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Sample records for catalytic ozonation-biological coupled

  1. Catalytic ozonation-biological coupled processes for the treatment of industrial wastewater containing refractory chlorinated nitroaromatic compounds*

    OpenAIRE

    Li, Bing-zhi; Xu, Xiang-Yang; Zhu, Liang

    2010-01-01

    A treatability study of industrial wastewater containing chlorinated nitroaromatic compounds (CNACs) by a catalytic ozonation process (COP) with a modified Mn/Co ceramic catalyst and an aerobic sequencing batch reactor (SBR) was investigated. A preliminary attempt to treat the diluted wastewater with a single SBR resulted in ineffective removal of the color, ammonia, total organic carbon (TOC) and chemical oxygen demand (COD). Next, COP was applied as a pretreatment in order to obtain a bio-c...

  2. Direct catalytic cross-coupling of organolithium compounds

    Science.gov (United States)

    Giannerini, Massimo; Fañanás-Mastral, Martín; Feringa, Ben L.

    2013-08-01

    Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern synthetic chemistry. However, the high reactivity and poor selectivity of common organolithium reagents have largely prohibited their use as a viable partner in direct catalytic cross-coupling. Here we report that in the presence of a Pd-phosphine catalyst, a wide range of alkyl-, aryl- and heteroaryl-lithium reagents undergo selective cross-coupling with aryl- and alkenyl-bromides. The process proceeds quickly under mild conditions (room temperature) and avoids the notorious lithium halogen exchange and homocoupling. The preparation of key alkyl-, aryl- and heterobiaryl intermediates reported here highlights the potential of these cross-coupling reactions for medicinal chemistry and material science.

  3. Catalytic conversion of methane: Carbon dioxide reforming and oxidative coupling

    KAUST Repository

    Takanabe, Kazuhiro

    2012-01-01

    Natural gas conversion remains one of the essential technologies for current energy needs. This review focuses on the mechanistic aspects of the development of efficient and durable catalysts for two reactions, carbon dioxide reforming and the oxidative coupling of methane. These two reactions have tremendous technological significance for practical application in industry. An understanding of the fundamental aspects and reaction mechanisms of the catalytic reactions reviewed in this study would support the design of industrial catalysts. CO 2 reforming of methane utilizes CO 2, which is often stored in large quantities, to convert as a reactant. Strategies to eliminate carbon deposition, which is the major problem associated with this reaction, are discussed. The oxidative coupling of methane directly produces ethylene in one reactor through a slightly exothermic reaction, potentially minimizing the capital cost of the natural gas conversion process. The focus of discussion in this review will be on the attainable yield of C 2 products by rigorous kinetic analyses.

  4. Coupling between catalytic loop motions and enzyme global dynamics.

    Directory of Open Access Journals (Sweden)

    Zeynep Kurkcuoglu

    Full Text Available Catalytic loop motions facilitate substrate recognition and binding in many enzymes. While these motions appear to be highly flexible, their functional significance suggests that structure-encoded preferences may play a role in selecting particular mechanisms of motions. We performed an extensive study on a set of enzymes to assess whether the collective/global dynamics, as predicted by elastic network models (ENMs, facilitates or even defines the local motions undergone by functional loops. Our dataset includes a total of 117 crystal structures for ten enzymes of different sizes and oligomerization states. Each enzyme contains a specific functional/catalytic loop (10-21 residues long that closes over the active site during catalysis. Principal component analysis (PCA of the available crystal structures (including apo and ligand-bound forms for each enzyme revealed the dominant conformational changes taking place in these loops upon substrate binding. These experimentally observed loop reconfigurations are shown to be predominantly driven by energetically favored modes of motion intrinsically accessible to the enzyme in the absence of its substrate. The analysis suggests that robust global modes cooperatively defined by the overall enzyme architecture also entail local components that assist in suitable opening/closure of the catalytic loop over the active site.

  5. Transition-metal nitro-nitrosyl redox couple: catalytic oxidation of olefins to ketones

    International Nuclear Information System (INIS)

    A new nitroso-nitrosyl redox couple based on the readily prepared complex bis(acetonitrile)chloronitropalladium(II) is reported which catalytically air oxidizes olefines to ketones. Results of 18O labelling mechanistic studies are included, and spectroscopic evidence for an intermediate involved in oxygen-atom transfer by a nitro group is presented. The effects of olefin substituents were also investigated

  6. Modular, Catalytic Enantioselective Construction of Quaternary Carbon Stereocenters by Sequential Cross-Coupling Reactions.

    Science.gov (United States)

    Potter, Bowman; Edelstein, Emma K; Morken, James P

    2016-07-01

    The catalytic Suzuki-Miyaura cross-coupling with chiral γ,γ-disubstituted allylboronates in the presence of RuPhos ligand occurs with high regioselectivity and enantiospecificity, furnishing nonracemic compounds with quaternary centers. Mechanistic experiments suggest that the reaction occurs by transmetalation with allyl migration, followed by rapid reductive elimination. PMID:27310927

  7. A non-stationary problem coupling PDEs and ODEs modelizing an automotive catalytic converter

    OpenAIRE

    Hoernel, J. -D.

    2005-01-01

    In this paper we prove the existence and uniqueness of the solution of a non-stationary problem that modelizes the behaviour of the concentrations and the temperature of gases going through a cylindrical passage of an automotive catalytic converter. This problem couples parabolic partial differential equations in a domain with one parabolic partial differential equation and some ordinary differential equations on a part of its boundary.

  8. Advanced power systems featuring a closely coupled catalytic gasification carbonate fuel cell plant

    Energy Technology Data Exchange (ETDEWEB)

    Steinfeld, G.; Wilson, W.G.

    1993-06-01

    Pursuing the key national goal of clean and efficient uulization of the abundant domestic coal resources for power generation, a study was conducted with DOE/METC support to evaluate the potential of integrated gasification/carbonate fuel cell power generation systems. By closely coupling the fuel cell with the operation of a catalytic gasifier, the advantages of both the catalytic gasification and the high efficiency fuel cell complement each other, resulting in a power plant system with unsurpassed efficiencies approaching 55% (HHV). Low temperature catalytic gasification producing a high methane fuel gas offers the potential for high gas efficiencies by operating with minimal or no combustion. Heat required for gasification is provided by combination of recycle from the fuel cell and exothermic methanation and shift reactions. Air can be supplemented if required. In combination with internally reforming carbonate fuel cells, low temperature catalytic gasification can achieve very attractive system efficiencies while producing extremely low emissions compared to conventional plants utilizing coal. Three system configurations based on recoverable and disposable gasification catalysts were studied. Experimental tests were conducted to evaluate these gasification catalysts. The recoverable catalyst studied was potassium carbonate, and the disposable catalysts were calcium in the form of limestone and iron in the form of taconite. Reactivities of limestone and iron were lower than that of potassium, but were improved by using the catalyst in solution form. Promising results were obtained in the system evaluations as well as the experimental testing of the gasification catalysts. To realize the potential of these high efficiency power plant systems more effort is required to develop catalytic gasification systems and their integration with carbonate fuel cells.

  9. Advanced power systems featuring a closely coupled catalytic gasification carbonate fuel cell plant

    Energy Technology Data Exchange (ETDEWEB)

    Steinfeld, G.; Wilson, W.G.

    1993-01-01

    Pursuing the key national goal of clean and efficient uulization of the abundant domestic coal resources for power generation, a study was conducted with DOE/METC support to evaluate the potential of integrated gasification/carbonate fuel cell power generation systems. By closely coupling the fuel cell with the operation of a catalytic gasifier, the advantages of both the catalytic gasification and the high efficiency fuel cell complement each other, resulting in a power plant system with unsurpassed efficiencies approaching 55% (HHV). Low temperature catalytic gasification producing a high methane fuel gas offers the potential for high gas efficiencies by operating with minimal or no combustion. Heat required for gasification is provided by combination of recycle from the fuel cell and exothermic methanation and shift reactions. Air can be supplemented if required. In combination with internally reforming carbonate fuel cells, low temperature catalytic gasification can achieve very attractive system efficiencies while producing extremely low emissions compared to conventional plants utilizing coal. Three system configurations based on recoverable and disposable gasification catalysts were studied. Experimental tests were conducted to evaluate these gasification catalysts. The recoverable catalyst studied was potassium carbonate, and the disposable catalysts were calcium in the form of limestone and iron in the form of taconite. Reactivities of limestone and iron were lower than that of potassium, but were improved by using the catalyst in solution form. Promising results were obtained in the system evaluations as well as the experimental testing of the gasification catalysts. To realize the potential of these high efficiency power plant systems more effort is required to develop catalytic gasification systems and their integration with carbonate fuel cells.

  10. Palladium nanoparticle anchored polyphosphazene nanotubes: preparation and catalytic activity on aryl coupling reactions

    Indian Academy of Sciences (India)

    V Devi; A Ashok Kumar; S Sankar; K Dinakaran

    2015-06-01

    Highly accessible-supported palladium (Pd) nanoparticles anchored polyphosphazene (PPZ) nanotubes (NTs) having average diameter of 120 nm were synthesized rapidly at room temperature and homogeneously decorated with Pd nanoparticles. The resultant PPZ–Pd nanocomposites were morphologically and structurally characterized by means of transmission electron microscope equipped with energy-dispersive X-ray spectroscopy and X-ray diffraction analysis. Characterization results showed that the Pd nanoparticles with good dispersibility could be well anchored onto the surfaces of the PPZ NTs. The PPZ–Pd NTs show enhanced catalytic activity for the Suzuki coupling of aryl bromides with arylboronic acid. In addition, these PPZ–Pd NTs show excellent behaviour as reusable catalysts of the Suzuki and Heck coupling reactions.

  11. Rate turnover in mechano-catalytic coupling: A model and its microscopic origin

    International Nuclear Information System (INIS)

    A novel aspect in the area of mechano-chemistry concerns the effect of external forces on enzyme activity, i.e., the existence of mechano-catalytic coupling. Recent experiments on enzyme-catalyzed disulphide bond reduction in proteins under the effect of a force applied on the termini of the protein substrate reveal an unexpected biphasic force dependence for the bond cleavage rate. Here, using atomistic molecular dynamics simulations combined with Smoluchowski theory, we propose a model for this behavior. For a broad range of forces and systems, the model reproduces the experimentally observed rates by solving a reaction-diffusion equation for a “protein coordinate” diffusing in a force-dependent effective potential. The atomistic simulations are used to compute, from first principles, the parameters of the model via a quasiharmonic analysis. Additionally, the simulations are also used to provide details about the microscopic degrees of freedom that are important for the underlying mechano-catalysis

  12. Rate turnover in mechano-catalytic coupling: A model and its microscopic origin

    Energy Technology Data Exchange (ETDEWEB)

    Roy, Mahua; Grazioli, Gianmarc; Andricioaei, Ioan, E-mail: andricio@uci.edu [Department of Chemistry, University of California, Irvine, California 92697 (United States)

    2015-07-28

    A novel aspect in the area of mechano-chemistry concerns the effect of external forces on enzyme activity, i.e., the existence of mechano-catalytic coupling. Recent experiments on enzyme-catalyzed disulphide bond reduction in proteins under the effect of a force applied on the termini of the protein substrate reveal an unexpected biphasic force dependence for the bond cleavage rate. Here, using atomistic molecular dynamics simulations combined with Smoluchowski theory, we propose a model for this behavior. For a broad range of forces and systems, the model reproduces the experimentally observed rates by solving a reaction-diffusion equation for a “protein coordinate” diffusing in a force-dependent effective potential. The atomistic simulations are used to compute, from first principles, the parameters of the model via a quasiharmonic analysis. Additionally, the simulations are also used to provide details about the microscopic degrees of freedom that are important for the underlying mechano-catalysis.

  13. A study of measurement and analysis of flow distribution in a close-coupled catalytic converter

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Y.S.; Kim, D.S. [Kookmin University, Seoul (Korea); Joo, Y.C. [Soonchunhyang University, Asan (Korea)

    2001-04-01

    In this study, results from an experimental and numerical study of flow distribution in a close-coupled catalytic converter (CCC) are presented. The experiments were carried out using a flow measurement system. Flow distribution at the exit of the first monolith in the CCC was measured using a pitot tube under steady and transient flow conditions. Numerical analysis was done using a CF D code at the same test conditions, and the results were compared with the experimental results. Experimental results showed that the uniformity index of exhaust gas velocity decreases as Reynolds number increases. Under the steady flow conditions, flow through each exhaust pipe concentrates on a small region of the monolith. Under the transient flow conditions, flow through each exhaust pipe with the engine firing order interacts with each other to spread the flow over the monolith face. The numerical analysis results support the experimental results, and help explain the flow pattern in the entry region of the CCC. (author). 6 refs., 8 figs.

  14. Ozone-biological activated carbon as a pretreatment process for reverse osmosis brine treatment and recovery.

    Science.gov (United States)

    Lee, Lai Yoke; Ng, How Yong; Ong, Say Leong; Hu, Jiang Yong; Tao, Guihe; Kekre, Kiran; Viswanath, Balakrishnan; Lay, Winson; Seah, Harry

    2009-09-01

    Ozonation was used in this study to improve biodegradability of RO brine from water reclamation facilities. An ozone dosage ranging from 3 to 10 mg O(3)/L and contact times of 10 and 20 min in batch studies were found to increase the biodegradability (BOD(5)/TOC ratio) of the RO brine by 1.8-3.5 times. At the same time, total organic carbon (TOC) removal was in the range of 5.3-24.5%. The lab-scale ozone-biological activated carbon (BAC) at an ozone dosage of 6.0mg O(3)/L with 20-min contact time was able to achieve 3 times higher TOC removal compared to using BAC alone. Further processing with Capacitive Deionization (CDI) process was able to generate a product water with better water quality than the RO feed water, i.e., with more than 80% ions removal and a lower TOC concentration. The ozone-BAC pretreatment has the potential of reducing fouling in the CDI process. PMID:19580984

  15. High catalytic efficiency of palladium nanoparticles immobilized in a polymer membrane containing poly(ionic liquid) in Suzuki–Miyaura cross-coupling reaction

    OpenAIRE

    Gu, Yingying; Favier, Isabelle; Pradel, Christian; Gin, Douglas L.; Lahitte, Jean-Francois; Noble, Richard D.; Gómez, Montserrat; Remigy, Jean-Christophe

    2015-01-01

    The elaboration of a polymeric catalytic membrane containing palladium nanoparticles is presented. The membrane was prepared using a photo-grafting process with imidazolium-based ionic liquid monomers as modifying agent and microPES® as support membrane. Ionic liquid serves as a stabilizer and immobilizer for the catalytic species, i.e. palladium nanoparticles. The Suzuki–Miyaura cross-coupling reaction was carried out on the catalytic membrane in flow-through configuration. Complete conversi...

  16. Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles.

    Science.gov (United States)

    Lambert, Kyle M; Bobbitt, James M; Eldirany, Sherif A; Kissane, Liam E; Sheridan, Rose K; Stempel, Zachary D; Sternberg, Francis H; Bailey, William F

    2016-04-01

    Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98 % isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products. PMID:26868873

  17. Application of novel catalytic-ceramic-filler in a coupled system for long-chain dicarboxylic acids manufacturing wastewater treatment.

    Science.gov (United States)

    Wu, Suqing; Qi, Yuanfeng; Fan, Chunzhen; He, Shengbing; Dai, Bibo; Huang, Jungchen; Zhou, Weili; Gao, Lei

    2016-02-01

    To gain systematic technology for long-chain dicarboxylic acids (LDCA) manufacturing wastewater treatment, catalytic micro-electrolysis (CME) coupling with adsorption-biodegradation sludge (AB) process was studied. Firstly, novel catalytic-ceramic-filler was prepared from scrap iron, clay and copper sulfate solution and packed in the CME reactor. To remove residual n-alkane and LDCA, the CME reactor was utilized for LDCA wastewater pretreatment. The results revealed that about 94% of n-alkane, 98% of LDCA and 84% of chemical oxygen demand (COD) were removed by the aerated CME reactor at the optimum hydraulic retention time (HRT) of 3.0 h. In this process, catalysis from Cu and montmorillonites played an important role in improving the contaminants removal. Secondly, to remove residual COD in the wastewater, AB process was designed for the secondary biological treatment, about 90% of the influent COD could be removed by biosorption, bio-flocculation and biodegradation effects. Finally, the effluent COD (about 150 mg L(-1)) discharged from the coupled CME-AB system met the requirement of the national discharged standard (COD ≤ 300 mg L(-1)). All of these results suggest that the coupled CME-AB system is a promising technology due to its high-efficient performance, and has the potential to be applied for the real LDCA wastewater treatment. PMID:26619310

  18. Catalytic B-N Dehydrogenation Using Frustrated Lewis Pairs: Evidence for a Chain-Growth Coupling Mechanism.

    Science.gov (United States)

    Mo, Zhenbo; Rit, Arnab; Campos, Jesús; Kolychev, Eugene L; Aldridge, Simon

    2016-03-16

    The catalytic dehydrogenation of ammonia- and amine-boranes by a dimethylxanthene-derived frustrated Lewis pair is described. Turnover is facilitated on a thermodynamic basis by the ready release of H2 from the weakly basic PPh2-containing system. In situ NMR studies and the isolation of intermediates from stoichiometric reactions support a mechanism initiated by B-H activation, followed by end-growth BN coupling involving the terminal NH bond of the bound BN fragment and a BH bond of the incoming borane monomer. PMID:26918906

  19. Visible to near-infrared plasmon-enhanced catalytic activity of Pd hexagonal nanoplates for the Suzuki coupling reaction

    Science.gov (United States)

    Trinh, T. Thuy; Sato, Ryota; Sakamoto, Masanori; Fujiyoshi, Yoshifumi; Haruta, Mitsutaka; Kurata, Hiroki; Teranishi, Toshiharu

    2015-07-01

    Photocatalytic conversion of solar energy to chemical energy is an efficient process in green chemistry because it facilitates room temperature chemical transformations by generating electronically excited states in photocatalysts. We report here on the robust synthesis, detailed structural characterization, and especially photocatalytic properties of plasmonic Pd hexagonal nanoplates for chemical reactions. The Pd hexagonal nanoplates are twin crystals, and composed of the top and bottom faces enclosed by the {111} planes with stacking faults and the side surfaces bound by mixed six {111} and six {100} planes. The Pd hexagonal nanoplates with well-defined and tunable longitudinal localized surface plasmon resonance (LSPR) have enabled the direct harvesting of visible to near-infrared light for catalytic cross coupling reactions. Upon plasmon excitation, the catalytic Suzuki coupling reactions of iodobenzene and phenylboronic acid accelerate by a plasmonic photocatalytic effect of plasmon induced hot electrons. The turnover frequency (TOF) of the Pd hexagonal nanoplates in a reaction illuminated with a λ = 300-1000 nm Xenon lamp at 176 mW cm-2 was 2.5 and 2.7 times higher than that of non-plasmonic {111}-enclosed Pd nanooctahedra and {100}-enclosed Pd nanocubes, respectively, and 1.7 times higher than the TOF obtained when the reaction was thermally heated to the same temperature.Photocatalytic conversion of solar energy to chemical energy is an efficient process in green chemistry because it facilitates room temperature chemical transformations by generating electronically excited states in photocatalysts. We report here on the robust synthesis, detailed structural characterization, and especially photocatalytic properties of plasmonic Pd hexagonal nanoplates for chemical reactions. The Pd hexagonal nanoplates are twin crystals, and composed of the top and bottom faces enclosed by the {111} planes with stacking faults and the side surfaces bound by mixed six {111

  20. Thermal reliability and performance improvement of close-coupled catalytic converter

    Energy Technology Data Exchange (ETDEWEB)

    Hijikata, Toshihiko; Kurachi, Hiroshi; Katsube, Fumio [NGK Insulators, Ltd., Nagoya (Japan); Honacker, H. van

    1996-09-01

    This paper proposes a high temperature catalytic converter design using a ceramic substrate and intumescent matting. It also describes the improvement of converter performance using an advanced thin wall ceramic substrate. Due to future tightening of emission regulations and improvement of fuel economy, higher exhaust gas temperatures are suggested. Therefore, reduction of thermal reliability of an intumescent mat will be a concern because the catalytic converter will be exposed to high temperatures. For this reason, a new design converter has been developed using a dual cone structure for both the inlet and outlet cones. This minimizes heat conduction through the cone and decreases the temperature affecting the mat area. This design converter, without the use of a heat-shield, reduces the converter surface temperature to 441 C despite a catalyst bed temperature of 1,050 C. The long term durability of the converter is demonstrated by the hot vibration test. Since the new design converter does not need a heat-shield, the catalyst diameter can be enlarged by the width of the air gap used in the current design converter. By using an advanced thin wall ceramic substrate, such as 0.11 mm/620 kcpsm (4 mil/400 cpsi), it is possible to improve emission performance and pressure drop compared with the conventional 0.16 mm/620 kcpsm (6 mil/400 cpsi) ceramic substrate.

  1. Catalytic spectrophotometric determination of cerium by ion exchange separation coupled to a flow injection system

    International Nuclear Information System (INIS)

    A flow injection method is described intended for the determination of cerium based on its catalytic effect on the oxidation of gallocyanine by peroxydisulfate in acidic media. The proposed flow injection manifold incorporates a ion exchange separation system in the carrier stream. The decolorisation of gallocyanine due to its oxidation was used to monitor the reaction by spectrophotometry at 524 nm. The variables which affected the reaction rate were fully investigated. By this method cerium(4) can be determined in the range of 0.30-10.0 μg with a limit of detection of 0.25 μg. The relative standard deviation for ten replicate determinations of 1.0 μg of cerium(4) was 1.8 %

  2. Environmentally benign synthesis of amides and ureas via catalytic dehydrogenation coupling of volatile alcohols and amines in a Pd-Ag membrane reactor

    KAUST Repository

    Chen, Tao

    2016-05-31

    In this study, we report the direct synthesis of amides and ureas via the catalytic dehydrogenation of volatile alcohols and amines using the Milstein catalyst in a Pd-Ag/ceramic membrane reactor. A series of amides and ureas, which could not be synthesized in an open system by catalytic dehydrogenation coupling, were obtained in moderate to high yields via catalytic dehydrogenation of volatile alcohols and amines. This process could be monitored by the hydrogen produced. Compared to the traditional method of condensation, this catalytic system avoids the stoichiometric pre-activation or in situ activation of reagents, and is a much cleaner process with high atom economy. This methodology, only possible by employing the Pd-Ag/ceramic membrane reactor, not only provides a new environmentally benign synthetic approach of amides and ureas, but is also a potential method for hydrogen storage.

  3. Catalytic Coupling of Carbon Dioxide with Terpene Scaffolds: Access to Challenging Bio-Based Organic Carbonates.

    Science.gov (United States)

    Fiorani, Giulia; Stuck, Moritz; Martín, Carmen; Belmonte, Marta Martínez; Martin, Eddy; Escudero-Adán, Eduardo C; Kleij, Arjan W

    2016-06-01

    The challenging coupling of highly substituted terpene oxides and carbon dioxide into bio-based cyclic organic carbonates catalyzed by Al(aminotriphenolate) complexes is reported. Both acyclic as well as cyclic terpene oxides were used as coupling partners, showing distinct reactivity/selectivity behavior. Whereas cyclic terpene oxides showed excellent chemoselectivity towards the organic carbonate product, acyclic substrates exhibited poorer selectivities owing to concomitant epoxide rearrangement reactions and the formation of undesired oligo/polyether side products. Considering the challenging nature of these coupling reactions, the isolated yields of the targeted bio-carbonates are reasonable and in most cases in the range 50-60 %. The first crystal structures of tri-substituted terpene based cyclic carbonates are reported and their stereoconnectivity suggests that their formation proceeds through a double inversion pathway. PMID:27159151

  4. A Novel and Efficient Catalytic System for Aerobic Oxidative Coupling of 2-Naphthol Derivatives

    Institute of Scientific and Technical Information of China (English)

    Li CHEN; Jing Bo LAN; Zhi Hua MAO; Xiao Qi YU; Ru Gang XIE

    2004-01-01

    The paper reported a novel and efficient aerobic oxidative coupling reaction of 2-naphthol derivatives catalyzed by CuCu (I or II)N-alkylimidazole complexes in excellent yields.The crystal structure of CuCu (II)N-methylimidazole complex to be determined by X-Ray.

  5. Catalytic conjunctive cross-coupling enabled by metal-induced metallate rearrangement.

    Science.gov (United States)

    Zhang, Liang; Lovinger, Gabriel J; Edelstein, Emma K; Szymaniak, Adam A; Chierchia, Matteo P; Morken, James P

    2016-01-01

    Transition metal catalysis plays a central role in contemporary organic synthesis. Considering the tremendously broad array of transition metal-catalyzed transformations, it is remarkable that the underlying elementary reaction steps are relatively few in number. Here, we describe an alternative to the organometallic transmetallation step that is common in many metal-catalyzed reactions, such as Suzuki-Miyaura coupling. Specifically, we demonstrate that vinyl boronic ester ate complexes, prepared by combining organoboronates and organolithium reagents, engage in palladium-induced metallate rearrangement wherein 1,2-migration of an alkyl or aryl group from boron to the vinyl α-carbon occurs concomitantly with C-Pd σ-bond formation. This elementary reaction enables a powerful cross-coupling reaction in which a chiral Pd catalyst merges three simple starting materials-an organolithium, an organoboronic ester, and an organotriflate-into chiral organoboronic esters with high enantioselectivity. PMID:26721996

  6. Catalytic Chemo- and Regioselective Coupling of 1,3-Dicarbonyls with N-Heterocyclic Nucleophiles.

    Science.gov (United States)

    Kenny, Miles; Kitson, Daniel J; Franckevičius, Vilius

    2016-06-17

    The development of a decarboxylative palladium-catalyzed coupling of 1,3-dicarbonyl compounds with indole, pyrrole, imidazole, and pyrazole nucleophiles via an allylic linker under neutral conditions is disclosed. This process enables the installation of an all-carbon quaternary center and new C-C and C-N bonds in a single operation. Despite the weakly acidic nature of N-heterocycles, the reactions proceed with good efficiency and complete regio- and chemoselectivity. PMID:27211875

  7. Catalytic Asymmetric Coupling of 2-Naphthols by Chiral Tridentate Oxovanadium(IV) Complexes

    Institute of Scientific and Technical Information of China (English)

    HON; Sang-Wen

    2001-01-01

    A series of chiral oxovanadium(IV) complexes derived from tridentate N-3,5-substituted-, N-3,4-benzo-and N-5,6-benzo-salicylidene-α-amino acids can serve as efficient catalysts for the enantioselective oxidative couplings of various 3-, 6-, and 7-substituted 2-naphthols under O2. The best scenario involves the use of a vanadyl complex arising from 2-hydroxy-l-naphthaldehyde and valine (or phenylalanine) in CCl4, leading to BINOLs in good yields (75-100%) and with enantioselectivities of up to 68%.……

  8. Catalytic Asymmetric Coupling of 2-Naphthols by Chiral Tridentate Oxovanadium(IV) Complexes

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ A series of chiral oxovanadium(IV) complexes derived from tridentate N-3,5-substituted-, N-3,4-benzo-and N-5,6-benzo-salicylidene-α-amino acids can serve as efficient catalysts for the enantioselective oxidative couplings of various 3-, 6-, and 7-substituted 2-naphthols under O2. The best scenario involves the use of a vanadyl complex arising from 2-hydroxy-l-naphthaldehyde and valine (or phenylalanine) in CCl4, leading to BINOLs in good yields (75-100%) and with enantioselectivities of up to 68%.

  9. The effect of external magnetic fields on the catalytic activity of Pd nanoparticles in Suzuki cross-coupling reactions

    Science.gov (United States)

    Gao, Lei; Wang, Changlai; Li, Ren; Li, Ran; Chen, Qianwang

    2016-04-01

    Pd nanoparticles supported on Co3[Co(CN)6]2 nanoparticles (marked as Pd@Co3[Co(CN)6]2 nanoparticles) were prepared as catalysts for the Suzuki cross-coupling reaction under external magnetic fields (MFs). It is shown that a weak external MF can increase the rate of the Suzuki cross-coupling reaction at room temperature, and with the increase of the strength of external MFs the reaction rate also increased. At 30 °C, the yield was increased by nearly 50% under a 0.5 T external MF after 24 hours compared to that without a MF applied. Theoretical calculations revealed that the adsorption energy changed from -1.07 to -1.12 eV in the presence of MFs, which increased by 5% compared with the absence of MFs, leading to a lower total energy of the adsorption system, which is beneficial to the reaction. From the analysis of the partial density states, it could be seen that the 2p orbital of the carbon atom in bromobenzene and the 4d orbital of the Pd atom overlap more closely in the presence of MFs, which is beneficial for the electron transfer from the Pd substrate to the bromobenzene molecule. This study is helpful in understanding the interaction between MFs and catalysts and regulating the process of catalytic reactions via MFs.Pd nanoparticles supported on Co3[Co(CN)6]2 nanoparticles (marked as Pd@Co3[Co(CN)6]2 nanoparticles) were prepared as catalysts for the Suzuki cross-coupling reaction under external magnetic fields (MFs). It is shown that a weak external MF can increase the rate of the Suzuki cross-coupling reaction at room temperature, and with the increase of the strength of external MFs the reaction rate also increased. At 30 °C, the yield was increased by nearly 50% under a 0.5 T external MF after 24 hours compared to that without a MF applied. Theoretical calculations revealed that the adsorption energy changed from -1.07 to -1.12 eV in the presence of MFs, which increased by 5% compared with the absence of MFs, leading to a lower total energy of the

  10. LDV measurement, flow visualization and numerical analysis of flow distribution in a close-coupled catalytic converter

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Duk Sang; Cho, Yong Seok [Kookmin Univ., Seoul (Korea, Republic of)

    2004-11-01

    Results from an experimental study of flow distribution in a Close-coupled Catalytic Converter (CCC) are presented. The experiments were carried out with a flow measurement system specially designed for this study under steady and transient flow conditions. A pitot tube was a tool for measuring flow distribution at the exit of the first monolith. The flow distribution of the CCC was also measured by LDV system and flow visualization. Results from numerical analysis are also presented. Experimental results showed that the flow uniformity index decreases as flow Reynolds number increases. In steady flow conditions, the flow through each exhaust pipe made some flow concentrations on a specific region of the CCC inlet. The transient test results showed that the flow through each exhaust pipe in the engine firing order, interacted with each other to ensure that the flow distribution was uniform. The results of numerical analysis were qualitatively accepted with experimental results. They supported and helped explain the flow in the entry region of CCC.

  11. Multifunctional phosphine stabilized gold nanoparticles: an active catalytic system for three-component coupling reaction.

    Science.gov (United States)

    Borah, Bibek Jyoti; Borah, Subrat Jyoti; Dutta, Dipak Kumar

    2013-07-01

    Multifunctional phosphine based ligands, 1,1,1-tris(diphenylphosphinomethyl)ethane [CH3C(CH2 PPh2)3][P3] and 1,1,1-tris(diphenylphosphinomethyl)ethane trisulphide [CH3C(CH2P(S)Ph2)3][P3S3] have been introduced to stabilize Au(o)-nanoparticles having small core diameter and narrow size distribution. The Au(o)-nanoparticles were synthesized by the reduction of HAuCl4 precursor with NaBH4 in the presence of ligand P3 or P3S3 using two phases, one pot reaction at room temperature. The Au(o)-nanoparticles exhibit face centered cubic (fcc) lattice having different crystalline shape i.e., single crystallite stabilized by P3 while P3S3 forms decahedral shapes. Surface plasmon bands at -520 nm and TEM study indicate particle size below 2 and 4 nm for Au(o)-nanoparticles stabilized by P3 and P3S3 respectively, which are attributable to the stronger interaction of Au(o) (Soft) with P (Soft) than Au(o) (Soft) with S (less Softer than P). Au(o)-nanoparticles stabilized by P3S3 shows higher thermal stability than that of P3. The synthesized Au(o)-nanoparticles serve as an efficient catalyst for one-pot, three-component (A3) coupling of an aldehyde, an amine and an alkyne via C-H alkyne-activation to synthesize propargylamines (85-96%) without any additives and precaution to exclude air. PMID:23901533

  12. Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions. Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Cong [Argonne National Lab. (ANL), Argonne, IL (United States); Evans, Tabitha J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Cheng, Lei [Argonne National Lab. (ANL), Argonne, IL (United States); Nimlos, Mark R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Mukarakate, Calvin [National Renewable Energy Lab. (NREL), Golden, CO (United States); Robichaud, David J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Assary, Rajeev S. [Argonne National Lab. (ANL), Argonne, IL (United States); Curtiss, Larry A. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2015-10-02

    These catalytic C–C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Major products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. Moreover, the computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C–C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.

  13. [Removal characters of ozone-biological activated carbon process for typical pollutants in southern brooky regions of China].

    Science.gov (United States)

    Lin, Tao; Chen, Wei; Wang, Lei-Lei

    2009-05-15

    The products of relative molecular weight (Mr) distribution, bromate (BrO3(-)) and trihalomethanes (THMs) were studied by ozone-biological activated carbon (O3-BAC) process for treating organic matters and bromide (Br(-)) in water source of southern brooky regions of China. The experimental results showed that dissolved organic matters (DOC) with Mr lower than 10(3) accounted for 80% of the total. The removal rate of DOC and SUVA (UV254/DOC) were 8% and 14% respectively by traditional treatment process with main removalonly for ones with Mr higher than 100 x 10(3). Only 30% of DOC and 31% of SUVA were decreased by O3-BAC process for the removal of ones with Mr between 10(3) and 5 x 10(3), in which the biotic degradation was certainly restricted by predominant organic matters of hydrophilic and Mr was lower than 1000. An obvious increase of BrO3(-) occurred in the effluent from ozone oxidation process when the dose of ozone beyond 2 mg/L which increased Br(-) concentration. This could increase the product of BrO3(-). A poor and unstable removal effect of BrO3(-) was observed in the effluent of BAC process during the experiment. Each species of THMs, decreasing 40% of total, was reduced by O3-BAC treatment compared with the traditional treatment process. But the products of brominated trihalomethanes, especially CHBr3 would be markedly increased by enhanced chlorine dosage and Br(-) concentration. PMID:19558108

  14. Catalytic Performance of CeO2/ZnO Nanocatalysts on the Oxidative Coupling of Methane with Carbon Dioxide and their Fractal Features

    Institute of Scientific and Technical Information of China (English)

    Yongjun He; Blun Yang; Haimin Pan; Guozhi Li

    2004-01-01

    CeO2/ZnO nanocatalysts were prepared from the coupling route of homogeneous precipitation with microemulsion and the impregnation method. The catalytic performance of these two kinds of catalysts on the oxidative coupling of methane with carbon dioxide was tested and compared; the fractal behavior of the nanocatalysts was analyzed using fractal theory. The CeO2/ZnO nanocatalysts had much higher activity than the catalysts prepared by impregnation method. There was no regular relationship between the average size of CeO2/ZnO nanocatalysts and their catalytic performance; however, the conversion of methane increased with the increase of the fractal dimension of CeO2/ZnO nanocatalysts.

  15. Details in the catalytic mechanism of mammalian thioredoxin reductase 1 revealed using point mutations and juglone-coupled enzyme activities.

    Science.gov (United States)

    Xu, Jianqiang; Cheng, Qing; Arnér, Elias S J

    2016-05-01

    The mammalian selenoprotein thioredoxin reductase 1 (TrxR1) is a key enzyme in redox regulation, antioxidant defense, and cellular growth. TrxR1 can catalyze efficient reduction of juglone (5-hydroxy-1,4-naphthoquinone; walnut toxin) in a reaction which, in contrast to reduction of most other substrates of TrxR1, is not dependent upon an intact selenocysteine (Sec, U) residue of the enzyme. Using a number of TrxR1 mutant variants, we here found that a sole Cys residue at the C-terminal tail of TrxR1 is required for high-efficiency juglone-coupled NADPH oxidase activity of Sec-deficient enzyme, occurring with mixed one- and two-electron reactions producing superoxide. The activity also utilizes the FAD and the N-terminal redox active disulfide/dithiol motif of TrxR1. If a sole Cys residue at the C-terminal tail of TrxR1, in the absence of Sec, was moved further towards the C-terminal end of the protein compared to its natural position at residue 497, juglone reduction was, surprisingly, further increased. Ala substitutions of Trp407, Asn418 and Asn419 in a previously described "guiding bar", thought to mediate interactions of the C-terminal tail of TrxR1 with the FAD/dithiol site at the N-terminal domain of the other subunit in the dimeric enzyme, lowered turnover with juglone about 4.5-fold. Four residues of Sec-deficient TrxR1 were found to be easily arylated by juglone, including the Cys residue at position 497. Based upon our observations we suggest a model for involvement of the juglone-arylated C-terminal motif of TrxR1 to explain its high activity with juglone. This study thus provides novel insights into the catalytic mechanisms of TrxR1. One-electron juglone reduction by TrxR1 producing superoxide should furthermore contribute to the well-known prooxidant cytotoxicity of juglone. PMID:26898501

  16. Nickel(II) complexes containing ONS donor ligands: Synthesis, characterization, crystal structure and catalytic application towards C-C cross-coupling reactions

    Indian Academy of Sciences (India)

    Panneerselvam Anitha; Rajendran Manikandan; Paranthaman Vijayan; Govindan Prakash; Periasamy Viswanathamurthi; Ray Jay Butcher

    2015-04-01

    Nickel(II) complexes containing thiosemicarbazone ligands [Ni(L)2] (1-3) (L = 9,10-phenanthrenequinonethiosemicarbazone (HL1), 9,10-phenanthrenequinone-N-methylthio semicarbazone (HL2) and 9, 10-phenanthrenequinone-N-phenylthiosemicarbazone (HL3)) have been synthesized and characterized by elemental analysis and spectroscopic (IR, UV-Vis, 1H, 13C-NMR and ESI mass) methods. The molecular structures of complexes 1 and 2 were identified by means of single-crystal X-ray diffraction analysis. The analysis revealed that the complexes possess a distorted octahedral geometry with the ligand coordinating in a uni-negative tridentate ONS fashion. The catalytic activity of complexes towards some C–C coupling reactions (viz., Kumada-Corriu, Suzuki-Miyaura and Sonogashira) has been examined. The complexes behave as efficient catalysts in the Kumada-Corriu and Sonogashira coupling reactions rather than Suzuki-Miyaura coupling.

  17. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, October 1--December 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, H.; Iglesia, E.; Perry, D.L.

    1993-12-01

    This report covers the time period from October 1 through December 31, 1993. A description of tasks for fiscal year 1994 is included in this report. Highlights and progress of work performed during this quarter is reported in (a) catalytic steam gasification of coals and cokes; (b) oxidative coupling of methane; and (c) synthesis and characterization of catalysts. Attached to this report is a copy of a manuscript submitted to Proceeding of Fuels Technology Contractors Meeting {open_quotes}Steady-State and Transient Catalytic Oxidation and Coupling of Methane{close_quotes} by Heinemann, Iglesia, and Perry.

  18. Determination of trace uranium by resonance fluorescence method coupled with photo-catalytic technology and dual cloud point extraction.

    Science.gov (United States)

    Li, Jiekang; Li, Guirong; Han, Qian

    2016-12-01

    In this paper, two kinds of salophens (Sal) with different solubilities, Sal1 and Sal2, have been respectively synthesized, and they all can combine with uranyl to form stable complexes: [UO2(2+)-Sal1] and [UO2(2+)-Sal2]. Among them, [UO2(2+)-Sal1] was used as ligand to extract uranium in complex samples by dual cloud point extraction (dCPE), and [UO2(2+)-Sal2] was used as catalyst for the determination of uranium by photocatalytic resonance fluorescence (RF) method. The photocatalytic characteristic of [UO2(2+)-Sal2] on the oxidized pyronine Y (PRY) by potassium bromate which leads to the decrease of RF intensity of PRY were studied. The reduced value of RF intensity of reaction system (ΔF) is in proportional to the concentration of uranium (c), and a novel photo-catalytic RF method was developed for the determination of trace uranium (VI) after dCPE. The combination of photo-catalytic RF techniques and dCPE procedure endows the presented methods with enhanced sensitivity and selectivity. Under optimal conditions, the linear calibration curves range for 0.067 to 6.57ngmL(-1), the linear regression equation was ΔF=438.0 c (ngmL(-1))+175.6 with the correlation coefficient r=0.9981. The limit of detection was 0.066ngmL(-1). The proposed method was successfully applied for the separation and determination of uranium in real samples with the recoveries of 95.0-103.5%. The mechanisms of the indicator reaction and dCPE are discussed. PMID:27380304

  19. Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, Ruth; Bhaumik, Asim [Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India); Dutta, Saikat [Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan (China)

    2014-11-01

    A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state {sup 13}C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N{sub 2} sorption, HR-TEM, and NH{sub 3} temperature programmed desorption-thermal conductivity detector (TPD-TCD) analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, β-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H)-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

  20. Synthesis, characterization, and catalytic activity in Suzuki coupling and catalase-like reactions of new chitosan supported Pd catalyst.

    Science.gov (United States)

    Baran, Talat; Inanan, Tülden; Menteş, Ayfer

    2016-07-10

    The aim of this study is to analyze the synthesis of a new chitosan supported Pd catalyst and examination of its catalytic activity in: Pd catalyst was synthesized using chitosan as a biomaterial and characterized with FTIR, TG/DTG, XRD, (1)H NMR, (13)C NMR, SEM-EDAX, ICP-OES, Uv-vis spectroscopies, and magnetic moment, along with molar conductivity analysis. Biomaterial supported Pd catalyst indicated high activity and long life time as well as excellent turnover number (TON) and turnover frequency (TOF) values in Suzuki reaction. Biomaterial supported Pd catalyst catalyzed H2O2 decomposition reaction with considerable high activity using comparatively small loading catalyst (10mg). Redox potential of biomaterial supported Pd catalyst was still high without negligible loss (13% decrease) after 10 cycles in reusability tests. As a consequence, eco-friendly biomaterial supported Pd catalyst has superior properties such as high thermal stability, long life time, easy removal from reaction mixture and durability to air, moisture and high temperature. PMID:27106147

  1. Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

    Directory of Open Access Journals (Sweden)

    Ruth Gomes

    2014-11-01

    Full Text Available A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state 13C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N2 sorption, HR-TEM, and NH3 temperature programmed desorption-thermal conductivity detector (TPD-TCD analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, β-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

  2. Coupling of photocatalytic and biological processes as a contribution to the detoxification of water: catalytic and technological aspects

    OpenAIRE

    Parra Cardona, Sandra Patricia; Pulgarin, César

    2005-01-01

    This research contributes to the study and development of a new degradation technique that couples solar and biological processes for the treatment of biorecalcitrant, nonbiodegradable, and/or toxic organic substances present in the aqueous medium. Efficient physicochemical pretreatments are necessary to modify the structure of the pollutants, by transforming them into less toxic and biodegradable intermediates, allowing then, a biological procedure to complete the degradation of the pollutan...

  3. Green synthesis of Pd/CuO nanoparticles by Theobroma cacao L. seeds extract and their catalytic performance for the reduction of 4-nitrophenol and phosphine-free Heck coupling reaction under aerobic conditions.

    Science.gov (United States)

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Bagherzadeh, Mojtaba

    2015-06-15

    We report the green synthesis of palladium/CuO nanoparticles (Pd/CuO NPs) using Theobroma cacao L. seeds extract and their catalytic activity for the reduction of 4-nitrophenol and Heck coupling reaction under aerobic conditions. The catalyst was characterized using the powder XRD, TEM, EDS, UV-vis and FT-IR. This method has the advantages of high yields, elimination of surfactant, ligand and homogeneous catalysts, simple methodology and easy work up. The catalyst can be recovered from the reaction mixture and reused several times without any significant loss of catalytic activity. PMID:25721860

  4. Catalytic conversion of sugarcane bagasse to cellulosic ethanol: TiO2 coupled nanocellulose as an effective hydrolysis enhancer.

    Science.gov (United States)

    Jabasingh, S Anuradha; Lalith, D; Prabhu, M Arun; Yimam, Abubekker; Zewdu, Taye

    2016-01-20

    The present study deals with the production of cellulosic ethanol from bagasse using the synthesized TiO2 coupled nanocellulose (NC-TiO2) as catalyst. Aspergillus nidulans AJSU04 cellulase was used for the hydrolysis of bagasse. NC-TiO2 at various concentrations was added to bagasse in order to enhance the yield of reducing sugars. Complex interaction between cellulase, bagasse, NC-TiO2 and the reaction environment is thoroughly studied. A mathematical model was developed to describe the hydrolysis reaction. Ethanol production from enzymatically hydrolyzed sugarcane bagasse catalyzed with NC-TiO2 was carried out using Saccharomyces cerevisiae ATCC 20602. The glucose release rates and ethanol concentrations were determined. Ethanol produced was found to be strongly dependent on pretreatment given, hydrolysis and fermentation conditions. The study confirmed the promising accessibility of NC-TiO2, for enhanced glucose production rates and improved ethanol yield. PMID:26572403

  5. Low-temperature catalytic oxidative coupling of methane in an electric field over a Ce–W–O catalyst system

    OpenAIRE

    Sugiura, Kei; Ogo, Shuhei; Iwasaki, Kousei; Yabe, Tomohiro; Sekine, Yasushi

    2016-01-01

    We examined oxidative coupling of methane (OCM) over various Ce–W–O catalysts at 423 K in an electric field. Ce2(WO4)3/CeO2 catalyst showed high OCM activity. In a periodic operation test over Ce2(WO4)3/CeO2 catalyst, C2 selectivity exceeded 60% during three redox cycles. However, Ce2(WO4)3/CeO2 catalyst without the electric field showed low activity, even at 1073 K: CH4 Conv., 6.0%; C2 Sel., 2.1%. A synergetic effect between the Ce2(WO4)3 structure and electric field created the reactive oxy...

  6. Low-temperature catalytic oxidative coupling of methane in an electric field over a Ce–W–O catalyst system

    Science.gov (United States)

    Sugiura, Kei; Ogo, Shuhei; Iwasaki, Kousei; Yabe, Tomohiro; Sekine, Yasushi

    2016-04-01

    We examined oxidative coupling of methane (OCM) over various Ce–W–O catalysts at 423 K in an electric field. Ce2(WO4)3/CeO2 catalyst showed high OCM activity. In a periodic operation test over Ce2(WO4)3/CeO2 catalyst, C2 selectivity exceeded 60% during three redox cycles. However, Ce2(WO4)3/CeO2 catalyst without the electric field showed low activity, even at 1073 K: CH4 Conv., 6.0%; C2 Sel., 2.1%. A synergetic effect between the Ce2(WO4)3 structure and electric field created the reactive oxygen species for selective oxidation of methane. Results of XAFS, in-situ Raman and periodic operation tests demonstrated that OCM occurred as the lattice oxygen in Ce2(WO4)3 (short W–O bonds in distorted WO4 unit) was consumed. The consumed oxygen was reproduced by a redox mechanism in the electric field.

  7. Low-temperature catalytic oxidative coupling of methane in an electric field over a Ce-W-O catalyst system.

    Science.gov (United States)

    Sugiura, Kei; Ogo, Shuhei; Iwasaki, Kousei; Yabe, Tomohiro; Sekine, Yasushi

    2016-01-01

    We examined oxidative coupling of methane (OCM) over various Ce-W-O catalysts at 423 K in an electric field. Ce2(WO4)3/CeO2 catalyst showed high OCM activity. In a periodic operation test over Ce2(WO4)3/CeO2 catalyst, C2 selectivity exceeded 60% during three redox cycles. However, Ce2(WO4)3/CeO2 catalyst without the electric field showed low activity, even at 1073 K: CH4 Conv., 6.0%; C2 Sel., 2.1%. A synergetic effect between the Ce2(WO4)3 structure and electric field created the reactive oxygen species for selective oxidation of methane. Results of XAFS, in-situ Raman and periodic operation tests demonstrated that OCM occurred as the lattice oxygen in Ce2(WO4)3 (short W-O bonds in distorted WO4 unit) was consumed. The consumed oxygen was reproduced by a redox mechanism in the electric field. PMID:27118726

  8. Supramolecular Macrocyclic Pd(II) and Pt(II) Squares and Rectangles with Aryldithiolate Ligands and their Excellent Catalytic Activity in Suzuki C-C Coupling Reaction.

    Science.gov (United States)

    Vivekananda, K V; Dey, S; Maity, D K; Bhuvanesh, N; Jain, V K

    2015-11-01

    Addition of 1,4-benezenedithiol and 4,4'-biphenyldithiol to M(OTf)2 (M = cis-[Pt(PEt3)2](2+) or cis-[Pd(dppe)](2+)) (dppe = 1,2-bis(diphenylphosphino)ethane) gave self-assembled tetranuclear complexes [M2{S(C6H4)nS}]2(OTf)4 (n = 1, 2). The same reaction with 1,4-benezenedimethanethiol yielded octanuclear supramolecular coordination complexes (SCC) [M2{SCH2C6H4CH2S}]4(OTf)8. These complexes were characterized by NMR, mass, and UV-vis spectroscopies, cyclic voltammetry, as well as density functional theory studies and represent the first examples of SCCs constructed by thiolate groups and square-planar metal ions. The rectangular shape of tetranuclear complexes and square shape of octanuclear complex are confirmed by single-crystal structures and computational studies. The palladium complexes showed excellent catalytic activity in Suzuki C-C cross-coupling reactions with high turnover numbers (2 × 10(7)), even with low catalyst loading. PMID:26444245

  9. Application Of Ozone-Biological Activated Carbon Technology On Drinking Water%臭氧活性炭技术在饮用水深度处理中的作用

    Institute of Scientific and Technical Information of China (English)

    刘丽仪; 谢茵茵; 黄剑明

    2014-01-01

    This paper introduces the application of ozone-biological activated carbon technology on drinking water .It indicates the ozone-biological activated carbon technology, mechanism and application in water treatment, and refers to the problems in the application and partly suggests possible solution to the problems as well ,through presenting the development and application of a process for ozone-biological activated carbon in our country and others.%本文介绍了臭氧化活性炭技术在生活饮用水深度处理中的应用。通过研究国内外臭氧生物活性炭工艺的发展现状和应用实践,综述臭氧化-生物活性炭联用技术的作用机理及在水处理中的应用研究,并提出了此项技术在应用中存在的问题,并介绍提高此项技术的应用措施。

  10. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, 1 January--31 March 1994

    Energy Technology Data Exchange (ETDEWEB)

    Iglesia, E.; Heinemann, H.; Perry, D.L. [Lawrence Berkeley Lab., CA (United States). Center for Advanced Materials

    1994-03-01

    This report describes work in progress on three tasks: (1) Catalytic steam gasification of coals and cokes; (2) Oxidative coupling of methane; and (3) Synthesis and characterization of catalysts. Since Task 1 is complete, a final report has been written. This report describes membrane reactors, cyclic methane conversion reactors, theoretical descriptions of reaction-separation schemes, and time-space relationships in cyclic and membrane reactors, all subtasks of Task 2. Initial studies under Task 3 are briefly described.

  11. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, January 1, 1995--March 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Iglesia, E.; Perry, D.L.; Heinemann, H.

    1995-03-01

    The synthesis of ethane and ethylene from methane and oxygen will be carried out in novel hydrogen transport inorganic membranes and in cyclic reactors in order to prevent undesirable secondary reactions of C{sub 2} molecules to CO and CO{sub 2}. Neither inorganic membrane reactors nor cyclic tubular reactors are presently used in commercial processes. Their application to catalytic reactions represents a novel application of engineering and solid-state chemistry concepts to catalytic reactions. Our approach combines high temperature membrane and cyclic experimental reactors, synthesis and characterization of thin membrane films and of high surface area catalysts, and detailed models of complex gas phase and surface reactions involved in oxidative coupling. We anticipate that this approach will lead to novel reactors for carrying our kinetic-controlled sequential reactions, such as the oxidative coupling of methane. Careful spectrographic and wet chemical analyses of fresh and silent catalysts have shown considerable differences which have permitted conclusions as to the source of deactivation. Our activities in the first quarter FYI 995 have focused on the synthesis, structural characterization, and catalytic evaluation of membrane films, disks, and reactors. We have also continued to exploit reaction-transport models to predict the performance of membrane, cyclic, and recycle reactors in the oxidative coupling of methane.

  12. Nickel-doped zinc aluminate oxides: starch-assisted synthesis, structural, optical properties, and their catalytic activity in oxidative coupling of methane

    Energy Technology Data Exchange (ETDEWEB)

    Visinescu, Diana; Papa, Florica [' Ilie Murgulescu' Institute of Physical Chemistry, Romanian Academy (Romania); Ianculescu, Adelina C., E-mail: a.ianculescu@rdslink.ro [Polytechnica University, Department of Oxide Materials Science and Engineering (Romania); Balint, Ioan; Carp, Oana, E-mail: ocarp@icf.ro [' Ilie Murgulescu' Institute of Physical Chemistry, Romanian Academy (Romania)

    2013-03-15

    Nanosized nickel-substituted zinc aluminate oxides were obtained by the gradual insertion of nickel cations within the zinc aluminate lattice, using starch as active ingredient. The obtained (Ni{sub x}Zn{sub 1-x}Al{sub 2})-starch (x = 0.1, 0.2, 0.4, 0.6, 0.8, 1) gel precursors were characterized through infrared spectroscopy and thermal analysis. The thermal behavior of the precursors are influenced by the nickel content, the DTA curves for the richer nickel samples revealing stronger, faster and overlapping exothermic reactions, that can be completed at lower temperatures. The corresponding spinelic oxides were obtained after calcination treatments at 800 Degree-Sign C and analyzed by means of NIR-UV-Vis spectroscopy, XRD measurements, SEM, TEM, and HRTEM investigations. The spinelic structure for all oxide samples is confirmed by XRD analysis, although small amounts of NiO cannot be neglected. TEM/HRTEM analysis revealed mesopores embedded in plate-like large (68.8 nm) particles of Ni{sub 0.2}Zn{sub 0.8}Al{sub 2}O{sub 4} sample and smaller (15.7 nm) uniform equiaxial particles, with a more pronounced tendency of agglomeration for Ni{sub 0.8}Zn{sub 0.2}Al{sub 2}O{sub 4} oxide. A formation mechanism for Ni{sub 0.2}Zn{sub 0.8}Al{sub 2}O{sub 4} oxides was proposed based on DTA/TG, XRD, and SEM analyses. NIR-UV-Vis spectra for Ni{sub x}Zn{sub 1-x}Al{sub 2}O{sub 4} showed a significant presence of tetrahedral nickel cations that augments with nickel concentration increase. CIE-L{sup *}a{sup *}b{sup *} color parameters shown a variation of the lightness and also of the green and blue color components with x, the best color characteristics being obtained for x = 0.6. The oxides with a substitution degree x = 0.2 and 0.8 tested in the oxidative coupled of methane reaction (OCM) showed positive catalytic activity and selectivity due to an interesting synergetic effect of Zn(II) and Ni(II) ions.

  13. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, October 1--December 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, H.; Somorjai, G.A.; Perry, D.L.

    1992-12-01

    Work on catalytic steam gasification with chars and coals will be extended from atmospheric to elevated pressures using the newly built pressure unit. The novel finding that coking of petroleum in the presence of small amounts of caustic greatly improves the gasification rates and characteristics of the coke will be extended to chars; in the oxidative coupling of methane over ternary catalysts, emphasis will be placed on low temperature coupling and on the oxidative production of syngas from methane at low temperature. Experimental work will continue on the synthesis of the mixed catalyst, and they will be characterized by a number of techniques, including elemental analyses, x-ray diffraction, and surface area determination.

