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Sample records for water-gas shift reaction

  1. Water-gas shift reaction

    SciTech Connect

    Newsome, D.S.

    1980-01-01

    A review covers the industrial applications of the water-gas shift reaction in hydrogen manufacturing, removing CO from ammonia synthesis feeds, and detoxifying town gas; and the catalyst characteristics, reaction kinetics, and reaction mechanisms of the water-gas shift reactions catalyzed by iron-based, copper-based, or sulfided cobalt-molybdenum catalysts.

  2. Water-gas shift reaction

    SciTech Connect

    Newsome, D.S.

    1980-01-01

    Recent kinetic and mechanistic studies of the water-gas shift reaction, H/sub 2/O(g) + CO(g) reversible CO/sub 2/ + H/sub 2/(g), catalyzed by iron and copper catalysts are reviewed. Composition, structure, active sites, preparation methods, additives, and poisons are discussed relative to each catalyst. New water-gas shift reaction catalyst systems studied are Mo-magnesia, Ni - Mo, Co - Mo, sulfided Co - Mo - Cs, sulfided Co - Mo, sulfided Ni - Mo, Co - Mo - Ni with added alkaki, and Co - Mo with added alkali, Cesium carbonate - cesium acetate - potassium carbonate or potassium acetate - Co - Mo is claimed to be an especially active catalyst. These new catalyst systems are sulfur tolerant and hold promise as catalysts for hydrogenation of high-sulfur coals. (BLM)

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

    SciTech Connect

    Lin, Jerry Y.S.

    2013-01-29

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

  4. Effects of water-gas shift reaction on simulated performance of a molten carbonate fuel cell

    NASA Astrophysics Data System (ADS)

    Kim, Mi-Hyun; Park, Hong-Kyu; Chung, Gui-Yung; Lim, Hee-Chun; Nam, Suk-Woo; Lim, Tae-Hoon; Hong, Seong-Ahn

    A molten carbonate fuel cell (MCFC) is simulated. In order to determine the effects of the water-gas shift reaction, the calculated results such as temperature distribution, voltage distribution, conversion and performance, are compared with those calculated excluding the shift reaction. Uniformity in the temperature profile is deteriorated due to the shift reaction. At the entrance, hydrogen is consumed rapidly in order to reach the equilibrium state of the shift reaction. The conversion of hydrogen decreases along the direction of gas flow because of hydrogen generated by the shift reaction. Therefore, when the shift reaction is excluded, the conversion of hydrogen is higher than that in a practical cell. Additionally, at the same current density, the voltage calculated without the shift reaction would be higher than the real value. The effect of the shift reaction on the voltage distribution and cell performances is quite small.

  5. Low temperature, sulfur tolerant homogeneous catalysts for the water-gas shift reaction

    SciTech Connect

    Laine, R.M.; Wood, B.J.; Krishnan, G.N.

    1986-04-01

    The objective of this project is to identify, prepare, test, characterize, and evaluate a practical, homogeneous catalyst for a water-gas shift process. The project effort is divided into the following five tasks: (1) Update SRI's recent review of the literature on the catalysis of the water-gas shift reaction (WGSR) to include references after 1982 and those in the patent literature. Based on this review, SRI will choose ten candidate systems to be evaluated as to their abilities to catalyze the WGSR using syngas derived from gasified coal. (2) Develop a test plan designed to effectively evaluate both the catalysts and, to some extent, reactor configuration for WGSR catalysis. (3) Perform a series of experiments to identify the most effective and economical of the ten candidate catalysts and then further evaluate the reaction kinetics of at least one selected catalyst system to develop sufficient data to provide the basis for the work in Task 4. (4) Develop a mathematical model of the final candidate system that uses rate expressions to describe the catalytic process. (5) Perform a techno-economical evaluation of the catalyst in terms of a proposed plant design based on the reaction model, current costs, and standard chemical engineering practice and compare the proposed design with a conventional hydrogen plant.

  6. Minimization of steam requirements and enhancement of water-gas shift reaction with warm gas temperature CO2 removal

    DOEpatents

    Siriwardane, Ranjani V; Fisher, II, James C

    2013-12-31

    The disclosure utilizes a hydroxide sorbent for humidification and CO.sub.2 removal from a gaseous stream comprised of CO and CO.sub.2 prior to entry into a water-gas-shift reactor, in order to decrease CO.sub.2 concentration and increase H.sub.2O concentration and shift the water-gas shift reaction toward the forward reaction products CO.sub.2 and H.sub.2. The hydroxide sorbent may be utilized for absorbtion of CO.sub.2 exiting the water-gas shift reactor, producing an enriched H.sub.2 stream. The disclosure further provides for regeneration of the hydroxide sorbent at temperature approximating water-gas shift conditions, and for utilizing H.sub.2O product liberated as a result of the CO.sub.2 absorption.

  7. Alkali-Stabilized Pt-OHx Species Catalyze Low-Temperature Water-Gas Shift Reactions

    SciTech Connect

    Zhai, Y.; Pierre, D; Si, R; Deng, W; Ferrin, P; Nilekar, A; Peng, G; Herron, J; Bell, D; et. al.

    2010-01-01

    We report that alkali ions (sodium or potassium) added in small amounts activate platinum adsorbed on alumina or silica for the low-temperature water-gas shift (WGS) reaction (H{sub 2}O + CO {yields} H{sub 2} + CO{sub 2}) used for producing H{sub 2}. The alkali ion-associated surface OH groups are activated by CO at low temperatures ({approx}100 C) in the presence of atomically dispersed platinum. Both experimental evidence and density functional theory calculations suggest that a partially oxidized Pt-alkali-O{sub x}(OH){sub y} species is the active site for the low-temperature Pt-catalyzed WGS reaction. These findings are useful for the design of highly active and stable WGS catalysts that contain only trace amounts of a precious metal without the need for a reducible oxide support such as ceria.

  8. Plasmon-enhanced reverse water gas shift reaction over oxide supported Au catalysts

    SciTech Connect

    Upadhye, AA; Ro, I; Zeng, X; Kim, HJ; Tejedor, I; Anderson, MA; Dumesic, JA; Huber, GW

    2015-01-01

    We show that localized surface plasmon resonance (LSPR) can enhance the catalytic activities of different oxide-supported Au catalysts for the reverse water gas shift (RWGS) reaction. Oxide-supported Au catalysts showed 30 to 1300% higher activity for RWGS under visible light compared to dark conditions. Au/TiO2 catalyst prepared by the deposition-precipitation (DP) method with 3.5 nm average Au particle size showed the highest activity for the RWGS reaction. Visible light is converted into chemical energy for this reaction with up to a 5% overall efficiency. A shift in the apparent activation energy (from 47 kJ mol(-1) in dark to 35 kJ mol(-1) in light) and apparent reaction order with respect to CO2 (from 0.5 in dark to 1.0 in light) occurs due to the LSPR. Our kinetic results indicate that the LSPR increases the rate of either the hydroxyl hydrogenation or carboxyl decomposition more than any other steps in the reaction network.

  9. Iron Oxides from Volcanic Soils as Potential Catalysts in the Water Gas Shift Reaction

    NASA Astrophysics Data System (ADS)

    Pizarro, C.; Escudey, M.; Moya, S. A.; Fabris, J. D.

    2005-04-01

    This study was focused on changes of the iron oxide mineralogy with temperature of two Chilean soils (Andisol and Ultisol) derived from volcanic materials and their use as iron-based catalysts in the water gas shift reaction (WGSR). Ultisol materials produced about twice as much hydrogen than did those from Andisol upon WGSR, but in both cases hydrogen yielding increased as the heating temperature of the soil materials increased from 124°C to 500°C. The room temperature Mössbauer spectra showed an increase of the relative proportion of the magnetically ordered components as temperature increased. Higher heating temperature produced a negative effect on the catalytic activity, whereas the organic matter destruction led to a positive effect, due to an increasing exposition of the iron oxide surfaces; heating the soil sample at 600 °C induced changes on the iron oxide mineralogy with a significant decrease of the catalytic activity.

  10. Low temperature, sulfur tolerant homogeneous catalysts for the water-gas shift reaction

    SciTech Connect

    Laine, R.M.

    1986-01-20

    The purpose of this report is to update and reorganize our recent review on homogeneous catalysis of the water-gas shift reaction (WGSR) based on recent literature publications and patents. This updated version will serve as a means of selecting 10 candidate catalyst systems for use in developing effective, sulfur-tolerant, low temperature WGSR catalysts. This report discusses the variations possible in the basic chemistry associated with WGSR catalytic cycles, including basic, acidic, and neutral conditions. Then individual mechanism for specific WGSR catalyst systems are discussed. Finally, on the basis of the literature reports, a list is presented of candidate catalysts and basic systems we have chosen for study in Task 3.

  11. Iron Oxides from Volcanic Soils as Potential Catalysts in the Water Gas Shift Reaction

    SciTech Connect

    Pizarro, C.; Escudey, M.; Moya, S.A.; Fabris, J.D.

    2005-04-26

    This study was focused on changes of the iron oxide mineralogy with temperature of two Chilean soils (Andisol and Ultisol) derived from volcanic materials and their use as iron-based catalysts in the water gas shift reaction (WGSR). Ultisol materials produced about twice as much hydrogen than did those from Andisol upon WGSR, but in both cases hydrogen yielding increased as the heating temperature of the soil materials increased from 124 deg. C to 500 deg. C. The room temperature Moessbauer spectra showed an increase of the relative proportion of the magnetically ordered components as temperature increased. Higher heating temperature produced a negative effect on the catalytic activity, whereas the organic matter destruction led to a positive effect, due to an increasing exposition of the iron oxide surfaces; heating the soil sample at 600 deg. C induced changes on the iron oxide mineralogy with a significant decrease of the catalytic activity.

  12. Water gas shift reaction: homogeneous catalysis by ruthenium and other metal carbonyls

    SciTech Connect

    Ford, P.C.

    1981-02-01

    A number of chemical systems are active for homogeneous, solution phase catalysis of the water gas shift reaction (WGSR). Catalysis of the shift reaction appears to be a quite general property of carbonyl complexes in alkaline solutions. The key mechanistic steps for which some kinetics information is available are the activation of coordinated CO by reaction with hydroxide and the reductive elimination of dihydrogen from a resulting metal hydride. Which of these is rate limiting in a cycle is a function of the specific metal system and the specific reaction conditions. A basic solution is not a necessary condition for WGSR catalysis. Although WGSR catalysis is not as general a phenomenon in acidic media, several such systems have been characterized with activities which compare very favorably to those seen in basic solutions. While logical mechanisms have been proposed for several of the better characterized catalysts, it is clear that a more complete mechanistic understanding of the key steps in potential cycles is greatly needed. Recognition of such needs has led to fundamental studies into the acid/base natures of metal carbonyl hydride clusters, of CO activation on cluster and mononuclear metal carbonyls by bases, and of dihydrogen elimination from and declusterification and clusterification reactions of metal carbonyl hydrides. While none of these processes is in itself catalytic, the sum of several represents possible cycles. With regard to the future of homogeneous WGSR catalysts, it is obvious that under the conditions which these have been tested, the known systems are not commercially viable. Certainly, for a reaction such as the WGSR for which effective heterogeneous catalysts are known, it will take substantial advantages for a new system to be an attractive alternative to established technology.

  13. Mechanisms of the Water-Gas Shift Reaction Catalyzed by Ruthenium Carbonyl Complexes.

    PubMed

    Liu, Naying; Guo, Ling; Cao, Zhaoru; Li, Wenli; Zheng, Xiaoli; Shi, Yayin; Guo, Juan; Xi, Yaru

    2016-04-21

    Density functional theory (DFT) is employed to study the water-gas shift (WGS) reaction in the gas phase for two complexes, Ru3(CO)12 and Ru(CO)5. Here we report four mechanisms of ruthenium carbonyl complexes catalyzed for WGS reaction. The energetic span model is applied to evaluate efficiency of the four catalytic pathways. Our results indicate that mechanism C and D show a good catalytic behavior, which is in agreement with results from the literature. The mechanism C and D not only include the important intermediate Ru3(CO)11H(-) but also exclude the energy-demanding OH(-) desorption and revise an unfavorable factor of the previous mechanism. Two complexes along mechanisms B have the highest turnover frequency (TOF) values. The trinuclear carbonyl complexes-Ru3(CO)12 is preferred over mononuclear carbonyl Ru(CO)5 by comparing TOF due to the fact that metal-metal cooperativity can enhance activity to the WGS reaction. In this work, the nature of interaction between transition states and intermediates is also analyzed by the detailed electronic densities of states, and we further clarify high catalytic activity of ruthenium carbonyl complexes as well. Our conclusions provide a guide to design catalysts for the WGS reaction. PMID:27064302

  14. The effect of PdZn particle size on reverse-water-gas-shift reaction

    SciTech Connect

    Lebarbier, Vanessa MC; Dagle, Robert A.; Datye, A. K.; Wang, Yong

    2010-05-15

    The effect of PdZn particle size on the catalytic activity of Pd/ZnO catalysts for the reverse-water-gas-shift (RWGS) reaction was studied. The PdZn particle size was varied by adjusting Pd loading and reducing the catalysts at different temperatures. XRD and IR spectroscopy characterization confirmed the absence of metallic Pd on the catalyst surface. Consequently, the effect of PdZn alloy particle size on the RWGS reaction can be unambiguously studied without the complication of reactions catalyzed by metallic Pd. The results indicated that the turnover frequency increases as the PdZn crystallite size decreases. Interestingly, this structure relationship between PdZn particle size and RWGS activity is consistent with that previously observed for the steam reforming of methanol, i.e., higher CO selectivity on smaller PdZn particles. Thus, RWGS has been identified as a likely potential reaction pathway to undesired CO formation in methanol steam reforming on Pd/ZnO catalysts for hydrogen production.

  15. On the Mechanism of Low-Temperature Water Gas Shift Reaction on Copper

    SciTech Connect

    Gokhale, Amit A.; Dumesic, James A.; Mavrikakis, Manos

    2008-01-30

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Periodic, self-consistent density functional theory (DFT-GGA) calculations are used to investigate the water gas shift reaction (WGSR) mechanism on Cu(111). The thermochemistry and activation energy barriers for all the elementary steps of the commonly accepted redox mechanism, involving complete water activation to atomic oxygen, are presented. Through our calculations, we identify carboxyl, a new reactive intermediate, which plays a central role in WGSR on Cu(111). The thermochemistry and activation energy barriers of the elementary steps of a new reaction path, involving carboxyl, are studied. A detailed DFTbased microkinetic model of experimental reaction rates, accounting for both the previous and the new WGSR mechanism show that, under relevant experimental conditions, (1) the carboxyl-mediated route is the dominant path, and (2) the initial hydrogen abstraction from water is the rate-limiting step. Formate is a stable “spectator” species, formed predominantly through CO₂ hydrogenation. In addition, the microkinetic model allows for predictions of (i) surface coverage of intermediates, (ii) WGSR apparent activation energy, and (iii) reaction orders with respect to CO, H₂O, CO₂, and H₂.

  16. Hydrodesulphurization of Light Gas Oil using hydrogen from the Water Gas Shift Reaction

    NASA Astrophysics Data System (ADS)

    Alghamdi, Abdulaziz

    2009-12-01

    The production of clean fuel faces the challenges of high production cost and complying with stricter environmental regulations. In this research, the ability of using a novel technology of upgrading heavy oil to treat Light Gas Oil (LGO) will be investigated. The target of this project is to produce cleaner transportation fuel with much lower cost of production. Recently, a novel process for upgrading of heavy oil has been developed at University of Waterloo. It is combining the two essential processes in bitumen upgrading; emulsion breaking and hydroprocessing into one process. The water in the emulsion is used to generate in situ hydrogen from the Water Gas Shift Reaction (WGSR). This hydrogen can be used for the hydrogenation and hydrotreating reaction which includes sulfur removal instead of the expensive molecular hydrogen. This process can be carried out for the upgrading of the bitumen emulsion which would improve its quality. In this study, the hydrodesulphurization (HDS) of LGO was conducted using in situ hydrogen produced via the Water Gas Shift Reaction (WGSR). The main objective of this experimental study is to evaluate the possibility of producing clean LGO over dispersed molybdenum sulphide catalyst and to evaluate the effect of different promoters and syn-gas on the activity of the dispersed Mo catalyst. Experiments were carried out in a 300 ml Autoclave batch reactor under 600 psi (initially) at 391°C for 1 to 3 hours and different amounts of water. After the hydrotreating reaction, the gas samples were collected and the conversion of carbon monoxide to hydrogen via WGSR was determined using a refinery gas analyzer. The sulphur content in liquid sample was analyzed via X-Ray Fluorescence. Experimental results showed that using more water will enhance WGSR but at the same time inhibits the HDS reaction. It was also shown that the amount of sulfur removed depends on the reaction time. The plan is to investigate the effect of synthesis gas (syngas

  17. SiC-BASED HYDROGEN SELECTIVE MEMBRANES FOR WATER-GAS-SHIFT REACTION

    SciTech Connect

    Paul K.T. Liu

    2001-10-16

    This technical report summarizes our activities conducted in Yr II. In Yr I we successfully demonstrated the feasibility of preparing the hydrogen selective SiC membrane with a chemical vapor deposition (CVD) technique. In addition, a SiC macroporous membrane was fabricated as a substrate candidate for the proposed SiC membrane. In Yr II we have focused on the development of a microporous SiC membrane as an intermediate layer between the substrate and the final membrane layer prepared from CVD. Powders and supported thin silicon carbide films (membranes) were prepared by a sol-gel technique using silica sol precursors as the source of silicon, and phenolic resin as the source of carbon. The powders and films were prepared by the carbothermal reduction reaction between the silica and the carbon source. The XRD analysis indicates that the powders and films consist of SiC, while the surface area measurement indicates that they contain micropores. SEM and AFM studies of the same films also validate this observation. The powders and membranes were also stable under different corrosive and harsh environments. The effects of these different treatments on the internal surface area, pore size distribution, and transport properties, were studied for both the powders and the membranes using the aforementioned techniques and XPS. Finally the SiC membrane materials are shown to have satisfactory hydrothermal stability for the proposed application. In Yr III, we will focus on the demonstration of the potential benefit using the SiC membrane developed from Yr I and II for the water-gas-shift (WGS) reaction.

  18. Flame made ceria supported noble metal catalysts for efficient H2 production via the water gas shift reaction

    NASA Astrophysics Data System (ADS)

    Cavusoglu, G.; Lichtenberg, H.; Gaur, A.; Goldbach, A.; Grunwaldt, J.-D.

    2016-05-01

    Rh/ceria catalysts were synthesized by flame spray pyrolysis for high temperature water gas shift (WGS) reactions. These catalysts show a high specific surface area due to a high degree of nanocrystallinity. X-ray absorption spectroscopy (XAS) unraveled the formation of small Rh particles under WGS reaction conditions. The catalytic activity was examined at atmospheric pressure by measuring CO conversion as a function of temperature. Some methane formation was observed above 310°C.

  19. In situ characterization of catalysts and membranes in a microchannel under high-temperature water gas shift reaction conditions

    NASA Astrophysics Data System (ADS)

    Cavusoglu, G.; Dallmann, F.; Lichtenberg, H.; Goldbach, A.; Dittmeyer, R.; Grunwaldt, J.-D.

    2016-05-01

    Microreactor technology with high heat transfer in combination with stable catalysts is a very attractive approach for reactions involving major heat effects such as methane steam reforming and to some extent, also the high temperature water gas shift (WGS) reaction. For this study Rh/ceria catalysts and an ultrathin hydrogen selective membrane were characterized in situ in a microreactor specially designed for x-ray absorption spectroscopic measurements under WGS conditions. The results of these experiments can serve as a basis for further development of the catalysts and membranes.

  20. Approach to equilibrium of the water-gas shift reaction on a Ni/zirconia anode under solid oxide fuel-cell conditions

    NASA Astrophysics Data System (ADS)

    Ahmed, K.; Föger, K.

    The reverse water-gas shift reaction is carried out in a solid oxide fuel-cell at a range of fuel utilization levels and the approach of this reaction to thermodynamic equilibrium is calculated from the experimental data. It is found that the water-gas shift reaction is close to equilibrium only at high levels of fuel utilization. This is an important finding for modeling and simulation of fuel-cells.

  1. Low temperature, sulfur tolerant homogeneous catalysts for the water-gas shift reaction. Task 2, Test plan

    SciTech Connect

    Laine, R.M.; Wood, B.J.; Krishnan, G.N.

    1986-04-01

    The objective of this project is to identify, prepare, test, characterize, and evaluate a practical, homogeneous catalyst for a water-gas shift process. The project effort is divided into the following five tasks: (1) Update SRI`s recent review of the literature on the catalysis of the water-gas shift reaction (WGSR) to include references after 1982 and those in the patent literature. Based on this review, SRI will choose ten candidate systems to be evaluated as to their abilities to catalyze the WGSR using syngas derived from gasified coal. (2) Develop a test plan designed to effectively evaluate both the catalysts and, to some extent, reactor configuration for WGSR catalysis. (3) Perform a series of experiments to identify the most effective and economical of the ten candidate catalysts and then further evaluate the reaction kinetics of at least one selected catalyst system to develop sufficient data to provide the basis for the work in Task 4. (4) Develop a mathematical model of the final candidate system that uses rate expressions to describe the catalytic process. (5) Perform a techno-economical evaluation of the catalyst in terms of a proposed plant design based on the reaction model, current costs, and standard chemical engineering practice and compare the proposed design with a conventional hydrogen plant.

