis. Char morphology and texture analysis showed more coke deposits on the catalyst surface using MSW raw material. Pyrolysis oils had K, S, P Cl, Ca, Zn, Fe, Cr, Br and Sb as contaminants; and the concentrations of K, S, P, Cl and Br could be decreased by the using of catalysts.

  2. Comparison of real waste (MSW and MPW) pyrolysis in batch reactor over different catalysts. Part II: contaminants, char and pyrolysis oil properties.

    PubMed

    Miskolczi, Norbert; Ateş, Funda; Borsodi, Nikolett

    2013-09-01

    Pyrolysis of real wastes (MPW and MSW) has been investigated at 500°C, 550°C and 600°C using Y-zeolite, β-zeolite, equilibrium FCC, MoO3, Ni-Mo-catalyst, HZSM-5 and Al(OH)3 as catalysts. The viscosity of pyrolysis oils could be decreased by the using of catalysts, especially by β-zeolite and MoO3. Both carbon frame and double bound isomerization was found in case of thermo-catalytic pyrolysis. Char morphology and texture analysis showed more coke deposits on the catalyst surface using MSW raw material. Pyrolysis oils had K, S, P Cl, Ca, Zn, Fe, Cr, Br and Sb as contaminants; and the concentrations of K, S, P, Cl and Br could be decreased by the using of catalysts. PMID:23891947

  3. Nanocrystalline Zeolites: Synthesis, Mechanism, and Applications

    NASA Astrophysics Data System (ADS)

    Severance, Michael Andrew

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

  4. Improved synthesis of isostearic acid using zeolite catalysts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Isostearic acids are unique and important biobased products with superior properties. Unfortunately, they are not widely utilized in industry because they are produced as byproducts from a process called clay-catalyzed oligomerization of tall oil fatty acids. Generally, this clay method results in...

  5. ZnO modified ZSM-5 and Y zeolites fabricated by atomic layer deposition for propane conversion.

    PubMed

    Gong, Ting; Qin, Lijun; Lu, Jian; Feng, Hao

    2016-01-01

    ZnO modified ZSM-5 and Y zeolites are synthesized by performing atomic layer deposition (ALD) of ZnO to HZSM-5 and HY using diethyl zinc and water as the precursors. The surface area and pore volume of ZSM-5 and Y zeolites are progressively reduced with the increasing number of ZnO ALD cycles. XRD and SEM characterization methods show that highly dispersed ZnO species are deposited on the internal and external surfaces of both zeolites. The ZnO species deposited on ZSM-5 are in an amorphous form while nano-crystallites of ZnO are present on Y zeolites after performing ≥2 cycles of ZnO ALD. XPS and TPR characterization methods reveal that isolated Zn(OH)(+) species are predominantly formed on both zeolites after the first cycle of ZnO ALD and the ZnO clusters gradually grow larger with the increasing number of ALD cycles. The type and strength of acid sites on the parent and the ALD ZnO modified zeolites are studied by FTIR spectra of adsorbed pyridine. Incorporation of ZnO into Y zeolite by ALD completely eliminates the Brønsted acid sites and increases the number of strong Lewis acid sites. Similar effects are obtained on ALD ZnO modified ZSM-5 except that the Brønsted acid sites are only partially removed. Catalytic properties of the ALD ZnO modified zeolites are evaluated in propane conversion. Introduction of ZnO species significantly improves the activities of both zeolites. Propylene is the major reaction product on ALD ZnO modified Y zeolite while high selectivities to aromatics are achieved on ALD ZnO modified ZSM-5. These results suggest that ZnO species merely promote the dehydrogenation reaction while the subsequent oligomerization and cyclization reactions require Brønsted acid sites. For both zeolites the catalyst fabricated by only 1 or 2 cycles of ZnO ALD performs better than those fabricated by multiple cycles of ALD, indicating that isolated Zn(OH)(+) species are more effective for the conversion of propane to propylene and aromatics. PMID

  6. ZnO modified ZSM-5 and Y zeolites fabricated by atomic layer deposition for propane conversion.

    PubMed

    Gong, Ting; Qin, Lijun; Lu, Jian; Feng, Hao

    2016-01-01

    ZnO modified ZSM-5 and Y zeolites are synthesized by performing atomic layer deposition (ALD) of ZnO to HZSM-5 and HY using diethyl zinc and water as the precursors. The surface area and pore volume of ZSM-5 and Y zeolites are progressively reduced with the increasing number of ZnO ALD cycles. XRD and SEM characterization methods show that highly dispersed ZnO species are deposited on the internal and external surfaces of both zeolites. The ZnO species deposited on ZSM-5 are in an amorphous form while nano-crystallites of ZnO are present on Y zeolites after performing ≥2 cycles of ZnO ALD. XPS and TPR characterization methods reveal that isolated Zn(OH)(+) species are predominantly formed on both zeolites after the first cycle of ZnO ALD and the ZnO clusters gradually grow larger with the increasing number of ALD cycles. The type and strength of acid sites on the parent and the ALD ZnO modified zeolites are studied by FTIR spectra of adsorbed pyridine. Incorporation of ZnO into Y zeolite by ALD completely eliminates the Brønsted acid sites and increases the number of strong Lewis acid sites. Similar effects are obtained on ALD ZnO modified ZSM-5 except that the Brønsted acid sites are only partially removed. Catalytic properties of the ALD ZnO modified zeolites are evaluated in propane conversion. Introduction of ZnO species significantly improves the activities of both zeolites. Propylene is the major reaction product on ALD ZnO modified Y zeolite while high selectivities to aromatics are achieved on ALD ZnO modified ZSM-5. These results suggest that ZnO species merely promote the dehydrogenation reaction while the subsequent oligomerization and cyclization reactions require Brønsted acid sites. For both zeolites the catalyst fabricated by only 1 or 2 cycles of ZnO ALD performs better than those fabricated by multiple cycles of ALD, indicating that isolated Zn(OH)(+) species are more effective for the conversion of propane to propylene and aromatics.

  7. Effects of catalyst support and chemical vapor deposition condition on synthesis of multi-walled carbon nanocoils

    NASA Astrophysics Data System (ADS)

    Suda, Yoshiyuki; Iida, Tetsuo; Takikawa, Hirofumi; Harigai, Toru; Ue, Hitoshi; Umeda, Yoshito

    2016-02-01

    Multi-walled carbon nanocoil (MWCNC) is a carbon nanotube (CNT) with helical shape. We have synthesized MWCNCs and MWCNTs hybrid by chemical vapor deposition (CVD). MWCNCs are considered to be a potential material in nanodevices, such as electromagnetic wave absorbers and field emitters. It is very important to take into account the purity of MWCNCs. In this study, we aimed to improve the composition ratio of MWCNCs to MWCNTs by changing catalyst preparation and CVD conditions. As a catalyst, Fe2O3/zeolite was prepared by dissolving Fe2O3 fine powder and Y-type zeolite (catalyst support material) in ethanol with an Fe density of 0.5wt.% and with a zeolite density of 3.5wt.%. The catalyst-coated Si substrate was transferred immediately onto a hotplate and was heated at 80°C for 5 min. Similarly, Fe2O3/Al2O3, Co/zeolite/Al2O3, Co/zeolite, and Co/Al2O3 were prepared. The effect of the difference of the composite catalysts on synthesis of MWCNCs was considered. The CVD reactor was heated in a tubular furnace to 660-790°C in a nitrogen atmosphere at a flow rate of 1000 ml/min. Subsequently, acetylene was mixed with nitrogen at a flow rate ratio of C2H2/N2 = 0.02-0.1. The reaction was kept under these conditions for 10 min. MWCNTs and MWCNCs were well grown by the catalysts of Co/zeolite and Co/Al2O3. The composition ratio of MWCNCs to MWCNTs was increased by using a combination of zeolite and Al2O3. The highest composition ratio of MWCNCs to MWCNTs was 12%.

  8. UTILITY OF ZEOLITES IN ARSENIC REMOVAL FROM WATER

    EPA Science Inventory

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

  9. Ship-in-a-bottle catalysts

    DOEpatents

    Haw, James F.; Song, Weiguo

    2006-07-18

    In accordance with the present invention there is provided a novel catalyst system in which the catalytic structure is tailormade at the nanometer scale using the invention's novel ship-in-a-bottle synthesis techniques. The invention describes modified forms of solid catalysts for use in heterogeneous catalysis that have a microporous structure defined by nanocages. Examples include zeolites, SAPOs, and analogous materials that have the controlled pore dimensions and hydrothermal stability required for many industrial processes. The invention provides for modification of these catalysts using reagents that are small enough to pass through the windows used to access the cages. The small reagents are then reacted to form larger molecules in the cages.

  10. Novel Approach for Clustering Zeolite Crystal Structures.

    PubMed

    Lach-Hab, M; Yang, S; Vaisman, I I; Blaisten-Barojas, E

    2010-04-12

    Informatics approaches play an increasingly important role in the design of new materials. In this work we apply unsupervised statistical learning for identifying four framework-type attractors of zeolite crystals in which several of the zeolite framework types are grouped together. Zeolites belonging to these super-classes manifest important topological, chemical and physical similarities. The zeolites form clusters located around four core framework types: LTA, FAU, MFI and the combination of EDI, HEU, LTL and LAU. Clustering is performed in a 9-dimensional space of attributes that reflect topological, chemical and physical properties for each individual zeolite crystalline structure. The implemented machine learning approach relies on hierarchical top-down clustering approach and the expectation maximization method. The model is trained and tested on ten partially independent data sets from the FIZ/NIST Inorganic Crystal Structure Database.

  11. Plasmonic nanostructures to enhance catalytic performance of zeolites under visible light

    PubMed Central

    Zhang, Xingguang; Ke, Xuebin; Du, Aijun; Zhu, Huaiyong

    2014-01-01

    Light absorption efficiency of heterogeneous catalysts has restricted their photocatalytic capability for commercially important organic synthesis. Here, we report a way of harvesting visible light efficiently to boost zeolite catalysis by means of plasmonic gold nanoparticles (Au-NPs) supported on zeolites. Zeolites possess strong Brønsted acids and polarized electric fields created by extra-framework cations. The polarized electric fields can be further intensified by the electric near-field enhancement of Au-NPs, which results from the localized surface plasmon resonance (LSPR) upon visible light irradiation. The acetalization reaction was selected as a showcase performed on MZSM-5 and Au/MZSM-5 (M = H+, Na+, Ca2+, or La3+). The density functional theory (DFT) calculations confirmed that the intensified polarized electric fields played a critical role in stretching the C = O bond of the reactants of benzaldehyde to enlarge their molecular polarities, thus allowing reactants to be activated more efficiently by catalytic centers so as to boost the reaction rates. This discovery should evoke intensive research interest on plasmonic metals and diverse zeolites with an aim to take advantage of sunlight for plasmonic devices, molecular electronics, energy storage, and catalysis. PMID:24448225

  12. Selective catalytic conversion of bio-oil over high-silica zeolites.

    PubMed

    Widayatno, Wahyu Bambang; Guan, Guoqing; Rizkiana, Jenny; Du, Xiao; Hao, Xiaogang; Zhang, Zhonglin; Abudula, Abuliti

    2015-03-01

    Four high silica zeolites, i.e., HSZ-385, 890, 960, and 990 were utilized for the selective catalytic conversion of bio-oil from Fallopia japonica to certain chemicals in a fixed-bed reactor. The Beta-type HSZ-960 zeolite showed the highest selectivity to hydrocarbons, especially to aromatics as well as PAH compounds with the lowest unwanted chemicals while HSZ-890 showed high selectivity to aromatics. NH3-Temperature Programmed Desorption (TPD) analysis indicated that different amounts of acid sites in different zeolites determined the catalytic activity for the oxygen removal from bio-oil, in which the acid sites at low temperature (LT) region gave more contribution within the utilized temperature region. The reusability test of HSZ-960 showed the stability of hydrocarbons yield at higher temperature due to the significant contribution of coke gasification which assisted further deoxygenation of bio-oil. These results provide a guidance to select suitable zeolite catalysts for the upgrading of bio-oil in a practical process. PMID:25576987

  13. Selective catalytic conversion of bio-oil over high-silica zeolites.

    PubMed

    Widayatno, Wahyu Bambang; Guan, Guoqing; Rizkiana, Jenny; Du, Xiao; Hao, Xiaogang; Zhang, Zhonglin; Abudula, Abuliti

    2015-03-01

    Four high silica zeolites, i.e., HSZ-385, 890, 960, and 990 were utilized for the selective catalytic conversion of bio-oil from Fallopia japonica to certain chemicals in a fixed-bed reactor. The Beta-type HSZ-960 zeolite showed the highest selectivity to hydrocarbons, especially to aromatics as well as PAH compounds with the lowest unwanted chemicals while HSZ-890 showed high selectivity to aromatics. NH3-Temperature Programmed Desorption (TPD) analysis indicated that different amounts of acid sites in different zeolites determined the catalytic activity for the oxygen removal from bio-oil, in which the acid sites at low temperature (LT) region gave more contribution within the utilized temperature region. The reusability test of HSZ-960 showed the stability of hydrocarbons yield at higher temperature due to the significant contribution of coke gasification which assisted further deoxygenation of bio-oil. These results provide a guidance to select suitable zeolite catalysts for the upgrading of bio-oil in a practical process.

  14. Coke induced stabilization of catalytic activity of silylated ZSM-5 zeolite

    SciTech Connect

    Bhat, Y.S.; Das, J.; Halgeri, A.B.

    1995-08-01

    One of the ways to synthesize dialkylbenzenes is to alkylate monoalkylbenzene with an alkylating agent such as alcohol or olefin over a Friedel-Crafts or zeolite catalyst. The latter is gaining importance as it is an environmentally friendly system. Dialkylbenzenes like paraxylene, para-ethyltoluene, and para-diethylbenzene are sources for various monomers. Several techniques have been reported in the literature to modify the zeolite characteristics in such a way that the dialkylbenzenes formed during monoalkylbenzene alkylation contain more para isomer. Among these techniques, the chemical vapor deposition of silica (CVD) is drawing the attention of researchers. The silylation results in fine control of pore opening size with the silica deposited on the external surface. The internal structure remains unaffected; only the pore entrance is narrowed. It was observed that the silylated zeolite used for synthesizing para-dialkylbenzene by monoalkylbenzene alkylation deactivates with increased time on stream. This paper deals with the coke-induced stabilization of catalytic activity of ZSM-5 zeolite during alkylation of ethylbenzene with ethanol.