  14. Simulation of thermally coupled catalytic distillation flowsheets for C3 alkyne selective hydrogenation%C3选择性加氢热耦合催化精馏流程模拟

    Institute of Scientific and Technical Information of China (English)

    王易卓; 罗祎青; 钱行; 袁希钢

    2016-01-01

    In order to reduce effectively the refrigeration cost for the process of selective hydrogenation of C3 alkyne into alkene, three novel thermally coupled catalytic distillation flowsheets are proposed. In the proposed flowsheets, the reactor for catalytic hydrogenation of C3 components is settled in the lower part of the deethanizer in the original process and the three columns are thermally coupled in different ways. The proposed flowsheets are rigorously simulated and evaluated. The results show that, compared with original process, the proposed processes raise the convert ratio of hydrogenation, and at the same time, significant energy saving can be achieved by the thermal couplings, leading to a decrease in the total annual cost by 4.107%, 6.420%and 10.337%respectively for the three proposed flowsheets.%针对C3选择性加氢过程中冷剂费用过高问题提出将选择性加氢催化反应器设置在脱乙烷精馏塔的提馏段,并通过原流程的3个精馏塔的不同热耦合方式所构成的3种热耦合催化精馏结构;对三热耦合催化精馏结构分别进行严格模拟和评价,表明通过分离和加氢反应的结合增加了加氢反应的转化率,并通过热耦合降低了分离能耗,年度总费用降低显著。模拟结果表明,3种方案的年度总费用节约效果分别为4.107%、6.420%和10.337%。

  15. DEACIDIFICATION AND ESTERIFACTION OF WASTE COOKING OIL: COMPARISON OF THE COUPLED PROCESS WITH STAND-ALONE CATALYTIC ESTERIFICATION AND EXTRACTION PROCESSES

    Directory of Open Access Journals (Sweden)

    Xianghong Lu

    2010-02-01

    Full Text Available The free fatty acids in waste oil with high acid value were removed and transformed into fatty acid methyl esters by the extraction-reaction coupled process. The de-acidification efficiency and esterification conversion in the extraction-reaction coupled process were studied and compared with those in the stand-alone extraction process and the esterification process, respectively. Compared with cross-current batch extraction, the de-acidification efficiency of the extraction-reaction coupled process was equivalent to that of seven equilibrium stages in the conditions of the oil/methanol mass ratio of 1:1 at 60 oC. Compared with the esterification process, the esterification conversion of the coupled process was 90.3%, which is much larger than 46% in the esterification process at the reaction time of 32 minutes. Based on these findings, it is suggested that the extraction-reaction coupled process is a very effective and promising method for biodiesel production from oils having high acid value.

  16. EFFECTS OF SOLVENT, BASE, AND TEMPERATURE IN THE OPTIMISATION OF A NEW CATALYTIC SYSTEM FOR SONOGASHIRA CROSS-COUPLING USING NCP PINCER PALLADACYCLE

    Directory of Open Access Journals (Sweden)

    Diego S. Rosa

    2015-05-01

    Full Text Available The optimisation of a new catalyst system using NCP pincer palladacycle 1 was investigated using the experimental design technique. NCP pincer palladacycle 1 was previously investigated in Suzuki-Miyaura and Heck-Mizoroki cross-couplings and found to be a highly efficient catalyst precursor. In this study, the effects of the type of base (K3PO4 or DABCO, solvent (DMF or dioxane and reaction temperature (130 or 150 ºC in the second step on the reactional yield in Sonogashira cross-coupling were assessed using the two-factor design. The results showed that temperature is statistically significant in relation to the reaction yield.

  17. Oxidative Photoredox-Catalytic Activation of Aliphatic Nucleophiles for C(sp3)-C(sp2) Cross-Coupling Reactions

    Czech Academy of Sciences Publication Activity Database

    Jahn, Emanuela; Jahn, Ullrich

    2014-01-01

    Roč. 53, č. 49 (2014), s. 13326-13328. ISSN 1433-7851 Institutional support: RVO:61388963 Keywords : amino acids * cross-coupling * nickel * persistent radical effect * photoredox catalysis Subject RIV: CC - Organic Chemistry Impact factor: 11.261, year: 2014

  18. Green synthesis of CuO nanoparticles by aqueous extract of Anthemis nobilis flowers and their catalytic activity for the A³ coupling reaction.

    Science.gov (United States)

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

    2015-12-01

    CuO nanoparticles (NPs) were prepared by Anthemis nobilis flowers extract as a reducing and stabilizing agent and employed in catalyzing an aldehyde-amine-alkyne coupling reaction. The synthesized CuO NPs was characterized by SEM, EDS, XRD, FT-IR and UV-visible techniques. A diverse range of propargylamines were obtained in a good to high yield. Furthermore, the separation and reuse of CuO NPs was very simple, effective and economical. PMID:26291574

  19. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, April 1, 1994--June 30, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Iglesia, E.; Perry, D.L.; Heinemann, H.

    1994-06-01

    Catalytic gasification work has been completed and no other work is planned in the general area of catalytic gasification of coals and chars has operated without a post-doctoral fellow because of budget limitations during the first two quarters of FY1994. Dr. S. Sundararajan joined the group in April 1994 and will be assigned to the project throughout the remaining of the fiscal year. Results published by Hamakawa, et al. in The Journal of the Electrochemical Society have confirmed the concept of methane coupling via a membrane reactor. These findings confirm our previous conclusion that thinner membranes and increased surface activity for C-H bond activation at low temperatures are required in order to reach commercially attractive rates of reaction. The initial analysis of a theoretical model comparing the membrane and cyclic processes has been completed. The results indicate that perovskite membranes on the order of 50 microns will be needed for the membrane operation to be superior to a cyclic one. Two techniques, laser ablation and spin-coating/sol-gel chemistry are being tried to prepare the thin membranes described above. Studies of the magnetochemical properties of the calcium-nickel-potassium oxide powdered catalysts have been concluded and a manuscript describing the work has been completed. Synchrotron x-ray fluorescence microprobe data for calcium-nickel-potassium films have been analyzed and an abstract of the results has been submitted for presentation at the Fall Meeting of the Materials Research Society. Initial films of strontium-zirconium oxide, using yttria-stabilized zirconia as a buffer layer, have been fabricated using pulsed laser deposition. X-ray diffraction data have been obtained for several of the strontium-zirconium-yttrium oxide films.

  20. Half-sandwich nickel complexes with ring-expanded NHC ligands - synthesis, structure and catalytic activity in Kumada-Tamao-Corriu coupling.

    Science.gov (United States)

    Banach, Ł; Guńka, P A; Buchowicz, W

    2016-06-01

    The general synthesis of [Ni(Cp)(X)(NHC)] complexes from a nickel halide, CpLi, and a carbene solution is reported. This procedure yields unprecedented complexes with ring-expanded NHC ligands (RE-NHC) of six- (1a, 1b), seven- (1c), and eight-membered (1d) heterocycles. The NMR spectra of 1a-1d are consistent with the hindered rotation of Ni-Ccarbene and N-CMes bonds, while X-ray analyses of 1b, 1c, and 1d reveal a pronounced trans influence of the RE-NHC ligands. Complexes 1a-1e are efficient pre-catalysts in Kumada-Tamao-Corriu coupling with the maximum efficiency observed for complexes bearing the six-membered NHC. PMID:26853761

  1. DNA-binding, catalytic oxidation, C—C coupling reactions and antibacterial activities of binuclear Ru(II thiosemicarbazone complexes: Synthesis and spectral characterization

    Directory of Open Access Journals (Sweden)

    Arumugam Manimaran

    2012-07-01

    Full Text Available New hexa-coordinated binuclear Ru(II thiosemicarbazone complexes of the type {[(B(EPh3(COClRu]2L} (where, E = P or As; B = PPh3 or AsPh3 or pyridine; L = mononucleating NS donor of N-substituted thiosemicarbazones have been synthesized and characterized by elemental analysis, FT-IR, UV–vis and 31P{1H} NMR cyclic voltammetric studies. The DNA-binding studies of Ru(II complexes with calf thymus DNA (CT-DNA were investigated by UV–vis, viscosity measurements, gel-electrophoresis and fluorescence spectroscopy. The new complexes have been used as catalysts in C—C coupling reaction and in the oxidation of alcohols to their corresponding carbonyl compounds by using NMO as co-oxidant and molecular oxygen (O2 atmosphere at ambient temperature. Further, the new binucleating thiosemicarbazone ligands and their Ru(II complexes were also screened for their antibacterial activity against Klebsiella pneumoniae, Shigella sp., Micrococcus luteus, Escherichia coli and Salmonella typhi. From this study, it was found out that the activity of the complexes almost reaches the effectiveness of the conventional bacteriocide.

  2. Catalytic mechanisms of direct pyrrole synthesis via dehydrogenative coupling mediated by PNP-Ir or PNN-Ru pincer complexes: Crucial role of proton-transfer shuttles in the PNP-Ir system

    KAUST Repository

    Qu, Shuanglin

    2014-04-02

    Kempe et al. and Milstein et al. have recently advanced the dehydrogenative coupling methodology to synthesize pyrroles from secondary alcohols (e.g., 3) and β-amino alcohols (e.g., 4), using PNP-Ir (1) and PNN-Ru (2) pincer complexes, respectively. We herein present a DFT study to characterize the catalytic mechanism of these reactions. After precatalyst activation to give active 1A/2A, the transformation proceeds via four stages: 1A/2A-catalyzed alcohol (3) dehydrogenation to give ketone (11), base-facilitated C-N coupling of 11 and 4 to form an imine-alcohol intermediate (18), base-promoted cyclization of 18, and catalyst regeneration via H2 release from 1R/2R. For alcohol dehydrogenations, the bifunctional double hydrogen-transfer pathway is more favorable than that via β-hydride elimination. Generally, proton-transfer (H-transfer) shuttles facilitate various H-transfer processes in both systems. Notwithstanding, H-transfer shuttles play a much more crucial role in the PNP-Ir system than in the PNN-Ru system. Without H-transfer shuttles, the key barriers up to 45.9 kcal/mol in PNP-Ir system are too high to be accessible, while the corresponding barriers (<32.0 kcal/mol) in PNN-Ru system are not unreachable. Another significant difference between the two systems is that the addition of alcohol to 1A giving an alkoxo complex is endergonic by 8.1 kcal/mol, whereas the addition to 2A is exergonic by 8.9 kcal/mol. The thermodynamic difference could be the main reason for PNP-Ir system requiring lower catalyst loading than the PNN-Ru system. We discuss how the differences are resulted in terms of electronic and geometric structures of the catalysts and how to use the features in catalyst development. © 2014 American Chemical Society.

  3. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, July 1--September 30, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, H.; Somorjai, G.A.; Perry, D.L.

    1992-09-01

    Work will continue on the oxidative coupling reaction of methane over ternary oxide catalysts to produce C{sub 2}, C{sub 3} and C{sub 4} hydrocarbons and Particularly Olefins with high selectivity. The work which has shown that close to 100% selectivity can be obtained has received wide attention and has resulted in collaborative efforts with industry (CRADA) towards the development of a commercial process. An immediate purpose of additional work is to increase the conversion without diminishing the extremely high selectivity of the reaction and also to permit operation at higher space velocity to reduce equipment size. The mechanism of this reaction is not understood and much additional work is needed to explain the role of carbon formation and of water as intermediates in the reaction and to investigate whether carbon oxides are intermediates. It has been found that oxides other than calcium-nickel-potassium oxides can be useful catalysts for this reaction in the presence of steam and at relatively low temperatures and long contact times. Better definition of the class of binary metal oxides is required and better catalyst characterization is needed to ensure reproducibility Of catalyst preparation and operational results. Pretreatment of the catalyst should be shortened and higher space velocities must be obtained. Close collaboration with Orion ACT is required to advance the project toward the pilot plant stage. In the area of coal and char catalytic steam gasification, the large volume of data obtained at atmospheric pressure will be extended to operations at higher pressures.

  4. 饮用水臭氧-生物活性炭深度处理工程调试运行%Commissioning and Operation of Ozone/Biological Activated Carbon Process for Advanced Treatment of Drinking Water

    Institute of Scientific and Technical Information of China (English)

    刘保超; 李家爱; 刘晓威

    2012-01-01

    连云港市第三水厂深度处理改造一期工程设计规模为20×104 m3/d,采用臭氧-生物活性炭工艺.从初期运行出水水质来看,改造效果较好,主要指标满足《生活饮用水卫生标准》( GB 5749-2006).总结了臭氧-生物活性炭深度处理工艺的调试运行经验,对类似水质达标改造工程的建设、设备安装、调试和运行提出了建议.%The treatment capacity of the first-phase project of advanced treatment of drinking water in Third Waterworks in Lianyungang City was 20×104 mVd. The ozone/biological activated carbon (O3/BAC) process was used. The main water quality indexes met the requirement of the Standards for Drinking Water Quality (GB 5749 - 2006 ). The commissioning and operation experience for O3/BAC process was summarized , and suggestions on the construction , equipment installation, commissioning and operation of similar water quality improvement projects were made.

  5. 臭氧-生物活性炭技术在水处理中的应用与研究%Study on the application of ozone-biological activated carbon process to water treatment

    Institute of Scientific and Technical Information of China (English)

    郭锋; 王潇; 肖强; 肖禾

    2011-01-01

    Ozone-biological activated carbon (O3-BAC) is a new type of efficient micro-polluted water treatment process. Its application to drinking water (surface water, ground water, domestic water, municipal water supply, etc. ) and industrial wastewater(membrane treatment discharge ,oilfield wastewater,oil refining wastewater, petrochemical wastewater, pharmaceutical wastewater, dyestuff wastewater, food processing wastewater, aquaculture wastewater, etc. ) and their research situations are introduced. The future development directions of the application of O3-BAC to water treatment are pointed out.%臭氧-生物活性炭(O-BAC)技术是一种新型高效的微污染水处理工艺.介绍了O-BAC技术在饮用水(地表水、地下水、生活污水、市政供水等制饮用水)及工业废水(膜处理排水、油田废水、炼油废水、石化废水、制药废水、焦化废水、印染废水、食品加工废水、水产养殖废水)等领域的应用和研究情况,指出了未来O-BAC技术在水处理中的发展研究方向.

  6. Catalytic cracking process

    Science.gov (United States)

    Lokhandwala, Kaaeid A.; Baker, Richard W.

    2001-01-01

    Processes and apparatus for providing improved catalytic cracking, specifically improved recovery of olefins, LPG or hydrogen from catalytic crackers. The improvement is achieved by passing part of the wet gas stream across membranes selective in favor of light hydrocarbons over hydrogen.

  7. Catalytic distillation structure

    Science.gov (United States)

    Smith, Jr., Lawrence A.

    1984-01-01

    Catalytic distillation structure for use in reaction distillation columns, a providing reaction sites and distillation structure and consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and being present with the catalyst component in an amount such that the catalytic distillation structure consist of at least 10 volume % open space.

  8. 臭氧-生物活性炭工艺设计中工程方案的选择%Selection of Engineering Scheme in Ozone/Biological Activated Carbon Process Design

    Institute of Scientific and Technical Information of China (English)

    李世峰

    2012-01-01

    Ozone/biological activated carbon ( O3/BAC ) process was developed on the basis of biological activated carbon process, which is recognized as one of the most effective advanced treatment processes in removing organic pollutants and odor from drinking water in the world at present. With the implementation of the Standards for Drinking Water Quality ( GB 5749 - 2006 ) , O3/BAC process has been widely used in upgrading and reconstruction of water treatment plants. In the design, selection of gas source for ozone generator and design of activated carbon tank type related to project investment, operation cost and operation management. In order to facilitate the upgrading and reconstruction project of water treatment plants, it needs to choose the ozone source and tank type reasonably according to the actual situation of the plant.%臭氧-生物活性炭(O3-BAC)工艺是在生物活性炭工艺基础上发展起来的,是目前世界上公认的去除饮用水中有机污染物、嗅味等较为有效的深度处理工艺之一.随着《生活饮用水卫生标准》( GB 5749-2006)的实施,臭氧-生物活性炭工艺广泛应用于给水厂的提标改造中.在其设计中,臭氧气源的选择和活性炭池池型的设计关系到工程的投资、运行成本的高低以及操作管理的难易,需根据各给水厂的实际情况,合理选择臭氧气源和活性炭池池型,以利于给水厂提标改造工程的实施.

  9. Catalytic Synthesis Lactobionic Acid

    Directory of Open Access Journals (Sweden)

    V.G. Borodina

    2014-07-01

    Full Text Available Gold nanoparticles are obtained, characterized and deposited on the carrier. Conducted catalytic synthesis of lactobionic acid from lactose. Received lactobionic acid identify on the IR spectrum.

  10. Catalytic distillation process

    Science.gov (United States)

    Smith, Jr., Lawrence A.

    1982-01-01

    A method for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C.sub.4 feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  11. Catalytic Coanda combustion

    Energy Technology Data Exchange (ETDEWEB)

    Coleman, J.D.; Smith, A.G.; Kopmels, M.

    1992-09-16

    A catalytic reaction is enhanced by the use of the Coanda effect to maximise contact between reactant and catalyst. A device utilising this principle comprises a Coanda surface which directs the flow of fuel from a slot to form a primary jet which entrains the surrounding ambient air and forms a combustible mixture for reaction on a catalytic surface. The Coanda surface may have an internal or external nozzle which may be axi-symmetric or two-dimensional. (author)

  12. Catalytic ignition of light hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    K. L. Hohn; C.-C. Huang; C. Cao

    2009-01-01

    Catalytic ignition refers to phenomenon where sufficient energy is released from a catalytic reaction to maintain further reaction without additional extemai heating. This phenomenon is important in the development of catalytic combustion and catalytic partial oxidation processes, both of which have received extensive attention in recent years. In addition, catalytic ignition studies provide experimental data which can be used to test theoretical hydrocarbon oxidation models. For these reasons, catalytic ignition has been frequently studied. This review summarizes the experimental methods used to study catalytic ignition of light hydrocarbons and describes the experimental and theoretical results obtained related to catalytic ignition. The role of catalyst metal, fuel and fuel concentration, and catalyst state in catalytic ignition are examined, and some conclusions are drawn on the mechanism of catalytic ignition.

  13. Catalytic hydrogenation of carbon monoxide

    International Nuclear Information System (INIS)

    Focus of this project is on developing new approaches for hydrogenation of carbon monoxide to produce organic oxygenates at mild conditions. The strategies to accomplish CO reduction are based on favorable thermodynamics manifested by rhodium macrocycles for producing a series of intermediates implicated in the catalytic hydrogenation of CO. Metalloformyl complexes from reactions of H2 and CO, and CO reductive coupling to form metallo α-diketone species provide alternate routes to organic oxygenates that utilize these species as intermediates. Thermodynamic and kinetic-mechanistic studies are used in guiding the design of new metallospecies to improve the thermodynamic and kinetic factors for individual steps in the overall process. Electronic and steric effects associated with the ligand arrays along with the influences of the reaction medium provide the chemical tools for tuning these factors. Non-macrocyclic ligand complexes that emulate the favorable thermodynamic features associated with rhodium macrocycles, but that also manifest improved reaction kinetics are promising candidates for future development

  14. Reducing catalytic converter pressure loss

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-06-01

    This article examines why approximately 30--40% of total exhaust-system pressure loss occurs in the catalytic converter and what can be done to reduce pressure loss. High exhaust-system backpressure is of concern in the design of power trains for passenger cars and trucks because it penalizes fuel economy and limits peak power. Pressure losses occur due to fluid shear and turning during turbulent flow in the converter headers and in entry separation and developing laminar-flow boundary layers within the substrate flow passages. Some of the loss mechanisms are coupled. For example, losses in the inlet header are influenced by the presence of the flow resistance of a downstream substrate. Conversely, the flow maldistribution and pressure loss of the substrate(s) depend on the design of the inlet header.

  15. Catalytic coherence transformations

    Science.gov (United States)

    Bu, Kaifeng; Singh, Uttam; Wu, Junde

    2016-04-01

    Catalytic coherence transformations allow the otherwise impossible state transformations using only incoherent operations with the aid of an auxiliary system with finite coherence that is not being consumed in any way. Here we find the necessary and sufficient conditions for the deterministic and stochastic catalytic coherence transformations between a pair of pure quantum states. In particular, we show that the simultaneous decrease of a family of Rényi entropies of the diagonal parts of the states under consideration is a necessary and sufficient condition for the deterministic catalytic coherence transformations. Similarly, for stochastic catalytic coherence transformations we find the necessary and sufficient conditions for achieving a higher optimal probability of conversion. We thus completely characterize the coherence transformations among pure quantum states under incoherent operations. We give numerous examples to elaborate our results. We also explore the possibility of the same system acting as a catalyst for itself and find that indeed self-catalysis is possible. Further, for the cases where no catalytic coherence transformation is possible we provide entanglement-assisted coherence transformations and find the necessary and sufficient conditions for such transformations.

  16. Pd Close Coupled Catalyst

    Institute of Scientific and Technical Information of China (English)

    Zhong Hua SHI; Mao Chu GONG; Yao Qiang CHEN

    2006-01-01

    A catalyst comprised novel high surface area alumina support was prepared to control emission of automobiles. The results showed that prepared catalyst could satisfy the requirements of a high performance close coupled catalyst for its good catalytic activity at low temperature and good stability at high temperature.

  17. Catalytic methanol dissociation

    International Nuclear Information System (INIS)

    Results of the methanol dissociation study on copper/potassium catalyst with alumina support at various temperatures are presented. The following gaseous and liquid products at. The catalytic methanol dissociation is obtained: hydrogen, carbon monoxide, carbon dioxide, methane, and dimethyl ether. Formation rates of these products are discussed. Activation energies of corresponding reactions are calculated

  18. Catalytic Phosphination and Arsination

    Institute of Scientific and Technical Information of China (English)

    Kwong Fuk Yee; Chan Kin Shing

    2004-01-01

    The catalytic, user-friendly phosphination and arsination of aryl halides and triflates by triphenylphosphine and triphenylarsine using palladium catalysts have provided a facile synthesis of functionalized aryl phosphines and arsines in neutral media. Modification of the cynaoarisne yielded optically active N, As ligands which will be screened in various asymmetric catalysis.

  19. Monolithic catalytic igniters

    Science.gov (United States)

    La Ferla, R.; Tuffias, R. H.; Jang, Q.

    1993-01-01

    Catalytic igniters offer the potential for excellent reliability and simplicity for use with the diergolic bipropellant oxygen/hydrogen as well as with the monopropellant hydrazine. State-of-the-art catalyst beds - noble metal/granular pellet carriers - currently used in hydrazine engines are limited by carrier stability, which limits the hot-fire temperature, and by poor thermal response due to the large thermal mass. Moreover, questions remain with regard to longevity and reliability of these catalysts. In this work, Ultramet investigated the feasibility of fabricating monolithic catalyst beds that overcome the limitations of current catalytic igniters via a combination of chemical vapor deposition (CVD) iridium coatings and chemical vapor infiltration (CVI) refractory ceramic foams. It was found that under all flow conditions and O2:H2 mass ratios tested, a high surface area monolithic bed outperformed a Shell 405 bed. Additionally, it was found that monolithic catalytic igniters, specifically porous ceramic foams fabricated by CVD/CVI processing, can be fabricated whose catalytic performance is better than Shell 405 and with significantly lower flow restriction, from materials that can operate at 2000 C or higher.

  20. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, October 1, 1994--December 31, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Iglesia, E.; Perry, D.L.; Heinemann, H.

    1994-12-01

    This report describes research on the oxidative coupling of methane and catalysts involved in coal gasification. Topics include methane pyrolysis and catalysts, and magnetic properties of the coal gasification catalyst Ca-Ni-K-O system.

  1. Catalytic converter with thermoelectric generator

    Energy Technology Data Exchange (ETDEWEB)

    Parise, R.J.

    1998-07-01

    The unique design of an electrically heated catalyst (EHC) and the inclusion of an ECO valve in the exhaust of an internal combustion engine will meet the strict new emission requirements, especially at vehicle cold start, adopted by several states in this country as well as in Europe and Japan. The catalytic converter (CC) has been a most useful tool in pollution abatement for the automobile. But the emission requirements are becoming more stringent and, along with other improvements, the CC must be improved to meet these new standards. Coupled with the ECO valve, the EHC can meet these new emission limits. In an internal combustion engine vehicle (ICEV), approximately 80% of the energy consumed leaves the vehicle as waste heat: out the tail pipe, through the radiator, or convected/radiated off the engine. Included with the waste heat out the tail pipe are the products of combustion which must meet strict emission requirements. The design of a new CC is presented here. This is an automobile CC that has the capability of producing electrical power and reducing the quantity of emissions at vehicle cold start, the Thermoelectric Catalytic Power Generator. The CC utilizes the energy of the exothermic reactions that take place in the catalysis substrate to produce electrical energy with a thermoelectric generator. On vehicle cold start, the thermoelectric generator is used as a heat pump to heat the catalyst substrate to reduce the time to catalyst light-off. Thus an electrically heated catalyst (EHC) will be used to augment the abatement of tail pipe emissions. Included with the EHC in the exhaust stream of the automobile is the ECO valve. This valve restricts the flow of pollutants out the tail pipe of the vehicle for a specified amount of time until the EHC comes up to operating temperature. Then the ECO valve opens and allows the full exhaust, now treated by the EHC, to leave the vehicle.

  2. The evolution of catalytic function

    Science.gov (United States)

    Maurel, Marie-Christine; Ricard, Jacques

    2006-03-01

    It is very likely that the main driving force of enzyme evolution is the requirement to improve catalytic and regulatory efficiency which results from the intrinsic performance as well as from the spatial and functional organization of enzymes in living cells. Kinetic co-operativity may occur in simple monomeric proteins if they display “slow” conformational transitions, at the cost of catalytic efficiency. Oligomeric enzymes on the other hand can be both efficient and co-operative. We speculate that the main reason for the emergence of co-operative oligomeric enzymes is the need for catalysts that are both cooperative and efficient. As it is not useful for an enzyme to respond to a change of substrate concentration in a complex kinetic way, the emergence of symmetry has its probable origin in a requirement for “functional simplicity”. In a living cell, enzyme are associated with other macromolecules and membranes. The fine tuning of their activity may also be reached through mutations of the microenvironment. Our hypothesis is that these mutations are related to the vectorial transport of molecules, to achieve the hysteresis loops of enzyme reactions generated by the coupling of reaction and diffusion, through the co-operativity brought about by electric interactions between a charged substrate and a membrane, and last but not least, through oscillations. As the physical origins of these effects are very simple and do not require complex molecular devices, it is very likely that the functional advantage generated by the spatial and functional organization of enzyme molecules within the cell have appeared in prebiotic catalysis or very early during the primeval stages of biological evolution. We shall began this paper by presenting the nature of the probable earliest catalysts in the RNA world.

  3. Catalytic thermal barrier coatings

    Science.gov (United States)

    Kulkarni, Anand A.; Campbell, Christian X.; Subramanian, Ramesh

    2009-06-02

    A catalyst element (30) for high temperature applications such as a gas turbine engine. The catalyst element includes a metal substrate such as a tube (32) having a layer of ceramic thermal barrier coating material (34) disposed on the substrate for thermally insulating the metal substrate from a high temperature fuel/air mixture. The ceramic thermal barrier coating material is formed of a crystal structure populated with base elements but with selected sites of the crystal structure being populated by substitute ions selected to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a higher rate than would the base compound without the ionic substitutions. Precious metal crystallites may be disposed within the crystal structure to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a lower light-off temperature than would the ceramic thermal barrier coating material without the precious metal crystallites.

  4. A non-stationary model for catalytic converters with cylindrical geometry

    OpenAIRE

    Hoernel, J. -D.

    2006-01-01

    We prove some existence and uniqueness results and some qualitative properties for the solution of a system modelling the catalytic conversion in a cylinder. This model couples parabolic partial differential equations posed in a cylindrical domain and on its boundary.

  5. Catalytic reforming process

    Energy Technology Data Exchange (ETDEWEB)

    Absil, R.P.; Huss, A. Jr.; McHale, W.D.; Partridge, R.D.

    1989-06-13

    This patent describes a catalytic reforming process which comprises contacting a naphtha range feed with a low acidity extrudate comprising an intermediate and/or a large pore acidic zeolite bound with a low acidity refractory oxide under reforming conditions to provide a reaction product of increased aromatic content, the extrudate having been prepared with at least an extrusion-facilitating amount of a low acidity refractory oxide in colloidal form and containing at least one metal species selected from the platinum group metals.

  6. Catalytic applications of bio-inspired nanomaterials

    Science.gov (United States)

    Pacardo, Dennis Kien Balaong

    The biomimetic synthesis of Pd nanoparticles was presented using the Pd4 peptide, TSNAVHPTLRHL, isolated from combinatorial phage display library. Using this approach, nearly monodisperse and spherical Pd nanoparticles were generated with an average diameter of 1.9 +/- 0.4 nm. The peptide-based nanocatalyst were employed in the Stille coupling reaction under energy-efficient and environmentally friendly reaction conditions of aqueous solvent, room temperature and very low catalyst loading. To this end, the Pd nanocatalyst generated high turnover frequency (TOF) value and quantitative yields using ≥ 0.005 mol% Pd as well as catalytic activities with different aryl halides containing electron-withdrawing and electron-donating groups. The Pd4-capped Pd nanoparticles followed the atom-leaching mechanism and were found to be selective with respect to substrate identity. On the other hand, the naturally-occurring R5 peptide (SSKKSGSYSGSKGSKRRIL) was employed in the synthesis of biotemplated Pd nanomaterials which showed morphological changes as a function of Pd:peptide ratio. TOF analysis for hydrogenation of olefinic alcohols showed similar catalytic activity regardless of nanomorphology. Determination of catalytic properties of these bio-inspired nanomaterials are important as they serve as model system for alternative green catalyst with applications in industrially important transformations.

  7. Novel Catalytic Membrane Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Stuart Nemser, PhD

    2010-10-01

    There are many industrial catalytic organic reversible reactions with amines or alcohols that have water as one of the products. Many of these reactions are homogeneously catalyzed. In all cases removal of water facilitates the reaction and produces more of the desired chemical product. By shifting the reaction to right we produce more chemical product with little or no additional capital investment. Many of these reactions can also relate to bioprocesses. Given the large number of water-organic compound separations achievable and the ability of the Compact Membrane Systems, Inc. (CMS) perfluoro membranes to withstand these harsh operating conditions, this is an ideal demonstration system for the water-of-reaction removal using a membrane reactor. Enhanced reaction synthesis is consistent with the DOE objective to lower the energy intensity of U.S. industry 25% by 2017 in accord with the Energy Policy Act of 2005 and to improve the United States manufacturing competitiveness. The objective of this program is to develop the platform technology for enhancing homogeneous catalytic chemical syntheses.

  8. Optical activity of catalytic elements of hetero-metallic nanostructures

    Science.gov (United States)

    Antosiewicz, Tomasz J.; Apell, S. Peter; Wadell, Carl; Langhammer, Christoph

    2015-05-01

    Interaction of light with metals in the form of surface plasmons is used in a wide range of applications in which the scattering decay channel is important. The absorption channel is usually thought of as unwanted and detrimental to the efficiency of the device. This is true in many applications, however, recent studies have shown that maximization of the decay channel of surface plasmons has potentially significant uses. One of these is the creation of electron-hole pairs or hot electrons which can be used for e.g. catalysis. Here, we study the optical properties of hetero-metallic nanostructures that enhance light interaction with the catalytic elements of the nanostructures. A hybridized LSPR that matches the spectral characteristic of the light source is excited. This LSPR through coupling between the plasmonic elements maximizes light absorption in the catalytic part of the nanostructure. Numerically calculated visible light absorption in the catalytic nanoparticles is enhanced 12-fold for large catalytic disks and by more 30 for small nanoparticles on the order of 5 nm. In experiments we measure a sizable increase in the absorption cross section when small palladium nanoparticles are coupled to a large silver resonator. These observations suggest that heterometallic nanostructures can enhance catalytic reaction rates.

  9. N, N′-Olefin functionalized Bis-Imidazolium Pd(II) chloride N-Heterocyclic carbene complex builds a supramolecular framework and shows catalytic efficacy for `C–C' coupling reactions

    Indian Academy of Sciences (India)

    Gourisankar Roymahapatra; Tapastaru Samanta; Saikat Kumar Seth; Ambikesh Mahapatra; Shyamal Kumar Chattopadhyay; Joydev Dinda

    2015-06-01

    The ligand 3,3′-(-phenylenedimethylene)bis{1-(2-methylallyl)} imidazolium bromide (1) and its Palladium(II) N-heterocyclic carbene (NHC) complex (3) has been synthesized and characterized by several spectroscopic techniques and the solid-state structure of 3 has been determined by single crystal X-ray diffraction studies. The Pd(II) complex possesses ring head to tail – stacking interactions (3.767 A°) through imidazole rings. Complex 3 catalyzes Suzuki-Miyaura `C–C' coupling reaction. DFT calculations have been used to understand the HOMO/LUMO energy and hence the stability and reactivity of Pd(II) complex in syn and anti-configuration.

  10. Evolution of random catalytic networks

    Energy Technology Data Exchange (ETDEWEB)

    Fraser, S.M. [Santa Fe Inst., NM (United States); Reidys, C.M. [Santa Fe Inst., NM (United States)]|[Los Alamos National Lab., NM (United States)

    1997-06-01

    In this paper the authors investigate the evolution of populations of sequences on a random catalytic network. Sequences are mapped into structures, between which are catalytic interactions that determine their instantaneous fitness. The catalytic network is constructed as a random directed graph. They prove that at certain parameter values, the probability of some relevant subgraphs of this graph, for example cycles without outgoing edges, is maximized. Populations evolving under point mutations realize a comparatively small induced subgraph of the complete catalytic network. They present results which show that populations reliably discover and persist on directed cycles in the catalytic graph, though these may be lost because of stochastic effects, and study the effect of population size on this behavior.

  11. Numerical Simulation of Fixed-Bed Catalytic Reforming Reactors: Hydrodynamics / Chemical Kinetics Coupling Simulation numérique des réacteurs de reformage catalytique en lit fixe : couplage hydrodynamique-cinétique chimique

    Directory of Open Access Journals (Sweden)

    Ferschneider G.

    2006-11-01

    Full Text Available Fixed bed reactors with a single fluid phase are widely used in the refining or petrochemical industries for reaction processes catalysed by a solid phase. The design criteria for industrial reactors are relatively well known. However, they rely on a one-dimensional writing and on the separate resolution of the equation of conservation of mass and energy, and of momentum. Thus, with complex geometries, the influence of hydrodynamics on the effectiveness of the catalyst bed cannot be taken into account. The calculation method proposed is based on the multi-dimensional writing and the simultaneous resolution of the local conservation equations. The example discussed concerns fixed-bed catalytic reactors. These reactors are distinguished by their annular geometry and the radial circulation of the feedstock. The flow is assumed to be axisymmetric. The reaction process is reflected by a simplified kinetic mechanism involving ten chemical species. Calculation of the hydrodynamic (mean velocities, pressure, thermal and mass fields (concentration of each species serves to identify the influence of internal components in two industrial reactor geometries. The map of the quantity of coke formed and deposited on the catalyst, calculated by the model, reveals potential areas of poor operation. Les réacteurs à lit fixe avec une seule phase fluide sont largement utilisés dans l'industrie du raffinage et de la pétrochimie, pour mettre en oeuvre un processus réactionnel catalysé par une phase solide. Les règles de conception des réacteurs industriels sont relativement bien connues. Cependant, elles reposent sur l'écriture monodimensionnelle et la résolution séparée, d'une part, des équations de conservation de la masse et de l'énergie et d'autre part, de la quantité de mouvement. Ainsi dans le cas de géométries complexes, l'influence de l'hydrodynamique sur l'efficacité du lit catalytique ne peut être prise en compte. La méthode de calcul

  12. Bifunctional catalytic electrode

    Science.gov (United States)

    Cisar, Alan (Inventor); Murphy, Oliver J. (Inventor); Clarke, Eric (Inventor)

    2005-01-01

    The present invention relates to an oxygen electrode for a unitized regenerative hydrogen-oxygen fuel cell and the unitized regenerative fuel cell having the oxygen electrode. The oxygen electrode contains components electrocatalytically active for the evolution of oxygen from water and the reduction of oxygen to water, and has a structure that supports the flow of both water and gases between the catalytically active surface and a flow field or electrode chamber for bulk flow of the fluids. The electrode has an electrocatalyst layer and a diffusion backing layer interspersed with hydrophilic and hydrophobic regions. The diffusion backing layer consists of a metal core having gas diffusion structures bonded to the metal core.

  13. Catalytic Combustion of Gasified Waste

    Energy Technology Data Exchange (ETDEWEB)

    Kusar, Henrik

    2003-09-01

    This thesis concerns catalytic combustion for gas turbine application using a low heating-value (LHV) gas, derived from gasified waste. The main research in catalytic combustion focuses on methane as fuel, but an increasing interest is directed towards catalytic combustion of LHV fuels. This thesis shows that it is possible to catalytically combust a LHV gas and to oxidize fuel-bound nitrogen (NH{sub 3}) directly into N{sub 2} without forming NO{sub x} The first part of the thesis gives a background to the system. It defines waste, shortly describes gasification and more thoroughly catalytic combustion. The second part of the present thesis, paper I, concerns the development and testing of potential catalysts for catalytic combustion of LHV gases. The objective of this work was to investigate the possibility to use a stable metal oxide instead of noble metals as ignition catalyst and at the same time reduce the formation of NO{sub x} In paper II pilot-scale tests were carried out to prove the potential of catalytic combustion using real gasified waste and to compare with the results obtained in laboratory scale using a synthetic gas simulating gasified waste. In paper III, selective catalytic oxidation for decreasing the NO{sub x} formation from fuel-bound nitrogen was examined using two different approaches: fuel-lean and fuel-rich conditions. Finally, the last part of the thesis deals with deactivation of catalysts. The various deactivation processes which may affect high-temperature catalytic combustion are reviewed in paper IV. In paper V the poisoning effect of low amounts of sulfur was studied; various metal oxides as well as supported palladium and platinum catalysts were used as catalysts for combustion of a synthetic gas. In conclusion, with the results obtained in this thesis it would be possible to compose a working catalytic system for gas turbine application using a LHV gas.

  14. Unsteady catalytic processes and sorption-catalytic technologies

    International Nuclear Information System (INIS)

    Catalytic processes that occur under conditions of the targeted unsteady state of the catalyst are considered. The highest efficiency of catalytic processes was found to be ensured by a controlled combination of thermal non-stationarity and unsteady composition of the catalyst surface. The processes based on this principle are analysed, in particular, catalytic selective reduction of nitrogen oxides, deep oxidation of volatile organic impurities, production of sulfur by the Claus process and by hydrogen sulfide decomposition, oxidation of sulfur dioxide, methane steam reforming and anaerobic combustion, selective oxidation of hydrocarbons, etc.

  15. Catalytic production of biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Theilgaard Madsen, A.

    2011-07-01

    The focus of this thesis is the catalytic production of diesel from biomass, especially emphasising catalytic conversion of waste vegetable oils and fats. In chapter 1 an introduction to biofuels and a review on different catalytic methods for diesel production from biomass is given. Two of these methods have been used industrially for a number of years already, namely the transesterification (and esterification) of oils and fats with methanol to form fatty acid methyl esters (FAME), and the hydrodeoxygenation (HDO) of fats and oils to form straight-chain alkanes. Other possible routes to diesel include upgrading and deoxygenation of pyrolysis oils or aqueous sludge wastes, condensations and reductions of sugars in aqueous phase (aqueous-phase reforming, APR) for monofunctional hydrocarbons, and gasification of any type of biomass followed by Fischer-Tropsch-synthesis for alkane biofuels. These methods have not yet been industrialised, but may be more promising due to the larger abundance of their potential feedstocks, especially waste feedstocks. Chapter 2 deals with formation of FAME from waste fats and oils. A range of acidic catalysts were tested in a model fat mixture of methanol, lauric acid and trioctanoin. Sulphonic acid-functionalised ionic liquids showed extremely fast convertion of lauric acid to methyl laurate, and trioctanoate was converted to methyl octanoate within 24 h. A catalyst based on a sulphonated carbon-matrix made by pyrolysing (or carbonising) carbohydrates, so-called sulphonated pyrolysed sucrose (SPS), was optimised further. No systematic dependency on pyrolysis and sulphonation conditions could be obtained, however, with respect to esterification activity, but high activity was obtained in the model fat mixture. SPS impregnated on opel-cell Al{sub 2}O{sub 3} and microporous SiO{sub 2} (ISPS) was much less active in the esterification than the original SPS powder due to low loading and thereby low number of strongly acidic sites on the

  16. Chemically-Modified Cellulose Paper as a Microstructured Catalytic Reactor

    Directory of Open Access Journals (Sweden)

    Hirotaka Koga

    2015-01-01

    Full Text Available We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

  17. Immigration process in catalytic medium

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The longtime behavior of the immigration process associated with a catalytic super-Brownian motion is studied. A large number law is proved in dimension d≤3 and a central limit theorem is proved for dimension d=3.

  18. Catalytic DNA with phosphatase activity

    OpenAIRE

    Chandrasekar, Jagadeeswaran; Silverman, Scott K.

    2013-01-01

    Catalytic DNA sequences (deoxyribozymes, DNA enzymes, or DNAzymes) have been identified by in vitro selection for various catalytic activities. Expanding the limits of DNA catalysis is an important fundamental objective and may facilitate practical utility of catalysts that can be obtained from entirely unbiased (random) sequence populations. In this study, we show that DNA can catalyze Zn2+-dependent phosphomonoester hydrolysis of tyrosine and serine side chains (i.e., exhibit phosphatase ac...

  19. Studies on catalytic reduction of nitrate in groundwater

    Institute of Scientific and Technical Information of China (English)

    GENG Bing; ZHU Yanfang; JIN Zhaohui; LI Tielong; KANG Haiyan; WANG Shuaima

    2007-01-01

    Catalytic reduction of nitrate in groundwater by sodium formate over the catalyst was investigated.Pd-Cu/γ-Al2O3 catalyst was prepared by impregnation and characterized by brunauer-emmett-teller (BET),inductive coupled plasma (ICP),X-ray diffraction (XRD),transmission electron microscopy (TEM) and energy dispersive X-ray (EDX).It was found that total nitrogen was effectively removed from the nitrate solution (100 mg/L) and the removal efficiency was 87%.The catalytic activity was affected by pH,catalyst amount used,concentration of sodium formate,and initial concentration of nitrate.As sodium formate was used as reductant,precise control in the initial pH was needed.Excessively high or low initial pH (7.0 or 3.0) reduced catalytic activity.At initial pH of 4.5,catalytic activity was enhanced by reducing the amount of catalyst,while concentrations of sodium formate increased with a considerable decrease in N2 selectivity.In which case,catalytic reduction followed the first order kinetics.

  20. Study of biomass combustion characteristics for the development of a catalytic combustor/gasifier

    OpenAIRE

    Dody, Joseph W.

    1985-01-01

    The research reported here explored, a "new" approach to biomass energy conversion for small-scale process heat-applications. The conversion process uses close-coupled catalytic. combustion to burn combustibles in effluent generated by primary combustion or gasification of biomass fuels. Computer control of primary and secondary air flow rates allow control of the devices output power while maintaining fuel-lean or stoichiometric conditions in the effluent entering the catalytic combustion...

  1. Catalytic arylation methods from the academic lab to industrial processes

    CERN Document Server

    Burke, Anthony J

    2014-01-01

    A current view of the challenging field of catalytic arylation reactions. Clearly structured, the chapters in this one-stop resource are arranged according to the reaction type, and focus on novel, efficient and sustainable processes, rather than the well-known and established cross-coupling methods.The entire contents are written by two authors with academic and industrial expertise to ensure consistent coverage of the latest developments in the field, as well as industrial applications, such as C-H activation, iron and gold-catalyzed coupling reactions, cycloadditions or novel methodologies

  2. Studies of coupled chemical and catalytic coal conversion methods

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.

    1988-01-01

    Liquefaction of coal by depolymerization in an organic solvent has been studied for several years. The liquefied coal extract which results from such a process is far more suitable for conversion into liquid fuel by hydrogenolysis than is the untreated coal. Investigations on the chemical structure and the reactive sites of coal can help to select useful reactions for the production of liquids from coal. Sternberg et al. demonstrated that the reductive alkylation method transforms bituminous coal into an enormously soluble substance, irrespective of the mild reaction conditions. The effectiveness of newly introduced alkyl groups for the disruption of intermolecular hydrogen bonds and pi-pi interactions between the aromatic sheets in coal macromolecules has been recognized. It has been reported by Ignasiak et al. that a C-alkylabon reaction using sodium or potassium amide in liquid ammonia can be used to introduce alkyl groups at acidic carbon sites. A method has been developed recently in this laboratory for the solubilization of high rank coals. In the previous reports it was shown that n-butyl lithium and potassium t-butoxide in refluxing heptane produced coal anions which could be alkylated with different alkyl halides. Such alkylated coals were soluble up to 92% in solvents like pyridine. Though the solubilization of coal depended very much on the length of the alkyl group, it also depended very much on the nature of the base used. Strong bases like n-butyl lithium (pKa=42) can cause proton abstraction from aromatic structures, if the more acidic benzylic protons are absent. The utility of this procedure, initially developed and used by Miyake and Stock, has now been tested with the high oxygen containing, low rank Illinois No. 6 and Wyodak coals.

  3. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne;

    2007-01-01

    Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change with par......Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change...... with particle size. We find that the fraction of low-coordinated Au atoms scales approximately with the catalytic activity, suggesting that atoms on the corners and edges of Au nanoparticles are the active sites. This effect is explained using density functional calculations....

  4. Catalytic distillation water recovery subsystem

    Science.gov (United States)

    Budininkas, P.; Rasouli, F.

    1985-01-01

    An integrated engineering breadboard subsystem for the recovery of potable water from untreated urine based on the vapor phase catalytic ammonia removal was designed, fabricated and tested. Unlike other evaporative methods, this process catalytically oxidizes ammonia and volatile hydrocarbons vaporizing with water to innocuous products; therefore, no pretreatment of urine is required. Since the subsystem is fabricated from commercially available components, its volume, weight and power requirements are not optimized; however, it is suitable for zero-g operation. The testing program consists of parametric tests, one month of daily tests and a continuous test of 168 hours duration. The recovered water is clear, odorless, low in ammonia and organic carbon, and requires only an adjustment of its pH to meet potable water standards. The obtained data indicate that the vapor phase catalytic ammonia removal process, if further developed, would also be competitive with other water recovery systems in weight, volume and power requirements.

  5. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    Vivek V Ranade

    2014-03-01

    Catalytic reactions are ubiquitous in chemical and allied industries. A homogeneous or heterogeneous catalyst which provides an alternative route of reaction with lower activation energy and better control on selectivity can make substantial impact on process viability and economics. Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is discussed. Some examples where performance enhancement was realized by catalyst design, appropriate choice of reactor, better injection and dispersion strategies and recent advances in process intensification/ multifunctional reactors are discussed to illustrate the approach.

  6. Silver-catalyzed coupling reactions of alkyl halides with indenyllithiums

    OpenAIRE

    Someya, Hidenori; Yorimitsu, Hideki; Oshima, Koichiro

    2010-01-01

    Coupling reactions of tertiary and secondary alkyl halides with indenyllithiums proceeded effectively in the presence of a catalytic amount of silver bromide to provide tertiary- and secondary-alkyl-substituted indene derivatives in good yields.

  7. Influence of physicochemical treatments on iron-based spent catalyst for catalytic oxidation of toluene.

    Science.gov (United States)

    Kim, Sang Chai; Shim, Wang Geun

    2008-06-15

    The catalytic oxidation of toluene was studied over an iron-based spent and regenerated catalysts. Air, hydrogen, or four different acid solutions (oxalic acid (C2H2O4), citric acid (C6H8O7), acetic acid (CH3COOH), and nitric acid (HNO3)) were employed to regenerate the spent catalyst. The properties of pretreated spent catalyst were characterized by the Brunauer Emmett Teller (BET), inductively coupled plasma (ICP), temperature programmed reduction (TPR), and X-ray diffraction (XRD) analyses. The air pretreatment significantly enhanced the catalytic activity of the spent catalyst in the pretreatment temperature range of 200-400 degrees C, but its catalytic activity diminished at the pretreatment temperature of 600 degrees C. The catalytic activity sequence with respect to the air pretreatment temperatures was 400 degrees C>200 degrees C>parent>600 degrees C. The TPR results indicated that the catalytic activity was correlated with both the oxygen mobility and the amount of available oxygen on the catalyst. In contrast, the hydrogen pretreatment had a negative effect on the catalytic activity, and toluene conversion decreased with increasing pretreatment temperatures (200-600 degrees C). The XRD and TPR results confirmed the formation of metallic iron which had a negative effect on the catalytic activity with increasing pretreatment temperature. The acid pretreatment improved the catalytic activity of the spent catalyst. The catalytic activity sequence with respect to different acids pretreatment was found to be oxalic acid>citric acid>acetic acid>or=nitric acid>parent. The TPR results of acid pretreated samples showed an increased amount of available oxygen which gave a positive effect on the catalytic activity. Accordingly, air or acid pretreatments were more promising methods of regenerating the iron-based spent catalyst. In particular, the oxalic acid pretreatment was found to be most effective in the formation of FeC2O4 species which contributed highly to the

  8. Influence of physicochemical treatments on iron-based spent catalyst for catalytic oxidation of toluene

    International Nuclear Information System (INIS)

    The catalytic oxidation of toluene was studied over an iron-based spent and regenerated catalysts. Air, hydrogen, or four different acid solutions (oxalic acid (C2H2O4), citric acid (C6H8O7), acetic acid (CH3COOH), and nitric acid (HNO3)) were employed to regenerate the spent catalyst. The properties of pretreated spent catalyst were characterized by the Brunauer Emmett Teller (BET), inductively coupled plasma (ICP), temperature programmed reduction (TPR), and X-ray diffraction (XRD) analyses. The air pretreatment significantly enhanced the catalytic activity of the spent catalyst in the pretreatment temperature range of 200-400 deg. C, but its catalytic activity diminished at the pretreatment temperature of 600 deg. C. The catalytic activity sequence with respect to the air pretreatment temperatures was 400 deg. C > 200 deg. C > parent > 600 deg. C. The TPR results indicated that the catalytic activity was correlated with both the oxygen mobility and the amount of available oxygen on the catalyst. In contrast, the hydrogen pretreatment had a negative effect on the catalytic activity, and toluene conversion decreased with increasing pretreatment temperatures (200-600 deg. C). The XRD and TPR results confirmed the formation of metallic iron which had a negative effect on the catalytic activity with increasing pretreatment temperature. The acid pretreatment improved the catalytic activity of the spent catalyst. The catalytic activity sequence with respect to different acids pretreatment was found to be oxalic acid > citric acid > acetic acid ≥ nitric acid > parent. The TPR results of acid pretreated samples showed an increased amount of available oxygen which gave a positive effect on the catalytic activity. Accordingly, air or acid pretreatments were more promising methods of regenerating the iron-based spent catalyst. In particular, the oxalic acid pretreatment was found to be most effective in the formation of FeC2O4 species which contributed highly to the

  9. Total Synthesis of Chiral Biaryl Natural Products by Asymmetric Biaryl Coupling

    OpenAIRE

    Kozlowski, Marisa C.; Morgan, Barbara J.; Linton, Elizabeth C.

    2009-01-01

    This tutorial review highlights the use of catalytic asymmetric 2-naphthol couplings in total synthesis. The types of chirality, chiral biaryl natural products, prior approaches to chiral biaryl natural products, and other catalytic asymmetric biaryl couplings are outlined. The three main categories of chiral catalysts for 2-naphthol coupling (Cu, V, Fe) are described with discussion of their limitations and advantages. Applications of the copper catalyzed couplings in biomimetic syntheses ar...

  10. Catalytic properties of niobium compounds

    International Nuclear Information System (INIS)

    The catalytic activity and selectivity of niobium compounds including oxides, salts, organometallic compounds and others are outlined. The application of these compounds as catalysts to diversified reactions is reported. The nature and action of niobium catalysts are characteristic and sometimes anomalous, suggesting the necessity of basic research and the potential use as catalysts for important processes in the chemical industry. (Author)

  11. Pair interaction of catalytically active colloids: from assembly to escape

    Science.gov (United States)

    Sharifi-Mood, Nima; Mozaffari, Ali; Córdova-Figueroa, Ubaldo M.

    2016-07-01

    The dynamics and pair trajectory of two self-propelled colloids are reported. The autonomous motions of the colloids are due to a catalytic chemical reaction taking place asymmetrically on their surfaces that generates a concentration gradient of interactive solutes around the particles and actuate particle propulsion. We consider two spherical particles with symmetric catalytic caps extending over the local polar angles $\\theta^1_{cap}$ and $\\theta^2_{cap}$ from the centers of active sectors in an otherwise quiescent fluid. A combined analytical-numerical technique was developed to solve the coupled mass transfer equation and the hydrodynamics in the Stokes flow regime. The ensuing pair trajectory of the colloids is controlled by the reacting coverages $\\theta^j_{cap}$ and their initial relative orientation with respect to each other. Our analysis indicates two possible scenarios for pair trajectories of catalytic self-propelled particles: either the particles approach, come into contact and assemble or they interact and move away from each other (escape). For arbitrary motions of the colloids, it is found that the direction of particle rotations is the key factor in determining the escape or assembly scenario. Based on the analysis, a phase diagram is sketched for the pair trajectory of the catalytically active particles as a function of active coverages and their initial relative orientations. We believe this study has important implications in elucidation of collective behaviors of auotophoretically self-propelled colloids.

  12. Catalytic Fast Pyrolysis: A Review

    Directory of Open Access Journals (Sweden)

    Theodore Dickerson

    2013-01-01

    Full Text Available Catalytic pyrolysis is a promising thermochemical conversion route for lignocellulosic biomass that produces chemicals and fuels compatible with current, petrochemical infrastructure. Catalytic modifications to pyrolysis bio-oils are geared towards the elimination and substitution of oxygen and oxygen-containing functionalities in addition to increasing the hydrogen to carbon ratio of the final products. Recent progress has focused on both hydrodeoxygenation and hydrogenation of bio-oil using a variety of metal catalysts and the production of aromatics from bio-oil using cracking zeolites. Research is currently focused on developing multi-functional catalysts used in situ that benefit from the advantages of both hydrodeoxygenation and zeolite cracking. Development of robust, highly selective catalysts will help achieve the goal of producing drop-in fuels and petrochemical commodities from wood and other lignocellulosic biomass streams. The current paper will examine these developments by means of a review of existing literature.

  13. Combined catalytic converter and afterburner

    Energy Technology Data Exchange (ETDEWEB)

    Ma, T.T.-H.

    1994-11-30

    This patent describes the combined use of a catalytic converter and afterburner. An afterburner chamber and a catalyst matrix are disposed in series within a casing. A combustible premixed charge is ignited in the afterburner chamber before it enters the catalyst matrix. This invention overcomes the problem encountered in previous designs of some of the premixed charge passing unreacted through the device unless a very long afterburner chamber is used. (UK)

  14. Investigations for designing catalytic recombiners

    International Nuclear Information System (INIS)

    In case of a severe accident in pressurised water reactors (PWR) a high amount of hydrogen up to about 20,000 m3 might be generated and released into the containments. The mixture consisting of hydrogen and oxygen may either burn or detonate, if ignited. In case of detonation the generated shock wave may endanger the components of the plant or the plant itself. Consequently, effective removal of hydrogen is required. The fact that hydrogen and oxygen react exo-thermally on catalytically acting surfaces already at low temperatures generating steam and heat is made use of in catalytic recombiners. They consist of substrates coated with catalyst (mainly platinum or palladium) which are arranged inside a casing. Being passively acting measures, recombiners do not need any additional energy supply. Experimental investigations on catalytic hydrogen recombination are conducted at FZJ (Forschungszentrum Juelich) using three test facilities. The results yield insight in the development potential of contemporary recombiner systems as well as of innovative systems. Detailed investigations on a recombiner section show strong temperature gradients over the surface of a catalytically coated sample. Dependent on the flow velocity, ignition temperature may be reached at the leading edge already at an inlet hydrogen concentration of about 5 vol.-%. The thermal strain of the substrate leads to considerable detachment of catalyst particles probably causing unintended ignition of the flammable mixture. Temperature peaks can be prevented effectively by leaving the first part of the plate uncoated. In order to avoid overheating of the catalyst elements of a recombiner even at high hydrogen concentrations a modular system of porous substrates is proposed. The metallic substrates are coated with platinum at low catalyst densities thus limiting the activity of the single specimen. A modular arrangement of these elements provides high recombination rates over a large hydrogen concentration

  15. Catalytic Z-Selective Cross-Metathesis with Secondary Silyl- and Benzyl-Protected Allylic Ethers: Mechanistic Aspects and Applications to Natural Product Synthesis**

    OpenAIRE

    Mann, Tyler J.; Speed, Alexander W. H.; Schrock, Richard R.; Hoveyda, Amir H.

    2013-01-01

    Efficient catalytic cross-metathesis reactions that afford Z-disubstituted allylic silyl or benzyl ethers are reported (see scheme, MAP=monoalkoxide pyrrolide). The approach, in combination with catalytic cross-coupling, provides a general entry to otherwise difficult-to-access alkyne-containing Z olefins.

  16. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel

    2014-01-01

    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  17. Molecular catalytic coal liquid conversion

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.; Yang, Shiyong [Univ. of Chicago, IL (United States)

    1995-12-31

    This research, which is relevant to the development of new catalytic systems for the improvement of the quality of coal liquids by the addition of dihydrogen, is divided into two tasks. Task 1 centers on the activation of dihydrogen by molecular basic reagents such as hydroxide ion to convert it into a reactive adduct (OH{center_dot}H{sub 2}){sup {minus}} that can reduce organic molecules. Such species should be robust withstanding severe conditions and chemical poisons. Task 2 is focused on an entirely different approach that exploits molecular catalysts, derived from organometallic compounds that are capable of reducing monocyclic aromatic compounds under very mild conditions. Accomplishments and conclusions are discussed.