  2. Heat Integration of the Water-Gas Shift Reaction System for Carbon Sequestration Ready IGCC Process with Chemical Looping

    SciTech Connect

    Juan M. Salazara; Stephen E. Zitney; Urmila M. Diwekara

    2010-01-01

    Integrated gasification combined cycle (IGCC) technology has been considered as an important alternative for efficient power systems that can reduce fuel consumption and CO2 emissions. One of the technological schemes combines water-gas shift reaction and chemical-looping combustion as post gasification techniques in order to produce sequestration-ready CO2 and potentially reduce the size of the gas turbine. However, these schemes have not been energetically integrated and process synthesis techniques can be applied to obtain an optimal flowsheet. This work studies the heat exchange network synthesis (HENS) for the water-gas shift reaction train employing a set of alternative designs provided by Aspen energy analyzer (AEA) and combined in a process superstructure that was simulated in Aspen Plus (AP). This approach allows a rigorous evaluation of the alternative designs and their combinations avoiding all the AEA simplifications (linearized models of heat exchangers). A CAPE-OPEN compliant capability which makes use of a MINLP algorithm for sequential modular simulators was employed to obtain a heat exchange network that provided a cost of energy that was 27% lower than the base case. Highly influential parameters for the pos gasification technologies (i.e. CO/steam ratio, gasifier temperature and pressure) were calculated to obtain the minimum cost of energy while chemical looping parameters (oxidation and reduction temperature) were ensured to be satisfied.

  3. Structure Sensitivity of the Low-temperature Water-gas Shift Reaction on Cu–CeO2 catalysts

    SciTech Connect

    Si, R.; Zhang, L.; Raitano, J.; Yi, N.; Chan, S.-W.; Flytzani-Stephanopoulos, M.

    2012-01-17

    We have investigated the structure sensitivity of the water-gas shift (WGS) reaction on Cu-CeO{sub 2} catalysts prepared at the nanoscale by different techniques. On the surface of ceria, different CuO{sub x} structures exist. We show here that only the strongly bound Cu-[O{sub x}]-Ce species, probably associated with the surface oxygen vacancies of ceria, are active for catalyzing the low-temperature WGS reaction. Weakly bound CuO{sub x} clusters and CuO nanoparticles are spectator species in the reaction. Isolated Cu{sup 2+} ions doping the ceria surface are not active themselves, but they are important in that they create oxygen vacancies and can be used as a reservoir of copper to replenish surface Cu removed by leaching or sintering. Accordingly, synthesis techniques such as coprecipitation that allow for extensive solubility of Cu in ceria should be preferred over impregnation, deposition-precipitation, ion exchange or another two-step method whereby the copper precursor is added to already made ceria nanocrystals. For the synthesis of different structures, we have used two methods: a homogeneous coprecipitation (CP), involving hexamethylenetetramine as the precipitating agent and the pH buffer; and a deposition-precipitation (DP) technique. In the latter case, the ceria supports were first synthesized at the nanoscale with different shapes (rods, cubes) to investigate any potential shape effect on the reaction. Cu-CeO{sub 2} catalysts with different copper contents up to ca. 20 at.% were prepared. An indirect shape effect of CeO{sub 2}, manifested by the propensity to form oxygen vacancies and strongly bind copper in the active form, was established; i.e. the water-gas shift reaction is not structure-sensitive. The apparent activation energy of the reaction on all samples was similar, 50 {+-} 10 kJ/mol, in a product-free (2% CO-10% H{sub 2}O) gas mixture.

  4. Carbon capture by sorption-enhanced water-gas shift reaction process using hydrotalcite-based material

    SciTech Connect

    van Selow, E.R.; Cobden, P.D.; Verbraeken, P.A.; Hufton, J.R.; van den Brink, R.W.

    2009-05-15

    A novel route for precombustion decarbonization is the sorption-enhanced water-gas shift (SEWGS) process. In this process carbon dioxide is removed from a synthesis gas at elevated temperature by adsorption. Simultaneously, carbon monoxide is converted to carbon dioxide by the water-gas shift reaction. The periodic adsorption and desorption of carbon dioxide is induced by a pressure swing cycle, and the cyclic capacity can be amplified by purging with steam. From previous studies is it known that for SEWGS applications, hydrotalcite-based materials are particularly attractive as sorbent, and commercial high-temperature shift catalysts can be used for the conversion of carbon monoxide. Tablets of a potassium promoted hydrotalcite-based material are characterized in both breakthrough and cyclic experiments in a 2 m tall fixed-bed reactor. When exposed to a mixture of carbon dioxide, steam, and nitrogen at 400{sup o}C, the material shows a breakthrough capacity of 1.4 mmol/g. In subsequent experiments the material was mixed with tablets of promoted iron-chromium shift catalyst and exposed to a mixture of carbon dioxide, carbon monoxide, steam, hydrogen, and nitrogen. It is demonstrated that carbon monoxide conversion can be enhanced to 100% in the presence of a carbon dioxide sorbent. At breakthrough, carbon monoxide and carbon dioxide simultaneously appear at the end of the bed. During more than 300 cycles of adsorption/reaction and desorption, the capture rate, and carbon monoxide conversion are confirmed to be stable. Two different cycle types are investigated: one cycle with a CO{sub 2} rinse step and one cycle with a steam rinse step. The performance of both SEWGS cycles are discussed.

  5. Water-gas shift reaction on oxide/Cu(111): Rational catalyst screening from density functional theory

    NASA Astrophysics Data System (ADS)

    Liu, Ping

    2010-11-01

    Developing improved catalysts based on a fundamental understanding of reaction mechanism has become one of the grand challenges in catalysis. A theoretical understanding and screening the metal-oxide composite catalysts for the water-gas shift (WGS) reaction is presented here. Density functional theory was employed to identify the key step for the WGS reaction on the Au, Cu-oxide catalysts, where the calculated reaction energy for water dissociation correlates well with the experimental measured WGS activity. Accordingly, the calculated reaction energy for water dissociation was used as the scaling descriptor to screen the inverse model catalysts, oxide/Cu(111), for the better WGS activity. Our calculations predict that the WGS activity increases in a sequence: Cu(111), ZnO/Cu(111) < TiO2/Cu(111), ZrO2/Cu(111) < MoO3/Cu(111). Our results imply that the high performances of Au, Cu-oxide nanocatalysts in the WGS reaction rely heavily on the direct participation of both oxide and metal sites. The degree that the oxide is reduced by Cu plays an important role in determining the WGS activity of oxide/Cu catalysts. The reducible oxide can be transformed from the fully oxidized form to the reduced form due to the interaction with Cu and, therefore, the transfer of electron density from Cu, which helps in releasing the bottleneck water dissociation and, therefore, facilitating the WGS reaction on copper.

  6. Water-gas Shift Reaction on oxide/Cu(111): Rational Catalyst Screening from Density Functional Theory

    SciTech Connect

    Liu, P.

    2010-11-28

    Developing improved catalysts based on a fundamental understanding of reaction mechanism has become one of the grand challenges in catalysis. A theoretical understanding and screening the metal-oxide composite catalysts for the water-gas shift (WGS) reaction is presented here. Density functional theory was employed to identify the key step for the WGS reaction on the Au, Cu-oxide catalysts, where the calculated reaction energy for water dissociation correlates well with the experimental measured WGS activity. Accordingly, the calculated reaction energy for water dissociation was used as the scaling descriptor to screen the inverse model catalysts, oxide/Cu(111), for the better WGS activity. Our calculations predict that the WGS activity increases in a sequence: Cu(111), ZnO/Cu(111) < TiO{sub 2}/Cu(111), ZrO{sub 2}/Cu(111) < MoO{sub 3}/Cu(111). Our results imply that the high performances of Au, Cu-oxide nanocatalysts in the WGS reaction rely heavily on the direct participation of both oxide and metal sites. The degree that the oxide is reduced by Cu plays an important role in determining the WGS activity of oxide/Cu catalysts. The reducible oxide can be transformed from the fully oxidized form to the reduced form due to the interaction with Cu and, therefore, the transfer of electron density from Cu, which helps in releasing the bottleneck water dissociation and, therefore, facilitating the WGS reaction on copper.

  7. On the importance of steady-state isotopic techniques for the investigation of the mechanism of the reverse water-gas-shift reaction.

    PubMed

    Tibiletti, Daniele; Goguet, Alexandre; Meunier, Frederic C; Breen, John P; Burch, Robbie

    2004-07-21

    The formation and reactivity of surface intermediates in the reverse water-gas-shift reaction on a Pt/CeO2 catalyst are critically dependent on the reaction conditions so that conclusions regarding the reaction mechanism cannot be inferred using ex operando conditions. PMID:15263955

  8. Low temperature, sulfur tolerant homogeneous catalysts for the water-gas shift reaction. Task 1, Topical report No. 1

    SciTech Connect

    Laine, R.M.

    1986-01-20

    The purpose of this report is to update and reorganize our recent review on homogeneous catalysis of the water-gas shift reaction (WGSR) based on recent literature publications and patents. This updated version will serve as a means of selecting 10 candidate catalyst systems for use in developing effective, sulfur-tolerant, low temperature WGSR catalysts. This report discusses the variations possible in the basic chemistry associated with WGSR catalytic cycles, including basic, acidic, and neutral conditions. Then individual mechanism for specific WGSR catalyst systems are discussed. Finally, on the basis of the literature reports, a list is presented of candidate catalysts and basic systems we have chosen for study in Task 3.

  9. SiC-BASED HYDROGEN SELECTIVE MEMBRANES FOR WATER-GAS-SHIFT REACTION

    SciTech Connect

    Unknown

    2000-12-01

    A hydrogen selective membrane as a membrane reactor (MR) can significantly improve the power generation efficiency with a reduced capital and operating cost for the waster-gas-shift reaction. Existing hydrogen selective ceramic membranes are not suitable for the proposed MR due to their poor hydrothermal stability. In this project we have focused on the development of innovative silicon carbide (SiC) based hydrogen selective membranes, which can potentially overcome this technical barrier. During Year I, we have successfully fabricated SiC macro porous membranes via extrusion of commercially available SiC powder, which were then deposited with thin, micro-porous (6 to 40{angstrom} in pore size) films via sol-gel technique as intermediate layers. Finally, an SiC hydrogen selective thin film was deposited on this substrate via our CVD/I technique. The composite membrane thus prepared demonstrated excellent hydrogen selectivity at high temperature ({approx}600 C). More importantly, this membrane also exhibited a much improved hydrothermal stability at 600 C with 50% steam (atmospheric pressure) for nearly 100 hours. In parallel, we have explored an alternative approach to develop a H{sub 2} selective SiC membrane via pyrolysis of selected pre-ceramic polymers. Building upon the positive progress made in the Year I preliminary study, we will conduct an optimization study in Year II to develop an optimized H{sub 2} selective SiC membrane with sufficient hydrothermal stability suitable for the WGS environment.

  10. SIC-BASED HYDROGEN SELECTIVE MEMBRANES FOR WATER-GAS-SHIFT REACTION

    SciTech Connect

    Paul K.T. Liu

    2003-12-01

    A hydrogen selective membrane as a membrane reactor (MR) can significantly improve the power generation efficiency with a reduced capital and operating cost for the waster-gas-shift reaction. Existing hydrogen selective ceramic membranes are not suitable for the proposed MR due to their poor hydrothermal stability. In this project we have focused on the development of innovative silicon carbide (SiC) based hydrogen selective membranes, which can potentially overcome this technical barrier. SiC macro-porous membranes have been successfully fabricated via extrusion of commercially available SiC powder. Also, an SiC hydrogen selective thin film was prepared via our CVD/I technique. This composite membrane demonstrated excellent hydrogen selectivity at high temperature ({approx}600 C). More importantly, this membrane also exhibited a much improved hydrothermal stability at 600 C with 50% steam (atmospheric pressure) for nearly 100 hours. In parallel, we have explored an alternative approach to develop a H{sub 2} selective SiC membrane via pyrolysis of selected pre-ceramic polymers and sol-gel techniques. Building upon the positive progress made in the membrane development study, we conducted an optimization study to develop an H{sub 2} selective SiC membrane with sufficient hydrothermal stability suitable for the WGS environment. In addition, mathematical simulation has been performed to compare the performance of the membrane reactor (MR) vs conventional packed bed reactor for WGS reaction. Our result demonstrates that >99.999% conversion can be accomplished via WGS-MR using the hydrogen selective membrane developed by us. Further, water/CO ratio can be reduced, and >97% hydrogen recovery and <200 ppm CO can be accomplished according to the mathematical simulation. Thus, we believe that the operating economics of WGS can be improved significantly based upon the proposed MR concept. In parallel, gas separations and hydrothermal and long-term-storage stability of the

  11. DFT study of the water gas shift reaction on Ni(111), Ni(100) and Ni(110) surfaces

    NASA Astrophysics Data System (ADS)

    Mohsenzadeh, Abas; Richards, Tobias; Bolton, Kim

    2016-02-01

    Density functional theory (DFT) calculations were used to study the water gas shift (WGS) reaction on Ni(111), Ni(100) and Ni(110) surfaces. The adsorption energy for ten species involved in the reaction together with activation barriers and reaction energies for the nine most important elementary steps were determined using the same model and DFT methods. The results reveal that these energies are sensitive to the surface structure. In spite of this, the WGS reaction occurs mainly via the direct (also referred to as redox) pathway with the CO + O → CO2 reaction as the rate determining step on all three surfaces. The activation barrier obtained for this rate limiting step decreases in the order Ni(110) > Ni(111) > Ni(100). Therefore, if O species are present on the surfaces then the WGS reaction is fastest on the Ni(100) surface. However, the barrier for desorption of H2O (which is the source of the O species) is lower than its dissociation reaction on the Ni(111) and Ni(100) surfaces, but not on the Ni(110) surface. Hence, at low H2O(g) pressures, the direct pathway on the Ni(110) surface will dominate and will be the rate limiting step. The calculations also show that the reason that the WGS reaction does not primarily occur via the formate pathway is that this species is a stable intermediate on all surfaces. The reactions studied here support the Brønsted-Evans-Polanyi (BEP) principles with an R2 value of 0.99.

  12. The role of metals and influence of oxygen on ceria supported copper-palladium bimetallic catalysts for the oxygen-assisted water-gas shift reaction

    NASA Astrophysics Data System (ADS)

    Fox, Elise Bickford

    This study was focused to investigate the roles of Cu and Pd in CuPd/CeO 2 bimetallic catalysts containing 30 wt% Cu and 1 wt% Pd used in the oxygen-assisted water-gas shift (OWGS) reaction employing combined bulk and surface characterization techniques such as X-ray diffraction (XRD), temperature programmed reduction (TPR), CO chemisorption, and in-situ X-ray photoelectron spectroscopy (XPS). The role of oxygen in aiding the water-gas shift reaction was also studied to determine an overall mechanism for the water-gas shift reaction. The catalytic activity for CO conversion and the stability of catalyst during on-stream operation increased upon adding Pd to Cu/CeO2 monometallic catalysts, especially when the OWLS reaction was performed under low temperatures. In-situ XPS studies of reduced catalysts showed the existence of Cu and Pd in their metallic states. The spectra also showed a shift in Cu 2p peaks toward lower binding energy with concommitant shift in the Pd 3d peaks toward higher BE. Addition of Pd decreased the surface Cu concentration while the concentration of Pd remained unaltered. The improved catalytic activity and stability of CuPd/CeO2 bimetallic catalyst was attributed to the Cu-Pd interaction. When the catalyst series was reduced in-situ under UHV conditions in the XPS chamber in order to better understand the metal-support interactions, it was found that the addition of 1%Pd to the Cu/CeO2 catalyst would greatly improve the reduction properties of the Cu and Ce under UHV conditions. When compared with results from the oxygen-assisted water-gas-shift reaction, it was found that the increased reduction from the addition of Pd aided in the reaction. When reaction kinetics of the water-gas shift and the oxygen-assisted water-gas shift reaction were examined, it was found that the addition of a small amount of air improved the overall reaction kinetics. In general, the activation energies decreased for the catalyst series when air was added to the

  13. Activity and stability of nanostructured gold-cerium oxide catalysts for the water-gas shift reaction

    NASA Astrophysics Data System (ADS)

    Fu, Qi

    Advanced low-temperature water-gas shift (LTS) catalysts of high activity and stability are under development to produce essentially CO-free hydrogen to feed PEM fuel cells for power generation. Materials based on nanocrystalline cerium oxide (ceria) are among the most promising LTS catalysts. Understanding the structural properties relationship with the WGS activity is fundamentally important in order to rational design the catalysts. Various gold structures, such as metallic gold nanoparticles, cluster and cations were found in gold-ceria sample containing 4--8 at% gold. To discriminate between the various gold species, leaching of the gold-ceria in sodium cyanide was conducted. The metallic gold and all other gold species not in close association with ceria were removed by leaching. A small amount of gold remained in the leached samples. The exact content of non-leachable gold was a function of the parent catalyst properties. Similar data were collected from Pt-ceria samples. STEM or HRTEM, coupled with EDX showed no gold or platinum particles remaining; only what appeared to be very fine clusters or atomically dispersed gold or platinum. Cationic gold or platinum was identified in these samples by XPS. The unexpected finding was that the catalytic activity of the leached samples was similar or slightly better than that of the parent catalyst after removal of the metallic gold or platinum particles by cyanide leaching. Thus, metallic nanoparticles are not necessary; they are mere spectators in the water-gas shift reaction. Nonmetallic gold or platinum species strongly associated with surface cerium-oxygen groups are responsible for the activity, since the extra gold or platinum present in the parent material does not increase the reaction rate; nor does it change the activation energy of the reaction. The importance of the oxide support properties became clear by this work. The amount of gold or platinum retained in active form depends on the surface properties

  14. A theoretical study of surface-structural sensitivity of the reverse water-gas shift reaction over Cu( hkl) surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Gui-Chang; Jiang, Ling; Pang, Xian-Yong; Cai, Zun-Sheng; Pan, Yin-Ming; Zhao, Xue-Zhuang; Morikawa, Yoshitada; Nakamura, Junji

    2003-10-01

    The surface-structural sensitivity of the reverse water-gas shift (RWGS) reaction (CO 2 + H 2 → CO + H 2O) over the Cu(1 1 1), Cu(1 0 0), and Cu(1 1 0) surfaces has been studied by first-principle density functional calculations together with the UBI-QEP approach. Cluster models of the surface have been employed to simulate the adsorption of CO 2, H 2, H, O, OH, CO, and H 2O on the Cu( hkl) surfaces at low coverage. This sensitivity is determined by the difference in the activation barriers. It can be noticed that the most likely rate-determining step in RWGS reaction is the CO 2 dissociative adsorption, namely CO 2,g → CO s + O s. The trend in the calculated activation barriers for the reaction of CO 2 dissociative adsorption follows the order of Cu(1 1 0) < Cu(1 0 0) < Cu(1 1 1), suggesting that the most efficient crystal surface for catalyzing RWGS reaction by copper is Cu(1 1 0), and the more densely packed Cu(1 1 1) surface is the least active among the Cu( hkl) surfaces studied here. As expected, the activation barriers for the recombinative reactions over Cu( hkl) are in the order of Cu(1 1 0) > Cu(1 0 0) > Cu(1 1 1), just opposite to the dissociative reactions. The interesting thing is that there is a good correlation between the adsorption bond length and the adsorption energy: The preferred adsorption site is the one with the shortest adsorption bond length. The present calculations are in good agreement with experimental observations.

  15. Reaction mechanism of the reverse water-gas shift reaction using first-row middle transition metal catalysts L'M (M = Fe, Mn, Co): a computational study.