  15. Plasmonic nanostructures to enhance catalytic performance of zeolites under visible light

    NASA Astrophysics Data System (ADS)

    Zhang, Xingguang; Ke, Xuebin; Du, Aijun; Zhu, Huaiyong

    2014-01-01

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

  16. Catalytic conversion of cellulose over mesoporous Y zeolite.

    PubMed

    Park, Young-Kwon; Jun, Bo Ram; Park, Sung Hoon; Jeon, Jong-Ki; Lee, See Hoon; Kim, Seong-Soo; Jeong, Kwang-Eun

    2014-07-01

    Mesoporous Y zeolite (Meso-Y) was applied, for the first time, to the catalytic pyrolysis of cellulose which is a major constituent of lignocellulosic biomass, to produce high-quality bio-oil. A representative mesoporous catalyst Al-MCM-41 was also used to compare its catalytic activity with that of Meso-Y. Pyrolysis-gas chromatography/mass spectrometry was used for the experiments. Meso-Y, with higher acidity, led to larger yields of aromatics and furans with high value-added than Al-MCM-41, resulting in the production of bio-oil with higher quality. The effect of temperature on the catalytic pyrolysis was not significant within the range of 400-500 degrees C. When the Meso-Y to cellulose ratio was increased from 1/1 via 2/1 to 3/1, the deoxygenation efficiency increased, leading to increased yield of aromatics. PMID:24757989

  17. Fischer–Tropsch Synthesis: Effect of Reducing Agent for Aqueous-Phase Synthesis Over Ru Nanoparticle and Supported Ru Catalysts

    SciTech Connect

    Pendyala, Venkat Ramana Rao; Shafer, Wilson D.; Jacobs, Gary; Graham, Uschi M.; Khalid, Syed; Davis, Burtron H.

    2014-12-27

    The effect of the reducing agent on the performance of a ruthenium nanoparticle catalyst was investigated during aqueous-phase Fischer–Tropsch synthesis using a 1 L stirred tank reactor in the batch mode of operation. For the purpose of comparison, the activity and selectivity of NaY zeolite supported Ru catalyst were also studied. NaBH4 and hydrogen were used as reducing agents in our study, and hydrogen reduced catalysts exhibited higher activities than the NaBH4 reduced catalysts, because of higher extent of reduction and a relatively lower tendency toward agglomeration of Ru particles. The Ru nanoparticle catalyst displayed higher activities than the NaY zeolite supported Ru catalyst for both reducing agents. NaBH4 reduced catalysts are less active and the carbon dioxide selectivity is higher than the hydrogen reduced catalysts. The activity of the supported Ru catalyst (Ru/NaY) was 75 % of that of the Ru nanoparticle catalyst, and has the benefit of easy wax/catalyst slurry separation by filtration. Finally, the hydrogen reduced supported Ru catalyst exhibited superior selectivity towards hydrocarbons (higher C5+ selectivity and lower selectivity to methane) than all other catalysts tested.

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

    PubMed

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

    2010-01-19

    Zeolites are one of humanity's most important synthetic products. These aluminosilicate-based materials represent a large segment of the global economy. Indeed, the value of zeolites used in petroleum refining as catalysts and in detergents as water softeners is estimated at $350 billion per year. A major current goal in zeolite chemistry is to create a structure in which metal ions and functionalizable organic units make up an integral part of the framework. Such a structure, by virtue of the flexibility with which metal ions and organic moieties can be varied, is viewed as a key to further improving zeolite properties and accessing new applications. Recently, it was recognized that the Si-O-Si preferred angle in zeolites (145 degrees ) is coincident with that of the bridging angle in the M-Im-M fragment (where M is Zn or Co and Im is imidazolate), and therefore it should be possible to make new zeolitic imidazolate frameworks (ZIFs) with topologies based on those of tetrahedral zeolites. This idea was successful and proved to be quite fruitful; within the last 5 years over 90 new ZIF structures have been reported. The recent application of high-throughput synthesis and characterization of ZIFs has expanded this structure space significantly: it is now possible to make ZIFs with topologies previously unknown in zeolites, in addition to mimicking known structures. In this Account, we describe the general preparation of crystalline ZIFs, discussing the methods that have been developed to create and analyze the variety of materials afforded. We include a comprehensive list of all known ZIFs, including structure, topology, and pore metrics. We also examine how complexity might be introduced into new structures, highlighting how link-link interactions might be exploited to effect particular cage sizes, create polarity variations between pores, or adjust framework robustness, for example. The chemical and thermal stability of ZIFs permit many applications, such as the

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

    PubMed

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

    2010-01-19

    Zeolites are one of humanity's most important synthetic products. These aluminosilicate-based materials represent a large segment of the global economy. Indeed, the value of zeolites used in petroleum refining as catalysts and in detergents as water softeners is estimated at $350 billion per year. A major current goal in zeolite chemistry is to create a structure in which metal ions and functionalizable organic units make up an integral part of the framework. Such a structure, by virtue of the flexibility with which metal ions and organic moieties can be varied, is viewed as a key to further improving zeolite properties and accessing new applications. Recently, it was recognized that the Si-O-Si preferred angle in zeolites (145 degrees ) is coincident with that of the bridging angle in the M-Im-M fragment (where M is Zn or Co and Im is imidazolate), and therefore it should be possible to make new zeolitic imidazolate frameworks (ZIFs) with topologies based on those of tetrahedral zeolites. This idea was successful and proved to be quite fruitful; within the last 5 years over 90 new ZIF structures have been reported. The recent application of high-throughput synthesis and characterization of ZIFs has expanded this structure space significantly: it is now possible to make ZIFs with topologies previously unknown in zeolites, in addition to mimicking known structures. In this Account, we describe the general preparation of crystalline ZIFs, discussing the methods that have been developed to create and analyze the variety of materials afforded. We include a comprehensive list of all known ZIFs, including structure, topology, and pore metrics. We also examine how complexity might be introduced into new structures, highlighting how link-link interactions might be exploited to effect particular cage sizes, create polarity variations between pores, or adjust framework robustness, for example. The chemical and thermal stability of ZIFs permit many applications, such as the

  20. Bimetallic Catalysts.

    ERIC Educational Resources Information Center

    Sinfelt, John H.

    1985-01-01

    Chemical reaction rates can be controlled by varying composition of miniscule clusters of metal atoms. These bimetallic catalysts have had major impact on petroleum refining, where work has involved heterogeneous catalysis (reacting molecules in a phase separate from catalyst.) Experimentation involving hydrocarbon reactions, catalytic…

  1. Oxyhydrochlorination catalyst

    DOEpatents

    Taylor, Charles E.; Noceti, Richard P.

    1992-01-01

    An improved catalyst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HCl and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride.

  2. MgO encapsulated mesoporous zeolite for the side chain alkylation of toluene with methanol.

    PubMed

    Jiang, Nanzhe; Jin, Hailian; Jeong, Eun-Young; Park, Sang-Eon

    2010-01-01

    Side chain alkylation of toluene with methanol was studied over mesoporous zeolite supported MgO catalysts. MgO were supported onto the carbon templated mesoporous silicalite-1 by direct synthesis route under microwave conditions. This direct synthesis route yields the majority of MgO highly dispersed into the mesopores of the silicalite-1 crystals. The vapor phase alkylation of toluene with methanol was performed over these catalysts under vapor phase conditions at atmospheric pressure. Mesoporous silicalite-1 supported MgO catalysts gave improved yields towards side chain alkylated products compared to the bulk MgO. The higher activity exhibited by 5% MgO supported on mesoporous silicalite compared to the one with 1% MgO can be attributed to the large number of weak basic sites observed from the CO2 TPD.

  3. Zeolites on Mars: Prospects for Remote Sensing

    NASA Technical Reports Server (NTRS)

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

    1985-01-01

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

  4. Method and apparatus for combination catalyst for reduction of NO.sub.x in combustion products

    DOEpatents

    Socha, Richard F.; Vartuli, James C.; El-Malki, El-Mekki; Kalyanaraman, Mohan; Park, Paul W.

    2010-09-28

    A method and apparatus for catalytically processing a gas stream passing therethrough to reduce the presence of NO.sub.x therein, wherein the apparatus includes a first catalyst composed of a silver containing alumina that is adapted for catalytically processing the gas stream at a first temperature range, and a second catalyst composed of a copper containing zeolite located downstream from the first catalyst, wherein the second catalyst is adapted for catalytically processing the gas stream at a lower second temperature range relative to the first temperature range.

  5. Anthemis xylopoda flowers aqueous extract assisted in situ green synthesis of Cu nanoparticles supported on natural Natrolite zeolite for N-formylation of amines at room temperature under environmentally benign reaction conditions.

    PubMed

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Hatamifard, Arezo

    2015-12-15

    Zeolites, which are nontoxic, abundant, and cheap, are very promising supports for the design and preparation of new and environmentally benign catalysts. In this study, Cu nanoparticles (NPs) were immobilized on the surface of natural Natrolite zeolite by Anthemis xylopoda flowers aqueous extract as a reducing and stabilizing agent. Afterward, the catalytic performance of the prepared catalyst was investigated for N-formylation of amines at room temperature under environmentally benign reaction conditions. The catalyst could be reused at least 5 times without any decrease in activity. The advantages of the present protocol include the use of green catalyst, easy isolation of the products, reusability of catalyst, absence of nontoxic reagents, and excellent yield of the products.

  6. Domino-cyclisation and hydrogenation of citronellal to menthol over bifunctional Ni/Zr-Beta and Zr-beta/Ni-MCM-41 catalysts.

    PubMed

    Nie, Yuntong; Chuah, Gaik-Khuan; Jaenicke, Stephan

    2006-02-21

    The one-pot conversion of (+/-)-citronellal to menthol can be selectively catalysed by either a bifunctional Ni/Zr-zeolite beta catalyst or a dual catalyst system of Zr-beta and Ni/MCM-41, giving a high diastereoselectivity to (+/-)-menthol of 90-94%.

  7. Catalytic conversion of Chlorella pyrenoidosa to biofuels in supercritical alcohols over zeolites.

    PubMed

    Yang, Le; Ma, Rui; Ma, Zewei; Li, Yongdan

    2016-06-01

    Microalgae have been considered as the feedstock for the third generation biofuels production, given its high lipid content and fast productivity. Herein, a catalytic approach for microalgae liquefaction to biocrude is examined in a temperature range of 250-300°C in methanol and ethanol over zeolites. Higher biocrude yield was achieved in ethanol and at lower temperatures, while better quality biocrude with higher light biocrude ratio and lower average molecular weight (Mw) was favored in methanol and at higher temperatures. Application of zeolites improves the biocrude quality significantly. Among the catalysts, HY shows the strongest acidity and performs the best to produce high quality biocrude. Solid residues have been extensively explored with thermal gravity analysis and elemental analysis. It is reported for the first time that up to 99wt.% of sulfur is deposited in the solid residue at 250°C for both solvents. PMID:26990399

  8. Ion distribution in copper exchanged zeolites by using Si-29 spin lattice relaxation analysis

    NASA Astrophysics Data System (ADS)

    Palamara, Joseph; Seidel, Karsten; Moini, Ahmad; Prasad, Subramanian

    2016-06-01

    Transition metal-containing zeolites, particularly those with smaller pore size, have found extensive application in the selective catalytic reduction (SCR) of environmental pollutants containing nitrogen oxides. We report these zeolites have dramatically faster silicon-29 (Si-29) spin lattice relaxation times (T1) compared to their sodium-containing counterparts. Paramagnetic doping allows one to acquire Si-29 MAS spectra in the order of tens of seconds without significantly affecting the spectral resolution. Moreover, relaxation times depend on the method of preparation and the next-nearest neighbor silicon Qn(mAl) sites, where n = 4 and m = 0-4, respectively. A clear trend is noted between the effectiveness of Cu exchange and the Si-29 NMR relaxation times. It is anticipated that the availability of this tool, and the enhanced understanding of the nature of the active sites, will provide the means for designing improved SCR catalysts.

  9. Ion distribution in copper exchanged zeolites by using Si-29 spin lattice relaxation analysis.

    PubMed

    Palamara, Joseph; Seidel, Karsten; Moini, Ahmad; Prasad, Subramanian

    2016-06-01

    Transition metal-containing zeolites, particularly those with smaller pore size, have found extensive application in the selective catalytic reduction (SCR) of environmental pollutants containing nitrogen oxides. We report these zeolites have dramatically faster silicon-29 (Si-29) spin lattice relaxation times (T1) compared to their sodium-containing counterparts. Paramagnetic doping allows one to acquire Si-29 MAS spectra in the order of tens of seconds without significantly affecting the spectral resolution. Moreover, relaxation times depend on the method of preparation and the next-nearest neighbor silicon Qn(mAl) sites, where n=4 and m=0-4, respectively. A clear trend is noted between the effectiveness of Cu exchange and the Si-29 NMR relaxation times. It is anticipated that the availability of this tool, and the enhanced understanding of the nature of the active sites, will provide the means for designing improved SCR catalysts. PMID:27055207

  10. Synthesis, characterization and energetics of zeolites

    NASA Astrophysics Data System (ADS)

    Sun, Pingping

    Zeolites are microporous aluminosilicates, and Al or Si can be substituted by other elements, such as Ge, Ga, or P. Zeolites have been studied for more than two hundred years, because of their wide application and importance in mineralogy and technology. With high acidity and special pore system, zeolite beta (IZA code BEA) receives much attention. In the dissertation, the formation and dehydration enthalpy of cation exchanged zeolite beta, Li/Na/K/Rb/Cs/Mg/Ca/Sr/Ba -BEA 14 (14 is the Si/Al ratio), Mg/Ca - BEA 4 (4 is the Si/Al ratio), were studied by high-temperature oxide melt solution calorimetry. From an energetic point of view, zeolites beta are less stable than other zeolites of similar Si/Al ratio and cation content. Their enthalpies of formation and dehydration become more endothermic with increasing average ionic potential of the cations in the channels. The unfavorable enthalpy of low silica Mg-BEA 4 and Ca-BEA 4 suggests a possible energy barrier in their direct synthesis. The formation and partial molar dehydration enthalpy of Li-BEA 3 and Na-BEA 3.67 are also investigated by high temperature calorimetry. The partial molar dehydration enthalpies are a linear function of water content. Molecular mechanics simulations explore the cation and water molecule positions in the framework at several water contents. Ga substitution is of great interest due to the special catalytic character of Ga zeolites and the directing agent effect of Ga atoms. The energetics of gallosilicate zeolites Ga-NaSOD, Ga-NaFAU, Ga-NaNAT, Ga-KNAT, Ga-KLTL and Ga-KTUN-1 were studied. The lattice parameters and adsorbed water content increase after Ga substitution of Al. Compared to analogous aluminosilicate zeolites, the gallosilicate zeolites have a similar dehydration enthalpy per mole of tetrahedra, but a less endothermic dehydration enthalpy per mole of water. The gallosilicate zeolites also have less exothermic formation enthalpies from oxide components. The energetics of Ga

  11. Copper-Exchanged Zeolite L Traps Oxygen

    NASA Technical Reports Server (NTRS)

    Sharma, Pramod K.; Seshan, Panchalam K.