  18. Studies of Catalytic Model Systems

    DEFF Research Database (Denmark)

    Holse, Christian

    the Cu/ZnO nanoparticles is highly relevant to industrial methanol synthesis for which the direct interaction of Cu and ZnO nanocrystals synergistically boost the catalytic activity. The dynamical behavior of the nanoparticles under reducing and oxidizing environments were studied by means of ex situ...... observed by XPS as the nanoparticles are reduced. The Cu/ZnO nanoparticles are tested on a  µ-reactor platform and prove to be active towards methanol synthesis, making it an excellent model system for further investigations into activity depended morphology changes....

  19. Catalytic Spectrophotometric Determination of Chromium

    OpenAIRE

    STOYANOVA, Angelina Miltcheva

    2005-01-01

    The catalytic effect of chromium(III) and chromium(VI) on the oxidation of sulfanilic acid by hydrogen peroxide was studied. The reaction was followed spectrophotometrically by measuring the absorbance of the reaction product at 360 nm. Under the optimum conditions 2 calibration graphs (for chromium(III) up to 100 ng mL-1, and for chromium(VI) up to 200 ng mL-1) were obtained, using the ``fixed time'' method with detection limits of 4.9 ng mL-1 and 3.8 ng mL-1, respectively...

  20. Catalytic Combustion of Ethyl Acetate

    OpenAIRE

    ÖZÇELİK, Tuğba GÜRMEN; ATALAY, Süheyda; ALPAY, Erden

    2007-01-01

    The catalytic combustion of ethyl acetate over prepared metal oxide catalysts was investigated. CeO, Co2O3, Mn2O3, Cr2O3, and CeO-Co2O3 catalysts were prepared on monolith supports and they were tested. Before conducting the catalyst experiments, we searched for the homogeneous gas phase combustion reaction of ethyl acetate. According to the homogeneous phase experimental results, 45% of ethyl acetate was converted at the maximum reactor temperature tested (350 °C). All the prepare...

  1. Estimating the temperature of a catalytic converter

    Energy Technology Data Exchange (ETDEWEB)

    Ma, T.T.-H.

    1994-11-02

    A method is described for estimating the temperature in a catalytic converter used in the exhaust system of an internal combustion engine. Pressure sensors monitor the flow resistance across the catalytic converter to provide an indication of the temperature inside. This feedback system allows heating devices to be switched off and thus avoid overheating, while maintaining the catalytic converter's efficiency by assuring that it does not operate below its light off temperature. (UK)

  2. Estimating the temperature of a catalytic converter

    Energy Technology Data Exchange (ETDEWEB)

    Ma, T.T.-H.

    1994-11-02

    A method of estimating the temperature of a catalytic converter used in the exhaust system of an internal combustion engine is described. Heated exhaust gas oxygen (HEGO) sensors are placed upstream and downstream of the catalytic converter. The temperature of the catalytic converter shortly after start-up is measured by monitoring the resistance of the HEGO sensor's heating element. The downstream sensor is used for mixture control and to double check results of the upstream sensor. (UK)

  3. Oxo-rhenium catalyzed reductive coupling and deoxygenation of alcohols.

    Science.gov (United States)

    Kasner, Gabrielle R; Boucher-Jacobs, Camille; Michael McClain, J; Nicholas, Kenneth M

    2016-06-01

    Representative benzylic, allylic and α-keto alcohols are deoxygenated to alkanes and/or reductively coupled to alkane dimers by reaction with PPh3 catalyzed by (PPh3)2ReIO2 (1). The newly discovered catalytic reductive coupling reaction is a rare C-C bond-forming transformation of alcohols. PMID:27174412

  4. Nanostructured Catalytic Reactors for Air Purification Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This SBIR Phase II project proposes the development of lightweight compact nanostructured catalytic reactors for air purification from toxic gaseous organic...

  5. Nanostructured Catalytic Reactors for Air Purification Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This SBIR Phase I project proposes the development of lightweight compact nanostructured catalytic reactors for air purification from toxic gaseous organic...

  6. Atmospheric methanol measurement using selective catalytic methanol to formaldehyde conversion

    Directory of Open Access Journals (Sweden)

    S. J. Solomon

    2005-05-01

    Full Text Available A novel atmospheric methanol measurement technique, employing selective gas-phase catalytic conversion of methanol to formaldehyde followed by detection of the formaldehyde product, has been developed and tested. The effects of temperature, gas flow rate, gas composition, reactor-bed length, and reactor-bed composition on the methanol conversion efficiency of a molybdenum-rich, iron-molybdate catalyst [Mo-Fe-O] were studied. Best results were achieved using a 1:4 mixture (w/w of the catalyst in quartz sand. Optimal methanol to formaldehyde conversion (>95% efficiency occurred at a catalyst housing temperature of 345°C and an estimated sample-air/catalyst contact time of <0.2 s. Potential interferences arising from conversion of methane and a number of common volatile organic compounds (VOC to formaldehyde were found to be negligible under most atmospheric conditions and catalyst housing temperatures. Using the new technique, atmospheric measurements of methanol were made at the University of Bremen campus from 1 to 15 July 2004. Methanol mixing ratios ranged from 1 to 5 ppb with distinct maxima at night. Formaldehyde mixing ratios, obtained in conjunction with methanol by periodically bypassing the catalytic converter, ranged from 0.2 to 1.6 ppb with maxima during midday. These results suggest that selective, catalytic methanol to formaldehyde conversion, coupled with existing formaldehyde measurement instrumentation, is an inexpensive and effective means for monitoring atmospheric methanol.

  7. Catalytic Polymer Multilayer Shell Motors for Separation of Organics.

    Science.gov (United States)

    Lin, Zhihua; Wu, Zhiguang; Lin, Xiankun; He, Qiang

    2016-01-26

    A catalytic polymer multilayer shell motor has been developed, which effects fast motion-based separation of charged organics in water. The shell motors are fabricated by sputtering platinum onto the exposed surface of silica templates embedded in Parafilm, followed by layer-by-layer assembly of polyelectrolyte multilayers to the templates. The catalytic shell motors display high bubble propulsion with speeds of up to 260 μm s(-1) (13 body lengths per second). Moreover, the polyelectrolyte multilayers assembled at high pH (pH>9.0) adsorb approximately 89% of dye molecules from water, owing to the electrostatic interaction between the positively charged polymers and the anionic dye molecules, and subsequently release them at neutral pH in a microfluidic device. The efficient propulsion coupled with the effective adsorption behavior of the catalytic shell motors in a microfluidic device results in accelerated separation of organics in water and thus holds considerable promise for water analysis. PMID:26632275

  8. Atmospheric methanol measurement using selective catalytic methanol to formaldehyde conversion

    Directory of Open Access Journals (Sweden)

    S. J. Solomon

    2005-01-01

    Full Text Available A novel atmospheric methanol measurement technique, employing selective gas-phase catalytic conversion of methanol to formaldehyde followed by detection of the formaldehyde product, has been developed and tested. The effects of temperature, gas flow rate, gas composition, reactor-bed length, and reactor-bed composition on the methanol conversion efficiency of a molybdenum-rich, iron-molybdate catalyst [Mo-Fe-O] were studied. Best results were achieved using a 1:4 mixture (w/w of the catalyst in quartz sand. Optimal methanol to formaldehyde conversion (>95% efficiency occurred at a catalyst housing temperature of 345°C and an estimated sample-air/catalyst contact time of <0.2 seconds. Potential interferences arising from conversion of methane and a number of common volatile organic compounds (VOC to formaldehyde were found to be negligible under most atmospheric conditions and catalyst housing temperatures. Using the new technique, atmospheric measurements of methanol were made at the University of Bremen campus from 1 to 15 July 2004. Methanol mixing ratios ranged from 1 to 5 ppb with distinct maxima at night. Formaldehyde mixing ratios, obtained in conjunction with methanol by periodically bypassing the catalytic converter, ranged from 0.2 to 1.6 ppb with maxima during midday. These results suggest that selective, catalytic methanol to formaldehyde conversion, coupled with existing formaldehyde measurement instrumentation, is an inexpensive and effective means for monitoring atmospheric methanol.

  9. 四川什邡市某水厂臭氧-生物活性炭深度处理工艺分析%Process of Advanced Water Treatment with Ozone-Biological Activated Carbon in Shifang Water Treatment Plant in Shichuan Province of China

    Institute of Scientific and Technical Information of China (English)

    罗本福; 宁海燕; 杨曦

    2013-01-01

    Ozone-Biological Activated Carbon (BAC/O3 ) process design was introduced in one first bulited water treatmen plant in Shifang Shichuan China.This paper discussed the experience and measures for O 3/BAC technology project.If the thecholgy for separa-ting oxygen from air was provided in project location , when the ozone consumption Q o3≤60 kgo3/h , purchase of liquid oxygen as the raw material would be more economical , when Qo3 >60 kgo3/h, adopting the separated oxygen from air whould be better .In pre-ozona-tion reactor, O3 charging quantity Q had more effect on the ozone oxidation effect than contact time T ,but if the raw water needed to kill alga, adviced T≥5 min;In post-ozonation reactor,usually divided into three phases , the best dosing ratio was 4∶3∶3,and the CT value (CT≥4 min・ mg/L) had representation meaning to kill “two bug”.The key indicators value of the Activated carbon adsorption and structure properties were introduced:iodine value was 900 mg・ g-1 , and JiaLan value was 150 mg・ g-1 , or specific surface area of 1000 1000 m 2・ g-1 , total pore volume was 0.6 cc・ g-1 , etc.; The light seal cover should be bulited above carbon filter , 500 mm sand was added under the carbon layer and design filter speed should be reduced to ensure safety operation and reduce the risk of mi -crobial penetration filter layer.%  对四川什邡市某水厂臭氧-生物活性炭(O3/BAC)深度处理工艺进行分析,阐述了O3/BAC工艺的工程经验和措施,具体工艺方案为:在有空气分离制氧企业的城市,当臭氧耗量Q≤60 kgO3/h时选择外购液氧,反之可考虑现场空气分离制氧;预臭氧氧化效果与O3加注量Q的相关性大于接触时间T的影响,若原水需杀藻,T建议≥5 min;主臭氧接触池三段式最佳投加比例为4∶3∶3,控制CT值(CT≥4 min・ mg/L)对杀灭“两虫”有表征意义;活性炭吸附与结构性能的关键指标建议值为:碘值≥900

  10. Catalytic conversion of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.

    1992-06-30

    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  11. Catalytic converters in the fireplace

    International Nuclear Information System (INIS)

    In addition to selecting the appropriate means of heating and using dry fuel, the amount of harmful emissions contained by flue gases produced by fireplaces can be reduced by technical means. One such option is to use an oxidising catalytic converter. Tests at TTS Institute's Heating Studies Experimental Station have focused on two such converters (dense and coarse) mounted in light-weight iron heating stoves. The ability of the dense catalytic converter to oxidise carbon monoxide gases proved to be good. The concentration of carbon monoxide in the flue gases was reduced by as much as 90 %. Measurements conducted by VTT (Technical Research Centre of Finland) showed that the conversion of other gases, e.g. of methane, was good. The exhaust resistance caused by the dense converter was so great as to necessitate the mounting of a fluegas evacuation fan in the chimney for the purpose of creating sufficient draught. When relying on natural draught, the dense converter requires a chimney of at least 7 metres and a by-pass connection while the fire is being lit. In addition, the converter will have to be constructed to be less dense and this will mean that it's capability to oxidise non-combusted gases will be reduced. The coarse converter did not impair the draught but it's oxidising property was insufficient. With the tests over, the converter was not observed to have become blocked up by impurities

  12. Catalytic reforming feed characterisation technique

    Energy Technology Data Exchange (ETDEWEB)

    Larraz Mora, R.; Arvelo Alvarez, R. [Univ. of La Laguna, Chemical Engineering Dept., La Laguna (Spain)

    2002-09-01

    The catalytic reforming of naphtha is one of the major refinery processes, designed to increase the octane number of naphtha or to produce aromatics. The naphtha used as catalytic reformer feedstock usually contains a mixture of paraffins, naphthenes, and aromatics in the carbon number range C{sub 6} to C{sub 10}. The detailed chemical composition of the feed is necessary to predict the aromatics and hydrogen production as well as the operation severity. The analysis of feed naphtha is usually reported in terms of its ASTM distillation curve and API or specific gravity. Since reforming reactions are described in terms of lumped chemical species (paraffins, naphthenes and aromatics), a feed characterisation technique should be useful in order to predict reforming operating conditions and detect feed quality changes. Unfortunately online analyzer applications as cromatography or recently introduced naphtha NMR [1] are scarce in most of refineries. This work proposes an algorithmic characterisation method focusing on its main steps description. The method could help on the subjects previously described, finally a calculation example is shown. (orig.)

  13. Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

    KAUST Repository

    Hong, Jongsup

    2013-10-01

    The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

  14. A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia

    DEFF Research Database (Denmark)

    Janssens, Ton V.W.; Falsig, Hanne; Lundegaard, Lars Fahl;

    2015-01-01

    For the first time, the standard and fast selective catalytic reduction of NO by NH3 are described in a complete catalytic cycle, that is able to produce the correct stoichiometry, while only allowing adsorption and desorption of stable molecules. The standard SCR reaction is a coupling of the ac......For the first time, the standard and fast selective catalytic reduction of NO by NH3 are described in a complete catalytic cycle, that is able to produce the correct stoichiometry, while only allowing adsorption and desorption of stable molecules. The standard SCR reaction is a coupling...... of the activation of NO by O2 with the fast SCR reaction, enabled by the release of NO2. According to the scheme, the SCR reaction can be divided in an oxidation of the catalyst by NO + O2 and a reduction by NO + NH3; these steps together constitute a complete catalytic cycle. Furthermore both NO and NH3...... spectroscopy (FTIR). A consequence of the reaction scheme is that all intermediates in fast SCR are also part of the standard SCR cycle. The calculated activation energy by density functional theory (DFT) indicates that the oxidation of an NO molecule by O2 to a bidentate nitrate ligand is rate determining...

  15. Catalytic pyrolysis of microalgae to high-quality liquid bio-fuels

    International Nuclear Information System (INIS)

    The pyrolytic conversion of chlorella algae to liquid fuel precursor in presence of a catalyst (Na2CO3) has been studied. Thermal decomposition studies of the algae samples were performed using TGA coupled with MS. Liquid oil samples were collected from pyrolysis experiments in a fixed-bed reactor and characterized for water content and heating value. The oil composition was analyzed by GC-MS. Pretreatment of chlorella with Na2CO3 influences the primary conversion of chlorella by shifting the decomposition temperature to a lower value. In the presence of Na2CO3, gas yield increased and liquid yield decreased when compared with non-catalytic pyrolysis at the same temperatures. However, pyrolysis oil from catalytic runs carries higher heating value and lower acidity. Lower content of acids in the bio-oil, higher aromatics, combined with higher heating value show promise for production of high-quality bio-oil from algae via catalytic pyrolysis, resulting in energy recovery in bio-oil of 40%. -- Highlights: → The pyrolytic catalytic conversion of chlorella algae to liquid fuel precursor. → Na2CO3 as a catalyst for the primary conversion of chlorella. → Pyrolysis oil from catalytic runs carries higher heating value and lower acidity. → High-quality bio-oil from algae via catalytic pyrolysis with energy recovery in bio-oil of 40%.

  16. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement.

    Science.gov (United States)

    Suárez-Ojeda, María Eugenia; Kim, Jungkwon; Carrera, Julián; Metcalfe, Ian S; Font, Josep

    2007-06-18

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture. PMID:17363148

  17. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

    International Nuclear Information System (INIS)

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15bar of oxygen partial pressure (PO2) and at 180, 200 and 220deg. C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and PO2 were 140-160deg. C and 2-9bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160deg. C and 2 bar of PO2, which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (CODRB) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture

  18. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

    Energy Technology Data Exchange (ETDEWEB)

    Suarez-Ojeda, Maria Eugenia [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain); Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Kim, Jungkwon [Chemical Engineering and Analytical Sciences Department, University of Manchester, Manchester (United Kingdom); Carrera, Julian [Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Metcalfe, Ian S. [Chemical Engineering and Advanced Materials Department, University of Newcastle upon Tyne, Newcastle upon Tyne (United Kingdom); Font, Josep [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain)]. E-mail: jose.font@urv.cat

    2007-06-18

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15bar of oxygen partial pressure (P{sub O{sub 2}}) and at 180, 200 and 220deg. C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P{sub O{sub 2}} were 140-160deg. C and 2-9bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160deg. C and 2 bar of P{sub O{sub 2}}, which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD{sub RB}) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.

  19. Acoustics of automotive catalytic converter assemblies

    Science.gov (United States)

    Dickey, Nolan S.; Selamet, Ahmet; Parks, Steve J.; Tallio, Kevin V.; Miazgowicz, Keith D.; Radavich, Paul M.

    2003-10-01

    In an automotive exhaust system, the purpose of the catalytic converter is to reduce pollutant emissions. However, catalytic converters also affect the engine and exhaust system breathing characteristics; they increase backpressure, affect exhaust system acoustic characteristics, and contribute to exhaust manifold tuning. Thus, radiated sound models should include catalytic converters since they can affect both the source characteristics and the exhaust system acoustic behavior. A typical catalytic converter assembly employs a ceramic substrate to carry the catalytically active noble metals. The substrate has numerous parallel tubes and is mounted in a housing with swelling mat or wire mesh around its periphery. Seals at the ends of the substrate can be used to help force flow through the substrate and/or protect the mat material. Typically, catalytic converter studies only consider sound propagation in the small capillary tubes of the substrate. Investigations of the acoustic characteristics of entire catalytic converter assemblies (housing, substrate, seals, and mat) do not appear to be available. This work experimentally investigates the acoustic behavior of catalytic converter assemblies and the contributions of the separate components to sound attenuation. Experimental findings are interpreted with respect to available techniques for modeling sound propagation in ceramic substrates.

  20. Understanding catalytic biomass conversion through data mining

    NARCIS (Netherlands)

    E.J. Ras; B. McKay; G. Rothenberg

    2010-01-01

    Catalytic conversion of biomass is a key challenge that we chemists face in the twenty-first century. Worldwide, research is conducted into obtaining bulk chemicals, polymers and fuels. Our project centres on glucose valorisation via furfural derivatives using catalytic hydrogenation. We present her

  1. Silver nanocluster catalytic microreactors for water purification

    Science.gov (United States)

    Da Silva, B.; Habibi, M.; Ognier, S.; Schelcher, G.; Mostafavi-Amjad, J.; Khalesifard, H. R. M.; Tatoulian, M.; Bonn, D.

    2016-07-01

    A new method for the elaboration of a novel type of catalytic microsystem with a high specific area catalyst is developed. A silver nanocluster catalytic microreactor was elaborated by doping a soda-lime glass with a silver salt. By applying a high power laser beam to the glass, silver nanoclusters are obtained at one of the surfaces which were characterized by BET measurements and AFM. A microfluidic chip was obtained by sealing the silver coated glass with a NOA 81 microchannel. The catalytic activity of the silver nanoclusters was then tested for the efficiency of water purification by using catalytic ozonation to oxidize an organic pollutant. The silver nanoclusters were found to be very stable in the microreactor and efficiently oxidized the pollutant, in spite of the very short residence times in the microchannel. This opens the way to study catalytic reactions in microchannels without the need of introducing the catalyst as a powder or manufacturing complex packed bed microreactors.

  2. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)

    1996-12-31

    In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

  3. Catalytic Graphitization of Phenolic Resin

    Institute of Scientific and Technical Information of China (English)

    Mu Zhao; Huaihe Song

    2011-01-01

    The catalytic graphitization of thermal plastic phenolic-formaldehyde resin with the aid of ferric nitrate (FN) was studied in detail. The morphologies and structural features of the products including onion-like carbon nanoparticles and bamboo-shaped carbon nanotubes were investigated by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction and Raman spectroscopy measurements. It was found that with the changes of loading content of FN and residence time at 1000℃, the products exhibited various morphologies. The TEM images showed that bamboo-shaped carbon nanotube consisted of tens of bamboo sticks and onion-like carbon nanoparticle was made up of quasi-spherically concentrically closed carbon nanocages.

  4. Non-catalytic recuperative reformer

    Energy Technology Data Exchange (ETDEWEB)

    Khinkis, Mark J.; Kozlov, Aleksandr P.; Kurek, Harry

    2015-12-22

    A non-catalytic recuperative reformer has a flue gas flow path for conducting hot flue gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is embedded in the flue gas flow path to permit heat transfer from the hot flue gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, extended surfaces of metal material such as stainless steel or metal alloy that are high in nickel content are included within at least a portion of the reforming mixture flow path.

  5. Fluctuations in catalytic surface reactions

    CERN Document Server

    Imbihl, R

    2003-01-01

    The internal reaction-induced fluctuations which occur in catalytic CO oxidation on a Pt field emitter tip have been studied using field electron microscopy (FEM) as a spatially resolving method. The structurally heterogeneous Pt tip consists of facets of different orientations with nanoscale dimensions. The FEM resolution of roughly 2 nm corresponds to a few hundred reacting adsorbed particles whose variations in the density are imaged as brightness fluctuations. In the bistable range of the reaction one finds fluctuation-induced transitions between the two stable branches of the reaction kinetics. The fluctuations exhibit a behaviour similar to that of an equilibrium phase transition, i.e. the amplitude diverges upon approaching the bifurcation point terminating the bistable range of the reaction. Simulations with a hybrid Monte Carlo/mean-field model reproduce the experimental observations. Fluctuations on different facets are typically uncorrelated but within a single facet a high degree of spatial cohere...

  6. Catalytic, enantioselective, vinylogous aldol reactions.

    Science.gov (United States)

    Denmark, Scott E; Heemstra, John R; Beutner, Gregory L

    2005-07-25

    In 1935, R. C. Fuson formulated the principle of vinylogy to explain how the influence of a functional group may be felt at a distant point in the molecule when this position is connected by conjugated double-bond linkages to the group. In polar reactions, this concept allows the extension of the electrophilic or nucleophilic character of a functional group through the pi system of a carbon-carbon double bond. This vinylogous extension has been applied to the aldol reaction by employing "extended" dienol ethers derived from gamma-enolizable alpha,beta-unsaturated carbonyl compounds. Since 1994, several methods for the catalytic, enantioselective, vinylogous aldol reaction have appeared, with which varying degrees of regio- (site), enantio-, and diastereoselectivity can be attained. In this Review, the current scope and limitations of this transformation, as well as its application in natural product synthesis, are discussed. PMID:15940727

  7. Electrochemical promotion of catalytic reactions

    Science.gov (United States)

    Imbihl, R.

    2010-05-01

    The electrochemical promotion of heterogeneously catalyzed reactions (EPOC) became feasible through the use of porous metal electrodes interfaced to a solid electrolyte. With the O 2- conducting yttrium stabilized zirconia (YSZ), the Na + conducting β″-Al 2O 3 (β-alumina), and several other types of solid electrolytes the EPOC effect has been demonstrated for about 100 reaction systems in studies conducted mainly in the mbar range. Surface science investigations showed that the physical basis for the EPOC effect lies in the electrochemically induced spillover of oxygen and alkali metal, respectively, onto the surface of the metal electrodes. For the catalytic promotion effect general concepts and mechanistic schemes were proposed but these concepts and schemes are largely speculative. Applying surface analytical tools to EPOC systems the proposed mechanistic schemes can be verified or invalidated. This report summarizes the progress which has been achieved in the mechanistic understanding of the EPOC effect.

  8. Computer-aided modeling framework – a generic modeling template for catalytic membrane fixed bed reactors

    DEFF Research Database (Denmark)

    Fedorova, Marina; Sin, Gürkan; Gani, Rafiqul

    2013-01-01

    This work focuses on development of computer-aided modeling framework. The framework is a knowledge-based system that is built on a generic modeling language and structured based on workflows for different general modeling tasks. The overall objective of this work is to support the model develope...... catalytic membrane fixed bed models is developed. The application of the modeling template is highlighted with a case study related to the modeling of a catalytic membrane reactor coupling dehydrogenation of ethylbenzene with hydrogenation of nitrobenzene....

  9. Revolutionary systems for catalytic combustion and diesel catalytic particulate traps.

    Energy Technology Data Exchange (ETDEWEB)

    Stuecker, John Nicholas; Witze, Peter O.; Ferrizz, Robert Matthew; Cesarano, Joseph, III; Miller, James Edward

    2004-12-01

    This report is a summary of an LDRD project completed for the development of materials and structures conducive to advancing the state of the art for catalyst supports and diesel particulate traps. An ancillary development for bio-medical bone scaffolding was also realized. Traditionally, a low-pressure drop catalyst support, such as a ceramic honeycomb monolith, is used for catalytic reactions that require high flow rates of gases at high-temperatures. A drawback to the traditional honeycomb monoliths under these operating conditions is poor mass transfer to the catalyst surface in the straight-through channels. ''Robocasting'' is a unique process developed at Sandia National Laboratories that can be used to manufacture ceramic monoliths with alternative 3-dimensional geometries, providing tortuous pathways to increase mass transfer while maintaining low-pressure drops. These alternative 3-dimensional geometries may also provide a foundation for the development of self-regenerating supports capable of trapping and combusting soot particles from a diesel engine exhaust stream. This report describes the structures developed and characterizes the improved catalytic performance that can result. The results show that, relative to honeycomb monolith supports, considerable improvement in mass transfer efficiency is observed for robocast samples synthesized using an FCC-like geometry of alternating rods. Also, there is clearly a trade-off between enhanced mass transfer and increased pressure drop, which can be optimized depending on the particular demands of a given application. Practical applications include the combustion of natural gas for power generation, production of syngas, and hydrogen reforming reactions. The robocast lattice structures also show practicality for diesel particulate trapping. Preliminary results for trapping efficiency are reported as well as the development of electrically resistive lattices that can regenerate the structure

  10. Stable solutions for a catalytic converter

    Energy Technology Data Exchange (ETDEWEB)

    Byrne, H.; Norbury, J. (Univ. of Oxford (United Kingdom). Mathematical Inst.)

    1994-06-01

    A coupled system of partial differential equations that describes the evolution of solid and gas temperatures and gas concentration inside a catalytic converter is derived and examined. The use of a reaction term, which is a discontinuous function of the solid temperature and gas concentration, implies that two types of nontrivial solutions may occur. These are characterized by the manner in which the reaction switches off: either the solid temperature becomes too low (U-solutions) or the gaseous concentration is exhausted (G-solutions). This reaction term differs from the usual combustion term because the reaction is modeled as two-stage, with the large activation-energy limit then justifying the step-function approach adopted. First, steady solutions for which the gas and solid are in thermal equilibrium are studied, and a constraint relating the system's parameters is derived as a necessary condition for the existence of such solutions. Explicit solutions are presented for a particular class of reaction rates, with a linear stability analysis of one case indicating that G-solutions are stable while U-solutions are not. Steady solutions for which the solid and gas are no longer in thermal equilibrium are then considered. For a particular asymptotic limit (and choice of the reaction term), the construction of asymptotic power series expansions shows that the gas temperature exceeds the solid temperature at all points inside the converter. The analysis indicates that separate treatment of the solid and gaseous temperatures has no effect on the qualitative nature of the steady solutions, that is, their existence, stability, and parameter dependence.

  11. The Multiple Facets of Iodine(III) Compounds in an Unprecedented Catalytic Auto-amination for Chiral Amine Synthesis.

    Science.gov (United States)

    Buendia, Julien; Grelier, Gwendal; Darses, Benjamin; Jarvis, Amanda G; Taran, Frédéric; Dauban, Philippe

    2016-06-20

    Iodine(III) reagents are used in catalytic one-pot reactions, first as both oxidants and substrates, then as cross-coupling partners, to afford chiral polyfunctionalized amines. The strategy relies on an initial catalytic auto C(sp(3) )-H amination of the iodine(III) oxidant, which delivers an amine-derived iodine(I) product that is subsequently used in palladium-catalyzed cross-couplings to afford a variety of useful building blocks with high yields and excellent stereoselectivities. This study demonstrates the concept of self-amination of the hypervalent iodine reagents, which increases the value of the aryl moiety. PMID:27158802

  12. Optical coupling

    Energy Technology Data Exchange (ETDEWEB)

    Bock, J J [Jet Propulsion Laboratory, 4800 Oak Grove Drive, Pasadena, CA 91109 (United States); Gundersen, J [Department of Physics, University of Miami, Coral Gables, FL 33146 (United States); Lee, A T [Department of Physics, University of California, Berkeley CA 94720 Physics Division, Lawrence Berkeley National Laboratory, Berkeley CA 94720 (United States); Richards, P L [Department of Physics, University of California, Berkeley CA 94720 (United States); Wollack, E, E-mail: James.Bock@jpl.nasa.go, E-mail: gunder@physics.miami.ed, E-mail: Adrian.Lee@berkeley.ed, E-mail: Richards@cosmology.berkeley.ed, E-mail: Edward.j.wollack@nasa.go [Observational Cosmology Laboratory, NASA/GSFC, Greenbelt, MD 20771 (United States)

    2009-03-01

    This paper describes contributions to the CMBpol Technology Study Workshop concerning optical coupling structures. These are structures in or near the focal plane which convert the free space wave to a superconducting microstrip on a SI wafer, or to the waveguide input to a HEMT receiver. In addition to an introduction and conclusions by the editor, this paper includes independent contributions by Bock on 'Planar Antenna-Coupled Bolometers for CMB Polarimetry', by Gunderson and Wollack on 'Millimeter-Wave Platlet Feeds', and by Lee on 'Multi-band Dual-Polarization Lens-coupled Planar Antennas for Bolometric CMB polarimetry.'

  13. Structure-based identification of catalytic residues.

    Science.gov (United States)

    Yahalom, Ran; Reshef, Dan; Wiener, Ayana; Frankel, Sagiv; Kalisman, Nir; Lerner, Boaz; Keasar, Chen

    2011-06-01

    The identification of catalytic residues is an essential step in functional characterization of enzymes. We present a purely structural approach to this problem, which is motivated by the difficulty of evolution-based methods to annotate structural genomics targets that have few or no homologs in the databases. Our approach combines a state-of-the-art support vector machine (SVM) classifier with novel structural features that augment structural clues by spatial averaging and Z scoring. Special attention is paid to the class imbalance problem that stems from the overwhelming number of non-catalytic residues in enzymes compared to catalytic residues. This problem is tackled by: (1) optimizing the classifier to maximize a performance criterion that considers both Type I and Type II errors in the classification of catalytic and non-catalytic residues; (2) under-sampling non-catalytic residues before SVM training; and (3) during SVM training, penalizing errors in learning catalytic residues more than errors in learning non-catalytic residues. Tested on four enzyme datasets, one specifically designed by us to mimic the structural genomics scenario and three previously evaluated datasets, our structure-based classifier is never inferior to similar structure-based classifiers and comparable to classifiers that use both structural and evolutionary features. In addition to the evaluation of the performance of catalytic residue identification, we also present detailed case studies on three proteins. This analysis suggests that many false positive predictions may correspond to binding sites and other functional residues. A web server that implements the method, our own-designed database, and the source code of the programs are publicly available at http://www.cs.bgu.ac.il/∼meshi/functionPrediction. PMID:21491495

  14. Development of Catalytic Cooking Plates

    Energy Technology Data Exchange (ETDEWEB)

    Hjelm, Anna-Karin; Silversand, Fredrik [CATATOR AB, Lund (Sweden); Tena, Emmanuel; Berger, Marc [Gaz de France (France)

    2004-04-01

    Gas catalytic combustion for gas stoves or cooking plates (closed catalytic burner system with ceramic plates) is a very promising technique in terms of ease of cleaning, power modulation and emissions. Previous investigations show that wire mesh catalysts, prepared and supplied by Catator AB (CAT), seem to be very well suited for such applications. Beside significantly reducing the NOx-emissions, these catalysts offer important advantages such as good design flexibility, low pressure drop and high heat transfer capacity, where the latter leads to a quick thermal response. Prior to this project, Gaz de France (GdF) made a series of measurements with CAT's wire mesh catalysts in their gas cooking plates and compared the measured performance with similar results obtained with theirs cordierite monolith catalysts. Compared to the monolith catalyst, the wire mesh catalyst was found to enable very promising results with respect to both emission levels (<10 mg NO{sub x} /kWh, <5 mg CO/kWh) and life-time (>8000 h vs. 700 h at 200 kW/m{sup 2}). It was however established that the radiation and hence, the thermal efficiency of the cooking plate, was significantly less than is usually measured in combination with the monolith (15 % vs. 32 %). It was believed that the latter could be improved by developing new burner designs based on CAT's wire mesh concept. As a consequence, a collaboration project between GdF, CAT and the Swedish Gas Technology AB was created. This study reports on the design, the construction and the evaluation of new catalytic burners, based on CAT's wire mesh catalysts, used for the combustion of natural gas in gas cooking stoves. The evaluation of the burners was performed with respect to key factors such as thermal efficiency, emission quality and pressure drop, etc, by the use of theoretical simulations and experimental tests. Impacts of parameters such as the the wire mesh number, the wire mesh structure (planar or folded), the

  15. Catalytic reaction in confined flow channel

    Energy Technology Data Exchange (ETDEWEB)

    Van Hassel, Bart A.

    2016-03-29

    A chemical reactor comprises a flow channel, a source, and a destination. The flow channel is configured to house at least one catalytic reaction converting at least a portion of a first nanofluid entering the channel into a second nanofluid exiting the channel. The flow channel includes at least one turbulating flow channel element disposed axially along at least a portion of the flow channel. A plurality of catalytic nanoparticles is dispersed in the first nanofluid and configured to catalytically react the at least one first chemical reactant into the at least one second chemical reaction product in the flow channel.

  16. A catalytic approach to estimate the redox potential of heme-peroxidases

    International Nuclear Information System (INIS)

    The redox potential of heme-peroxidases varies according to a combination of structural components within the active site and its vicinities. For each peroxidase, this redox potential imposes a thermodynamic threshold to the range of oxidizable substrates. However, the instability of enzymatic intermediates during the catalytic cycle precludes the use of direct voltammetry to measure the redox potential of most peroxidases. Here we describe a novel approach to estimate the redox potential of peroxidases, which directly depends on the catalytic performance of the activated enzyme. Selected p-substituted phenols are used as substrates for the estimations. The results obtained with this catalytic approach correlate well with the oxidative capacity predicted by the redox potential of the Fe(III)/Fe(II) couple

  17. Cross-catalytic peptide nucleic acid (PNA) replication based on templated ligation

    DEFF Research Database (Denmark)

    Singhal, Abhishek; Nielsen, Peter E

    2014-01-01

    We report the first PNA self-replicating system based on template directed cross-catalytic ligation, a process analogous to biological replication. Using two template PNAs and four pentameric precursor PNAs, all four possible carbodiimide assisted amide ligation products were detected and...... identified by HPLC and MALDI-TOF analysis. We conclude that the two template complementary reaction products are generated via cross-catalysis, while the other two self-complementary (and in principle auto-catalytic) products are formed via intra-complex coupling between the two sets of complementary PNA...... precursors. Cross-catalytic product formation followed product inhibited kinetics, but approximately two replication rounds were observed. Analogous but less efficient replication was found for a similar tetrameric system. These results demonstrate that simpler nucleobase replication systems than natural...

  18. Catalytic Chemistry on Oxide Nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Asthagiri, Aravind; Dixon, David A.; Dohnalek, Zdenek; Kay, Bruce D.; Rodriquez, Jose A.; Rousseau, Roger J.; Stacchiola, Dario; Weaver, Jason F.

    2016-05-29

    Metal oxides represent one of the most important and widely employed materials in catalysis. Extreme variability of their chemistry provides a unique opportunity to tune their properties and to utilize them for the design of highly active and selective catalysts. For bulk oxides, this can be achieved by varying their stoichiometry, phase, exposed surface facets, defect, dopant densities and numerous other ways. Further, distinct properties from those of bulk oxides can be attained by restricting the oxide dimensionality and preparing them in the form of ultrathin films and nanoclusters as discussed throughout this book. In this chapter we focus on demonstrating such unique catalytic properties brought by the oxide nanoscaling. In the highlighted studies planar models are carefully designed to achieve minimal dispersion of structural motifs and to attain detailed mechanistic understanding of targeted chemical transformations. Detailed level of morphological and structural characterization necessary to achieve this goal is accomplished by employing both high-resolution imaging via scanning probe methods and ensemble-averaged surface sensitive spectroscopic methods. Three prototypical examples illustrating different properties of nanoscaled oxides in different classes of reactions are selected.

  19. Halogen Chemistry on Catalytic Surfaces.

    Science.gov (United States)

    Moser, Maximilian; Pérez-Ramírez, Javier

    2016-01-01

    Halogens are key building blocks for the manufacture of high-value products such as chemicals, plastics, and pharmaceuticals. The catalytic oxidation of HCl and HBr is an attractive route to recover chlorine and bromine in order to ensure the sustainability of the production processes. Very few materials withstand the high corrosiveness and the strong exothermicity of the reactions and among them RuO2 and CeO2-based catalysts have been successfully applied in HCl oxidation. The search for efficient systems for HBr oxidation was initiated by extrapolating the results of HCl oxidation based on the chemical similarity of these reactions. Interestingly, despite its inactivity in HCl oxidation, TiO2 was found to be an outstanding HBr oxidation catalyst, which highlighted that the latter reaction is more complex than previously assumed. Herein, we discuss the results of recent comparative studies of HCl and HBr oxidation on both rutile-type (RuO2, IrO2, and TiO2) and ceria-based catalysts using a combination of advanced experimental and theoretical methods to provide deeper molecular-level understanding of the reactions. This knowledge aids the design of the next-generation catalysts for halogen recycling. PMID:27131113

  20. Vacuum-insulated catalytic converter

    Energy Technology Data Exchange (ETDEWEB)

    Benson, David K. (Golden, CO)

    2001-01-01

    A catalytic converter has an inner canister that contains catalyst-coated substrates and an outer canister that encloses an annular, variable vacuum insulation chamber surrounding the inner canister. An annular tank containing phase-change material for heat storage and release is positioned in the variable vacuum insulation chamber a distance spaced part from the inner canister. A reversible hydrogen getter in the variable vacuum insulation chamber, preferably on a surface of the heat storage tank, releases hydrogen into the variable vacuum insulation chamber to conduct heat when the phase-change material is hot and absorbs the hydrogen to limit heat transfer to radiation when the phase-change material is cool. A porous zeolite trap in the inner canister absorbs and retains hydrocarbons from the exhaust gases when the catalyst-coated substrates and zeolite trap are cold and releases the hydrocarbons for reaction on the catalyst-coated substrate when the zeolite trap and catalyst-coated substrate get hot.

  1. Catalytic models developed through social work

    DEFF Research Database (Denmark)

    Jensen, Mogens

    2015-01-01

    The article develops the concept of catalytic processes in relation to social work with adolescents in an attempt to both reach a more nuanced understanding of social work and at the same time to develop the concept of catalytic processes in psychology. The social work is pedagogical treatment of...... adolescents placed in out-of-home care and is characterised using three situated cases as empirical data. Afterwards the concept of catalytic processes is briefly presented and then applied in an analysis of pedagogical treatment in the three cases. The result is a different conceptualisation of the social...... work with new possibilities of development of the work, but also suggestions for development of the concept of catalytic processes....

  2. Catalytic converters as a source of platinum

    Directory of Open Access Journals (Sweden)

    A. Fornalczyk

    2011-10-01

    Full Text Available The increase of Platinum Group Metals demand in automotive industry is connected with growing amount of cars equipped with the catalytic converters. The paper presents the review of available technologies during recycling process. The possibility of removing platinum from the used catalytic converters applying pyrometallurgical and hyrdometallurgical methods were also investigated. Metals such as Cu, Pb, Ca, Mg, Cd were used in the pyrometallurgical research (catalytic converter was melted with Cu, Pb and Ca or Mg and Cd vapours were blown through the whole carrier. In hydrometallurgical research catalytic converters was dissolved in aqua regia. Analysis of Pt contents in the carrier before and after the process was performed by means of atomic absorption spectroscopy. Obtained result were discussed.

  3. Kinetic catalytic studies of scorpion's hemocyanin

    International Nuclear Information System (INIS)

    Hemocyanins are copper proteins which function as oxygen carriers in the haemolymph of Molluscs and Arthropods. They possess enzymatic properties: peroxidatic and catalatic activities, although they have neither iron nor porphyrin ring at the active site. The kinetics of the catalytic reaction is described. The reaction of superoxide anion with hemocyanin has been studied using pulse radiolysis at pH 9. The catalytic rate constant is 3.5 X 107 mol-1.l.s-1

  4. Characterization of Aqueous Peroxomolybdates with Catalytic Applicability

    OpenAIRE

    Taube, Fabian

    2003-01-01

    Abstract This thesis is a summary of five papers, containing equilibrium and structure studies of aqueous molybdate and peroxomolybdate species. Some of the peroxomolybdate species have also been studied in terms of their dynamic and catalytic properties. The primary objective was to characterize species with potential catalytic activity, with emphasis on thebleach process of kraft pulp. For this, potentiometry, EXAFS and 17O, 31P, 1H and 95 Mo NMR have been used. The molybdate speciation in ...

  5. MOBILE COMPLEX FOR CATALYTIC THERMAL WASTE TREATMENT

    OpenAIRE

    Vedi V.E.; Rovenskii A.I.

    2012-01-01

    The design and purpose of the basic units of the mobile waste processing complex “MPK” are described. Experimental data of catalytic purification of exhaust gases are presented. Experimental data on catalytic clearing of final gases of a designed mobile incinerator plant are shown. It is defined, that concentrating of parasitic bridging in waste gases of the complex are considerably smaller, rather than allowed by normative documents.

  6. MOBILE COMPLEX FOR CATALYTIC THERMAL WASTE TREATMENT

    Directory of Open Access Journals (Sweden)

    Vedi V.E.

    2012-12-01

    Full Text Available The design and purpose of the basic units of the mobile waste processing complex “MPK” are described. Experimental data of catalytic purification of exhaust gases are presented. Experimental data on catalytic clearing of final gases of a designed mobile incinerator plant are shown. It is defined, that concentrating of parasitic bridging in waste gases of the complex are considerably smaller, rather than allowed by normative documents.

  7. Temperature Modulation of a Catalytic Gas Sensor

    OpenAIRE

    Eike Brauns; Eva Morsbach; Sebastian Kunz; Marcus Baeumer; Walter Lang

    2014-01-01

    The use of catalytic gas sensors usually offers low selectivity, only based on their different sensitivities for various gases due to their different heats of reaction. Furthermore, the identification of the gas present is not possible, which leads to possible misinterpretation of the sensor signals. The use of micro-machined catalytic gas sensors offers great advantages regarding the response time, which allows advanced analysis of the sensor response. By using temperature modulation, additi...

  8. Catalytic ammonia oxidation to nitrogen (I) oxide

    OpenAIRE

    MASALITINA NATALIYA YUREVNA; SAVENKOV ANATOLIY SERGEEVICH

    2015-01-01

    The process of synthesis of nitrous oxide by low-temperature catalytical oxidation of NH has been investigated for organic synthesis. The investigation has been carried out by the stage separation approach with NH oxidation occurring in several reaction zones, which characterized by different catalytic conditions. The selectivity for N₂O was 92–92,5 % at the ammonia conversion of 98–99.5 % in the optimal temperature range.

  9. Preparation and Catalytic Oxidation Activity on 2-mercaptoethanol of a Novel Catalytic Cellulose Fibres

    Institute of Scientific and Technical Information of China (English)

    YAO Yu-yuan; LI Ying-jie; CHEN Wen-xing; Lü Wang-yang; Lü Su-fang; XU Min-hong; LIU Fan

    2007-01-01

    Cobalt tetra(N-carbonylacylic) aminophthalocyanine was supported on cellulose fibres by graft reaction to obtain a novel polymer catalyst, catalytic cellulose fibres (CCF),and the optimal supporting conditions were pH = 6, 80℃,t = 120 min. The catalytic oxidation activity of CCF towards oxidation of 2-mereaptoethanol (MEA) in aqueous solution was investigated. The experimental results demonstrated that CCF had good catalytic oxidation activity on MEA at room temperature, causing no secondary pollution and remaining efficient for the repetitive tests with no obvious decrease of catalytic activity.

  10. Thicker is better? Synthesis and evaluation of well-defined polymer brushes with controllable catalytic loadings.

    Science.gov (United States)

    Fernandes, Antony E; Dirani, Ali; d'Haese, Cécile; Deumer, Gladys; Guo, Weiming; Hensenne, Peter; Nahra, Fady; Laloyaux, Xavier; Haufroid, Vincent; Nysten, Bernard; Riant, Olivier; Jonas, Alain M

    2012-12-01

    Polymer brushes (PBs) have been used as supports for the immobilization of palladium complexes on silicon surfaces. The polymers were grown by surface-initiated atom-transfer radical polymerization (SI-ATRP) and postdecorated with dipyridylamine (dpa) ligands. The pendant dpa units were in turn complexed with [Pd(OAc)(2)] to afford hybrid catalytic surfaces. A series of catalytic samples of various thicknesses (ca. 20-160 nm) and associated palladium loadings (ca. 10-45 nmol  cm(-2)) were obtained by adjusting the SI-ATRP reaction time and characterized by ellipsometry, X-ray reflectivity, X-ray photoelectron spectroscopy, and inductively coupled plasma mass spectrometry (ICP-MS). ICP-MS revealed a near-linear relationship between thickness of the polymer brush and palladium content, which confirmed the robustness of the preparation and postmodification sequence presented herein, rendering possible the creation of functional architectures with predefined catalytic potential. The activities of the catalytic PBs were determined by systematically exploring a full range of substrate-to-catalyst ratios in a model palladium(0)-catalyzed reaction. Quantitative transformations were observed for loadings down to 0.03 mol % and a maximum turnover number (TON) of around 3500 was established for the system. Comparison of the catalytic performances evidenced a singular influence of the thickness on conversions and TONs. The limited recyclability of the hairy catalysts has been attributed to palladium leaching. PMID:23032959

  11. Low efficiency deasphalting and catalytic cracking

    International Nuclear Information System (INIS)

    This patent describes a process for converting an asphaltene and metals containing heavy hydrocarbon feed to lighter, more valuable products the metals comprising Ni and V. It comprises: demetallizing the feed by deasphalting the feed in a solvent deasphalting means operating at solvent deasphalting conditions including a solvent: feed volume ratio of about 1:1 to 4:1, using a solvent selected from the group of C4 to 400 degrees F. hydrocarbons and mixtures thereof; recovering from the solvent rich fraction a demetallized oil intermediate product, having a boiling range and containing at least 10 wt.% of the asphaltenes, and 5 to 30% of the Ni and V, and at least 10 wt.% of the solvent present in the solvent rich phase produced in the deasphalting means; catalytically cracking the demetallized oil intermediate product in a catalytic cracking means operating at catalytic cracking conditions to produce a catalytically cracked product vapor fraction having a lower boiling range than the boiling range of the demetallized oil intermediate product; and fractionating the catalytically cracked product in a fractionation means to produce catalytically cracked product fractions

  12. Prosthesis coupling

    Science.gov (United States)

    Reswick, J. B.; Mooney, V.; Bright, C. W.; Owens, L. J. (Inventor)

    1979-01-01

    A coupling for use in an apparatus for connecting a prosthesis to the bone of a stump of an amputated limb is described which permits a bio-compatible carbon sleeve forming a part of the prosthesis connector to float so as to prevent disturbing the skin seal around the carbon sleeve. The coupling includes a flexible member interposed between a socket that is inserted within an intermedullary cavity of the bone and the sleeve. A lock pin is carried by the prosthesis and has a stem portion which is adapted to be coaxially disposed and slideably within the tubular female socket for securing the prosthesis to the stump. The skin around the percutaneous carbon sleeve is able to move as a result of the flexing coupling so as to reduce stresses caused by changes in the stump shape and/or movement between the bone and the flesh portion of the stump.

  13. Entrepreneurial Couples

    DEFF Research Database (Denmark)

    Dahl, Michael S.; Van Praag, Mirjam; Thompson, Peter

    We study possible motivations for co-entrepenurial couples to start up a joint firm, using a sample of 1,069 Danish couples that established a joint enterprise between 2001 and 2010. We compare their pre-entry characteristics, firm performance and postdissolution private and financial outcomes with......, are larger in co-entrepreneurial firms, both during the life of the business and post-dissolution. The start-up of co-entrepreneurial firms seems therefore a sound investment in the human capital of both spouses as well as in the reduction of income inequality in the household. We find no evidence of...

  14. Entrepreneurial Couples

    DEFF Research Database (Denmark)

    Dahl, Michael S.; Van Praag, Mirjam; Thompson, Peter

    We study possible motivations for co-entrepenurial couples to start up a joint firm, us-ing a sample of 1,069 Danish couples that established a joint enterprise between 2001 and 2010. We compare their pre-entry characteristics, firm performance and post-dissolution private and financial outcomes...... female, are larger in co-entrepreneurial firms, both during the life of the business and post-dissolution. The start-up of co-entrepreneurial firms seems therefore a sound in-vestment in the human capital of both spouses as well as in the reduction of income inequality in the household. We find no...

  15. Entrepreneurial Couples

    DEFF Research Database (Denmark)

    2015-01-01

    We study possible motivations for co-entreprenurial couples to start up a joint firm, using a sample of 1,069 Danish couples that established a joint enterprise between 2001 and 2010. We compare their pre-entry characteristics, firm performance and post-dissolution private and financial outcomes...... female, are larger in co-entrepreneurial firms, both during the life of the business and post-dissolution. The start-up of co-entrepreneurial firms seems therefore a sound investment in the human capital of both spouses as well as in the reduction of income inequality in the household. We find no...

  16. Catalytic and surface oxidation processes on transition metal surfaces

    OpenAIRE

    Jaatinen, Sampsa

    2007-01-01

    Transition metals are technologically important catalytic materials. The transition metal catalysts are used for example in petroleum and fertilizer industry. In the car industry the catalytic materials are used in the catalytic converters. Because of the industrial importance the catalytic metals have been widely studied throughout the past decades. Nonetheless, the oxidation mechanisms of small molecules and the effect of alloying to catalytic properties of metals are not fully understood. ...

  17. On the Structural Context and Identification of Enzyme Catalytic Residues

    OpenAIRE

    Yu-Tung Chien; Shao-Wei Huang

    2013-01-01

    Enzymes play important roles in most of the biological processes. Although only a small fraction of residues are directly involved in catalytic reactions, these catalytic residues are the most crucial parts in enzymes. The study of the fundamental and unique features of catalytic residues benefits the understanding of enzyme functions and catalytic mechanisms. In this work, we analyze the structural context of catalytic residues based on theoretical and experimental structure flexibility. The...

  18. Deep desulfurization of diesel fuels by catalytic oxidation

    Institute of Scientific and Technical Information of China (English)

    YU Guoxian; CHEN Hui; LU Shanxiang; ZHU Zhongnan

    2007-01-01

    Reaction feed was prepared by dissolving dibenzothiophene (DBT),which was selected as a model organosulfur compound in diesel fuels,in n-octane.The oxidant was a 30 wt-% aqueous solution of hydrogen peroxide.Catalytic performance of the activated carbons with saturation adsorption of DBT was investigated in the presence of formic acid.In addition,the effects of activated carbon dosage,formic acid concentration,initial concentration of hydrogen peroxide,initial concentration of DBT and reaction temperature on the oxidation of DBT were investigated.Experimental results indicated that performic acid and the hydroxyl radicals produced are coupled to oxidize DBT with a conversion ratio of 100%.Catalytic performance of the combination of activated carbon and formic acid is higher than that ofouly formic acid.The concentration of formic acid,activated carbon dosage,initial concentration of hydrogen peroxide and reaction temperature affect the oxidative removal of DBT.The higher the initial concentration of DBT in the n-octane solution,the more difficult the deep desulfurization by oxidation is.

  19. Catalytically active single-atom niobium in graphitic layers.

    Science.gov (United States)

    Zhang, Xuefeng; Guo, Junjie; Guan, Pengfei; Liu, Chunjing; Huang, Hao; Xue, Fanghong; Dong, Xinglong; Pennycook, Stephen J; Chisholm, Matthew F

    2013-01-01

    Carbides of groups IV through VI (Ti, V and Cr groups) have long been proposed as substitutes for noble metal-based electrocatalysts in polymer electrolyte fuel cells. However, their catalytic activity has been extremely limited because of the low density and stability of catalytically active sites. Here we report the excellent performance of a niobium-carbon structure for catalysing the cathodic oxygen reduction reaction. A large number of single niobium atoms and ultra small clusters trapped in graphitic layers are directly identified using state-of-the-art aberration-corrected scanning transmission electron microscopy. This structure not only enhances the overall conductivity for accelerating the exchange of ions and electrons, but it suppresses the chemical/thermal coarsening of the active particles. Experimental results coupled with theory calculations reveal that the single niobium atoms incorporated within the graphitic layers produce a redistribution of d-band electrons and become surprisingly active for O2 adsorption and dissociation, and also exhibit high stability. PMID:23715283

  20. CFD SIMULATION OF FLUID CATALYTIC CRACKING IN DOWNER REACTORS

    Institute of Scientific and Technical Information of China (English)

    Fei; Liu; Fei; Wei; Yu; Zheng; Yong; Jin

    2006-01-01

    A mathematical model has been developed for the simulation of gas-particle flow and fluid catalytic cracking in downer reactors. The model takes into account both cracking reaction and flow behavior through a four-lump reaction kinetics coupled with two-phase turbulent flow. The prediction results show that the relatively large change of gas velocity affects directly the axial distribution of solids velocity and void fraction, which significantly interact with the chemical reaction. Furthermore, model simulations are carried out to determine the effects of such parameters on product yields, as bed diameter, reaction temperature and the ratio of catalyst to oil, which are helpful for optimizing the yields of desired products. The model equations are coded and solved on CFX4.4.

  1. Kinetically controlled E-selective catalytic olefin metathesis.

    Science.gov (United States)

    Nguyen, Thach T; Koh, Ming Joo; Shen, Xiao; Romiti, Filippo; Schrock, Richard R; Hoveyda, Amir H

    2016-04-29

    A major shortcoming in olefin metathesis, a chemical process that is central to research in several branches of chemistry, is the lack of efficient methods that kinetically favor E isomers in the product distribution. Here we show that kinetically E-selective cross-metathesis reactions may be designed to generate thermodynamically disfavored alkenyl chlorides and fluorides in high yield and with exceptional stereoselectivity. With 1.0 to 5.0 mole % of a molybdenum-based catalyst, which may be delivered in the form of air- and moisture-stable paraffin pellets, reactions typically proceed to completion within 4 hours at ambient temperature. Many isomerically pure E-alkenyl chlorides, applicable to catalytic cross-coupling transformations and found in biologically active entities, thus become easily and directly accessible. Similarly, E-alkenyl fluorides can be synthesized from simpler compounds or more complex molecules. PMID:27126041

  2. Catalytic activity of nuclease P1: Experiment and theory

    International Nuclear Information System (INIS)

    Nuclease P1 from Penicillium citrinum is a zinc dependent glyco-enzyme that recognizes single stranded DNA and RNA as substrates and hydrolyzes the phosphate ester bond. Nuclease Pl seems to recognize particular conformations of the phosphodiester backbone and shows significant variation in the rate of hydrolytic activity depending upon which nucleosides are coupled by the phosphodiester bond. The efficiency of nuclease Pl in hydrolyzing the phosphodiester bonds of a substrate can be altered by modifications to one of the substrate bases induced by ionizing radiation or oxidative stress. Measurements have been made of the effect of several radiation induced lesions on the catalytic rate of nuclease Pl. A model of the structure of the enzyme has been constructed in order to better understand the binding and activity of this enzyme on various ssDNA substrates

  3. Catalytic Oxygen Evolution by Cobalt Oxido Thin Films.

    Science.gov (United States)

    Bediako, D Kwabena; Ullman, Andrew M; Nocera, Daniel G

    2016-01-01

    The contemporary demand to generate fuels from solar energy has stimulated intense effort to develop water splitting catalysts that can be coupled to light-absorbing materials. Cobalt oxido catalyst (Co-OECs) films deposited from buffered Co(II) solutions have emerged as arguably the most studied class of heterogeneous oxygen evolution catalysts. The interest in these materials stems from their formation by self-assembly, their self-healing properties, and their promising catalytic activity under a variety of conditions. The structure and function of these catalysts are reviewed here together with studies of molecular Co-O cluster compounds, which have proven invaluable in elucidating the chemistry of the Co-OECs. PMID:26245626

  4. Oscillatory three-phase flow reactor for studies of bi-phasic catalytic reactions.

    Science.gov (United States)

    Abolhasani, Milad; Bruno, Nicholas C; Jensen, Klavs F

    2015-05-28

    A multi-phase flow strategy, based on oscillatory motion of a bi-phasic slug within a fluorinated ethylene propylene (FEP) tubular reactor, under inert atmosphere, is designed and developed to address mixing and mass transfer limitations associated with continuous slug flow chemistry platforms for studies of bi-phasic catalytic reactions. The technique is exemplified with C-C and C-N Pd catalyzed coupling reactions. PMID:25876959

  5. Catalytically stabilized combustion of lean methane-air-mixtures: a numerical model

    Energy Technology Data Exchange (ETDEWEB)

    Dogwiler, U.; Benz, P.; Mantharas, I. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    The catalytically stabilized combustion of lean methane/air mixtures has been studied numerically under conditions closely resembling the ones prevailing in technical devices. A detailed numerical model has been developed for a laminar, stationary, 2-D channel flow with full heterogeneous and homogeneous reaction mechanisms. The computations provide direct information on the coupling between heterogeneous-homogeneous combustion and in particular on the means of homogeneous ignitions and stabilization. (author) 4 figs., 3 refs.