    PubMed

    Liu, Cong; Cundari, Thomas R; Wilson, Angela K

    2011-09-19

    The mechanism of the reverse water-gas shift reaction (CO(2) + H(2) → CO + H(2)O) was investigated using the 3d transition metal complexes L'M (M = Fe, Mn, and Co, L' = parent β-diketiminate). The thermodynamics and reaction barriers of the elementary reaction pathways were studied with the B3LYP density functional and two different basis sets: 6-311+G(d) and aug-cc-pVTZ. Plausible reactants, intermediates, transition states, and products were modeled, with different conformers and multiplicities for each identified. Different reaction pathways and side reactions were also considered. Reaction Gibbs free energies and activation energies for all steps were determined for each transition metal. Calculations indicate that the most desirable mechanism involves mostly monometallic complexes. Among the three catalysts modeled, the Mn complex shows the most favorable catalytic properties. Considering the individual reaction barriers, the Fe complex shows the lowest barrier for activation of CO(2). PMID:21838224

  16. Kinetic and equilibrium study on formic acid decomposition in relation to the water-gas-shift reaction.

    PubMed

    Yasaka, Yoshiro; Yoshida, Ken; Wakai, Chihiro; Matubayasi, Nobuyuki; Nakahara, Masaru

    2006-09-28

    Kinetics and equilibrium are studied on the hydrothermal decarbonylation and decarboxylation of formic acid, the intermediate of the water-gas-shift (WGS) reaction, in hot water at temperatures of 170-330 degrees C, to understand and control the hydrothermal WGS reaction. (1)H and (13)C NMR spectroscopy is applied to analyze as a function of time the quenched reaction mixtures in both the liquid and gas phases. Only the decarbonylation is catalyzed by HCl, and the reaction is first-order with respect to both [H(+)] and [HCOOH]. Consequently, the reaction without HCl is first and a half (1.5) order due to the unsuppressed ionization of formic acid. The HCl-accelerated decarbonylation path can thus be separated in time from the decarboxylation. The rate and equilibrium constants for the decarbonylation are determined separately by using the Henry constant (gas solubility data) for carbon monoxide in hot water. The rate constant for the decarbonylation is 1.5 x 10(-5), 2.0 x 10(-4), 3.7 x 10(-3), and 6.3 x 10(-2) mol(-1) kg s(-1), respectively, at 170, 200, 240, and 280 degrees C on the liquid branch of the saturation curve. The Arrhenius plot of the decarbonylation is linear and gives the activation energy as 146 +/- 3 kJ mol(-1). The equilibrium constant K(CO) = [CO]/[HCOOH] is 0.15, 0.33, 0.80, and 4.2, respectively, at 170, 200, 240, and 280 degrees C. The van't Hoff plot results in the enthalpy change of DeltaH = 58 +/- 6 kJ mol(-1). The decarboxylation rate is also measured at 240-330 degrees C in both acidic and basic conditions. The rate is weakly dependent on the solution pH and is of the order of 10(-4) mol kg(-1) s(-1) at 330 degrees C. Furthermore, the equilibrium constant K(CO2) = [CO(2)][H(2)]/[HCOOH] is estimated to be 1.0 x10(2) mol kg(-1) at 330 degrees C. PMID:16986841

  17. Water-Gas Shift and CO Methanation Reactions over Ni-CeO2(111) Catalysts

    SciTech Connect

    Senanayake, Sanjaya D; Evans, Jaime; Agnoli, Stefano; Barrio, Laura; Chen, Tsung-Liang; Hrbek, Jan; Radriguez, Jose

    2011-01-01

    X-ray and ultraviolet photoelectron spectroscopies were used to study the interaction of Ni atoms with CeO2(111) surfaces. Upon adsorption on CeO2(111) at 300 K, nickel remains in a metallic state. Heating to elevated temperatures (500 800 K) leads to partial reduction of the ceria substrate with the formation of Ni2? species that exists as NiO and/or Ce1-xNixO2-y. Interactions of nickel with the oxide substrate significantly reduce the density of occupied Ni 3d states near the Fermi level. The results of core-level photoemission and near-edge X-ray absorption fine structure point to weakly bound CO species on CeO2(111) which are clearly distinguishable from the formation of chemisorbed carbonates. In the presence of Ni, a stronger interaction is observed with chemisorption of CO on the admetal. When the Ni is in contact with Ce?3 cations, CO dissociates on the surface at 300 K forming NiCx compounds that may be involved in the formation of CH4 at higher temperatures. At medium and large Ni coverages ([0.3 ML), the Ni/CeO2(111) surfaces are able to catalyze the production of methane from CO and H2, with an activity slightly higher than that of Ni(100) or Ni(111). On the other hand, at small coverages of Ni (\\0.3 ML), the Ni/CeO2(111) surfaces exhibit a very low activity for CO methanation but are very good catalysts for the water gas shift reaction.

  18. CO2 SELECTIVE CERAMIC MEMBRANE FOR WATER-GAS-SHIFT REACTION WITH CONCOMITANT RECOVERY OF CO2

    SciTech Connect

    Paul K.T. Liu

    2005-07-15

    A high temperature membrane reactor (MR) has been developed to enhance the water-gas-shift (WGS) reaction efficiency with concomitant CO{sub 2} removal for sequestration. This improved WGS-MR with CO{sub 2} recovery capability is ideally suitable for integration into the Integrated Gasification Combined-Cycle (IGCC) power generation system. Two different CO{sub 2}-affinity materials were selected in this study. The Mg-Al-CO{sub 3}-layered double hydroxide (LDH) was investigated as an adsorbent or a membrane for CO{sub 2} separation. The adsorption isotherm and intraparticle diffusivity for the LDH-based adsorbent were experimentally determined, and suitable for low temperature shift (LTS) of WGS. The LDH-based membranes were synthesized using our commercial ceramic membranes as substrate. These experimental membranes were characterized comprehensively in terms of their morphology, and CO{sub 2} permeance and selectivity to demonstrate the technical feasibility. In parallel, an alternative material-base membrane, carbonaceous membrane developed by us, was characterized, which also demonstrated enhanced CO{sub 2} selectivity at the LTS-WGS condition. With optimization on membrane defect reduction, these two types of membrane could be used commercially as CO{sub 2}-affinity membranes for the proposed application. Based upon the unique CO{sub 2} affinity of the LDHs at the LTS/WGS environment, we developed an innovative membrane reactor, Hybrid Adsorption and Membrane Reactor (HAMR), to achieve {approx}100% CO conversion, produce a high purity hydrogen product and deliver a concentrated CO{sub 2} stream for disposal. A mathematical model was developed to simulate this unique one -step process. Finally a benchtop reactor was employed to generate experimental data, which were consistent with the prediction from the HAMR mathematical model. In summary, the project objective, enhancing WGS efficiency for hydrogen production with concomitant CO{sub 2} removal for

  19. Supported Copper, Nickel and Copper-Nickel Nanoparticle Catalysts for Low Temperature Water-Gas-Shift Reaction

    NASA Astrophysics Data System (ADS)

    Lin, Jiann-Horng

    Hydrogen is being considered worldwide as a future replacement for gasoline, diesel fuel, natural gas in both the transportation and non-transportation sectors. Hydrogen is a versatile energy carrier that can be produced from a variety of widely available primary energy sources, including coal, natural gas, biomass, solar, wind, and nuclear power. Coal, the most abundant fossil fuel on the planet, is being looked at as the possible future major source of H2, due to the development of the integrated gasification combined cycle (IGCC) and integrated gasification fuel cell technologies (IGFC). The gasification of coal produces syngas consisting of predominately carbon monoxide and hydrogen with some remaining hydrocarbons, carbon dioxide and water. Then, the water-gas shift reaction is used to convert CO to CO2 and additional hydrogen. The present work describes the synthesis of model Cu, Ni and Cu-Ni catalysts prepared from metal colloids, and compares their behavior in the WGS reaction to that of traditional impregnation catalysts. Initially, we systematically explored the performance of traditional Cu, Ni and Cu-Ni WGS catalysts made by impregnation methods. Various bimetallic Cu-Ni catalysts were prepared by supported impregnation and compared to monometallic Cu and Ni catalysts. The presence of Cu in bimetallic catalysts suppressed undesirable methanation side reaction, while the Ni component was important for high WGS activity. Colloidal Cu, Ni and Cu-Ni alloy nanoparticles obtained by chemical reduction were deposited onto alumina to prepare supported catalysts. The resulting Cu and Ni nanoparticle catalysts were found to be 2.5 times more active in the WGS reaction per unit mass of active metal as compared to catalysts prepared by the conventional impregnation technique. The powder XRD and HAADF-STEM provided evidence supporting the formation of Cu-Ni particles containing the Cu core and Cu-Ni alloy shell. The XPS data indicated surface segregation of Cu in

  20. Charge polarization at a Au-TiC interface and the generation of highly active and selective catalysts for the low-temperature water-gas shift reaction.

    PubMed

    Rodriguez, José A; Ramírez, Pedro J; Asara, Gian Giacomo; Viñes, Francesc; Evans, Jaime; Liu, Ping; Ricart, Josep M; Illas, Francesc

    2014-10-13

    Au atoms in contact with TiC(001) undergo significant charge polarization. Strong metal-support interactions make Au/TiC(001) an excellent catalyst for the low-temperature water-gas shift (WGS), with turnover frequencies orders of magnitude larger than those observed for conventional metal/oxide catalysts. DFT calculations indicate that the WGS reaction follows an associative mechanism with HOCO as a key intermediate. PMID:25196121

  1. The synthesis of methanol and the reverse water-gas shift reaction over Zn-deposited Cu(100) and Cu(110) surfaces: comparison with Zn/Cu(111)

    NASA Astrophysics Data System (ADS)

    Nakamura, I.; Fujitani, T.; Uchijima, T.; Nakamura, J.

    1998-03-01

    The catalytic activity of Zn vapor-deposited Cu(100) and Cu(110) surfaces for methanol synthesis by the hydrogenation of CO 2 and the reverse water-gas shift reaction were studied using an XPS apparatus combined with a high-pressure flow reactor (18 atm). At a reaction temperature of 523 K, no promotional effect of Zn was observed for the methanol synthesis on both Zn/Cu(100) and Zn/Cu(110). The results were quite different from those for Zn/Cu(111), on which a significant promotion of methanol synthesis activity appeared to be due to the deposition of Zn, indicating that the promotional effect of Zn was sensitive to the surface structure of Cu. However, hysteresis was observed in the catalytic activity for methanol synthesis over the Zn/Cu(110) surface upon heating above 543 K in the reaction mixture. The activity became twice that measured before heating, which was close to the methanol synthesis activity of Zn/Cu(111) at the same Zn coverage. On the other hand, no such hysteresis was observed for the reverse water-gas shift reaction on Zn/Cu(110), indicating that the active site for methanol synthesis was not identical to that for the reverse water-gas shift reaction. In the post-reaction surface analysis, formate species was detected on both Zn/Cu(100) and Zn/Cu(110), whose coverage increased with increasing Zn coverage at 0< ΘZn<0.2. No correlation between the formate coverage and the methanol synthesis activity was obtained, which was in contrast to the results for Zn/Cu(111). Thus, the structure sensitivity observed in the catalytic activity of methanol synthesis over Zn-deposited Cu surfaces is ascribed to the significant difference in the reactivity of the formate intermediate.

  2. Theoretical study of gas-phase reactions of Fe(CO){sub 5} with OH{sup {minus}} and their relevance for the water gas shift reaction

    SciTech Connect

    Torrent, M.; Sola, M.; Frenking, G.

    1999-07-19

    Revision of the homogeneously Fe(CO){sub 5}-catalyzed water gas shift reaction in the gas phase has been performed by means of quantum chemical calculations using gradient-corrected density functional theory (B3LYP) and ab initio methods at the CCSD(T) level. The classically assumed reaction path has been scrutinized step by step, and enlarged with novel mechanistic proposals. The calculations lend additional credit to some of the previously accepted steps in the catalytic cycle, such as the initial attack of OH{sup {minus}} to Fe(CO){sub 5} and also to the recently accepted decarboxylation of (CO){sub 4}FeCOOH{sup {minus}} (via a concerted mechanism involving a four-centered transition state), as well as to the acidification of the metal hydride (CO){sub 4}Fe{sub 4}H{sub {minus}} with water to yield the dihydride (CO){sub 4}FeH{sub 2}. The present investigation also examines in terms of energies and activation barriers the existence/participation of new intermediates (in particular, a metalloformate species, a water-hydride adduct, and a dihydrogen complex), not mentioned in prior studies. Finally, a transition-metal-containing S{sub N}2-type reaction is explored for the last stages of this chemical process as a mechanistic alternative to regenerate the starting catalyst.

  3. Advanced Water-Gas Shift Membrane Reactor

    SciTech Connect

    Sean Emerson; Thomas Vanderspurt; Susanne Opalka; Rakesh Radhakrishnan; Rhonda Willigan

    2009-01-07

    The overall objectives for this project were: (1) to identify a suitable PdCu tri-metallic alloy membrane with high stability and commercially relevant hydrogen permeation in the presence of trace amounts of carbon monoxide and sulfur; and (2) to identify and synthesize a water gas shift catalyst with a high operating life that is sulfur and chlorine tolerant at low concentrations of these impurities. This work successfully achieved the first project objective to identify a suitable PdCu tri-metallic alloy membrane composition, Pd{sub 0.47}Cu{sub 0.52}G5{sub 0.01}, that was selected based on atomistic and thermodynamic modeling alone. The second objective was partially successful in that catalysts were identified and evaluated that can withstand sulfur in high concentrations and at high pressures, but a long operating life was not achieved at the end of the project. From the limited durability testing it appears that the best catalyst, Pt-Re/Ce{sub 0.333}Zr{sub 0.333}E4{sub 0.333}O{sub 2}, is unable to maintain a long operating life at space velocities of 200,000 h{sup -1}. The reasons for the low durability do not appear to be related to the high concentrations of H{sub 2}S, but rather due to the high operating pressure and the influence the pressure has on the WGS reaction at this space velocity.

  4. Studies related to the homogeneous catalysis of the water gas shift reaction. Technical progress report, December 1, 1983-November 30, 1984

    SciTech Connect

    Ford, P.C.

    1984-01-01

    Proposed are investigations related to the catalytic activation of carbon monoxide. These studies will be concerned with the design of catalysts for the water gas shift reaction and related processes such as the hydroformylation of olefins by homogeneous solution phase systems as well as by selected metal catalysts heterogenized by complexation to functional polymers. Also under investigation will be quantitative mechanistic aspects of reactions considered key to probable catalyst cycles. These are principally concerned with the fundamental chemistry of metal carbonyl and metal carbnyl hydride complexes including acid/base properties, reductive elimination, substitution and cluster fragmentation reactions and the nucleophilic activation of metal coordinated carbonyls toward reaction with water or dihydrogen. Goal of these studies is to provide chemical guidelines for the molecular design of new and more efficient catalysts for the utilization of carbonaceous materials such as coal for the production of fuels and other organic chemicals.

  5. Studies relevant to the catalytic activation of carbon monoxide: the water gas shift reaction and related processes. Technical progress report, December 1, 1983-November 30, 1984

    SciTech Connect

    Ford, P.C.

    1984-01-01

    Proposed are investigations related to the catalytic activation of carbon monoxide. These studies will be concerned with the design of catalysts for the water gas shift reaction and related processes such as the hydroformylation of olefins by homogeneous solution phase systems as well as by selected metal catalysts heterogenized by complexation to functionalized polymers. Also under investigation will be quantitative mechanistic aspects of reactions considered key to probable catalyst cycles. These are principally concerned with the fundamental chemistry of metal carbonyl and metal carbonyl hydride complexes including acid/base properties, reductive elimination, substitution and cluster fragmentation reactions and the nucleophilic activation of metal coordinated carbonyls toward reaction with water or dihydrogen. The goal of these studies is to provide chemical guidelines for the molecular design of new and more efficient catalysts for the utilization of carbonaceous materials such as coal for the production of fuels and other organic chemicals. 70 references.

  6. Analysis and modeling of PEM fuel cell stack performance: Effect of in situ reverse water gas shift reaction and oxygen bleeding

    NASA Astrophysics Data System (ADS)

    Karimi, G.; Li, Xianguo

    In this study the performance of a polymer electrolyte membrane (PEM) fuel cell stack is analyzed with a mathematical model when the stack operates on hydrocarbon reformate gas as the anode feed stream. It is shown that the effect of carbon dioxide dilution of the hydrogen dominated reformate gas has a minimal impact on the stack performance. However, the CO-poisoning effect due to the in situ reverse water gas shift reaction in the anode feed stream could have a very serious adverse impact on the stack performance, especially at high current densities. Thermodynamic calculations indicate that the equilibrium concentrations of CO could be as high as 100 ppm, generated by the in situ reverse water gas shift reaction, under the typical conditions of PEM fuel cell operation; and are influenced by the stack operating temperature and water content of the reformate anode feed. This CO-poisoning of the stack performance is shown mitigated effectively by introducing about 0.5-1% oxygen to the anode feed.

  7. Atomically Dispersed Au-(OH)x Species Bound on Titania Catalyze the Low-Temperature Water-Gas Shift Reaction

    SciTech Connect

    Yang, Ming; Allard, Lawrence F; Flytzani-Stephanopoulos, Maria

    2013-03-27

    We report a new method for stabilizing appreciable loadings (~1 wt %) of isolated gold atoms on titania and show that these catalyze the low-temperature water-gas shift reaction. The method combines a typical gold deposition/precipitation method with UV irradiation of the titania support suspended in ethanol. Dissociation of H2O on the thus-created Au–O–TiOx sites is facile. At higher gold loadings, nanoparticles are formed, but they were shown to add no further activity to the atomically bound gold on titania. Removal of this “excess” gold by sodium cyanide leaching leaves the activity intact and the atomically dispersed gold still bound on titania. The new materials may catalyze a number of other reactions that require oxidized active metal sites.

  8. Pulse studies to decipher the role of surface morphology in CuO/CeO₂ nanocatalysts for the water gas shift reaction

    SciTech Connect

    Rodriguez, Jose A.; Zhao, Fuzhen; Liu, Zongyuan; Xu, Wenqian; Yao, Siyu; Si, Rui; Johnston-Peck, Aaron C.; Martinez-Arias, Arturo; Hanson, Jonathan C.; Senanayake, Sanjaya D.

    2015-01-23

    The water-gas shift reaction (WGS, CO + H₂O → CO₂) was studied over CuO/CeO₂ catalysts with two different ceria particle morphohologies, in the form of nanospheres (ns) and nanocubes (nc). To understand the strong dependence of the WGS reaction activity on the ceria nanoshapes, pulses of CO (without and with water vapor) were employed during in situ X-ray diffraction (XRD) and X-ray absoprtion near edge structure (XANES) measurements done to characterize the catalysts. The results showed that CuO/CeO₂ (ns) exhibited a substantially better activity than CuO/CeO₂ (nc). The higher activity was associated with the unique properties of CuO/CeO₂ (ns), such as the easier reduction of highly dispersed CuO to metallic Cu, the stability of metallic Cu and a larger concentration Ce³⁺ in CeO₂ (ns).

  9. Pulse studies to decipher the role of surface morphology in CuO/CeO₂ nanocatalysts for the water gas shift reaction

    DOE PAGESBeta

    Rodriguez, Jose A.; Zhao, Fuzhen; Liu, Zongyuan; Xu, Wenqian; Yao, Siyu; Si, Rui; Johnston-Peck, Aaron C.; Martinez-Arias, Arturo; Hanson, Jonathan C.; Senanayake, Sanjaya D.

    2015-01-23

    The water-gas shift reaction (WGS, CO + H₂O → CO₂) was studied over CuO/CeO₂ catalysts with two different ceria particle morphohologies, in the form of nanospheres (ns) and nanocubes (nc). To understand the strong dependence of the WGS reaction activity on the ceria nanoshapes, pulses of CO (without and with water vapor) were employed during in situ X-ray diffraction (XRD) and X-ray absoprtion near edge structure (XANES) measurements done to characterize the catalysts. The results showed that CuO/CeO₂ (ns) exhibited a substantially better activity than CuO/CeO₂ (nc). The higher activity was associated with the unique properties of CuO/CeO₂ (ns), suchmore » as the easier reduction of highly dispersed CuO to metallic Cu, the stability of metallic Cu and a larger concentration Ce³⁺ in CeO₂ (ns).« less

  10. Characterization of CeO2-Supported Cu-Pd Bimetallic Catalyst for the Oxygen-Assisted Water-Gas Shift Reaction

    SciTech Connect

    Fox, Elise; Velu, Subramani; Engelhard, Mark H.; Chin, Ya-Huei; Miller, Jeffrey T.; Kropf, Jeremy; Song, Chunshan

    2008-12-10

    This study was focused to investigate the roles of Cu and Pd in CuPd/CeO2 bimetallic catalysts containing 20-30 wt% Cu and 0.5-1 wt% Pd used in the oxygen-assisted water-gas shift (OWGS) reaction employing a combined bulk and surface characterization techniques such as XRD, TPR, CO chemisorption, and in-situ XPS. The catalytic activity for CO conversion and the stability of catalyst during on-stream operation increased by the addition of Cu to Pd/CeO2 or Pd to Cu/CeO2 monometallic catalysts, especially when the OWGS reaction was performed under low temperatures, below 200oC. The bimetallic catalyst after leaching with nitric acid retained about 60% of its original activity. The TPR of monometallic Cu/CeO2 showed reduction of CuO supported on CeO2 in two distinct regions, around 150 and 250oC. The high temperature peak disappeared and reduction occurred in a single step around 150oC upon Pd addition. The Pd dispersion decreased from 38.5% for Pd/CeO2 to below 1% for CuPd/CeO2 bimetallic catalyst. In-situ XPS studies showed a shift in Cu 2p peaks toward lower binding energy (BE) with concommitant shift in the Pd 3d peaks toward higher BE. Addition of Pd decreased the surface Cu concentration while the concentration of Pd remained unaltered. All these observations indicated the formation of Cu-Pd surface alloy. The valence band XP spectra collected below 10 eV corroborated the core level XP spectra and indicated that Cu is mainly involved in the catalytic reaction. The improved catalytic activity and stability of CuPd/CeO2 bimetallic catalyst was attributed to the alloy formation.

  11. On the Importance of the Associative Carboxyl Mechanism for the Water-Gas Shift Reaction at Pt/CeO2 Interface Sites

    SciTech Connect

    Aranifard, Sara; Ammal, Salai Cheettu; Heyden, Andreas

    2014-03-06

    Periodic density functional theory calculations and microkinetic modeling are used to investigate the associative carboxyl pathways of the water-gas shift (WGS) reaction at the Pt/CeO2 (111) interface. Analysis of a microkinetic model based on parameters obtained from first principles suggests that the turnover frequencies for the CO-assisted associative carboxyl mechanism are comparable to experimental results. However, this microkinetic model containing various associative carboxyl pathways at interface sites cannot explain the experimentally observed activation barriers and reaction orders of Pt/CeO2 catalysts. Considering furthermore that a model of an associative carboxyl mechanism with redox regeneration, also derived from first principles and recently published by us, accurately predicts all kinetic parameters while displaying a 2 orders of magnitude higher turnover frequency, we conclude that at Pt/CeO2 interface sites, the WGS reaction follows a bifunctional Mars-van Krevelen mechanism in which support oxygen vacancies facilitate water dissociation.