    1991-01-01

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

  12. Tetraethylenepentamine embedded zeolite A for carbon dioxide adsorption.

    PubMed

    Kim, Young-Ki; Mo, Yong-Hwan; Lee, Jun; You, Hyo-Sang; Yi, Chang-Keun; Park, Young Cheol; Park, Sang-Eon

    2013-04-01

    Tetraethylenepentamine (TEPA) embedded zeolite A crystals were synthesized by using TEPA and the preformed zeolite A precursor under the microwave irradiation. The presence of TEPA in zeolite A crystal was confirmed by TG analysis and FTIR, Raman spectra. The CO2 adsorptive behavior of TEPA embedded zeolite A samples was investigated by CO2 isotherms measured at 25 degrees C comparing with zeolite A. The optimum CO2 sorption capacity was found in the case of 7.5% TEPA embedded zeolite A, which showed 3.75 mmol g(-1) where as the zeolite A showed less CO2 adsorption capacity of 2.88 mmol g(-1). The adsorption capacity of TEPA embedded Zeolite A was sustained up to 90% during 4 cycles of temperature swing adsorption (TSA) from 40 degrees C to 140 degrees C, indicating that the TEPA embedded Zeolite A was found to be useful as one of the application to solid amine adsorbent for CO2.

  13. A comparative first principles study on trivalent ion incorporated SSZ-13 zeolites.

    PubMed

    Wen, Cui; Geng, Lu; Han, Lina; Wang, Jiancheng; Chang, Liping; Feng, Gang; Kong, Dejin; Liu, Jianwen

    2015-11-28

    The dispersion-corrected density functional theory has been used to study the trivalent ions B, Al, Ga, and Fe incorporated SSZ-13-type zeolites. The associated structure and Brønsted/Lewis acidity change caused by the incorporation ions were comparatively studied. It was found that the smaller the radius differences of the incorporation ions are, the smaller the changes in the structure will be and the less acidity will be enhanced for the Brønsted sites. The trivalent Al is found to be the most favorable trivalent incorporation ion and Na is found to be the most favorable charge balanced ion for the synthesis of SSZ-13-type zeolites due to size comparability, which are in line with the experimental observation. The substitution energies which show the relative synthesis difficulty level were also applied for B, Al, Ga, and Fe incorporated zeolites and found that the difficulty decreases with order of Fe > B > Ga ≫ Al, also in good agreement with the experimental observations. Adsorption studies for the NH3 and pyridine molecules indicate that adsorption on the Brønsted acid sites is more stable than on the Lewis acid sites. The Brønsted acidity was found to follow the order of HAl-SSZ-13 > HGa-SSZ-13 ≈ HFe-SSZ-13 > HB-SSZ-13 where the Lewis acidity was found to follow the order of HGa-SSZ-13 ≈ HFe-SSZ-13 > HAl-SSZ-13 > HB-SSZ-13. Our results provide new insights for the synthesis of the SSZ-13-type zeolites and fundamental information for the zeolitic catalyst designation to enhance the catalytic performance. PMID:26477513

  14. Correlating the Integral Sensing Properties of Zeolites with Molecular Processes by Combining Broadband Impedance and DRIFT Spectroscopy--A New Approach for Bridging the Scales.

    PubMed

    Chen, Peirong; Schönebaum, Simon; Simons, Thomas; Rauch, Dieter; Dietrich, Markus; Moos, Ralf; Simon, Ulrich

    2015-01-01

    Zeolites have been found to be promising sensor materials for a variety of gas molecules such as NH₃, NOx, hydrocarbons, etc. The sensing effect results from the interaction of the adsorbed gas molecules with mobile cations, which are non-covalently bound to the zeolite lattice. The mobility of the cations can be accessed by electrical low-frequency (LF; mHz to MHz) and high-frequency (HF; GHz) impedance measurements. Recent developments allow in situ monitoring of catalytic reactions on proton-conducting zeolites used as catalysts. The combination of such in situ impedance measurements with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), which was applied to monitor the selective catalytic reduction of nitrogen oxides (DeNOx-SCR), not only improves our understanding of the sensing properties of zeolite catalysts from integral electric signal to molecular processes, but also bridges the length scales being studied, from centimeters to nanometers. In this work, recent developments of zeolite-based, impedimetric sensors for automotive exhaust gases, in particular NH₃, are summarized. The electrical response to NH₃ obtained from LF impedance measurements will be compared with that from HF impedance measurements, and correlated with the infrared spectroscopic characteristics obtained from the DRIFTS studies of molecules involved in the catalytic conversion. The future perspectives, which arise from the combination of these methods, will be discussed. PMID:26580627

  15. Correlating the Integral Sensing Properties of Zeolites with Molecular Processes by Combining Broadband Impedance and DRIFT Spectroscopy—A New Approach for Bridging the Scales

    PubMed Central

    Chen, Peirong; Schönebaum, Simon; Simons, Thomas; Rauch, Dieter; Dietrich, Markus; Moos, Ralf; Simon, Ulrich

    2015-01-01

    Zeolites have been found to be promising sensor materials for a variety of gas molecules such as NH3, NOx, hydrocarbons, etc. The sensing effect results from the interaction of the adsorbed gas molecules with mobile cations, which are non-covalently bound to the zeolite lattice. The mobility of the cations can be accessed by electrical low-frequency (LF; mHz to MHz) and high-frequency (HF; GHz) impedance measurements. Recent developments allow in situ monitoring of catalytic reactions on proton-conducting zeolites used as catalysts. The combination of such in situ impedance measurements with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), which was applied to monitor the selective catalytic reduction of nitrogen oxides (DeNOx-SCR), not only improves our understanding of the sensing properties of zeolite catalysts from integral electric signal to molecular processes, but also bridges the length scales being studied, from centimeters to nanometers. In this work, recent developments of zeolite-based, impedimetric sensors for automotive exhaust gases, in particular NH3, are summarized. The electrical response to NH3 obtained from LF impedance measurements will be compared with that from HF impedance measurements, and correlated with the infrared spectroscopic characteristics obtained from the DRIFTS studies of molecules involved in the catalytic conversion. The future perspectives, which arise from the combination of these methods, will be discussed. PMID:26580627

  16. Correlating the Integral Sensing Properties of Zeolites with Molecular Processes by Combining Broadband Impedance and DRIFT Spectroscopy--A New Approach for Bridging the Scales.

    PubMed

    Chen, Peirong; Schönebaum, Simon; Simons, Thomas; Rauch, Dieter; Dietrich, Markus; Moos, Ralf; Simon, Ulrich

    2015-01-01

    Zeolites have been found to be promising sensor materials for a variety of gas molecules such as NH₃, NOx, hydrocarbons, etc. The sensing effect results from the interaction of the adsorbed gas molecules with mobile cations, which are non-covalently bound to the zeolite lattice. The mobility of the cations can be accessed by electrical low-frequency (LF; mHz to MHz) and high-frequency (HF; GHz) impedance measurements. Recent developments allow in situ monitoring of catalytic reactions on proton-conducting zeolites used as catalysts. The combination of such in situ impedance measurements with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), which was applied to monitor the selective catalytic reduction of nitrogen oxides (DeNOx-SCR), not only improves our understanding of the sensing properties of zeolite catalysts from integral electric signal to molecular processes, but also bridges the length scales being studied, from centimeters to nanometers. In this work, recent developments of zeolite-based, impedimetric sensors for automotive exhaust gases, in particular NH₃, are summarized. The electrical response to NH₃ obtained from LF impedance measurements will be compared with that from HF impedance measurements, and correlated with the infrared spectroscopic characteristics obtained from the DRIFTS studies of molecules involved in the catalytic conversion. The future perspectives, which arise from the combination of these methods, will be discussed.

  17. Catalyst and method for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C.

    2008-05-27

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  18. Catalyst and method for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C.

    2008-08-19

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  19. Sustainable production of acrylic acid: alkali-ion exchanged beta zeolite for gas-phase dehydration of lactic acid.

    PubMed

    Yan, Bo; Tao, Li-Zhi; Liang, Yu; Xu, Bo-Qing

    2014-06-01

    Gas-phase dehydration of lactic acid (LA) to acrylic acid (AA) was investigated over alkali-exchanged β zeolite (M(x)Na(1-x)β, M=Li(+), K(+), Rb(+), or Cs(+)) of different exchange degrees (x). The reaction was conducted under varying conditions to understand the catalyst selectivity for AA production and trends of byproduct formation. The nature and exchange degree of M(+) were found to be critical for the acid-base properties and catalytic performance of the exchanged zeolite. K(x)Na(1-x)β of x=0.94 appeared to be the best performing catalyst whereas Li(x)Na(1-x)β and Naβ were the poorest in terms of AA selectivity and yield. The AA yield as high as 61 mol % (selectivity: 64 mol %) could be obtained under optimized reaction conditions for up to 8 h over the best performing K0.94Na0.06β. The acid and base properties of the catalysts were probed, respectively by temperature-programmed desorption (TPD) of adsorbed NH3 and CO2, and were related to the electrostatic potentials of the alkali ions in the zeolite, which provided a basis for the discussion of the acid-base catalysis for sustainable AA formation from LA.

  20. Quantitative 3D Fluorescence Imaging of Single Catalytic Turnovers Reveals Spatiotemporal Gradients in Reactivity of Zeolite H-ZSM-5 Crystals upon Steaming

    PubMed Central

    2015-01-01

    Optimizing the number, distribution, and accessibility of Brønsted acid sites in zeolite-based catalysts is of a paramount importance to further improve their catalytic performance. However, it remains challenging to measure real-time changes in reactivity of single zeolite catalyst particles by ensemble-averaging characterization methods. In this work, a detailed 3D single molecule, single turnover sensitive fluorescence microscopy study is presented to quantify the reactivity of Brønsted acid sites in zeolite H-ZSM-5 crystals upon steaming. This approach, in combination with the oligomerization of furfuryl alcohol as a probe reaction, allowed the stochastic behavior of single catalytic turnovers and temporally resolved turnover frequencies of zeolite domains smaller than the diffraction limited resolution to be investigated with great precision. It was found that the single turnover kinetics of the parent zeolite crystal proceeds with significant spatial differences in turnover frequencies on the nanoscale and noncorrelated temporal fluctuations. Mild steaming of zeolite H-ZSM-5 crystals at 500 °C led to an enhanced surface reactivity, with up to 4 times higher local turnover rates than those of the parent H-ZSM-5 crystals, and revealed remarkable heterogeneities in surface reactivity. In strong contrast, severe steaming at 700 °C significantly dealuminated the zeolite H-ZSM-5 material, leading to a 460 times lower turnover rate. The differences in measured turnover activities are explained by changes in the 3D aluminum distribution due to migration of extraframework Al-species and their subsequent effect on pore accessibility, as corroborated by time-of-flight secondary ion mass spectrometry (TOF-SIMS) sputter depth profiling data. PMID:25867455

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

    SciTech Connect

    Lazau, C.; Ratiu, C.; Orha, C.; Pode, R.; Manea, F.

    2011-11-15

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

  2. Synthesis, spectral investigation and catalytic aspects of entrapped VO(IV) and Cu(II) complexes into the supercages of zeolite-Y.

    PubMed

    Modi, Chetan K; Gade, Bhagyashree G; Chudasama, Jiten A; Parmar, Digvijay K; Nakum, Haresh D; Patel, Arun L

    2015-04-01

    VO(IV) and Cu(II) complexes with Schiff base ligand derived from 1-phenyl-3-methyl-4-formyl-2-pyrazolin-5-one (PMFP) and 2-amino phenol have been synthesized as their neat and entrapped complexes into the supercages of zeolite-Y. The compounds were characterized by chemical analysis (ICP-OES and elemental), electronic and/or UV reflectance spectra, FTIR spectroscopy, X-ray powder diffraction patterns, SEMs, BET and thermogravimetric (TG) analysis. All the prepared catalysts were tested on the liquid phase limonene oxidation reaction, using 30% H2O2 as an oxidant. Limonene glycol, carveol, carvone and limonene 1,2-epoxide were the main products obtained. It was observed that zeolite-Y entrapped complexes exhibited higher catalytic activity than neat complexes. The catalysts undergo no metal leaching and can be easily recovered and reused. The use of inexpensive catalyst and oxidant are significant practical advantages of this environmentally friendly process.

  3. Synthesis, spectral investigation and catalytic aspects of entrapped VO(IV) and Cu(II) complexes into the supercages of zeolite-Y

    NASA Astrophysics Data System (ADS)

    Modi, Chetan K.; Gade, Bhagyashree G.; Chudasama, Jiten A.; Parmar, Digvijay K.; Nakum, Haresh D.; Patel, Arun L.

    2015-04-01

    VO(IV) and Cu(II) complexes with Schiff base ligand derived from 1-phenyl-3-methyl-4-formyl-2-pyrazolin-5-one (PMFP) and 2-amino phenol have been synthesized as their neat and entrapped complexes into the supercages of zeolite-Y. The compounds were characterized by chemical analysis (ICP-OES and elemental), electronic and/or UV reflectance spectra, FTIR spectroscopy, X-ray powder diffraction patterns, SEMs, BET and thermogravimetric (TG) analysis. All the prepared catalysts were tested on the liquid phase limonene oxidation reaction, using 30% H2O2 as an oxidant. Limonene glycol, carveol, carvone and limonene 1,2-epoxide were the main products obtained. It was observed that zeolite-Y entrapped complexes exhibited higher catalytic activity than neat complexes. The catalysts undergo no metal leaching and can be easily recovered and reused. The use of inexpensive catalyst and oxidant are significant practical advantages of this environmentally friendly process.

  4. Effect of internal noise on the oscillation of N{sub 2}O decomposition over Cu-ZSM-5 zeolites using a stochastic description

    SciTech Connect

    Liu, Fuliang; Li, Yaping Sun, Xiaoming

    2014-01-28

    When considering stochastic oscillations of heterogeneous catalyst systems, most researches have focused on the surface of a metal or its oxide catalysts, but there have been few studies on porous catalysts. In this work, the effects of internal noise on oscillations of N{sub 2}O decomposition over Cu-ZSM-5 zeolites are investigated, using the chemical Langevin equation and a mesoscopic stochastic model. Considering that Cu-ZSM-5 particles are finely divided particles, the number of Cu ions (N{sub s}) is proportional to the particle size at a certain Cu/Al, and the internal noise is inversely proportional to N{sub s}. Stochastic oscillations can be observed outside the deterministic oscillatory region. Furthermore, the performance of the oscillation characterized by the signal-to-noise ratio has a maximum within the optimal size range of 4–8 nm. This suggests that a nanometer-sized zeolite may be best for oscillations.

  5. Photo-oxidation catalysts

    DOEpatents

    Pitts, J. Roland; Liu, Ping; Smith, R. Davis

    2009-07-14

    Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

  6. TAILORING CATALYSTS FOR HYDRODECHLORINATING CHLORINATED HYDROCARBON CONTAMINANTS IN GROUNDWATER. (R825689C093)

    EPA Science Inventory

    Abstract

    A palladium-on-zeolite catalyst has been optimized for treating groundwater contaminated with halogenated hydrocarbon compounds (HHCs) by hydrodechlorination with dissolved hydrogen. Aqueous sulfite was used as the model poison and the dechlorination of 1,2-di...