  6. Oscillatory three-phase flow reactor for studies of bi-phasic catalytic reactions

    OpenAIRE

    Abolhasani, Milad; Bruno, Nicholas C.; Jensen, Klavs F.

    2015-01-01

    A multi-phase flow strategy, based on oscillatory motion of a bi-phasic slug within a fluorinated ethylene propylene (FEP) tubular reactor, under inert atmosphere, is designed and developed to address mixing and mass transfer limitations associated with continuous slug flow chemistry platforms for studies of bi-phasic catalytic reactions. The technique is exemplified with C–C and C–N Pd catalyzed coupling reactions.

  7. Nitrene Metathesis and Catalytic Nitrene Transfer Promoted by Niobium Bis(imido) Complexes.

    Science.gov (United States)

    Kriegel, Benjamin M; Bergman, Robert G; Arnold, John

    2016-01-13

    We report a metathesis reaction in which a nitrene fragment from an isocyanide ligand is exchanged with a nitrene fragment of an imido ligand in a series of niobium bis(imido) complexes. One of these bis(imido) complexes also promotes nitrene transfer to catalytically generate asymmetric dialkylcarbodiimides from azides and isocyanides in a process involving the Nb(V)/Nb(III) redox couple. PMID:26698833

  8. From Electronic Structure to Catalytic Activity: A Single Descriptor for Adsorption and Reactivity on Transition-Metal Carbides

    DEFF Research Database (Denmark)

    Vojvodic, A.; Hellman, Anders; Ruberto, C.;

    2009-01-01

    Adsorption and catalytic properties of the polar (111) surface of transition-metal carbides (TMC's) are investigated by density-functional theory. Atomic and molecular adsorption are rationalized with the concerted-coupling model, in which two types of TMC surface resonances (SR's) play key roles...

  9. Theoretical study of catalytic efficiency of a Diels-Alderase catalytic antibody: an indirect effect produced during the maturation process.

    Science.gov (United States)

    Martí, Sergio; Andrés, Juan; Moliner, Vicent; Silla, Estanislao; Tuñón, Iñaki; Bertrán, Juan

    2008-01-01

    The Diels-Alder reaction is one of the most important and versatile transformations available to organic chemists for the construction of complex natural products, therapeutics agents, and synthetic materials. Given the lack of efficient enzymes capable of catalyzing this kind of reaction, it is of interest to ask whether a biological catalyst could be designed from an antibody-combining site. In the present work, a theoretical study of the different behavior of a germline catalytic antibody (CA) and its matured form, 39 A-11, that catalyze a Diels-Alder reaction has been carried out. A free-energy perturbation technique based on a hybrid quantum-mechanics/molecular-mechanics scheme, together with internal energy minimizations, has allowed free-energy profiles to be obtained for both CAs. The profiles show a smaller barrier for the matured form, which is in agreement with the experimental observation. Free-energy profiles were obtained with this methodology, thereby avoiding the much more demanding two-dimensional calculations of the energy surfaces that are normally required to study this kind of reaction. Structural analysis and energy evaluations of substrate-protein interactions have been performed from averaged structures, which allows understanding of how the single mutations carried out during the maturation process can be responsible for the observed fourfold enhancement of the catalytic rate constant. The conclusion is that the mutation effect in this studied germline CA produces a complex indirect effect through coupled movements of the backbone of the protein and the substrate. PMID:17960540

  10. Simultaneous probing of bulk liquid phase and catalytic gas-liquid-solid interface under working conditions using attenuated total reflection infrared spectroscopy

    International Nuclear Information System (INIS)

    Design and performance of a reactor set-up for attenuated total reflection infrared (ATR-IR) spectroscopy suitable for simultaneous reaction monitoring of bulk liquid and catalytic solid-liquid-gas interfaces under working conditions are presented. As advancement of in situ spectroscopy an operando methodology for gas-liquid-solid reaction monitoring was developed that simultaneously combines catalytic activity and molecular level detection at the catalytically active site of the same sample. Semi-batch reactor conditions are achieved with the analytical set-up by implementing the ATR-IR flow-through cell in a recycle reactor system and integrating a specifically designed gas feeding system coupled with a bubble trap. By the use of only one spectrometer the design of the new ATR-IR reactor cell allows for simultaneous detection of the bulk liquid and the catalytic interface during the working reaction. Holding two internal reflection elements (IRE) the sample compartments of the horizontally movable cell are consecutively flushed with reaction solution and pneumatically actuated, rapid switching of the cell (<1 s) enables to quasi simultaneously follow the heterogeneously catalysed reaction at the catalytic interface on a catalyst-coated IRE and in the bulk liquid on a blank IRE. For a complex heterogeneous reaction, the asymmetric hydrogenation of 2,2,2-trifluoroacetophenone on chirally modified Pt catalyst the elucidation of catalytic activity/enantioselectivity coupled with simultaneous monitoring of the catalytic solid-liquid-gas interface is shown. Both catalytic activity and enantioselectivity are strongly dependent on the experimental conditions. The opportunity to gain improved understanding by coupling measurements of catalytic performance and spectroscopic detection is presented. In addition, the applicability of modulation excitation spectroscopy and phase-sensitive detection are demonstrated

  11. A novel liquid system of catalytic hydrogenation

    Institute of Scientific and Technical Information of China (English)

    LI; XiaoNian; XIANG; YiZhi

    2007-01-01

    On the basis that endothermic aqueous-phase reforming of oxygenated hydrocarbons for H2 production and exothermic liquid phase hydrogenation of organic compounds are carried out under extremely close conditions of temperature and pressure over the same type of catalyst, a novel liquid system of catalytic hydrogenation has been proposed, in which hydrogen produced from aqueous-phase reforming of oxygenated hydrocarbons is in situ used for liquid phase hydrogenation of organic compounds. The usage of active hydrogen generated from aqueous-phase reforming of oxygenated hydrocarbons for liquid catalytic hydrogenation of organic compounds could lead to increasing the selectivity to H2 in the aqueous-phase reforming due to the prompt removal of hydrogen on the active centers of the catalyst. Meanwhile, this novel liquid system of catalytic hydrogenation might be a potential method to improve the selectivity to the desired product in liquid phase catalytic hydrogenation of organic compounds. On the other hand, for this novel liquid system of catalytic hydrogenation, some special facilities for H2 generation, storage and transportation in traditional liquid phase hydrogenation industry process are yet not needed. Thus, it would simplify the working process of liquid phase hydrogenation and increase the energy usage and hydrogen productivity.

  12. Power coupling

    OpenAIRE

    D. AlesiniLNF, INFN, Frascati

    2015-01-01

    Power coupling is the subject of a huge amount of literature and material since for each particular RF structure it is necessary to design a coupler that satisfies some requirements, and several approaches are in principle possible. The choice of one coupler with respect to another depends on the particular RF design expertise. Nevertheless some 'design criteria' can be adopted and the scope of this paper is to give an overview of the basic concepts in power coupler design and techniques. We ...

  13. Highly Dense Isolated Metal Atom Catalytic Sites

    DEFF Research Database (Denmark)

    Chen, Yaxin; Kasama, Takeshi; Huang, Zhiwei; Hu, Pingping; Chen, Jianmin; Liu, Xi; Tang, Xingfu

    2015-01-01

    Atomically dispersed noble-metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal...... loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface-mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X......-ray diffraction. A combination of electron microscopy images with X-ray absorption spectra demonstrated that the silver atoms were anchored on five-fold oxygen-terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation...

  14. ADAR proteins: structure and catalytic mechanism.

    Science.gov (United States)

    Goodman, Rena A; Macbeth, Mark R; Beal, Peter A

    2012-01-01

    Since the discovery of the adenosine deaminase (ADA) acting on RNA (ADAR) family of proteins in 1988 (Bass and Weintraub, Cell 55:1089-1098, 1988) (Wagner et al. Proc Natl Acad Sci U S A 86:2647-2651, 1989), we have learned much about their structure and catalytic mechanism. However, much about these enzymes is still unknown, particularly regarding the selective recognition and processing of specific adenosines within substrate RNAs. While a crystal structure of the catalytic domain of human ADAR2 has been solved, we still lack structural data for an ADAR catalytic domain bound to RNA, and we lack any structural data for other ADARs. However, by analyzing the structural data that is available along with similarities to other deaminases, mutagenesis and other biochemical experiments, we have been able to advance the understanding of how these fascinating enzymes function. PMID:21769729

  15. Catalytic microreactors for portable power generation

    Energy Technology Data Exchange (ETDEWEB)

    Karagiannidis, Symeon [Paul Scherer Institute, Villigen (Switzerland)

    2011-07-01

    ''Catalytic Microreactors for Portable Power Generation'' addresses a problem of high relevance and increased complexity in energy technology. This thesis outlines an investigation into catalytic and gas-phase combustion characteristics in channel-flow, platinum-coated microreactors. The emphasis of the study is on microreactor/microturbine concepts for portable power generation and the fuels of interest are methane and propane. The author carefully describes numerical and experimental techniques, providing a new insight into the complex interactions between chemical kinetics and molecular transport processes, as well as giving the first detailed report of hetero-/homogeneous chemical reaction mechanisms for catalytic propane combustion. The outcome of this work will be widely applied to the industrial design of micro- and mesoscale combustors. (orig.)

  16. Catalytic nanoarchitectonics for environmentally compatible energy generation

    Directory of Open Access Journals (Sweden)

    Hideki Abe

    2016-01-01

    Full Text Available Environmentally compatible energy management is one of the biggest challenges of the 21st century. Low-temperature conversion of chemical to electrical energy is of particular importance to minimize the impact to the environment while sustaining the consumptive economy. In this review, we shed light on one of the most versatile energy-conversion technologies: heterogeneous catalysts. We establish the integrity of structural tailoring in heterogeneous catalysts at different scales in the context of an emerging paradigm in materials science: catalytic nanoarchitectonics. Fundamental backgrounds of energy-conversion catalysis are first provided together with a perspective through state-of-the-art energy-conversion catalysis including catalytic exhaust remediation, fuel-cell electrocatalysis and photosynthesis of solar fuels. Finally, the future evolution of catalytic nanoarchitectonics is overviewed: possible combinations of heterogeneous catalysts, organic molecules and even enzymes to realize reaction-selective, highly efficient and long-life energy conversion technologies which will meet the challenge we face.

  17. Use catalytic combustion for LHV gases

    Energy Technology Data Exchange (ETDEWEB)

    Tucci, E.R.

    1982-03-01

    This paper shows how low heating value (LHV) waste gases can be combusted to recover energy even when the gases won't burn in a normal manner. Significant energy and economic savings can result by adopting this process. Catalytic combustion is a heterogeneous surface-catalyzed air oxidation of fuel, gaseous or liquid, to generate thermal energy in a flameless mode. The catalytic combustion process is quite complex since it involves numerous catalytic surface and gas-phase chemical reactions. During low temperature surface-catalyzed combustion, as in start-up, the combustion stage is under kinetically controlled conditions. The discussion covers the following topics - combustor substrates; combustor washcoating and catalyzing; combustor operational modes (turbine or tabular modes); applications in coal gasification and in-situ gasification; waste process gases. 16 refs.

  18. Xylan-Degrading Catalytic Flagellar Nanorods.

    Science.gov (United States)

    Klein, Ágnes; Szabó, Veronika; Kovács, Mátyás; Patkó, Dániel; Tóth, Balázs; Vonderviszt, Ferenc

    2015-09-01

    Flagellin, the main component of flagellar filaments, is a protein possessing polymerization ability. In this work, a novel fusion construct of xylanase A from B. subtilis and Salmonella flagellin was created which is applicable to build xylan-degrading catalytic nanorods of high stability. The FliC-XynA chimera when overexpressed in a flagellin deficient Salmonella host strain was secreted into the culture medium by the flagellum-specific export machinery allowing easy purification. Filamentous assemblies displaying high surface density of catalytic sites were produced by ammonium sulfate-induced polymerization. FliC-XynA nanorods were resistant to proteolytic degradation and preserved their enzymatic activity for a long period of time. Furnishing enzymes with self-assembling ability to build catalytic nanorods offers a promising alternative approach to enzyme immobilization onto nanostructured synthetic scaffolds. PMID:25966869

  19. Flow parameters of IC engine catalytic converters

    Energy Technology Data Exchange (ETDEWEB)

    Zmudka, Z.; Postrzednik, S. [Silesian Univ. of Tech., Gliwice (Poland)

    2007-07-01

    Conversion rate of harmful substances is the principal parameter of catalyst work in respect of ecology. However, resistance of exhaust gas flow through the catalytic converter is also essential problem, apart from its chemical efficiency because fitting the catalyst in exhaust system alters flow characteristic of this system significantly. Catalytic converter can be treated as local or linear resistance element of exhaust system. The first model, in which flow resistance generated by a catalyst is treated as local resistance, is more simplified. Resistance number of the converter was calculated using Darcy model. In the second case, exhaust gas flow resistance through catalyst is treated as linear resistance with energy dissipation (linear frictional resistance) distributed linearly along way of exhaust gas flow. Friction number for the tested converter was calculated and analysed. The problem has been illustrated by results of experimental researches of three-way catalytic converter installed in exhaust system of spark ignition engine and its basic analysis. (orig.)

  20. Electro Catalytic Oxidation (ECO) Operation

    Energy Technology Data Exchange (ETDEWEB)

    Morgan Jones

    2011-03-31

    The power industry in the United States is faced with meeting many new regulations to reduce a number of air pollutants including sulfur dioxide, nitrogen oxides, fine particulate matter, and mercury. With over 1,000 power plants in the US, this is a daunting task. In some cases, traditional pollution control technologies such as wet scrubbers and SCRs are not feasible. Powerspan's Electro-Catalytic Oxidation, or ECO{reg_sign} process combines four pollution control devices into a single integrated system that can be installed after a power plant's particulate control device. Besides achieving major reductions in emissions of sulfur dioxide (SO{sub 2}), nitrogen oxides (NOx), fine particulate matter (PM2.5) and mercury (Hg), ECO produces a highly marketable fertilizer, which can help offset the operating costs of the process system. Powerspan has been operating a 50-MW ECO commercial demonstration unit (CDU) at FirstEnergy Corp.'s R.E. Burger Plant near Shadyside, Ohio, since February 2004. In addition to the CDU, a test loop has been constructed beside the CDU to demonstrate higher NOx removal rates and test various scrubber packing types and wet ESP configurations. Furthermore, Powerspan has developed the ECO{reg_sign}{sub 2} technology, a regenerative process that uses a proprietary solvent to capture CO{sub 2} from flue gas. The CO{sub 2} capture takes place after the capture of NOx, SO{sub 2}, mercury, and fine particulate matter. Once the CO{sub 2} is captured, the proprietary solution is regenerated to release CO{sub 2} in a form that is ready for geological storage or beneficial use. Pilot scale testing of ECO{sub 2} began in early 2009 at FirstEnergy's Burger Plant. The ECO{sub 2} pilot unit is designed to process a 1-MW flue gas stream and produce 20 tons of CO{sub 2} per day, achieving a 90% CO{sub 2} capture rate. The ECO{sub 2} pilot program provided the opportunity to confirm process design and cost estimates, and prepare for large

  1. Cross-Coupling Chemistry at Mononuclear and Dinuclear Nickel Complexes

    OpenAIRE

    Lin, Sibo; Agapie, Theodor

    2011-01-01

    Nickel catalysts have been developed for a wide range of C–C bond formation reactions. Reaction mechanisms proposed for these transformations generally involve catalytic intermediates based on mononickel species. These reactions are reviewed and the possibility of dinickel species active in C–C cross-coupling chemistry is discussed.

  2. A catalytic surface for amyloid fibril formation

    Energy Technology Data Exchange (ETDEWEB)

    Hammarstroem, P; Ali, M M; Mishra, R; Tengvall, P; Lundstroem, I [Department of Physics, Biology and Chemistry, Linkoeping University, SE-581 83 Linkoeping (Sweden); Svensson, S [Astra Zeneca R and D, SE-151 85 Soedertaelje (Sweden)], E-mail: ingemar@ifm.liu.se

    2008-03-15

    A hydrophobic surface incubated in a solution of protein molecules (insulin monomers) was made into a catalytic surface for amyloid fibril formation by repeatedly incubate, rinse and dry the surface. The present contribution describes how this unexpected transformation occurred and its relation to rapid fibrillation of insulin solutions in contact with the surface. A tentative model of the properties of the catalytic surface is given, corroborated by ellipsometric measurements of the thickness of the organic layer on the surface and by atomic force microscopy. The surfaces used were spontaneously oxidized silicon made hydrophobic through treatment in dichlorodimethylsilane.

  3. Thermal and catalytic pyrolysis of plastic waste

    Directory of Open Access Journals (Sweden)

    Débora Almeida

    2016-02-01

    Full Text Available Abstract The amount of plastic waste is growing every year and with that comes an environmental concern regarding this problem. Pyrolysis as a tertiary recycling process is presented as a solution. Pyrolysis can be thermal or catalytical and can be performed under different experimental conditions. These conditions affect the type and amount of product obtained. With the pyrolysis process, products can be obtained with high added value, such as fuel oils and feedstock for new products. Zeolites can be used as catalysts in catalytic pyrolysis and influence the final products obtained.

  4. Catalytic Enantioselective Functionalization of Unactivated Terminal Alkenes.

    Science.gov (United States)

    Coombs, John R; Morken, James P

    2016-02-01

    Terminal alkenes are readily available functional groups which appear in α-olefins produced by the chemical industry, and they appear in the products of many contemporary synthetic reactions. While the organic transformations that apply to alkenes are amongst the most studied reactions in all of chemical synthesis, the number of reactions that apply to nonactivated terminal alkenes in a catalytic enantioselective fashion is small in number. This Minireview highlights the cases where stereocontrol in catalytic reactions of 1-alkenes is high enough to be useful for asymmetric synthesis. PMID:26764019

  5. Catalytic gasification of oil-shales

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.; Avakyan, T. [I.M. Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation); Strizhakova, Yu. [Samara State Univ. (Russian Federation)

    2012-07-01

    Nowadays, the problem of complex usage of solid fossil fuels as raw materials for obtaining of motor fuels and chemical products is becoming increasingly important. A one of possible solutions of the problem is their gasification with further processing of gaseous and liquid products. In this work we have investigated the process of thermal and catalytic gasification of Baltic and Kashpir oil-shales. We have shown that, as compared with non-catalytic process, using of nickel catalyst in the reaction increases the yield of gas, as well as hydrogen content in it, and decreases the amount of liquid products. (orig.)

  6. Heterogeneous Catalytic Ozonization of Sulfosalicylic Acid

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    This paper describes the potential of heterogeneous catalytic ozonization of sulfo-salicylic acid (SSal). It was found that catalytic ozonization in the presence of Mn-Zr-O (a modified manganese dioxide supported on silica gel) had significantly enhanced the removal rate (72%) of total organic carbon (TOC) compared with that of ozonization alone (19%). The efficient removal rate of TOC was probably due to increasing the adsorption ability of catalyst and accelerating decomposition of ozone to produce more powerful oxidants than ozone.

  7. Tubular Coupling

    Science.gov (United States)

    Rosenbaum, Bernard J. (Inventor)

    2000-01-01

    A system for coupling a vascular overflow graft or cannula to a heart pump. A pump pipe outlet is provided with an external tapered surface which receives the end of a compressible connula. An annular compression ring with a tapered internal bore surface is arranged about the cannula with the tapered internal surface in a facing relationship to the external tapered surface. The angle of inclination of the tapered surfaces is converging such that the spacing between the tapered surfaces decreases from one end of the external tapered surface to the other end thereby providing a clamping action of the tapered surface on a cannula which increases as a function of the length of cannula segment between the tapered surfaces. The annular compression ring is disposed within a tubular locking nut which threadedly couples to the pump and provides a compression force for urging the annular ring onto the cannula between the tapered surfaces. The nut has a threaded connection to the pump body. The threaded coupling to the pump body provides a compression force for the annular ring. The annular ring has an annular enclosure space in which excess cannula material from the compression between the tapered surfaces to "bunch up" in the space and serve as an enlarged annular ring segment to assist holding the cannula in place. The clamped cannula provides a seamless joint connection to the pump pipe outlet where the clamping force is uniformly applied to the cannula because of self alignment of the tapered surfaces. The nut can be easily disconnected to replace the pump if necessary.

  8. Palladium-Catalyzed Heck Coupling Reaction of Aryl Bromides in Aqueous Media Using Tetrahydropyrimidinium Salts as Carbene Ligands

    Directory of Open Access Journals (Sweden)

    İsmail Özdemir

    2010-01-01

    Full Text Available An efficient and stereoselective catalytic system for the Heck cross coupling reaction using novel 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (1, LHX and Pd(OAc2 loading has been reported. The palladium complexes derived from the salts 1a-f prepared in situ exhibit good catalytic activity in the Heck coupling reaction of aryl bromides under mild conditions.

  9. Toward a catalytic site in DNA

    DEFF Research Database (Denmark)

    Jakobsen, Ulla; Rohr, Katja; Vogel, Stefan

    2007-01-01

    A number of functionalized polyaza crown ether building blocks have been incorporated into DNA-conjugates as catalytic Cu(2+) binding sites. The effect of the DNA-conjugate catalyst on the stereochemical outcome of a Cu(2+)-catalyzed Diels-Alder reaction will be presented....

  10. SELECTIVE CATALYTIC REDUCTION MERCURY FIELD SAMPLING PROJECT

    Science.gov (United States)

    A lack of data still exists as to the effect of selective catalytic reduction (SCR), selective noncatalytic reduction (SNCR), and flue gas conditioning on the speciation and removal of mercury (Hg) at power plants. This project investigates the impact that SCR, SNCR, and flue gas...

  11. Toward Facilitative Mentoring and Catalytic Interventions

    Science.gov (United States)

    Smith, Melissa K.; Lewis, Marilyn

    2015-01-01

    In TESOL teacher mentoring, giving advice can be conceptualized as a continuum, ranging from directive to facilitative feedback. The goal, over time, is to lead toward the facilitative end of the continuum and specifically to catalytic interventions that encourage self-reflection and autonomous learning. This study begins by examining research on…

  12. Catalytic reaction dynamics in inhomogeneous networks.

    Science.gov (United States)

    Watanabe, Akitomo; Yakubo, Kousuke

    2014-05-01

    Biochemical reactions in a cell can be modeled by a catalytic reaction network (CRN). It has been reported that catalytic chain reactions occur intermittently in the CRN with a homogeneous random-graph topology and its avalanche-size distribution obeys a power law with the exponent 4/3 [A. Awazu and K. Kaneko, Phys. Rev. E 80, 010902(R) (2009)]. This fact indicates that the catalytic reaction dynamics in homogeneous CRNs exhibits self-organized criticality (SOC). Structures of actual CRNs are, however, known to be highly inhomogeneous. We study the influence of various types of inhomogeneities found in real-world metabolic networks on the universality class of SOC. Our numerical results clarify that SOC keeps its universality class even for networks possessing structural inhomogeneities such as the scale-free property, community structures, and degree correlations. In contrast, if the CRN has inhomogeneous catalytic functionality, the universality class of SOC depends on how widely distributed the number of reaction paths catalyzed by a single chemical species is. PMID:25353843

  13. Novel Metal Nanomaterials and Their Catalytic Applications.

    Science.gov (United States)

    Wang, Jiaqing; Gu, Hongwei

    2015-01-01

    In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe₂O₃ nanowires and bimetallic Pt@Ir nanocomplexes; Pt-Au heterostructures, Au-Pt bimetallic nanocomplexes and Pt/Pd bimetallic nanodendrites; Au nanowires, CuO@Ag nanowires and a series of Pd nanocatalysts) and their new catalytic applications in our group, to establish heterogeneous catalytic system in "green" environments. Further study shows that these materials have a higher catalytic activity and selectivity than previously reported nanocrystal catalysts in organic reactions, or show a superior electro-catalytic activity for the oxidation of methanol. The whole process might have a great impact to resolve the energy crisis and the environmental crisis that were caused by traditional chemical engineering. Furthermore, we hope that this article will provide a reference point for the noble metal nanomaterials' development that leads to new opportunities in nanocatalysis. PMID:26393550

  14. Catalytic dehydrogenations of ethylbenzene to styrene

    NARCIS (Netherlands)

    Nederlof, C.

    2012-01-01

    This research work on the catalytic dehydrogenation of ethylbenzene (EB) to styrene (ST) had a primary goal of developing improved catalysts for dehydrogenation processes both in CO2 as well as with O2 that can compete with the conventional dehydrogenation process in steam. In order to achieve this

  15. Electrochemical Promotion of Catalytic Reactions Using

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Cleemann, Lars Nilausen;

    2007-01-01

    This paper presents the results of a study on electrochemical promotion (EP) of catalytic reactions using Pt/C/polybenzimidazole(H3PO4)/Pt/C fuel cell performed by the Energy and Materials Science Group (Technical University of Denmark) during the last 6 years[1-4]. The development of our...

  16. Shungite carbon catalytic effect on coal treatment

    Energy Technology Data Exchange (ETDEWEB)

    Grigorieva, E.N.; Rozhkova, N.N. [Russian Academy of Sciences, Moscow (Russian Federation). Institute for High Temperature

    1999-07-01

    The catalytic ability of shungite carbon in reactions of coal organic matter models appeared to be due to its fullerene structure only. Transition metal sulphides present in shungite carbon are not active in the conditions of coal treatment. Shungite carbon was shown to exhibit an acceleration of thermolysis of coal and organic matter models, mainly dehydrogenation. 5 refs., 1 tabs.

  17. Catalytic oxidation of industrial organic solvent vapors.

    Science.gov (United States)

    Tzortzatou, Katerina; Grigoropoulou, Eleni

    2010-01-01

    In the present study the catalytic oxidation of an industrial organic solvent consisting predominantly of C-9 to C-10 paraffins and napthtenics and derived from low aromatic white spirit on CuO and Pt catalysts was investigated at ambient pressure and temperatures between 330 and 770 K. Catalysts were prepared in the laboratory and compared to commercial ones. Characterization was based on x-ray diffraction (XRD) analysis, x-ray fluorescence (XRF) analysis, scanning electron microscope (SEM) analysis and nitrogen adsorption data. The commercial platinum catalyst was proved highly efficient in the oxidation of the commercial solvent, necessitating lower temperatures for total oxidation. Catalyst loading in active component is clearly not of primordial importance, since its dispersion and crystallinity as well as the presence of other metallic compounds influence also the catalytic activity. In the case of copper catalysts studied, the different support (alumina) characteristics also would contribute to the difference in catalytic activity. Finally, the power law kinetics may successfully be used in order to explain the catalytic oxidation data of the organic solvent, where its constituents are modeled as a single carbon-containing compound. PMID:20390900

  18. Catalytic Converters Maintain Air Quality in Mines

    Science.gov (United States)

    2014-01-01

    At Langley Research Center, engineers developed a tin-oxide based washcoat to prevent oxygen buildup in carbon dioxide lasers used to detect wind shears. Airflow Catalyst Systems Inc. of Rochester, New York, licensed the technology and then adapted the washcoat for use as a catalytic converter to treat the exhaust from diesel mining equipment.

  19. Novel Metal Nanomaterials and Their Catalytic Applications

    Directory of Open Access Journals (Sweden)

    Jiaqing Wang

    2015-09-01

    Full Text Available In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe2O3 nanowires and bimetallic Pt@Ir nanocomplexes; Pt-Au heterostructures, Au-Pt bimetallic nanocomplexes and Pt/Pd bimetallic nanodendrites; Au nanowires, CuO@Ag nanowires and a series of Pd nanocatalysts and their new catalytic applications in our group, to establish heterogeneous catalytic system in “green” environments. Further study shows that these materials have a higher catalytic activity and selectivity than previously reported nanocrystal catalysts in organic reactions, or show a superior electro-catalytic activity for the oxidation of methanol. The whole process might have a great impact to resolve the energy crisis and the environmental crisis that were caused by traditional chemical engineering. Furthermore, we hope that this article will provide a reference point for the noble metal nanomaterials’ development that leads to new opportunities in nanocatalysis.

  20. Performance characterization of a hydrogen catalytic heater.

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Terry Alan; Kanouff, Michael P.

    2010-04-01

    This report describes the performance of a high efficiency, compact heater that uses the catalytic oxidation of hydrogen to provide heat to the GM Hydrogen Storage Demonstration System. The heater was designed to transfer up to 30 kW of heat from the catalytic reaction to a circulating heat transfer fluid. The fluid then transfers the heat to one or more of the four hydrogen storage modules that make up the Demonstration System to drive off the chemically bound hydrogen. The heater consists of three main parts: (1) the reactor, (2) the gas heat recuperator, and (3) oil and gas flow distribution manifolds. The reactor and recuperator are integrated, compact, finned-plate heat exchangers to maximize heat transfer efficiency and minimize mass and volume. Detailed, three-dimensional, multi-physics computational models were used to design and optimize the system. At full power the heater was able to catalytically combust a 10% hydrogen/air mixture flowing at over 80 cubic feet per minute and transfer 30 kW of heat to a 30 gallon per minute flow of oil over a temperature range from 100 C to 220 C. The total efficiency of the catalytic heater, defined as the heat transferred to the oil divided by the inlet hydrogen chemical energy, was characterized and methods for improvement were investigated.

  1. Exact Results for Kinetics of Catalytic Reactions

    OpenAIRE

    Frachebourg, L.; Krapivsky, P. L.

    1995-01-01

    The kinetics of an irreversible catalytic reaction on substrate of arbitrary dimension is examined. In the limit of infinitesimal reaction rate (reaction-controlled limit), we solve the dimer-dimer surface reaction model (or voter model) exactly in arbitrary dimension $D$. The density of reactive interfaces is found to exhibit a power law decay for $D

  2. Catalytic asymmetric synthesis of mycocerosic acid

    NARCIS (Netherlands)

    ter Horst, B.; Feringa, B.L.; J. Minnaard, A.

    2007-01-01

    The first catalytic asymmetric total synthesis of mycocerosic acid was achieved via the application of iterative enantioselective 1,4-addition reactions and allows for the efficient construction of 1,3-polymethyl arrays with full stereocontrol; further exemplified by the synthesis of tetramethyl-dec

  3. Electrochemical promotion of sulfur dioxide catalytic oxidation

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bandur, Viktor; Cappeln, Frederik Vilhelm;

    2000-01-01

    The effect of electrochemical polarization on the catalytic SO2 oxidation in the molten V2O5-K2S2O7 system has been studied using a gold working electrode in the temperature range 400-460 degrees C. A similar experiment has been performed with the industrial catalyst VK-58. The aim of the present...

  4. Catalytic site interactions in yeast OMP synthase

    DEFF Research Database (Denmark)

    Hansen, Michael Riis; Barr, Eric W.; Jensen, Kaj Frank; Willemoës, Martin; Grubmeyer, Charles; Winther, Jakob R.

    2014-01-01

    45 (2006) 5330-5342]. This behavior was investigated in the yeast enzyme by mutations in the conserved catalytic loop and 5-phosphoribosyl-1-diphosphate (PRPP) binding motif. Although the reaction is mechanistically sequential, the wild-type (WT) enzyme shows parallel lines in double reciprocal...

  5. Catalytic treatment of diesel engines, NOx emissions

    International Nuclear Information System (INIS)

    Some aspects of the operation of diesel engines are revised together with the pollutant emissions they produce, as well as the available catalytic technologies for the treatment of diesel emissions. Furthermore the performance of a catalyst developed in the environmental catalysis group for NOx reduction using synthetic gas mixtures simulating the emissions from diesel engines is presented

  6. Dual-Bed Catalytic System for Direct Conversion of Methane to Liquid Hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    N.A.S.Amin; Sriraj Ammasi

    2006-01-01

    A dual-bed catalytic system is proposed for the direct conversion of methane to liquid hydrocarbons. In this system, methane is converted in the first stage to oxidative coupling of methane (OCM) products by selective catalytic oxidation with oxygen over La-supported MgO catalyst. The second bed, comprising of the HZSM-5 zeolite catalyst, is used for the oligomerization of OCM light hydrocarbon products to liquid hydrocarbons. The effects of temperature (650-800 ℃), methane to oxygen ratio (4-10), and SiO2/Al2O3 ratio of the HZSM-5 zeolite catalyst on the process are studied. At higher reaction temperatures, there is considerable dealumination of HZSM-5, and thus its catalytic performance is reduced. The acidity of HZSM-5 in the second bed is responsible for the oligomerization reaction that leads to the formation of liquid hydrocarbons. The activities of the oligomerization sites were unequivocally affected by the SiO2/Al2O3 ratio. The relation between the acidity and the activity of HZSM-5 is studied by means of TPD-NH3 techniques. The rise in oxygen concentration is not beneficial for the C5+ selectivity, where the combustion reaction of intermediate hydrocarbon products that leads to the formation of carbon oxide (CO+CO2) products is more dominant than the oligomerization reaction. The dual-bed catalytic system is highly potential for directly converting methane to liquid fuels.

  7. High-pressure catalytic reactions over single-crystal metal surfaces

    Science.gov (United States)

    Rodriguez, JoséA.; Wayne Goodman, D.

    1991-11-01

    Studies dealing with high-pressure catalytic reactions over single-crystal surfaces are reviewed. The coupling of an apparatus for the measurement of reaction kinetics at elevated pressures with an ultrahigh vacuum system for surface analysis allows detailed study of structure sensitivity, the effects of promoters and inhibitors on catalytic activity, and, in certain cases, identification of reaction intermediates by post-reaction surface analysis. Examples are provided which demonstrate the relevance of single-crystal studies for modeling the behaviour of high-surface-area supported catalysts. Studies of CO methanation and CO oxidation over single-crystal surfaces provide convincing evidence that these reactions are structure insensitive. For structure-sensitive reactions (ammonia synthesis, alkane hydrogenolysis, alkane isomerization, water-gas shift reaction, etc.) model single-crystal studies allow correlations to be established between surface structure and catalytic activity. The effects of both electronegative (S and P) and electropositive (alkali metals) impurities upon the catalytic activity of metal single crystals for ammonia synthesis, CO methanation, alkane hydrogenolysis, ethylene epoxidation and water-gas shift are discussed. The roles of "ensemble" and "ligand" effects in bimetallic catalysts are examined in light of data obtained using surfaces prepared by vapor-depositing one metal onto a crystal face of a dissimilar metal.

  8. Coupling of α,α-difluoro-substituted organozinc reagents with 1-bromoalkynes.

    Science.gov (United States)

    Zemtsov, Artem A; Volodin, Alexander D; Levin, Vitalij V; Struchkova, Marina I; Dilman, Alexander D

    2015-01-01

    α,α-Difluoro-substituted organozinc reagents generated from conventional organozinc compounds and difluorocarbene couple with 1-bromoalkynes affording gem-difluorinated alkynes. The cross-coupling proceeds in the presence of catalytic amounts of copper iodide in dimethylformamide under ligand-free conditions. PMID:26664635

  9. Final Technical Report [Development of Catalytic Alkylation and Fluoroalkylation Methods

    Energy Technology Data Exchange (ETDEWEB)

    Vicic, David A.

    2014-05-01

    In the early stages of this DOE-funded research project, we sought to prepare and study a well-defined nickel-alkyl complex containing tridentate nitrogen donor ligands. We found that reaction of (TMEDA)NiMe2 (1) with terpyridine ligand cleanly led to the formation of (terpyridyl)NiMe (2), which we also determined to be an active alkylation catalyst. The thermal stability of 2 was unlike that seen for any of the active pybox ligands, and enabled a number of key studies on alkyl transfer reactions to be performed, providing new insights into the mechanism of nickel-mediated alkyl-alkyl cross-coupling reactions. In addition to the mechanistic studies, we showed that the terpyridyl nickel compounds can catalytically cross-couple alkyl iodides in yields up to 98% and bromides in yields up to 46 %. The yields for the bromides can be increased up to 67 % when the new palladium catalyst [(tpy’)Pd-Ph]I is used. The best route to the targeted [(tpy)NiBr] (1) was found to involve the comproportionation reaction of [(dme)NiBr{sub 2}] and [Ni(COD){sub 2}] in the presence of two equivalents of terpyridine. This reaction was driven to high yields of product formation (72 % isolated) by the precipitation of 1 from THF solvent.

  10. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    FENG; XiaoMing

    2001-01-01

    Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.  ……

  11. Asymmetric Catalytic Reactions Catalyzed by Chiral Titanium Complexes

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Chiral titanium complexes is very importance catalyst to asymmetric catalytic reactions. A series of catalytic systems based on titanium-chiral ligands complexes has been reported. This presentation will discuss some of our recent progress on asymmetric catalytic reactions catalyzed by chiral titanium complexes.

  12. Catalytic Activity of Metal and Metal-Oxide Catalysts in Oxidative Coupling of CH4 with CO2 under Pulse Corona Plasma%等离子体条件下金属和金属氧化物对甲烷氧化反应的催化活性

    Institute of Scientific and Technical Information of China (English)

    张秀玲; 朱爱民; 刘中凡; 李学慧; 宫为民

    2003-01-01

    @@ The uses of methane, the major component in natural gas, have been investigated by many research groups throughout the world. A number of catalysts, single or binary, have been proposed for the oxidative coupling of CH4 with CO2 as the oxidant[1~6]. Binary metal-oxide catalysts, such as La2O3-ZnO and CaO-ZnO, showed higher C2 hydrocarbon selectivity (>80%) with low CH4 conversion (<6%) at high temperatures (750~850 ℃)[7~9].

  13. Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

    Energy Technology Data Exchange (ETDEWEB)

    Klier, Kamil; Herman, Richard G

    2005-11-30

    This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Brnsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. The latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with

  14. Cross-coupling of propargylated arabinogalactan with 2-bromothiophene.

    Science.gov (United States)

    Parshina, Lidiya N; Grishchenko, Lyudmila A; Larina, Lyudmila I; Novikova, Lyubov N; Trofimov, Boris A

    2016-10-01

    Novel pharmacologically prospective derivatives of arabinogalactan (a polysaccharide from larch wood) containing acetylenic and thiophene moieties have been obtained in up to 90% yield by cross-coupling of propargylic ethers of arabinogalactan with 2-bromothiophene. The reaction proceeds in the presence of the catalytic system Pd(Ph3P)4/CuBr/LiBr and piperidine in DMSO at 80-85°С. An advantageous feature of the synthesis is that it requires 5-25 times lesser catalytic loading than in common Sonogashira protocols thus making the reaction particularly beneficial to synthesize pharmaceutically-oriented polysaccharides. PMID:27312616

  15. Reforming of methane in tubes with a catalytic active wall

    International Nuclear Information System (INIS)

    The heterogeneous steam reforming process in tubes with catalytic active inner surface is studied. The purpose of this ivestigation is to find a method of predicting the reaction rate of the catalytic conversion of methane by steam. The dependency of the reaction rate upon the temperature, pressure, gas composition, Reynolds number, geometrical sizes of tubes and catalytic behaviour of the catalytic active inner wall of these tubes has been examined. It was found that the reaction rate mainly depends on the temperature. The reaction rate is limited by the catalytic behaviour and the heat resisting properties of the materials used. (author)

  16. Physico-chemical and catalytic properties of poly-oxo-metalate surfactants

    International Nuclear Information System (INIS)

    Hydrophilic poly-oxo-metalates (POM) are made surface active by coupling them to cationic amphiphilic moieties to form catalytic surfactants (catasurfs). In controlled conditions this procedure results in the formation of water and organic solvent insoluble nanoparticles that show the ability to stabilize water-in-oil emulsions, the so-called Pickering emulsions. Formation of monomolecular catasurf films, and their deposition on solid substrate by the Langmuir-Blodgett technique, is also investigated. It is shown that the catalytic activity of POM is maintained in the solid state, i.e. as nanoparticle or 2D nano-crystallite in the deposited film. The supramolecular structure of catasurfs is explored by means of physical characterisation techniques such as small angle X-ray/neutron/light scattering, electron diffraction and X-ray reflectivity. (authors)

  17. Synthetic and Thermodynamic Investigations of Ancillary Ligand Influence on Catalytic Organometallic Systems. Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Nolan, Steven

    2003-03-20

    During the grant period we have been involved in synthesizing and experimentally determining solution enthalpy values associated with partially fluorinated ligands. This has lead to the publication of manuscripts dealing with synthetic, calorimetric and catalytic behavior of partially fluorinated ligands. The collaboration with Los Alamos researchers has lead to the publication of catalytic results in sc CO{sub 2} which have proven very interesting. Furthermore, we have also examined ligands that behave as phosphine mimics. The N-heterocyclic carbenes have been explored as alternatives for tertiary phosphines and have resulted in the design and construction of efficient palladium and nickel system capable of performing C-C and C-N cross coupling reactions. The initial studies in this areas were made possible by exploratory work conducted under the DOE/EPSCoR grant.

  18. Catalytic C-H bond functionalisation chemistry: the case for quasi-heterogeneous catalysis.

    Science.gov (United States)

    Reay, Alan J; Fairlamb, Ian J S

    2015-11-25

    This feature article examines the potential of heterogeneous Pd species to mediate catalytic C-H bond functionalisation processes employing suitable substrates (e.g. aromatic/heteroaromatic compounds). A focus is placed on the reactivity of supported and non-supported Pd nanoparticle (PdNPs) catalysts, in addition to the re-appropriation of well-established heterogeneous Pd catalysts such as Pd/C. Where possible, reasonable comparisons are made between PdNPs and traditional 'homogeneous' Pd precatalyst sources (which form PdNPs). The involvement of higher order Pd species in traditional cross-coupling processes, such as Mizoroki-Heck, Sonogashira and Suzuki-Miyaura reactions, allows the exemplification of potential future topics for study in the area of catalytic C-H bond functionalisation processes. PMID:26439875

  19. H2CAP - Hydrogen assisted catalytic biomass pyrolysis for green fuels

    DEFF Research Database (Denmark)

    Arndal, Trine Marie Hartmann; Høj, Martin; Jensen, Peter Arendt;

    2014-01-01

    Pyrolysis of biomass produces a high yield of condensable oil at moderate temperature and low pressure.This bio-oil has adverse properties such as high oxygen and water contents, high acidity and immiscibility with fossil hydrocarbons. Catalytic hydrodeoxygenation (HDO) is a promising technology...... that can be used to upgrade the crude bio-oil to fuel-grade oil. The development of the HDO process is challenged by rapid catalyst deactivation, instability of the pyrolysis oil, poorly investigated reaction conditions and a high complexity and variability of the input oil composition. However......, continuous catalytic hydropyrolysis coupled with downstream HDO of the pyrolysis vapors before condensation shows promise (Figure 1). A bench scale experimental setup will be constructed for the continuous conversion of solid biomass (100g /h) to low oxygen, fuel-grade bio-oil. The aim is to provide a proof...

  20. Imaging Isolated Gold Atom Catalytic Sites in Zeolite NaY

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Jing; Aydin, C.; Browning, Nigel D.; Gates, Bruce C.

    2012-06-11

    Gold, the most stable metallic element, attracted wide attention as a catalyst only after the discovery that gold nanoclusters on oxide supports are highly active and selective for reactions including numerous oxidation,[1–8] hydrogenation,[9–11] hydroamination,[12, 13] ring expansion,[14, 15] and coupling[16, 17] reactions. The catalytic properties of supported gold strongly dependent on the gold–support interactions and the size of the active species, which must be small—typically clusters with diameters of the order of 1 nm.[18–20] Frequent discoveries of new gold-catalyzed reactions are leading the science; understanding has been slow to emerge.[21] Major challenges are to identify the catalytically active species and to characterize gold–support interactions.

  1. Chiral linker-bridged bis-N-heterocyclic carbenes: design, synthesis, palladium complexes, and catalytic properties.

    Science.gov (United States)

    Zhang, Dao; He, Yu; Tang, Junkai

    2016-08-01

    A series of chiral bis(benzimidazolium) salts 10-19 with (1R,2R)-cyclohexene, (1R,2R)-diphenylethylene and (aR)-binaphthylene linkers have been designed and synthesized in 30-94% yield. Ten chiral bis(NHC) palladium complexes 20-28 have been synthesized and characterized by NMR, HRMS, elemental analysis and further confirmed by X-ray single crystal analysis. These bis(NHC)-Pd complexes showed obviously different catalytic properties in the asymmetric Suzuki-Miyaura coupling reactions. The (1R,2R)-cyclohexene-bridged bis(NHC)-Pd complex, (R,R)-23, achieved the highest yield of 90%, while complex (aR)-28, with a binaphthylene linker, showed the best enantioselectivity of 60 ee%. The structural analysis of these complexes suggested that such difference of catalytic performance has a close relationship with their coordination surroundings around metal centres. PMID:27230553

  2. Porous manganese oxide synthesized through organic-electrolyte templates and their catalytic applications

    International Nuclear Information System (INIS)

    We report a facile approach to the preparation of porous manganese oxide materials by the organic-electrolyte templates based on strategy. The final products are thoroughly characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), field-emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-optical emission spectroscopy (ICP-OES), and Brunauer-Emmett-Teller (BET) techniques. The results reveal that porosity (pore size and distribution, surface area) of these manganese oxides has strong relationship with the templates used, which implies a simple way to obtain a series of porous materials. By comparing the catalytic effects of these manganese oxides in oxidation of indene and benzyl alcohol, we find that the pore size and distribution are also crucial to the catalytic properties of these porous materials.

  3. Engineering a hyper-catalytic enzyme by photo-activated conformation modulation

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, Pratul K [ORNL

    2012-01-01

    Enzyme engineering for improved catalysis has wide implications. We describe a novel chemical modification of Candida antarctica lipase B that allows modulation of the enzyme conformation to promote catalysis. Computational modeling was used to identify dynamical enzyme regions that impact the catalytic mechanism. Surface loop regions located distal to active site but showing dynamical coupling to the reaction were connected by a chemical bridge between Lys136 and Pro192, containing a derivative of azobenzene. The conformational modulation of the enzyme was achieved using two sources of light that alternated the azobenzene moiety in cis and trans conformations. Computational model predicted that mechanical energy from the conformational fluctuations facilitate the reaction in the active-site. The results were consistent with predictions as the activity of the engineered enzyme was found to be enhanced with photoactivation. Preliminary estimations indicate that the engineered enzyme achieved 8-52 fold better catalytic activity than the unmodulated enzyme.

  4. Analysis of hapten binding and catalytic determinants in a family of catalytic antibodies.

    Science.gov (United States)

    Ulrich, H D; Schultz, P G

    1998-01-01

    We report here the cloning and kinetic analysis of a family of catalytic antibodies raised against a common transition state (TS) analog hapten, which accelerate a unimolecular oxy-Cope rearrangement. Sequence analysis revealed close homologies among the heavy chains of the catalytically active members of this set of antibodies, which derive mainly from a single germline gene, whereas the light chains can be traced back to several different, but related germline genes. The requirements for hapten binding and catalytic activity were determined by the construction of hybrid antibodies. Characterization of the latter antibodies again indicates a strong conservation of binding site structure among the catalytically active clones. The heavy chain was found to be the determining factor for catalytic efficiency, while the light chain exerted a smaller modulating effect that depended on light chain gene usage and somatic mutations. Within the heavy chain, the catalytic activity of a clone, but not hapten binding affinity, depended on the sequence of the third complementarity determining region (CDR). No correlation between high affinity for the hapten and high rate enhancement was found in the oxy-Cope system, a result that stands in contrast to the expectations from transition state theory. A mechanistic explanation for this observation is provided based on the three-dimensional crystal structure of the most active antibody, AZ-28, in complex with the hapten. This study demonstrates the utility of catalytic antibodies in examining the relationship between binding energy and catalysis in the evolution of biological catalysis, as well as expanding our understanding of the molecular basis of an immune response. PMID:9451442

  5. Structure, microstructure, and size dependent catalytic properties of nanostructured ruthenium dioxide

    International Nuclear Information System (INIS)

    Nanostructured powders of ruthenium dioxide RuO2 were synthesized via a sol gel route involving acidic solutions with pH varying between 0.4 and 4.5. The RuO2 nanopowders were characterized by X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM). Rietveld refinement of mean crystal structure was performed on RuO2 nanopowders and crystallized standard RuO2 sample. Crystallite sizes measured from X-ray diffraction profiles and TEM analysis varied in the range of 4-10 nm, with a minimum of crystallite dimension for pH=1.5. A good agreement between crystallite sizes calculated from Williamson Hall approach of X-ray data and from direct TEM observations was obtained. The tetragonal crystal cell parameter (a) and cell volumes of nanostructured samples were characterized by values greater than the values of standard RuO2 sample. In addition, the [Ru-O6] oxygen octahedrons of rutile structure also depended on crystal size. Catalytic conversion of methane by these RuO2 nanostructured catalysts was studied as a function of pH, catalytic interaction time, air methane composition, and catalysis temperature, by the way of Fourier transform infrared (FTIR) spectroscopy coupled to homemade catalytic cell. The catalytic efficiency defined as FTIR absorption band intensities I(CO2) was maximum for sample prepared at pH=1.5, and mainly correlated to crystallite dimensions. No significant catalytic effect was observed from sintered RuO2 samples. - Graphical abstract: Nanosized crystals of RuO2 prepared by sol gel route, at pH=0.4 and 1.5. Mean size values , respectively, 10 and 8 nm

  6. Structure, microstructure, and size dependent catalytic properties of nanostructured ruthenium dioxide

    Science.gov (United States)

    Nowakowski, Pawel; Dallas, Jean-Pierre; Villain, Sylvie; Kopia, Agnieszka; Gavarri, Jean-Raymond

    2008-05-01

    Nanostructured powders of ruthenium dioxide RuO 2 were synthesized via a sol gel route involving acidic solutions with pH varying between 0.4 and 4.5. The RuO 2 nanopowders were characterized by X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM). Rietveld refinement of mean crystal structure was performed on RuO 2 nanopowders and crystallized standard RuO 2 sample. Crystallite sizes measured from X-ray diffraction profiles and TEM analysis varied in the range of 4-10 nm, with a minimum of crystallite dimension for pH=1.5. A good agreement between crystallite sizes calculated from Williamson Hall approach of X-ray data and from direct TEM observations was obtained. The tetragonal crystal cell parameter (a) and cell volumes of nanostructured samples were characterized by values greater than the values of standard RuO 2 sample. In addition, the [Ru-O 6] oxygen octahedrons of rutile structure also depended on crystal size. Catalytic conversion of methane by these RuO 2 nanostructured catalysts was studied as a function of pH, catalytic interaction time, air methane composition, and catalysis temperature, by the way of Fourier transform infrared (FTIR) spectroscopy coupled to homemade catalytic cell. The catalytic efficiency defined as FTIR absorption band intensities I(CO 2) was maximum for sample prepared at pH=1.5, and mainly correlated to crystallite dimensions. No significant catalytic effect was observed from sintered RuO 2 samples.

  7. Janus droplet as a catalytic micromotor

    CERN Document Server

    Shklyaev, Sergey

    2015-01-01

    Self-propulsion of a Janus droplet in a solution of surfactant, which reacts on a half of a drop surface, is studied theoretically. The droplet acts as a catalytic motor creating a concentration gradient, which generates its surface-tension-driven motion; the self-propulsion speed is rather high, $60\\; {\\rm \\mu m/s}$ and more. This catalytic motor has several advantages over other micromotors: simple manufacturing, easily attained neutral buoyancy. In contrast to a single-fluid droplet, which demonstrates a self-propulsion as a result of symmetry breaking instability, for Janus one no stability threshold exists; hence, the droplet radius can be scaled down to micrometers. The paper was finalized and submitted by Denis S. Goldobin after Sergey Sklyaev had sadly passed away on June 2, 2014.

  8. From Catalytic Reaction Networks to Protocells

    Science.gov (United States)

    Kaneko, Kunihiko

    2013-12-01

    In spite of recent advances, there still remains a large gape between a set of chemical reactions and a biological cell. Here we discuss several theoretical efforts to fill in the gap. The topics cover (i) slow relaxation to equilibrium due to glassy behavior in catalytic reaction networks (ii) consistency between molecule replication and cell growth, as well as energy metabolism (iii) control of a system by minority molecules in mutually catalytic system, which work as a carrier of genetic information, and leading to evolvability (iv) generation of a compartmentalized structure as a cluster of molecules centered around the minority molecule, and division of the cluster accompanied by the replication of minority molecule (v) sequential, logical process over several states from concurrent reaction dynamics, by taking advantage of discreteness in molecule number.

  9. Catalytic extraction processing of contaminated scrap metal

    International Nuclear Information System (INIS)

    Molten Metal Technology was awarded a contract to demonstrate the applicability of the Catalytic Extraction Process, a proprietary process that could be applied to US DOE's inventory of low level mixed waste. This paper is a description of that technology, and included within this document are discussions of: (1) Program objectives, (2) Overall technology review, (3) Organic feed conversion to synthetic gas, (4) Metal, halogen, and transuranic recovery, (5) Demonstrations, (6) Design of the prototype facility, and (7) Results

  10. Thermal and catalytic pyrolysis of plastic waste

    OpenAIRE

    Débora Almeida; Maria de Fátima Marques

    2016-01-01

    Abstract The amount of plastic waste is growing every year and with that comes an environmental concern regarding this problem. Pyrolysis as a tertiary recycling process is presented as a solution. Pyrolysis can be thermal or catalytical and can be performed under different experimental conditions. These conditions affect the type and amount of product obtained. With the pyrolysis process, products can be obtained with high added value, such as fuel oils and feedstock for new products. Zeolit...

  11. Materials for High-Temperature Catalytic Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Ersson, Anders

    2003-04-01

    Catalytic combustion is an environmentally friendly technique to combust fuels in e.g. gas turbines. Introducing a catalyst into the combustion chamber of a gas turbine allows combustion outside the normal flammability limits. Hence, the adiabatic flame temperature may be lowered below the threshold temperature for thermal NO{sub X} formation while maintaining a stable combustion. However, several challenges are connected to the application of catalytic combustion in gas turbines. The first part of this thesis reviews the use of catalytic combustion in gas turbines. The influence of the fuel has been studied and compared over different catalyst materials. The material section is divided into two parts. The first concerns bimetallic palladium catalysts. These catalysts showed a more stable activity compared to their pure palladium counterparts for methane combustion. This was verified both by using an annular reactor at ambient pressure and a pilot-scale reactor at elevated pressures and flows closely resembling the ones found in a gas turbine combustor. The second part concerns high-temperature materials, which may be used either as active or washcoat materials. A novel group of materials for catalysis, i.e. garnets, has been synthesised and tested in combustion of methane, a low-heating value gas and diesel fuel. The garnets showed some interesting abilities especially for combustion of low-heating value, LHV, gas. Two other materials were also studied, i.e. spinels and hexa aluminates, both showed very promising thermal stability and the substituted hexa aluminates also showed a good catalytic activity. Finally, deactivation of the catalyst materials was studied. In this part the sulphur poisoning of palladium, platinum and the above-mentioned complex metal oxides has been studied for combustion of a LHV gas. Platinum and surprisingly the garnet were least deactivated. Palladium was severely affected for methane combustion while the other washcoat materials were

  12. Materials for High-Temperature Catalytic Combustion

    OpenAIRE

    Ersson, Anders

    2003-01-01

    Catalytic combustion is an environmentally friendlytechnique to combust fuels in e.g. gas turbines. Introducing acatalyst into the combustion chamber of a gas turbine allowscombustion outside the normal flammability limits. Hence, theadiabatic flame temperature may be lowered below the thresholdtemperature for thermal NOXformation while maintaining a stable combustion.However, several challenges are connected to the application ofcatalytic combustion in gas turbines. The first part of thisthe...