  12. A common single-site Pt(II)-O(OH)x- species stabilized by sodium on "active" and "inert" supports catalyzes the water-gas shift reaction.

    PubMed

    Yang, Ming; Liu, Jilei; Lee, Sungsik; Zugic, Branko; Huang, Jun; Allard, Lawrence F; Flytzani-Stephanopoulos, Maria

    2015-03-18

    While it has long been known that different types of support oxides have different capabilities to anchor metals and thus tailor the catalytic behavior, it is not always clear whether the support is a mere carrier of the active metal site, itself not participating directly in the reaction pathway. We report that catalytically similar single-atom-centric Pt sites are formed by binding to sodium ions through -O ligands, the ensemble being equally effective on supports as diverse as TiO2, L-zeolites, and mesoporous silica MCM-41. Loading of 0.5 wt % Pt on all of these supports preserves the Pt in atomic dispersion as Pt(II), and the Pt-O(OH)x- species catalyzes the water-gas shift reaction from ∼120 to 400 °C. Since the effect of the support is "indirect," these findings pave the way for the use of a variety of earth-abundant supports as carriers of atomically dispersed platinum for applications in catalytic fuel-gas processing. PMID:25746682

  13. Gold(III)-CO and gold(III)-CO2 complexes and their role in the water-gas shift reaction.

    PubMed

    Roşca, Dragoş-Adrian; Fernandez-Cestau, Julio; Morris, James; Wright, Joseph A; Bochmann, Manfred

    2015-10-01

    The water-gas shift (WGS) reaction is an important process for the generation of hydrogen. Heterogeneous gold catalysts exhibit good WGS activity, but the nature of the active site, the oxidation state, and competing reaction mechanisms are very much matters of debate. Homogeneous gold WGS systems that could shed light on the mechanism are conspicuous by their absence: gold(I)-CO is inactive and gold(III)-CO complexes were unknown. We report the synthesis of the first example of an isolable CO complex of Au(III). Its reactivity demonstrates fundamental differences between the CO adducts of the neighboring d (8) ions Pt(II) and Au(III): whereas Pt(II)-CO is stable to moisture, Au(III)-CO compounds are extremely susceptible to nucleophilic attack and show WGS reactivity at low temperature. The key to understanding these dramatic differences is the donation/back-donation ratio of the M-CO bond: gold-CO shows substantially less back-bonding than Pt-CO, irrespective of closely similar ν(CO) frequencies. Key WGS intermediates include the gold-CO2 complex [(C^N^C)Au]2(μ-CO2), which reductively eliminates CO2. The species identified here are in accord with Au(III) as active species and a carboxylate WGS mechanism. PMID:26601313

  14. Genesis and Evolution of Surface Species during Pt Atomic Layer Deposition on Oxide Supports Characterized by in Situ XAFS Analysis and Water-Gas Shift Reaction

    SciTech Connect

    Setthapun, Worajit; Williams, W. Damion; Kim, Seung Min; Feng, Hao; Elam, Jeffrey W.; Rabuffetti, Federico A.; Poeppelmeier, Kenneth R.; Stair, Peter C.; Stach, Eric A.; Ribeiro, Fabio H.; Miller, Jeffrey T.; Marshall, Christopher L.

    2010-06-03

    Platinum atomic layer deposition (ALD) using MeCpPtMe₃ was employed to prepare high loadings of uniform-sized, 1-2 nm Pt nanoparticles on high surface area Al₂O₃, TiO₂, and SrTiO₃ supports. X-ray absorption fine structure was utilized to monitor the changes in the Pt species during each step of the synthesis. The temperature, precursor exposure time, treatment gas, and number of ALD cycles were found to affect the Pt particle size and density. Lower-temperature MeCpPtMe₃ adsorption yielded smaller particles due to reduced thermal decomposition. A 300 °C air treatment of the adsorbed MeCpPtMe₃ leads to PtO. In subsequent ALD cycles, the MeCpPtMe₃ reduces the PtO to metallic Pt in the ratio of one precursor molecule per PtO. A 200 °C H₂ treatment of the adsorbed MeCpPtMe₃ leads to the formation of 1-2 nm, metallic Pt nanoparticles. During subsequent ALD cycles, MeCpPtMe₃ adsorbs on the support, which, upon reduction, yields additional Pt nanoparticles with a minimal increase in size of the previously formed nanoparticles. The catalysts produced by ALD had identical water-gas shift reaction rates and reaction kinetics to those of Pt catalysts prepared by standard solution methods. ALD synthesis of catalytic nanoparticles is an attractive method for preparing novel model and practical catalysts.

  15. Gold(III)-CO and gold(III)-CO2 complexes and their role in the water-gas shift reaction

    PubMed Central

    Roşca, Dragoş-Adrian; Fernandez-Cestau, Julio; Morris, James; Wright, Joseph A.; Bochmann, Manfred

    2015-01-01

    The water-gas shift (WGS) reaction is an important process for the generation of hydrogen. Heterogeneous gold catalysts exhibit good WGS activity, but the nature of the active site, the oxidation state, and competing reaction mechanisms are very much matters of debate. Homogeneous gold WGS systems that could shed light on the mechanism are conspicuous by their absence: gold(I)–CO is inactive and gold(III)–CO complexes were unknown. We report the synthesis of the first example of an isolable CO complex of Au(III). Its reactivity demonstrates fundamental differences between the CO adducts of the neighboring d8 ions Pt(II) and Au(III): whereas Pt(II)-CO is stable to moisture, Au(III)–CO compounds are extremely susceptible to nucleophilic attack and show WGS reactivity at low temperature. The key to understanding these dramatic differences is the donation/back-donation ratio of the M–CO bond: gold-CO shows substantially less back-bonding than Pt-CO, irrespective of closely similar ν(CO) frequencies. Key WGS intermediates include the gold-CO2 complex [(C^N^C)Au]2(μ-CO2), which reductively eliminates CO2. The species identified here are in accord with Au(III) as active species and a carboxylate WGS mechanism. PMID:26601313

  16. Development of Ni-Mo/Al2O3 catalyst for reverse water gas shift (RWGS) reaction.

    PubMed

    Kharaji, Abolfazl Gharibi; Shariati, Ahmad; Ostadi, Mohammad

    2014-09-01

    In the present study, Mo/Al2O3 catalyst was prepared using impregnation method. Then it was promoted with Ni ions to produce Ni-Mo/Al2O3 catalyst. The structures of the catalysts were studied using X-ray diffraction (XRD), Energy dispersive X-ray (EDAX), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), CO chemisorption, temperature programmed reduction of hydrogen (H2-TPR) and scanning electron microscope (SEM) techniques. Catalytic performances of the two catalysts were investigated in a fixed-bed reactor for RWGS reaction. The results indicated that addition of nickel promoter to Mo/Al2O3 catalyst enhances its activity. It is reasonable for the electron deficient state of the Ni species and existence of NiMoO4 phase to possess high activity in RWGS reaction. Stability test of Ni-Mo/Al2O3 catalyst was carried out in a fixed bed reactor and a high CO2 conversion for 60 h time on stream was demonstrated. This study introduces a new catalyst, Ni-Mo/Al2O3, with high activity and stability for RWGS reaction. PMID:25924339

  17. Theoretical studies on the catalysis of the reverse water-gas shift reaction using first-row transition metal beta-diketiminato complexes.

    PubMed

    Liu, Cong; Munjanja, Lloyd; Cundari, Thomas R; Wilson, Angela K

    2010-06-01

    The reverse water-gas shift reaction CO(2) + H(2) --> H(2)O + CO has been investigated using a set of homogeneous catalyst models L'M(I) (L' = beta-diketiminate, C(3)N(2)H(5)(-); M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn). The thermodynamics of prototypical reaction pathways were simulated at two levels of theory: B3LYP/6-311+G(d) and B3LYP/aug-cc-pVTZ. The modeled catalytic reaction has been considered in the following steps: coordination of CO(2) by the catalyst to generate a carbon dioxide complex, L'M(CO(2)); scission of L'M(CO(2)) to yield L'M(CO) and L'M(O); L'M(O) hydrogenation to form L'M(H(2)O). The final products, H(2)O and CO, were obtained from the dissociation of L'M(H(2)O) and L'M(CO). All of the reactants, intermediates, and products were modeled, where different possible conformers and multiplicities were identified and considered as potential minima. The reaction enthalpy DeltaH, of all steps for each catalyst as a function of transition metal have been determined. The Mn and Fe catalysts show more thermodynamically accessible pathways than the other catalyst models studied. The overall reaction enthalpy has been determined not only by B3LYP/6-311+G(d) and B3LYP/aug-cc-pVTZ but also via a more rigorous ab initio electron-correlation-based approach, the correlation consistent Composite Approach (ccCA). PMID:20462216

  18. Determination of CO, H{sub 2}O and H{sub 2} coverage by XANES and EXAFS on Pt and Au during water gas shift reaction.

    SciTech Connect

    Guo, N.; Fingland, B. R.; Williams, W. D.; Kispersky, V. F.; Jelic, J.; Delgass, W. N.; Ribeiro, F. H.; Meyer, R. J.; Miller, J. T.; Purdue Univ.; Univ. of Illinois

    2010-01-01

    The turn over rate (TOR) for the water gas shift (WGS) reaction at 200C, 7%CO, 9%CO{sub 2}, 22% H{sub 2}O, 37% H, and balance Ar, of 1.4 nm Au/Al{sub 2}O{sub 3} is approximately 20 times higher than that of 1.6 nm Pt.Al{sub 2}O{sub 3}. Operando EXFAS experiments at both the Au and Pt L{sub 3} edges reveal tht under reaction conditions, the catalysts are fully metallic. In the absence of adsorbates, the metal-metal bond distance of Pt and Au catalysts are 0.07 {angstrom} and 0.13 {angstrom} smaller than those of bulk Pt and Au foils, respectively. Adsorption of H{sub 2} or CO on the Pt catalysts leads to significantly longer Pt-Pt bond distances, while there is little change in the Au-Au bond distance with adsorbates. Adsorption of CO, H{sub 2} and H{sub 2}O leads to changes in the XANES spectra that can be used to determine the surface coverage of each adsorbate under reaction conditions. During WGS, the coverage of CO, H{sub 2}O and H{sub 2} are obtained by the linear combination fitting of the difference XANES or {Delta}XANES, spectra. Pt catalysts adsorb CO,H{sub 2} and H{sub 2}O more strongly than the Au, in agreement with the lower CO reaction order and higher reaction temperatures.

  19. Interaction of CO with OH on Au(111): HCOO, CO3, and HOCO as Key Intermediates in the Water-Gas Shift Reaction

    SciTech Connect

    Senanayake, S.; Stacchiola, D; Liu, P; Mullins, C; Hrbek, J; Rodriguez, J

    2009-01-01

    We have investigated the role of formate (HCOO), carbonate (CO{sub 3}), and carboxyl (HOCO) species as possible intermediates in the OH{sub ads} + CO{sub gas} {yields} CO{sub 2,gas} + 0.5H{sub 2,gas} reaction on Au(111) using synchrotron-based core level photoemission, near-edge X-ray absorption fine structure (NEXAFS), and infrared absorption spectroscopy (IR). Adsorbed HCOO, CO{sub 3}, and OH species were prepared by adsorbing formic acid, carbon dioxide, and water on a Au(111) surface precovered with 0.2 ML of atomic oxygen, respectively. HCOOH interacts weakly with Au(111), but on O/Au(111) it dissociates its acidic H to yield adsorbed formate. The results of NEXAFS, IR, and density-functional calculations indicate that the formate adopts a bidentate configuration on Au(111). Since the HCOO groups are stable on Au(111) up to temperatures near 350 K, it is not likely that formate is a key intermediate for the OH{sub ads} + CO{sub gas} {yields} CO{sub 2,gas} + 0.5H{sub 2,gas} reaction at low temperatures. In fact, the formation of this species could lead eventually to surface poisoning. When compared to a formate species, a carbonate species formed by the reaction of CO{sub 2} with O/Au(111) has low stability, decomposing at temperatures between 100 and 125 K, and should not poison the gold surface. Neither HCOO nor CO{sub 3} was detected during the reaction of CO with OH on Au(111) at 90-120 K. The results of photoemission and IR spectroscopy point to HO {leftrightarrow} CO interactions, consistent with the formation of an unstable HOCO intermediate which has a very short lifetime on the gold surface. The possible mechanism for the low-temperature water-gas shift on gold catalysts is discussed in light of these results.

  20. Highly Active and Stable Pt-Loaded Ce0.75Zr0.25O2 Yolk-Shell Catalyst for Water-Gas Shift Reaction.

    PubMed

    Shim, Jae-Oh; Hong, Young Jun; Na, Hyun-Suk; Jang, Won-Jun; Kang, Yun Chan; Roh, Hyun-Seog

    2016-07-13

    Multishelled, Pt-loaded Ce0.75Zr0.25O2 yolk-shell microspheres were prepared by a simple spray pyrolysis process for use in the water-gas shift (WGS) reaction. The Pt-loading was optimized, obtaining highly active Pt/Ce0.75Zr0.25O2 yolk-shell nanostructures for the WGS. Of the prepared catalysts, a 2% Pt loading of the Ce0.75Zr0.25O2 yolk-shell microspheres showed the highest CO conversion. The high catalytic activity of the 2% Pt/Ce0.75Zr0.2O2 catalyst was mainly due to its easier reducibility and the maintenance of active catalytic Pt species. The Pt-loaded Ce0.75Zr0.25O2 catalyst microspheres were highly resistant to Pt sintering because of their unique yolk-shell structure. Spray pyrolysis was found to be highly efficient for the production of precious-metal-loaded, multicomponent metal oxide yolk-shell microspheres for catalytic applications. PMID:27315135

  1. Water-gas shift reaction over gold nanoparticles dispersed on nanostructured CeOx-TiO2(110) surfaces: Effects of high ceria coverage

    NASA Astrophysics Data System (ADS)

    Grinter, D. C.; Park, J. B.; Agnoli, S.; Evans, J.; Hrbek, J.; Stacchiola, D. J.; Senanayake, S. D.; Rodriguez, J. A.

    2016-08-01

    Scanning tunnelling microscopy has been used to study the morphology of an overlayer of ceria in contact with a TiO2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO2(110)-(1 × 1). The other half of the surface comprised CeOx nanoparticles and reconstructed TiOx supported on TiO2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film and TiO2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeOx/TiO2(110) model system proved to be a good catalyst for the water-gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO2(110) and Au/CeO2(111) systems. For Au/CeOx/TiO2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce3 + formed during WGS reaction conditions.

  2. Morphological effects of the nanostructured ceria support on the activity and stability of CuO/CeO2 catalysts for the water-gas shift reaction.

    PubMed

    Yao, S Y; Xu, W Q; Johnston-Peck, A C; Zhao, F Z; Liu, Z Y; Luo, S; Senanayake, S D; Martínez-Arias, A; Liu, W J; Rodriguez, J A

    2014-08-28

    Three CuO/CeO2 catalyst with different morphologies of ceria, namely nanospheres, nanorods and nanocubes, were synthesized and used to catalyze the water-gas shift (WGS) reaction. The reactivity tests showed that the Cu supported on the ceria nanospheres exhibited both the highest activity and superior stability when compared with the nanocube and nanorod ceria catalysts. Operando X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) and diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) methods were used to characterize these catalysts in their working state. High resolution electron microscopy (HRTEM, STEM) was used to look at the local atomic structure and nano-scale morphology. Our results show that the morphology of the ceria support, which can involve different crystal faces and concentrations of defects and imperfections, has a critical impact on the catalytic properties and influences: (1) the dispersion of CuO in the as-synthesized catalyst; (2) the particle size of metallic Cu upon reduction during the WGS reaction, (3) the stability of the metallic Cu upon variations of temperature, and (4) the dissociation of water on the ceria support. The nanosphere ceria catalyst showed an excellent water dissociation capability, the best dispersion of Cu and a strong Cu-Ce interaction, therefore delivering the best performance among the three WGS catalysts. The metallic Cu, which is the active species during the WGS reaction, was more stabilized on the nanospheres than on the nanorods and nanocubes and thus led to a better stability of the nanosphere catalyst than the other two architectures. Each catalyst exhibited a distinctive line-shape in the 800-1600 cm(-1) region of the DRIFTS spectra, pointing to the existence of different types of carbonate or carboxylate species as surface intermediates for the WGS. PMID:25012908

  3. Ceria-based Catalysts for the Production of H2 Through the Water-gas-shift Reaction: Time-Resolved XRD and XAFS Studies

    SciTech Connect

    Wang,X.; Rodriguez, J.; Hanson, J.; Gamarra, D.; Marinez-Arias, A.; Fernandez-Garcia, M.

    2008-01-01

    Hydrogen is a potential alternate energy source for satisfying many of our energy needs. In this work, we studied H2 production from the water-gas-shift (WGS) reaction over Ce1-x Cu x O2 catalysts, prepared with a novel microemulsion method, using two synchrotron-based techniques: time-resolved X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS). The results are compared with those reported for conventional CuO x /CeO2 and AuO x /CeO2 catalysts obtained through impregnation of ceria. For the fresh Ce1-x Cu x O2 catalysts, the results of XAFS measurements at the Cu K-edge indicate that Cu is in an oxidation state higher than in CuO. Nevertheless, under WGS reaction conditions the Ce1-x Cu x O2 catalysts undergo reduction and the active phase contains very small particles of metallic Cu and CeO2-x . Time-resolved XRD and XAFS results also indicate that Cud+ and Aud+ species present in fresh CuO x /CeO2 and AuO x /CeO2 catalysts do not survive above 200 C under the WGS conditions. In all these systems, the ceria lattice displayed a significant increase after exposure to CO and a decrease in H2O, indicating that CO reduced ceria while H2O oxidized it. Our data suggest that H2O dissociation occurred on the Ovacancy sites or the Cu-Ovacancy and Au-Ovacancy interfaces. The rate of H2 generation by a Ce0.95Cu0.05O2 catalyst was comparable to that of a 5 wt% CuO x /CeO2 catalyst and much bigger than those of pure ceria or CuO.

  4. Genesis and evolution of surface species during Pt atomic layer deposition on oxide supports characterized by in-situ XAFS analysis and water-gas shift reaction.

    SciTech Connect

    Setthapun, W.; Williams, W.; Kim, S.; Feng, H.; Elam, J.; Rabuffetti, F.; Poeppelmeier, K.; Stair, P.; Stach, E.; Ribeiro, F.; Miller, J.; Marshall, C.; Northwestern Univ.; Purdue Univ.

    2010-06-03

    Platinum atomic layer deposition (ALD) using MeCpPtMe{sub 3} was employed to prepare high loadings of uniform-sized, 1-2 nm Pt nanoparticles on high surface area Al{sub 2}O{sub 3}, TiO{sub 2}, and SrTiO{sub 3} supports. X-ray absorption fine structure was utilized to monitor the changes in the Pt species during each step of the synthesis. The temperature, precursor exposure time, treatment gas, and number of ALD cycles were found to affect the Pt particle size and density. Lower-temperature MeCpPtMe{sub 3} adsorption yielded smaller particles due to reduced thermal decomposition. A 300 C air treatment of the adsorbed MeCpPtMe{sub 3} leads to PtO. In subsequent ALD cycles, the MeCpPtMe{sub 3} reduces the PtO to metallic Pt in the ratio of one precursor molecule per PtO. A 200 C H{sub 2} treatment of the adsorbed MeCpPtMe{sub 3} leads to the formation of 1-2 nm, metallic Pt nanoparticles. During subsequent ALD cycles, MeCpPtMe{sub 3} adsorbs on the support, which, upon reduction, yields additional Pt nanoparticles with a minimal increase in size of the previously formed nanoparticles. The catalysts produced by ALD had identical water-gas shift reaction rates and reaction kinetics to those of Pt catalysts prepared by standard solution methods. ALD synthesis of catalytic nanoparticles is an attractive method for preparing novel model and practical catalysts.

  5. Unusual Physical and Chemical Properties of Ni in Ce1-xNixO2-y Oxides: Structural Characterization and Catalytic Activity for the Water Gas Shift Reaction

    SciTech Connect

    Rodriguez, J.A.; Barrio, L.; Kubacka, A.; Zhou, G.; Estrella, M.; Martınez-Arias, A.; Hanson, J.C.; Fernandez-Garcıa, M.

    2010-07-29

    The structural and electronic properties of Ce{sub 1-x}Ni{sub x}O{sub 2-y} nanosystems prepared by a reverse microemulsion method were characterized with synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, Raman spectroscopy, and density functional calculations. The Ce{sub 1-x}Ni{sub x}O{sub 2-y} systems adopt a lattice with a fluorite-type structure with an acute local order where Ni displays a strongly distorted (oxygen) nearest-neighbor coordination and the presence of Ni atoms as first cation distances, pointing to the existence of Ni-O-Ni entities embedded into the ceria lattice. A Ni {leftrightarrow} Ce exchange within the CeO{sub 2} leads to a charge redistribution and the appearance of O vacancies. The Ni?O bonds in Ce{sub 1-x}Ni{sub x}O{sub 2-y} are more difficult to reduce than the bonds in pure NiO. The specific structural configuration of Ni inside the mixed-metal oxide leads to a unique catalyst with a high activity for the water gas shift (CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2}) reaction and a simultaneous reduction of the methanation activity of nickel. Characterization results indicate that small particles of metallic Ni at the interface position of a ceria network may be the key for high WGS activity and that the formate?carbonate route is operative for the production of hydrogen.