  7. TAILORING CATALYSTS FOR HYDRODECHLORINATING CHLORINATED HYDROCARBON CONTAMINANTS IN GROUNDWATER. (R825689C078)

    EPA Science Inventory

    Abstract

    A palladium-on-zeolite catalyst has been optimized for treating groundwater contaminated with halogenated hydrocarbon compounds (HHCs) by hydrodechlorination with dissolved hydrogen. Aqueous sulfite was used as the model poison and the dechlorination of 1,2-di...

  8. Dye house wastewater treatment through advanced oxidation process using Cu-exchanged Y zeolite: a heterogeneous catalytic approach.

    PubMed

    Fathima, Nishtar Nishad; Aravindhan, Rathinam; Rao, Jonnalagadda Raghava; Nair, Balachandran Unni

    2008-01-01

    Catalytic wet hydrogen peroxide oxidation of an anionic dye has been explored in this study. Copper(II) complex of NN'-ethylene bis(salicylidene-aminato) (salenH2) has been encapsulated in super cages of zeolite-Y by flexible ligand method. The catalyst has been characterized by Fourier transforms infra red spectroscopy, X-ray powder diffractograms, Thermo-gravimetric and differential thermal analysis and nitrogen adsorption studies. The effects of various parameters such as pH, catalyst and hydrogen peroxide concentration on the oxidation of dye were studied. The results indicate that complete removal of color has been obtained after a period of less than 1h at 60 degrees C, 0.175M H2O2 and 0.3g l(-1) catalyst. More than 95% dye removal has been achieved using this catalyst for commercial effluent. These studies indicate that copper salen complex encapsulated in zeolite framework is a potential heterogeneous catalyst for removal of color from wastewaters.

  9. In –Situ Spectroscopic Investigation of Immobilized Organometallic Catalysts

    SciTech Connect

    Davis, Robert, J.

    2007-11-14

    Immobilized organometallic catalysts, in principle, can give high rates and selectivities like homogeneous catalysts with the ease of separation enjoyed by heterogeneous catalysts. However, the science of immobilized organometallics has not been developed because the field lies at the interface between the homogeneous and heterogeneous catalysis communities. By assembling an interdisciplinary research team that can probe all aspects of immobilized organometallic catalyst design, the entire reacting system can be considered, where the transition metal complex, the complex-support interface and the properties of the support can all be considered simultaneously from both experimental and theoretical points of view. Researchers at Georgia Tech and the University of Virginia are studying the fundamental principles that can be used to understand and design future classes of immobilized organometallic catalysts. In the framework of the overall collaborative project with Georgia Tech, our work focused on (a) the X-ray absorption spectroscopy of an immobilized Pd-SCS-O complex (b) the mode of metal leaching from supported Pd catalysts during Heck catalysis and (c) the mode of deactivation of Jacobsen’s Co-salen catalysts during the hydrolytic kinetic resolution of terminal epoxides. Catalysts containing supported Pd pincer complexes, functionalized supports containing mercapto and amine groups, and oligomeric Co-salen catalysts were synthesized at Georgia Tech and sent to the University of Virginia. Incorporation of Pd onto several different kinds of supports (silica, mercapto-functionalized silica, zeolite Y) was performed at the University of Virginia.

  10. Thermodynamic modeling of natural zeolite stability

    SciTech Connect

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

    1997-06-01

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

  11. Three Mile Island zeolite vitirification demonstration program

    SciTech Connect

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

    1981-06-01

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

  12. Probing zeolites by vibrational spectroscopies.

    PubMed

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

    2015-10-21

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

  13. The zeolite deposits of Greece

    USGS Publications Warehouse

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

    1996-01-01

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

  14. Catalysts for converting syngas into liquid hydrocarbons and methods thereof

    DOEpatents

    Yu, Fei; Yan, Qiangu; Batchelor, William

    2016-03-15

    The presently-disclosed subject matter includes methods for producing liquid hydrocarbons from syngas. In some embodiments the syngas is obtained from biomass and/or comprises a relatively high amount of nitrogen and/or carbon dioxide. In some embodiments the present methods can convert syngas into liquid hydrocarbons through a one-stage process. Also provided are catalysts for producing liquid hydrocarbons from syngas, wherein the catalysts include a base material, a transition metal, and a promoter. In some embodiments the base material includes a zeolite-iron material or a cobalt-molybdenum carbide material. In still further embodiments the promoter can include an alkali metal.

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

    SciTech Connect

    Richardson, J.W. Jr.

    1996-12-31

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

  16. Aromatization of Ethanol Over Desilicated ZSM-5 Zeolites: Effect of Pore Size in the Mesoporous Region.

    PubMed

    Jun, Jong Won; Hasan, Zubair; Kim, Chul-Ung; Jeong, Soon-Yong; Jhung, Sung Hwa

    2016-05-01

    Mesoporous ZSM-5 zeolites were obtained from microporous ZSM-5 by desilication using aqueous NaOH solutions, and their catalytic activity in the aromatization of ethanol was investigated in order to understand the effects of pore size, in the mesoporous region, on the product distribution and stability of the catalysts. Mesopores generally enhanced the selectivities towards aromatics and stability for aromatization. Mesopores with a maximum pore diameter of around 13 nm were the most effective in the aromatization process (especially for benzene and toluene), suggesting that pore-diameter optimization is necessary for efficient catalysis such as aromatization.

  17. The impact of aqueous medium on zeolite framework integrity

    SciTech Connect

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

    2015-05-12

    Understanding the zeolite framework stability in aqueous phase is crucial to develop stable catalysts. Al K–edge, extended X–ray absorption fine structure and 27Al MAS NMR spectroscopies in combination with DFT calculations have been used to monitor both qualitative and quantitative structural changes of two well–characterized samples with BEA structure. The effects of various properties on stability were explored, including Al concentration, Al distribution, particle size and structural defects. As the samples were degraded by treatment in hot liquid water, the local structure about the Al T–site remained mostly intact, including the Al–O–Si angles and bond distances, while the nano–scale crystalline structure as measured by XRD and TEM was disrupted. The combined data suggest a three–step mechanism in which, initially, the HBEA framework crystallinity decreases via hydrolysis of T–O bonds along polymorph stacking faults and inter–grain boundaries in a mode similar to crack propagation in glass. With prolonged exposure, amorphization occurs via hydrolysis of surface Si–OH groups propagating inward through the zeolite lattice. In parallel, cracks propagate within the crystalline micro–domains along paths through specific T–O–T groups. Authors thank B. W. Arey (PNNL) for HIM measurements, T. Huthwelker for support during Al XAFS measurements at the Swiss Light Source (PSI, Switzerland) and M. Y. Hu (PNNL) for support during NMR experiments. This work was supported by the U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. NMR experiments were performed at the Environmental Molecular Science Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research, and Physical Science Laboratory both located at Pacific Northwest National Laboratory (PNNL). PNNL is a multi–program national laboratory

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

    PubMed

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

    2016-04-01

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

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

    PubMed

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

    2016-04-01

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

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

    PubMed

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

    2014-03-15

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

  1. Quantification of thickness and wrinkling of exfoliated two-dimensional zeolite nanosheets

    PubMed Central

    Kumar, Prashant; Agrawal, Kumar Varoon; Tsapatsis, Michael; Mkhoyan, K. Andre

    2015-01-01

    Some two-dimensional (2D) exfoliated zeolites are single- or near single-unit cell thick silicates that can function as molecular sieves. Although they have already found uses as catalysts, adsorbents and membranes precise determination of their thickness and wrinkling is critical as these properties influence their functionality. Here we demonstrate a method to accurately determine the thickness and wrinkles of a 2D zeolite nanosheet by comprehensive 3D mapping of its reciprocal lattice. Since the intensity modulation of a diffraction spot on tilting is a fingerprint of the thickness, and changes in the spot shape are a measure of wrinkling, this mapping is achieved using a large-angle tilt-series of electron diffraction patterns. Application of the method to a 2D zeolite with MFI structure reveals that the exfoliated MFI nanosheet is 1.5 unit cells (3.0 nm) thick and wrinkled anisotropically with up to 0.8 nm average surface roughness. PMID:25958985

  2. Deactivation Mechanisms of Base Metal/Zeolite Urea Selective Catalytic Reduction Materials, and Development of Zeolite-Based Hydrocarbon Adsorber Materials

    SciTech Connect

    Kwak, Ja Hun; Lee, Jong H.; Kim, Do Heui; Li, Xiaohong S.; Tran, Diana N.; Peden, Charles HF

    2011-12-22

    This annual report describes recent progress on a collaborative project between scientists and engineers in the Institute for Integrated Catalysis at PNNL and at Ford Motor Company, involving investigations of laboratory- and engine-aged SCR catalysts, containing mainly base metal zeolites. These studies are leading to a better understanding of various aging factors that impact the long-term performance of SCR catalysts and improve the correlation between laboratory and engine aging, saving experimental time and cost. We are investigating SCR catalysts with reduced ammonia slip, increased low temperature activity, and increased product selectivity to N2. More recent recognition that high temperature performance, under regimes that sometimes cause deactivation, also needs to be improved is driving current work focused on catalyst materials modifications needed to achieve this enhanced performance. We are also studying materials effective for the temporary storage of HC species during the cold-start period. In particular, we examine the adsorption and desorption of various HC species produced during the combustion with different fuels (e.g., gasoline, E85, diesel) over potential HC adsorber materials, and measure the kinetic parameters to update Ford’s HC adsorption model.

  3. Application of high silica zeolite ZSM-5 in a hybrid treatment process based on sequential adsorption and ozonation for VOCs elimination.

    PubMed

    Zaitan, Hicham; Manero, Marie Hélène; Valdés, Héctor

    2016-03-01

    In this study, a hydrophobic synthetic zeolite, namely ZSM-5 is chosen as an adsorbent/catalyst for toluene removal. Experimental results showed that toluene adsorption onto ZSM-5 was favourable, following a Langmuir adsorption isotherm model. ZSM-5 zeolite was regenerated using gaseous ozone at low temperature. Adsorbed toluene was oxidised, releasing mainly CO2 and H2O. Traces of oxidation by-products such as acetic acid and acetaldehyde were formed and remained adsorbed after the oxidativate regeneration with ozone. After four successive cycles of adsorption/ozonation, the adsorption efficiency was not affected (92%-99%). These results showed that volatile organic compound (VOC) removal by adsorption onto ZSM-5 zeolite followed by ozone regeneration could be used as a promising hybrid process for the control of VOC emissions in terms of efficiency.

  4. Transition Metal Ions in Zeolites: Coordination and activation of O2

    PubMed Central

    Smeets, Pieter J.; Woertink, Julia S.; Sels, Bert F.; Solomon, Edward I.; Schoonheydt, Robert A.

    2010-01-01

    Zeolites containing transition metal ions (TMI) often show promising activity as heterogeneous catalysts in pollution abatement and selective oxidation reactions. In this paper, two aspects of research on the TMI Cu, Co and Fe in zeolites are discussed: (i) coordination to the lattice and (ii) activated oxygen species. At low loading, TMI preferably occupy exchange sites in six-membered oxygen rings (6MR) where the TMI preferentially coordinate with the oxygen atoms of Al tetrahedra. High TMI loadings result in a variety of TMI species formed at the zeolite surface. Removal of the extra-lattice oxygens during high temperature pretreatments can result in auto-reduction. Oxidation of reduced TMI sites often results in the formation of highly reactive oxygen species. In Cu-ZSM-5, calcination with O2 results in the formation of a species, which was found to be a crucial intermediate in both the direct decomposition of NO and N2O and the selective oxidation of methane into methanol. An activated oxygen species, called α-oxygen, is formed in Fe-ZSM5 and reported to be the active site in the partial oxidation of methane and benzene into methanol and phenol, respectively. However, this reactive α-oxygen can only be formed with N2O, not with O2. O2 activated Co intermediates in Faujasite (FAU) zeolites can selectively oxidize α-pinene and epoxidize styrene. In Co-FAU, CoIII superoxo and peroxo complexes are suggested to be the active cores, whereas in Cu and Fe-ZSM-5 various monomeric and dimeric sites have been proposed, but no consensus has been obtained. Very recently, the active site in Cu-ZSM-5 was identified as a bent [Cu-O-Cu]2+ core (Proc. Natl. Acad. Sci. USA 2009, 106, 18908-18913). Overall, O2 activation depends on the interplay of structural factors such as type of zeolite, size of the channels and cages and chemical factors such as Si/Al ratio and the nature, charge and distribution of the charge balancing cations. The presence of several different TMI sites

  5. Catalyst activator

    DOEpatents

    McAdon, Mark H.; Nickias, Peter N.; Marks, Tobin J.; Schwartz, David J.

    2001-01-01

    A catalyst activator particularly adapted for use in the activation of metal complexes of metals of Group 3-10 for polymerization of ethylenically unsaturated polymerizable monomers, especially olefins, comprising two Group 13 metal or metalloid atoms and a ligand structure including at least one bridging group connecting ligands on the two Group 13 metal or metalloid atoms.

  6. Catalysts as sensors--a promising novel approach in automotive exhaust gas aftertreatment.

    PubMed

    Moos, Ralf

    2010-01-01

    Sensors that detect directly and in situ the status of automotive exhaust gas catalysts by monitoring the electrical properties of the catalyst coating itself are overviewed. Examples included in this review are the in-situ determination of the electrical impedance of three-way catalysts based on ceria-zirconia solutions and of lean NO(x) traps of earth-alkaline based coatings, as well as approaches to determine the ammonia loading in Fe-SCR-zeolites with electrical ac measurements. Even more sophisticated approaches based on interactions with electromagnetic waves are also reviewed. For that purpose, metallic stick-like antennas are inserted into the exhaust pipe. The catalyst properties are measured in a contactless manner, directly indicating the catalyst status. The radio frequency probes gauge the oxygen loading degree of three-way catalysts, the NO(x)-loading of lean NO(x) traps, and the soot loading of Diesel particulate filters. PMID:22163575

  7. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2011 Progress Report

    SciTech Connect

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; Rummel, Becky L.

    2011-10-01

    Pacific Northwest National Laboratory has been conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). In recent years, this research has primarily involved the further development of catalysts containing rhodium and manganese based on the results of earlier catalyst screening tests. Research during FY 2011 continued to examine the performance of RhMn catalysts on alternative supports including selected zeolite, silica, and carbon supports. Catalyst optimization continued using both the Davisil 645 and Merck Grade 7734 silica supports. Research also was initiated in FY 2011, using the both Davisil 645 silica and Hyperion CS-02C-063 carbon supports, to evaluate the potential for further improving catalyst performance, through the addition of one or two additional metals as promoters to the catalysts containing Rh, Mn, and Ir.