  13. Catalytic fast pyrolysis of lignocellulosic biomass

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Changjun; Wang, Huamin; Karim, Ayman M.; Sun, Junming; Wang, Yong

    2014-11-21

    Increasing energy demand, especially in the transportation sector, and soaring CO2 emissions necessitate the exploitation of renewable sources of energy. Despite the large variety of new energy Q3 carriers, liquid hydrocarbon still appears to be the most attractive and feasible form of transportation fuel taking into account the energy density, stability and existing infrastructure. Biomass is an abundant, renewable source of energy; however, utilizing it in a cost-effective way is still a substantial challenge. Lignocellulose is composed of three major biopolymers, namely cellulose, hemicellulose and lignin. Fast pyrolysis of biomass is recognized as an efficient and feasible process to selectively convert lignocellulose into a liquid fuel—bio-oil. However bio-oil from fast pyrolysis contains a large amount of oxygen, distributed in hundreds of oxygenates. These oxygenates are the cause of many negative properties, such as low heating values, high corrosiveness, high viscosity, and instability; they also greatly Q4 limit the application of bio-oil particularly as transportation fuel. Hydrocarbons derived from biomass are most attractive because of their high energy density and compatibility with the existing infrastructure. Thus, converting lignocellulose into transportation fuels via catalytic fast pyrolysis has attracted much attention. Many studies related to catalytic fast pyrolysis of biomass have been published. The main challenge of this process is the development of active and stable catalysts that can deal with a large variety of decomposition intermediates from lignocellulose. This review starts with the current understanding of the chemistry in fast pyrolysis of lignocellulose and focuses on the development of catalysts in catalytic fast pyrolysis. Recent progress in the experimental studies on catalytic fast pyrolysis of biomass is also summarized with the emphasis on bio-oil yields and quality.

  14. Computer Aided Enzyme Design and Catalytic Concepts

    OpenAIRE

    Frushicheva, Maria P.; Mills, Matthew J. L.; Schopf, Patrick; Singh, Manoj K.; Warshel, Arieh

    2014-01-01

    Gaining a deeper understanding of enzyme catalysis is of great practical and fundamental importance. Over the years it has become clear that despite advances made in experimental mutational studies, a quantitative understanding of enzyme catalysis will not be possible without the use of computer modeling approaches. While we believe that electrostatic preorganization is by far the most important catalytic factor, convincing the wider scientific community of this may require the demonstration ...

  15. Ubiquitous "glassy" relaxation in catalytic reaction networks

    OpenAIRE

    Awazu, Akinori; Kaneko, Kunihiko

    2009-01-01

    Study of reversible catalytic reaction networks is important not only as an issue for chemical thermodynamics but also for protocells. From extensive numerical simulations and theoretical analysis, slow relaxation dynamics to sustain nonequlibrium states are commonly observed. These dynamics show two types of salient behaviors that are reminiscent of glassy behavior: slow relaxation along with the logarithmic time dependence of the correlation function and the emergence of plateaus in the rel...

  16. Probing catalytic rate enhancement during intramembrane proteolysis.

    Science.gov (United States)

    Arutyunova, Elena; Smithers, Cameron C; Corradi, Valentina; Espiritu, Adam C; Young, Howard S; Tieleman, D Peter; Lemieux, M Joanne

    2016-09-01

    Rhomboids are ubiquitous intramembrane serine proteases involved in various signaling pathways. While the high-resolution structures of the Escherichia coli rhomboid GlpG with various inhibitors revealed an active site comprised of a serine-histidine dyad and an extensive oxyanion hole, the molecular details of rhomboid catalysis were unclear because substrates are unknown for most of the family members. Here we used the only known physiological pair of AarA rhomboid with its psTatA substrate to decipher the contribution of catalytically important residues to the reaction rate enhancement. An MD-refined homology model of AarA was used to identify residues important for catalysis. We demonstrated that the AarA active site geometry is strict and intolerant to alterations. We probed the roles of H83 and N87 oxyanion hole residues and determined that substitution of H83 either abolished AarA activity or reduced the transition state stabilization energy (ΔΔG‡) by 3.1 kcal/mol; substitution of N87 decreased ΔΔG‡ by 1.6-3.9 kcal/mol. Substitution M154, a residue conserved in most rhomboids that stabilizes the catalytic general base, to tyrosine, provided insight into the mechanism of nucleophile generation for the catalytic dyad. This study provides a quantitative evaluation of the role of several residues important for hydrolytic efficiency and oxyanion stabilization during intramembrane proteolysis. PMID:27071148

  17. Catalytic pyrolysis of olive mill wastewater sludge

    Science.gov (United States)

    Abdellaoui, Hamza

    From 2008 to 2013, an average of 2,821.4 kilotons/year of olive oil were produced around the world. The waste product of the olive mill industry consists of solid residue (pomace) and wastewater (OMW). Annually, around 30 million m3 of OMW are produced in the Mediterranean area, 700,000 m3 year?1 in Tunisia alone. OMW is an aqueous effluent characterized by an offensive smell and high organic matter content, including high molecular weight phenolic compounds and long-chain fatty acids. These compounds are highly toxic to micro-organisms and plants, which makes the OMW a serious threat to the environment if not managed properly. The OMW is disposed of in open air evaporation ponds. After evaporation of most of the water, OMWS is left in the bottom of the ponds. In this thesis, the effort has been made to evaluate the catalytic pyrolysis process as a technology to valorize the OMWS. The first section of this research showed that 41.12 wt. % of the OMWS is mostly lipids, which are a good source of energy. The second section proved that catalytic pyrolysis of the OMWS over red mud and HZSM-5 can produce green diesel, and 450 °C is the optimal reaction temperature to maximize the organic yields. The last section revealed that the HSF was behind the good fuel-like properties of the OMWS catalytic oils, whereas the SR hindered the bio-oil yields and quality.

  18. Modeling the Complete Catalytic Cycle of Aspartoacylase.

    Science.gov (United States)

    Kots, Ekaterina D; Khrenova, Maria G; Lushchekina, Sofya V; Varfolomeev, Sergei D; Grigorenko, Bella L; Nemukhin, Alexander V

    2016-05-12

    The complete catalytic cycle of aspartoacylase (ASPA), a zinc-dependent enzyme responsible for cleavage of N-acetyl-l-aspartate, is characterized by the methods of molecular modeling. The reaction energy profile connecting the enzyme-substrate (ES) and the enzyme-product (EP) complexes is constructed by the quantum mechanics/molecular mechanics (QM/MM) method assisted by the molecular dynamics (MD) simulations with the QM/MM potentials. Starting from the crystal structure of ASPA complexed with the intermediate analogue, the minimum-energy geometry configurations and the corresponding transition states are located. The stages of substrate binding to the enzyme active site and release of the products are modeled by MD calculations with the replica-exchange umbrella sampling technique. It is shown that the first reaction steps, nucleophilic attack of a zinc-bound nucleophilic water molecule at the carbonyl carbon and the amide bond cleavage, are consistent with the glutamate-assisted mechanism hypothesized for the zinc-dependent hydrolases. The stages of formation of the products, acetate and l-aspartate, and regeneration of the enzyme are characterized for the first time. The constructed free energy diagram from the reactants to the products suggests that the enzyme regeneration, but not the nucleophilic attack of the catalytic water molecule, corresponds to the rate-determining stage of the full catalytic cycle of ASPA. PMID:27089954

  19. Catalytic hydrogen recombination for nuclear containments

    International Nuclear Information System (INIS)

    Catalytic recombiners appear to be a credible option for hydrogen mitigation in nuclear containments. The passive operation, versatility and ease of back fitting are appealing for existing stations and new designs. Recently, a generation of wet-proofed catalyst materials have been developed at AECL which are highly specific to H2-O2, are active at ambient temperatures and are being evaluated for containment applications. Two types of catalytic recombiners were evaluated for hydrogen removal in containments based on the AECL catalyst. The first is a catalytic combustor for application in existing air streams such as provided by fans or ventilation systems. The second is an autocatalytic recombiner which uses the enthalpy of reaction to produce natural convective flow over the catalyst elements. Intermediate-scale results obtained in 6 m3 and 10 m3 spherical and cylindrical vessels are given to demonstrate self-starting limits, operating limits, removal capacity, scaling parameters, flow resistance, mixing behaviour in the vicinity of an operating recombiner and sensitivity to poisoning, fouling and radiation. (author). 13 refs., 10 figs

  20. IFP solutions for revamping catalytic reforming units

    Energy Technology Data Exchange (ETDEWEB)

    Gendler, J.L. [HRI, Inc., Princeton, NJ (United States); Domergue, B.; Mank, L. [Inst. Francais du Petrole, Rueil Malmaison (France)

    1996-12-01

    The decision-making process for the refiner considering a revamp of a catalytic reforming unit comprises many factors. These may be grouped in two broad areas: technical and economic. This paper presents the results of a study performed by IFP that illustrates catalytic reforming unit revamp options. Three IFP processes are described and operating conditions, expected yields, and economic data are presented. The following options are discussed: base case Conventional, fixed-bed, semi-regenerative catalytic reformer; Case 1--revamp using IFP Dualforming technology; Case 2--revamp using IFP Dualforming Plus technology; and Case 3--revamp to IFP Octanizing technology. The study illustrates various options for the refiner to balance unit performance improvements with equipment, site, and economic constraints. The study was performed assuming design feedrate of 98.2 tons/hour (20,000 BPSD) in all cases. Because of the increased need for octane in many refineries, the study assumed that operating severity was set at a design value of 100 research octane number clear (RON). In all of the cases in this study, it was assumed that the existing recycle compressor was reused. Operating pressure differences between the cases is discussed separately. Also, in all cases, a booster compressor was included in order to return export hydrogen pressure to that of the conventional unit.

  1. Electrochemical catalytic treatment of phenol wastewater

    International Nuclear Information System (INIS)

    The slurry bed catalytic treatment of contaminated water appears to be a promising alternative for the oxidation of aqueous organic pollutants. In this paper, the electrochemical oxidation of phenol in synthetic wastewater catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum operating condition, the orthogonal experiments were devised and the results revealed that the system of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of phenol was 0.52 g/L (the initial COD 1214 mg/L), up to 99% chemical oxygen demand (COD) removal was obtained in 40 min. According to the experimental results, a possible mechanism of catalytic degradation of phenol was proposed. Environmental estimation was also done and the results showed that the treated wastewater have little impact on plant growth and could totally be applied to irrigation.

  2. Session 6: The catalytic oxidation of selected chlorinated hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Oszczudlowski, J. [Institute of Chemistry, Swietokrzyska Academy, Kielce (Poland)

    2004-07-01

    The catalytic oxidation of selected chlorinated hydrocarbons was investigated in the presence of natural zeolites modified with 3M HCl and chromium and lanthanum from aqueous solutions. Natural zeolites of the structure of clinoptilolite or mordenite possess unique physical and chemical properties such as high sorptive capacity and ion-exchange selectivity, relatively high heat and mechanical resistance. The activation of samples of natural zeolites was carried out in a 3M aqueous solution of HCl using a Soxhlet apparatus, whereas the ion exchange from aqueous solutions of chromium (III) and lanthanum (III) nitrates. Samples of activated zeolites were calcinated at 500 C with a programmable temperature increase within 4 hours The amounts of Cr and La on zeolite were 3,0 % wt and 4,5 % wt, respectively. Catalytic tests were conducted in a micro-reactor coupled with a gas chromatograph. The conditions of reaction were as follows: temperature range: 473-723 K, substrate composition: chlorinated hydrocarbon (1000-10000 ppm), steam (0-10000 ppm) and air. Under standard conditions volatile chlorinated hydrocarbons were introduced into a gas flux as vapours, whereas low-volatile ones in a mixture with n-hexane or cyclohexane. The quantity of the deposits on the surface of a catalyst was analysed by the thermogravimetric and GC-MS methods. The composition of oxidation products of chlorinated hydrocarbons was chromatographically analysed indirectly with the techniques SPME-GC-ECD and SPME-GCFID. The total quantity of the products was stored in gas containers-Tedlars and the quantitative and qualitative composition was analysed by the method SPME-HS-GC-ECD (solid phase micro-extraction-headspace-gas chromatography-electron capture detector). The total oxidation of CCl{sub 4} and C{sub 2}Cl{sub 6} in the presence of the Cr/zeolite catalyst occurs at 400 C. The conversion of the catalytic oxidation of chloro-olefins in the presence of the La/zeolite catalyst increases within

  3. Concept and progress in coupling of dehydrogenation and hydrogenation reactions through catalysts

    Indian Academy of Sciences (India)

    C V Pramod; C Raghavendra; K Hari Prasad Reddy; G V Ramesh Babu; K S Rama Rao; B David Raju

    2014-03-01

    This review focuses on the importance of coupling of catalytic reactions which involves dehydrogenation and hydrogenation simultaneously and the study of catalytic materials that are designed, adopted and/or modified for these reactions. The special features of these reactions are minimization of H2 utilization and reduction in production cost. Structural and textural properties also play a decisive role in this kind of coupled reactions. This particular review although not comprehensive discusses the significant progress made in the area of coupled reactions and also helps future researchers or engineers to find out the improvements required in areas such as advancements in catalytic material preparation, design of the new reactors and the application of new technologies.

  4. Heterogeneous catalytic materials solid state chemistry, surface chemistry and catalytic behaviour

    CERN Document Server

    Busca, Guido

    2014-01-01

    Heterogeneous Catalytic Materials discusses experimental methods and the latest developments in three areas of research: heterogeneous catalysis; surface chemistry; and the chemistry of catalysts. Catalytic materials are those solids that allow the chemical reaction to occur efficiently and cost-effectively. This book provides you with all necessary information to synthesize, characterize, and relate the properties of a catalyst to its behavior, enabling you to select the appropriate catalyst for the process and reactor system. Oxides (used both as catalysts and as supports for cata

  5. The Quasicatalytic Mechanism: A Variation of the Catalytic (EC′) Mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Feldberg, S.W.; Campbell, J.F.

    2009-11-01

    The classic electrochemical catalytic mechanism, often referred to as the EC{prime} mechanism, is traditionally represented by the two reactions A + e {r_reversible} B (E{sub A/B}{sup 0}, k{sub A/B}{sup 0}, {alpha}{sub A/B}) and B + P {r_reversible} A + Q (K{sub eq}, k{sub f}, k{sub b}). Implicit in this mechanism is the additional heterogeneous electron transfer P + e {r_reversible} Q (E{sub P/Q}{sup 0}, k{sub P/Q}{sup 0}, {alpha}{sub P/Q}). To observe EC{prime} behavior, the following conditions must be met (we focus on cyclic voltammetric responses): (1) E{sub P/Q}{sup 0} > E{sub A/B}{sup 0} (ensuring that K{sub eq} > 1), (2) k{sub P/Q}{sup 0}c{sub P} exp[-{alpha}{sub P/Q}(F/RT)(E-E{sub P/Q}{sup 0})]/(0.446c{sub A}(FD{sub A}|v|/RT){sup 1/2}) << 1 over the potential range of interest (ensuring that the reaction P + e {r_reversible} Q does not occur to any significant extent relative to the peak current for reaction A + e {r_reversible} B alone), (3) k{sub f}c{sub P}RT/F|v| > 1 (ensuring that the catalytic effect is significant). We offer arguments based on Marcus theory that when condition 2 is met, fulfilling condition 3 will be difficult. This could explain why EC{prime} behavior is rare. In the present work we show that EC{prime}-like cyclic voltammetric responses can be obtained even when P + e {r_reversible} Q is facile if D{sub P,Q} (the diffusion coefficient for the substrate-couple species P and Q) is much smaller than D{sub A,B} (the diffusion coefficient for the mediator-couple species A and B). When D{sub P,Q}/D{sub A,B} is sufficiently small, the system behavior becomes identical to that seen for the classical EC{prime} system. We suggest that this 'quasicatalytic' behavior should be considered when EC{prime}-like behavior is observed and when the electrochemical system involves a substrate couple whose diffusion coefficients are much smaller than those of the mediator couple. As has been known for some time, when the diffusion coefficients

  6. Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions.

    Science.gov (United States)

    Collins, Gillian; Holmes, Justin D

    2016-07-01

    Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor-made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs. PMID:26823380

  7. Catalytic bioscavengers in nerve agent poisoning: A promising approach?

    Science.gov (United States)

    Worek, Franz; Thiermann, Horst; Wille, Timo

    2016-02-26

    The repeated use of the nerve agent sarin against civilians in Syria in 2013 emphasizes the continuing threat by chemical warfare agents. Multiple studies demonstrated a limited efficacy of standard atropine-oxime treatment in nerve agent poisoning and called for the development of alternative and more effective treatment strategies. A novel approach is the use of stoichiometric or catalytic bioscavengers for detoxification of nerve agents in the systemic circulation prior to distribution into target tissues. Recent progress in the design of enzyme mutants with reversed stereo selectivity resulting in improved catalytic activity and their use in in vivo studies supports the concept of catalytic bioscavengers. Yet, further research is necessary to improve the catalytic activity, substrate spectrum and in vivo biological stability of enzyme mutants. The pros and cons of catalytic bioscavengers will be discussed in detail and future requirements for the development of catalytic bioscavengers will be proposed. PMID:26200600

  8. Selectivity, Compatibility, Downstream Functionalization, and Silver Effect in the Gold and Palladium Dual-Catalytic Synthesis of Lactones

    OpenAIRE

    Al-Amin, Mohammad; Johnson, Joel S.; Blum, Suzanne A.

    2014-01-01

    The chemo- and regioselectivity and functional group compatibility in gold and palladium cooperatively catalyzed cross-coupling reactions were determined in the synthesis of lactones; the selectivity in the gold and palladium dual-metal catalysis system was distinct from that available for the same class of substrates in systems with only gold catalysis or only palladium catalysis rather than dual catalysis. The dual-catalytic rearrangement reaction selectively promoted oxidative addition at ...

  9. Fluid catalytic cracking of biomass pyrolysis vapors

    Energy Technology Data Exchange (ETDEWEB)

    Mante, Ofei Daku [Virginia Polytechnic Institute and State University, Biological Systems Engineering, Blacksburg, VA (United States); Agblevor, Foster A. [Utah State University, Biological Engineering, Logan, UT (United States); McClung, Ron [BASF Inc, Florham, NJ (United States)

    2011-12-15

    Catalytic cracking of pyrolysis oils/vapors offers the opportunity of producing bio-oils which can potentially be coprocessed with petroleum feedstocks in today's oil refinery to produce transportation fuel and chemicals. Catalyst properties and process conditions are critical in producing and maximizing desired product. In our studies, catalyst matrix (kaolin) and two commercial fluid catalytic cracking (FCC) catalysts, FCC-H and FCC-L, with different Y-zeolite contents were investigated. The catalytic cracking of hybrid poplar wood was conducted in a 50-mm bench-scale bubbling fluidized-bed pyrolysis reactor at 465 C with a weight hourly space velocity of 1.5 h{sup -1}. The results showed that the yields and quality of the bio-oils was a function of the Y-zeolite content of the catalyst. The char/coke yield was highest for the higher Y-zeolite catalyst. The organic liquid yields decreased inversely with increase in zeolite content of the catalyst whereas the water and gas yields increased. Analysis of the oils by both Fourier-transform infrared and {sup 13}C-nuclear magnetic resonance indicated that the catalyst with higher zeolite content (FCC-H) was efficient in the removal of compounds like levoglucosan, carboxylic acids and the conversion of methoxylated phenols to substituted phenols and benzenediols. The cracking of pyrolysis products by kaolin suggests that the activity of the FCC catalyst on biomass pyrolysis vapors can be attributed to both Y-zeolite and matrix. The FCC-H catalyst produced much more improved oil. The oil was low in oxygen (22.67 wt.%), high in energy (29.79 MJ/kg) and relatively stable over a 12-month storage period. (orig.)

  10. Catalytic Mechanism of Human Alpha-galactosidase

    Energy Technology Data Exchange (ETDEWEB)

    Guce, A.; Clark, N; Salgado, E; Ivanen, D; Kulinskaya, A; Brumer, H; Garman, S

    2010-01-01

    The enzyme {alpha}-galactosidase ({alpha}-GAL, also known as {alpha}-GAL A; E.C. 3.2.1.22) is responsible for the breakdown of {alpha}-galactosides in the lysosome. Defects in human {alpha}-GAL lead to the development of Fabry disease, a lysosomal storage disorder characterized by the buildup of {alpha}-galactosylated substrates in the tissues. {alpha}-GAL is an active target of clinical research: there are currently two treatment options for Fabry disease, recombinant enzyme replacement therapy (approved in the United States in 2003) and pharmacological chaperone therapy (currently in clinical trials). Previously, we have reported the structure of human {alpha}-GAL, which revealed the overall structure of the enzyme and established the locations of hundreds of mutations that lead to the development of Fabry disease. Here, we describe the catalytic mechanism of the enzyme derived from x-ray crystal structures of each of the four stages of the double displacement reaction mechanism. Use of a difluoro-{alpha}-galactopyranoside allowed trapping of a covalent intermediate. The ensemble of structures reveals distortion of the ligand into a {sup 1}S{sub 3} skew (or twist) boat conformation in the middle of the reaction cycle. The high resolution structures of each step in the catalytic cycle will allow for improved drug design efforts on {alpha}-GAL and other glycoside hydrolase family 27 enzymes by developing ligands that specifically target different states of the catalytic cycle. Additionally, the structures revealed a second ligand-binding site suitable for targeting by novel pharmacological chaperones.

  11. Modeling the oxidative coupling of methane:Heterogeneous chemistry coupled with 3D flow field simulation

    Institute of Scientific and Technical Information of China (English)

    Yaghobi Nakisa; Ghoreishy Mir Hamid Reza

    2009-01-01

    The oxidative coupling of methane (OCM) over titanate perovskite catalyst has been developed by three-dimensional numerical simulations of flow field coupled with heat transfer as well as heterogeneous kinetic model.The reaction was assumed to take place both in the gas phase and on the catalytic surface.Kinetic rate constants were experimentally obtained using a ten step kinetic model.The simulation results agree quite well with the data of OCM experiments,which were used to investigate the effect of temperature on the selectivity and conversion obtained in the methane oxidative coupling process.The conversion of methane linearly increased with temperature and the selectivity of C2 was practically constant in the temperature range of 973-1073 K.The study shows that CFD tools make it possible to implement the heterogeneous kinetic model even for high exothermic reaction such as OCM.

  12. One-pot synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines using supported gold and base as catalysts

    DEFF Research Database (Denmark)

    Kegnæs, Søren; Mielby, Jerrik Jørgen; Mentzel, Uffe Vie;

    2012-01-01

    Synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines via intermediate formation of methyl esters is highly efficient and selective when using a catalytic system comprised of supported gold nanoparticles and added base in methanol.......Synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines via intermediate formation of methyl esters is highly efficient and selective when using a catalytic system comprised of supported gold nanoparticles and added base in methanol....

  13. De novo design of catalytic proteins

    OpenAIRE

    Kaplan, J; DeGrado, W. F.

    2004-01-01

    The de novo design of catalytic proteins provides a stringent test of our understanding of enzyme function, while simultaneously laying the groundwork for the design of novel catalysts. Here we describe the design of an O2-dependent phenol oxidase whose structure, sequence, and activity are designed from first principles. The protein catalyzes the two-electron oxidation of 4-aminophenol (kcat/KM = 1,500 M·1·min·1) to the corresponding quinone monoimine by using a diiron cofactor. The catalyti...

  14. Transport in a Microfluidic Catalytic Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Park, H G; Chung, J; Grigoropoulos, C P; Greif, R; Havstad, M; Morse, J D

    2003-04-30

    A study of the heat and mass transfer, flow, and thermodynamics of the reacting flow in a catalytic microreactor is presented. Methanol reforming is utilized in the fuel processing system driving a micro-scale proton exchange membrane fuel cell. Understanding the flow and thermal transport phenomena as well as the reaction mechanisms is essential for improving the efficiency of the reforming process as well as the quality of the processed fuel. Numerical studies have been carried out to characterize the transport in a silicon microfabricated reactor system. On the basis of these results, optimized conditions for fuel processing are determined.

  15. Asymmetric catalytic aziridination of cyclic enones.

    Science.gov (United States)

    De Vincentiis, Francesco; Bencivenni, Giorgio; Pesciaioli, Fabio; Mazzanti, Andrea; Bartoli, Giuseppe; Galzerano, Patrizia; Melchiorre, Paolo

    2010-07-01

    The first catalytic method for the asymmetric aziridination of cyclic enones is described. The presented organocatalytic strategy is based on the use of an easily available organocatalyst that is able to convert a wide range of cyclic enones into the desired aziridines with very high enantiomeric purity and good chemical yield. Such a method may very well open up new opportunities to stereoselectively prepare complex chiral molecules that possess an indane moiety, a framework that is found in a large number of bioactive and pharmaceutically important molecules. PMID:20512797

  16. Catalytic Pyrolysis of Olive Mill Wastewater Sludge

    OpenAIRE

    Abdellaoui, Hamza

    2015-01-01

    Olive mill wastewater sludge (OMWS) is the solid residue that remains in the evaporation ponds after evaporation of the majority of water in the olive mill wastewater (OMW). OMWS is a major environmental pollutant in the olive oil producing regions. Approximately 41.16 wt. % of the OMWS was soluble in hexanes (HSF). The fatty acids in this fraction consist mainly of oleic and palmitic acid. Catalytic pyrolysis of the OMWS over red mud and HZSM-5 has been demonstrated to be an effective techno...

  17. Electrospun Catalytic Support Prepared by Electrospinning Technique

    Czech Academy of Sciences Publication Activity Database

    Soukup, Karel; Topka, Pavel; Petráš, D.; Klusoň, Petr; Šolcová, Olga

    Praha : Orgit, 2012, C4.1. ISBN 978-80-905035-1-9. [International Congress of Chemical and Process Engineering CHISA 2012 and 15th Conference PRES 2012 /20./. Prague (CZ), 25.08.2012-29.08.2012] R&D Projects: GA ČR GPP106/11/P459; GA ČR(CZ) GAP204/11/1206 Institutional support: RVO:67985858 Keywords : catalytic tests * electrospun * gas transport properties Subject RIV: CI - Industrial Chemistry, Chemical Engineering www.chisa.cz/2012

  18. Tritium stripping by a catalytic exchange stripper

    International Nuclear Information System (INIS)

    A catalytic exchange process for stripping elemental tritium from gas streams has been demonstrated. The process uses a catalyzed isotopic exchange reaction between tritium in the gas phase and protium or deuterium in the solid phase on alumina. The reaction is catalyzed by platinum deposited on the alumina. The process has been tested with both tritium and deuterium. Decontamination factors (ration of inlet and outlet tritium concentrations) as high as 1000 have been achieved, depending on inlet concentration. The test results and some demonstrated applications are presented

  19. Catalytic Synthesis Methods for Triazolopyrimidine Derivatives

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A new method for catalyzed synthesis of triazolopyrimidine derivatives is reported. Aikylamine reaction with dialkyl cyanodithioiminocarbonate was catalyzed by quaternary ammonium salts at room temperature to yield 3-alkylamine-5-amino-1,2,4-triazole in good quality and high yields. After imidization and reaction with an α,β-unsaturated acid derivative, the reaction intermediate was hydrolyzed in the presence of a Lewis acid to obtain the target product. This novel catalytic method for triazolopyrimidine derivatives can be carried out under inexpen-sive and mild conditions, and is safe and environmentally friendly. IH NMR results for all intermediates are re-ported.

  20. Thin film porous membranes for catalytic sensors

    Energy Technology Data Exchange (ETDEWEB)

    Hughes, R.C.; Boyle, T.J.; Gardner, T.J. [and others

    1997-06-01

    This paper reports on new and surprising experimental data for catalytic film gas sensing resistors coated with nanoporous sol-gel films to impart selectivity and durability to the sensor structure. This work is the result of attempts to build selectivity and reactivity to the surface of a sensor by modifying it with a series of sol-gel layers. The initial sol-gel SiO{sub 2} layer applied to the sensor surprisingly showed enhanced O{sub 2} interaction with H{sub 2} and reduced susceptibility to poisons such as H{sub 2}S.

  1. Temperature control of a catalytic converter

    Energy Technology Data Exchange (ETDEWEB)

    Ma, T.T.-H.

    1994-06-08

    In an ic engine having a catalytic convertor, the catalyst heater is controlled in dependence upon an estimate of the temperature of the catalyst so that there is no need for a sensor in the hostile environment of the exhaust. A valve indicative of the catalyst temperature is stored and modified in accordance with a model of the catalyst temperature. The model can be a mathematical mood carried out by a signal processor or an electrical model with the catalyst temperature being represented by the charge stored on a capacitor. (Author)

  2. Catalytic asymmetric formal synthesis of beraprost

    Science.gov (United States)

    Kobayashi, Yusuke; Kuramoto, Ryuta

    2015-01-01

    Summary The first catalytic asymmetric synthesis of the key intermediate for beraprost has been achieved through an enantioselective intramolecular oxa-Michael reaction of an α,β-unsaturated amide mediated by a newly developed benzothiadiazine catalyst. The Weinreb amide moiety and bromo substituent of the Michael adduct were utilized for the C–C bond formations to construct the scaffold. All four contiguous stereocenters of the tricyclic core were controlled via Rh-catalyzed stereoselective C–H insertion and the subsequent reduction from the convex face. PMID:26734111

  3. Catalytic deallylation of allyl- and diallylmalonates.

    Science.gov (United States)

    Necas, David; Turský, Matyás; Kotora, Martin

    2004-08-25

    Substituted allylmalonates undergo the selective C-C bond cleavage in the presence of triethylaluminum and a catalytic amount of nickel and ruthenium phosphine complexes, resulting in the loss of the allyl moiety and formation of monosubstituted malonates. Comparison of reactivity of the nickel and ruthenium complexes showed that the use of the former is general with respect to the structure of the substituted allylmalonates, and the activity of the latter depended on the substitution pattern of the double bond of the allylic moiety. The smooth deallylation may encourage the use of the allyl group as a protective group for the acidic hydrogen in malonates. PMID:15315416

  4. Catalytic multi-stage liquefaction (CMSL)

    Energy Technology Data Exchange (ETDEWEB)

    Comolli, A.G.; Ganguli, P.; Karolkiewicz, W.F.; Lee, T.L.K.; Pradhan, V.R.; Popper, G.A.; Smith, T.; Stalzer, R.

    1996-11-01

    Under contract with the U.S. Department of Energy, Hydrocarbon Technologies, Inc. has conducted a series of eleven catalytic, multi-stage, liquefaction (CMSL) bench scale runs between February, 1991, and September, 1995. The purpose of these runs was to investigate novel approaches to liquefaction relating to feedstocks, hydrogen source, improved catalysts as well as processing variables, all of which are designed to lower the cost of producing coal-derived liquid products. This report summarizes the technical assessment of these runs, and in particular the evaluation of the economic impact of the results.

  5. Biomimetic, Catalytic Oxidation in Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    Shun-lchi Murahashi

    2005-01-01

    @@ 1Introduction Oxidation is one of the most fundamental reactions in organic synthesis. Owing to the current need to develop forward-looking technology that is environmentally acceptable with respect many aspects. The most attractive approaches are biomimetic oxidation reactions that are closely related to the metabolism of living things. The metabolisms are governed by a variety of enzymes such as cytochrome P-450 and flavoenzyme.Simulation of the function of these enzymes with simple transition metal complex catalyst or organic catalysts led to the discovery of biomimetic, catalytic oxidations with peroxides[1]. We extended such biomimetic methods to the oxidation with molecular oxygen under mild conditions.

  6. Heterogeneous Photooxidation of Phenol by Catalytic Membranes

    Institute of Scientific and Technical Information of China (English)

    Enrica Fontananova; Enrico Drioli; Laura Donato; Marcella Bonchio; Mauro Carraro; Gianfranco Scorrano

    2006-01-01

    In this work the heterogenization in polymeric membranes of decatungstate, a photocatalyst for oxidation reactions,was reported. Solid state characterization techniques confirmed that the catalyst structure was preserved within the polymeric membranes. The catalytic membranes were successfully applied in the aerobic photo-oxidation of phenol, one of the main organic pollutants in wastewater, providing stable and recyclable photocatalytic systems. The dependence of the phenol degradation rate by the catalyst loading and transmembrane pressure was shown. By comparison with homogeneous reaction,the catalyst heterogenized in membrane appears to be more efficient concerning the rate of phenol photodegradation and mineralization.

  7. Submicron Polyethylene Particles from Catalytic Emulsion Polymerization

    OpenAIRE

    Bauers, Florian Martin; Thomann, Ralf; Mecking, Stefan

    2003-01-01

    Particles of linear polyethylene (Mn = (2-3)X 10000 g mol-1; Mw/Mn = 2-4) obtained by catalytic emulsion polymerization of ethylene possess a nonspherical, lentil-like shape with an average aspect ratio of ca. 10 and diameters from 30 to > 300 nm, as determined by TEM and AFM. The particle structure results from a stacking of the lamellae along the one shorter axis of the lentils (i.e., their height, by contrast to the diameter). In addition to these multilamellae particles, remarkably, a con...

  8. Catalytic conversion of sulfur dioxide and trioxide

    Energy Technology Data Exchange (ETDEWEB)

    Solov' eva, E.L.; Shenfel' d, B.E.; Kuznetsova, S.M.; Khludenev, A.G.

    1987-11-10

    The reclamation and utilization of sulfur-containing wastes from the flue gas of fossil-fuel power plants and the subsequent reduction in sulfur emission is addressed in this paper. The authors approach this problem from the standpoint of the catalytic oxidation of sulfur dioxide on solid poison-resistant catalysts with subsequent sorption of the sulfur trioxide and its incorporation into the manufacture of sulfuric acid. The catalyst they propose is a polymetallic dust-like waste from the copper-smelting industry comprised mainly of iron and copper oxides. Experiments with this catalyst were carried out using multifactorial experiment planning.

  9. The catalytic residues of Tn3 resolvase

    OpenAIRE

    Olorunniji, F.J.; Stark, W M

    2009-01-01

    To characterize the residues that participate in the catalysis of DNA cleavage and rejoining by the site-specific recombinase Tn3 resolvase, we mutated conserved polar or charged residues in the catalytic domain of an activated resolvase variant. We analysed the effects of mutations at 14 residues on proficiency in binding to the recombination site ('site I'), formation of a synaptic complex between two site Is, DNA cleavage and recombination. Mutations of Y6, R8, S10, D36, R68 and R71 result...

  10. Study and Analysis on Naphtha Catalytic Reforming Reactor Simulation

    Institute of Scientific and Technical Information of China (English)

    Liang Ke min; Song Yongji; Pan Shiwei

    2004-01-01

    A naphtha catalytic reforming unit with four reactors connected in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reaction characteristics based on idealizing the complex naphtha mixture to represent the paraffin, naphthene, and aromatic groups with individual compounds. The simulation results based on above models agree very well with actual operating data of process unit.

  11. Including lateral interactions into microkinetic models of catalytic reactions

    DEFF Research Database (Denmark)

    Hellman, Anders; Honkala, Johanna Karoliina

    2007-01-01

    In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

  12. Non-thermal plasmas for non-catalytic and catalytic VOC abatement

    International Nuclear Information System (INIS)

    Highlights: → We review the current status of catalytic and non-catalytic VOC abatement based on a vast number of research papers. → The underlying mechanisms of plasma-catalysis for VOC abatement are discussed. → Critical process parameters that determine the influent are discussed and compared. - Abstract: This paper reviews recent achievements and the current status of non-thermal plasma (NTP) technology for the abatement of volatile organic compounds (VOCs). Many reactor configurations have been developed to generate a NTP at atmospheric pressure. Therefore in this review article, the principles of generating NTPs are outlined. Further on, this paper is divided in two equally important parts: plasma-alone and plasma-catalytic systems. Combination of NTP with heterogeneous catalysis has attracted increased attention in order to overcome the weaknesses of plasma-alone systems. An overview is given of the present understanding of the mechanisms involved in plasma-catalytic processes. In both parts (plasma-alone systems and plasma-catalysis), literature on the abatement of VOCs is reviewed in close detail. Special attention is given to the influence of critical process parameters on the removal process.

  13. Catalytically favorable surface patterns in Pt-Au nanoclusters

    KAUST Repository

    Mokkath, Junais Habeeb

    2013-01-01

    Motivated by recent experimental demonstrations of novel PtAu nanoparticles with highly enhanced catalytic properties, we present a systematic theoretical study that explores principal catalytic indicators as a function of the particle size and composition. We find that Pt electronic states in the vicinity of the Fermi level combined with a modified electron distribution in the nanoparticle due to Pt-to-Au charge transfer are the origin of the outstanding catalytic properties. From our model we deduce the catalytically favorable surface patterns that induce ensemble and ligand effects. © The Royal Society of Chemistry 2013.

  14. Light-concentrating plasmonic Au superstructures with significantly visible-light-enhanced catalytic performance.

    Science.gov (United States)

    Yang, Jinhu; Li, Ying; Zu, Lianhai; Tong, Lianming; Liu, Guanglei; Qin, Yao; Shi, Donglu

    2015-04-22

    Noble metals are well-known for their surface plasmon resonance effect that enables strong light absorption typically in the visible regions for gold and silver. However, unlike semiconductors, noble metals are commonly considered incapable of catalyzing reactions via photogenerated electron-hole pairs due to their continuous energy band structures. So far, photonically activated catalytic system based on pure noble metal nanostructures has seldom been reported. Here, we report the development of three different novel plasmonic Au superstructures comprised of Au nanoparticles, multiple-twinned nanoparticles and nanoworms assembling on the surfaces of SiO2 nanospheres respectively via a well-designed synthetic strategy. It is found that these novel Au superstructures show enhanced broadband visible-light absorption due to the plasmon resonance coupling within the superstructures, and thus can effectively focus the energy of photon fluxes to generate much more excited hot electrons and holes for promoting catalytic reactions. Accordingly, these Au superstructures exhibit significantly visible-light-enhanced catalytic efficiency (up to ∼264% enhancement) for the commercial reaction of p-nitrophenol reduction. PMID:25840556

  15. Palladium coupling catalysts for pharmaceutical applications.

    Science.gov (United States)

    Doucet, Henri; Hierso, Jean-Cyrille

    2007-11-01

    This review discusses recent advances made in the area of palladium-catalyzed coupling reactions and describes a selection of the catalytic systems that are useful in the preparation of valuable compounds for the pharmaceutical industry. Most of these types of syntheses have used either simple palladium salts or palladium precursors associated with electron-rich mono- or bidentate phosphine ligands as catalysts. For some reactions, ligands such as triphenyl phosphine, 1,1'-bis(diphenylphosphino)ferrocene, a carbene or a bipyridine have also been employed. Several new procedures for the Suzuki cross-coupling reaction, the activation of aryl chlorides, the functionalization of aromatics and the synthesis of heteroaromatics are discussed. The C-H activation/ functionalization reactions of aryl and heteroaryl derivatives have emerged as powerful tools for the preparation of biaryl compounds, and the recent procedures and catalysts employed in this promising field are also highlighted herein. PMID:17987520

  16. Catalytic hydrothermal liquefaction of water hyacinth.

    Science.gov (United States)

    Singh, Rawel; Balagurumurthy, Bhavya; Prakash, Aditya; Bhaskar, Thallada

    2015-02-01

    Thermal and catalytic hydrothermal liquefaction of water hyacinth was performed at temperatures from 250 to 300 °C under various water hyacinth:H2O ratio of 1:3, 1:6 and 1:12. Reactions were also carried out under various residence times (15-60 min) as well as catalytic conditions (KOH and K2CO3). The use of alkaline catalysts significantly increased the bio-oil yield. Maximum bio-oil yield (23 wt%) comprising of bio-oil1 and bio-oil2 as well as conversion (89%) were observed with 1N KOH solution. (1)H NMR and (13)C NMR data showed that both bio-oil1 and bio-oil2 have high aliphatic carbon content. FTIR of bio-residue indicated that the usage of alkaline catalyst resulted in bio-residue samples with lesser oxygen functionality indicating that catalyst has a marked effect on nature of the bio-residue and helps to decompose biomass to a greater extent compared to thermal case. PMID:25240515

  17. Aluminosilicate nanoparticles for catalytic hydrocarbon cracking.

    Science.gov (United States)

    Liu, Yu; Pinnavaia, Thomas J

    2003-03-01

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

  18. Catalytic converter for next generation turbine engines

    Energy Technology Data Exchange (ETDEWEB)

    Saruhan, B.; Schulz, U.; Leyens, C. [German Aerospace Center (DLR), Inst. of Materials Research, Cologne (Germany)

    2004-07-01

    EB-PVD thermal barrier coatings (TBCs) are used on advanced turbine blades to increase the engine efficiency and improve the blade performance. partially yttria stabilized zirconia (PYSZ) is the standard material for current TBC applications. Lower thermal stability of the PYSZ-based TBCs, however, seriously affects the performance at demanding service temperatures. For the new generation turbines where higher operating gas temperatures (> 1200 C) are to expect, the performance of turbine blades can be improved by replacing the state-art-of-material PYSZ with superior thermal barrier coatings which belong to different crystal structures such as magnetoplumbite. Magnetoplumbite structure through its interlocking grain morphology and unique crystal structure provides essentially a sintering resistant, low thermal conductive layer, but also imparts a catalytic layer to reduce the environmentally harmful substances produced during propulsion and increase the catalytic performance. The complex structures of these compounds make it difficult to realize by conventional methods and requires careful adjustment of process parameters. The morphology and crystallographic aspects of these coatings as well as the mechanisms controlling the improvement are highlighted. (orig.)

  19. Study of catalytic phenomena in radiation chemistry

    International Nuclear Information System (INIS)

    Two phenomena have been studied: the action of γ rays from radio-cobalt on the adsorption and catalytic properties of ZnO and NiO in. relationship with the heterogeneous oxidation of CO, and the homogeneous catalysis by OsO4 of the oxidation of various aqueous phase solutes by the same radiation. The prior irradiation of ZnO and of NiO does not modify their catalytic activity but generally increases the adsorption energy of -the gases CO and O2. The influence of the radiations appears to be connected with the presence of traces of water on ZnO and of an excess of oxygen on NiO. Osmium tetroxide which is not degraded by irradiation in acid solution, accelerates the radiolytic oxidation of certain compounds (TeIV, Pt11, As111) in the presence of oxygen, as a result of its sensitizing effect on the oxidation by H2O2. In the case of phosphites on the other hand, OsO4 has a protecting action under certain conditions of acidity and may suppress entirely the chain reaction which characterizes the oxidation of this solute byγ rays. A general mechanism is proposed for these phenomena. The rate constant for the OsO4 + HO2 reaction is calculated to be 5.7 x 105 l.mol-1. sec-1. (author)

  20. Catalytic converter for next generation turbine engines

    International Nuclear Information System (INIS)

    EB-PVD thermal barrier coatings (TBCs) are used on advanced turbine blades to increase the engine efficiency and improve the blade performance. partially yttria stabilized zirconia (PYSZ) is the standard material for current TBC applications. Lower thermal stability of the PYSZ-based TBCs, however, seriously affects the performance at demanding service temperatures. For the new generation turbines where higher operating gas temperatures (> 1200 C) are to expect, the performance of turbine blades can be improved by replacing the state-art-of-material PYSZ with superior thermal barrier coatings which belong to different crystal structures such as magnetoplumbite. Magnetoplumbite structure through its interlocking grain morphology and unique crystal structure provides essentially a sintering resistant, low thermal conductive layer, but also imparts a catalytic layer to reduce the environmentally harmful substances produced during propulsion and increase the catalytic performance. The complex structures of these compounds make it difficult to realize by conventional methods and requires careful adjustment of process parameters. The morphology and crystallographic aspects of these coatings as well as the mechanisms controlling the improvement are highlighted. (orig.)

  1. Numerical and experimental investigations on catalytic recombiners

    International Nuclear Information System (INIS)

    Numerous containments of European light water reactors (LWR) are equipped with passive auto-catalytic recombiners (PAR). These devices are designed for the removal of hydrogen generated during a severe accident in order to avoid serious damage caused by a detonation. PARs make use of the fact that hydrogen and oxygen react exothermally on catalytic surfaces generating steam and heat even below conventional ignition concentrations and temperatures. Activities at ISR aim at overcoming existing limitations of today's systems. These are e.g. limited conversion capacity or unintended ignition of the gaseous mixture due to overheating of the catalyst elements caused by strong reaction heat generation. Experiments at the REKO facilities are conducted in order to achieve a profound understanding of the processes inside a recombiner, such as reaction kinetics or heat and mass transfer. Innovative PAR designs which may overcome existing limitations can be developed based on the knowledge obtained from these experiments. For the analysis of the processes inside a PAR the numerical code REKO-DIREKT is being developed. The code calculates the local catalyst temperatures and the concentration regression along the catalyst plates. For the validation of the model numerous experiments have been performed with different types of coating and different plate arrangements. The first calculations fit well with the experimental results indicating a proper understanding of the fundamental processes. The paper describes the experiments as well as the numerical model and presents model calculations in comparison with experimental results. (authors)

  2. Catalytic combustion in gas stoves - Phase II

    Energy Technology Data Exchange (ETDEWEB)

    Hjelm, Anna-Karin [CATATOR AB, Lund (Sweden)

    2003-06-01

    Several independent studies show that gas stoves to some degree contribute to the indoor emissions of NO{sub x} especially in situations were the ventilation flow is poor. The peak-NO{sub x} concentrations can reach several hundred ppb but the integral concentration seldom exceeds about 20 - 50 ppb, which corresponds to an indoor-outdoor ratio of about 1 - 2.5. Epidemiological studies indicate increasing problems with respiratory symptoms in sensitive people at concentrations as low as 15 ppb of NO{sub 2}. Consequently, the NO{sub x}-concentration in homes where gas stoves are used is high enough to cause health effects. However, in situations where the ventilation flow is high (utilisation of ventilation hoods) the NO{sub x}-emissions are not likely to cause any health problems. This study has been aimed at investigating the possibilities to reduce the NO{sub x} emissions from gas stoves by replacing the conventional flame combustion with catalytic combustion. The investigation is requested by Swedish Gas Center, and is a following-up work of an earlier conducted feasibility study presented in April-2002. The present investigation reports on the possibility to use cheap and simple retro-fit catalytic design suggestions for traditional gas stoves. Experiments have been conducted with both natural and town gas, and parameters such as emissions of NO{sub x}, CO and unburned fuel gas and thermal efficiency, etc, have been examined and are discussed. The results show that it is possible to reduce the NO{sub x} emissions up to 80% by a simple retro-fit installation, without decreasing the thermal efficiency of the cooking plate. The measured source strengths correspond to indoor NO{sub x} concentrations that are below or equal to the average outdoor concentration, implying that no additional detrimental health effects are probable. The drawback of the suggested installations is that the concentration of CO and in some cases also CH{sub 4} are increased in the flue gases

  3. Structured materials for catalytic and sensing applications

    Science.gov (United States)

    Hokenek, Selma

    The optical and chemical properties of the materials used in catalytic and sensing applications directly determine the characteristics of the resultant catalyst or sensor. It is well known that a catalyst needs to have high activity, selectivity, and stability to be viable in an industrial setting. The hydrogenation activity of palladium catalysts is known to be excellent, but the industrial applications are limited by the cost of obtaining catalyst in amounts large enough to make their use economical. As a result, alloying palladium with a cheaper, more widely available metal while maintaining the high catalytic activity seen in monometallic catalysts is, therefore, an attractive option. Similarly, the optical properties of nanoscale materials used for sensing must be attuned to their application. By adjusting the shape and composition of nanoparticles used in such applications, very fine changes can be made to the frequency of light that they absorb most efficiently. The design, synthesis, and characterization of (i) size controlled monometallic palladium nanoparticles for catalytic applications, (ii) nickel-palladium bimetallic nanoparticles and (iii) silver-palladium nanoparticles with applications in drug detection and biosensing through surface plasmon resonance, respectively, will be discussed. The composition, size, and shape of the nanoparticles formed were controlled through the use of wet chemistry techniques. After synthesis, the nanoparticles were analyzed using physical and chemical characterization techniques such as X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and Scanning Transmission Electron Microscopy- Energy-Dispersive Spectrometry (STEM-EDX). The Pd and Ni-Pd nanoparticles were then supported on silica for catalytic testing using mass spectrometry. The optical properties of the Ag-Pd nanoparticles in suspension were further investigated using ultraviolet-visible spectrometry (UV-Vis). Monometallic palladium particles have

  4. Polarographic catalytic wave of hydrogen--Parallel catalytic hydrogen wave of bovine serum albumin in thepresence of oxidants

    Institute of Scientific and Technical Information of China (English)

    过玮; 刘利民; 林洪; 宋俊峰

    2002-01-01

    A polarographic catalytic hydrogen wave of bovine serum albumin (BSA) at about -1.80 V (vs. SCE) in NH4Cl-NH3@H2O buffer is further catalyzed by such oxidants as iodate, persulfate and hydrogen peroxide, producing a kinetic wave. Studies show that the kinetic wave is a parallel catalytic wave of hydrogen, which resulted from that hydrogen ion is electrochemically reduced and chemically regenerated through oxidation of its reduction product, atomic hydrogen, by oxidants mentioned above. It is a new type of poralographic catalytic wave of protein, which is suggested to be named as a parallel catalytic hydrogen wave.

  5. Facile preparation of modified carbon black-LaMnO3 hybrids and the effect of covalent coupling on the catalytic activity for oxygen reduction reaction%改性炭黑-LaMnO3复合材料的制备及其共价复合效应对氧还原性能的影响

    Institute of Scientific and Technical Information of China (English)

    刘景军; 金学民; 宋薇薇; 王峰; 王楠; 宋夜

    2014-01-01

    Covalent coupling between LaMnO3 nanoparticles and carbon black to produce a composite catalyst for oxygen reduction reaction (ORR) was achieved by physical mixing of modified carbon and per-ovskite-type LaMnO3 nanoparticles, followed by sintering at different temperatures. Perovskite-type LaMnO3 nanoparticles were first synthesized via chemical precipitation, and the carbon sup-port (Vulcan XC-72) was modified using graphitization, followed by HNO3 and ammonia treatments. The morphology and electronic states of the carbon black-LaMnO3 hybrid catalyst were character-ized by scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The loaded LaMnO3 particles featured rod-like, three bars-like, and bamboo rod-like structures and were homogeneously dispersed in the carbon matrix that featured a hollow spherical structure. At a sintering temperature of about 300 °C, C-O-M (M = La, Mn) bonds formed at the interface between the carbon and LaMnO3 nanoparticles. Electrochemical measurements in 1 mol/L NaOH showed that the carbon-LaMnO3 hybrid prepared at a LaMnO3/GCB mass ratio of 2:3 displayed the highest electrocatalytic activity towards ORR among all the synthesized hybrid catalysts. The electrocata-lytic activity was comparable with that obtained by commercial Pt/C catalyst (E-TEK). The average electron transfer number of ORR was ~3.81, and the corresponding yield of the hydrogen peroxide intermediate was ~9.5%. The remarkably improved electrocatalytic activity towards ORR was likely because of the formation of covalent bonds (C-O-M) between the LaMnO3 nanoparticles and carbon that can effectively enhance the ORR kinetics. This information is important to understand the physical origin of the electrocatalytic activity of carbon-supported rare earth oxides as catalysts for ORR.%以Vulcan XC-72炭黑为载体,通过对炭载体石墨化处理和表面化学修饰,将其与化学沉淀法制备的纳米级LaMnO3颗粒共混,再经特定温

  6. Membrane Assembly Driven by a Biomimetic Coupling Reaction

    OpenAIRE

    Budin, Itay; Devaraj, Neal K.

    2011-01-01

    One of the major goals of synthetic biology is the development of non-natural cellular systems. In this work we describe a catalytic biomimetic coupling reaction capable of driving the de novo self-assembly of phospholipid membranes. Our system features a copper catalyzed azide-alkyne cycloaddition that results in the formation of a triazole containing phospholipid analog. Concomitant assembly of membranes occurs spontaneously, not requiring preexisting membranes to house catalysts or precurs...

  7. The influence of copper in dealloyed binary platinum–copper electrocatalysts on methanol electroxidation catalytic activities

    International Nuclear Information System (INIS)

    In this study, we prepared and characterized carbon paper-supported dealloyed binary Pt–Cu core–shell electrocatalysts (denoted as PtxCu(100−x)/CP) by cyclic co-electrodeposition and selective copper dealloying in an acidic medium, and we investigated the effect of the copper content in the samples on the catalytic activities toward methanol electroxidation reaction (MOR). X-ray photo-emission spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES) indicated that the structure of dealloyed binary Pt–Cu catalysts possessed a Pt-rich shell and a Cu rich core. X-ray absorption near edge spectroscopy (XANES) displayed that the oxidation states of Pt and Cu were zero and one, respectively, implying the formation of metallic Pt and Cu2O, respectively. X-ray diffraction spectroscopy (XRD) confirmed that Cu was inserted into a face-centered cubic Pt structure forming Pt–Cu alloys. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) displayed a cubic shape of Pt/CP and a spherical shape of PtxCu(100−x)/CP with several hundred nanometer sizes of agglomeration that depended on the Cu content. Cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy were performed to confirm that the sample of Pt70Cu30/CP exhibited the best catalytic activities in terms of the specific current, current density, catalytic poisoning tolerance, and stability. - Graphical abstract: Display Omitted - Highlights: • Binary electrocatalysts of PtxCu(100−x)/CP were prepared by cyclic co-electrodeposition and selective copper dealloying. • The structures of PtxCu(100−x)/CP were a Pt rich shell and a Cu rich core. • The Pt70Cu30/CP was the excellent catalytic activity towards methanol electrooxidation and COads tolerance

  8. Desorption and catalytic study of vanadium modified MCM-41 silica by 11C radiolabeled methanol

    International Nuclear Information System (INIS)

    Complete text of publication follows. Vanadium modified MCM-41 (V-MCM-41) materials were prepared by solid state reduction technique with V2O5 and catalytically tested in ethylacetate oxidation. In the recent study, 11C-labeling methanol is introduced as a probe molecule for characterization of the state of various catalytic active sites, which were obtained after the V-MCM-41 treatment in oxidative (V-MCM-41o) or reductive (VMCM- 41r) atmosphere. Solid state vanadium modified mesoporous MCM-41 silica is characterised by XRD, N2 physisorption, FTIR and UV-Vis spectroscopies. Novel consecutive 11C- and 12C-methanol adsorption technique was used for the elucidation of the contribution of various vanadium species in methanol conversion. The radiodetectors are placed in front of the reactor to follow the methanol desorption at different temperatures as well as for radio-GC analysis (including FID coupled on-line with radiodetector) of methanol conversion. The rates of 11C-methanol desorption was negligible for V-MCM-41o, while a sharp increase is observed for V-MCM-41r in the temperature range of 160-180 deg C, indicating the presence of various types of catalytic active sites for both materials. Radio-GC results also reveal different catalytic behaviour for these vanadium modifications. On V-MCM- 41o, at lower temperature (250-280 deg C) a small amount of dimethyl ether (DME) was registered. The selectivity to CH4, CO, CO2, HCHO and methylal was strongly increased between 280-360 deg C. On V-MCM-41r, no DME and only a negligible amount of methylal were detected. The process was carried out exclusively to HCHO, and similarly to V-MCM- 41o, at higher temperatures - to CO formation. The desorption and catalytic measurements reveal that the variation in the pretreatment medium provides the formation of catalytic centers with different redox and acidic activity. While the products of methanol decomposition (CH4, CO, HCHO, CO2) are typical of the presence of redox sites

  9. CFD simulation of hydrogen mixing and mitigation by means of passive auto-catalytic recombiners

    Energy Technology Data Exchange (ETDEWEB)

    Kelm, S.; Reinecke, E-A.; Jahn, W., E-mail: s.kelm@fz-juelich.de [Forschungszentrum Juelich GmbH, Juelich (Germany); Allelein, H-J. [RWTH Aachen Univ.. Aachen (Germany)

    2011-07-01

    Modeling of passive auto-catalytic recombiners (PARs) operation in containment geometries involves a large variety of scales; thus, a CFD calculation resolving all these scales would be much too expensive. Therefore, the mechanistic PAR model REKO-DIREKT, developed at Forschungszentrum Juelich, has been coupled with the commercial CFD code ANSYS CFX in order to simulate PAR operation as well as the induced flow and transport phenomena. Based on a short introduction of REKO-DIREKT, its interface to CFX and the explicit coupling scheme is discussed. The paper is finalized by a first demonstration of simulation capabilities on the basis of the ThAI PAR-4 experiment (Becker Technologies GmbH, Eschborn, Germany). (author)

  10. Packed-bed catalytic cracking of oak derived pyrolytic vapors

    Science.gov (United States)

    Catalytic upgrading of pyrolysis vapors derived from oak was carried out using a fixed-bed catalytic column at 425 deg C. The vapors were drawn by splitting a fraction from the full stream of vapors produced at 500 deg C in a 5 kg/hr bench-scale fast pyrolysis reactor system downstream the cyclone s...