  6. Unusual Physical and Chemical Properties of Ni in Ce1-xNixO2-y Oxides: Structural Characterization and Catalytic Activity for the Water Gas Shift Reaction

    SciTech Connect

    Barrio, L.; Kubacka, A; Zhou, G; Estrella, M; Martinez-Arias, A; Hanson, J; Fernandez-Garcia, M; Rodriguez, J

    2010-01-01

    The structural and electronic properties of Ce{sub 1-x}Ni{sub x}O{sub 2-y} nanosystems prepared by a reverse microemulsion method were characterized with synchrotron-based X-ray diffraction, X-ray absorption spectroscopy, Raman spectroscopy, and density functional calculations. The Ce{sub 1-x}Ni{sub x}O{sub 2-y} systems adopt a lattice with a fluorite-type structure with an acute local order where Ni displays a strongly distorted (oxygen) nearest-neighbor coordination and the presence of Ni atoms as first cation distances, pointing to the existence of Ni-O-Ni entities embedded into the ceria lattice. A Ni {leftrightarrow} Ce exchange within the CeO{sub 2} leads to a charge redistribution and the appearance of O vacancies. The Ni-O bonds in Ce{sub 1-x}Ni{sub x}O{sub 2-y} are more difficult to reduce than the bonds in pure NiO. The specific structural configuration of Ni inside the mixed-metal oxide leads to a unique catalyst with a high activity for the water gas shift (CO + H{sub 2}O {yields} H{sub 2} + CO{sub 2}) reaction and a simultaneous reduction of the methanation activity of nickel. Characterization results indicate that small particles of metallic Ni at the interface position of a ceria network may be the key for high WGS activity and that the formate-carbonate route is operative for the production of hydrogen.

  7. Flame Synthesis of Nanosized Cu-Ce-O, Ni-Ce-O, and Fe-Ce-O Catalysts for the Water-Gas Shift (WGS) Reaction

    SciTech Connect

    Pati, R.; Lee, I; Hou, S; Akhuemonkhan, O; Gaskell, K; Wang, Q; Frenkel, A; Chu, D; Salamanca-Riba, L; Ehrman, S

    2009-01-01

    A flame synthesis method has been used to prepare nanosized, high-surface-area Cu-Ce-O, Ni-Ce-O, and Fe-Ce-O catalysts from aqueous solutions of metal acetate precursors. The particles were formed by vaporization of the precursors followed by reaction and then gas to particle conversion. The specific surface areas of the synthesized powders ranged from 127 to 163 m{sup 2}/g. High-resolution transmission electron microscope imaging showed that the particle diameters for the ceria materials are in the range of 3-10 nm, and a thin layer of amorphous material was observed on the surface of the particles. The presence and surface enrichment of the transition-metal oxides (CuO, NiO, and Fe{sub 2}O{sub 3}) on the ceria particles were detected using X-ray photoelectron spectroscopy. Electron energy-loss spectroscopic studies suggest the formation of a core-shell structure in the as-prepared particles. Extended X-ray absorption fine structure studies suggest that the dopants in all M-Ce-O systems are almost isostructural with their oxide counterparts, indicating the doping materials form separate oxide phases (CuO, Fe{sub 2}O{sub 3}, NiO) within the host matrix (CeO{sub 2}). Etching results confirm that most of the transition-metal oxides are present on the surface of CeO{sub 2}, easily dissolved by nitric acid. The performance of the flame-synthesized catalysts was examined toward water-gas shift (WGS) activity for fuel processing applications. The WGS activity of metal ceria catalysts decreases in the order Cu-Ce-O > Ni-Ce-O > Fe-Ce-O > CeO{sub 2} with a feed mixture having a hydrogen to carbon monoxide (H{sub 2}/CO) ratio of 1. There was no methane formation for these catalysts under the tested conditions.

  8. Process Intensification with Integrated Water-Gas-Shift Membrane Reactor

    SciTech Connect

    2009-11-01

    This factsheet describes a research project whose objective is to develop hydrogen-selective membranes for an innovative gas-separation process based on a water-gas-shift membrane reactor (WGS-MR) for the production of hydrogen.

  9. WATER-GAS SHIFT WITH INTEGRATED HYDROGEN SEPARATION

    SciTech Connect

    Maria Flytzani-Stephanopoulos; Jerry Meldon; Xiaomei Qi

    2001-12-01

    Optimization of the water-gas shift (WGS) reaction system for hydrogen production for fuel cells is of particular interest to the energy industry. To this end, it is desirable to couple the WGS reaction to hydrogen separation using a semi-permeable membrane, with both processes carried out at high temperature to improve reaction kinetics. Reduced equilibrium conversion of the WGS reaction at high temperatures is overcome by product H{sub 2} removal via the membrane. This project involves fundamental research and development of novel cerium oxide-based catalysts for the water-gas-shift reaction and the integration of these catalysts with Pd-alloy H{sub 2}-separation membranes supplying high purity hydrogen for fuel cell use. Conditions matching the requirements of coal gasifier-exit gas streams will be examined in the project. In the first year of the project, we prepared a series of nanostructured Cu- and Fe-containing ceria catalysts by a special gelation/precipitation technique followed by air calcination at 650 C. Each sample was characterized by ICP for elemental composition analysis, BET-N2 desorption for surface area measurement, and by temperature-programmed reduction in H{sub 2} to evaluate catalyst reducibility. Screening WGS tests with catalyst powders were conducted in a flow microreactor at temperatures in the range of 200-550 C. On the basis of both activity and stability of catalysts in simulated coal gas, and in CO{sub 2}-rich gases, a Cu-CeO{sub 2} catalyst formulation was selected for further study in this project. Details from the catalyst development and testing work are given in this report. Also in this report, we present H{sub 2} permeation data collected with unsupported flat membranes of pure Pd and Pd-alloys over a wide temperature window.

  10. High-Temperature Water-Gas Shift Membrane Reactor Study

    SciTech Connect

    Ciocco, M.V.; Iyoha, O.; Enick, R.M.; Killmeyer, R.P.

    2007-06-01

    NETL’s Office of Research and Development is exploring the integration of membrane reactors into coal gasification plants as a way of increasing efficiency and reducing costs. Water-Gas Shift Reaction experiments were conducted in membrane reactors at conditions similar to those encountered at the outlet of a coal gasifier. The changes in reactant conversion and product selectivity due to the removal of hydrogen via the membrane reactor were quantified. Research was conducted to determine the influence of residence time and H2S on CO conversion in both Pd and Pd80wt%Cu membrane reactors. Effects of the hydrogen sulfide-to-hydrogen ratio on palladium and a palladium-copper alloy at high-temperature were also investigated. These results were compared to thermodynamic calculations for the stability of palladium sulfides.

  11. WATER-GAS SHIFT WITH INTEGRATED HYDROGEN SEPARATION PROCESS

    SciTech Connect

    Maria Flytzani-Stephanopoulos; Xiaomei Qi; Scott Kronewitter

    2004-02-01

    This project involved fundamental research and development of novel cerium oxide-based catalysts for the water-gas-shift reaction and the integration of these catalysts with Pd-alloy H{sub 2} -separation membranes supplying high purity hydrogen for fuel cell use. Conditions matching the requirements of coal gasifier-exit gas streams were examined in the project. Cu-cerium oxide was identified as the most promising high-temperature water-gas shift catalyst for integration with H{sub 2}-selective membranes. Formulations containing iron oxide were found to deactivate in the presence of CO{sub 2}. Cu-containing ceria catalysts, on the other hand, showed high stability in CO{sub 2}-rich gases. This type gas will be present over much of the catalyst, as the membrane removes the hydrogen produced from the shift reaction. The high-temperature shift catalyst composition was optimized by proper selection of dopant type and amount in ceria. The formulation 10at%Cu-Ce(30at%La)O{sub x} showed the best performance, and was selected for further kinetic studies. WGS reaction rates were measured in a simulated coal-gas mixture. The apparent activation energy, measured over aged catalysts, was equal to 70.2 kJ/mol. Reaction orders in CO, H{sub 2}O, CO{sub 2} and H{sub 2} were found to be 0.8, 0.2, -0.3, and -0.3, respectively. This shows that H{sub 2}O has very little effect on the reaction rate, and that both CO{sub 2} and H{sub 2} weakly inhibit the reaction. Good stability of catalyst performance was found in 40-hr long tests. A flat (38 cm{sup 2}) Pd-Cu alloy membrane reactor was used with the catalyst washcoated on oxidized aluminum screens close coupled with the membrane. To achieve higher loadings, catalyst granules were layered on the membrane itself to test the combined HTS activity/ H{sub 2} -separation efficiency of the composite. Simulated coal gas mixtures were used and the effect of membrane on the conversion of CO over the catalyst was evidenced at high space

  12. Unique properties of ceria nanoparticles supported on metals: novel inverse ceria/copper catalysts for CO oxidation and the water-gas shift reaction.

    PubMed

    Senanayake, Sanjaya D; Stacchiola, Dario; Rodriguez, Jose A

    2013-08-20

    a standard catalyst for reactions such as CO oxidation and the water-gas shift (WGS). This metal serves as an ideal replacement for other noble metals that are neither abundant nor cost effective. To prepare the inverse system we deposited nanoparticles (2-20 nm) of cerium oxide onto the Cu(111) surface. During this process, the Cu(111) surface grows an oxide layer that is characteristic of Cu₂O (Cu¹⁺). This oxide can influence the growth of ceria nanoparticles. Evidence suggests triangular-shaped CeO₂(111) grows on Cu₂O(111) surfaces while rectangular CeO₂(100) grows on Cu₄O₃(111) surfaces. We used the CeOx/Cu₂O/Cu(111) inverse system to study two catalytic processes: the WGS (CO + H₂O → CO₂ + H₂) and CO oxidation (2CO + O₂ → 2CO₂). We discovered that the addition of small amounts of ceria nanoparticles can activate the Cu(111) surface and achieve remarkable enhancement of catalytic activity in the investigated reactions. In the case of the WGS, the CeOx nanoparticle facilitated this process by acting at the interface with Cu to dissociate water. In the CO oxidation case, an enhancement in the dissociation of O₂ by the nanoparticles was a key factor. The strong interaction between CeOx nanoparticles and Cu(111) when preoxidized and reduced in CO resulted in a massive surface reconstruction of the copper substrate with the introduction of microterraces that covered 25-35% of the surface. This constitutes a new mechanism for surface reconstruction not observed before. These microterraces helped to facilitate a further enhancement of activity towards the WGS by opening an additional channel for the dissociation of water. In summary, inverse catalysts of CeOx/Cu(111) and CeO₂/Cu₂O/Cu(111) demonstrate the versatility of a model system to obtain insightful knowledge of catalytic processes. These systems will continue to offer a unique opportunity to probe key catalytic components and elucidate the relationship between structure and

  13. Nature of Ptn/TiO2(110) Interface under Water-Gas Shift Reaction Conditions: A Constrained ab Initio Thermodynamics Study

    SciTech Connect

    Ammal, Salai Cheettu; Heyden, Andreas

    2011-10-06

    The electronic structure of small Ptn (n = 1-8) clusters supported on the stoichiometric and partially reduced rutile TiO2(110) surface have been investigated using density functional theory. Pt atoms prefer to form a close-packed structure with (111) facet near an oxygen vacancy of the TiO2 support and a less dense structure with (100) facet away from oxygen vacant sites. Themain focus of this study is on identifying a realistic catalyst model for the Pt/TiO2 interface under watergas shift (WGS) reaction conditions. Constrained ab initio thermodynamic simulations on the stability of oxygen vacancies and formation of adsorbed gas phase molecules such as oxygen, CO, and hydrogen at the metal/oxide interface reveal that under WGS reaction conditions the formation of surface oxygen vacancies are thermodynamically favorable, platinum oxide species (PtOx) can easily be reduced and should not be present, CO adsorbs only weakly on interfacial Pt atoms, and CO poisoning of these sites should be less important. While hydrogen generally interacts weakly with interfacial Pt atoms, it forms very stable hydride species on Pt atoms neighboring an oxygen vacancy of the TiO2(110) support, possibly negatively affecting the WGS reaction rate.

  14. In Situ Studies of the Active Sites for the Water Gas Shift Reaction over Cu-CeO2 Catalysts: Complex Interaction Between Metallic Copper and Oxygen Vacancies of Ceria

    SciTech Connect

    Wang,X.; Rodriguez, J.; Hanson, J.; Gamarra, D.; Martinez-Arias, A.; Fernandez-Garcia, M.

    2006-01-01

    New information about the active sites for the water gas shift (WGS) reaction over Cu-CeO{sub 2} systems was obtained using in-situ, time-resolved X-ray diffraction (TR-XRD), X-ray absorption spectroscopy (TR-XAS, Cu K and Ce L3 edges), and infrared spectroscopy (DRIFTS). Cu-CeO{sub 2} nanoparticles prepared by a novel reversed microemulsion method (doped Ce1-xCuxO2 sample) and an impregnation method (impregnated CuO{sub x}/CeO{sub 2} sample) were studied. The results from all of the samples indicate that both metallic copper and oxygen vacancies in ceria were involved in the generation of active sites for the WGS reaction. Evidence was found for a synergistic Cu-O vacancy interaction. This interaction enhances the chemical activity of Cu, and the presence of Cu facilitates the formation of O vacancies in ceria under reaction conditions. Water dissociation occurred on the O vacancy sites or the Cu-O vacancy interface. No significant amounts of formate were formed on the catalysts during the WGS reaction. The presence of strongly bound carbonates is an important factor for the deactivation of the catalysts at high temperatures. This work identifies for the first time the active sites for the WGS reaction on Cu-CeO{sub 2} catalysts and illustrates the importance of in situ structural studies for heterogeneous catalytic reactions.

  15. Selective hydrogenation of 1,3-cyclooctadiene and diphenylacetylene on copper using the water-gas shift reaction as a hydrogen source

    SciTech Connect

    Fragale, C.; Gargano, M.; Rossi, M.

    1983-04-01

    Selective catalytic hydrogenation of polyenes and acetylenes to monoolefins of a particular configuration is a matter of great interest in synthetic chemistry. Studies in this field have been principally devoted to the efficiency of catalytic systems and to the mechanism of the dihydrogen activation; many examples of stereo and regioselectivities have been discussed using either homogeneous or heterogeneous catalysts for the reduction of various compounds (substrates) with molecular hydrogen. In the course of studies on selective hydrogenation reactions catalyzed by transition metal derivatives, it has been found that water and carbon monoxide can be employed as reagents in place of the more expensive pure dihydrogen for the partial hydrogenation of 1,3-cyclooctadiene (C/sub 8/H/sub 12/) and of diphenylethyne (C/sub 14/H/sub 10/); these reactions are promoted by copper catalysts under relatively mild conditions. Experimental conditions and results are reported.

  16. Development of Novel Water-Gas Shift Membrane Reactor

    SciTech Connect

    Ho, W. S. Winston

    2004-12-29

    This report summarizes the objectives, technical barrier, approach, and accomplishments for the development of a novel water-gas-shift (WGS) membrane reactor for hydrogen enhancement and CO reduction. We have synthesized novel CO{sub 2}-selective membranes with high CO{sub 2} permeabilities and high CO{sub 2}/H{sub 2} and CO{sub 2}/CO selectivities by incorporating amino groups in polymer networks. We have also developed a one-dimensional non-isothermal model for the countercurrent WGS membrane reactor. The modeling results have shown that H{sub 2} enhancement (>99.6% H{sub 2} for the steam reforming of methane and >54% H{sub 2} for the autothermal reforming of gasoline with air on a dry basis) via CO{sub 2} removal and CO reduction to 10 ppm or lower are achievable for synthesis gases. With this model, we have elucidated the effects of system parameters, including CO{sub 2}/H{sub 2} selectivity, CO{sub 2} permeability, sweep/feed flow rate ratio, feed temperature, sweep temperature, feed pressure, catalyst activity, and feed CO concentration, on the membrane reactor performance. Based on the modeling study using the membrane data obtained, we showed the feasibility of achieving H{sub 2} enhancement via CO{sub 2} removal, CO reduction to {le} 10 ppm, and high H{sub 2} recovery. Using the membrane synthesized, we have obtained <10 ppm CO in the H{sub 2} product in WGS membrane reactor experiments. From the experiments, we verified the model developed. In addition, we removed CO{sub 2} from a syngas containing 17% CO{sub 2} to about 30 ppm. The CO{sub 2} removal data agreed well with the model developed. The syngas with about 0.1% CO{sub 2} and 1% CO was processed to convert the carbon oxides to methane via methanation to obtain <5 ppm CO in the H{sub 2} product.

  17. WATER-GAS SHIFT KINETICS OVER IRON OXIDE CATALYSTS AT MEMBRANE REACTOR CONDITIONS

    SciTech Connect

    Carl R.F. Lund

    2002-08-02

    The kinetics of water-gas shift were studied over ferrochrome catalysts under conditions with high carbon dioxide partial pressures, such as would be expected in a membrane reactor. The catalyst activity is inhibited by increasing carbon dioxide partial pressure. A microkinetic model of the reaction kinetics was developed. The model indicated that catalyst performance could be improved by decreasing the strength of surface oxygen bonds. Literature data indicated that adding either ceria or copper to the catalyst as a promoter might impart this desired effect. Ceria-promoted ferrochrome catalysts did not perform any better than unpromoted catalyst at the conditions tested, but copper-promoted ferrochrome catalysts did offer an improvement over the base ferrochrome material. A different class of water-gas shift catalyst, sulfided CoMo/Al{sub 2}O{sub 3} is not affected by carbon dioxide and may be a good alternative to the ferrochrome system, provided other constraints, notably the requisite sulfur level and maximum temperature, are not too limiting. A model was developed for an adiabatic, high-temperature water-gas shift membrane reactor. Simulation results indicate that an excess of steam in the feed (three moles of water per mole of CO) is beneficial even in a membrane reactor as it reduces the rate of adiabatic temperature rise. The simulations also indicate that much greater improvement can be attained by improving the catalyst as opposed to improving the membrane. Further, eliminating the inhibition by carbon dioxide will have a greater impact than will increasing the catalyst activity (assuming inhibition is still operative). Follow-up research into the use of sulfide catalysts with continued kinetic and reactor modeling is suggested.

  18. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Chanenchuk, C.A.; Yates, I.C.; Satterfield, C.N.

    1990-01-01

    A Co/MgO/SiO[sub 2] Fischer-Tropsch catalyst was operated simultaneously with a Cu/ZnO/Al[sub 2]O[sub 3] water-gas-shift catalyst in a slurry reactor for over 400 hours. The process conditions were held constant at a temperature of 240[degrees]C, a pressure of 0.79 MPa, and a 1.1 H[sub 2]/CO feed of 0.065 Nl/min-g.cat. The Fischer-Tropsch activity remained constant at the level predicted by the operation of the Co/MgO/SiO[sub 2] catalyst alone. The water-gas-shift reaction was near equilibrium. The hydrocarbon product distribution of the combined catalyst system was stable and matched that of the CO/MgO/SiO[sub 2] operating alone under similar conditions. The combined catalyst system exhibited a high selectivity to n-alkanes. Neither catalysts's operation appeared to have a detrimental effect on that of the other, showing promise for future option.

  19. Water-Gas Shift and Methane Reactivity on Reducible Perovskite-Type Oxides

    PubMed Central

    2015-01-01

    Comparative (electro)catalytic, structural, and spectroscopic studies in hydrogen electro-oxidation, the (inverse) water-gas shift reaction, and methane conversion on two representative mixed ionic–electronic conducting perovskite-type materials La0.6Sr0.4FeO3−δ (LSF) and SrTi0.7Fe0.3O3−δ (STF) were performed with the aim of eventually correlating (electro)catalytic activity and associated structural changes and to highlight intrinsic reactivity characteristics as a function of the reduction state. Starting from a strongly prereduced (vacancy-rich) initial state, only (inverse) water-gas shift activity has been observed on both materials beyond ca. 450 °C but no catalytic methane reforming or methane decomposition reactivity up to 600 °C. In contrast, when starting from the fully oxidized state, total methane oxidation to CO2 was observed on both materials. The catalytic performance of both perovskite-type oxides is thus strongly dependent on the degree/depth of reduction, on the associated reactivity of the remaining lattice oxygen, and on the reduction-induced oxygen vacancies. The latter are clearly more reactive toward water on LSF, and this higher reactivity is linked to the superior electrocatalytic performance of LSF in hydrogen oxidation. Combined electron microscopy, X-ray diffraction, and Raman measurements in turn also revealed altered surface and bulk structures and reactivities. PMID:26045733

  20. The Integration of a Structural Water Gas Shift Catalyst with a Vanadium Alloy Hydrogen Transport Device

    SciTech Connect

    Barton, Thomas; Argyle, Morris; Popa, Tiberiu

    2009-06-30

    component of conventional high temperature water gas shift iron oxide based catalysts. The catalysts contained Fe-Al-Cr-Cu-O and were synthesized by co-precipitation. A series of catalysts were prepared with 5 to 50 wt% Al2O3, with 8 wt% Cr2O3, 4 wt% CuO, and the balance Fe2O3. All of the catalysts were compared to a reference WGS catalyst (88 wt% FeOx, 8 wt% Cr2O3, and 4 wt% CuO) with no alumina. Alumina addition to conventional high temperature water gas shift catalysts at concentrations of approximately 15 wt% increased CO conversion rates and increase thermal stability. A series of high temperature water gas shift catalysts containing iron, chromia, and copper oxides were prepared with small amounts of added ceria in the system Fe-Cr-Cu-Ce-O. The catalysts were also tested kinetically under WGS conditions. 2-4 wt% ceria addition (at the expense of the iron oxide content) resulted in increased reaction rates (from 22-32% higher) compared to the reference catalyst. The project goal of a 10,000 liter per day WGS-membrane reactor was achieved by a device operating on coal derived syngas containing significant amounts of carbon monoxide and hydrogen sulfide. The membrane flux was equivalent to 52 scfh/ft2 based on a 600 psi syngas inlet pressure and corresponded to membranes costing $191 per square foot. Over 40 hours of iv exposure time to syngas has been achieved for a double membrane reactor. Two modules of the Chart reactor were tested under coal syngas for over 75 hours with a single module tested for 50 hours. The permeance values for the Chart membranes were similar to the REB reactor though total flux was reduced due to significantly thicker membranes. Overall testing of membrane reactors on coal derived syngas was over 115 hours for all reactors tested. Testing of the REB double membrane device exceeded 40 hours. Performance of the double membrane reactor has been similar to the results for the single reactor with good maintenance of flux even after these long

  1. Operation, Modeling and Analysis of the Reverse Water Gas Shift Process

    NASA Technical Reports Server (NTRS)

    Whitlow, Jonathan E.