  8. Catalysts as Sensors—A Promising Novel Approach in Automotive Exhaust Gas Aftertreatment

    PubMed Central

    Moos, Ralf

    2010-01-01

    Sensors that detect directly and in situ the status of automotive exhaust gas catalysts by monitoring the electrical properties of the catalyst coating itself are overviewed. Examples included in this review are the in-situ determination of the electrical impedance of three-way catalysts based on ceria-zirconia solutions and of lean NOx traps of earth-alkaline based coatings, as well as approaches to determine the ammonia loading in Fe-SCR-zeolites with electrical ac measurements. Even more sophisticated approaches based on interactions with electromagnetic waves are also reviewed. For that purpose, metallic stick-like antennas are inserted into the exhaust pipe. The catalyst properties are measured in a contactless manner, directly indicating the catalyst status. The radio frequency probes gauge the oxygen loading degree of three-way catalysts, the NOx-loading of lean NOx traps, and the soot loading of Diesel particulate filters. PMID:22163575

  9. Catalysts as sensors--a promising novel approach in automotive exhaust gas aftertreatment.

    PubMed

    Moos, Ralf

    2010-01-01

    Sensors that detect directly and in situ the status of automotive exhaust gas catalysts by monitoring the electrical properties of the catalyst coating itself are overviewed. Examples included in this review are the in-situ determination of the electrical impedance of three-way catalysts based on ceria-zirconia solutions and of lean NO(x) traps of earth-alkaline based coatings, as well as approaches to determine the ammonia loading in Fe-SCR-zeolites with electrical ac measurements. Even more sophisticated approaches based on interactions with electromagnetic waves are also reviewed. For that purpose, metallic stick-like antennas are inserted into the exhaust pipe. The catalyst properties are measured in a contactless manner, directly indicating the catalyst status. The radio frequency probes gauge the oxygen loading degree of three-way catalysts, the NO(x)-loading of lean NO(x) traps, and the soot loading of Diesel particulate filters.

  10. Pulsed-field gradient nuclear magnetic resonance study of transport properties of fluid catalytic cracking catalysts.

    PubMed

    Kortunov, P; Vasenkov, S; Kärger, J; Fé Elía, M; Perez, M; Stöcker, M; Papadopoulos, G K; Theodorou, D; Drescher, B; McElhiney, G; Bernauer, B; Krystl, V; Kocirik, M; Zikanova, A; Jirglova, H; Berger, C; Gläser, R; Weitkamp, J; Hansen, E W

    2005-02-01

    Pulsed-field gradient nuclear magnetic resonance (PFG NMR) has been applied to study molecular diffusion in industrial fluid catalytic cracking (FCC) catalysts and in USY zeolite for a broad range of molecular displacements and temperatures. The results of this study have been used to elucidate the relevance of molecular transport on various displacements for the rate of molecular exchange between catalyst particles and their surroundings. It turned out that this rate, which may determine the overall rate and selectivity of FCC process, is primarily related to the diffusion mode associated with displacements larger than the size of zeolite crystals located in the particles but smaller than the size of the particles. This conclusion has been confirmed by comparative studies of the catalytic performance of different FCC catalysts.

  11. Suppressed N2O formation during NH3 selective catalytic reduction using vanadium on zeolitic microporous TiO2

    PubMed Central

    Lee, Seung Gwan; Lee, Hyun Jeong; Song, Inhak; Youn, Seunghee; Kim, Do Heui; Cho, Sung June

    2015-01-01

    Emission of N2O from mobile and off-road engine is now being currently regulated because of its high impact compared to that of CO2, thereby implying that N2O formation from the exhaust gas after-treatment system should be suppressed. Selective catalytic reduction using vanadium supported TiO2 catalyst in mobile and off-road engine has been considered to be major source for N2O emission in the system. Here we have demonstrated that vanadium catalyst supported on zeolitic microporous TiO2 obtained from the hydrothermal reaction of bulk TiO2 at 400 K in the presence of LiOH suppresses significantly the N2O emission compared to conventional VOx/TiO2 catalyst, while maintaining the excellent NOx reduction, which was ascribed to the location of VOx domain in the micropore of TiO2, resulting in the strong metal support interaction. The use of zeolitic microporous TiO2 provides a new way of preparing SCR catalyst with a high thermal stability and superior catalytic performance. It can be also extended further to the other catalytic system employing TiO2-based substrate. PMID:26235671

  12. Suppressed N2O formation during NH3 selective catalytic reduction using vanadium on zeolitic microporous TiO2.

    PubMed

    Lee, Seung Gwan; Lee, Hyun Jeong; Song, Inhak; Youn, Seunghee; Kim, Do Heui; Cho, Sung June

    2015-08-03

    Emission of N2O from mobile and off-road engine is now being currently regulated because of its high impact compared to that of CO2, thereby implying that N2O formation from the exhaust gas after-treatment system should be suppressed. Selective catalytic reduction using vanadium supported TiO2 catalyst in mobile and off-road engine has been considered to be major source for N2O emission in the system. Here we have demonstrated that vanadium catalyst supported on zeolitic microporous TiO2 obtained from the hydrothermal reaction of bulk TiO2 at 400 K in the presence of LiOH suppresses significantly the N2O emission compared to conventional VOx/TiO2 catalyst, while maintaining the excellent NOx reduction, which was ascribed to the location of VOx domain in the micropore of TiO2, resulting in the strong metal support interaction. The use of zeolitic microporous TiO2 provides a new way of preparing SCR catalyst with a high thermal stability and superior catalytic performance. It can be also extended further to the other catalytic system employing TiO2-based substrate.

  13. Suppressed N2O formation during NH3 selective catalytic reduction using vanadium on zeolitic microporous TiO2

    NASA Astrophysics Data System (ADS)

    Lee, Seung Gwan; Lee, Hyun Jeong; Song, Inhak; Youn, Seunghee; Kim, Do Heui; Cho, Sung June

    2015-08-01

    Emission of N2O from mobile and off-road engine is now being currently regulated because of its high impact compared to that of CO2, thereby implying that N2O formation from the exhaust gas after-treatment system should be suppressed. Selective catalytic reduction using vanadium supported TiO2 catalyst in mobile and off-road engine has been considered to be major source for N2O emission in the system. Here we have demonstrated that vanadium catalyst supported on zeolitic microporous TiO2 obtained from the hydrothermal reaction of bulk TiO2 at 400 K in the presence of LiOH suppresses significantly the N2O emission compared to conventional VOx/TiO2 catalyst, while maintaining the excellent NOx reduction, which was ascribed to the location of VOx domain in the micropore of TiO2, resulting in the strong metal support interaction. The use of zeolitic microporous TiO2 provides a new way of preparing SCR catalyst with a high thermal stability and superior catalytic performance. It can be also extended further to the other catalytic system employing TiO2-based substrate.

  14. The nature of ruthenium sulfide cluster encaged in a Y zeolite

    SciTech Connect

    Moraweck, B.; Bergeret, G.; Cattenot, M.

    1997-01-01

    Catalysts of ruthenium sulfide supported in a dealuminated KY zeolite were prepared by ion exchange and subsequent sulfidation using several atmospheres containing sulfur. They were characterized by means of HREM, EDX, TPR, and EXAFS. The activity for the tetralin hydrogenation, carried out in presence of large amounts of H{sub 2}S (1.85%), was very high and roughly 300 times the activity (expressed per metal atom) of an industrial NiMo/Al{sub 2}O{sub 3} hydrotreating catalyst. A simple modeling of the results obtained by the physicochemical techniques suggests that the active phase consists of clusters of less than 50 ruthenium atoms of a ruthenium sulfide-like phase with very small domains of ruthenium metal. 20 refs., 10 figs., 3 tabs.

  15. Hydrogen Purification Using Natural Zeolite Membranes

    NASA Technical Reports Server (NTRS)

    DelValle, William

    2003-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  17. Active Fe-Containing Superoxide Dismutase and Abundant sodF mRNA in Nostoc commune (Cyanobacteria) after Years of Desiccation

    PubMed Central

    Shirkey, Breanne; Kovarcik, Don Paul; Wright, Deborah J.; Wilmoth, Gabriel; Prickett, Todd F.; Helm, Richard F.; Gregory, Eugene M.; Potts, Malcolm

    2000-01-01

    Active Fe-superoxide dismutase (SodF) was the third most abundant soluble protein in cells of Nostoc commune CHEN/1986 after prolonged (13 years) storage in the desiccated state. Upon rehydration, Fe-containing superoxide disumutase (Fe-SOD) was released and the activity was distributed between rehydrating cells and the extracellular fluid. The 21-kDa Fe-SOD polypeptide was purified, the N terminus was sequenced, and the data were used to isolate sodF from the clonal isolate N. commune DRH1. sodF encodes an open reading frame of 200 codons and is expressed as a monocistronic transcript (of approximately 750 bases) from a region of the genome which includes genes involved in nucleic acid synthesis and repair, including dipyrimidine photolyase (phr) and cytidylate monophosphate kinase (panC). sodF mRNA was abundant and stable in cells after long-term desiccation. Upon rehydration of desiccated cells, there was a turnover of sodF mRNA within 15 min and then a rise in the mRNA pool to control levels (quantity of sodF mRNA in cells in late logarithmic phase of growth) over approximately 24 h. The extensive extracellular polysaccharide (glycan) of N. commune DRH1 generated superoxide radicals upon exposure to UV-A or -B irradiation, and these were scavenged by SOD. Despite demonstrated roles for the glycan in the desiccation tolerance of N. commune, it may in fact be a significant source of damaging free radicals in vivo. It is proposed that the high levels of SodF in N. commune, and release of the enzyme from dried cells upon rehydration, counter the effects of oxidative stress imposed by multiple cycles of desiccation and rehydration during UV-A or -B irradiation in situ. PMID:10613879

  18. Studies of anions sorption on natural zeolites.

    PubMed

    Barczyk, K; Mozgawa, W; Król, M

    2014-12-10

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

  19. Optimizing anti-coking abilities of zeolites by ethylene diamine tetraacetie acid modification on catalytic fast pyrolysis of corn stalk

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Zhong, Zhaoping; Song, Zuwei; Ding, Kuan; Chen, Paul; Ruan, Roger

    2015-12-01

    In order to minimize coke yield during biomass catalytic fast pyrolysis (CFP) process, ethylene diamine tetraacetie acid (EDTA) chemical modification method is carried out to selectively remove the external framework aluminum of HZSM-5 catalyst. X-ray diffraction (XRD), nitrogen (N2)-adsorption and ammonia-temperature programmed desorption (NH3-TPD) techniques are employed to investigate the porosity and acidity characteristics of original and modified HZSM-5 samples. Py-GC/MS and thermo-gravimetric analyzer (TGA) experiments are further conducted to explore the catalytic effect of modified HZSM-5 samples on biomass CFP and to verify the positive effect on coke reduction. Results show that EDTA treatment does not damage the crystal structure of HZSM-5 zeolites, but leads to a slight increase of pore volume and pore size. Meanwhile, the elimination of the strong acid peak indicates the dealumination of outer surface of HZSM-5 zeolites. Treatment time of 2 h (labeled EDTA-2H) is optimal for acid removal and hydrocarbon formation. Among all modified catalysts, EDTA-2H performs the best for deacidification and can obviously increase the yields of positive chemical compositions in pyrolysis products. Besides, EDTA modification can improve the anti-coking properties of HZSM-5 zeolites, and EDTA-2H gives rise to the lowest coke yield.

  20. Decomposition of NO over [Co]-ZSM-5 zeolite: Effect of co-adsorbed O{sub 2}

    SciTech Connect

    Chang, Y.; McCarty, J.G.

    1998-09-10

    The decomposition of NO over four Co-containing ZSM-5 zeolites and Pr, Ga-, and Cu-exchanged ZSM-5 zeolites was investigated using the isotope labeled {sup 15}N{sup 18}O and a temperature-programmed desorption (TPD) technique. The authors found that [Co]-ZSM-5 that contains Co in the framework had the highest activity for NO decomposition, almost an order of magnitude greater than that previously reported for a zeolite catalyst, namely Cu-ZSM-5 obtained under steady-state conditions. The phenomenally high activity of [Co]-ZSM-5 is due to the unique incorporation of Co{sup 2+} in the siliceous MFI structure. For all the catalysts investigated, co-adsorption of NO and O{sub 2} led to a substantial increase in the amount of NO{sub x} adsorbed. However, the adsorbed species were not necessarily NO{sub 2} as reported by others. The authors believe that the interaction between adsorbed NO{sub x} species and O{sub 2} is responsible for enhancing the rate of NO{sub x} decomposition. It is obvious that the framework Co{sup 2+} behaves very differently from Co{sup 2+} in the countercation position and from extra-framework CoO such as that supported on or dispersed on the surface of silicalite also having the same MFI structure.

  1. Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis.

    PubMed

    Vogt, E T C; Weckhuysen, B M

    2015-10-21

    Fluid catalytic cracking (FCC) is one of the major conversion technologies in the oil refinery industry. FCC currently produces the majority of the world's gasoline, as well as an important fraction of propylene for the polymer industry. In this critical review, we give an overview of the latest trends in this field of research. These trends include ways to make it possible to process either very heavy or very light crude oil fractions as well as to co-process biomass-based oxygenates with regular crude oil fractions, and convert these more complex feedstocks in an increasing amount of propylene and diesel-range fuels. After providing some general background of the FCC process, including a short history as well as details on the process, reactor design, chemical reactions involved and catalyst material, we will discuss several trends in FCC catalysis research by focusing on ways to improve the zeolite structure stability, propylene selectivity and the overall catalyst accessibility by (a) the addition of rare earth elements and phosphorus, (b) constructing hierarchical pores systems and (c) the introduction of new zeolite structures. In addition, we present an overview of the state-of-the-art micro-spectroscopy methods for characterizing FCC catalysts at the single particle level. These new characterization tools are able to explain the influence of the harsh FCC processing conditions (e.g. steam) and the presence of various metal poisons (e.g. V, Fe and Ni) in the crude oil feedstocks on the 3-D structure and accessibility of FCC catalyst materials. PMID:26382875

  2. Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis

    PubMed Central

    2015-01-01

    Fluid catalytic cracking (FCC) is one of the major conversion technologies in the oil refinery industry. FCC currently produces the majority of the world's gasoline, as well as an important fraction of propylene for the polymer industry. In this critical review, we give an overview of the latest trends in this field of research. These trends include ways to make it possible to process either very heavy or very light crude oil fractions as well as to co-process biomass-based oxygenates with regular crude oil fractions, and convert these more complex feedstocks in an increasing amount of propylene and diesel-range fuels. After providing some general background of the FCC process, including a short history as well as details on the process, reactor design, chemical reactions involved and catalyst material, we will discuss several trends in FCC catalysis research by focusing on ways to improve the zeolite structure stability, propylene selectivity and the overall catalyst accessibility by (a) the addition of rare earth elements and phosphorus, (b) constructing hierarchical pores systems and (c) the introduction of new zeolite structures. In addition, we present an overview of the state-of-the-art micro-spectroscopy methods for characterizing FCC catalysts at the single particle level. These new characterization tools are able to explain the influence of the harsh FCC processing conditions (e.g. steam) and the presence of various metal poisons (e.g. V, Fe and Ni) in the crude oil feedstocks on the 3-D structure and accessibility of FCC catalyst materials. PMID:26382875

  3. Formation of the active surface of Ag/SiO2 catalysts in the presence of FeOx additives

    NASA Astrophysics Data System (ADS)

    Savel'eva, A. S.; Vodyankina, O. V.