  11. In situ and operando transmission electron microscopy of catalytic materials

    DEFF Research Database (Denmark)

    Crozier, Peter A.; Hansen, Thomas Willum

    2015-01-01

    measurements of gas-phase catalytic products. To overcome this deficiency, operando TEM techniques are being developed that combine atomic characterization with the simultaneous measurement of catalytic products. This article provides a short review of the current status and major developments in the...

  12. Catalytic pyrolysis of oilsand bitumen over nanoporous catalysts.

    Science.gov (United States)

    Lee, See-Hoon; Heo, Hyeon Su; Jeong, Kwang-Eun; Yim, Jin-Heong; Jeon, Jong-Ki; Jung, Kyeong Youl; Ko, Young Soo; Kim, Seung-Soo; Park, Young-Kwon

    2011-01-01

    The catalytic cracking of oilsand bitumen was performed over nanoporous materials at atmospheric conditions. The yield of gas increased with application of nanoporous catalysts, with the catalytic conversion to gas highest for Meso-MFI. The cracking activity seemed to correlate with pore size rather than weak acidity or surface area. PMID:21446540

  13. Fabrication of Au–Pd nanoparticles/graphene oxide and their excellent catalytic performance

    Energy Technology Data Exchange (ETDEWEB)

    He, Yongqiang, E-mail: heyongqiang@126.com [Department of Applied Chemistry, Yuncheng University, Yuncheng 044000 (China); Zhang, Nana; Zhang, Lei [School of Science, Tianjin University, Tianjin 300072 (China); Gong, Qiaojuan [Department of Applied Chemistry, Yuncheng University, Yuncheng 044000 (China); Yi, Maocong [School of Science, Tianjin University, Tianjin 300072 (China); Wang, Wei [School of Chemical Engineering, Tianjin University, Tianjin 300072 (China); Qiu, Haixia, E-mail: qhx@tju.edu.cn [School of Science, Tianjin University, Tianjin 300072 (China); Gao, Jianping [School of Science, Tianjin University, Tianjin 300072 (China)

    2014-03-01

    Graphical abstract: - Highlights: • Au and Pd nanoparticles loaded on GO were fabricated without adding any reducing agents. • The Au–Pd NPs/GO were excellent catalysts for the reduction of 4-nitrophenol. • The Au–Pd NPs/GO showed superior catalytic activity for the Suzuki reaction. • The Au–Pd NPs/GO exhibit good reusability. - Abstract: A simple method to fabricate clean Au–Pd nanoparticles on graphene oxide (Au–Pd NPs/GO) without using any reducing agent or surfactant has been developed. GO simultaneously reduced the Au and Pd precursors to form a stable suspension of the Au–Pd NPs/GO. The nanoparticles were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and inductively coupled plasma. The Au–Pd NPs/GO exhibited catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol and for the Suzuki–Miyaura coupling reaction of chlorobenzene and phenylboronic acid in aqueous media.

  14. Fabrication of Au–Pd nanoparticles/graphene oxide and their excellent catalytic performance

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Au and Pd nanoparticles loaded on GO were fabricated without adding any reducing agents. • The Au–Pd NPs/GO were excellent catalysts for the reduction of 4-nitrophenol. • The Au–Pd NPs/GO showed superior catalytic activity for the Suzuki reaction. • The Au–Pd NPs/GO exhibit good reusability. - Abstract: A simple method to fabricate clean Au–Pd nanoparticles on graphene oxide (Au–Pd NPs/GO) without using any reducing agent or surfactant has been developed. GO simultaneously reduced the Au and Pd precursors to form a stable suspension of the Au–Pd NPs/GO. The nanoparticles were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and inductively coupled plasma. The Au–Pd NPs/GO exhibited catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol and for the Suzuki–Miyaura coupling reaction of chlorobenzene and phenylboronic acid in aqueous media

  15. Catalytic hydrocarbon reactions over supported metal oxides. Final report, August 1, 1986--July 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1995-10-20

    Oxide catalysis plays a central role in hydrocarbon processing and improvements in catalytic activity or selectivity are of great technological importance because these improvements will translate directly into more efficient utilization of hydrocarbon supplies and lower energy consumption in separation processes. An understanding of the relationships between surface structure and catalytic properties is needed to describe and improve oxide catalysts. The approach has been to prepare supported oxides that have a specific structure and oxidation state and then employ these structures in reaction studies. The current research program is focused on studying the fundamental relationships between structure and reactivity for two important reactions that are present in many oxide-catalyzed processes, partial oxidation and carbon-carbon bond formation. During the course of these studies the author has: (1) developed methods to form and stabilize various Mo and W oxide structures on silica; (2) studied C-H abstraction reactions over the fully oxidized cations; (3) studied C-C bond coupling by metathesis and reductive coupling of aldehydes and ketones over reduced cation structures; and (4) initiated a study of hydrogenation and hydrogenolysis over reduced cation structures.

  16. Facile synthesis of pristine graphene-palladium nanocomposites with extraordinary catalytic activities using swollen liquid crystals.

    Science.gov (United States)

    Vats, T; Dutt, S; Kumar, R; Siril, P F

    2016-01-01

    Amazing conductivity, perfect honeycomb sp(2) arrangement and the high theoretical surface area make pristine graphene as one of the best materials suited for application as catalyst supports. Unfortunately, the low reactivity of the material makes the formation of nanocomposite with inorganic materials difficult. Here we report an easy approach to synthesize nanocomposites of pristine graphene with palladium (Pd-G) using swollen liquid crystals (SLCs) as a soft template. The SLC template gives the control to deposit very small Pd particles of uniform size on G as well as RGO. The synthesized nanocomposite (Pd-G) exhibited exceptionally better catalytic activity compared with Pd-RGO nanocomposite in the hydrogenation of nitrophenols and microwave assisted C-C coupling reactions. The catalytic activity of Pd-G nanocomposite during nitrophenol reduction reaction was sixteen times higher than Pd nanoparticles and more than double than Pd-RGO nanocomposite. The exceptionally high activity of pristine graphene supported catalysts in the organic reactions is explained on the basis of its better pi interacting property compared to partially reduced RGO. The Pd-G nanocomposite showed exceptional stability under the reaction conditions as it could be recycled upto a minimum of 15 cycles for the C-C coupling reactions without any loss in activity. PMID:27619321

  17. Catalytic Decomposition of Methylene Chloride by Sulfated Titania Catalysts

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Catalytic decomposition of methylene chloride in air below 300℃ was studied.Sulfated titania was very effective in converting 959ppm methylene chloride selectively to CO,CO2 and HCl.Complete decomposition of methylene chloride was achieved at low temperature(275℃).It was found that the acidic property of catalyst was a determinant factor for the catalytic activity.The presence of water vapor in the feed stream remarkably reduced the catalytic activity,which could be due to the blockage of acidic sites on the surface of catalyst by water molecules.A bifunctional catalyst comprising copper oxide was developed to improve the selectivity of catalytic oxidation,which indicated that copper oxide can promote the deep oxidation of methylene chloride.The crystal form of TiO2 imposes an important influence upon the catalytic oxidation.

  18. Relationship between structure and catalytic performance of dealuminated Y zeolites

    International Nuclear Information System (INIS)

    Dealuminated Y zeolites which have been prepared by hydrothermal and chemical treatments show differences in catalytic performance when tested fresh; however, these differences disappear after the zeolites have been steamed. The catalytic behavior of fresh and steamed zeolites is directly related to zeolite structural and chemical characteristics. Such characteristics determine the strength and density of acid sites for catalytic cracking. Dealuminated zeolites were characterized using x-ray diffraction, porosimetry, solid-state NMR and elemental analysis. Hexadecane cracking was used as a probe reaction to determine catalytic properties. Cracking activity was found to be proportional to total aluminum content in the zeolite. Product selectivity was dependent on unit cell size, presence of extra framework alumina and spatial distribution of active sites. The results from this study elucidate the role that zeolite structure plays in determining catalytic performance

  19. Resting State and Elementary Steps of the Coupling of Aryl Halides with Thiols Catalyzed by Alkylbisphosphine Complexes of Palladium

    OpenAIRE

    Alvaro, Elsa; Hartwig, John F.

    2009-01-01

    Detailed mechanistic studies on the coupling of aryl halides with thiols catalyzed by palladium complexes of the alkylbisphosphine ligand CyPF-tBu (1-dicyclohexylphosphino-2-di-tert-butylphosphinoethylferrocene) are reported. The elementary steps that constitute the catalytic cycle, i.e. oxidative addition, transmetalation and reductive elimination, have been studied, and their relative rates are reported. Each of the steps of the catalytic process occurs at temperatures that are much lower t...

  20. Catalytically defective ganglioside neuraminidase in mucolipidosis IV

    International Nuclear Information System (INIS)

    Cultured skin fibroblasts from patients with mucolipidosis IV were found to be deficient in neuraminidase activity toward GDsub(la) and GDsub(lb) gangliosides radiolabelled in C3 and C7 analogs of their sialic acid residues. Neuraminidase activities toward 4-methylumbelliferyl-N-acetyl-neuraminic acid, neuraminlactose, and radiolabelled neuraminlactitol, fetuin and α1-acid glycoprotein were within the range of normal controls. Fibroblasts from parents of patients with mucolipidosis IV demonstrated intermediate levels of ganglioside neuraminidase activity and normal levels of glycoprotein neuraminidase activity. The redidual acidic neuraminidase activity toward GDsub(1a) ganglioside in the patients' fibroblasts did not differ from that of controls in its pH optimum and thermostability, but had an abnormal apparent Ksub(m) which was about 18 times higher than that of the normal enzyme. These findings suggest that mucolipidosis IV ia a ganglioside sialidosis due to a catalytically defective ganglioside neuraminidase. (author)

  1. Carbon nanofibers: a versatile catalytic support

    Directory of Open Access Journals (Sweden)

    Nelize Maria de Almeida Coelho

    2008-09-01

    Full Text Available The aim of this article is present an overview of the promising results obtained while using carbon nanofibers based composites as catalyst support for different practical applications: hydrazine decomposition, styrene synthesis, direct oxidation of H2S into elementary sulfur and as fuel-cell electrodes. We have also discussed some prospects of the use of these new materials in total combustion of methane and in ammonia decomposition. The macroscopic carbon nanofibers based composites were prepared by the CVD method (Carbon Vapor Deposition employing a gaseous mixture of hydrogen and ethane. The results showed a high catalytic activity and selectivity in comparison to the traditional catalysts employed in these reactions. The fact was attributed, mainly, to the morphology and the high external surface of the catalyst support.

  2. Scanning electrochemical microscopy of individual catalytic nanoparticles.

    Science.gov (United States)

    Sun, Tong; Yu, Yun; Zacher, Brian J; Mirkin, Michael V

    2014-12-15

    Electrochemistry at individual metal nanoparticles (NPs) can provide new insights into their electrocatalytic behavior. Herein, the electrochemical activity of single AuNPs attached to the catalytically inert carbon surface is mapped by using extremely small (≥3 nm radius) polished nanoelectrodes as tips in the scanning electrochemical microscope (SECM). The use of such small probes resulted in the spatial resolution significantly higher than in previously reported electrochemical images. The currents produced by either rapid electron transfer or the electrocatalytic hydrogen evolution reaction at a single 10 or 20 nm NP were measured and quantitatively analyzed. The developed methodology should be useful for studying the effects of nanoparticle size, geometry, and surface attachment on electrocatalytic activity in real-world application environment. PMID:25332196

  3. Catalytic cracking process with vanadium passivation

    Energy Technology Data Exchange (ETDEWEB)

    Kennedy, J.V.; Jossens, L.W.

    1991-03-26

    This paper discusses a process for the catalytic cracking of metal-containing hydrocarbonaceous feedstock. It comprises contacting the feedstock under cracking conditions with a dual component catalyst composition. The catalyst composition comprises a first component comprising an active cracking catalyst; and a second component, as a separate and distinct entity, the second component comprising the following materials: a calcium and magnesium containing material selected from the group consisting of dolomite, substantially amorphous calcium magnesium silicate, calcium magnesium oxide, calcium magnesium acetate, calcium magnesium carbonate, and calcium magnesium subcarbonate; a magnesium containing material comprising a hydrous magnesium silicate; and a binder selected from the group consisting of kaolin, bentonite, montmorillonite, saponite, hectorite, alumina, silica, titania, zirconia, silica-alumina, and combinations thereof.

  4. Catalytic Conia-ene and related reactions.

    Science.gov (United States)

    Hack, Daniel; Blümel, Marcus; Chauhan, Pankaj; Philipps, Arne R; Enders, Dieter

    2015-10-01

    Since its initial inception, the Conia-ene reaction, known as the intramolecular addition of enols to alkynes or alkenes, has experienced a tremendous development and appealing catalytic protocols have emerged. This review fathoms the underlying mechanistic principles rationalizing how substrate design, substrate activation, and the nature of the catalyst work hand in hand for the efficient synthesis of carbocycles and heterocycles at mild reaction conditions. Nowadays, Conia-ene reactions can be found as part of tandem reactions, and the road for asymmetric versions has already been paved. Based on their broad applicability, Conia-ene reactions have turned into a highly appreciated synthetic tool with impressive examples in natural product synthesis reported in recent years. PMID:26031492

  5. Smoke emissions from a catalytic wood stove

    International Nuclear Information System (INIS)

    The work reported here was concerned with testing a catalytic wood burning stove (roomheater) following the most applicable UK procedures. The identical stove has also been tested in several other nations to their individual procedures. The results will be submitted to the International Energy Agency (IEA) such that appropriate comparisons can be made. The results comprised: burning rate; an indicative appliance efficiency; heat output; carbon dioxide emissions; carbon monoxide emissions; and smoke emissions. These results were determined with the appliance at three nominal burning rates (high, medium and low). Comparing the results with those obtained in other countries indicates good agreement except when the appliance was operated at low burning rates, under which conditions the UK results indicate significantly worse smoke emissions than those measured by other researchers. (author)

  6. Lignin Valorization using Heterogenous Catalytic Oxidation

    DEFF Research Database (Denmark)

    Melián Rodríguez, Mayra; Shunmugavel, Saravanamurugan; Kegnæs, Søren;

    The research interests in biomass conversion to fuels and chemicals has increased significantly in the last decade in view of current problems such as global warming, high oil prices, food crisis and other geopolitical scenarios. Many different reactions and processes to convert biomass into high......-value products and fuels have been proposed in the literature, giving special attention to the conversion of lignocellulosic biomass, which does not compete with food resources and is widely available as a low cost feedstock 1. Lignocellulose biomass is a complex material composed of three main fractions...... complex so different model compounds are often used to study lignin valorization. These model compounds contain the linkages present in lignin, simplifying catalytic analysis and present analytical challenges related to the study of the complicated lignin polymer and the plethora of products that could be...

  7. Ubiquitous ``glassy'' relaxation in catalytic reaction networks

    Science.gov (United States)

    Awazu, Akinori; Kaneko, Kunihiko

    2009-10-01

    Study of reversible catalytic reaction networks is important not only as an issue for chemical thermodynamics but also for protocells. From extensive numerical simulations and theoretical analysis, slow relaxation dynamics to sustain nonequlibrium states are commonly observed. These dynamics show two types of salient behaviors that are reminiscent of glassy behavior: slow relaxation along with the logarithmic time dependence of the correlation function and the emergence of plateaus in the relaxation-time course. The former behavior is explained by the eigenvalue distribution of a Jacobian matrix around the equilibrium state that depends on the distribution of kinetic coefficients of reactions. The latter behavior is associated with kinetic constraints rather than metastable states and is due to the absence of catalysts for chemicals in excess and the negative correlation between two chemical species. Examples are given and generality is discussed with relevance to bottleneck-type dynamics in biochemical reactions as well.

  8. Soluble organic nanotubes for catalytic systems

    Science.gov (United States)

    Xiong, Linfeng; Yang, Kunran; Zhang, Hui; Liao, Xiaojuan; Huang, Kun

    2016-03-01

    In this paper, we report a novel method for constructing a soluble organic nanotube supported catalyst system based on single-molecule templating of core-shell bottlebrush copolymers. Various organic or metal catalysts, such as sodium prop-2-yne-1-sulfonate (SPS), 1-(2-(prop-2-yn-1-yloxy)ethyl)-1H-imidazole (PEI) and Pd(OAc)2 were anchored onto the tube walls to functionalize the organic nanotubes via copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Depending on the ‘confined effect’ and the accessible cavity microenvironments of tubular structures, the organic nanotube catalysts showed high catalytic efficiency and site-isolation features. We believe that the soluble organic nanotubes will be very useful for the development of high performance catalyst systems due to their high stability of support, facile functionalization and attractive textural properties.

  9. Catalytic hot gas cleaning of gasification gas

    Energy Technology Data Exchange (ETDEWEB)

    Simell, P. [VTT Energy, Espoo (Finland). Energy Production Technologies

    1997-12-31

    The aim of this work was to study the catalytic cleaning of gasification gas from tars and ammonia. In addition, factors influencing catalytic activity in industrial applications were studied, as well as the effects of different operation conditions and limits. Also the catalytic reactions of tar and ammonia with gasification gas components were studied. The activities of different catalyst materials were measured with laboratory-scale reactors fed by slip streams taken from updraft and fluid bed gasifiers. Carbonate rocks and nickel catalysts proved to be active tar decomposing catalysts. Ammonia decomposition was in turn facilitated by nickel catalysts and iron materials like iron sinter and iron dolomite. Temperatures over 850 deg C were required at 2000{sup -1} space velocity at ambient pressure to achieve almost complete conversions. During catalytic reactions H{sub 2} and CO were formed and H{sub 2}O was consumed in addition to decomposing hydrocarbons and ammonia. Equilibrium gas composition was almost achieved with nickel catalysts at 900 deg C. No deactivation by H{sub 2}S or carbon took place in these conditions. Catalyst blocking by particulates was avoided by using a monolith type of catalyst. The apparent first order kinetic parameters were determined for the most active materials. The activities of dolomite, nickel catalyst and reference materials were measured in different gas atmospheres using laboratory apparatus. This consisted of nitrogen carrier, toluene as tar model compound, ammonia and one of the components H{sub 2}, H{sub 2}O, CO, CO{sub 2}, CO{sub 2}+H{sub 2}O or CO+CO{sub 2}. Also synthetic gasification gas was used. With the dolomite and nickel catalyst the highest toluene decomposition rates were measured with CO{sub 2} and H{sub 2}O. In gasification gas, however, the rate was retarded due to inhibition by reaction products (CO, H{sub 2}, CO{sub 2}). Tar decomposition over dolomite was modelled by benzene reactions with CO{sub 2}, H

  10. Contact structure for use in catalytic distillation

    Science.gov (United States)

    Jones, Jr., Edward M.

    1984-01-01

    A method for conducting catalytic chemical reactions and fractionation of the reaction mixture comprising feeding reactants into a distillation column reactor contracting said reactant in liquid phase with a fixed bed catalyst in the form of a contact catalyst structure consisting of closed porous containers containing the catatlyst for the reaction and a clip means to hold and support said containers, which are disposed above, i.e., on the distillation trays in the tower. The trays have weir means to provide a liquid level on the trays to substantially cover the containers. In other words, the trays function in their ordinary manner with the addition thereto of the catalyst. The reaction mixture is concurrently fractionated in the column.

  11. Biofuel from fast pyrolysis and catalytic hydrodeoxygenation.

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, Douglas C.

    2015-09-04

    This review addresses recent developments in biomass fast pyrolysis bio-oil upgrading by catalytic hydrotreating. The research in the field has expanded dramatically in the past few years with numerous new research groups entering the field while existing efforts from others expand. The issues revolve around the catalyst formulation and operating conditions. Much work in batch reactor tests with precious metal catalysts needs further validation to verify long-term operability in continuous flow systems. The effect of the low level of sulfur in bio-oil needs more study to be better understood. Utilization of the upgraded bio-oil for feedstock to finished fuels is still in an early stage of understanding.

  12. Catalytic combustion in small wood burning appliances

    Energy Technology Data Exchange (ETDEWEB)

    Oravainen, H. [VTT Energy, Jyvaeskylae (Finland)

    1996-12-31

    There is over a million hand fired small heating appliances in Finland where about 5,4 million cubic meters of wood fuel is used. Combustion in such heating appliances is a batch-type process. In early stages of combustion when volatiles are burned, the formation of carbon monoxide (CO) and other combustible gases are difficult to avoid when using fuels that have high volatile matter content. Harmful emissions are formed mostly after each fuel adding but also during char burnout period. When the CO-content in flue gases is, say over 0.5 %, also other harmful emissions will be formed. Methane (CH{sub 4}) and other hydrocarbons are released and the amount of polycyclic aromatic hydrocarbons (PAH)-compounds can be remarkable. Some PAH-compounds are very carcinogenic. It has been estimated that in Finland even more than 90 % of hydrocarbon and PAH emissions are due to small scale wood combustion. Emissions from transportation is excluded from these figures. That is why wood combustion has a net effect on greenhouse gas phenomena. For example carbon monoxide emissions from small scale wood combustion are two fold compared to that of energy production in power plants. Methane emission is of the same order as emission from transportation and seven fold compared with those of energy production. Emissions from small heating appliances can be reduced by developing the combustion techniques, but also by using other means, for example catalytic converters. In certain stages of the batch combustion, temperature is not high enough, gas mixing is not good enough and residence time is too short for complete combustion. When placed to a suitable place inside a heating appliance, a catalytic converter can oxidize unburned gases in the flue gas into compounds that are not harmful to the environment. (3 refs.)

  13. Plasma Catalytic Synthesis of Silver Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yu-Tao; GUO Ying; MA Teng-Cai

    2011-01-01

    We present the experimental results of plasma catalytic synthesis of colloidal silver nanoparticles, using AgNO3 as the precursor, ethanol as the solvent and reducing agent, and poly vinyl pyrrolidone (PVP) as the macromolecular surfactant. The plasma is generated by an atmospheric argon dielectric barrier discharge jet. Silver nanoparticles are produced instantly once the plasma is ignited. The system is not heated so it is necessary to use traditional chemical methods. The samples are characterized by UV-visible absorbance and transmission electron microscopy. For glow discharge mode no obvious silver nanoparticles are observed. For low voltage filamentary streamer discharge mode a lot of silver nanoparticles with the mean diameter of ~3.5nm are generated and a further increase of the voltage causes the occurrence of agglomeration.%We present the experimental results of plasma catalytic synthesis of colloidal silver nanoparticles,using AgNO3 as the precursor,ethanol as the solvent and reducing agent,and poly vinyl pyrrolidone (PVP) as the macromolecular surfactant.The plasma is generated by an atmospheric argon dielectric barrier discharge jet.Silver nanoparticles are produced instantly once the plasma is ignited.The system is not heated so it is necessary to use traditional chemical methods.The samples are characterized by UV-visible absorbance and transmission electron microscopy.For glow discharge mode no obvious silver nanoparticles are observed.For low voltage filamentary streamer discharge mode a lot of silver nanoparticles with the mean diameter of ~3.5nm are generated and a further increase of the voltage causes the occurrence of agglomeration.The study of silver nanoparticles has been an extremely active area in recent years because of their important physical and chemical properties as a catalyst and antimicrobial reagent,for example.A number of methods for silver nanoparticle preparation have been developed,[1-3] among them chemical reduction is

  14. Experimental catalytic isotopic exchange column control

    International Nuclear Information System (INIS)

    Full text: In this paper we present a method for monitoring and control of the experimental catalytic isotopic exchange column which is part of ETRF (experimental tritium removal facility) of the ICIT Rm. Valcea. The initial data acquisition system based on analogue instruments is now upgraded to a fully digital system. Therefore we chose to use Compact Field Point which is a programmable automation controller (PAC) and LabVIEW software. To operate the catalytic isotopic exchange column there are some control loops that need to be operated simultaneously, namely: the heavy water column feed temperature and flow rate; the hydrogen gas column feed temperature; the flow rate and pressure at the top of the column; the water vapor flow rate; the hydrogen gas temperature at the condenser output. The human machine interface (HMI) realized with LabVIEW software is very friendly. The use of the PAC graphics interface makes isotopic exchange process operation easier for operators and researchers. The HMI has the functions to provide visualization of process parameters, to enable interaction with the process and also to provide alarms and event notification to operators about any abnormal situation in the plant. To interact with the process, detailed displays which contain specific control functions to operate the column, can be used. Usually, the faceplate display shows the controlled process variable and the output of the control loop. Furthermore, the set point and the operating mode of the control loop can be changed. Additionally, detailed information is available related to the parameters of PID controller and the different alarms that can be authorized in this control loop with its corresponding values of activation. (authors)

  15. Modelling of automotive catalytic converter; Modellierung von Autoabgaskatalysatoren

    Energy Technology Data Exchange (ETDEWEB)

    Mladenov, Nikolay

    2010-07-01

    This thesis focuses on the numerical modeling of monolithic converters coupling diverse gas-phase and porous media transport models and detailed heterogeneous reaction mechanisms. It investigates the impact of a wide spectrum of model parameters on the conversion rate of the catalysts using the CFD software package DETCHEM. The first part of the work presents a parameter study based on the fundamentals of the conventional laminar and recently developed turbulent converters. It has been found out that an optimization at every step of the catalytic process is required in order to increase the efficiency of the exhaust gas converters. Here, calculations with a single steady-state isothermal channel of cylindrical shape are carried out using the boundary layer approach. The simulated channel is coated by a porous washcoat layer containing platinum as an active component. The transport limitation within the washcoat is described by means of a reaction-diffusion model which accounts for the distribution of macro- and micro-pores in the porous media. The study shows that an optimization with respect to operating temperature, washcoat thickness, pore radius distribution and noble metal loading results in increased conversion of carbon monoxide and hydrocarbons. However, these parameters can be varied only in certain ranges of values due to limitations such as catalyst deactivation and manufacturing costs. Structured channels and perforated metal foils represent a further option to increase the efficiency of catalytic converters. The local turbulence effects within these constructions lead to intensification of the mass transport. In the current work, this intensification is taken into account by introducing an enhanced plug-flow model with amplified mass transfer coefficients. The second part of the thesis handles the thermal aging of three way catalysts (TWC). The applied simulation approach allows for qualitative prediction of the deactivation state along the catalyst

  16. Preparation of Pt-Ru hydrophobic catalysts and catalytic activities for liquid phase catalytic exchange reaction

    International Nuclear Information System (INIS)

    Pt/C and Pt-Ru/C catalysts with different ratios of Pt to Ru were synthesized, using ethylene glycol as both the dispersant and reducing agent at 1-2 MPa by microwave-assisted method. The catalysts were characterized by XRD, TEM and XPS. The mean particle sizes of the Pt/C and Pt-Ru/C catalysts were 1.9-2.0 nm. Pt and Ru existed as Pt(0), Pt(II), Pt(IV), Ru(0) and Ru(IV) for Pt-Ru/C catalysts, respectively. The face-centered cubic structure of the active mental particles would be changed upon the addition of Ru gradually. Then polytetrafluoroethylene and carbon-supported Pt and Pt-Ru catalysts were supported on foamed nickel to obtain hydrophobic catalysts. The catalytic activity was increased for liquid phase catalytic exchange (LPCE) when uniform Pt based hydrophobic catalysts was mixed into appropriate Ru. Hydrogen isotope exchange reaction occurs between hydration layer(H2O)nH+(ads)(n≥2) and D atoms due to intact water molecules being on Pt surface for LPCE. Water molecules have a tendency to dissociate to OH(ads) and H(ads) on metal Ru surface, and there is the other reaction path for Pt-Ru binary catalysts, which is probably the main reason of the increase of the catalytic activity of the hydrophobic Pt-Ru catalyst. (authors)

  17. Targeted Catalytic Inactivation of Angiotensin Converting Enzyme by Lisinopril-Coupled Transition Metal Chelates

    OpenAIRE

    Joyner, Jeff C.; Hocharoen, Lalintip; Cowan, J. A.

    2012-01-01

    A series of compounds that target reactive transition metal chelates to somatic Angiotensin Converting Enzyme (sACE-1) have been synthesized. Half maximal inhibitory concentrations (IC50) and rate constants for both inactivation and cleavage of full length sACE-1 have been determined and evaluated in terms of metal-chelate size, charge, reduction potential, coordination unsaturation, and coreactant selectivity. Ethylenediamine-tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), 1,4,7,10-tet...

  18. Studies of coupled chemical and catalytic coal conversion methods. Fifth quarterly report, October--December 1988

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.

    1988-12-31

    Liquefaction of coal by depolymerization in an organic solvent has been studied for several years. The liquefied coal extract which results from such a process is far more suitable for conversion into liquid fuel by hydrogenolysis than is the untreated coal. Investigations on the chemical structure and the reactive sites of coal can help to select useful reactions for the production of liquids from coal. Sternberg et al. demonstrated that the reductive alkylation method transforms bituminous coal into an enormously soluble substance, irrespective of the mild reaction conditions. The effectiveness of newly introduced alkyl groups for the disruption of intermolecular hydrogen bonds and pi-pi interactions between the aromatic sheets in coal macromolecules has been recognized. It has been reported by Ignasiak et al. that a C-alkylabon reaction using sodium or potassium amide in liquid ammonia can be used to introduce alkyl groups at acidic carbon sites. A method has been developed recently in this laboratory for the solubilization of high rank coals. In the previous reports it was shown that n-butyl lithium and potassium t-butoxide in refluxing heptane produced coal anions which could be alkylated with different alkyl halides. Such alkylated coals were soluble up to 92% in solvents like pyridine. Though the solubilization of coal depended very much on the length of the alkyl group, it also depended very much on the nature of the base used. Strong bases like n-butyl lithium (pKa=42) can cause proton abstraction from aromatic structures, if the more acidic benzylic protons are absent. The utility of this procedure, initially developed and used by Miyake and Stock, has now been tested with the high oxygen containing, low rank Illinois No. 6 and Wyodak coals.

  19. Catalytic Wet Air Oxidation Coupled with an Aerobic Treatment to Deal with Industrial Wastewater

    OpenAIRE

    Suárez Ojeda, María Eugenia

    2006-01-01

    La reducción del agua residual y su tratamiento es uno de los retos a los que se enfrenta nuestra sociedad de consumo. Por ejemplo, en la UE se vierten 5400 toneladas al año de efluentes industriales de compuestos aromáticos, los cuales presentan efectos tóxicos y bactericidas. Hoy en día, existen varias tecnologías que han demostrado su potencial para tratar este tipo de efluentes industriales. La mayoría de ellas están basadas en la oxidación del contaminante orgánico, el cual es transforma...

  20. Palladium/Imidazolium Salts: A General and Highly Efficient Catalytic System for Coupling Reaction

    Institute of Scientific and Technical Information of China (English)

    YANG Chu-Luo; Steven P. Nolan

    2003-01-01

    @@ Nucleophilic N-heterocyclic carbenes have attracted considerable attention. These ligands are strong σ-donor with negligible π-accepting ability, and in this regard, they resemble electron-donor phosphines and can be addressed as "phosphine mimics". [ 1

  1. Improved catalytic activity of laser generated bimetallic and trimetallic nanoparticles.

    Science.gov (United States)

    Singh, Rina; Soni, R K

    2014-09-01

    We report synthesis of silver nanoparticles, bimetallic (Al2O3@Ag) nanoparticles and trimetallic (Al2O3@AgAu) nanoparticles by nanosecond pulse laser ablation (PLA) in deionized water. Two-step laser ablation methodologies were adopted for the synthesis of bi- and tri-metallic nanoparticles. In this method a silver or gold target was ablated in colloidal solution of γ-alumina nanoparticles prepared by PLA. The TEM image analysis of bimetallic and trimetallic particles reveals deposition of fine silver particles and Ag-Au alloy particles, respectively, on large alumina particles. The laser generated nanoparticles were tested for catalytic reduction of 4-nitrophenol to 4-aminophenol and showed excellent catalytic behaviour. The catalytic rate was greatly improved by incorporation of additional metal in silver nanoparticles. The catalytic efficiency of trimetallic Al2O3@AgAu for reduction of 4-nitrophenol to 4-aminophenol was remarkably enhanced and the catalytic reaction was completed in just 5 sec. Even at very low concentration, both Al2O3@Ag nanoparticles and Al2O3@AgAu nanoparticles showed improved rate of catalytic reduction than monometallic silver nanoparticles. Our results demonstrate that alumina particles in the solution not only provide the active sites for particle dispersion but also improve the catalytic activity. PMID:25924343

  2. Numerical Study of Passive Catalytic Recombiner for Hydrogen Mitigation

    Directory of Open Access Journals (Sweden)

    Pavan K Sharma

    2010-10-01

    Full Text Available A significant amount of hydrogen is expected to be released within the containment of a water cooled power reactor after a severe accident. To reduce the risk of deflagration/detonation various means for hydrogen control have been adopted all over the world. Passive catalytic recombiner with vertical flat catalytic plate is one of such hydrogen mitigating device. Passive catalytic recombiners are designed for the removal of hydrogen generated in order to limit the impact of possible hydrogen combustion. Inside a passive catalytic recombiner, numerous thin steel sheets coated with catalyst material are vertically arranged at the bottom opening of a sheet metal housing forming parallel flow channels for the surrounding gas atmosphere. Already below conventional flammability limits, hydrogen and oxygen react exothermally on the catalytic surfaces forming harmless steam. Detailed numerical simulations and experiments are required for an in-depth knowledge of such plate type catalytic recombiners. Specific finite volume based in-house CFD code has been developed to model and analyse the working of these recombiner. The code has been used to simulate the recombiner device used in the Gx-test series of Battelle-Model Containment (B-MC experiments. The present paper briefly describes the working principle of such passive catalytic recombiner and salient feature of the CFD model developed at Bhabha Atomic Research Centre (BARC. Finally results of the calculations and comparison with existing data are discussed.

  3. Orion EFT-1 Catalytic Tile Experiment Overview and Flight Measurements

    Science.gov (United States)

    Salazar, Giovanni; Amar, Adam; Hyatt, Andrew; Rezin, Marc D.

    2016-01-01

    This paper describes the design and results of a surface catalysis flight experiment flown on the Orion Multipurpose Crew Vehicle during Exploration Flight Test 1 (EFT1). Similar to previous Space Shuttle catalytic tile experiments, the present test consisted of a highly catalytic coating applied to an instrumented TPS tile. However, the present catalytic tile experiment contained significantly more instrumentation in order to better resolve the heating overshoot caused by the change in surface catalytic efficiency at the interface between two distinct materials. In addition to collecting data with unprecedented spatial resolution of the "overshoot" phenomenon, the experiment was also designed to prove if such a catalytic overshoot would be seen in turbulent flow in high enthalpy regimes. A detailed discussion of the results obtained during EFT1 is presented, as well as the challenges associated with data interpretation of this experiment. Results of material testing carried out in support of this flight experiment are also shown. Finally, an inverse heat conduction technique is employed to reconstruct the flight environments at locations upstream and along the catalytic coating. The data and analysis presented in this work will greatly contribute to our understanding of the catalytic "overshoot" phenomenon, and have a significant impact on the design of future spacecraft.

  4. Methane Coupling Using Hydrogen Plasma and Pt/γ-Al2O3 Catalyst

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    In this paper, methane coupling at ambient temperature, under atmospheric pressure and in the presence of hydrogen was firstly investigated by using pulse corona plasma and Pt/γ-Al2O3 catalyst. Experimental results showed that Pt/γ-Al2O3 catalyst has catalytic activity for methane coupling to C2H4. Over sixty percent of outcomes of C2 hydrocarbons were detected to be ethylene.

  5. Pd(II/HPMoV-Catalyzed Direct Oxidative Coupling Reaction of Benzenes with Olefins

    Directory of Open Access Journals (Sweden)

    Yasutaka Ishii

    2010-03-01

    Full Text Available The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc2/molybdovanadophosphoric acid (HPMoV as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation.

  6. Efficient Sonogashira and Suzuki-Miyaura coupling reaction catalyzed by Pd-Nanoparticles

    Indian Academy of Sciences (India)

    Kishor E Balsane; Suresh S Shendage; Jayashree M Nagarkar

    2015-03-01

    The Pd nano particles were electrochemically deposited on nafion-graphene. They showed excellent catalytic activity towards Sonogashira and Suzuki-Miyaura cross-coupling reaction. Benzenediazonium salts were used as alternative to aromatic halide. The developed protocol offers recyclability, easy workups with short reaction time and good-to-excellent product yield.

  7. Cu(I)-NHC-catalyzed silylation of allenes: diastereoselective three-component coupling with aldehydes.

    Science.gov (United States)

    Rae, James; Hu, Ya Chu; Procter, David J

    2014-10-01

    Copper-catalyzed silylation of aryl allenes using a silylborane reagent affords vinyl silane building blocks with high efficiency. The use of a seven-membered NHC ligand proved crucial for high regioselectivity. The catalytically generated allylcoppper intermediates were intercepted by aldehydes in a diastereoselective three-component coupling to furnish homoallylic alcohols. PMID:25146221

  8. Controlled synthesis of porous platinum nanostructures for catalytic applications.

    Science.gov (United States)

    Cao, Yanqin; Zhang, Junwei; Yang, Yong; Huang, Zhengren; Long, Nguyen Viet; Nogami, Masayuki

    2014-02-01

    Porous platinum, that has outstanding catalytic and electrical properties and superior resistant characteristics to corrosion, has been widely applied in chemical, petrochemical, pharmaceutical, electronic, and automotive industries. As the catalytic activity and selectivity depend on the size, shape and structure of nanomaterials, the strategies for controlling these factors of platinum nanomaterials to get excellent catalytic properties are discussed. Here, recent advances in the design and preparation of various porous platinum nanostructures are reviewed, including wet-chemical synthesis, electro-deposition, galvanic replacement reaction and de-alloying technology. The applications of various platinum nanostructures are also discussed, especially in fuel cells. PMID:24749422

  9. Biorhythm in Couple Counseling

    Science.gov (United States)

    Araoz, Daniel L.

    1977-01-01

    Twelve couples in marital counseling were studied during 12 months on the basis of their biorhythms. For each couple a compatibility percentage was obtained. It was found that difficulties in their interaction correlated highly with dissonance in their biorhythms. (Author)

  10. Synthesis and Characterization of Metal Complexes to be Employed in the Catalytic Depolymerization of Lignin Model Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Chmely, S. C.; Kim, S.; Beckham, G. T.

    2012-01-01

    Lignin is an earth-abundant biopolymer that is grossly underutilized as a value stream in current biomass conversion technologies because there exist no economic and technically feasible routes for lignin depolymerization and upgrading to fuels and chemicals. The development of new mild and selective catalytic routes to depolymerize this recalcitrant biopolymer is required to more effectively utilize lignin. To that end, our group aims to synthesize and characterize a collection of organometallic catalysts to promote atom-economical catalytic lignin deconstruction. These catalysts have been screened against dimeric lignin model compounds in order to gain mechanistic insights into their modes of action. In addition, experimental efforts have been coupled with quantum mechanical calculations to elucidate solution behavior of the catalysts as well as the mechanisms of lignin depolymerization. Detailed synthetic procedures, as well as spectroscopic and crystallographic characterization and DFT calculations will be presented.

  11. Catalytic hydrocarbon reactions over supported metal oxides. Progress report, April 1, 1994--January 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1995-01-31

    Oxide catalysis plays a central role in hydrocarbon processing and improvements in catalytic activity or selectivity are of great technological importance because these improvements will translate directly into more efficient utilization of hydrocarbon supplies and lower energy consumption in separation processes. An understanding of the relationships between surface structure and catalytic properties is needed to describe and improve oxide catalysts. Our approach has been to prepare supported oxides that have a specific structure and oxidation state and then employ these structures in reaction studies. Our current research program is focused on studying the fundamental relationships between structure and reactivity for two important reactions that are present in many oxide-catalyzed processes, partial oxidation and carbon-carbon bond formation. Oxide catalysis can be a complex process with both metal cation and oxygen anions participating in the chemical reactions. From an energy perspective carbon-carbon bond formation is particularly relevant to CO hydrogenation in isosynthesis. Hydrogenolysis and hydrogenation form the basis for heteroatom removal in fuels processing. Understanding the catalysis of these processes (and others) requires isolating reaction steps in the overall cycle and determining how structure and composition influence the individual reaction steps. Specially designed oxides, such as we use, permit one to study some of the steps in oxidation, carbon-carbon coupling and heteroatom removal catalysis. During the course of our studies we have: (1) developed methods to form and stabilize various Mo and W oxide structures on silica; (2) studied C-H abstraction reactions over the fully oxidized cations; (3) studied C-C bond coupling by methathesis and reductive coupling of aldehydes and ketones over reduced cation structures; and (4) initiated a study of hydrogenation and hydrogenolysis over reduced cation structures.

  12. Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions

    Science.gov (United States)

    Cuba Torres, Christian Martin

    On a global scale, the energy demand is largely supplied by the combustion of non-renewable fossil fuels. However, their rapid depletion coupled with environmental and sustainability concerns are the main drivers to seek for alternative energetic strategies. To this end, the sustainable generation of hydrogen from renewable resources such as biodiesel would represent an attractive alternative solution to fossil fuels. Furthermore, hydrogen's lower environmental impact and greater independence from foreign control make it a strong contender for solving this global problem. Among a wide variety of methods for hydrogen production, the catalytic partial oxidation offers numerous advantages for compact and mobile fuel processing systems. For this reaction, the present work explores the versatility of the Mo--O--C catalytic system under different synthesis methods and reforming conditions using methyl oleate as a surrogate biodiesel. MoO2 exhibits good catalytic activity and exhibits high coke-resistance even under reforming conditions where long-chain oxygenated compounds are prone to form coke. Moreover, the lattice oxygen present in MoO2 promotes the Mars-Van Krevelen mechanism. Also, it is introduced a novel beta-Mo2C synthesis by the in-situ formation method that does not utilize external H2 inputs. Herein, the MoO 2/Mo2C system maintains high catalytic activity for partial oxidation while the lattice oxygen serves as a carbon buffer for preventing coke formation. This unique feature allows for longer operation reforming times despite slightly lower catalytic activity compared to the catalysts prepared by the traditional temperature-programmed reaction method. Moreover, it is demonstrated by a pulse reaction technique that during the phase transformation of MoO2 to beta-Mo2C, the formation of Mo metal as an intermediate is not responsible for the sintering of the material wrongly assumed by the temperature-programmed method.

  13. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    Science.gov (United States)

    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.

  14. Catalytic glycerol steam reforming for hydrogen production

    International Nuclear Information System (INIS)

    Hydrogen production from glycerol by steam reforming combine two major advantages: (i) using glycerol as raw material add value to this by product of bio-diesel production which is obtained in large quantities around the world and have a very limited utilization now, and (ii) by implication of water molecules in the reaction the efficiency of hydrogen generation is increased as each mol of glycerol produces 7 mol of H2. In this work we present the results obtained in the process of steam reforming of glycerol on Ni/Al2O3. The catalyst was prepared by wet impregnation method and characterized through different methods: N2 adsorption-desorption, XRD, TPR. The catalytic study was performed in a stainless steel tubular reactor at atmospheric pressure by varying the reaction conditions: steam/carbon ratio (1-9), gas flow (35 ml/min -133 ml/min), temperature (450-650°C). The gaseous fraction of the reaction products contain: H2, CH4, CO, CO2. The optimum reaction conditions as resulted from this study are: temperature 550°C, Gly:H2O ratio 9:1 and Ar flow 133 ml/min. In these conditions the glycerol conversion to gaseous products was 43% and the hydrogen yield was 30%

  15. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    Energy Technology Data Exchange (ETDEWEB)

    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.

  16. Radioisotope applications on fluidized catalytic cracking units

    International Nuclear Information System (INIS)

    Radioisotopes are used to trace the flow of all the phases of Fluidized Catalytic Cracking process in oil refineries. The gaseous phases, steam, hydrocarbon vapour and air, are generally traced using a noble-gas isotope, 41Ar, 79Kr or 85Kr. An appropriate tracer for the catalyst is produced by irradiating a catalyst sample in a nuclear reactor. The activation products,140La and 24Na provide appropriate radioactive 'labels' for the catalyst, which is reinjected into the FCC. An advantage of this approach is that it facilitates the study of the behaviour of different particle size fractions. Radioisotopes as sealed sources of gamma radiation are used to measure catalyst density variations and density distributions in critical parts of the unit. An important trend in radioisotope applications is the increasing use of the information they produce as inputs to or as validation of, mathematical process models. In line with the increasing sophistication of the models, the technology is undergoing continuous refinement. Developments include the investigation of more efficient, more convenient tracers, the introduction of systems to facilitate more rapid and comprehensive data acquisition and software refinements for enhanced data analysis

  17. Catalytic partial oxidation of pyrolysis oils

    Science.gov (United States)

    Rennard, David Carl

    2009-12-01

    This thesis explores the catalytic partial oxidation (CPO) of pyrolysis oils to syngas and chemicals. First, an exploration of model compounds and their chemistries under CPO conditions is considered. Then CPO experiments of raw pyrolysis oils are detailed. Finally, plans for future development in this field are discussed. In Chapter 2, organic acids such as propionic acid and lactic acid are oxidized to syngas over Pt catalysts. Equilibrium production of syngas can be achieved over Rh-Ce catalysts; alternatively mechanistic evidence is derived using Pt catalysts in a fuel rich mixture. These experiments show that organic acids, present in pyrolysis oils up to 25%, can undergo CPO to syngas or for the production of chemicals. As the fossil fuels industry also provides organic chemicals such as monomers for plastics, the possibility of deriving such species from pyrolysis oils allows for a greater application of the CPO of biomass. However, chemical production is highly dependent on the originating molecular species. As bio oil comprises up to 400 chemicals, it is essential to understand how difficult it would be to develop a pure product stream. Chapter 3 continues the experimentation from Chapter 2, exploring the CPO of another organic functionality: the ester group. These experiments demonstrate that equilibrium syngas production is possible for esters as well as acids in autothermal operation with contact times as low as tau = 10 ms over Rh-based catalysts. Conversion for these experiments and those with organic acids is >98%, demonstrating the high reactivity of oxygenated compounds on noble metal catalysts. Under CPO conditions, esters decompose in a predictable manner: over Pt and with high fuel to oxygen, non-equilibrium products show a similarity to those from related acids. A mechanism is proposed in which ethyl esters thermally decompose to ethylene and an acid, which decarbonylates homogeneously, driven by heat produced at the catalyst surface. Chapter 4

  18. Catalytic extraction processing of contaminated scrap metal

    Energy Technology Data Exchange (ETDEWEB)

    Griffin, T.P.; Johnston, J.E.; Payea, B.M. [Molten Metal Technology, Inc., Waltham, MA (United States)] [and others

    1995-10-01

    The U.S. Department of Energy issued a Planned Research and Development Announcement (PRDA) in 1993, with the objective of identifying unique technologies which could be applied to the most hazardous waste streams at DOE sites. The combination of radioactive contamination with additional contamination by hazardous constituents such as those identified by the Resource Conservation and Recovery Act (RCRA) pose an especially challenging problem. Traditional remediation technologies are increasingly becoming less acceptable to stakeholders and regulators because of the risks they pose to public health and safety. Desirable recycling technologies were described by the DOE as: (1) easily installed, operated, and maintained; (2) exhibiting superior environmental performance; (3) protective of worker and public health and safety; (4) readily acceptable to a wide spectrum of evaluators; and (5) economically feasible. Molten Metal Technology, Inc. (MMT) was awarded a contract as a result of the PRDA initiative to demonstrate the applicability of Catalytic Extraction Processing (CEP), MMT`s proprietary elemental recycling technology, to DOE`s inventory of low level mixed waste. This includes DOE`s inventory of radioactively- and RCRA-contaminated scrap metal and other waste forms expected to be generated by the decontamination and decommissioning (D&D) of DOE sites.

  19. Catalytic glycerol steam reforming for hydrogen production

    Energy Technology Data Exchange (ETDEWEB)

    Dan, Monica, E-mail: monica.dan@itim-cj.ro; Mihet, Maria, E-mail: maria.mihet@itim-cj.ro; Lazar, Mihaela D., E-mail: diana.lazar@itim-cj.ro [National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103 Donat Street, 400293 Cluj Napoca (Romania)

    2015-12-23

    Hydrogen production from glycerol by steam reforming combine two major advantages: (i) using glycerol as raw material add value to this by product of bio-diesel production which is obtained in large quantities around the world and have a very limited utilization now, and (ii) by implication of water molecules in the reaction the efficiency of hydrogen generation is increased as each mol of glycerol produces 7 mol of H{sub 2}. In this work we present the results obtained in the process of steam reforming of glycerol on Ni/Al{sub 2}O{sub 3}. The catalyst was prepared by wet impregnation method and characterized through different methods: N{sub 2} adsorption-desorption, XRD, TPR. The catalytic study was performed in a stainless steel tubular reactor at atmospheric pressure by varying the reaction conditions: steam/carbon ratio (1-9), gas flow (35 ml/min -133 ml/min), temperature (450-650°C). The gaseous fraction of the reaction products contain: H{sub 2}, CH{sub 4}, CO, CO{sub 2}. The optimum reaction conditions as resulted from this study are: temperature 550°C, Gly:H{sub 2}O ratio 9:1 and Ar flow 133 ml/min. In these conditions the glycerol conversion to gaseous products was 43% and the hydrogen yield was 30%.

  20. Catalytic Preparation of Pyrrolidones from Renewable Resources

    Energy Technology Data Exchange (ETDEWEB)

    Frye, John G.; Zacher, Alan H.; Werpy, Todd A.; Wang, Yong

    2005-12-01

    Use of renewable resources for production of valuable chemical commodities is becoming a topic of great national interest and importance. This objective fits well with the USDOE’s objective of promoting the industrial bio-refinery concept in which a wide array of valuable chemical, fuel, food, nutraceuticals and animal feed products all result from the integrated processing of grains, oil seeds and other bio-mass materials. The bio-refinery thus serves to enhance the overall utility and profitability of the agriculture industry as well as helping to reduce the dependence on petroleum. Pyrrolidones fit well with the bio-refinery concept since they may be produced in a scheme beginning with the fermentation of a portion of the bio-refinery’s sugar product into succinate. Pyrrolidones are a class of industrially important chemicals with a variety of uses including as polymer intermediates, cleaners, and “green solvents” which can replace hazardous chlorinated compounds. Battelle has developed an efficient process for the thermo – catalytic conversion of succinate into pyrrolidones, especially n-methylpyrrolidone. The process uses both novel Rh based catalysts and novel aqueous process conditions and results in high selectivities and yields of pyrrolidone compounds. The process also includes novel methodology for enhancing yields by recycling and converting non-useful side products of the catalysis into additional pyrrolidone. The process has been demonstrated in both batch and continuous reactors. Additionally, stability of the unique Rh-based catalyst has been demonstrated.

  1. Microchannel Reactor System for Catalytic Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Adeniyi Lawal; Woo Lee; Ron Besser; Donald Kientzler; Luke Achenie

    2010-12-22

    We successfully demonstrated a novel process intensification concept enabled by the development of microchannel reactors, for energy efficient catalytic hydrogenation reactions at moderate temperature, and pressure, and low solvent levels. We designed, fabricated, evaluated, and optimized a laboratory-scale microchannel reactor system for hydrogenation of onitroanisole and a proprietary BMS molecule. In the second phase of the program, as a prelude to full-scale commercialization, we designed and developed a fully-automated skid-mounted multichannel microreactor pilot plant system for multiphase reactions. The system is capable of processing 1 – 10 kg/h of liquid substrate, and an industrially relevant immiscible liquid-liquid was successfully demonstrated on the system. Our microreactor-based pilot plant is one-of-akind. We anticipate that this process intensification concept, if successfully demonstrated, will provide a paradigm-changing basis for replacing existing energy inefficient, cost ineffective, environmentally detrimental slurry semi-batch reactor-based manufacturing practiced in the pharmaceutical and fine chemicals industries.

  2. Catalytic Polymerization of Acrylonitrile by Khulays Bentonite

    Directory of Open Access Journals (Sweden)

    Matar M. Al-Esaimi

    2007-04-01

    Full Text Available The aqueous polymerization of acrylonitrile (AN catalyzed with exchanged Khulays bentonite . The influence of various polymerization parameters ( e.g., concentrations of Potassium Persulfate (K2S2O8 and monomer , various of organic solvents, and different temperature has been investigated. It was found that the rate of polymerization of AN was found to be dependent on monomer concentration, initiator and temperature. The activation energy of polymerization was calculated .Thermal properties of the polymer were studied by TGA and DSC techniques. © 2007 CREC UNDIP. All rights reserved.Received: 5 February 2007; Received in revised: 19 April 2007; Accepted: 7 May 2007[How to Cite: M. M. Al-Esaimi. (2007. Catalytic Polymerization of Acrylonitrile by Khulays Bentonite. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 32-36.  doi:10.9767/bcrec.2.1.4.6-10][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.1.4.6-10 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/4] 

  3. Catalytic extraction processing of contaminated scrap metal

    International Nuclear Information System (INIS)

    The contract was conceived to establish the commercial capability of Catalytic Extraction Processing (CEP) to treat contaminated scrap metal in the DOE inventory. In so doing, Molten Metal Technology, Inc. (MMT), pursued the following objectives: demonstration of the recycling of ferrous and non-ferrous metals--to establish that radioactively contaminated scrap metal can be converted to high-grade, ferrous and non-ferrous alloys which can be reused by DOE or reintroduced into commerce; immobilize radionuclides--that CEP will concentrate the radionuclides in a dense vitreous phase, minimize secondary waste generation and stabilize and reduce waste volume; destroy hazardous organics--that CEP will convert hazardous organics to valuable industrial gases, which can be used as feed gases for chemical synthesis or as an energy source; recovery volatile heavy metals--that CEP's off-gas treatment system will capture volatile heavy metals, such as mercury and lead; and establish that CEP is economical for processing contaminated scrap metal in the DOE inventory--that CEP is a more cost-effective and, complete treatment and recycling technology than competing technologies for processing contaminated scrap. The process and its performance are described

  4. Process for catalytic flue gas denoxing

    International Nuclear Information System (INIS)

    With the increasing concern for the environment, stringency of legislation and industry's awareness of its own environmental responsibility, the demand for the reduction of emission levels of nitrogen oxides is becoming increasingly urgent. This paper reports that Shell has developed a low temperature catalytic deNOx system for deep removal of nitrogen oxides, which includes a low-pressure-drop reactor. This process is able to achieve over 90% removal of nitrogen oxides and therefore can be expected to meet legislation requirements for the coming years. The development of a low-temperature catalyst makes it possible to operate at temperatures as low as 120 degrees C, compared to 300-400 degrees C for the conventional honeycomb and plate-type catalysts. This allows an add-on construction, which is most often a more economical solution than the retrofits in the hot section required with conventional deNOx catalysts. The Lateral Flow Reactor (LFR), which is used for dust-free flue gas applications, and the Parallel Passage Reactor (PPR) for dust-containing flue gas applications, have been developed to work with pressure drops below 10 mbar

  5. Catalytic glycerol steam reforming for hydrogen production

    Science.gov (United States)

    Dan, Monica; Mihet, Maria; Lazar, Mihaela D.

    2015-12-01

    Hydrogen production from glycerol by steam reforming combine two major advantages: (i) using glycerol as raw material add value to this by product of bio-diesel production which is obtained in large quantities around the world and have a very limited utilization now, and (ii) by implication of water molecules in the reaction the efficiency of hydrogen generation is increased as each mol of glycerol produces 7 mol of H2. In this work we present the results obtained in the process of steam reforming of glycerol on Ni/Al2O3. The catalyst was prepared by wet impregnation method and characterized through different methods: N2 adsorption-desorption, XRD, TPR. The catalytic study was performed in a stainless steel tubular reactor at atmospheric pressure by varying the reaction conditions: steam/carbon ratio (1-9), gas flow (35 ml/min -133 ml/min), temperature (450-650°C). The gaseous fraction of the reaction products contain: H2, CH4, CO, CO2. The optimum reaction conditions as resulted from this study are: temperature 550°C, Gly:H2O ratio 9:1 and Ar flow 133 ml/min. In these conditions the glycerol conversion to gaseous products was 43% and the hydrogen yield was 30%.

  6. Enhancing catalytic performance of palladium in gold and palladium alloy nanoparticles for organic synthesis reactions through visible light irradiation at ambient temperatures.