    2001-01-01

    The Reverse Water Gas Shift process is a candidate technology for water and oxygen production on Mars under the In-Situ Propellant Production project. This report focuses on the operation and analysis of the Reverse Water Gas Shift (RWGS) process, which has been constructed at Kennedy Space Center. A summary of results from the initial operation of the RWGS, process along with an analysis of these results is included in this report. In addition an evaluation of a material balance model developed from the work performed previously under the summer program is included along with recommendations for further experimental work.

  2. Nucleophilic activation of coordinated carbon monoxide. Part 3. Hydroxide and methoxide reactions with the trinuclear clusters M/sub 3/(CO)/sub 12/ (M = Fe, Ru, or Os): implications with regard to catalysis of the water gas shift reaction

    SciTech Connect

    Gross, D.C.; Ford, P.C.

    1985-02-06

    Reported are quantitative investigations of the reactions of the triangular clusters M/sub 3/(CO)/sub 12/ (M = Fe, Ru, or Os) with methoxide ion in solution. In methanol under a CO atmosphere, both the osmium and ruthenium species form stable 1:1 methoxycarbonyl adducts (M/sub 3/(CO)/sub 12/ + NaOCH/sub 3/ in equilibrium (M/sub 3/(CO)/sub 11/(CO/sub 2/CH/sub 3/))Na); however, for the triiron analogue this adduct undergoes fragmentation to give Fe(CO)/sub 4/(CO/sub 2/CH/sub 3/)/sup -/. Initial adduct formation in each case occurs with an equilibrium constant of about 10/sup 3/ M/sup -1/. In mixed tetrahydrofuran/methanol solutions, K/sub eq/ for Ru/sub 3/(CO)/sub 11/(CO/sub 2/CH/sub 3/)/sup -/ is much larger, an indication of the greater activity of NaOCH/sub 3/ in the less protic solvent. Notably, in such solvent mixtures, the presence of excess methoxide also led to the formation of 2:1 adducts. Rates of adduct formation were examined by using stopped-flow kinetics techniques, and it was shown that in methanol the second-order rate constants (25/sup 0/C) are 11.3 x 10/sup 3/, 2.1 x 10/sup 3/, and 0.6 x 10/sup 3/ M/sup -1/ s/sup -1/ for Fe/sub 3/(CO)/sub 12/, Ru/sub 3/(CO)/sub 12/, and Os/sub 3/(CO)/sub 12/, respectively. Rates were much higher in the mixed THF(tetrahydro-furan)/CH/sub 3/OH solutions; for example, k/sub 1/ (25/sup 0/C) for Ru/sub 3/(CO)/sub 12/ is 2.0 x 10/sup 5/ M/sup -1/ s/sup -1/ in 90/10 THF/CH/sub 3/OH (v/v). Monosubstitution of the ruthenium cluster with (CH/sub 3/O)/sub 3/P markedly reduced the reactivity toward the anionic nucleophile. The reaction of the triruthenium species with hydroxide (Ru/sub 3/(CO)/sub 12/ + OH/sup -/ in equilibrium Ru/sub 3/(CO)/sub 11/(CO/sub 2/H)/sup -/ ..-->.. HRu/sub 3/(CO)/sub 11//sup -/ + CO/sub 2/) was also investigated. Analysis of the reaction kinetics leads to the conclusion that formation of the initial hydroxycarbonyl adduct is somewhat less favorable and is slower than the analogous reaction of

  3. Simulation and control of water-gas shift packed bed reactor with inter-stage cooling

    NASA Astrophysics Data System (ADS)

    Saw, S. Z.; Nandong, J.

    2016-03-01

    Water-Gas Shift Reaction (WGSR) has become one of the well-known pathways for H2 production in industries. The issue with WGSR is that it is kinetically favored at high temperatures but thermodynamically favored at low temperatures, thus requiring careful consideration in the control design in order to ensure that the temperature used does not deactivate the catalyst. This paper studies the effect of a reactor arrangement with an inter-stage cooling implemented in the packed bed reactor to look at its effect on outlet temperature. A mathematical model is developed based on one-dimensional heat and mass transfers which incorporate the intra-particle effects. It is shown that the placement of the inter-stage cooling and the outlet temperature exiting the inter-stage cooling have strong influence on the reaction conversion. Several control strategies are explored for the process. It is shown that a feedback- feedforward control strategy using Multi-scale Control (MSC) is effective to regulate the reactor temperature profile which is critical to maintaining the catalysts activity.

  4. A Cu/Pt Near-Surface Alloy for Water-Gas Shift Catalysis.

    SciTech Connect

    Knudsen, Jan; Nilekar, Anand U.; Vang, Ronnie T.; Schnadt, Joachim; Kunkes, Edward L.; Dumesic, James A.; Mavrikakis, Manos; Besenbacher, Fleming

    2007-05-01

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The primary route to hydrogen production from fossil fuels involves the water-gas shift (WGS) reaction, and an improvement in the efficiency of WGS catalysts could therefore lead to a major leap forward in the realization of hydrogen economy. On the basis of a combination of high-resolution scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations, we suggest the existence of a new thermodynamically stable Cu/Pt near-surface alloy (NSA). Temperature-programmed desorption and DFT reveal that this Cu/Pt NSA binds CO significantly more weakly than does Pt alone, thereby implying a considerable reduction in the potential for CO poisoning of the Cu/Pt NSA surface as compared to that of pure Pt. In addition, DFT calculations show that this Cu/Pt NSA is able to activate H2O easily, which is the rate-determining step for the WGS on several metal surfaces, and, at the same time, to bind the products of that reaction and formate intermediates rather weakly, thus avoiding possible poisoning of the catalyst surface. The Cu/Pt NSA is thus a promising candidate for an improved WGS catalyst.

  5. Au-mixed lanthanum/cerium oxide catalysts for water-gas-shift

    SciTech Connect

    Wang, Yanan; Liang, Shuang; Cao, Anmin; Thompson, Robert L; Veser, Goetz

    2010-08-01

    We report on the synthesis of highly homogeneous mixed La/Ce-oxides via a microemulsion-templated approach, and their evaluation as active supports for Au in the water gas shift (WGS) reaction. Both structure and reducibility of the oxides could be tailored by adjusting the La content across the entire range of La:Ce-ratios. The reducibility of the Au-free oxides shows an optimum at ∼25% La content, which can be traced back to improved oxygen mobility due to formation of oxygen vacancies and to the formation of more strongly bound oxygen upon La addition. Deposition of Au onto these oxides gives rise to an additional, low-temperature reduction peak, presumably due to hydrogen spill-over from the noble metal onto the oxide support. The WGS activity of Au/La{sub x}Ce{sub 1−x}O{sub 2−0.5x} catalysts correlates closely with the reducibility of the oxide supports, and hence with La content, demonstrating that carefully controlled synthesis of nanostructured catalysts with uniform, tailored composition allows for fine control of reactive properties of these materials, and might ultimately open the way towards a more rational design of catalysts.

  6. Microkinetics of water-gas shift over sulfided Mo/Al{sub 2}O{sub 3} catalysts

    SciTech Connect

    Lund, C.R.F.

    1996-08-01

    A microkinetic model was developed to explain the catalysis of the water-gas shift reaction by sulfided, alumina-supported molybdenum. IN this model, the reaction takes place through a regenerative (reduction-oxidation) scheme wherein the catalyst surface is alternately oxidized by water and then reduced by carbon monoxide. The surface of the catalyst is equilibrated with gas-phase H{sub 2}S under all reaction conditions studied. Coverages predicted by the model are consistent with the adsorption behavior of molybdenum sulfide catalysts. Simulations indicate that the effects of steam and H{sub 2}S levels are closely related. A maximum in CO conversion with increasing steam level may only occur at certain H{sub 2}S levels, and the ordering of CO conversion with increasing H{sub 2}S levels may invert as the steam level is changed.

  7. Integrated Water Gas Shift Membrane Reactors Utilizing Novel, Non Precious Metal Mixed Matrix Membrane

    SciTech Connect

    Ferraris, John

    2013-09-30

    Nanoparticles of zeolitic imidazolate frameworks and other related hybrid materials were prepared by modifying published synthesis procedures by introducing bases, changing stoichiometric ratios, or adjusting reaction conditions. These materials were stable at temperatures >300 °C and were compatible with the polymer matrices used to prepare mixed- matrix membranes (MMMs). MMMs tested at 300 °C exhibited a >30 fold increase in permeability, compared to those measured at 35 °C, while maintaining H{sub 2}/CO{sub 2} selectivity. Measurements at high pressure (up to 30 atm) and high temperature (up to 300 °C) resulted in an increase in gas flux across the membrane with retention of selectivity. No variations in permeability were observed at high pressures at either 35 or 300 °C. CO{sub 2}-induced plasticization was not observed for Matrimid®, VTEC, and PBI polymers or their MMMs at 30 atm and 300 °C. Membrane surface modification by cross-linking with ethanol diamine resulted in an increase in H{sub 2}/CO{sub 2} selectivity at 35 °C. Spectrometric analysis showed that the cross-linking was effective to temperatures <150 °C. At higher temperatures, the cross-linked membranes exhibit a H{sub 2}/CO{sub 2} selectivity similar to the uncross-linked polymer. Performance of the polybenzimidazole (PBI) hollow fibers prepared at Santa Fe Science and Technology (SFST, Inc.) showed increased flux o to a flat PBI membrane. A water-gas shift reactor has been built and currently being optimized for testing under DOE conditions.

  8. Catalytic and surface properties of nanocrystalline gold water gas shift catalysts

    NASA Astrophysics Data System (ADS)

    Kim, Chang Hwan

    A series of CeO2 supported gold catalysts were prepared and found to possess a high activities for the water gas shift reaction (WGS), a critical step in the production of H2 for use in petroleum refining, chemicals synthesis, and proton exchange membrane fuel cells. The deposition-precipitation method was employed in synthesizing these highly active, nanocrystalline gold catalysts. X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and dynamic sorption analyses were performed to characterize the gold catalysts. While some of these catalysts were initially four times more active than a commercial Cu-based catalyst, they were susceptible to deactivation. Characterization using techniques including temperature programmed oxidation, XPS, and FT-IR indicated that the deactivation was caused primarily by blockage of the active sites by carbonates and/or formates. Formation of these carbonaceous species appeared to be facilitated by oxygen deficient sites on the ceria surface and may have been associated with hydroxyl groups formed on the nanocrystalline gold particles under the H2 rich conditions. The deactivation could be managed by conditioning the CeO2 surface or adding constituents to minimize oxygen deficiency. The catalytic activity was fully recovered by calcining the deactivated materials in flowing air at elevated temperatures. The gold catalyst was washcoated onto microporous Fe-Al alloy foams for use in a micro-channel WGS reactor. The performance of these coated foams was inferior to that of the powder catalyst; however, a two stage micro-channel WGS reactor employing the gold catalyst was sufficient for a 100 W fuel processor system.

  9. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1988-01-01

    A cobalt Fischer-Tropsch catalyst (CO/MgO/silica) was reduced and slurried in combination with reduced Cu/ZnO/Al[sub 2]0[sub 3] water-gas-shift catalyst. Combined catalyst system was run at fixed process conditions for more than 400 hours. The system showed stable selectivity. The Cu/ZnO/Al[sub 2]0[sub 3] water-gas-shift catalyst remained reasonably active in the presence of the cobalt catalyst. Hydrocarbon selectivity of the cobalt and Cu/ZnO/Al[sub 2]0[sub 3] catalyst system compared favorably to selectivity of iron-based catalysts. Methane selectivity was slightly higher for the cobalt-based system, but C[sub 5][sup +] selectivity was essentially the same. The hydrocarbon product distribution appeared to exhibit a double-a behavior. a[sub 1] was near 0.80 which is higher than that of iron catalysts, while a[sub 2] was calculated to be 0.86 which is somewhat lower than would be typical for an iron-based catalyst.

  10. Iron-ceria Aerogels Doped with Palladium as Water-gas Shift Catalysts for the Production of Hydrogen

    SciTech Connect

    Bali, S.; Huggins, F; Ernst, R; Pugmire, R; Huffman, G; Eyring, E

    2010-01-01

    Mixed 4.5% iron oxide-95.5% cerium oxide aerogels doped with 1% and 2% palladium (Pd) by weight have been synthesized, and their activities for the catalysis of water-gas shift (WGS) reaction have been determined. The aerogels were synthesized using propylene oxide as the proton scavenger for the initiation of hydrolysis and polycondensation of a homogeneous alcoholic solution of cerium(III) chloride heptahydrate and iron(III) chloride hexahydrate precursor. Palladium was doped onto some of these materials by gas-phase incorporation (GPI) using ({eta}{sup 3}-allyl)({eta}{sup 5}-cyclopentadienyl)palladium as the volatile Pd precursor. Water-gas shift catalytic activities were evaluated in a six-channel fixed-bed reactor at atmospheric pressure and reaction temperatures ranging from 150 to 350 C. Both 1% and 2% Pd-doped 4.5% iron oxide-95.5% cerium oxide aerogels showed WGS activities that increased significantly from 150 to 350 C. The activities of 1% Pd-doped 4.5% iron oxide-95.5% cerium oxide aerogels were also compared with that of the 1% Pd-doped ceria aerogel without iron. The WGS activity of 1% Pd on 4.5% iron oxide-95.5% cerium oxide aerogels is substantially higher (5 times) than the activity of 1% Pd-doped ceria aerogel without iron. The gas-phase incorporation results in a better Pd dispersion. Ceria aerogel provides a nonrigid structure wherein iron is not significantly incorporated inside the matrix, thereby resulting in better contact between the Fe and Pd and thus enhancing the WGS activity. Further, neither Fe nor Pd is reduced during the ceria-aerogel-catalyzed WGS reaction. This behavior contrasts with that noted for other Fe-based WGS catalysts, in which the original ferric oxide is typically reduced to a nonstoichiometric magnetite form.

  11. An innovative catalyst system for slurry-phase Fischer-Tropsch synthesis: Cobalt plus a water-gas-shift catalyst

    SciTech Connect

    Satterfield, C.N.; Yates, I.C.; Chanenchuk, C.

    1991-07-01

    The feasibility of using a mechanical mixture of a Co/MgO/SiO{sub 2} Fischer-Tropsch catalyst and a Cu-ZnO/Al{sub 2}O{sub 3} water-gas-shift (WGS) catalyst for hydrocarbon synthesis in a slurry reactor has been established. Such a mixture can combine the superior product distribution from cobalt with the high activity for the WGS reaction characteristic of iron. Weight ratios of Co/MgO/SiO{sub 2} to Cu-ZnO/Al{sub 2}O{sub 3} of 0.27 and 0.51 for the two catalysts were studied at 240{degrees}C, 0.79 MPa, and in situ H{sub 2}/CO ratios between 0.8 and 3.0. Each catalyst mixture showed stable Fischer-Tropsch activity for about 400 hours-on-stream at a level comparable to the cobalt catalyst operating alone. The Cu-ZnO/Al{sub 2}O{sub 3} catalyst exhibited a very slow loss of activity under these conditions, but when operated alone it was stable in a slurry reactor at 200--220{degrees}C, 0.79--1.48 MPa, and H{sub 2}/CO in situ ratios between 1.0 and 2.0. The presence of the water-gas-shift catalyst did not affect the long-term stability of the primary Fischer-Tropsch selectivity, but did increase the extent of secondary reactions, such as l-alkene hydrogenation and isomerization.

  12. An Investigation of the Reverse Water Gas Shift Process and Operating Alternatives

    NASA Technical Reports Server (NTRS)

    Whitlow, Jonathan E.

    2002-01-01

    The Reverse Water Gas Shift (RWGS) process can produce water and ultimately oxygen through electrolysis. This technology is being investigated for possible use in the exploration of Mars as well as a potential process to aid in the regeneration of oxygen from carbon dioxide. The initial part of this report summarizes the results obtained from operation of the RWGS process at Kennedy Space Center during May and June of this year. It has been demonstrated that close to complete conversion can be achieved with the RWGS process under certain operating conditions. The report also presents results obtained through simulation for an alternative staged configuration for RWGS which eliminates the recycle compressor. This configuration looks promising and hence seems worthy of experimental investigation.

  13. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1988-01-01

    This report details experiments performed on three different copper-based catalysts: Cu/Cr[sub 2]O[sub 3], Cu/MnO/Cr[sub 2]O[sub 3] and Cu/ZnO/Al[sub 2]O[sub 3]. Of these three catalysts, the Cu/ZnO/Al[sub 2]O[sub 3] exhibits the greatest stability when slurried in octacosane. More than 1000 hours-on-stream indicate that the catalyst activity is not detrimentally affected by high pressure, high H[sub 2]/CO ratio, or the presence of alkenes. All of these are necessary stability characteristics for the water-gas shift catalyst, if it is to be used in combination with a cobalt Fischer-Tropsch catalyst. A review of documented reduction procedures for cobalt-based Fischer-Tropsch catalysts is presented.

  14. In situ/operando studies for the production of hydrogen through the water-gas shift on metal oxide catalysts.

    PubMed

    Rodriguez, José A; Hanson, Jonathan C; Stacchiola, Dario; Senanayake, Sanjaya D

    2013-08-01

    In this perspective article, we show how a series of in situ techniques {X-ray diffraction (XRD), pair-distribution-function analysis (PDF), X-ray absorption fine structure (XAFS), environmental transmission electron microscopy (ETEM), infrared spectroscopy (IR), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)} can be combined to perform detailed studies of the structural, electronic and chemical properties of metal oxide catalysts used for the production of hydrogen through the water-gas shift reaction (WGS, CO + H2O → H2 + CO2). Under reaction conditions most WGS catalysts undergo chemical transformations that drastically modify their composition with respect to that obtained during the synthesis process. Experiments of time-resolved in situ XRD, XAFS, and PDF indicate that the active phase of catalysts which combine Cu, Au or Pt with oxides such as ZnO, CeO2, TiO2, CeOx/TiO2 and Fe2O3 essentially involves nanoparticles of the reduced noble metals. The oxide support undergoes partial reduction and is not a simple spectator, facilitating the dissociation of water and in some cases modifying the chemical properties of the supported metal. Therefore, to optimize the performance of these catalysts one must take into consideration the properties of the metal and oxide phases. IR and AP-XPS have been used to study the reaction mechanism for the WGS on metal oxide catalysts. Data of IR spectroscopy indicate that formate species are not necessarily involved in the main reaction path for the water-gas shift on Cu-, Au- and Pt-based catalysts. Thus, a pure redox mechanism or associative mechanisms that involve either carbonate-like (CO3, HCO3) or carboxyl (HOCO) species should be considered. In the last two decades, there have been tremendous advances in our ability to study catalytic materials under reaction conditions and we are moving towards the major goal of fully understanding how the active sites for the production of hydrogen through the WGS actually

  15. Design of water gas shift catalysts for hydrogen production in fuel processors

    NASA Astrophysics Data System (ADS)

    Opalka, S. M.; Vanderspurt, T. H.; Radhakrishnan, R.; She, Y.; Willigan, R. R.

    2008-02-01

    Low sulfur hydrocarbon fuels can be converted to fuel cell grade H2 using a compact fuel processor architecture. The necessary high volumetric activity water gas shift (WGS) Pt on ceria-zirconia catalysts reacts CO-rich reformate with steam to yield H2 and CO2. Such highly selective, non-pyrophoric noble metal/Ce[1-(x+y)]ZrxDpyO2 catalysts were developed through coordinated atomic modeling, syntheses, structural characterization, kinetic performance tests, and micro-kinetic analyses. Density functional simulations made with the VASP code suggested that the undoped catalyst WGS activity would be limited by the strong binding of CO intermediates, blocking the reoxidation of the reduced oxide by water. These predictions were confirmed by in situ cylindrical internal reflection-Fourier transform infrared spectroscopy and by micro-kinetic analyses of the micro-reactor results. Atomic simulations were used to evaluate the impact transition metal dopants had on the surface chemistry of cubic ceria-zirconia. VASP predicted that acidic transition metal dopants such as Nb, Mo, Ta, and W would increase the oxide surface affinity for water and thus increase the turnover rate of the catalyst. The efficacy of Mo-doped ceria-zirconia compositions was confirmed at lower temperatures in replicated catalyst synthesis-reactor studies.