    2014-12-01

    Supported FeOx-modified silver catalysts based on commercial silica gel and prepared via impregnation with a solution of Fe- and Ag-containing salts while varying the amount of modifier from 1 to 10 wt % are studied. It is found that the introduction of Fe-containing compounds leads to the distribution of silver in the form of clusters/ions on the surface of SiO2, improving the reducibility of the systems in the H2 TPR mode. After reduction at 800°C, the catalysts containing 10 wt % iron and 5 wt % silver comprise a Fe2SiO4 iron silicate phase.

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

    PubMed

    Valdés, Héctor; Alejandro, Serguei; Zaror, Claudio A

    2012-08-15

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

  5. Synthesis of zeolite as ordered multicrystal arrays.

    PubMed

    Lee, Jin Seok; Lee, Yun-Jo; Tae, Eunju Lee; Park, Yong Soo; Yoon, Kyung Byung

    2003-08-01

    Zeolites are crystalline nanoporous aluminosilicates widely used in industry. In order for zeolites to find applications as innovative materials, they need to be organized into large two- and three-dimensional (2D and 3D) arrays. We report that uniformly aligned polyurethane films can serve as templates for the synthesis of uniformly aligned 2D and possibly 3D arrays of silicalite-1 crystals, in which the orientations of the crystals are controlled by the nature of the polymers. We propose that the supramolecularly organized organic-inorganic composites that consist of the hydrolyzed organic products and the seed crystals are responsible for this phenomenon.

  6. Congressionally Directed Project for Passive NOx Removal Catalysts Research

    SciTech Connect

    Schneider, William

    2014-08-29

    The Recipient proposes to produce new scientific and technical knowledge and tools to enable the discovery and deployment of highly effective materials for the selective catalytic reduction (SCR) of nitrogen oxides (NOx) from lean combustion exhaust. A second goal is to demonstrate a closely coupled experimental and computational approach to heterogeneous catalysis research. These goals will be met through the completion of four primary technical objectives: First, an in-depth kinetic analysis will be performed on two prominent classes of NOx SCR catalysts, Fe- and Cu-exchanged beta and ZSM-5 zeolites, over a wide range of catalyst formulation and under identical, high conversion conditions as a function of gas phase composition. Second, the nanoscale structure and adsorption chemistry of these high temperature (HT) and low temperature (LT) catalysts will be determined using in situ and operando spectroscopy under the same reaction conditions. Third, first-principles molecular simulations will be used to model the metal-zeolite active sites, their adsorption chemistry, and key steps in catalytic function. Fourth, this information will be integrated into chemically detailed mechanistic and kinetic descriptions and models of the operation of these well- defined NOx SCR catalysts under practically relevant reaction conditions. The new knowledge and models that derive from this work will be published in the scientific literature.

  7. Comparision of real waste (MSW and MPW) pyrolysis in batch reactor over different catalysts. Part I: product yields, gas and pyrolysis oil properties.

    PubMed

    Ateş, Funda; Miskolczi, Norbert; Borsodi, Nikolett

    2013-04-01

    Pyrolysis of municipal solid waste (MSW) and municipal plastic waste (MPW) have been investigated in batch reactor at 500, 550 and 600°C both in absence and presence of catalysts (Y-zeolite, β-zeolite, equilibrium FCC, MoO3, Ni-Mo-catalyst, HZSM-5 and Al(OH)3). The effect of the parameters on the product properties was investigated. Products were characterized using gas-chromatography, GC/MS, (13)C NMR. Yields of volatile fractions increased, while reaction time necessity for the total cracking decreased in the presence of catalysts. Catalysts have productivity and selectivity in converting aliphatic hydrocarbons to aromatic and cyclic compounds in oil products. Gases from MSW consisted of hydrogen CO, CO2, while exclusively hydrogen and hydrocarbons were detected from MPW. Catalyst efficiency was higher using MPW than MSW. Pyrolysis oils contained aliphatic hydrocarbons, aromatics, cyclic compounds and less ketones, alcohols, acids or esters depending on the raw materials. PMID:23455219

  8. Effects of Hydrothermal Aging on NH3-SCR reaction over Cu/zeolites

    SciTech Connect

    Kwak, Ja Hun; Tran, Diana N.; Burton, Sarah D.; Szanyi, Janos; Lee, Jong H.; Peden, Charles HF

    2012-02-06

    The effects of hydrothermal treatment on model Cu/zeolite catalysts were investigated to better understand the nature of Cu species for the selective catalytic reduction of NO{sub x} by NH{sub 3}. After hydrothermal aging at 800 C for 16 h, the NO{sub x} reduction performance of Cu-ZSM-5 and Cu-beta were significantly reduced at low temperatures, while that of Cu-SSZ-13 was not affected. When the zeolite framework aluminum species were probed using solid state {sup 27}Al-NMR, significant reduction in the intensities of the tetrahedral aluminum peak was observed for Cu-ZSM-5 and Cu-beta, although no increase in the intensities of the octahedral aluminum peak was observed. When the redox behavior of Cu species was examined using H{sub 2}-TPR, it was found that Cu{sup 2+} could be reduced to Cu{sup +} and to Cu{sup 0} fir Cu-ZSM-5 and Cu-beta catalysts, while Cu{sup 2+} could be reduced to Cu{sup +} only for Cu-SSZ-13. After hydrothermal aging, CuO and Cu-aluminate species were found to form in Cu-ZSM-5 and Cu-beta, while little changes were observed for Cu-SSZ-13.

  9. Extended Catalyst Longevity Via Supercritical Isobutane Regeneration of a Partially Deactivated USY Alkylation Catalyst

    SciTech Connect

    Daniel M. Ginosar; David N. Thompson; Kyle C. Burch; David J. Zalewski

    2005-05-01

    Off-line, in situ activity recovery of a partially deactivated USY zeolite catalyst used for isobutane/butene alkylation was examined in a continuous-flow reaction system employing supercritical isobutane. Catalyst samples were deactivated in a controlled manner by running them to either to a fixed butene conversion level of 95% or a fixed time on stream of three hours, and then exposing the catalyst to supercritical isobutane to restore activity. Activity recovery was determined by comparing alkylation activity before and after the regeneration step. Both single and multiple regenerations were performed. Use of a 95% butene conversion level criterion to terminate the reaction step afforded 86% activity recovery for a single regeneration and provided nine sequential reaction steps for the multiple regeneration studies. Employing a fixed 3 h time on stream criterion resulted in nearly complete activity recovery for a single regeneration, and 24 reaction steps were demonstrated in sequence for the multiple regeneration process, producing only minor product yield declines per step. This resulted in a 12-fold increase in catalyst longevity versus unregenerated catalyst.

  10. Catalyst suppliers consolidate further, offer more catalysts

    SciTech Connect

    Rhodes, A.K.

    1995-10-02

    The list of suppliers of catalysts to the petroleum refining industry has decreased by five since Oil and Gas Journal`s survey of refining catalysts and catalytic additives was last published. Despite the consolidation, the list of catalyst designations has grown to about 950 in this latest survey, compared to 820 listed in 1993. The table divides the catalysts by use and gives data on their primary differentiating characteristics, feedstock, products, form, bulk density,catalyst support, active agents, availability, and manufactures.

  11. Rigid zeolite containing polyurethane foams

    DOEpatents

    Frost, Charles B.

    1985-01-01

    A closed cell rigid polyurethane foam has been prepared which contains up to about 60% by weight of molecular sieves capable of sorbing molecules with effective critical diameters of up to about 10 .ANG.. The molecular sieve component of the foam can be preloaded with catalysts or with reactive compounds that can be released upon activation of the foam to control and complete crosslinking after the foam is formed. The foam can also be loaded with water or other flame-retarding agents, after completion. Up to about 50% of the weight of the isocyanate component of the foam can be replaced by polyimide resin precursors for incorporation into the final polymeric network.

  12. Rigid zeolite containing polyurethane foams

    DOEpatents

    Frost, C.B.

    1984-05-18

    A closed cell rigid polyurethane foam has been prepared which contains up to about 60% by weight of molecular sieves capable of sorbing molecules with effective critical diameters of up to about 10 A. The molecular sieve component of the foam can be preloaded with catalysts or with reactive compounds that can be released upon activation of the foam to control and complete crosslinking after the foam is formed. The foam can also be loaded with water or other flame-retarding agents, after completion. Up to about 50% of the weight of the isocyanate component of the foam can be replaced by polyimide resin precursors for incorporation into the final polymeric network.

  13. Photodecomposition of carbaryl in the presence of silver-doped zeolite Y and Suwannee River natural organic matter.

    PubMed

    Kanan, Marsha C; Kanan, Sofian M; Austin, Rachel N; Patterson, Howard H

    2003-05-15

    The synthesis and characterization of a novel catalyst for the photodecomposition of carbaryl (1-naphthyl, N-methylcarbamate) is reported. In the absence of a catalyst, but in the presence of UV light a 30 ppm solution of carbaryl decomposes with a first-order rate constant of (5.6 +/- 0.3) x 10(-5) s(-1) (298 K) and a quantum efficiency of 4.8 x 10(-3) molecules/photon. In the presence of the Ag-zeolite Y catalyst with 2.42% Ag by weight, the photodecomposition rate becomes 80 times faster. The addition of Suwannee River natural organic matter (NOM), which can inactivate photocatalysts, has a minimal effect on this system. In the presence of three different concentrations of NOM and 30 ppm carbaryl, our results indicate that the NOM increases or decreases the catalytic photodecomposition rate by only a factor of 3 at most. PMID:12785537

  14. Decoupling HZSM-5 catalyst activity from deactivation during upgrading of pyrolysis oil vapors.

    PubMed

    Wan, Shaolong; Waters, Christopher; Stevens, Adam; Gumidyala, Abhishek; Jentoft, Rolf; Lobban, Lance; Resasco, Daniel; Mallinson, Richard; Crossley, Steven

    2015-02-01

    The independent evaluation of catalyst activity and stability during the catalytic pyrolysis of biomass is challenging because of the nature of the reaction system and rapid catalyst deactivation that force the use of excess catalyst. In this contribution we use a modified pyroprobe system in which pulses of pyrolysis vapors are converted over a series of HZSM-5 catalysts in a separate fixed-bed reactor controlled independently. Both the reactor-bed temperature and the Si/Al ratio of the zeolite are varied to evaluate catalyst activity and deactivation rates independently both on a constant surface area and constant acid site basis. Results show that there is an optimum catalyst-bed temperature for the production of aromatics, above which the production of light gases increases and that of aromatics decrease. Zeolites with lower Si/Al ratios give comparable initial rates for aromatics production, but far more rapid catalyst deactivation rates than those with higher Si/Al ratios. PMID:25504857

  15. Rationalizing inter- and intracrystal heterogeneities in dealuminated acid mordenite zeolites by stimulated Raman scattering microscopy correlated with super-resolution fluorescence microscopy.

    PubMed

    Liu, Kuan-Lin; Kubarev, Alexey V; Van Loon, Jordi; Uji-i, Hiroshi; De Vos, Dirk E; Hofkens, Johan; Roeffaers, Maarten B J

    2014-12-23

    Dealuminated zeolites are widely used acid catalysts in research and the chemical industry. Bulk-level studies have revealed that the improved catalytic performance results from an enhanced molecular transport as well as from changes in the active sites. However, fully exploiting this information in rational catalyst design still requires insight in the intricate interplay between both. Here we introduce fluorescence and stimulated Raman scattering microscopy to quantify subcrystal reactivity as well as acid site distribution and to probe site accessibility in the set of individual mordenite zeolites. Dealumination effectively introduces significant heterogeneities between different particles and even within individual crystals. Besides enabling direct rationalization of the nanoscale catalytic performance, these observations reveal valuable information on the industrial dealumination process itself.

  16. Rationalizing Inter- and Intracrystal Heterogeneities in Dealuminated Acid Mordenite Zeolites by Stimulated Raman Scattering Microscopy Correlated with Super-resolution Fluorescence Microscopy

    PubMed Central

    2014-01-01

    Dealuminated zeolites are widely used acid catalysts in research and the chemical industry. Bulk-level studies have revealed that the improved catalytic performance results from an enhanced molecular transport as well as from changes in the active sites. However, fully exploiting this information in rational catalyst design still requires insight in the intricate interplay between both. Here we introduce fluorescence and stimulated Raman scattering microscopy to quantify subcrystal reactivity as well as acid site distribution and to probe site accessibility in the set of individual mordenite zeolites. Dealumination effectively introduces significant heterogeneities between different particles and even within individual crystals. Besides enabling direct rationalization of the nanoscale catalytic performance, these observations reveal valuable information on the industrial dealumination process itself. PMID:25402756

  17. Interaction of water and ammonium in NaHY zeolite as detected by combined IR and gravimetric analysis (AGIR).

    PubMed

    Bazin, Philippe; Alenda, Aurélie; Thibault-Starzyk, Frédéric

    2010-09-28

    Qualitative as well as quantitative information is obtained simultaneously by combining thermogravimetry and operando IR spectroscopy with on line mass spectrometry. A microbalance has been adapted to an infrared reactor cell. The weight and IR spectra of a solid sample can be measured together in real time in operando conditions, in a gas flow at temperature between room temperature and 773 K. Molar absorbance coefficients epsilons can be obtained directly. The new technique was first applied to adsorbed water and ammonia on a solid acid catalyst, HY zeolite. Epsilon coefficients for water bands were measured. They are influence by the hydration level, and the nu+delta combination band is shown to be a much better option to determine the amount of adsorbed water on zeolites. Epsilon has also been measured for ammonium ions, and water was shown to greatly influence the spectral response of these ions.