    Science.gov (United States)

    Sarina, Sarina; Zhu, Huaiyong; Jaatinen, Esa; Xiao, Qi; Liu, Hongwei; Jia, Jianfeng; Chen, Chao; Zhao, Jian

    2013-04-17

    The intrinsic catalytic activity of palladium (Pd) is significantly enhanced in gold (Au)-Pd alloy nanoparticles (NPs) under visible light irradiation at ambient temperatures. The alloy NPs strongly absorb light and efficiently enhance the conversion of several reactions, including Suzuki-Miyaura cross coupling, oxidative addition of benzylamine, selective oxidation of aromatic alcohols to corresponding aldehydes and ketones, and phenol oxidation. The Au/Pd molar ratio of the alloy NPs has an important impact on performance of the catalysts since it determines both the electronic heterogeneity and the distribution of Pd sites at the NP surface, with these two factors playing key roles in the catalytic activity. Irradiating with light produces an even more profound enhancement in the catalytic performance of the NPs. For example, the best conversion rate achieved thermally at 30 °C for Suzuki-Miyaura cross coupling was 37% at a Au/Pd ratio of 1:1.86, while under light illumination the yield increased to 96% under the same conditions. The catalytic activity of the alloy NPs depends on the intensity and wavelength of incident light. Light absorption due to the Localized Surface Plasmon Resonance of gold nanocrystals plays an important role in enhancing catalyst performance. We believe that the conduction electrons of the NPs gain the light absorbed energy producing energetic electrons at the surface Pd sites, which enhances the sites' intrinsic catalytic ability. These findings provide useful guidelines for designing efficient catalysts composed of alloys of a plasmonic metal and a catalytically active transition metal for various organic syntheses driven by sunlight. PMID:23566035

  7. Structural, electrical and catalytic properties of ion-implanted oxides

    OpenAIRE

    Hassel, van, E Edwin; Burggraaf, A.J.

    1989-01-01

    The potential application of ion implantation to modify the surfaces of ceramic materials is discussed. Changes in the chemical composition and microstructure result in important variations of the electrical and catalytic properties of oxides.

  8. Enantiocontrol in Macrocycle Formation from Catalytic MetalCarbene Transformations

    Institute of Scientific and Technical Information of China (English)

    DOYLE, Michael P.; DOYLE, Michael P; HU, Wen-Hao(胡文浩); 胡文浩

    2001-01-01

    The development of catalytic metal carbene transformations for the construction of macrocyclic lactones has dramatically increased their synthetic advantages.This is the first review of this developing methodology.

  9. Size-dependent catalytic activity of supported metal clusters

    Science.gov (United States)

    Xu, Z.; Xiao, F.-S.; Purnell, S. K.; Alexeev, O.; Kawi, S.; Deutsch, S. E.; Gates, B. C.

    1994-11-01

    BECAUSE catalysis by metals is a surface phenomenon, many technological catalysts contain small (typically nanometre-sized) supported metal particles with a large fraction of the atoms exposed1. Many reactions, such as hydrocarbon hydrogenations, are structure-insensitive, proceeding at approximately the same rate on metal particles of various sizes provided that they are larger than about 1 nm and show bulk-like metallic behaviour1. But it is not known whether the catalytic properties of metal particles become size-dependent as the particles become so small that they are no longer metallic in character. Here we investigate the catalytic behaviour of precisely defined clusters of just four and six iridium atoms on solid supports. We find that the Ir4 and Ir6 clusters differ in catalytic activity both from each other and from metallic Ir particles. This raises the possibility of tailoring the catalytic behaviour of metal clusters by controlling the cluster size.

  10. Catalytic synthesis of ammonia using vibrationally excited nitrogen molecules

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Henriksen, Niels Engholm; Billing, Gert D.; Guldberg, Annette

    The dissociation of nitrogen is the rate-limiting step in the catalytic synthesis of ammonia. Theoretical calculations have shown that the dissociative sticking probability of molecular nitrogen on catalytic active metal surfaces is enhanced by orders of magnitude when the molecules are vibration......The dissociation of nitrogen is the rate-limiting step in the catalytic synthesis of ammonia. Theoretical calculations have shown that the dissociative sticking probability of molecular nitrogen on catalytic active metal surfaces is enhanced by orders of magnitude when the molecules are...... vibrationally excited to states with quantum numbers 3-10. The rate and equilibrium constants for the process using vibrationally excited nitrogen molecules are calculated and expressions for the reaction rates are derived. A comparison with the ordinary process, where the nitrogen molecules are in the...

  11. Scaling behavior of optimally structured catalytic microfluidic reactors

    DEFF Research Database (Denmark)

    Okkels, Fridolin; Bruus, Henrik

    2007-01-01

    In this study of catalytic microfluidic reactors we show that, when optimally structured, these reactors share underlying scaling properties. The scaling is predicted theoretically and verified numerically. Furthermore, we show how to increase the reaction rate significantly by distributing the...

  12. Plasma Catalytic Extraction of Oxygen from the Martian Atmosphere Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Plasma catalytic techniques are proposed for the extraction of oxygen from the abundant carbon dioxide contained in the Martian atmosphere (95% CO2).. The Phase I...

  13. Optimized Combination of Residue Hydrodesulfurization and Residue Fluid Catalytic Cracking

    Institute of Scientific and Technical Information of China (English)

    Chen Junwu

    2003-01-01

    @@1 Introduction Combination of residue hydrodesulfurization (HDS) and resi-due fluid catalytic cracking (RFCC) is a unique technologyfor processing high-sulfur residue. This paper discusses theoptimized combination of these two processes.

  14. Electromagnetic clutches and couplings

    CERN Document Server

    Vorob'Yeva, T M; Fry, D W; Higinbotham, W

    2013-01-01

    Electromagnetic Clutches and Couplings contains a detailed description of U.S.S.R. electromagnetic friction clutches, magnetic couplings, and magnetic particle couplings. This book is divided into four chapters. The first chapter discusses the design and construction of magnetic (solenoid-operated) couplings, which are very quick-acting devices and used in low power high-speed servo-systems. Chapter 2 describes the possible fields of application, design, construction, and utilization of magnetic particle couplings. The aspects of construction, design, and utilization of induction clutches (sli

  15. Northwestern University Facility for Clean Catalytic Process Research

    Energy Technology Data Exchange (ETDEWEB)

    Marks, Tobin Jay [Northwestern University

    2013-05-08

    Northwestern University with DOE support created a Facility for Clean Catalytic Process Research. This facility is designed to further strengthen our already strong catalysis research capabilities and thus to address these National challenges. Thus, state-of-the art instrumentation and experimentation facility was commissioned to add far greater breadth, depth, and throughput to our ability to invent, test, and understand catalysts and catalytic processes, hence to improve them via knowledge-based design and evaluation approaches.

  16. Catalytic Ozonation of Phenolic Wastewater: Identification and Toxicity of Intermediates

    OpenAIRE

    Mahdi Farzadkia; Yousef Dadban Shahamat; Simin Nasseri; Amir Hossein Mahvi; Mitra Gholami; Ali Shahryari

    2014-01-01

    A new strategy in catalytic ozonation removal method for degradation and detoxification of phenol from industrial wastewater was investigated. Magnetic carbon nanocomposite, as a novel catalyst, was synthesized and then used in the catalytic ozonation process (COP) and the effects of operational conditions such as initial pH, reaction time, and initial concentration of phenol on the degradation efficiency and the toxicity assay have been investigated. The results showed that the highest catal...

  17. Catalytic Processes for Clean Hydrogen Production from Hydrocarbons

    OpenAIRE

    ÖNSAN, Zeynep İlsen

    2007-01-01

    Conversion of hydrocarbon fuels to hydrogen with a high degree of purity acceptable for fuel cell operation presents interesting challenges for the design of new selective catalysts and catalytic processes. Natural gas, LPG, gasoline, and diesel are regarded as promising hydrocarbon fuels. Methanol has received attention despite its toxicity, and ethanol has recently become of interest as a much less toxic and renewable resource. Selective catalytic processes considered for commerci...

  18. Catalytic Upgrading of Sugars to Hydrocarbons Technology Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Biddy, M.; Jones, S.

    2013-03-01

    This technology pathway case investigates the catalytic conversion of solubilized carbohydrate streams to hydrocarbon biofuels, utilizing data from recent efforts within the National Advanced Biofuels Consortium (NABC) in collaboration with Virent, Inc. Technical barriers and key research needs that should be pursued for the catalytic conversion of sugars pathway to be competitive with petroleum-derived gasoline-, diesel-, and jet-range hydrocarbon blendstocks have been identified.

  19. Resolving the Structure of Active Sites on Platinum Catalytic Nanoparticles

    DEFF Research Database (Denmark)

    Chang, Lan Yun; Barnard, Amanda S.; Gontard, Lionel Cervera; Dunin-Borkowski, Rafal E.

    2010-01-01

    Accurate understanding of the structure of active sites is fundamentally important in predicting catalytic properties of heterogeneous nanocatalysts. We present an accurate determination of both experimental and theoretical atomic structures of surface monatomic steps on industrial platinum...... nanoparticles. This comparison reveals that the edges of nanoparticles can significantly alter the atomic positions of monatomic steps in their proximity, which can lead to substantial deviations in the catalytic properties compared with the extended surfaces....

  20. Water recovery by catalytic treatment of urine vapor

    Science.gov (United States)

    Budininkas, P.; Quattrone, P. D.; Leban, M. I.

    1980-01-01

    The objective of this investigation was to demonstrate the feasibility of water recovery on a man-rated scale by the catalytic processing of untreated urine vapor. For this purpose, two catalytic systems, one capable of processing an air stream containing low urine vapor concentrations and another to process streams with high urine vapor concentrations, were designed, constructed, and tested to establish the quality of the recovered water.

  1. Discreteness-Induced Criticality in Random Catalytic Reaction Networks

    OpenAIRE

    Awazu, Akinori; Kaneko, Kunihiko

    2009-01-01

    Universal intermittent dynamics in a random catalytic reaction network, induced by smallness in the molecule number is reported. Stochastic simulations for a random catalytic reaction network subject to a flow of chemicals show that the system undergoes a transition from a stationary to an intermittent reaction phase when the flow rate is decreased. In the intermittent reaction phase, two temporal regimes with active and halted reactions alternate. The number frequency of reaction events at e...

  2. Emerging catalytic processes for the production of adipic acid

    OpenAIRE

    Van de Vyver, Stijn; Roman, Yuriy

    2012-01-01

    Research efforts to find more sustainable pathways for the synthesis of adipic acid have led to the introduction of new catalytic processes for producing this commodity chemical from alternative resources. With a focus on the performance of oxygen and hydrogen peroxide as preferred oxidants, this minireview summarizes recent advances made in the selective oxidation of cyclohexene, cyclohexane, cyclohexanone and n-hexane to adipic acid. Special attention is paid to the exploration of catalytic...

  3. Basic Aspects Related to Operation of Engine Catalytic Converters

    OpenAIRE

    Stefan POSTRZEDNIK; Zmudka, Zbigniew; Ciesiolkiewicz, Adam

    2004-01-01

    Experimental research on the diesel engine 6C107 equipped with selected oxidation catalytic converters was carried out. Specific emissions of toxic substances were investigated in the whole operation range of the engine before and after catalysts. Thus, changes of the emission indices within the catalysts and conversion efficiencies of the harmful substances were evaluated. Besides, temperature threshold of the catalytic action was determined too. Apart from chemical efficiency of the convert...

  4. Graphene-based materials in catalytic wet peroxide oxidation

    OpenAIRE

    Gomes, Helder; Ribeiro, Rui; Pastrana-Martínez, Luisa; Figueiredo, José; Faria, Joaquim; Silva, Adrián

    2014-01-01

    In catalytic wet peroxide oxidation (CWPO),an advanced oxidation process, hydrogen peroxide (H2O2) is decomposed catalytically giving rise to hydroxyl radicals (HO•).These radicals, exhibiting high oxidizing potential, serve as effective and non selective species for the degradation of several organic pollutants in liquid phase. Since the report of Lücking et al. [1], carbon materials have been explored as catalysts for CWPO[2]. Recent reports address process intensification issues, br...

  5. Catalytic flash pyrolysis of oil-impregnated-wood and jatropha cake using sodium based catalysts

    NARCIS (Netherlands)

    Ali Imran, A.; Bramer, E.A.; Seshan, K.; Brem, G.

    2016-01-01

    Catalytic pyrolysis of wood with impregnated vegetable oil was investigated and compared with catalytic pyrolysis of jatropha cake making use of sodium based catalysts to produce a high quality bio-oil. The catalytic pyrolysis was carried out in two modes: in-situ catalytic pyrolysis and post treatm

  6. Coupled Dynamics and Entropic Contribution to the Allosteric Mechanism of Pin1.

    Science.gov (United States)

    Barman, Arghya; Hamelberg, Donald

    2016-08-25

    Allosteric communication in proteins regulates a plethora of downstream processes in subcellular signaling pathways. Describing the effects of cooperative ligand binding on the atomic level is a key to understanding many regulatory processes involving biomolecules. Here, we use microsecond-long molecular dynamics simulations to investigate the allosteric mechanism of Pin1, a potential therapeutic target and a phosphorylated-Ser/Thr dependent peptidyl-prolyl cis-trans isomerase that regulates several subcellular processes and has been implicated in many diseases, including cancer and Alzheimer's. Experimental studies suggest that the catalytic domain and the noncatalytic WW domain are allosterically coupled; however, an atomic level description of the dynamics associated with the interdomain communication is lacking. We show that binding of the substrate to the WW domain is directly coupled to the dynamics of the catalytic domain, causing rearrangement of the residue-residue contact dynamics from the WW domain to the catalytic domain. The binding affinity of the substrate in the catalytic domain is also enhanced upon binding of the substrate to the WW domain. Modulation of the dynamics of the catalytic domain upon binding of the substrate to the WW domain leads to prepayment of the entropic cost of binding the substrate to the catalytic domain. This study shows that Ile 28 at the interfacial region between the catalytic and WW domains is certainly one of the residues responsible for bridging the communication between the two domains. The results complement previous experiments and provide valuable atomistic insights into the role of dynamics and possible entropic contribution to the allosteric mechanism of proteins. PMID:27077947

  7. Qualification of a passive catalytic module for hydrogen mitigation

    International Nuclear Information System (INIS)

    The advantage of passive catalytic modules for hydrogen mitigation during core-melt accidents, as compared with active devices like forced-flow recombiners or ignitors, is given by the high reliability of operation and the elimination of potentially violent combustion events. An important step in the qualification of a passive catalytic module system is the determination of the total required capacity and its distribution at various locations in the containment. Experiments and analytic modeling work were performed to qualify the installation of a system of catalytic modules for a large dry pressurized water reactor (PWR) containment. The operational capacity of a prototype catalytic module was determined experimentally, and a corresponding model correlation was developed and integrated into the GOTHIC containment code. This modified code was validated against experimental data. As an application, predictions of the effects, resulting from backfitting a large, dry PWR containment with 50 catalytic modules, were done using the modified code. The catalytic modules keep the hydrogen concentrations below a level of 10% where violent deflagrations could be expected. Local higher concentrations near the release location are inert due to associated low oxygen and high steam concentrations. A proper distribution of the modules in the containment guarantees full mixing of the atmosphere due to natural convective currents

  8. Catalytic decarboxylations of fatty acids in immature oil source rocks

    Institute of Scientific and Technical Information of China (English)

    李哲; 张再龙; 孙燕华; 劳永新; 蔺五正; 吴卫芳

    2003-01-01

    Catalytic decarboxylations of fatty acids in immature oil source rock samples were examined in this study. The rock samples were obtained from seven oil fields in China. In order to clarify the effect of each mineral matter in the rock samples, both the Fe M?ssbauer effect and the X-ray diffraction (XRD) were used to determine the relative content of each mineral in the rock samples, and the catalytic activities of several minerals like clays, carbonates and pyrite were determined. The Fe M?ssbauer effect and the XRD studies show that clays are the main mineral components in the rock samples except for the samples from Biyang and Jianghan in which the main mineral component is ankerite. The other mineral components include calcite, plagioclase, quartz, feldspar, siderite, aragonite, pyrite, analcime, pyroxene and anhydrite. The studies of the catalytic decarboxylations of fatty acids suggest that carbonates and pyrite can make much greater contributions to the catalytic activities of the rock samples than clays. It is found that the overall catalytic activities of the rock samples are well related to the relative contents and the catalytic activities of clays, carbonates and pyrite in the rock samples.

  9. Treatment of waste metalworking fluid by a hybrid ozone-biological process.

    Science.gov (United States)

    Jagadevan, Sheeja; Graham, Nigel J; Thompson, Ian P

    2013-01-15

    In metal machining processes, the regulation of heat generation and lubrication at the contact point are achieved by application of a fluid referred to as metalworking fluid (MWF). MWFs inevitably become operationally exhausted with age and intensive use, which leads to compromised properties, thereby necessitating their safe disposal. Disposal of this waste through a biological route is an increasingly attractive option, since it is effective with relatively low energy demands. However, successful biological treatment is challenging since MWFs are chemically complex, and include biocides specifically to retard microbial deterioration whilst the fluids are operational. In this study remediation of the recalcitrant component of a semi-synthetic MWF by a novel hybrid ozone-bacteriological treatment, was investigated. The hybrid treatment proved to be effective and reduced the chemical oxygen demand by 72% (26.9% and 44.9% reduction after ozonation and biological oxidation respectively). Furthermore, a near-complete degradation of three non-biodegradable compounds (viz. benzotriazole, monoethanolamine, triethanolamine), commonly added as biocides and corrosion inhibitors in MWF formulations, under ozonation was observed. PMID:23274939

  10. Form Follows Function: Structural and Catalytic Variation in the Class A Flavoprotein Monooxygenases

    Directory of Open Access Journals (Sweden)

    Graham R. Moran

    2012-11-01

    Full Text Available Flavoprotein monooxygenases (FPMOs exhibit an array of mechanistic solutions to a common chemical objective; the monooxygenation of a target substrate. Each FPMO efficiently couples reduction of a flavin cofactor by NAD(PH to oxygenation of the target substrate via a (hydroperoxyflavin intermediate. This purpose of this review is to describe in detail the Class A flavoprotein hydroxylases (FPMO in the context of the other FPMO classes (B–F. Both one and two component FPMOs are found in nature. Two-component enzymes require, in addition to the monooxygenase, the involvement of a reductase that first catalyzes the reduction of the flavin by NAD(PH. The Class A and B FPMOs are single-component and manage to orchestrate the same net reaction within a single peptide. The Class A enzymes have, by some considerable margin, the most complete research record. These enzymes use choreographed movements of the flavin ring that facilitate access of the organic substrates to the active site, provide a means for interaction of NADPH with the flavin, offer a mechanism to sequester the dioxygen reduction chemistry from solvent and a means to release the product. The majority of the discrete catalytic events of the catalytic cycle can be observed directly in exquisite detail using spectrophotometric kinetic methods and many of the key mechanistic conclusions are further supported by structural data. This review attempts to compile each of the key observations made for both paradigm and newly discovered examples of Class A FPMOs into a complete catalytic description of one enzymatic turnover.

  11. Modelling of procecces in catalytic recombiners

    International Nuclear Information System (INIS)

    In order to achieve a high degree of safety in nuclear power plants and prevent possible accident scenarios, their consequences are calculated and analysed with numeric codes. One of the most important part of nuclear safety research of hazardous incidents are development and validation of these numeric models, which are implemented into accident codes. The severe hydrogen release during a core meltdown is one of the considered scenario of performed accident analyses. One of the most important measure for the elimination of the hydrogen is catalytic recombiners. Converting the hydrogen with the atmospheric oxygen to water vapor in an exothermic reaction will prevent possible detonation of the hydrogen/air atmosphere. Within the dissertation the recombiner simulation REKO-DIREKT was developed and validated by an extensive experimental database. The performance of recombiners with regard to the conversion of the hydrogen and the temperature development is modelled. The REKO-DIREKT program is unique and has made significant revolution in research of hydrogen safety. For the first time it has been possible to show the performance of the recombiner so great in detail by using REKO-DIREKT. In the future engineers of nuclear power plants will have opportunity to have precise forecasts about the process of the possible accidents with hydrogen release. Also with presence of water vapor or with oxygen depletion which are included in the model. The major discussion of the hydrogen ignition at hot catalyst steel plates can be evaluated in the future with REKO-DIREKT more reliably than the existing used models. (orig.)

  12. Catalytic Preparation of Pyrrolidones from Renewable Resources

    Energy Technology Data Exchange (ETDEWEB)

    Frye, John G.; Zacher, Alan H.; Werpy, Todd A.; Wang, Yong

    2005-06-01

    Abstract Use of renewable resources for production of valuable chemical commodities is becoming a topic of great national interest and importance. This objective fits well with the U.S. DOE’s objective of promoting the industrial bio-refinery concept in which a wide array of valuable chemical, fuel, food, nutraceuticals, and animal feed products all result from the integrated processing of grains, oil seeds, and other bio-mass materials. The bio-refinery thus serves to enhance the overall utility and profitability of the agriculture industry as well as helping to reduce the USA’s dependence on petroleum. Pyrrolidones fit well into the bio-refinery concept since they may be produced in a scheme beginning with the fermentation of a portion of the bio-refinery’s sugar product into succinate. Pyrrolidones are a class of industrially important chemicals with a variety of uses including polymer intermediates, cleaners, and “green solvents” which can replace hazardous chlorinated compounds. Battelle has developed an efficient process for the thermo-catalytic conversion of succinate into pyrrolidones, especially n-methyl-2-pyrrolidone. The process uses both novel Rh based catalysts and novel aqueous process conditions and results in high selectivities and yields of pyrrolidone compounds. The process also includes novel methodology for enhancing yields by recycling and converting non-useful side products of the catalysis into additional pyrrolidone. The process has been demonstrated in both batch and continuous reactors. Additionally, stability of the unique Rh-based catalyst has been demonstrated.

  13. Aconitase: its source of catalytic protons

    International Nuclear Information System (INIS)

    An ordinary isotope partition experiment was performed to determine the rate of dissociation of the proton from the donor site for the hydration of cis-aconitate. Aconitase in [3H] water was efficiently diluted into well-mixed solutions of cis-aconitate. Citrate and isocitrate that were formed within 2 s were more heavily labeled than could be explained by consideration of an isotope effect in the processing of one proton per enzyme equivalent. Control experiments indicate that mixing was much more rapid than catalytic turnover, ruling out incompletely diluted [3H] water as a significant isotope source. Therefore, it appears that significantly more than one enzyme-bound tritium atom (protons) must have been used in the course of the multiple turnover of the enzyme after the dilution was complete. Isotope incorporation reached values in excess of four proton equivalent as a limit with simple Michaelis dependence on cis-aconitate. From the half-saturation concentration value for trapping, 0.15 mM, the t/sub 1/2/ for exchange of each of these protons with solvent appears to be ∼0.1 s at 00C. The large number of protons trapped seems to suggest the existence of a structurally stabilized pool of protons, or water, that communicates between the active site base and the medium in the hydration of cis-aconitate. The proton abstracted in the dehydration of [3H] citrate is transferred directly to undissociated cis-aconitate to form isocitrate without dilution, or cis-aconitate having dissociated, the tritium passes to the medium, presumably through the pool of bound protons indicated above. All of the citrate-derived protons can be found in isocitrate if cis-aconitate is added in sufficient concentration. Therefore, the abstracted proton dissociates slowly, if at all, from the enzyme in all intermediates except those from which cis-aconitate has dissociated

  14. Catalytic conversion of chloromethane to methanol and dimethyl ether over two catalytic beds: a study of acid strength

    Energy Technology Data Exchange (ETDEWEB)

    Fernandes, D.R.; Leite, T.C.M.; Mota, C.J.A. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Quimica], e-mail: cmota@iq.ufrj.br

    2010-07-15

    The catalytic hydrolysis of chloromethane to methanol and dimethyl ether (DME) was studied over metal-exchanged Beta and Mordenite zeolites, acidic MCM-22 and SAPO-5. The use of a second catalytic bed with HZSM-5 zeolite increased the selectivity to DME, due to methanol dehydration on the acid sites. The effect was more significant on catalysts presenting medium and weak acid site distribution, showing that dehydration of methanol to DME is accomplished over sites of higher acid strength. (author)

  15. Synthesis and catalytic application of palladium nanoparticles supported on kaolinite-based nanohybrid materials.

    Science.gov (United States)

    Ngnie, Gaelle; Dedzo, Gustave K; Detellier, Christian

    2016-05-31

    Palladium nanoparticles (PdNPs) were deposited on the surface of the modified clay mineral, kaolinite. To improve compatibility, abundance and control of the size of the nanoparticles, kaolinite was modified by the grafting of an amino alcohol (triethanolamine (TEA)) and an ionic liquid (1-(2-hydroxyethyl)-3-methylimidazolium (ImIL)). Characterization techniques (XRD, TGA, solid state (13)C NMR and FTIR spectroscopy) confirmed the effective grafting of these compounds on the internal surface of kaolinite. After the synthesis of PdNPs onto clay particles, TEM allowed the visualization of abundant PdNPs with sizes ranging from 4 to 6 nm, uniformly distributed onto the platelets of modified kaolinite. Unmodified clay showed low abundance and random distribution of the nanoparticles. The catalysts obtained were effective for the catalytic reduction of 4-nitrophenol (4-NP), the material with TEA being the most effective. These materials have exhibited excellent performance during the Heck and particularly the Suzuki-Miyaura coupling reactions, with reaction yields up to 100%. These catalysts showed a very slight loss in activity for three consecutive catalytic cycles (less than 10% decrease of the activity compared to the first cycle). This was an evidence that the prior grafting modification of kaolinite helps in significantly improving the quality of the synthesized NPs and also promotes their strong attachment onto the clay mineral surface. PMID:27160392

  16. An experimental and computational investigation of structural dependence of catalytic properties of Pt-Ru nanoparticles

    Science.gov (United States)

    Prasai, Binay

    An approach to determining the 3D atomic structure of metallic nanoparticles (NPs) in fine detail is described and exemplified on Pt-Ru alloy NPs of importance to the development of devices for clean energy conversion such as fuel cells. NPs are characterized structurally by total scattering experiments involving high-energy synchrotron X-ray diffraction coupled to atomic pair distribution functions (PDFs) analysis. 3D structure models are built by molecular dynamics simulations and further refined against the experimental PDF data by reverse Monte Carlo simulations and analyzed in terms of structural characteristics. Structural characteristics of activated NPs and data for their catalytic activity are compared side by side and strong evidence found that electronic effects, indicated by significant changes in Pt-Pt and Ru-Ru metal bond lengths at NP surface, and practically unrecognized so far atomic ensemble effects, indicated by distinct stacking of atomic layers near NP surface and prevalence of particular configurations of Pt and Ru atoms in these layers, contribute to the observed enhancement of the catalytic activity of PtxRu100 -x alloy NPs at x ~ 50. Central Michigan University, Department of Energy.

  17. Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

    Institute of Scientific and Technical Information of China (English)

    LI Ning; LI Guangming; YAO Zhenya; ZHAO Jianfu

    2007-01-01

    Catalytic wet air oxidation(CWAO)is one of the most promising technologies for pollution abatement.Developing catalysts with high activity and stability is crucial for the application of the CWAO process.The Mn/Ce complex oxide catalyrsts for CWAO of high concentration phenol containing wastewater were prepared by coprecipitation.The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis.The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller(BET)analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry(ICP-AES).The results show that the catalysts have high catalytic activities even at a low temperature(80℃)and low oxygen partial pressure(0.5 MPa)in a batch reactor.The metallic ion leaching is comparatively low(Mn<6.577 mg/L and Ce<0.6910 mg/L,respectively)in the CWAO process.The phenol,CODCD and TOC removal efficiencies in the solution exceed 98.5% using the optimal catalyst(named CSP).The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater.

  18. Structural Characterization of the Catalytic Sites of Mononuclear Nonheme Fe Hydroxylases Using ²H-ESEEM.

    Science.gov (United States)

    McCracken, John

    2015-01-01

    Aromatic amino acid hydroxylases are members of a larger group of enzymes that use a mononuclear nonheme Fe center to catalyze a variety of thermodynamically challenging reactions in which O2 is used in the oxidative transformation of substrates. The hydroxylase enzymes are catalytically active in the ferrous oxidation state and are high-spin. To render the catalytic site EPR-active, we have used nitric oxide (NO) as a surrogate for substrate O2 to form an S=3/2 paramagnetic center. While the continuous-wave (cw)-EPR spectra of NO-enzyme adducts are rather generic, they provide electron spin echo envelope modulation (ESEEM) data that are rich with structural information derived from ligand hyperfine couplings. This chapter will focus on (2)H-ESEEM spectroscopy, an approach that we have taken for assigning these spectra and harvesting the unique information on Fe(II) coordination chemistry that they provide. While these spectroscopic measurements are routine, an emphasis will be placed on the analysis of cw-EPR and (2)H-ESEEM data using an unconstrained nonlinear optimization approach. These analysis methods are based on simple custom "scripts" that run in the MATLAB environment and that use EasySpin, a public-domain EPR simulation package, as their calculation engine. The examples provided here use a strategy that can be adapted for the treatment of most EPR measurements. PMID:26478489

  19. A hybrid process combining homogeneous catalytic ozonation and membrane distillation for wastewater treatment.

    Science.gov (United States)

    Zhang, Yong; Zhao, Peng; Li, Jie; Hou, Deyin; Wang, Jun; Liu, Huijuan

    2016-10-01

    A novel catalytic ozonation membrane reactor (COMR) coupling homogeneous catalytic ozonation and direct contact membrane distillation (DCMD) was developed for refractory saline organic pollutant treatment from wastewater. An ozonation process took place in the reactor to degrade organic pollutants, whilst the DCMD process was used to recover ionic catalysts and produce clean water. It was found that 98.6% total organic carbon (TOC) and almost 100% salt were removed and almost 100% metal ion catalyst was recovered. TOC in the permeate water was less than 16 mg/L after 5 h operation, which was considered satisfactory as the TOC in the potassium hydrogen phthalate (KHP) feed water was as high as 1000 mg/L. Meanwhile, the membrane distillation flux in the COMR process was 49.8% higher than that in DCMD process alone after 60 h operation. Further, scanning electron microscope images showed less amount and smaller size of contaminants on the membrane surface, which indicated the mitigation of membrane fouling. The tensile strength and FT-IR spectra tests did not reveal obvious changes for the polyvinylidene fluoride membrane after 60 h operation, which indicated the good durability. This novel COMR hybrid process exhibited promising application prospects for saline organic wastewater treatment. PMID:27372262

  20. Catalytic combustion over high temperature stable metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Berg, M. [TPS Termiska Processer AB, Nykoeping (Sweden)

    1996-12-31

    This thesis presents a study of the catalytic effects of two interesting high temperature stable metal oxides - magnesium oxide and manganese substituted barium hexa-aluminate (BMA) - both of which can be used in the development of new monolithic catalysts for such applications. In the first part of the thesis, the development of catalytic combustion for gas turbine applications is reviewed, with special attention to alternative fuels such as low-BTU gas, e.g. produced in an air blown gasifier. When catalytic combustion is applied for such a fuel, the primary advantage is the possibility of decreasing the conversion of fuel nitrogen to NO{sub x}, and achieving flame stability. In the experimental work, MgO was shown to have a significant activity for the catalytic combustion of methane, lowering the temperature needed to achieve 10 percent conversion by 270 deg C compared with homogeneous combustion.The reaction kinetics for methane combustion over MgO was also studied. It was shown that the heterogeneous catalytic reactions were dominant but that the catalytically initiated homogeneous gas phase reactions were also important, specially at high temperatures. MgO and BMA were compared. The latter showed a higher catalytic activity, even when the differences in activity decreased with increasing calcination temperature. For BMA, CO{sub 2} was the only product detected, but for MgO significant amounts of CO and C{sub 2}-hydrocarbons were formed. BMA needed a much lower temperature to achieve total conversion of other fuels, e.g. CO and hydrogen, compared to the temperature for total conversion of methane. This shows that BMA-like catalysts are interesting for combustion of fuel mixtures with high CO and H{sub 2} content, e.g. gas produced from gasification of biomass. 74 refs

  1. Coupling Reduces Noise

    OpenAIRE

    Kia, Behnam; Kia, Sarvenaz; Lindner, John. F.; Sinha, Sudeshna; Ditto, William L.

    2014-01-01

    We demonstrate how coupling nonlinear dynamical systems can reduce the effects of noise. For simplicity we investigate noisy coupled map lattices. Noise from different lattice nodes can diffuse across the lattice and lower the noise level of individual nodes. We develop a theoretical model that explains this observed noise evolution and show how the coupled dynamics can naturally function as an averaging filter. Our numerical simulations are in excellent agreement with the model predictions.

  2. Nonlinearity Induced Critical Coupling

    CERN Document Server

    Reddy, K Nireekshan; Gupta, S Dutta

    2013-01-01

    We study a critically coupled system (Opt. Lett., \\textbf{32}, 1483 (2007)) with a Kerr-nonlinear spacer layer. Nonlinearity is shown to inhibit null-scattering in a critically coupled system at low powers. However, a system detuned from critical coupling can exhibit near-complete suppression of scattering by means of nonlinearity-induced changes in refractive index. Our studies reveal clearly an important aspect of critical coupling as a delicate balance in both the amplitude and the phase relations, while a nonlinear resonance in dispersive bistability concerns only the phase.

  3. DGKθ Catalytic Activity Is Required for Efficient Recycling of Presynaptic Vesicles at Excitatory Synapses

    Directory of Open Access Journals (Sweden)

    Hana L. Goldschmidt

    2016-01-01

    Full Text Available Synaptic transmission relies on coordinated coupling of synaptic vesicle (SV exocytosis and endocytosis. While much attention has focused on characterizing proteins involved in SV recycling, the roles of membrane lipids and their metabolism remain poorly understood. Diacylglycerol, a major signaling lipid produced at synapses during synaptic transmission, is regulated by diacylglycerol kinase (DGK. Here, we report a role for DGKθ in the mammalian CNS in facilitating recycling of presynaptic vesicles at excitatory synapses. Using synaptophysin- and vGlut1-pHluorin optical reporters, we found that acute and chronic deletion of DGKθ attenuated the recovery of SVs following neuronal stimulation. Rescue of recycling kinetics required DGKθ kinase activity. Our data establish a role for DGK catalytic activity at the presynaptic nerve terminal in SV recycling. Altogether, these data suggest that DGKθ supports synaptic transmission during periods of elevated neuronal activity.

  4. Carbon supported trimetallic nickel-palladium-gold hollow nanoparticles with superior catalytic activity for methanol electrooxidation

    Science.gov (United States)

    Shang, Changshuai; Hong, Wei; Wang, Jin; Wang, Erkang

    2015-07-01

    In this paper, Ni nanoparticles (NPs) are prepared in an aqueous solution by using sodium borohydride as reducing agent. With Ni NPs as the sacrificial template, hollow NiPdAu NPs are successfully prepared via partly galvanic displacement reaction between suitable metal precursors and Ni NPs. The as-synthesized hollow NiPdAu NPs can well dispersed on the carbon substrate. Transmission electron microscopy, X-ray diffraction and inductively coupled plasma mass spectrometry are taken to analyze the morphology, structure and composition of the as-synthesized catalysts. The prepared catalysts show superior catalytic activity and stability for methanol electrooxidation in alkaline media compared with commercial Pd/C and Pt/C. Catalysts prepared in this work show great potential to be anode catalysts in direct methanol fuel cells.

  5. Electro-catalytic effect of manganese oxide on oxygen reduction at teflonbonded carbon electrode

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Oxygen reduction(OR)on Teflon-bonded carbon electrodes with manganese oxide as catalyst in 6 mol/L KOH solution was investigated using AC impedance spectroscopy combined with other techniques. For OR at this electrode, the Tafel slope is-0.084V/dec and the apparent exchange current density is (1.02-3.0)×10-7 A/cm2. In the presence of manganese oxide on carbon electrode,the couple Mn3+/Mn4+ reacts with the O2 adsorbed on carbon sites forming O2- radicals and acceletes the dismutation of O2-, which contributes to the catalytic effect of manganese oxide for OR reaction.

  6. Nickel(II) complexes containing thiosemicarbazone and triphenylphosphine: Synthesis, spectroscopy, crystallography and catalytic activity

    Science.gov (United States)

    Priyarega, S.; Kalaivani, P.; Prabhakaran, R.; Hashimoto, T.; Endo, A.; Natarajan, K.

    2011-09-01

    Four new Ni(II) complexes of the general formula [Ni(PPh 3)(L)] (L = dibasic tridentate ligand derived from 4-diethylamino-salicylaldehyde and thiosemicarbazide or 4-N-substituted thiosemicarbazide) have been reported. The new complexes have been synthesized and characterized by analytical and spectroscopic (IR, electronic, 1H NMR and 31P NMR) techniques. Molecular structure of one of the complexes has been determined by X-ray crystallography. The complex, [Ni(PPh 3)(L4)] (H 2L4 = thiosemicarbazone prepared from 4-diethylamino-salicylaldehyde and 4-phenylthiosemicarbazide) crystallized in monoclinic space group with two molecules per unit cell and has the dimensions of a = 13.232(6) Å, b = 10.181(5) Å, c = 13.574(7) Å, α = 90°, β = 98.483(2)° and γ = 90°. Catalytic activity of the complexes has been explored for aryl-aryl coupling reaction.

  7. A theoretical study for one-dimensional modeling for VOC in a catalytic converter

    Science.gov (United States)

    Chauhan, S.; Sharma, L.; Srivastava, V. K.

    2010-07-01

    Modeling for catalytic oxidation of a volatile organic compound, acetaldehyde for the purpose of controlling tail-pipe emissions from vehicular exhaust was carried out. The model developed was one-dimensional unsteady state model, using mass and energy balance equations to predict results for acetaldehyde conversion in an adiabatic monolith operating under warm-up conditions. The equations consisted of a set of partial differential equations that are coupled and solved using Backward Implicit Scheme. Analysis of the behavior of the converter during warm up period was carried out and it was observed that the warm up was faster for a fresh catalyst and this warm up period could be reduced by introducing hot incoming exhaust gas at higher temperature.

  8. Dynamic\tmodelling of catalytic three-phase reactors for hydrogenation and oxidation processes

    Directory of Open Access Journals (Sweden)

    Salmi T.

    2000-01-01

    Full Text Available The dynamic modelling principles for typical catalytic three-phase reactors, batch autoclaves and fixed (trickle beds were described. The models consist of balance equations for the catalyst particles as well as for the bulk phases of gas and liquid. Rate equations, transport models and mass balances were coupled to generalized heterogeneous models which were solved with respect to time and space with algorithms suitable for stiff differential equations. The aspects of numerical solution strategies were discussed and the procedure was illustrated with three case studies: hydrogenation of aromatics, hydrogenation of aldehydes and oxidation of ferrosulphate. The case studies revealed the importance of mass transfer resistance inside the catalyst pallets as well as the dynamics of the different phases being present in the reactor. Reliable three-phase reactor simulation and scale-up should be based on dynamic heterogeneous models.

  9. Precursor type affecting surface properties and catalytic activity of sulfated zirconia

    Directory of Open Access Journals (Sweden)

    Zarubica Aleksandra R.

    2007-01-01

    Full Text Available Zirconium-hydroxide precursor samples are synthesized from Zr-hydroxide, Zr-nitrate, and Zr-alkoxide, by precipitation/impregnation, as well as by a modified sol-gel method. Precursor samples are further sulphated for the intended SO4 2- content of 4 wt.%, and calcined at 500-700oC. Differences in precursors’ origin and calcination temperature induce the incorporation of SO4 2- groups into ZrO2 matrices by various mechanisms. As a result, different amounts of residual sulphates are coupled with other structural, as well as surface properties, resulting in various catalytic activities of sulphated zirconia samples. Catalyst activity and selectivity are a complex synergistic function of tetragonal phase fraction, sulphates contents, textural and surface characteristics. Superior activity of SZ of alkoxide origin can be explained by a beneficial effect of meso-pores owing to a better accommodation of coke deposits.

  10. Crystal Structure and Catalytic Properties of Tetrakis(4-hydroxyphenyl) Porphyrinato Manganese (Ⅲ) Chloride (MnTHPPCl)

    Institute of Scientific and Technical Information of China (English)

    YANG Jun-wei; HUANG Xiao-chun; LIU Jin-bin; CHEN Tie; XIANG Jing; TONG Shan-ling; YANG Ke-er; YAN Yan

    2007-01-01

    The crystal structure of meso-tetrakis (4-hydroxyphenyl) porphyrinato manganese chloride (MnTHPPCl) and its supramolecular architecture based on the hydrogen bonds of one counter Cl anion with four hydrogen atoms of four -OH groups from different MnTHPPCl molecules cooperated by self-assembly of the porphyrin units were first reported. This compound crystallized in the tetragonal space group I4/m with a = 1.39928(7) nm, b = 1.39928(7) nm,c =0.94498(10) nm, V = 1.8503(2) nm3, and Z = 2.As a catalyst, MnTHPPCl also showed a high catalytic activity in the conversion from 1-naphthylamine (1-NA) to bis (4-oxo-benzo-2-cyclohexen-1-yl) amine ( BOBCHA ) via oxidative coupling under mild conditions.

  11. Carboxylic acid derivatives via catalytic carboxylation of unsaturated hydrocarbons: whether the nature of a reductant may determine the mechanism of CO2 incorporation?

    OpenAIRE

    Kirillov, E.; Carpentier, J.-F.; Bunel, E

    2015-01-01

    International audience Application of CO2 as a renewable feedstock and C1 building block for prodn. of commodity and fine chems. is a highly challenging but obvious industry-relevant task. Of particular interest is the catalytic coupling of CO2 with inexpensive unsatd. hydrocarbons (olefins, dienes, styrenes, alkynes), providing direct access to carboxylic acids and their derivs. Although not brand new for the scientific community, it is still a complete challenge, as no truly effective ca...

  12. Metal triflate-mediated coupling of allylgermanes with thiols: a facile route to thiogermanes.

    Science.gov (United States)

    Kuciński, K; Pawluć, P; Hreczycho, G

    2015-06-28

    A novel coupling reaction of thiols with (2-methylallyl)germanes catalyzed by metal triflates has been developed. This reaction provides a direct and efficient method to afford thiogermanes and opens a valuable and general synthetic route for the Ge-S cross-coupling with the elimination of isobutylene as a single by-product. Scandium(iii) triflate demonstrates the highest catalytic activity among the tested triflates. All reactions were carried out under extremely mild conditions to give thiogermanes in excellent yields. This Ge-S coupling reaction shows high generality for the variety of thiols. PMID:26006777

  13. Palladium supported on natural phosphate: Catalyst for Suzuki coupling reactions in water

    KAUST Repository

    Hassine, Ayoub

    2013-01-01

    The Suzuki-Miyaura coupling reaction is one of the most important synthetic catalytic reactions developed in the 20th century. However, the use of toxic organic solvents for this reaction still poses a scientific challenge and is an aspect of economical and ecological relevance. The use of water as a reaction medium overcomes this issue. In the present work, we described efficient Suzuki coupling reactions in water, without any phase transfer reagents and it is possible to couple challenging substrates like aryl chlorides. Notably, this protocol also works with ultra-low loading of catalyst with high turnover numbers. © 2012 Elsevier B.V.

  14. Coupling Integrable Couplings of an Equation Hierarchy

    International Nuclear Information System (INIS)

    Based on a kind of Lie algebra G proposed by Zhang, one isospectral problem is designed. Under the framework of zero curvature equation, a new kind of integrable coupling of an equation hierarchy is generated using the methods proposed by Ma and Gao. With the help of variational identity, we get the Hamiltonian structure of the hierarchy. (general)

  15. The influence of copper in dealloyed binary platinum–copper electrocatalysts on methanol electroxidation catalytic activities

    Energy Technology Data Exchange (ETDEWEB)

    Poochai, Chatwarin [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Veerasai, Waret, E-mail: waret.vee@mahidol.ac.th [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Somsook, Ekasith [Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand); Dangtip, Somsak [Department of Physics, and NANOTEC COE at Mahidol University, Faculty of Science, Mahidol University, Bangkok 10400 (Thailand)

    2015-08-01

    In this study, we prepared and characterized carbon paper-supported dealloyed binary Pt–Cu core–shell electrocatalysts (denoted as Pt{sub x}Cu{sub (100−x)/}CP) by cyclic co-electrodeposition and selective copper dealloying in an acidic medium, and we investigated the effect of the copper content in the samples on the catalytic activities toward methanol electroxidation reaction (MOR). X-ray photo-emission spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES) indicated that the structure of dealloyed binary Pt–Cu catalysts possessed a Pt-rich shell and a Cu rich core. X-ray absorption near edge spectroscopy (XANES) displayed that the oxidation states of Pt and Cu were zero and one, respectively, implying the formation of metallic Pt and Cu{sub 2}O, respectively. X-ray diffraction spectroscopy (XRD) confirmed that Cu was inserted into a face-centered cubic Pt structure forming Pt–Cu alloys. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) displayed a cubic shape of Pt/CP and a spherical shape of Pt{sub x}Cu{sub (100−x)/}CP with several hundred nanometer sizes of agglomeration that depended on the Cu content. Cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy were performed to confirm that the sample of Pt{sub 70}Cu{sub 30}/CP exhibited the best catalytic activities in terms of the specific current, current density, catalytic poisoning tolerance, and stability. - Graphical abstract: Display Omitted - Highlights: • Binary electrocatalysts of Pt{sub x}Cu{sub (100−x)}/CP were prepared by cyclic co-electrodeposition and selective copper dealloying. • The structures of Pt{sub x}Cu{sub (100−x)}/CP were a Pt rich shell and a Cu rich core. • The Pt{sub 70}Cu{sub 30}/CP was the excellent catalytic activity towards methanol electrooxidation and CO{sub ads} tolerance.

  16. Tunable Plasmonic Nanoparticles with Catalytically Active High-Index Facets

    Science.gov (United States)

    Jing, Hao; Large, Nicolas; Zhang, Qinfeng; Nordlander, Peter; Wang, Hui

    2015-03-01

    Noble metal nanoparticles have been of tremendous interest due to their intriguing size- and shape-dependent plasmonic and catalytic properties. Combining tunable plasmon resonances with superior catalytic activities on the same metallic nanoparticle, however, has long been challenging because nanoplasmonics and nanocatalysis typically require nanoparticles in two drastically different size regimes. Here, we demonstrate that creation of high-index facets on subwavelength metallic nanoparticles provides a unique approach to the integration of desired plasmonic and catalytic properties on the same nanoparticle. Through site-selective surface etching of metallic nanocuboids whose surfaces are dominated by low-index facets, we have controllably fabricated nanorice and nanodumbbell shaped particles, which exhibit drastically enhanced catalytic activities arising from the catalytically active high-index facets abundant on the particle surfaces. The nanorice and nanodumbbell particles also possess appealing tunable plasmonic properties that allow us to gain quantitative insights into nanoparticle-catalyzed reactions with unprecedented sensitivity and detail through time-resolved plasmon-enhanced spectroscopic measurements. Past affiliation: Rice University.

  17. Reduction of nitrate from groundwater: powder catalysts and catalytic membrane

    Institute of Scientific and Technical Information of China (English)

    CHEN Ying-xu; ZHANG Yan; LIU Hong-yuan

    2003-01-01

    The reduction of nitrate contaminant in groundwater has gained renewed and intensive attention due to the environmental problems and health risks. Catalytic denetrification presents one of the most promising approaches for the removal of nitrate from water. Catalytic nitrate reduction from water by powder catalysts and catalytic membrane in a batch reactor was studied. And the effects of the initial concentration, the amounts of catalyst, and the flux H2 on the nitrate reduction were also discussed. The results demonstrated that nitrate reduction activity and the selectivity to nitrogen gas were mainly controlled by diffusion limitations and the mass transfer of the reactants. The selectivity can improved while retaining a high catalytic activity under controlled diffusion condition or the intensification of the mass transfer, and a good reaction condition. The total nitrogen removal efficiency reached above 80%. Moreover, catalytic membrane can create a high effective gas/liquid/solid interface, and show a good selectivity to nitrogen in comparative with the powder catalyst, the selectivity to nitrogen was improved from 73.4% to 89.4%.

  18. Catalytic conversion of biomass to fuels. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Garten, R. L.; Ushiba, K. K.; Cooper, M.; Mahawili, I.

    1978-01-01

    This report presents an assessment and perspective concerning the application of catalytic technologies to the thermochemical conversion of biomass resources to fuels. The major objectives of the study are: to provide a systematic assessment of the role of catalysis in the direct thermochemical conversion of biomass into gaseous and liquid fuels; to establish the relationship between potential biomass conversion processes and catalytic processes currently under development in other areas, with particular emphasis on coal conversion processes; and to identify promising catalytic systems which could be utilized to reduce the overall costs of fuels production from biomass materials. The report is divided into five major parts which address the above objectives. In Part III the physical and chemical properties of biomass and coal are compared, and the implications for catalytic conversion processes are discussed. With respect to chemical properties, biomass is shown to have significant advantages over coal in catalytic conversion processes because of its uniformly high H/C ratio and low concentrations of potential catalyst poisons. The physical properties of biomass can vary widely, however, and preprocessing by grinding is difficult and costly. Conversion technologies that require little preprocessing and accept a wide range of feed geometries, densities, and particle sizes appear desirable. Part IV provides a comprehensive review of existing and emerging thermochemical conversion technologies for biomass and coal. The underlying science and technology for gasification and liquefaction processes are presented.

  19. A compact process for the treatment of olive mill wastewater by combining wet hydrogen peroxide catalytic oxidation and biological techniques

    International Nuclear Information System (INIS)

    A system based on combined actions of catalytic wet oxidation and microbial technologies for the treatment of highly polluted OMW containing polyphenols was studied. The wet hydrogen peroxide catalytic oxidation (WHPCO) process has been investigated in the semi-batch mode at atmospheric pressure, using aluminium-iron-pillared inter layer clay ((Al-Fe)PILC), under two different catalytic processes: ((Al-Fe)PILC/H2O2/ultraviolet radiations) at 25 deg. C and ((Al-Fe)PILC/H2O2) at 50 deg. C. The results show that raw OMW was resistant to the photocatalytic process. However ((Al-Fe)PILC/H2O2), system operating at 50 deg. C reduced considerably the COD, colour and total phenolic contents, and thus decreased the inhibition of the marine photobacteria Vibrio fischeri luminescence by 70%. This study also examined the feasibility of coupling WHPCO and anaerobic digestion treatment. Biomethanisation experiments performed with raw OMW or pre-treated OMW proved that pre-treatments with ((Al-Fe)PILC/H2O2) system, for more than 2 h, resulted in higher methane production. Both untreated OMW as well as 2-h pre-treated OMW revealed as toxic to anaerobic bacteria.

  20. Photo-catalytic Activities of Plant Hormones on Semiconductor Nanoparticles by Laser-Activated Electron Tunneling and Emitting

    Science.gov (United States)

    Tang, Xuemei; Huang, Lulu; Zhang, Wenyang; Jiang, Ruowei; Zhong, Hongying

    2015-03-01

    Understanding of the dynamic process of laser-induced ultrafast electron tunneling is still very limited. It has been thought that the photo-catalytic reaction of adsorbents on the surface is either dependent on the number of resultant electron-hole pairs where excess energy is lost to the lattice through coupling with phonon modes, or dependent on irradiation photon wavelength. We used UV (355 nm) laser pulses to excite electrons from the valence band to the conduction band of titanium dioxide (TiO2), zinc oxide (ZnO) and bismuth cobalt zinc oxide (Bi2O3)0.07(CoO)0.03(ZnO)0.9 semiconductor nanoparticles with different photo catalytic properties. Photoelectrons are extracted, accelerated in a static electric field and eventually captured by charge deficient atoms of adsorbed organic molecules. A time-of-flight mass spectrometer was used to detect negative molecules and fragment ions generated by un-paired electron directed bond cleavages. We show that the probability of electron tunneling is determined by the strength of the static electric field and intrinsic electron mobility of semiconductors. Photo-catalytic dissociation or polymerization reactions of adsorbents are highly dependent on the kinetic energy of tunneling electrons as well as the strength of laser influx. By using this approach, photo-activities of phytohormones have been investigated.

  1. A compact process for the treatment of olive mill wastewater by combining wet hydrogen peroxide catalytic oxidation and biological techniques

    Energy Technology Data Exchange (ETDEWEB)

    Azabou, Samia [Laboratoire des BioProcedes, Centre de Biotechnologie de Sfax, BP 1177, 3018 Sfax (Tunisia); Najjar, Wahiba [Laboratoire de Chimie des Materiaux et Catalyse, Faculte des Sciences de Tunis, Campus Universitaire, 2092 Tunis (Tunisia); Bouaziz, Mohamed [Laboratoire des BioProcedes, Centre de Biotechnologie de Sfax, BP 1177, 3018 Sfax (Tunisia); Ghorbel, Abdelhamid [Laboratoire de Chimie des Materiaux et Catalyse, Faculte des Sciences de Tunis, Campus Universitaire, 2092 Tunis (Tunisia); Sayadi, Sami, E-mail: sami.sayadi@cbs.rnrt.tn [Laboratoire des BioProcedes, Centre de Biotechnologie de Sfax, BP 1177, 3018 Sfax (Tunisia)

    2010-11-15

    A system based on combined actions of catalytic wet oxidation and microbial technologies for the treatment of highly polluted OMW containing polyphenols was studied. The wet hydrogen peroxide catalytic oxidation (WHPCO) process has been investigated in the semi-batch mode at atmospheric pressure, using aluminium-iron-pillared inter layer clay ((Al-Fe)PILC), under two different catalytic processes: ((Al-Fe)PILC/H{sub 2}O{sub 2}/ultraviolet radiations) at 25 deg. C and ((Al-Fe)PILC/H{sub 2}O{sub 2}) at 50 deg. C. The results show that raw OMW was resistant to the photocatalytic process. However ((Al-Fe)PILC/H{sub 2}O{sub 2}), system operating at 50 deg. C reduced considerably the COD, colour and total phenolic contents, and thus decreased the inhibition of the marine photobacteria Vibrio fischeri luminescence by 70%. This study also examined the feasibility of coupling WHPCO and anaerobic digestion treatment. Biomethanisation experiments performed with raw OMW or pre-treated OMW proved that pre-treatments with ((Al-Fe)PILC/H{sub 2}O{sub 2}) system, for more than 2 h, resulted in higher methane production. Both untreated OMW as well as 2-h pre-treated OMW revealed as toxic to anaerobic bacteria.

  2. Multireference Coupled Cluster Ansatz

    OpenAIRE

    Jeziorski, Bogumil

    2010-01-01

    Abstract The origin of the multireference coupled cluster Ansatz for the wave function and the wave operator, discovered in Quantum Theory Project in 1981, is presented from the historical perspective. Various methods of obtaining the cluster amplitudes - both state universal and state selective are critically reviewed and further prospects of using the multireference coupled cluster Ansatz in electronic structure theory are briefly discussed.

  3. Translation-coupling systems

    Science.gov (United States)

    Pfleger, Brian; Mendez-Perez, Daniel

    2013-11-05

    Disclosed are systems and methods for coupling translation of a target gene to a detectable response gene. A version of the invention includes a translation-coupling cassette. The translation-coupling cassette includes a target gene, a response gene, a response-gene translation control element, and a secondary structure-forming sequence that reversibly forms a secondary structure masking the response-gene translation control element. Masking of the response-gene translation control element inhibits translation of the response gene. Full translation of the target gene results in unfolding of the secondary structure and consequent translation of the response gene. Translation of the target gene is determined by detecting presence of the response-gene protein product. The invention further includes RNA transcripts of the translation-coupling cassettes, vectors comprising the translation-coupling cassettes, hosts comprising the translation-coupling cassettes, methods of using the translation-coupling cassettes, and gene products produced with the translation-coupling cassettes.

  4. International Migration of Couples

    DEFF Research Database (Denmark)

    Munk, Martin D.; Junge, Martin; Poutvaara, Panu

    2016-01-01

    We develop a theoretical model regarding the migration of dual-earner couples and test it in the context of international migration. Our model predicts that the probability that a couple emigrates increases with the income of the primary earner, whereas the income of the secondary earner may affect...

  5. OXIDATIVE COUPLING OF METHANE USING INORGANIC MEMBRANE REACTORS

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Y.H. Ma; Dr. W.R. Moser; Dr. A.G. Dixon; Dr. A.M. Ramachandra; Dr. Y. Lu; C. Binkerd

    1998-04-01

    The objective of this research is to study the oxidative coupling of methane in catalytic inorganic membrane reactors. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and higher yields than in conventional non-porous, co-feed, fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for the formation of CO{sub x} products. Such gas phase reactions are a cause of decreased selectivity in the oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Membrane reactor technology also offers the potential for modifying the membranes both to improve catalytic properties as well as to regulate the rate of the permeation/diffusion of reactants through the membrane to minimize by-product generation. Other benefits also exist with membrane reactors, such as the mitigation of thermal hot-spots for highly exothermic reactions such as the oxidative coupling of methane. The application of catalytically active inorganic membranes has potential for drastically increasing the yield of reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity.

  6. Synthesis and catalytic properties of highly branched palladium nanostructures using seeded growth

    Science.gov (United States)

    Graham, L.; Collins, G.; Holmes, J. D.; Tilley, R. D.