  16. Lyapunov-Based Sensor Failure Detection And Recovery For The Reverse Water Gas Shift Process

    NASA Technical Reports Server (NTRS)

    Haralambous, Michael G.

    2001-01-01

    Livingstone, a model-based AI software system, is planned for use in the autonomous fault diagnosis, reconfiguration, and control of the oxygen-producing reverse water gas shift (RWGS) process test-bed located in the Applied Chemistry Laboratory at KSC. In this report the RWGS process is first briefly described and an overview of Livingstone is given. Next, a Lyapunov-based approach for detecting and recovering from sensor failures, differing significantly from that used by Livingstone, is presented. In this new method, models used are in terms of the defining differential equations of system components, thus differing from the qualitative, static models used by Livingstone. An easily computed scalar inequality constraint, expressed in terms of sensed system variables, is used to determine the existence of sensor failures. In the event of sensor failure, an observer/estimator is used for determining which sensors have failed. The theory underlying the new approach is developed. Finally, a recommendation is made to use the Lyapunov-based approach to complement the capability of Livingstone and to use this combination in the RWGS process.

  17. LYAPUNOV-Based Sensor Failure Detection and Recovery for the Reverse Water Gas Shift Process

    NASA Technical Reports Server (NTRS)

    Haralambous, Michael G.

    2002-01-01

    Livingstone, a model-based AI software system, is planned for use in the autonomous fault diagnosis, reconfiguration, and control of the oxygen-producing reverse water gas shift (RWGS) process test-bed located in the Applied Chemistry Laboratory at KSC. In this report the RWGS process is first briefly described and an overview of Livingstone is given. Next, a Lyapunov-based approach for detecting and recovering from sensor failures, differing significantly from that used by Livingstone, is presented. In this new method, models used are in t e m of the defining differential equations of system components, thus differing from the qualitative, static models used by Livingstone. An easily computed scalar inequality constraint, expressed in terms of sensed system variables, is used to determine the existence of sensor failures. In the event of sensor failure, an observer/estimator is used for determining which sensors have failed. The theory underlying the new approach is developed. Finally, a recommendation is made to use the Lyapunov-based approach to complement the capability of Livingstone and to use this combination in the RWGS process.

  18. Modeling and Analysis of the Reverse Water Gas Shift Process for In-Situ Propellant Production

    NASA Technical Reports Server (NTRS)

    Whitlow, Jonathan E.

    2000-01-01

    This report focuses on the development of mathematical models and simulation tools developed for the Reverse Water Gas Shift (RWGS) process. This process is a candidate technology for oxygen production on Mars under the In-Situ Propellant Production (ISPP) project. An analysis of the RWGS process was performed using a material balance for the system. The material balance is very complex due to the downstream separations and subsequent recycle inherent with the process. A numerical simulation was developed for the RWGS process to provide a tool for analysis and optimization of experimental hardware, which will be constructed later this year at Kennedy Space Center (KSC). Attempts to solve the material balance for the system, which can be defined by 27 nonlinear equations, initially failed. A convergence scheme was developed which led to successful solution of the material balance, however the simplified equations used for the gas separation membrane were found insufficient. Additional more rigorous models were successfully developed and solved for the membrane separation. Sample results from these models are included in this report, with recommendations for experimental work needed for model validation.

  19. Atomic level study of water-gas shift catalysts via transmission electron microscopy and x-ray spectroscopy

    NASA Astrophysics Data System (ADS)

    Akatay, Mehmed Cem

    Water-gas shift (WGS), CO + H2O ⇆ CO2 + H2 (DeltaH° = -41 kJ mol -1), is an industrially important reaction for the production of high purity hydrogen. Commercial Cu/ZnO/Al2O3 catalysts are employed to accelerate this reaction, yet these catalysts suffer from certain drawbacks, including costly regeneration processes and sulfur poisoning. Extensive research is focused on developing new catalysts to replace the current technology. Supported noble metals stand out as promising candidates, yet comprise intricate nanostructures complicating the understanding of their working mechanism. In this study, the structure of the supported Pt catalysts is explored by transmission electron microscopy and X-ray spectroscopy. The effect of the supporting phase and the use of secondary metals on the reaction kinetics is investigated. Structural heterogeneities are quantified and correlated with the kinetic descriptors of the catalysts to develop a fundamental understanding of the catalytic mechanism. The effect of the reaction environment on catalyst structure is examined by in-situ techniques. This study benefitted greatly from the use of model catalysts that provide a convenient medium for the atomic level characterization of nanostructures. Based on these studies, Pt supported on iron oxide nano islands deposited on inert spherical alumina exhibited 48 times higher WGS turnover rate (normalized by the total Pt surface area) than Pt supported on bulk iron oxide. The rate of aqueous phase glycerol reforming reaction of Pt supported on multiwall carbon nanotubes (MWCNT) is promoted by co-impregnating with cobalt. The synthesis resulted in a variety of nanostructures among which Pt-Co bimetallic nanoparticles are found to be responsible for the observed promotion. The unprecedented WGS rate of Pt supported on Mo2C is explored by forming Mo 2C patches on top of MWCNTs and the rate promotion is found to be caused by the Pt-Mo bimetallic entities.

  20. Kinetic and spectroscopic study of catalysts for water-gas shift and nitrogen oxide removal

    NASA Astrophysics Data System (ADS)

    Kispersky, Vincent Frederick

    Hy variants modeled on Cu. The redox nature of the Cu active site was further investigated in a follow up study isolating the reducing portion of the SCR by removing O 2 from the reaction feed. Cutting off O2 drove the catalyst into a highly reduced state dominated by Cu(I) while removing a reductant drove the Cu into the fully oxidized state. Our research shows that not only is redox a vital part of the SCR reaction on Cu/zeolites, but that the oxidation state of the active site is highly sensitive to the gas environment. The water-gas shift (WGS) reaction is an industrially important step in H2 generation from steam reforming. I have had the opportunity to contribute to a number of studies in WGS by studying the catalysts in FTIR. We studied numerous catalytic formulations including Fe promoted Pd/Al 2O3 and Au/TiO2. We found that the Fe promoted the WGS rate of the catalyst by a factor of 160 compared to the Fe free Pd/Al 2O3. The reduced Fe promoter efficiently split H2O, typically the role performed by reducible supports, and the nearby noble metal particles provided spillover H2 to maintain the reduced Fe phase necessary to split H2O. Our study of Au/TiO2 involved the development of a modified operando transmission IR cell with ultra-low dead volume allowing for fast switching isotope experiments over the catalyst. The isotope switching experiments showed that only CO adsorbed on Au0 sites was an active surface intermediate at 120°C. Counting the amount of active surface Au atoms for the reaction ruled out the Au particle surface and perimeter atoms as the dominant active sites and confirmed our previous finding that the active site was composed mostly of low coordinated corner Au atoms.

  1. Kinetics of oxygen-enhanced water gas shift on bimetallic catalysts and the roles of metals and support

    NASA Astrophysics Data System (ADS)

    Kugai, Junichiro

    The post-processing of reformate is an important step in producing hydrogen (H2) with low carbon monoxide (CO) for low temperature fuel cells from syn-gas. However, the conventional process consists of three steps, i.e. two steps of water gas shift (WGS) and preferential oxidation (PROX) of CO, and it is not suitable for mobile applications due to the large volume of water gas shift (WGS) catalysts and conditioning and/or regeneration necessary for these catalysts. Aiming at replacing those three steps by a simple one-step process, small amount of oxygen was added to WGS (the reaction called oxygen-enhanced water gas shift or OWGS) to promote the reaction kinetics and low pyrophoric ceria-supported bimetallic catalysts were employed for stable performance in this reaction. Not only CO conversion, but also H2 yield was found to increase by the O2 addition on CeO2-supported catalysts. The characteristics of OWGS, high H2 production rate at 200 to 300°C at short contact time where unreacted O2 exists, evidenced the impact of O2 addition on surface species on the catalyst. Around 1.5 of reaction order in CO for various CeO2-supported metal catalysts for OWGS compared to reaction orders in CO ranging from -0.1 to 0.6 depending on metal species for WGS shows O2 addition decreases CO coverage to free up the active sites for co-reactant (H2O) adsorption and activation. Among the monometallic and bimetallic catalysts, Pt-Cu and Pd-Cu bimetallic catalysts were superior to monometallic catalysts in OWGS. These bimetallic components were found to form alloys where noble metal is surrounded mainly by Cu to have strong interaction between noble metal and copper resulting in high OWGS activity and low pyrophoric property. The metal loadings were optimized for CeO2-supported Pd-Cu bimetallic system and 2 wt% Pd with 5 -- 10 wt% Cu were found to be the optimum for the present OWGS condition. In the kinetic study, Pd in Pd-Cu was shown to increase the active sites for H2O

  2. Pilot Scale Water Gas Shift - Membrane Device for Hydrogen from Coal

    SciTech Connect

    Barton, Tom

    2013-06-30

    The objectives of the project were to build pilot scale hydrogen separation systems for use in a gasification product stream. This device would demonstrate fabrication and manufacturing techniques for producing commercially ready facilities. The design was a 2 lb/day hydrogen device which included composite hydrogen separation membranes, a water gas shift monolith catalyst, and stainless steel structural components. Synkera Technologies was to prepare hydrogen separation membranes with metallic rims, and to adjust the alloy composition in their membranes to a palladium-gold composition which is sulfur resistant. Chart was to confirm their brazing technology for bonding the metallic rims of the composite membranes to their structural components and design and build the 2 lbs/day device incorporating membranes and catalysts. WRI prepared the catalysts and completed the testing of the membranes and devices on coal derived syngas. The reactor incorporated eighteen 2'' by 7'' composite palladium alloy membranes. These membranes were assembled with three stacks of three paired membranes. Initial vacuum testing and visual inspection indicated that some membranes were cracked, either in transportation or in testing. During replacement of the failed membranes, while pulling a vacuum on the back side of the membranes, folds were formed in the flexible composite membranes. In some instances these folds led to cracks, primarily at the interface between the alumina and the aluminum rim. The design of the 2 lb/day device was compromised by the lack of any membrane isolation. A leak in any membrane failed the entire device. A large number of tests were undertaken to bring the full 2 lb per day hydrogen capacity on line, but no single test lasted more than 48 hours. Subsequent tests to replace the mechanical seals with brazing have been promising, but the technology remains promising but not proven.

  3. Parametric Gasification of Oak and Pine Feedstocks Using the TCPDU and Slipstream Water-Gas Shift Catalysis

    SciTech Connect

    Hrdlicka, J.; Feik, C.; Carpenter, D.; Pomeroy, M.

    2008-12-01

    With oak and pine feedstocks, the Gasification of Biomass to Hydrogen project maximizes hydrogen production using the Full Stream Reformer during water-gas shift fixed-bed reactor testing. Results indicate that higher steam-to-biomass ratio and higher thermal cracker temperature yield higher hydrogen concentration. NREL's techno-economic models and analyses indicate hydrogen production from biomass may be viable at an estimated cost of $1.77/kg (current) and $1.47/kg (advanced in 2015). To verify these estimates, NREL used the Thermochemical Process Development Unit (TCPDU), an integrated system of unit operations that investigates biomass thermochemical conversion to gaseous and liquid fuels and chemicals.

  4. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, July 1, 1990--September 30, 1990

    SciTech Connect

    Chanenchuk, C.A.; Yates, I.C.; Satterfield, C.N.

    1990-12-31

    A Co/MgO/SiO{sub 2} Fischer-Tropsch catalyst was operated simultaneously with a Cu/ZnO/Al{sub 2}O{sub 3} water-gas-shift catalyst in a slurry reactor for over 400 hours. The process conditions were held constant at a temperature of 240{degrees}C, a pressure of 0.79 MPa, and a 1.1 H{sub 2}/CO feed of 0.065 Nl/min-g.cat. The Fischer-Tropsch activity remained constant at the level predicted by the operation of the Co/MgO/SiO{sub 2} catalyst alone. The water-gas-shift reaction was near equilibrium. The hydrocarbon product distribution of the combined catalyst system was stable and matched that of the CO/MgO/SiO{sub 2} operating alone under similar conditions. The combined catalyst system exhibited a high selectivity to n-alkanes. Neither catalysts`s operation appeared to have a detrimental effect on that of the other, showing promise for future option.

  5. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Final technical progress report, September 12, 1991--December 11, 1994

    SciTech Connect

    Klier, K.; Herman, R.G.; Deemer, M.; Richards-Babb, M.; Carr, T.

    1995-07-01

    The objective of this research was to investigate sulfur-resistant catalysts for the conversion of synthesis gas having H{sub 2}/CO {le} 1 into C{sub 1}--C{sub 4} alcohols, especially ethanol, by a highly selective and efficient pathway, while also promoting the water gas shift reaction (WGSR). The catalysts chosen are bifunctional, base-hydrogenation, sulfur-tolerant transition metal sulfides with heavy alkali, e.g. Cs{sup +}, promoter dispersed on their surfaces. The modes of activation of H{sub 2} and CO on MoS{sub 2} and alkali-doped MoS{sub 2} were considered, and computational analyses of the thermodynamic stability of transition metal sulfides and of the electronic structure of these sulfide catalysts were carried out. In the preparation of the cesium-promoted MoS{sub 2} catalysts, a variety of preparation methods using CsOOCH were examined. In all cases, doping with CsOOCH led to a lost of surface area. The undoped molybdenum disulfide catalyst only produced hydrocarbons. Cs-doped MoS{sub 2} catalysts all produced linear alcohols, along with smaller amounts of hydrocarbons. With a 20 wt% CsOOCH/MoS{sub 2} catalyst, temperature, pressure, and flow rate dependences of the synthesis reactions were investigated in the presence and absence of H{sub 2}S in the H{sub 2}/CO = 1/1 synthesis gas during short term testing experiments. It was shown that with a carefully prepared 10 wt% CsOOCH/MoS{sub 2} catalyst, reproducible and high alcohol synthesis activity could be obtained. For example, at 295 C with H{sub 2}/CO = 1 synthesis gas at 8.3 MPa and with GHSV = 7,760 l/kg cat/hr, the total alcohol space time yield was ca 300 g/kg cat/hr (accompanied with a hydrocarbon space time yield of ca 60 g/kg cat/hr). Over a testing period of ca 130 hr, no net deactivation of the catalyst was observed. 90 refs., 82 figs., 14 tabs.

  6. An innovative catalyst system for slurry-phase Fischer-Tropsch synthesis: Cobalt plus a water-gas-shift catalyst. Final technical report

    SciTech Connect

    Satterfield, C.N.; Yates, I.C.; Chanenchuk, C.

    1991-07-01

    The feasibility of using a mechanical mixture of a Co/MgO/SiO{sub 2} Fischer-Tropsch catalyst and a Cu-ZnO/Al{sub 2}O{sub 3} water-gas-shift (WGS) catalyst for hydrocarbon synthesis in a slurry reactor has been established. Such a mixture can combine the superior product distribution from cobalt with the high activity for the WGS reaction characteristic of iron. Weight ratios of Co/MgO/SiO{sub 2} to Cu-ZnO/Al{sub 2}O{sub 3} of 0.27 and 0.51 for the two catalysts were studied at 240{degrees}C, 0.79 MPa, and in situ H{sub 2}/CO ratios between 0.8 and 3.0. Each catalyst mixture showed stable Fischer-Tropsch activity for about 400 hours-on-stream at a level comparable to the cobalt catalyst operating alone. The Cu-ZnO/Al{sub 2}O{sub 3} catalyst exhibited a very slow loss of activity under these conditions, but when operated alone it was stable in a slurry reactor at 200--220{degrees}C, 0.79--1.48 MPa, and H{sub 2}/CO in situ ratios between 1.0 and 2.0. The presence of the water-gas-shift catalyst did not affect the long-term stability of the primary Fischer-Tropsch selectivity, but did increase the extent of secondary reactions, such as l-alkene hydrogenation and isomerization.

  7. Transition metal carbides, nitrides and borides, and their oxygen containing analogs useful as water gas shift catalysts

    DOEpatents

    Thompson, Levi T.; Patt, Jeremy; Moon, Dong Ju; Phillips, Cory

    2003-09-23

    Mono- and bimetallic transition metal carbides, nitrides and borides, and their oxygen containing analogs (e.g. oxycarbides) for use as water gas shift catalysts are described. In a preferred embodiment, the catalysts have the general formula of M1.sub.A M2.sub.B Z.sub.C O.sub.D, wherein M1 is selected from the group consisting of Mo, W, and combinations thereof; M2 is selected from the group consisting of Fe, Ni, Cu, Co, and combinations thereof; Z is selected from the group consisting of carbon, nitrogen, boron, and combinations thereof; A is an integer; B is 0 or an integer greater than 0; C is an integer; O is oxygen; and D is 0 or an integer greater than 0. The catalysts exhibit good reactivity, stability, and sulfur tolerance, as compared to conventional water shift gas catalysts. These catalysts hold promise for use in conjunction with proton exchange membrane fuel cell powered systems.

  8. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Chanenchuk, C.A.; Yates, I.C.; Satterfield, C.N.

    1990-01-01

    Experiments to study the cobalt-catalyzed and iron-catalyzed reactions of light 1-alkenes added to synthesis gas have been performed and analyzed. On cobalt, data have been obtained at 220{degrees}C, 0.45 to 1.48 MPA and a synthesis gas flow rate between 0.015 and 0.030 Nl/gcat/min with H{sub 2}/CO feeds of 1.45 to 2.25. On fused iron, data were collected at 248{degrees}C, 0.79 to 1.48 MPa and a synthesis gas flow rate between 0.005 and 0.030 Nl/gcat/min of H{sub 2}/CO feeds of 0.5 to 1.5 C{sub 2}H{sub 4}, C{sub 3}H{sub 6}, and 1-C{sub 4}H{sub 8} were added to the synthesis gas feed in concentrations ranging from 0.5 to 1.2 mol. % of total feed. 1-Alkenes incorporate into growing chains on the catalyst surface of both catalysts, probably by initiating and/or terminating the chain growth process. Only ethene is believed to propagate chain growth significantly. The propensity of the 1-alkenes to incorporate decreases with increasing carbon number of the 1-alkene. The double-{alpha} behavior which is exhibited by most Fischer-Tropsch catalysts can be explained as the sum of two growth processes, one stepwise single-carbon growth and the other 1-alkene incorporation. Both alkene addition study data and the effects of process variables on the selectivity of Fischer-Tropsch catalysts can be explained within the framework of this theory. 19 refs., 12 figs., 2 tabs.

  9. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1990-01-01

    Experiments on cobalt-catalyzed reactions of light 1-alkenes added to synthesis gas were performed. Data have been collected at 220C, 0.45 to 1.48 MPa and a synthesis gas flow rate between 0.015 and 0.030 Nl/(gcat[center dot]min) with H[sub 2]/CO of 1.45 to 2.25. Ethylene, propene, and butene were added to synthesis gas feed from 0.5 to 1.2 mole% of total feed. For each material balance in which 1-alkenes were added, a material balance was performed at similar process conditions without 1-alkenes added, as base case''. Material balances without added 1-alkenes were also repeated to verify of catalyst selectivity stability. 49 material balances were performed during a single run lasting over 2,500 hours-on-stream. The hydrocarbon data have been completely analyzed; data correlations are still being made. Since C[sub 3]/C[sub 1] ratios by ethene addition, C[sub 4]/C[sub 1] ratios by propene addition, and C[sub 5]/C[sub 1] ratios by 1-butene addition, it appears that 1-alkenes may incorporate into growing chains on the surface of the catalyst. Further evidence for incorporation can be seen by comparing selectivity to n-alcohol one carbon number higher than added 1-alkene. Yield of this n-alcohol increases when alkenes are present. Sensitivity of hydrocarbon distribution to process variables seems to be greater on Co than on Fe catalysts.

  10. Robust Low-Cost Water-Gas Shift Membrane Reactor for High-Purity Hydrogen Production form Coal-Derived Syngas

    SciTech Connect

    James Torkelson; Neng Ye; Zhijiang Li; Decio Coutinho; Mark Fokema

    2008-05-31

    This report details work performed in an effort to develop a low-cost, robust water gas shift membrane reactor to convert coal-derived syngas into high purity hydrogen. A sulfur- and halide-tolerant water gas shift catalyst and a sulfur-tolerant dense metallic hydrogen-permeable membrane were developed. The materials were integrated into a water gas shift membrane reactor in order to demonstrate the production of >99.97% pure hydrogen from a simulated coal-derived syngas stream containing 2000 ppm hydrogen sulfide. The objectives of the program were to (1) develop a contaminant-tolerant water gas shift catalyst that is able to achieve equilibrium carbon monoxide conversion at high space velocity and low steam to carbon monoxide ratio, (2) develop a contaminant-tolerant hydrogen-permeable membrane with a higher permeability than palladium, (3) demonstrate 1 L/h purified hydrogen production from coal-derived syngas in an integrated catalytic membrane reactor, and (4) conduct a cost analysis of the developed technology.