  18. Multicomponent liquid ion exchange with chabazite zeolites

    SciTech Connect

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

    1993-10-01

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

  19. MERCURY SEPARATION FROM POLLUTANT WATER USING ZEOLITES

    EPA Science Inventory

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

  20. Zeolite 5A Catalyzed Etherification of Diphenylmethanol

    ERIC Educational Resources Information Center

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

    2009-01-01

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

  1. Energetics of sodium-calcium exchanged zeolite A.

    PubMed

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

    2015-05-01

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

  2. Zeolite Nanoparticles for Selective Sorption of Plasma Proteins

    PubMed Central

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

    2015-01-01

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

  3. Zeolite Nanoparticles for Selective Sorption of Plasma Proteins.

    PubMed

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

    2015-01-01

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

  4. Zeolite Nanoparticles for Selective Sorption of Plasma Proteins

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  5. Tuning interactions between zeolite and supported metal by physical-sputtering to achieve higher catalytic performances

    PubMed Central

    Li, Xin-Gang; Liu, Cheng; Sun, Jian; Xian, Hui; Tan, Yi-Sheng; Jiang, Zheng; Taguchi, Akira; Inoue, Mitsuhiro; Yoneyama, Yoshiharu; Abe, Takayuki; Tsubaki, Noritatsu

    2013-01-01

    To substitute for petroleum, Fischer-Tropsch synthesis (FTS) is an environmentally benign process to produce synthetic diesel (n-paraffin) from syngas. Industrially, the synthetic gasoline (iso-paraffin) can be produced with a FTS process followed by isomerization and hydrocracking processes over solid-acid catalysts. Herein, we demonstrate a cobalt nano-catalyst synthesized by physical-sputtering method that the metallic cobalt nano-particles homogeneously disperse on the H-ZSM5 zeolite support with weak Metal-Support Interactions (MSI). This catalyst performed the high gasoline-range iso-paraffin productivity through the combined FTS, isomerization and hydrocracking reactions. The weak MSI results in the easy reducibility of the cobalt nano-particles; the high cobalt dispersion accelerates n-paraffin diffusion to the neighboring acidic sites on the H-ZSM5 support for isomerization and hydrocracking. Both factors guarantee its high CO conversion and iso-paraffin selectivity. This physical-sputtering technique to synthesize the supported metallic nano-catalyst is a promising way to solve the critical problems caused by strong MSI for various processes. PMID:24085106

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

    EPA Science Inventory

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

  7. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst. Technical progress report No. 17, 1 November 1993--31 December 1993

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1994-06-01

    Very high cobalt catalysts have been prepared on steamed and acid-washed y zeolite. These catalysts are very active. Some of them have proven to be very stable. Additionally, if provisions are made to control the temperature build up on the catalyst bed, low methane selectivities result. Additional work is indicated, for instance, perhaps even higher activity catalysts can result from higher levels of cobalt or changes in the catalyst preparation procedure. Since the issue of whether small amounts of ruthenium can promote the catalyst is not completely resolved, catalyst preparation procedure experiments should continue with ruthenium vs. ruthenium-free catalysts. For instance, different methods of impregnation and/or activation should be investigated.

  8. CO2 SEPARATIONS USING ZEOLITE MEMBRANES

    SciTech Connect

    Richard D. Noble; John L. Falconer

    2001-06-30

    Zeolite and other inorganic molecular sieve membranes have shown potential for separations based on molecular size and shape because of their small pore sized, typically less than 1 nm, and their narrow pore size distribution. The high thermal and chemical stability of these inorganic crystals make them ideal materials for use in high temperature applications such as catalytic membrane reactors. Most of the progress with zeolite membranes has been with MFI zeolites prepared on porous disks and tubes. The MFI zeolite is a medium pore size structure having nearly circular pores with diameters between .53 and .56 nm. Separation experiments through MFI membranes indicate that competitive adsorption separates light gas mixtures. Light gas selectivities are typically small, however, owing to small differences in adsorption strengths and their small sizes relative to the MFI pore opening. Furthermore, competitive adsorption does not work well at high temperature where zeolite membranes are stable and have potential application. Separation by differences in size has a greater potential to work at high temperature than competitive adsorption, but pores smaller than those in MFI zeolites are required. Therefore, some studies focused on the synthesis of a small, 8-membered-pore structures such as zeolite A (0.41-nm pore diameter) and SAPO-34, a chabazite (about .4-nm pore diameter with about 1.4 nm cages) analog. The small pore size of the zeolite A and SAPO-34 structures made the separation of smaller molecules by differences in size possible. Zeolite MFI and SAPO-34 membranes were prepared on the inside surface of porous alumina tubes by hydrothermal synthesis, and single gas and binary mixture permeances were measured to characterize the membrane's performance. A mathematical diffusion model was developed to determine the relative quantities of zeolite and non-zeolite pores in different membranes by modeling the permeation date of CO{sub 2}. This model expresses the total

  9. [Catalyst research]. Final Report

    SciTech Connect

    Ian P Rothwell; David R McMillin

    2005-03-14

    Research results are the areas of catalyst precursor synthesis, catalyst fluxionality, catalyst stability, polymerization of {alpha}-olefins as well as the chemistry of Group IV and Group V metal centers with aryloxide and arylsulfide ligands.

  10. Pt-free carbon-based fuel cell catalyst prepared from spherical polyimide for enhanced oxygen diffusion.

    PubMed

    Nabae, Yuta; Nagata, Shinsuke; Hayakawa, Teruaki; Niwa, Hideharu; Harada, Yoshihisa; Oshima, Masaharu; Isoda, Ayano; Matsunaga, Atsushi; Tanaka, Kazuhisa; Aoki, Tsutomu

    2016-03-18

    The development of a non-precious metal (NPM) fuel cell catalyst is extremely important to achieve globalization of polymer electrolyte fuel cells due to the cost and scarcity of platinum. Here, we report on a NPM cathode catalyst prepared by the pyrolysis of spherical polyimide nanoparticles that contain small amounts of Fe additive. 60 nm diameter Fe-containing polyimide nanoparticles were successfully synthesized by the precipitation polymerization of pyromellitic acid dianhydride and 1,3,5-tris(4-aminophenyl)benzene with Fe(acac)3 (acac = acetylacetonate) as an additive. The particles were subsequently carbonized by multistep pyrolysis to obtain the NPM catalyst while retaining the small particle size. The catalyst has good performance and promising durability for fuel cell applications. The fuel cell performance under a 0.2 MPa air atmosphere at 80 °C of 1.0 A cm(-2) at 0.46 V is especially remarkable and better than that previously reported.

  11. [The Application of X-Ray Photoelectron Spectroscopy on Refining Catalyst].

    PubMed

    Qiu, Li-mei; Xu, Guang-tong

    2015-12-01

    Abstract XPS analysis provides qualitative, quantitative and chemical state information for surface elements of solid materials. Therefore, XPS is widely applied in the characterization of refining catalyst. In the present paper, the applications of XPS in the field of typical refining catalysts, including hydrogenation catalyst, S Zorb sorbent and rare-earth modified Y zeolite, are illustrated and exemplified. For sulfided Co (Ni)-Mo (W)/Al₂O₃(-SiO₂) hydrodesulfurization catalysts, the anhydrous oxygen-free transfer process from the reactor to XPS chamber was illustrated. The identification and peak fitting of S(2p) , Mo(3d), W (4f), Co(2p) and Ni(2p) XPS spectra were summarized. The typical chemical states of the active elements were described. Based on these results, the sulfidation extents of the active metals and the cause for the sulfidation inadequency of the catalysts were deduced. As for the application of XPS in S Zorb sorbent, the existence form of zinc was obtained from ZnLMM Auger spectra, and the fracture mechanism and deactivation reason of the sorbent were derived. The distribution of sulfur along the vertical direction was investigated using XPS and argon ion sputtering XPS. Besides, in situ XPS was applied to study the conversion of sulfur- and nickel-containing species for spent sorbent under hydrogen condition. Finally, for cerium modified Y zeolite, the location of cerium ion inside and outside Y zeolite cage was investigated. The results indicate that the liquid phase method is more suitable for the migration of cerium ion toward zeolite as compared with the solid phase method. PMID:26964241

  12. Optimization of levulinic acid from lignocellulosic biomass using a new hybrid catalyst.

    PubMed

    Ya'aini, Nazlina; Amin, Nor Aishah Saidina; Asmadi, Mohd

    2012-07-01

    Conversion of glucose, empty fruit bunch (efb) and kenaf to levulinic acid over a new hybrid catalyst has been investigated in this study. The characterization and catalytic performance results revealed that the physico-chemical properties of the new hybrid catalyst comprised of chromium chloride and HY zeolite increased the levulinic acid production from glucose compared to the parent catalysts. Optimization of the glucose conversion process using two level full factorial designs (2(3)) with two center points reported 55.2% of levulinic acid yield at 145.2 °C, 146.7 min and 12.0% of reaction temperature, reaction time and catalyst loading, respectively. Subsequently, the potential of efb and kenaf for producing levulinic acid at the optimum conditions was established after 53.2% and 66.1% of efficiencies were reported. The observation suggests that the hybrid catalyst has a potential to be used in biomass conversion to levulinic acid. PMID:22609656

  13. Nickel and vanadium on equilibrium cracking catalysts by imaging secondary ion mass spectroscopy

    SciTech Connect

    Kugler, E.L.; Leta, D.P.

    1988-02-01

    The distribution of nickel and vanadium has been determined on refinery samples of several types of fluidized catalytic cracking catalyst. Data from imaging secondary ion mass spectrometry show that metals in catalytic cracking feedstocks initially deposit near the external surface of catalyst particles. Nickel remains in the area where it was deposited, while vanadium shows both intraparticle and interparticle mobility. Vanadium accumulates throughout catalyst particles, but shows a preference for both rare earth exchanged Y-zeolite and alumina phases in composite catalyst. By contrast, nickel shows no preference for catalyst phases and accumulates monotonically with time. The lack of mobility in deposited nickel makes it a good measure to determine the age of individual particles.

  14. 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

  15. In Situ Confinement of Ultrasmall Pd Clusters within Nanosized Silicalite-1 Zeolite for Highly Efficient Catalysis of Hydrogen Generation.

    PubMed

    Wang, Ning; Sun, Qiming; Bai, Risheng; Li, Xu; Guo, Guanqi; Yu, Jihong

    2016-06-22

    Well-dispersed and ultrasmall Pd clusters in nanosized silicalite-1 (MFI) zeolite have been prepared under direct hydrothermal conditions using [Pd(NH2CH2CH2NH2)2]Cl2 as precursor. High-resolution scanning transmission electron microscopy studies indicate that the Pd clusters are encapsulated within the intersectional channels of MFI, and the Pd clusters in adjacent channels visually aggregate, forming nanoparticles (NPs) of ∼1.8 nm. The resultant catalysts show an excellent activity and highly efficient H2 generation toward the complete decomposition of formic acid (FA) under mild conditions. Notably, thanks to the further reduced Pd NP size (∼1.5 nm) and the additionally introduced basic sites, the Pd/S-1-in-K catalyst affords turnover frequency values up to 856 h(-1) at 25 °C and 3027 h(-1) at 50 °C. The easy in situ confinement synthesis of metal clusters in zeolites endows the catalysts with superior catalytic activities, excellent recyclability, and high thermal stability, thus opening new perspectives for the practical application of FA as a viable and effective H2 storage material for use in fuel cells. PMID:27248462

  16. Preparation of Robust, Thin Zeolite Membrane Sheet for Molecular Separation

    SciTech Connect

    Liu, Wei; Zhang, Jian; Canfield, Nathan L.; Saraf, Laxmikant V.

    2011-10-19

    This paper reports a feasibility study on the preparation of zeolite membrane films on a thin, porous metal support sheet (50-{micro}m thick). Zeolite sodium A (NaA) and silicalite zeolite frameworks are chosen to represent synthesis of respective hydrophilic-type and hydrophobic-type zeolite membranes on this new support. It is found that a dense, continuous inter-grown zeolite crystal layer at a thickness less than 2 {micro}m can be directly deposited on such a support by using direct and secondary growth techniques. The resulting membrane shows excellent adhesion on the metal sheet. Molecular-sieving functions of the prepared membranes are characterized with ethanol/water separation, CO2 separation, and air dehumidification. The results show great potential to make flexible metal-foil-like zeolite membranes for a range of energy conversion and environmental applications.

  17. Prediction of Zeolite Framework Types by a Machine Learning Approach

    NASA Astrophysics Data System (ADS)

    Yang, Shujiang; Lach-Hab, Mohammed; Vaisman, Iosif; Blaisten-Barojas, Estela

    2009-03-01

    Zeolites are microporous crystalline materials with highly regular framework structures consisting of molecular-sized pores and channels. Characteristic framework types of zeolites are traditionally determined by the combined information of coordination sequences and vertex symbols. Here we present a machine learning model for classifying zeolite crystals according to their framework types. An eighteen-dimensional feature vector is defined including topological descriptors and physical/chemical properties of zeolite crystals [Microporous and Mesoporous Materials 117, 339 (2009)]. Trained with crystallographic data of known zeolites, the new model can predict the framework types of unknown zeolite crystals with up to 98 % accuracy. Compared with conventional methods, the machine learning model is more robust handling crystal disorder and/or crystal defects in a more effective manner. This model can be adapted for classifying and clustering other crystalline species.

  18. Zeolite and swine inoculum effect on poultry manure biomethanation

    NASA Astrophysics Data System (ADS)

    Kougias, P. G.; Fotidis, I. A.; Zaganas, I. D.; Kotsopoulos, T. A.; Martzopoulos, G. G.

    2013-03-01

    Poultry manure is an ammonia-rich substrate that inhibits methanogenesis, causing severe problems to the anaerobic digestion process. In this study, the effect of different natural zeolite concentrations on the mesophilic anaerobic digestion of poultry waste inoculated with well-digested swine manure was investigated. A significant increase in methane production was observed in treatments where zeolite was added, compared to the treatment without zeolite.Methane production in the treatment with 10 g dm-3 of natural zeolite was found to be 109.75% higher compared to the treatment without zeolite addition. The results appear to be influenced by the addition of zeolite, which reduces ammonia toxicity in anaerobic digestion and by the ammonia-tolerant swine inoculum.

  19. Inclusion of polyaniline filaments in zeolite molecular sieves

    SciTech Connect

    Enzel, P.; Bein, T. )

    1989-08-24

    Polyaniline has been synthesized in the channels of mordenite (one-dimensional) and zeolite Y (three-dimensional). Aniline was diffused from hexane solution into dehydrated zeolite pores containing different concentrations of framework hydroxyl groups. Addition of (NH{sub 4}){sub 2}S{sub 2}O{sub 8} to an aqueous suspension of the loaded zeolites afforded intrazeolite polyaniline chains, as demonstrated by FTIR, electronic absorption data, and recovery of the included polymer. Stoichiometric, kinetic, XPS, and microscopic data and the absence of bulk conductivity of the polymer/zeolite powders lead to the conclusion that the polymer is formed inside the host channel system. While the polyaniline chains in mordenite channels appear to be more highly oxidized than in Y zeolite, both systems show spectroscopic features typical of emeraldine base and emeraldine salt polymers. The polyaniline/zeolite hybrids represent a new class of materials containing synthetic conductors encapsulated in crystalline inorganic hosts with channel systems of molecular dimensions.

  20. Simultaneous SO{sub 2}/NO{sub x} abatement using zeolite-supported copper. Progress report, October 1, 1993--September 30, 1994

    SciTech Connect

    Mitchell, M.B.; White, M.G.