    2016-01-01

    In order to develop nanocatalysts with enhanced catalytic performance, it is important to be able to synthesize nanocrystals enclosed by high-index surface facets, due to their high density of low coordinated atoms at step, ledge and kink sites. Here, we report a facile seed-mediated route to the synthesis of highly branched Pd nanostructures with a combination of {113}, {115} and {220} high-index surface planes. The size of these nanostructures is readily controlled by a simple manipulation of the seed concentration. The selective use of oleylamine and oleic acid was also found to be critical to the synthesis of these structures, with Pd icosahedra enclosed by low-index {111} facets being produced when hexadecylamine was employed as capping ligand. The structure-property relationship of these nanostructures as catalysts in Suzuki-cross coupling reactions was then investigated and compared, with the high-index faceted branched Pd nanostructures found to be the most effective catalysts.In order to develop nanocatalysts with enhanced catalytic performance, it is important to be able to synthesize nanocrystals enclosed by high-index surface facets, due to their high density of low coordinated atoms at step, ledge and kink sites. Here, we report a facile seed-mediated route to the synthesis of highly branched Pd nanostructures with a combination of {113}, {115} and {220} high-index surface planes. The size of these nanostructures is readily controlled by a simple manipulation of the seed concentration. The selective use of oleylamine and oleic acid was also found to be critical to the synthesis of these structures, with Pd icosahedra enclosed by low-index {111} facets being produced when hexadecylamine was employed as capping ligand. The structure-property relationship of these nanostructures as catalysts in Suzuki-cross coupling reactions was then investigated and compared, with the high-index faceted branched Pd nanostructures found to be the most effective catalysts

  7. Ground energy coupling

    Science.gov (United States)

    Metz, P. D.

    The feasibility of ground coupling for various heat pump systems was investigated. Analytical heat flow models were developed to approximate design ground coupling devices for use in solar heat pump space conditioning systems. A digital computer program called GROCS (GRound Coupled Systems) was written to model 3-dimensional underground heat flow in order to simulate the behavior of ground coupling experiments and to provide performance predictions which have been compared to experimental results. GROCS also has been integrated with TRNSYS. Soil thermal property and ground coupling device experiments are described. Buried tanks, serpentine earth coils in various configurations, lengths and depths, and sealed vertical wells are being investigated. An earth coil used to heat a house without use of resistance heating is described.

  8. Exponentially modified QCD coupling

    International Nuclear Information System (INIS)

    We present a specific class of models for an infrared-finite analytic QCD coupling, such that at large spacelike energy scales the coupling differs from the perturbative one by less than any inverse power of the energy scale. This condition is motivated by the Institute for Theoretical and Experimental Physics operator product expansion philosophy. Allowed by the ambiguity in the analytization of the perturbative coupling, the proposed class of couplings has three parameters. In the intermediate energy region, the proposed coupling has low loop-level and renormalization scheme dependence. The present modification of perturbative QCD must be considered as a phenomenological attempt, with the aim of enlarging the applicability range of the theory of the strong interactions at low energies.

  9. Cobalt-Catalyzed Cross-Coupling of Grignards with Allylic and Vinylic Bromides: Use of Sarcosine as a Natural Ligand.

    Science.gov (United States)

    Frlan, Rok; Sova, Matej; Gobec, Stanislav; Stavber, Gaj; Časar, Zdenko

    2015-08-01

    Sarcosine was discovered to be an excellent ligand for cobalt-catalyzed carbon-carbon cross-coupling of Grignard reagents with allylic and vinylic bromides. The Co(II)/sarcosine catalytic system is shown to perform efficiently when phenyl and benzyl Grignards are coupled with alkenyl bromides. Notably, previously unachievable Co-catalyzed coupling of allylic bromides with Grignards to linearly coupled α-products was also realized with Co(II)/sarcosine catalyst. This method was used for efficient preparation of the key intermediate in an alternative synthesis of the antihyperglycemic drug sitagliptin. PMID:26158563

  10. 40 CFR 63.1564 - What are my requirements for metal HAP emissions from catalytic cracking units?

    Science.gov (United States)

    2010-07-01

    ... emissions from catalytic cracking units? 63.1564 Section 63.1564 Protection of Environment ENVIRONMENTAL... Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Catalytic Cracking... requirements for metal HAP emissions from catalytic cracking units? (a) What emission limitations and...

  11. 40 CFR 63.1565 - What are my requirements for organic HAP emissions from catalytic cracking units?

    Science.gov (United States)

    2010-07-01

    ... HAP emissions from catalytic cracking units? 63.1565 Section 63.1565 Protection of Environment... Petroleum Refineries: Catalytic Cracking Units, Catalytic Reforming Units, and Sulfur Recovery Units Catalytic Cracking Units, Catalytic Reforming Units, Sulfur Recovery Units, and Bypass Lines § 63.1565...

  12. Studies on Nitrogen Oxides Removal Using Plasma Assisted Catalytic Reactor

    Institute of Scientific and Technical Information of China (English)

    V. Ravi; Young Sun Mok; B. S. Rajanikanth; Ho-Chul Kang

    2003-01-01

    An electric discharge plasma reactor combined with a catalytic reactor was studied for removing nitrogen oxides. To understand the combined process thoroughly, discharge plasma and catalytic process were separately studied first, and then the two processes were combined for the study. The plasma reactor was able to oxidize NO to NO2 well although the oxidation rate decreased with temperature. The plasma reactor alone did not reduce the NOx (NO+NO2)level effectively, but the increase in the ratio of NO2 to NO as a result of plasma discharge led to the enhancement of NOx removal efficiency even at lower temperatures over the catalyst surface (V2O5-WOa/TiO2). At a gas temperature of 100℃, the NOx removal efficiency obtained using the combined plasma catalytic process was 88% for an energy input of 36 eV/molecule or 30 J/1.

  13. Design of Catalytically Amplified Sensors for Small Molecules

    Directory of Open Access Journals (Sweden)

    Olga V. Makhlynets

    2014-04-01

    Full Text Available Catalytically amplified sensors link an allosteric analyte binding site with a reactive site to catalytically convert substrate into colored or fluorescent product that can be easily measured. Such an arrangement greatly improves a sensor’s detection limit as illustrated by successful application of ELISA-based approaches. The ability to engineer synthetic catalytic sites into non-enzymatic proteins expands the repertoire of analytes as well as readout reactions. Here we review recent examples of small molecule sensors based on allosterically controlled enzymes and organometallic catalysts. The focus of this paper is on biocompatible, switchable enzymes regulated by small molecules to track analytes both in vivo and in the environment.

  14. Catalytic wet Air Oxidation of o-Chlorophenol in Wastewater

    Institute of Scientific and Technical Information of China (English)

    徐新华; 汪大翬

    2003-01-01

    Catalytic wet air oxidation (CWAO) was investigated in laboratory-scale experiments for the treatment of o-chlorophenol in wastewater. Experimental results showed that wet air oxidation (WAO) process in the absence of catalyst was also effective for o-chlorophenol in wastewater treatment. Up to 80% of the initial CODCr was removed by wet air oxidation at 270℃ with twice amount of the required stoichiometric oxygen supply. At temperature of 150℃, the removal rate of CODCr was only 30%. Fe2(SO4)3, CuSO4, Cu(NO3)2 and MnSO4 exhibited high catalytic activity. Higher removal rate of CODCr was obtained by CWAO. More than 96% of the initial CODCr was removed at 270℃ and 84.6%-93.6% of the initial CODCr was removed at 150℃. Mixed catalysts had better catalytic activity for the degradation of o-chlorophenol in wastewater.

  15. Heterogeneous-catalytic redox reactions in nitrate - formate systems

    International Nuclear Information System (INIS)

    It was found that an intensive destruction of various organic and mineral substances - usual components of aqueous waste solutions (oxalic acid, complexones, urea, hydrazine, ammonium nitrate, etc.) takes place under the conditions of catalytic denitration. Kinetics and mechanisms of urea and ammonium nitrate decomposition in the system HNO3 - HCOOH - Pt/SiO2 are comprehensively investigated. The behaviour of uranium, neptunium and plutonium under the conditions of catalytic denitration is studied. It is shown, that under the certain conditions the formic acid is an effective reducer of the uranium (VI), neptunium (VI, V) and plutonium (VI, IV) ions. Kinetics of heterogeneous-catalytic red-ox reactions of uranium (VI), neptunium (VI, V) and plutonium (VI, IV) with formic acid are investigated. The mechanisms of the appropriate reactions are evaluated. (authors)

  16. The effect of catalyst preparation on catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Schwarz, J.A.

    1992-01-01

    Three intrinsically connected phenomena occur during adsorption/impregnation of aqueous electrolytes onto oxide carriers. They are: pH-dependent development of surface carriers on the oxide; pH-dependent aqueous speciation of catalytic precursors; surface adsorption by complexation and coordination. Modeling of these processes yields basic thermodynamic properties of the adsorbed phase, which could provide useful information of the catalytic properties of the metal, support, and reveal metal-support interactions, thus contributing to design criteria for supported-metal catalysts. The spectrum of catalytic systems that can be studied using the above approach is greatly extended when both pure and composite oxide carriers are considered. This presentation will focus on three metal/support systems, each of which provides results of both practical and fundamental importance.

  17. A catalytic distillation process for light gas oil hydrodesulfurization

    Energy Technology Data Exchange (ETDEWEB)

    Vargas-Villamil, F.D.; Marroquin, J.O.; Paz, C. de la; Rodriguez, E. [Prog. de Matematicas Aplicadas y Computacion, Prog. de Tratamiento de Crudo Maya, Instituto Mexicano del Petroleo, Mexico City, DF (Mexico)

    2004-07-01

    A light gas oil hydrodesulfurization process via catalytic distillation is developed and compared to a conventional process. By integrating the separation and reaction into a single unit, the catalytic distillation may produce a diesel with low concentration of sulfur compounds at a lower cost than the traditional reaction/separation process. The process proposed in this work is compared to an optimised conventional hydrodesulfurization unit which represents fairly well a plant that belongs to the National System of Refineries. During the optimisation of the conventional process, a compromise is established among the production of diesel and naphtha and the operating costs. The results show that the light gas oil hydrodesulfurization via catalytic distillation is as or more efficient than the conventional process. However, the removal of the sulfur compounds is carried out under less rigorous conditions. This design reduces the fix and operational costs. (author)

  18. Catalytic Desulfurization of Benzothiophene Using Keggin Type Polyoxometalates as Catalyst

    Directory of Open Access Journals (Sweden)

    Aldes Lesbani

    2015-01-01

    Full Text Available Performance of catalytic desulfurization of benzothiophen (BT was studied using polyoxometalates as catalyst. Polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40], have different heteroatom in Keggin structure and catalytic activities. Polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] have high crystallinity with homogeneous distribution particles. Desulfurization of BT using polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] resulted % conversion up to 99% for 3 h reaction time and at temperature 40 oC. Application of polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] for crude oil desulfurization showed % conversion of 4-88%. The main functional groups of polyoxometalates still retained after catalytic desulfurization indicated the stability of polyoxometalate compounds

  19. Kinetic and catalytic performance of a BI-porous composite material in catalytic cracking and isomerisation reactions

    KAUST Repository

    Al-Khattaf, S.

    2012-01-10

    Catalytic behaviour of pure zeolite ZSM-5 and a bi-porous composite material (BCM) were investigated in transformation of m-xylene, while zeolite HY and the bi-porous composite were used in the cracking of 1,3,5-triisopropylbenzene (TIPB). The micro/mesoporous material was used to understand the effect of the presence of mesopores on these reactions. Various characterisation techniques, that is, XRD, SEM, TGA, FT-IR and nitrogen sorption measurements were applied for complete characterisation of the catalysts. Catalytic tests using CREC riser simulator showed that the micro/mesoporous composite catalyst exhibited higher catalytic activity as compared with the conventional microporous ZSM-5 and HY zeolite for transformation of m-xylene and for the catalytic cracking of TIPB, respectively. The outstanding catalytic reactivity of m-xylene and TIPB molecules were mainly attributed to the easier access of active sites provided by the mesopores. Apparent activation energies for the disappearance of m-xylene and TIPB over all catalysts were found to decrease in the order: EBCM>EZSM-5 and EBCM>EHY, respectively. © 2012 Canadian Society for Chemical Engineering.

  20. Palladium-catalyzed coupling reactions of tetrafluoroethylene with arylzinc compounds.

    Science.gov (United States)

    Ohashi, Masato; Kambara, Tadashi; Hatanaka, Tsubasa; Saijo, Hiroki; Doi, Ryohei; Ogoshi, Sensuke

    2011-03-16

    Organofluorine compounds are widely used in all aspects of the chemical industry. Although tetrafluoroethylene (TFE) is an example of an economical bulk organofluorine feedstock, the use of TFE is mostly limited to the production of poly(tetrafluoroethylene) and copolymers with other alkenes. Furthermore, no catalytic transformation of TFE that involves carbon-fluorine bond activation has been reported to date. We herein report the first example of a palladium-catalyzed coupling reaction of TFE with arylzinc reagents in the presence of lithium iodide, giving α,β,β-trifluorostyrene derivatives in excellent yields. PMID:21322557

  1. Site-specific growth of Au-Pd alloy horns on Au nanorods: a platform for highly sensitive monitoring of catalytic reactions by surface enhancement Raman spectroscopy.

    Science.gov (United States)

    Huang, Jianfeng; Zhu, Yihan; Lin, Ming; Wang, Qingxiao; Zhao, Lan; Yang, Yang; Yao, Ke Xin; Han, Yu

    2013-06-12

    Surface-enhanced Raman scattering (SERS) is a highly sensitive probe for molecular detection. The aim of this study was to develop an efficient platform for investigating the kinetics of catalytic reactions with SERS. To achieve this, we synthesized a novel Au-Pd bimetallic nanostructure (HIF-AuNR@AuPd) through site-specific epitaxial growth of Au-Pd alloy horns as catalytic sites at the ends of Au nanorods. Using high-resolution electron microscopy and tomography, we successfully reconstructed the complex three-dimensional morphology of HIF-AuNR@AuPd and identified that the horns are bound with high-index {11l} (0.25 facets. With an electron beam probe, we visualized the distribution of surface plasmon over the HIF-AuNR@AuPd nanorods, finding that strong longitudinal surface plasmon resonance concentrated at the rod ends. This unique crystal morphology led to the coupling of high catalytic activity with a strong SERS effect at the rod ends, making HIF-AuNR@AuPd an excellent bifunctional platform for in situ monitoring of surface catalytic reactions. Using the hydrogenation of 4-nitrothiophenol as a model reaction, we demonstrated that its first-order reaction kinetics could be accurately determined from this platform. Moreover, we clearly identified the superior catalytic activity of the rod ends relative to that of the rod bodies, owing to the different SERS activities at the two positions. In comparison with other reported Au-Pd bimetallic nanostructures, HIF-AuNR@AuPd offered both higher catalytic activity and greater detection sensitivity. PMID:23675958

  2. Site-specific growth of Au-Pd alloy horns on Au nanorods: A platform for highly sensitive monitoring of catalytic reactions by surface enhancement raman spectroscopy

    KAUST Repository

    Huang, Jianfeng

    2013-06-12

    Surface-enhanced Raman scattering (SERS) is a highly sensitive probe for molecular detection. The aim of this study was to develop an efficient platform for investigating the kinetics of catalytic reactions with SERS. To achieve this, we synthesized a novel Au-Pd bimetallic nanostructure (HIF-AuNR@AuPd) through site-specific epitaxial growth of Au-Pd alloy horns as catalytic sites at the ends of Au nanorods. Using high-resolution electron microscopy and tomography, we successfully reconstructed the complex three-dimensional morphology of HIF-AuNR@AuPd and identified that the horns are bound with high-index {11l} (0.25 < l < 0.43) facets. With an electron beam probe, we visualized the distribution of surface plasmon over the HIF-AuNR@AuPd nanorods, finding that strong longitudinal surface plasmon resonance concentrated at the rod ends. This unique crystal morphology led to the coupling of high catalytic activity with a strong SERS effect at the rod ends, making HIF-AuNR@AuPd an excellent bifunctional platform for in situ monitoring of surface catalytic reactions. Using the hydrogenation of 4-nitrothiophenol as a model reaction, we demonstrated that its first-order reaction kinetics could be accurately determined from this platform. Moreover, we clearly identified the superior catalytic activity of the rod ends relative to that of the rod bodies, owing to the different SERS activities at the two positions. In comparison with other reported Au-Pd bimetallic nanostructures, HIF-AuNR@AuPd offered both higher catalytic activity and greater detection sensitivity. © 2013 American Chemical Society.

  3. Roles of catalytic oxidation in control of vehicle exhaust emissions

    International Nuclear Information System (INIS)

    Catalytic oxidation was initially associated with the early development of catalysis and it subsequently became a part of many industrial processes, so it is not surprising it was used to remove hydrocarbons and CO when it became necessary to control these emissions from cars. Later NOx was reduced in a process involving reduction over a Pt/Rh catalyst followed by air injection in front of a Pt-based oxidation catalyst. If over-reduction of NO to NH3 took place, or if H2S was produced, it was important these undesirable species were converted to NOx and SOx in the catalytic oxidation stage. When exhaust gas composition could be kept stoichiometric hydrocarbons, CO and NOx were simultaneously converted over a single Pt/Rh three-way catalyst (TWC). With modern TWCs car tailpipe emissions can be exceptionally low. NO is not catalytically dissociated to O2 and N2 in the presence of O2, it can only be reduced to N2. Its control from lean-burn gasoline engines involves catalytic oxidation to NO2 and thence nitrate that is stored and periodically reduced to N2 by exhaust gas enrichment. This method is being modified for diesel engines. These engines produce soot, and filtration is being introduced to remove it. The exhaust temperature of heavy-duty diesels is sufficient (250-400oC) for NO to be catalytically oxidised to NO2 over an upstream platinum catalyst that smoothly oxidises soot in the filter. The exhaust gas temperature of passenger car diesels is too low for this to take place all of the time, so trapped soot is periodically burnt in O2 above 550oC. Catalytic oxidation of higher than normal amounts of hydrocarbon and CO over an upstream catalyst is used to give sufficient temperature for soot combustion with O2 to take place. (author)

  4. Fuel Flexible, Low Emission Catalytic Combustor for Opportunity Fuel Applications

    Energy Technology Data Exchange (ETDEWEB)

    Eteman, Shahrokh

    2013-06-30

    Limited fuel resources, increasing energy demand and stringent emission regulations are drivers to evaluate process off-gases or process waste streams as fuels for power generation. Often these process waste streams have low energy content and/or highly reactive components. Operability of low energy content fuels in gas turbines leads to issues such as unstable and incomplete combustion. On the other hand, fuels containing higher-order hydrocarbons lead to flashback and auto-ignition issues. Due to above reasons, these fuels cannot be used directly without modifications or efficiency penalties in gas turbine engines. To enable the use of these wide variety of fuels in gas turbine engines a rich catalytic lean burn (RCL®) combustion system was developed and tested in a subscale high pressure (10 atm.) rig. The RCL® injector provided stability and extended turndown to low Btu fuels due to catalytic pre-reaction. Previous work has shown promise with fuels such as blast furnace gas (BFG) with LHV of 85 Btu/ft3 successfully combusted. This program extends on this work by further modifying the combustor to achieve greater catalytic stability enhancement. Fuels containing low energy content such as weak natural gas with a Lower Heating Value (LHV) of 6.5 MJ/m3 (180 Btu/ft3 to natural gas fuels containing higher hydrocarbon (e.g ethane) with LHV of 37.6 MJ/m3 (1010 Btu/ft3) were demonstrated with improved combustion stability; an extended turndown (defined as the difference between catalytic and non-catalytic lean blow out) of greater than 250oF was achieved with CO and NOx emissions lower than 5 ppm corrected to 15% O2. In addition, for highly reactive fuels the catalytic region preferentially pre-reacted the higher order hydrocarbons with no events of flashback or auto-ignition allowing a stable and safe operation with low NOx and CO emissions.

  5. OPERATING SPECIFICATIONS OF CATALYTIC CLEANING OF GAS FROM BIOMASS GASIFICATION

    Directory of Open Access Journals (Sweden)

    Martin Lisý

    2015-12-01

    Full Text Available The paper focuses on the theoretical description of the cleaning of syngas from biomass and waste gasification using catalytic methods, and on the verification of the theory through experiments. The main obstruction to using syngas from fluid gasification of organic matter is the presence of various high-boiling point hydrocarbons (i.e., tar in the gas. The elimination of tar from the gas is a key factor in subsequent use of the gas in other technologies for cogeneration of electrical energy and heat. The application of a natural or artificial catalyst for catalytic destruction of tar is one of the methods of secondary elimination of tar from syngas. In our experiments, we used a natural catalyst (dolomite or calcium magnesium carbonate from Horní Lánov with great mechanical and catalytic properties, suitable for our purposes. The advantages of natural catalysts in contrast to artificial catalysts include their availability, low purchase prices and higher resilience to the so-called catalyst poison. Natural calcium catalysts may also capture undesired compounds of sulphure and chlorine. Our paper presents a theoretical description and analysis of catalytic destruction of tar into combustible gas components, and of the impact of dolomite calcination on its efficiency. The efficiency of the technology is verified in laboratories. The facility used for verification was a 150 kW pilot gasification unit with a laboratory catalytic filter. The efficiency of tar elimination reached 99.5%, the tar concentration complied with limits for use of the gas in combustion engines, and the tar content reached approximately 35 mg/mn3. The results of the measurements conducted in laboratories helped us design a pilot technology for catalytic gas cleaning.

  6. Phase composition and catalytic properties of molybdenum-containing catalysts

    International Nuclear Information System (INIS)

    Using the data on the study of phase composition of oxide silicon-, titanium-, phosphorus-molybdenum catalysts and their catalytic properties in propylene and methanol oxidation reactions it is shown, that in the process of conventional synthesis of oxide catalysts at least two types of molybdenum-containing compounds, stable under the reaction conditions are formed: molybdenum polycompounds, (heteropolyacids, their salts, products of their reversible dehydration) and compounds on the basis of molybdic acid (simple molybdates, MoO3). The compounds differ considerably as to their redox and catalytic properties

  7. Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes

    Science.gov (United States)

    Tian, Yuelong; Ge, Min; Zhang, Weigang; Lv, Xiaoxu; Yu, Shouquan

    2015-11-01

    Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

  8. DEVELOPMENT OF HIGH ACTIVITY, CATALYTIC SYSTEMS FOR NOx REDUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Unknown

    2001-12-01

    This project was directed at an investigation of catalytic NO{sub x} reduction on carbonaceous supports at low temperatures. The experimental work was conducted primarily in a packed bed reactor/gas flow system that was constructed for this work. The analytical techniques employed were mass spectrometry, NO{sub x} chemiluminescence, and gas chromatography. The experimental plan was focused on steady-state reactivity experiments, followed by temperature programmed desorption (TPD) of surface intermediates, and also selected temperature-programmed reaction (TPR) experiments. Both uncatalyzed and catalyzed (potassium-promoted) phenolic resin char, were investigated as well as the catalytic effect of additional CO in the gas phase.

  9. Catalytic Preparation of Methyl Formate from Methanol over Silver

    Institute of Scientific and Technical Information of China (English)

    YANG Zhi; LI Jing; YANG Xiang-guang; WU Yue

    2005-01-01

    A catalytic reaction over a silver catalyst performed in an unregarded temperature region(473-873 K) with a long catalytic lifetime for the production of methyl formate from methanol was provided as a potential preparing route. The optimal yield of methyl formate(ca. 14.8%) with a selectivity >90% was obtained at about 573 K. Because α-oxygen species and bulk oxygen species coexist in the unregarded temperature region, a synergistic process concerning α-oxygen species and bulk oxygen species was proved over Oα -rich and Oγ-rich samples.

  10. Sintering of Catalytic Nanoparticles: Particle Migration or Ostwald Ripening?

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; DeLaRiva, Andrew T.; Challa, Sivakumar R.;

    2013-01-01

    deactivation, is an important mechanism for the loss of catalyst activity. This is especially true for high temperature catalytic processes, such as steam reforming, automotive exhaust treatment, or catalytic combustion. With dwindling supplies of precious metals and increasing demand, fundamental...... process causing the growth of nanoparticle size. Consequently, this leads to the loss of surface area and activity. While particle migration could be controlled through suitable structuring of catalyst supports, it is more difficult to control the mobility of atomically dispersed species. These insights...

  11. Biofuel production from catalytic cracking of woody oils.

    Science.gov (United States)

    Xu, Junming; Jiang, Jianchun; Chen, Jie; Sun, Yunjuan

    2010-07-01

    The catalytic cracking reactions of several kinds of woody oils have been studied. The products were analyzed by GC-MS and FTIR and show the formation of olefins, paraffins and carboxylic acids. Several kinds of catalysts were compared. It was found that the fraction distribution of product was modified by using base catalysts such as CaO. The products from woody oils showed good cold flow properties compared with diesel used in China. The results presented in this work have shown that the catalytic cracking of woody oils generates fuels that have physical and chemical properties comparable to those specified for petroleum based fuels. PMID:20206508

  12. Catalytic hydrogen evolution by polyaminoacids using mercury electrode

    Directory of Open Access Journals (Sweden)

    Marko Živanovič

    2010-12-01

    Full Text Available It was shown that using constant current chronopotentiometricstripping (CPS peptides and proteins at nanomolar concentrations produce protein structure–sensitive peak H at mercury electrodes. This peak is due to the catalytic hydrogen evolution reaction (HER. Polyamino acids can be considered as an intermediate model system between peptides and macromolecular proteins. Here we used polyamino acids (poly(aa such as polylysine (polyLys and polyarginine (polyArg and cyclic voltammetry or CPS in combination with hanging mercury drop electrode to explore how different amino acid residues in proteins contribute to the catalyticHER.

  13. Local deposition and patterning of catalytic thin films in microsystems

    International Nuclear Information System (INIS)

    The local deposition of catalysts is desired in a wide range of catalytic microsystems (microreactors and sensors). In this study, we investigate technologies enabling deposition and patterning of catalyst thin films in a manner compatible with standard micromachining processes. We evaluate and compare deposition techniques based on a combination of a self-assembly, soft-lithography and conventional micromachining. Platinum (Pt) and palladium (Pd) were used as model catalysts, both as a sputtered thin film and as nanoparticles supported on γ-alumina. The thin films were characterized and tested in terms of their catalytic activity based on CO chemisorption measurements, stability and reproducibility. (paper)

  14. Degradation of Organic Pollutants in Water by Catalytic Ozonation

    Institute of Scientific and Technical Information of China (English)

    LI Xin; YAO Jun-hai; QI Jing-yao

    2007-01-01

    Different series of transition metal catalysts supported on Al2O3 were prepared by the impregnation method. The catalytic activity was measured in a batch reactor with ozone as the oxidizing reagent. The experimental results indicate that Cu/Al2O3 has a very effective catalytic activity during the ozonation of organic pollutants in water. The optimum conditions for preparing Cu/Al2O3 were systematically investigated with the orthogonal testing method. Furthermore, the results also show that the surface properties of catalyst are not compulsory for effective oxidation.

  15. Basic Aspects Related to Operation of Engine Catalytic Converters

    Directory of Open Access Journals (Sweden)

    Adam Ciesiolkiewicz

    2004-03-01

    Full Text Available Experimental research on the diesel engine 6C107 equipped with selected oxidation catalytic converters was carried out. Specific emissions of toxic substances were investigated in the whole operation range of the engine before and after catalysts. Thus, changes of the emission indices within the catalysts and conversion efficiencies of the harmful substances were evaluated. Besides, temperature threshold of the catalytic action was determined too. Apart from chemical efficiency of the converters, their resistance to exhaust gas flow also is an essential problem. Therefore selected quantities of exhaust gas flow through the catalysts were determined and analysed together with their termochemical efficiency.

  16. Catalytic Desulfurization of Benzothiophene Using Keggin Type Polyoxometalates as Catalyst

    OpenAIRE

    Aldes Lesbani; Arianti Marpaung; Marieska Verawaty; Hesti Rizki Amalia; Risfidian Mohadi

    2015-01-01

    Performance of catalytic desulfurization of benzothiophen (BT) was studied using polyoxometalates as catalyst. Polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40], have different heteroatom in Keggin structure and catalytic activities. Polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] have high crystallinity with homogeneous distribution particles. Desulfurization of BT using polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] resulted % conversion up to 99% for 3 h reaction time and at tempera...

  17. Simulation of Suspension Catalytic Distillation for Synthesis of Linear Alkylbenzene

    Institute of Scientific and Technical Information of China (English)

    王二强; 李成岳

    2003-01-01

    Suspension catalytic distillation (SCD) has been developed recently as an innovative technology in catalytic distillation. In this paper, a brief introduction to SCD is given and an equilibrium stage (EQ) model is developed to simulate this new process for synthesis of linear alkylbenzene (LAB) from benzene and 1-dodecene.Since non-ideality of this reaction system is not strong, EQ model developed could be applied to it successfully.Simulation results agree well with experimental data, and indicate some characteristics of SCD process as an advanced technology for the production of LAB: 100% conversion of olefins, low temperature (90-100℃) and low benzene/olefin mole ratio.

  18. Monomeric G protein-coupled receptor rhodopsin in solution activates its G protein transducin at the diffusion limit

    OpenAIRE

    Ernst, Oliver P.; Gramse, Verena; Kolbe, Michael; Hofmann, Klaus Peter; Heck, Martin

    2007-01-01

    G protein-coupled receptors mediate biological signals by stimulating nucleotide exchange in heterotrimeric G proteins (Gαβγ). Receptor dimers have been proposed as the functional unit responsible for catalytic interaction with Gαβγ. To investigate whether a G protein-coupled receptor monomer can activate Gαβγ, we used the retinal photoreceptor rhodopsin and its cognate G protein transducin (Gt) to determine the stoichiometry of rhodopsin/Gt binding and the rate of catalyzed nucleotide exchan...

  19. Application of bisphosphomide-palladium(II) pincer complex in Suzuki-Miyaura cross-coupling reaction under microwave irradiation

    Indian Academy of Sciences (India)

    Maruthai Kumaravel; Pawan Kumar; Maravanji S Balakrishna

    2014-05-01

    The bisphosphomide-based pincer complex [PdBr{2,6-{Ph2PC(O)}2(C6H3)}] (2) has shown very high catalytic activity in Suzuki-Miyaura cross coupling reaction under microwave irradiation for a variety of aryl bromides and aryl boronic acids. The complex showed the same efficiency for gram scale reactions.

  20. Depression: The Differing Narratives of Couples in Couple Therapy

    Science.gov (United States)

    Rautiainen, Eija-Liisa; Aaltonen, Jukka

    2010-01-01

    How does the spouse of a person with depression take part in constructing narratives of depression in couple therapy? In this study we examined couples' ways of co-constructing narratives of depression in couple therapy. Three couple therapy processes were chosen for the study, one spouse in each couple having been referred to an outpatient clinic…

  1. Hydrophobic catalysts for liquid phase catalytic exchange: a review of preparation methods and influencing factors of catalytic activities

    International Nuclear Information System (INIS)

    Liquid phase catalytic exchange (LPCE) between liquid water and gaseous hydro- gen has been developed for various applications, such as tritium recovery, water upgrade and heavy-water production. Good wetproofing properties of the hydrophobic catalysts can make the reaction to proceed smoothly. In this article, the preparation methods of the hydrophobic catalysts and the factors affecting the catalytic activities are reviewed. In particular, progress on the hydrophobic Pt/C/inert carrier catalysts is introduced, including the selection of inert carrier and active metal carrier, and the preparation methods of carbon- supported Pt based catalysts. Basic research activities on controllable fabrication of hydro- phobic catalysts are discussed, including the LPCE reaction mechanism, and the relation between the microstructure of active metal and the catalytic activity, etc. Finally, questions remaining to be answered and future directions in the field of hydrophobic catalysts are discussed. (authors)

  2. Plastics pipe couplings

    International Nuclear Information System (INIS)

    A method is described of making a pipe coupling of the type comprising a plastics socket and a resilient annular sealing member secured in the mouth thereof, in which the material of at least one component of the coupling is subjected to irradiation with high energy radiation whereby the material is caused to undergo cross-linking. As examples, the coupling may comprise a polyethylene or plasticised PVC socket the material of which is subjected to irradiation, and the sealing member may be moulded from a thermoplastic elastomer which is subjected to irradiation. (U.K.)

  3. Networks of High Mutual Information Define the Structural Proximity of Catalytic Sites: Implications for Catalytic Residue Identification

    DEFF Research Database (Denmark)

    Buslje, Cristina Marino; Teppa, Elin; Di Doménico, Tomas;

    2010-01-01

    to significantly outperform both the Shannon entropy and maximal frequency measurements. Residues in the proximity of catalytic sites were shown to be rich in shared MI. A structural proximity MI average score (termed pMI) was demonstrated to be a strong predictor for CR, thus confirming the proposed...... hypothesis. A structural proximity conservation average score (termed pC) was also calculated and demonstrated to carry distinct information from pMI. A catalytic likeliness score (Cls), combining the KL, pC and pMI measures, was shown to lead to significantly improved prediction accuracy. At a specificity...

  4. A structural basis for the activity of retro-Diels–Alder catalytic antibodies: Evidence for a catalytic aromatic residue

    OpenAIRE

    Hugot, Marina; Bensel, Nicolas; Vogel, Monique; Reymond, Martine T.; Stadler, Beda; Reymond, Jean-Louis; Baumann, Ulrich

    2002-01-01

    The nitroxyl synthase catalytic antibodies 10F11, 9D9, and 27C5 catalyze the release of nitroxyl from a bicyclic pro-drug by accelerating a retro-Diels–Alder reaction. The Fabs (antigen-binding fragments) of these three catalytic antibodies were cloned and sequenced. Fab 9D9 was crystallized in the apo-form and in complex with one transition state analogue of the reaction. Crystal structures of Fab 10F11 in complex with ligands mimicking substrate, transition state, and product have been dete...

  5. Coupling in the Tevatron

    Energy Technology Data Exchange (ETDEWEB)

    Gelfand, N.M.

    1994-12-01

    The performance of the Fermilab Tevatron Collider at the commencement of run Ib was far below expectations. After a frustrating period of several months, a low-{beta} quad downstream of the interaction point at B0 was found to be rolled. This rolled quadrupole coupled the horizontal and vertical motion of the Tevatron beams. It also made matching the beam from the Main Ring to the Tevatron impossible, resulting in emittance blow up on injection. The net result of the roll was a significant reduction in the Tevatron luminosity. When the roll in the quadrupole was corrected the performance of the Tevatron improved dramatically. This note will discuss the experimental data indicating the presence of coupling and subsequent calculations which show how coupling an affect the luminosity. It is not intended to exhaust a discussion of coupling, which hopefully will be understood well enough to be discussed in a subsequent note.

  6. Disformally coupled inflation

    CERN Document Server

    van de Bruck, Carsten; Longden, Chris

    2015-01-01

    A disformal coupling between two scalar fields is considered in the context of cosmological inflation. The coupling introduces novel derivative interactions mixing the kinetic terms of the fields but without introducing superluminal or unstable propagation of the two scalar fluctuation modes. Though the typical effect of the disformal coupling is to inhibit one of the fields from inflating the universe, the energy density of the other field can drive viable near Sitter -inflation in the presence of nontrivial disformal dynamics, in particular when one assumes exponential instead of power-law form for the couplings. The linear perturbation equations are written for the two-field system, its canonical degrees of freedom are quantised, their spectra are derived and the inflationary predictions are reported for numerically solved exponential models. A generic prediction is low tensor-to-scalar ratio.

  7. The subfertile couple.

    Science.gov (United States)

    McCusker, M P

    1982-01-01

    When pregnancy is achieved through fertility awareness, there are further long-range benefits to the couple: information which will permit them the choice to avoid, delay or achieve subsequent pregnancies. Thus, the opportunity for responsible parenthood continues. The goal of nursing in subfertility care is to identify factors which may contribute to lowered fertility, and to teach and/or refer appropriately. The most comprehensive single intervention may be to teach the couple awareness of their own fertility through the Billings Method of natural family planning. If conception does not occur, the couple may progress to infertility investigation, knowing that the expense, inconvenience, and possible trauma are justified. Whether pregnancy occurs or not, it is likely that the couple will have had the benefit of clarifying their relationship, further understanding their bodies, and generally growing toward fuller personhood. PMID:6920464

  8. Pneumatic flexible shaft couplings

    Directory of Open Access Journals (Sweden)

    Jaroslav HOMIŠIN

    2007-01-01

    Full Text Available Main effort of every design engineer is reduction of torsional oscillation in any mechanical system. At present this problem can be solved by means of a suitable modification of dynamic properties of flexible shaft couplings according to dynamics in the given systems. But the dynamic properties of nowadays-applied flexible couplings arenot unchangeable because of aging and fatigue processes occurring in flexible coupling elements. Result of this fact causes detuning of mechanical system. Taking into consideration the above-mentioned situation, we suggest for mechanical systems application of a newly developed pneumatic couplings that have constant characteristicfeatures during the whole current operation and thus they have a positive influence on the system running.

  9. Disformally coupled inflation

    Science.gov (United States)

    van de Bruck, Carsten; Koivisto, Tomi; Longden, Chris

    2016-03-01

    A disformal coupling between two scalar fields is considered in the context of cosmological inflation. The coupling introduces novel derivative interactions mixing the kinetic terms of the fields but without introducing superluminal or unstable propagation of the two scalar fluctuation modes. Though the typical effect of the disformal coupling is to inhibit one of the fields from inflating the universe, the energy density of the other field can drive viable near Sitter -inflation in the presence of nontrivial disformal dynamics, in particular when one assumes exponential instead of power-law form for the couplings. The linear perturbation equations are written for the two-field system, its canonical degrees of freedom are quantised, their spectra are derived and the inflationary predictions are reported for numerically solved exponential models. A generic prediction is low tensor-to-scalar ratio.

  10. Catalytic reduction of 4-nitrophenol by magnetically recoverable Au nanocatalyst.

    Science.gov (United States)

    Chang, Yang-Chuang; Chen, Dong-Hwang

    2009-06-15

    A novel magnetically recoverable Au nanocatalyst was fabricated by the simple adsorption-reduction of Au(III) ions on chitosan-coated iron oxide magnetic nanocarrier. Au nanoparticles with a mean diameter of 3.14 nm were well loaded on the surface of magnetic nanocarrier because chitosan layer provided an effective driving force in the formation and stabilization of Au nanoparticles. The resultant magnetically recoverable Au nanocatalyst exhibited excellent catalytic activity to the reduction of 4-nitrophenol (4-NP) with sodium borohydride. The rate constants evaluated in terms of pseudo-first-order kinetic model increased with increasing the amount of Au nanocatalyst, decreasing the initial 4-NP concentration, and increasing the temperature. Also, the kinetic data suggested that this catalytic reaction was diffusion controlled owing to the presence of chitosan layer. In addition, catalyst reuse showed no trace of deactivation or poisoning during the catalytic and separation processes, revealing the stable nature and good catalytic ability of this nanocatalyst. PMID:19022566

  11. Clay Minerals as Solid Acids and Their Catalytic Properties.

    Science.gov (United States)

    Helsen, J.

    1982-01-01

    Discusses catalytic properties of clays, attributed to acidity of the clay surface. The formation of carbonium ions on montmorillonite is used as a demonstration of the presence of surface acidity, the enhanced dissociation of water molecules when polarized by cations, and the way the surface can interact with organic substances. (Author/JN)

  12. Life and death of a single catalytic cracking particle

    NARCIS (Netherlands)

    Meirer, Florian; Kalirai, Samanbir; Morris, Darius; Soparawalla, Santosh; Liu, Yijin; Mesu, Gerbrand; Andrews, Joy C; Weckhuysen, Bert M

    2015-01-01

    Fluid catalytic cracking (FCC) particles account for 40 to 45% of worldwide gasoline production. The hierarchical complex particle pore structure allows access of long-chain feedstock molecules into active catalyst domains where they are cracked into smaller, more valuable hydrocarbon products (for

  13. Catalytic destruction of tar in biomass derived producer gas

    International Nuclear Information System (INIS)

    The purpose of this study is to investigate catalytic destruction of tar formed during gasification of biomass, with the goal of improving the quality of the producer gas. This work focuses on nickel based catalysts treated with alkali in an effort to promote steam gasification of the coke that deposits on catalyst surfaces. A tar conversion system consisting of a guard bed and catalytic reactor was designed to treat the producer gas from an air blown, fluidized bed biomass gasifier. The guard bed used dolomite to crack the heavy tars. The catalytic reactor was used to evaluate three commercial steam reforming catalysts. These were the ICI46-1 catalyst from Imperial Chemical Industry and Z409 and RZ409 catalysts from Qilu Petrochemical Corp. in China. A 0.5-3 l/min slipstream from a 5 tpd biomass gasifier was used to test the tar conversion system. Gas and tar were sampled before and after the tar conversion system to evaluate the effectiveness of the system. Changes in gas composition as functions of catalytic bed temperature, space velocity and steam/TOC (total organic carbon) ratio are presented. Structural changes in the catalysts during the tests are also described

  14. Catalytic behavior of Cu, Ag and Au nanoparticles. A comparison

    NARCIS (Netherlands)

    Lippits, Meindert Jan

    2010-01-01

    Clearly gold deposited as nanoparticles on a support is a very active catalyst in contrast to bulk gold which does not show any catalytic activity. The question arises if this particle size effect is exclusively valid for gold catalysis or can a similar effect be found in other metals? In the resear

  15. Catalytic Partial Oxidation of Biomass/Oil Mixture

    Czech Academy of Sciences Publication Activity Database

    Veselý, Václav; Hanika, Jiří; Tukač, V.; Lederer, J.; Kovač, D.

    2013-01-01

    Roč. 7, č. 10 (2013), s. 1940-1945. ISSN 1934-8983 R&D Projects: GA TA ČR TE01020080; GA MPO 2A-2TP1/024 Institutional support: RVO:67985858 Keywords : hydrocarbon oil * biomass * catalytic partial oxidation Subject RIV: CI - Industrial Chemistry, Chemical Engineering http://www.davidpublishing.com/journals_info.asp?jId=1718#

  16. Catalytic upgrading of biomass pyrolysis vapours using Faujasite zeolite catalysts

    NARCIS (Netherlands)

    Nguyen, T.S.; Zabeti, M.; Lefferts, L.; Brem, G.; Seshan, K.

    2012-01-01

    Bio-oil produced via fast pyrolysis of biomass has the potential to be processed in a FCC (fluid catalytic cracking) unit to generate liquid fuel. However, this oil requires a significant upgrade to become an acceptable feedstock for refinery plants due to its high oxygen content. One promising rout

  17. The tritium labelling of butibufen by herterogeneous catalytic exchange

    International Nuclear Information System (INIS)

    The labelling of a new non-steroidal antiinflammatory agent, butibufen (2-(4-isobutylphenyl) butyric acid) was studied. The method used was heterogeneous catalytic exchange between butibufen and tritiated water, obtained ''in situ''. Purification was accomplished through thin layer chromatography. Concentration, purity and specific activity of the labeled drug were determined by ultraviolet and liquid scintillation techniques. (author)

  18. Design parameters for measurements of local catalytic activity on surfaces

    DEFF Research Database (Denmark)

    Johansson, Martin; Johannessen, Tue; Jørgensen, Jan Hoffmann;

    2006-01-01

    Computational fluid dynamics in combination with experiments is used to characterize a gas sampling device for measurements of the local catalytic activity on surfaces. The device basically consists of a quartz capillary mounted concentrically inside an aluminum tube. Reactant gas is blown toward...

  19. Catalytic synthesis of ammonia using vibrationally excited nitrogen

    DEFF Research Database (Denmark)

    Henriksen, Niels Engholm; Billing, Gert D.; Hansen, Flemming Yssing

    1992-01-01

    In a previous study we have considered the catalytic synthesis of ammonia in the presence of vibrationally excited nitrogen. The distribution over vibrational states was assumed to be maintained during the reaction, and it was shown that the yield of ammonia increased considerably compared to tha...

  20. Building new catalytic sensors with plasma nanostructuring of metals

    International Nuclear Information System (INIS)

    Today, plasma nanostructuring of materials plays important role in improvement of different sensors including catalytic, by expanding the limits of operation in various directions. Herein a review of catalytic sensors based on metal-oxide layer for measuring the concentration of atom radicals of parent molecules is presented. Catalytic sensors are small pieces of suitable materials allowing for in-situ determination of the atom concentration. Oxygen atoms are detected using materials that form oxide films with moderate or high binding energy such as nickel and niobium oxides. Best sensitivity for oxygen atoms is obtained using catalytic sensors with nanostructured surface, more precisely metal-oxide nanowire surfaces. In any case, the sensing capacity depends on the probability for heterogeneous surface recombination of atoms to stable molecules. The sensors measure the atom densities in a broad range from roughly 1013 to 1016 cm-3, i.e. the ranges commonly found in material processing. Whereas new nanostructured surfaces expand the measurement detection range as well as add very interesting features to sensors, such as capacity to overcome radical overloads and temperature stresses. Several examples of application are presented and discussed. (author)

  1. Short hydrogen bonds in the catalytic mechanism of serine proteases

    Directory of Open Access Journals (Sweden)

    VLADIMIR LESKOVAC

    2008-04-01

    Full Text Available The survey of crystallographic data from the Protein Data Bank for 37 structures of trypsin and other serine proteases at a resolution of 0.78–1.28 Å revealed the presence of hydrogen bonds in the active site of the enzymes, which are formed between the catalytic histidine and aspartate residues and are on average 2.7 Å long. This is the typical bond length for normal hydrogen bonds. The geometric properties of the hydrogen bonds in the active site indicate that the H atom is not centered between the heteroatoms of the catalytic histidine and aspartate residues in the active site. Taken together, these findings exclude the possibility that short “low-barrier” hydrogen bonds are formed in the ground state structure of the active sites examined in this work. Some time ago, it was suggested by Cleland that the “low-barrier hydrogen bond” hypothesis is operative in the catalytic mechanism of serine proteases, and requires the presence of short hydrogen bonds around 2.4 Å long in the active site, with the H atom centered between the catalytic heteroatoms. The conclusions drawn from this work do not exclude the validity of the “low-barrier hydrogen bond” hypothesis at all, but they merely do not support it in this particular case, with this particular class of enzymes.

  2. Asymmetric catalytic synthesis of the proposed structure of trocheliophorolide B

    OpenAIRE

    Trost, Barry M.; Quintard, Adrien

    2012-01-01

    A concise catalytic asymmetric synthesis of the proposed structure of Trocheliophorolide B is reported. The synthetic sequence notably features an asymmetric acetaldehyde alkynylation, Ru-catalyzed alder-ene reaction and Zn-ProPhenol ynone aldol condensation. Comparison with the reported data suggests a miss-assignment of the natural product structure.

  3. DNAzyme catalytic beacon sensors that resist temperature-dependent variations†

    OpenAIRE

    Nagraj, Nandini; Liu, Juewen; Sterling, Stephanie; Wu, Jenny; Lu, Yi

    2009-01-01

    The temperature-dependent variability of a Pb2+-specific 8-17E DNAzyme catalytic beacon sensor has been addressed through the introduction of mismatches in the DNAzyme, and the resulting sensors resist temperature-dependent variations from 4 to 30 °C.

  4. Catalytic abatement of nitrous oxide from nitric and production

    NARCIS (Netherlands)

    Oonk, J.

    1998-01-01

    Nitric acid production is identified as a main source of nitrous oxide. Options for emission reduction however are not available. TNO and Hydro Agri studied the technological and economic feasibility of catalytic decomposition of nitrous oxide in nitric acid tail-gases. Although in literature promis

  5. Advanced catalytic converter system for natural gas powered diesel engines

    Energy Technology Data Exchange (ETDEWEB)

    Strots, V.O.; Bunimovich, G.A.; Matros, Y.S. [Matros Technologies Inc., Chesterfield, Missouri (United States); Zheng, M.; Mirosh, E.A. [Alternative Fuel Systems Inc., Calgary, Alberta (Canada)

    1998-12-31

    The paper discusses the development of catalytic converter for aftertreatment of exhaust gas from diesel engines powered with natural gas. The converter, operated with periodical reversals of the flow, ensures destruction of CO and hydrocarbons, including methane. Both computer simulation and engine testing results are presented. 8 refs.

  6. Demonstration of a Catalytic Converter Using a Lawn Mower Engine

    Science.gov (United States)

    Young, Mark A.

    2010-01-01

    Catalytic conversion is an important tool in environmental-remediation strategies and source removal of pollutants. Because a catalyst is regenerated, the chemistry can be extremely effective for conversion of undesirable pollutant species to less harmful products in situations where the pollutants have accumulated or are being continuously…

  7. Biodiesel by catalytic reactive distillation powered by metal oxides

    NARCIS (Netherlands)

    A.A. Kiss; A.C. Dimian; G. Rothenberg

    2008-01-01

    The properties and use of biodiesel as a renewable fuel as well as the problems associated with its current production processes are outlined. A novel sustainable esterification process based on catalytic reactive distillation is proposed. The pros and cons of manufacturing biodiesel via fatty acid

  8. Catalytic mechanisms by biological systems : Special issue introduction

    NARCIS (Netherlands)

    Fraaije, Marco W; Scrutton, Nigel S

    2013-01-01

    Research on enzyme mechanisms is advancing knowledge of the chemistry and biochemistry of catalytic mechanisms by biological systems. The structural-dynamical properties of enzymes are of key importance. Advanced methodological approaches and new insights into enzyme functioning, and new emerging ap

  9. Homogeneous catalytic hydrogenations of complex carbonaceous substrates. [16 references

    Energy Technology Data Exchange (ETDEWEB)

    Cox, J L; Wilcox, W A; Roberts, G L

    1976-11-05

    Results of homogeneous catalytic hydrogenation of complex unsaturated substrates including coal and coal-derived materials are reported, with organic soluble molecular complexes as catalysts. Among the substrates used were Hvab coal, solvent-refined coal, and COED pyrolysate. The hydrogenations were carried out in an autoclave. The results are summarized in tables.

  10. Review of literature on catalytic recombination of hydrogen--oxygen

    International Nuclear Information System (INIS)

    The results are reported of a literature search for information concerning the heterogeneous, gas phase, catalytic hydrogen-oxygen recombination. Laboratory scale experiments to test the performance of specific metal oxide catalysts under conditions simulating the atmosphere within a nuclear reactor containment vessel following a loss-of-coolant blowdown accident are suggested

  11. Catalytic oxidative cracking of hexane as a route to olefins

    NARCIS (Netherlands)

    Boyadjian, Cassia; Lefferts, Leon; Seshan, K.

    2010-01-01

    Catalytic oxidative cracking of naphtha is conceptually an alternative process to steam cracking. The performance of sol–gel synthesized Li/MgO in oxidative cracking of hexane as a model compound of naphtha, has been studied and compared to that of conventionally prepared catalyst. At a temperature

  12. The tritium labeling of Butibufen by heterogeneous catalytic exchange

    International Nuclear Information System (INIS)

    The labeling of a new non-steroidal antiinflammatory agent, Butibufen (2-(4-isobutylphenyl) butyric acid) was studied. The method used was heterogeneous catalytic exchange between Butibufen and tritiated water, obtained in situ. Purification was accomplished through thin layer chromatography. Concentration, purity and specific activity of the labeled drug were determined by ultraviolet and liquid scintillation techniques. (Author) 7 refs

  13. Ex-Situ Catalytic Fast Pyrolysis Technology Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Biddy, M.; Dutta, A.; Jones, S.; Meyer, A.

    2013-03-01

    This technology pathway case investigates converting woody biomass using ex-situ catalytic fast pyrolysis followed by upgrading to gasoline-, diesel-, and jet-range hydrocarbon blendstocks. Technical barriers and key research needs that should be pursued for this pathway to be competitive with petroleum-derived blendstocks have been identified.

  14. In-Situ Catalytic Fast Pyrolysis Technology Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Biddy, M.; Dutta, A.; Jones, S.; Meyer, A.

    2013-03-01

    This technology pathway case investigates converting woody biomass using in-situ catalytic fast pyrolysis followed by upgrading to gasoline-, diesel-, and jet-range hydrocarbon blendstocks. Technical barriers and key research needs that should be pursued for this pathway to be competitive with petroleum-derived blendstocks have been identified.

  15. Catalytic oxidation of volatile organic compounds (VOCs) - A review

    Science.gov (United States)

    Kamal, Muhammad Shahzad; Razzak, Shaikh A.; Hossain, Mohammad M.

    2016-09-01

    Emission of volatile organic compounds (VOCs) is one of the major contributors to air pollution. The main sources of VOCs are petroleum refineries, fuel combustions, chemical industries, decomposition in the biosphere and biomass, pharmaceutical plants, automobile industries, textile manufacturers, solvents processes, cleaning products, printing presses, insulating materials, office supplies, printers etc. The most common VOCs are halogenated compounds, aldehydes, alcohols, ketones, aromatic compounds, and ethers. High concentrations of these VOCs can cause irritations, nausea, dizziness, and headaches. Some VOCs are also carcinogenic for both humans and animals. Therefore, it is crucial to minimize the emission of VOCs. Among the available technologies, the catalytic oxidation of VOCs is the most popular because of its versatility of handling a range of organic emissions under mild operating conditions. Due to that fact, there are numerous research initiatives focused on developing advanced technologies for the catalytic destruction of VOCs. This review discusses recent developments in catalytic systems for the destruction of VOCs. Review also describes various VOCs and their sources of emission, mechanisms of catalytic destruction, the causes of catalyst deactivation, and catalyst regeneration methods.

  16. Trends in the Catalytic CO Oxidation Activity of Nanoparticles

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Falsig, Hanne; Larsen, Britt Hvolbæk;

    2008-01-01

    Going for gold: Density functional calculations show how gold nanoparticles are more active catalysts for CO oxidation than other metal nanoparticles. The high catalytic activity of nanosized gold clusters at low temperature is found to be related to the ability of low-coordinate metal atoms to a...

  17. Catalytic Deoxygenation of Fatty Acids: Elucidation of the Inhibition Process

    NARCIS (Netherlands)

    Hollak, S.A.W.; Jong, de K.P.; Es, van D.S.

    2014-01-01

    Catalytic deoxygenation of unsaturated fatty acids in the absence of H2 is known to suffer from significant catalyst inhibition. Thus far, no conclusive results have been reported on the cause of deactivation. Here we show that CC double bonds present in the feed or the products dramatically reduce

  18. Note on “Electrochemical promotion of catalytic reactions”

    Science.gov (United States)

    Vernoux, Philippe; Vayenas, Constantinos G.

    2011-05-01

    A recent review published in this Journal of the electrochemical promotion of catalysis (EPOC or NEMCA effect) is discussed. Some key aspects of the effect’s phenomenology and physicochemical origin are reviewed and clarified and the interplay of catalytic kinetics and mass transfer limitations in EPOC studies under high vacuum is discussed.

  19. Solid Waste Decontamination by Thermal Desorption and Catalytic Oxidation Methods

    Czech Academy of Sciences Publication Activity Database

    Šolcová, Olga; Topka, Pavel; Soukup, Karel; Jirátová, Květa; Váňová, H.; Kaštánek, František

    2014-01-01

    Roč. 68, č. 9 (2014), s. 1279-1282. ISSN 0366-6352 R&D Projects: GA MPO FR-TI1/059 Institutional support: RVO:67985858 Keywords : thermal desorption * catalytic oxidation * soil decontamination Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.468, year: 2014

  20. Mechanism of Ribonuclease III Catalytic Regulation by Serine Phosphorylation

    Science.gov (United States)

    Gone, Swapna; Alfonso-Prieto, Mercedes; Paudyal, Samridhdi; Nicholson, Allen W.

    2016-05-01

    Ribonuclease III (RNase III) is a conserved, gene-regulatory bacterial endonuclease that cleaves double-helical structures in diverse coding and noncoding RNAs. RNase III is subject to multiple levels of control, reflective of its global regulatory functions. Escherichia coli (Ec) RNase III catalytic activity is known to increase during bacteriophage T7 infection, reflecting the expression of the phage-encoded protein kinase, T7PK. However, the mechanism of catalytic enhancement is unknown. This study shows that Ec-RNase III is phosphorylated on serine in vitro by purified T7PK, and identifies the targets as Ser33 and Ser34 in the N-terminal catalytic domain. Kinetic experiments reveal a 5-fold increase in kcat and a 1.4-fold decrease in Km following phosphorylation, providing a 7.4–fold increase in catalytic efficiency. Phosphorylation does not change the rate of substrate cleavage under single-turnover conditions, indicating that phosphorylation enhances product release, which also is the rate-limiting step in the steady-state. Molecular dynamics simulations provide a mechanism for facilitated product release, in which the Ser33 phosphomonoester forms a salt bridge with the Arg95 guanidinium group, thereby weakening RNase III engagement of product. The simulations also show why glutamic acid substitution at either serine does not confer enhancement, thus underscoring the specific requirement for a phosphomonoester.