    1994-12-31

    The goals of this project have evolved from an investigation of ways of preparing Li and Hall`s Cu-ZSM-5 catalyst using new methods to yield a more robust catalyst, into an investigation of modified Cu-ZSM-5 catalysts for the simultaneous reduction of NO and oxidation of SO{sub 2}. This was not a conscious effort or decision on the part of the investigators, but resulted from a natural evolution of the project. The authors have developed a zeolite synthesis and characterization capability in the group and have prepared impregnated test materials for the investigation of different catalyst precursors. They have prepared different vanadium-impregnated aluminas, for evaluation of the impregnation method, and have succeeded in reproducing the results of Li and Hall`s Cu-ZSM-5 catalyst. This report reviews the progress during the first three quarters of the year, and includes progress from the last quarter. Results are discussed for the Raman spectroscopy of precursors; infrared spectroscopy of vanadium-impregnated alumina; zeolite overlayer on cordierite; reactivity of Cu-ZSM-5; and impregnation of vanadyl acetylacetonate on alumina.

  1. Asymmetric printing of molecules and zeolites on self assembled monolayers.

    PubMed

    Kehr, Nermin Seda; Schäfer, Andreas; Ravoo, Bart Jan; De Cola, Luisa

    2010-04-01

    Microcontact printing (mCP) is used to immobilize dyes and peptides asymmetrically, by a "peptide coupling" reaction, on monolayers of zeolite L crystals in the contact area between the stamp and the surface of the monolayer. Chemically patterned surfaces of monolayers of zeolite L crystals are obtained by using patterned stamps with different ink solutions. Additional printing of functionalized nano-objects on SAMs of zeolite L crystals is demonstrated.

  2. Large zeolites - Why and how to grow in space

    NASA Technical Reports Server (NTRS)

    Sacco, Albert, Jr.

    1991-01-01

    The growth of zeolite crystals which are considered to be the most valuable catalytic and adsorbent materials of the chemical processing industry are discussed. It is proposed to use triethanolamine as a nucleation control agent to control the time release of Al in a zeolite A solution and to increase the average and maximum crystal size by 25-50 times. Large zeolites could be utilized to make membranes for reactors/separators which will substantially increase their efficiency.

  3. Peculiarities of the dielectric response of natural zeolite composites prepared by using zeolite and silicon powders

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    We present the real and imaginary part of the dielectric permittivity of natural zeolite composites prepared by using zeolite and silicon powders. The dielectric response (DR) dependences on the frequency (3-300 GHz) of electric field and different Si concentrations (5-33%) are non-monotonic and a maximum peak is observed. This peak position is practically independent on the frequency and its maximum is observed in zeolite composites which included 9% of the Si-powder. Also the maximum peak is decreased by about an order of magnitude when frequency increases from 500 Hz to 5 kHz. Addition of the conductive Si-particles to zeolite-powder leads to two opposite effects. Firstly, the movement of electrons in the Si-particles provides increase of DR. Secondly, cations which leaving from zeolite pores can be neutralized by the particles of Si in the intercrystalline-space. Such a peculiar mechanism for recombination of Si electrons and cations from pores leads to a reduction of DR for large silicon concentrations. Due to the fact that the contribution of free carriers in the decreasing of the DR as the frequency increases, it is consistent with the suggestion that the maximum peak decreases with increasing frequency.

  4. Upgrading naphtha in a multiple riser fluid catalytic cracking operation employing a catalyst mixture

    SciTech Connect

    Herbst, J.A.; Owen, H.; Schipper, P.H.

    1989-05-16

    A process is described for producing gasoline comprising contacting a hydrocarbon feed having an initial boiling-point of at least 400/sup 0/F., a 50% boiling of at least 500/sup 0/F. and an end boiling point of at least 600/sup 0/F., in a first riser, with a two component catalyst under fluid catalytic cracking conditions. At least one component of the catalyst is stripped in a stripping unit to remove entrained hydrocarbons, and regenerated wherein the two component catalyst comprises a first catalyst component selected from the group consisting of an amorphous cracking catalyst and a large pore cracking catalyst, whereby a product comprising olefins and naphtha is produced. Ethylene introduced together with the two component catalyst to a second riser, for contacting ethylene with a second catalyst component which is a shape selective medium pore crystalline silicate zeolite to produce products heavier than ethylene and to increase the temperature of the catalyst to an optimum temperature for upgrading naphtha; and naphtha is introduced to the second riser, down stream of the point of ethylene introduction, for contact with the catalyst at the optimum temperature and the naphtha is upgraded to gasoline product.

  5. A unified single-event microkinetic model for alkane hydroconversion in different aggregation states on Pt/H-USY-zeolites.

    PubMed

    Laxmi Narasimhan, C S; Thybaut, Joris W; Martens, Johan A; Jacobs, Pierre A; Denayer, Joeri F; Marin, Guy B

    2006-04-01

    A single-event microkinetic model for the catalytic hydroconversion of hydrocarbons on Pt/H-US-Y bifunctional zeolite catalysts developed for low-pressure vapor phase conditions was extended to cover high-pressure vapor phase and liquid phase conditions. The effect of the density of the bulk hydrocarbon phase on the physisorption as well as on the protonation steps of the reaction network was accounted for explicitly and can be interpreted in terms of "compression" of the hydrocarbon sorbate inside the zeolite pores and "solvation" of the catalyst framework by the dense bulk hydrocarbon phase. The bulk phase density effect on the physisorbed state is described via a single excess free enthalpy of physisorption. A dense bulk hydrocarbon phase destabilizes the sorbate molecules inside the catalyst pores. An expression of the excess free enthalpy of physisorption involving the fugacity coefficient and a zeolite dependent factor allows description of physisorption data. Typical excess free enthalpy values are in the range 1.5-5.1 kJ mol(-1) increasing with carbon number in the series of C5-C16 alkanes. At high-pressure vapor phase and liquid phase conditions, the excess standard protonation enthalpy is estimated at -7.8 kJ mol(-1) leading to relatively more stable carbenium ions at dense bulk phase conditions. As a result of the excess physisorption and protonation properties, the lightest hydrocarbons in mixtures are more competitive at dense phase conditions and their conversion is enhanced compared to low-density conditions. PMID:16570981

  6. Supported Molecular Catalysts: Synthesis, in-situ Characterization and Performance

    SciTech Connect

    Haw, James F

    2010-12-14

    The technological advantages of solid catalysts (robustness for operation at high temperatures, lack of corrosion, and ease of separation of products) can be combined with the advantages of soluble catalysts (e.g., selectivity) by synthesis of structurally discrete, nearly uniform catalysts on supports. Our goal is to synthesize, characterize, test, and model such catalysts and their reactions, thereby opening a door to unprecedented fundamental understanding of the properties of such materials. We employ molecular chemistry in nano-scale cages of zeolites and on surfaces of tailored porous solids for the precise synthesis of catalysts with discrete, uniform, well-defined sites, primarily mononuclear metal complexes, characterizing them (sometimes in the functioning state) with a broad range of complementary experimental techniques and using computational chemistry to interpret the results, map out reaction paths, provide bases for the design of new catalysts, improve methods of data analysis, and identify key experiments. The effort is directly in support of DOE's energy, environmental, and national security missions as well as the support of DOE's basic science mission to develop the tools and understanding needed for the success of the applied mission areas. The research is demonstrating progress in understanding, modeling, and controlling chemical reactivity at interfaces to develop a fundamental understanding of how to control catalytic reactions for a broad range of applications.

  7. Separation of catalyst from Fischer-Tropsch slurry

    DOEpatents

    White, Curt M.; Quiring, Michael S.; Jensen, Karen L.; Hickey, Richard F.; Gillham, Larry D.

    1998-10-27

    In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc. The catalyst particles are returned to the Fischer-Tropsch Reactor by slurring them with a wax fraction of appropriate molecular weight, boiling point and viscosity to avoid reactor gelation.

  8. Separation of catalyst from Fischer-Tropsch slurry

    DOEpatents

    White, C.M.; Quiring, M.S.; Jensen, K.L.; Hickey, R.F.; Gillham, L.D.

    1998-10-27

    In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst-free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc. The catalyst particles are returned to the Fischer-Tropsch Reactor by mixing them with a wax fraction of appropriate molecular weight, boiling point and viscosity to avoid reactor gelation. 2 figs.

  9. Large zeolites: why and how to grow in space

    NASA Astrophysics Data System (ADS)

    Sacco, Albert, Jr.

    1991-12-01

    Zeolite crystals are one of the Chemical Process Industry's most valuable catalytic and adsorbent materials. Large, essentially defect-free zeolite crystals could be used to better understand zeolite catalysis mechanisms, and could help in designing better zeolite adsorption systems. In addition, if zeolites could be made large enough, they could be used to make zeolite membranes; these could be used as reactors/separators, resulting in highly improved efficiency. Space provides a unique environment to grow large zeolites by allowing them to continue to grow suspended in their nutrient field. In order to better utilize this microgravity environment, it is necessary to control the nucleation event. Triethanolamine (TEA) can be used to control the time release of aluminum in a zeolite A solution. In a 1 g environment, the use of TEA resulted in a 25 - 50X increase in average and maximum crystal size. It is proposed that if fluid motion can be controlled and the rate of nutrient transport increased, substantially larger zeolite crystals can be formed in microgravity, using such nucleation control agents.

  10. Zeolite Crystal Growth in Microgravity and on Earth

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Center for Advanced Microgravity Materials Processing (CAMMP), a NASA-sponsored Research Partnership Center, is working to improve zeolite materials for storing hydrogen fuel. CAMMP is also applying zeolites to detergents, optical cables, gas and vapor detection for environmental monitoring and control, and chemical production techniques that significantly reduce by-products that are hazardous to the environment. Shown here are zeolite crystals (top) grown in a ground control experiment and grown in microgravity on the USML-2 mission (bottom). Zeolite experiments have also been conducted aboard the International Space Station.

  11. Method for the recovery of silver from silver zeolite

    DOEpatents

    Reimann, George A.

    1986-01-01

    High purity silver is recovered from silver exchanged zeolite used to capture radioactive iodine from nuclear reactor and nuclear fuel reprocessing environments. The silver exchanged zeolite is heated with slag formers to melt and fluidize the zeolite and release the silver, the radioactivity removing with the slag. The silver containing metallic impurities is remelted and treated with oxygen and a flux to remove the metal impurities. About 98% of the silver in the silver exchanged zeolite having a purity of 99% or better is recoverable by the method.

  12. Method for the recovery of silver from silver zeolite

    DOEpatents

    Reimann, G.A.

    1985-03-05

    High purity silver is recovered from silver exchanged zeolite used to capture radioactive iodine from nuclear reactor and nuclear fuel reprocessing environments. The silver exchanged zeolite is heated with slag formers to melt and fluidize the zeolite and release the silver, the radioactivity removing with the slag. The silver containing metallic impurities is remelted and treated with oxygen and a flux to remove the metal impurities. About 98% of the silver in the silver exchanged zeolite having a purity of 99% or better is recoverable by the method.

  13. Dry method for recycling iodine-loaded silver zeolite

    DOEpatents

    Thomas, Thomas R.; Staples, Bruce A.; Murphy, Llewellyn P.

    1978-05-09

    Fission product iodine is removed from a waste gas stream and stored by passing the gas stream through a bed of silver-exchanged zeolite until the zeolite is loaded with iodine, passing dry hydrogen gas through the bed to remove the iodine and regenerate the bed, and passing the hydrogen stream containing the hydrogen iodide thus formed through a lead-exchanged zeolite which adsorbs the radioactive iodine from the gas stream and permanently storing the lead-exchanged zeolite loaded with radioactive iodine.

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

    PubMed

    Wajima, Takaaki

    2013-01-01

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

  15. Evidences of the presence of different types of active sites for the oxygen reduction reaction with Fe/N/C based catalysts

    NASA Astrophysics Data System (ADS)

    Pérez-Alonso, Francisco J.; Domínguez, Carlota; Al-Thabaiti, Shaeel A.; Al-Youbi, Abdulrahman O.; Abdel Salam, Mohamed; Alshehri, Abdulmohsen A.; Retuerto, María; Peña, Miguel A.; Rojas, Sergio

    2016-09-01

    Fe/N/C catalysts are very active for the oxygen reduction reaction (ORR); however, the nature of the active site(s) is not fully understood. In this work, we study the performance of different types of N/C and Fe/N/C catalysts for the ORR, and the effect of the addition of NaCN. Phthalocyanine and graphene have been studied as model metal-free catalysts for the ORR. Fe-phthalocyanine (FePhcy), Fe-phthalocyanine dispersed in graphene (FePhcy/G) and Fe/N/G, have been used as model Fe-containing catalysts. FePhcy and FePhcy/G only contain Fe atoms coordinated to 4 nitrogen atoms. On the other hand, different species such as Fe-Nx and Fe3C coexist in Fe/N/G. In addition, Csbnd C ensembles are present in the graphene present in FePhcy/G and Fe/N/G. The ORR activity is characteristic of each catalyst, being the highest for the catalysts containing FeN4 ensembles. The addition of CN- results in the selective poisoning of the Fe-containing sites but it does not suppress the ORR activity of the Graphene containing samples. In-situ infrared spectroscopy studies during the ORR reveal that CN- poisoning of the Fe sites is reversible, desorbing at potentials less positive than ca. 600 mV. As a consequence, the ORR activity of the Fe-containing sites is recovered gradually.

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

    SciTech Connect

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

    1999-08-15

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

  17. [Current research situation of H2S selective catalytic oxidation technologies and catalysts].

    PubMed

    Hao, Zheng-ping; Dou, Guang-yu; Zhang, Xin; Qu, Si-qiu

    2012-08-01

    This review summarizes and discusses different selective catalytic oxidation technologies and various catalysts for removing H2S, the undesirable byproduct of the fluid catalytic cracking (FCC) processing. Currently the selective oxidation technologies used include Superclaus, Euroclaus, Clinsulf-Do, BSR/Hi-Activity, Selectox and Modop techniques, which have various characteristics and application areas. Catalysts for H2S selective oxidation mainly contain the following systems: carbon, supported SiC, zeolite, oxide, and pillared clay. Former studies focused on carbon and oxide systems. The research interest on zeolite system decreased in recent years, while SiC is regarded as a typical support with great potential for this reaction and continues to be attractive. Pillared clay system is at the preliminary research stage, and is still far from practical application.

  18. Electrochemical catalyst recovery method

    DOEpatents

    Silva, Laura J.; Bray, Lane A.

    1995-01-01

    A method of recovering catalyst material from latent catalyst material solids includes: a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications.

  19. Electrochemical catalyst recovery method

    DOEpatents

    Silva, L.J.; Bray, L.A.

    1995-05-30

    A method of recovering catalyst material from latent catalyst material solids includes: (a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; (b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; (c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and (d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications. 3 figs.

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

    PubMed

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

    2010-02-16

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