  11. Kinetic and spectroscopic study of catalysts for water-gas shift and nitrogen oxide removal

    NASA Astrophysics Data System (ADS)

    Kispersky, Vincent Frederick

    adsorbed CO2 proved less competitive for NOx sorption sites, explaining the weak reduction of NSC by CO2 on low Ba loadings. Contrary to CO2, H2O exhibited both beneficial and inhibitory effects on the NSC. Over long periods of time, and at high Ba loadings, the addition of H2O in the feed increased the NSC, attributed to enhanced O2 spillover on the hydroxylated Ba surface allowing greater access to available NOx storage sites. When the Ba loading was reduced, the interaction sphere of Pt particles with the Ba storage component required for O2 to spillover to assist in NOx storage was reduced. Thus, despite the enhanced spillover capacity of oxygen on the hydroxylated storage component other NSC decreasing effects of H2O addition, such as Ba agglomeration, became more dominant and reduced the NSC. Recent developments in selective catalytic reduction have shown Cu and Fe/chabazite (CHA) based zeolites to be particularly well suited to sustaining high catalytic rates without degradation in the harsh environment of diesel engine exhaust. Little has been published about these catalysts as the academic community has just recently learned about the materials and their commercial implementation. Using operando X-ray absorption spectroscopy, combined with first-principles thermodynamics simulations and kinetic analysis, we have studied the nature of the Cu active site on Cu/SSZ-13, Cu/SAPO-34 and Cu/ZSM-5. Examining the catalysts under operando standard SCR conditions (300 ppm NO, 300 ppm NH3, 5% O2, 5% H2O and 5% CO2) showed the catalyst to be in a mixed Cu(I)-Cu(II) oxidation state. Neither the amount of Cu(I) nor Cu(II) individually correlated with the different rates measured on the various zeolite catalysts, and so we proposed that the SCR reaction progresses via a redox mechanism requiring both Cu(I) and Cu(II). First principles thermodynamic calculations found that the redox couple of Cu(I)H2O and Cu(II)(OH)2 were the most thermodynamically stable species of any of the Ox

  12. Reverse Water-Gas Shift or Sabatier Methanation on Ni(110)? Stable Surface Species at Near-Ambient Pressure.

    PubMed

    Roiaz, Matteo; Monachino, Enrico; Dri, Carlo; Greiner, Mark; Knop-Gericke, Axel; Schlögl, Robert; Comelli, Giovanni; Vesselli, Erik

    2016-03-30

    The interaction of CO, CO2, CO + H2, CO2 + H2, and CO + CO2 + H2 with the nickel (110) single crystal termination has been investigated at 10(-1) mbar in situ as a function of the surface temperature in the 300-525 K range by means of infrared-visible sum frequency generation (IR-vis SFG) vibrational spectroscopy and by near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). Several stable surface species have been observed and identified. Besides atomic carbon and precursors for graphenic C phases, five nonequivalent CO species have been distinguished, evidencing the role of coadsorption effects with H and C atoms, of H-induced activation of CO, and of surface reconstruction. At low temperature, carbonate species produced by the interaction of CO2 with atomic oxygen, which stems from the dissociation of CO2 into CO + O, are found on the surface. A metastable activated CO2(-) species is also detected, being at the same time a precursor state toward dissociation into CO and O in the reverse water-gas shift mechanism and a reactive species that undergoes direct conversion in the Sabatier methanation process. Finally, the stability of ethylidyne is deduced on the basis of our spectroscopic observations. PMID:26954458

  13. Water-Gas-Shift Membrane Reactor for High-Pressure Hydrogen Production. A comprehensive project report (FY2010 - FY2012)

    SciTech Connect

    Klaehn, John; Peterson, Eric; Orme, Christopher; Bhandari, Dhaval; Miller, Scott; Ku, Anthony; Polishchuk, Kimberly; Narang, Kristi; Singh, Surinder; Wei, Wei; Shisler, Roger; Wickersham, Paul; McEvoy, Kevin; Alberts, William; Howson, Paul; Barton, Thomas; Sethi, Vijay

    2013-01-01

    Idaho National Laboratory (INL), GE Global Research (GEGR), and Western Research Institute (WRI) have successfully produced hydrogen-selective membranes for water-gas-shift (WGS) modules that enable high-pressure hydrogen product streams. Several high performance (HP) polymer membranes were investigated for their gas separation performance under simulated (mixed gas) and actual syngas conditions. To enable optimal module performance, membranes with high hydrogen (H2) selectivity, permeance, and stability under WGS conditions are required. The team determined that the VTEC PI 80-051 and VTEC PI 1388 (polyimide from Richard Blaine International, Inc.) are prime candidates for the H2 gas separations at operating temperatures (~200°C). VTEC PI 80-051 was thoroughly analyzed for its H2 separations under syngas processing conditions using more-complex membrane configurations, such as tube modules and hollow fibers. These membrane formats have demonstrated that the selected VTEC membrane is capable of providing highly selective H2/CO2 separation (α = 7-9) and H2/CO separation (α = 40-80) in humidified syngas streams. In addition, the VTEC polymer membranes are resilient within the syngas environment (WRI coal gasification) at 200°C for over 1000 hours. The information within this report conveys current developments of VTEC PI 80-051 as an effective H2 gas separations membrane for high-temperature syngas streams.

  14. Sorption-Enhanced Synthetic Natural Gas (SNG) Production from Syngas. A Novel Process Combining CO Methanation, Water-Gas Shift, and CO2 Capture

    SciTech Connect

    Lebarbier, Vanessa M.C.; Dagle, Robert A.; Kovarik, Libor; Albrecht, Karl O.; Li, Xiaohong S.; Li, Liyu; Taylor, Charles E.; Bao, Xinhe; Wang, Yong

    2013-07-08

    Synthetic natural gas (SNG) production from syngas is under investigation again due to the desire for less dependency from imports and the opportunity for increasing coal utilization and reducing green house gas emission. CO methanation is highly exothermic and substantial heat is liberated which can lead to process thermal imbalance and deactivation of the catalyst. As a result, conversion per pass is limited and substantial syngas recycle is employed in conventional processes. Furthermore, the conversion of syngas to SNG is typically performed at moderate temperatures (275 to 325°C) to ensure high CH4 yields since this reaction is thermodynamically limited. In this study, the effectiveness of a novel integrated process for the SNG production from syngas at high temperature (i.e. 600°C) was investigated. This integrated process consists of combining a CO methanation nickel-based catalyst with a high temperature CO2 capture sorbent in a single reactor. Integration with CO2 separation eliminates the reverse-water-gas shift and the requirement for a separate water-gas shift (WGS) unit. Easing of thermodynamic constraint offers the opportunity of enhancing yield to CH4 at higher operating temperature (500-700ºC) which also favors methanation kinetics and improves the overall process efficiency due to exploitation of reaction heat at higher temperatures. Furthermore, simultaneous CO2 capture eliminates green house gas emission. In this work, sorption-enhanced CO methanation was demonstrated using a mixture of a 68% CaO/32% MgAl2O4 sorbent and a CO methanation catalyst (Ni/Al2O3, Ni/MgAl2O4, or Ni/SiC) utilizing a syngas ratio (H2/CO) of 1, gas-hour-space velocity (GHSV) of 22 000 hr-1, pressure of 1 bar and a temperature of 600°C. These conditions resulted in ~90% yield to methane, which was maintained until the sorbent

  15. Redox cycle stability of mixed oxides used for hydrogen generation in the cyclic water gas shift process

    SciTech Connect

    Datta, Pradyot

    2013-10-15

    Graphical abstract: - Highlights: • Fe{sub 2}O{sub 3} modified with CaO, SiO{sub 2} and Al{sub 2}O{sub 3} was studied in cyclic water gas shift reactor. • For the first time stability of such oxides were tested for 100 redox cycles. • Optimally added oxides significantly improved the activity and the stability of Fe{sub 2}O{sub 3}. • Increased stability was attributed to the impediment of neck formation. - Abstract: Repeated cycles of the reduction of Fe{sub 3}O{sub 4} with reductive gas, e.g. hydrogen and subsequent oxidation of the reduced iron material with water vapor can be harnessed as a process for the production of pure hydrogen. The redox behavior of iron oxide modified with various amounts of SiO{sub 2}, CaO and Al{sub 2}O{sub 3} was investigated in the present study. The total amount of the additional metal oxides was always below 15 wt%. The samples were prepared by co-precipitation using urea hydrolysis method. The influence of various metal oxides on the hydrogen production capacity and the material stability was studied in detail in terms of temperature-programmed reduction (TPR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET analysis. Furthermore, the activity and the stability of the samples were tested in repeated reduction with diluted H{sub 2} and re-oxidation cycles with H{sub 2}O. The results indicate that combination of several oxides as promoter increases the stability of the iron oxide material by mitigating the sintering process. The positive influence of the oxides in stabilizing the iron oxide material is attributed to the impediment of neck formation responsible for sintering.

  16. Highly Effective Pt-Based Water-Gas Shift Catalysts by Surface Modification with Alkali Hydroxide Salts

    SciTech Connect

    Kusche, Matthias; Bustillo, Karen; Agel, Friederike; Wasserscheid, Peter

    2015-01-29

    Here, we describe an economical and convenient method to improve the performance of Pt/alumina catalysts for the water–gas shift reaction through surface modification of the catalysts with alkali hydroxides according to the solid catalyst with ionic liquid layer approach. The results are in agreement with our findings reported earlier for methanol steam reforming. This report indicates that alkali doping of the catalyst plays an important role in the observed catalyst activation. In addition, the basic and hygroscopic nature of the salt coating contributes to a significant improvement in the performance of the catalyst. During the reaction, a partly liquid film of alkali hydroxide forms on the alumina surface, which increases the availability of H2O at the catalytically active sites. Kinetic studies reveal a negligible effect of the KOH coating on the rate dependence of CO and H2O partial pressures. In conclusion, TEM studies indicate an agglomeration of the active Pt clusters during catalyst preparation; restructuring of Pt nanoparticles occurs under reaction conditions, which leads to a highly active and stable system over 240h time on stream. Excessive pore fillings with KOH introduce a mass transfer barrier as indicated in a volcano-shaped curve of activity versus salt loading. The optimum KOH loading was found to be 7.5wt%.

  17. Highly Effective Pt-Based Water-Gas Shift Catalysts by Surface Modification with Alkali Hydroxide Salts

    DOE PAGESBeta

    Kusche, Matthias; Bustillo, Karen; Agel, Friederike; Wasserscheid, Peter

    2015-01-29

    Here, we describe an economical and convenient method to improve the performance of Pt/alumina catalysts for the water–gas shift reaction through surface modification of the catalysts with alkali hydroxides according to the solid catalyst with ionic liquid layer approach. The results are in agreement with our findings reported earlier for methanol steam reforming. This report indicates that alkali doping of the catalyst plays an important role in the observed catalyst activation. In addition, the basic and hygroscopic nature of the salt coating contributes to a significant improvement in the performance of the catalyst. During the reaction, a partly liquid filmmore » of alkali hydroxide forms on the alumina surface, which increases the availability of H2O at the catalytically active sites. Kinetic studies reveal a negligible effect of the KOH coating on the rate dependence of CO and H2O partial pressures. In conclusion, TEM studies indicate an agglomeration of the active Pt clusters during catalyst preparation; restructuring of Pt nanoparticles occurs under reaction conditions, which leads to a highly active and stable system over 240h time on stream. Excessive pore fillings with KOH introduce a mass transfer barrier as indicated in a volcano-shaped curve of activity versus salt loading. The optimum KOH loading was found to be 7.5wt%.« less

  18. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, October 1, 1988--December 31, 1988

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1988-12-31

    A cobalt Fischer-Tropsch catalyst (CO/MgO/silica) was reduced and slurried in combination with reduced Cu/ZnO/Al{sub 2}0{sub 3} water-gas-shift catalyst. Combined catalyst system was run at fixed process conditions for more than 400 hours. The system showed stable selectivity. The Cu/ZnO/Al{sub 2}0{sub 3} water-gas-shift catalyst remained reasonably active in the presence of the cobalt catalyst. Hydrocarbon selectivity of the cobalt and Cu/ZnO/Al{sub 2}0{sub 3} catalyst system compared favorably to selectivity of iron-based catalysts. Methane selectivity was slightly higher for the cobalt-based system, but C{sub 5}{sup +} selectivity was essentially the same. The hydrocarbon product distribution appeared to exhibit a double-a behavior. a{sub 1} was near 0.80 which is higher than that of iron catalysts, while a{sub 2} was calculated to be 0.86 which is somewhat lower than would be typical for an iron-based catalyst.

  19. Magnetic susceptibility as a direct measure of oxidation state in LiFePO4 batteries and cyclic water gas shift reactors.

    PubMed

    Kadyk, Thomas; Eikerling, Michael

    2015-08-14

    The possibility of correlating the magnetic susceptibility to the oxidation state of the porous active mass in a chemical or electrochemical reactor was analyzed. The magnetic permeability was calculated using a hierarchical model of the reactor. This model was applied to two practical examples: LiFePO4 batteries, in which the oxidation state corresponds with the state-of-charge, and cyclic water gas shift reactors, in which the oxidation state corresponds to the depletion of the catalyst. In LiFePO4 batteries phase separation of the lithiated and delithiated phases in the LiFePO4 particles in the positive electrode gives rise to a hysteresis effect, i.e. the magnetic permeability depends on the history of the electrode. During fast charge or discharge, non-uniform lithium distributionin the electrode decreases the hysteresis effect. However, the overall sensitivity of the magnetic response to the state-of-charge lies in the range of 0.03%, which makes practical measurement challenging. In cyclic water gas shift reactors, the sensitivity is 4 orders of magnitude higher and without phase separation, no hysteresis occurs. This shows that the method is suitable for such reactors, in which large changes of the magnetic permeability of the active material occurs. PMID:26156571

  20. Water Gas Shift Reaction with A Single Stage Low Temperature Membrane Reactor

    SciTech Connect

    Ciora, Richard J; Liu, Paul KT

    2013-12-31

    Palladium membrane and Palladium membrane reactor were developed under this project for hydrogen separation and purification for fuel cell applications. A full-scale membrane reactor was designed, constructed and evaluated for the reformate produced from a commercial scale methanol reformer. In addition, the Pd membrane and module developed from this project was successfully evaluated in the field for hydrogen purification for commercial fuel cell applications.

  1. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, June 30, 1988--September 30, 1988

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1988-12-31

    This report details experiments performed on three different copper-based catalysts: Cu/Cr{sub 2}O{sub 3}, Cu/MnO/Cr{sub 2}O{sub 3} and Cu/ZnO/Al{sub 2}O{sub 3}. Of these three catalysts, the Cu/ZnO/Al{sub 2}O{sub 3} exhibits the greatest stability when slurried in octacosane. More than 1000 hours-on-stream indicate that the catalyst activity is not detrimentally affected by high pressure, high H{sub 2}/CO ratio, or the presence of alkenes. All of these are necessary stability characteristics for the water-gas shift catalyst, if it is to be used in combination with a cobalt Fischer-Tropsch catalyst. A review of documented reduction procedures for cobalt-based Fischer-Tropsch catalysts is presented.

  2. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Technical progress report, September 1993--November 1993

    SciTech Connect

    Klier, K.; Herman, R.; Deemer, M.

    1994-03-01

    During calcination of the precipitated and dried MoS{sub 3} to form MOS{sub 2}, it was found that small sample sizes were needed to provide thermal control of the highly exothermic decomposition reaction in the 8 mm ID quartz tube used for this purpose. Characterization of MoS{sub 2} and Cs/MoS{sub 2} catalysts have been carried out by X-ray powder diffraction (XRD) after each synthesis step. In addition, the XRD analyses were conducted after prolonged air exposure of the Cs-doped MoS{sub 2} catalyst. It was shown that prolonged exposure to the ambient atmosphere led to segregation and crystallization of the cesium formate dopant. Thus, catalytic testing should be carried out with freshly prepared samples that are protected from the ambient atmosphere. Catalytic testing is underway to determine if there is an inverse correlation of catalytic activity and selectivity with prolonged air exposure of the catalyst.

  3. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst, January 1, 1990--March 30, 1990

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1990-01-01

    Experiments to study cobalt-catalyzed reactions of light 1-alkenes added to synthesis gas feed have been performed. Data have been collected at 220{degrees}C, 0.45 to 1.48 MPa and a synthesis gas flow rate between 0.015 and 0.030 Nl/(gcatmin) with H{sub 2}/CO of 1.45 to 2.25. C{sub 2}H{sub 4}, C{sub 3}H{sub 6}, and C{sub 4}H{sub 8} were added to the synthesis gas feed in concentrations ranging from 0.5 to 1.2 mole% of total feed. For each material balance in which 1-alkenes were added, a material balance was performed at similar process conditions without 1-alkenes added. This use of base case'' process conditions should make data analysis and interpretation easier. Material balances without 1-alkenes were also repeated to allow verification of catalyst selectivity stability. A total of 49 balances were performed during a single run which lasted over 2500 hours-on-stream. The hydrocarbon data have not yet been completed analyzed.

  4. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst, January 1, 1990--March 30, 1990

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1990-12-31

    Experiments to study cobalt-catalyzed reactions of light 1-alkenes added to synthesis gas feed have been performed. Data have been collected at 220{degrees}C, 0.45 to 1.48 MPa and a synthesis gas flow rate between 0.015 and 0.030 Nl/(gcatmin) with H{sub 2}/CO of 1.45 to 2.25. C{sub 2}H{sub 4}, C{sub 3}H{sub 6}, and C{sub 4}H{sub 8} were added to the synthesis gas feed in concentrations ranging from 0.5 to 1.2 mole% of total feed. For each material balance in which 1-alkenes were added, a material balance was performed at similar process conditions without 1-alkenes added. This use of ``base case`` process conditions should make data analysis and interpretation easier. Material balances without 1-alkenes were also repeated to allow verification of catalyst selectivity stability. A total of 49 balances were performed during a single run which lasted over 2500 hours-on-stream. The hydrocarbon data have not yet been completed analyzed.

  5. Determination of the Effect of Coal/Biomass-Derived Syngas Contaminants on the Performance of Fischer-Tropsch and Water-Gas-Shift Catalysts

    SciTech Connect

    Trembly, Jason; Cooper, Matthew; Farmer, Justin; Turk, Brian; Gupta, Raghubir

    2010-12-31

    Today, nearly all liquid fuels and commodity chemicals are produced from non-renewable resources such as crude oil and natural gas. Because of increasing scrutiny of carbon dioxide (CO{sub 2}) emissions produced using traditional fossil-fuel resources, the utilization of alternative feedstocks for the production of power, hydrogen, value-added chemicals, and high-quality hydrocarbon fuels such as diesel and substitute natural gas (SNG) is critical to meeting the rapidly growing energy needs of modern society. Coal and biomass are particularly attractive as alternative feedstocks because of the abundant reserves of these resources worldwide. The strategy of co-gasification of coal/biomass (CB) mixtures to produce syngas for synthesis of Fischer-Tropsch (FT) fuels offers distinct advantages over gasification of either coal or biomass alone. Co-feeding coal with biomass offers the opportunity to exploit economies of scale that are difficult to achieve in biomass gasification, while the addition of biomass to the coal gasifier feed leverages proven coal gasification technology and allows CO{sub 2} credit benefits. Syngas generated from CB mixtures will have a unique contaminant composition because coal and biomass possess different concentrations and types of contaminants, and the final syngas composition is also strongly influenced by the gasification technology used. Syngas cleanup for gasification of CB mixtures will need to address this unique contaminant composition to support downstream processing and equipment. To investigate the impact of CB gasification on the production of transportation fuels by FT synthesis, RTI International conducted thermodynamic studies to identify trace contaminants that will react with water-gas-shift and FT catalysts and built several automated microreactor systems to investigate the effect of single components and the synergistic effects of multiple contaminants on water-gas-shift and FT catalyst performance. The contaminants

  6. Effect of adding Co to MoS{sub 2}/Al{sub 2}O{sub 3} upon the kinetics of the water-gas shift

    SciTech Connect

    Lund, C.R.F.

    1996-09-01

    A microkinetic model for the kinetics of the water-gas shift over sulfided CoMo/Al{sub 2}O{sub 3} catalysts was developed starting from a similar model for unpromoted sulfided Mo/Al{sub 2}O{sub 3} catalysts. Co was found to promote the catalyst`s activity only at low CO/H{sub 2}O ratios; at high ratios the Mo catalyst was marginally more active than the CoMo catalyst. The most important different between the two models was the strength of interactions between the surface and hydroxyl groups. The addition of Co increased the stability of hydroxyl groups relative to sulfhydryl groups, and at higher H{sub 2}O concentrations this allowed oxidized surface sites to more readily participate in both steam adsorption and hydrogen desorption steps. The results are most easily reconciled in terms of a promotional model where the Co and Mo are in close proximity and the active sites are similar to sites on unpromoted Mo catalysts.

  7. Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

    SciTech Connect

    Alptekin, Gokhan

    2013-02-15

    Co-gasification of biomass and coal in large-scale, Integrated Gasification Combined Cycle (IGCC) plants increases the efficiency and reduces the environmental impact of making synthesis gas ("syngas") that can be used in Coal-Biomass-to-Liquids (CBTL) processes for producing transportation fuels. However, the water-gas shift (WGS) and Fischer-Tropsch synthesis (FTS) catalysts used in these processes may be poisoned by multiple contaminants found in coal-biomass derived syngas; sulfur species, trace toxic metals, halides, nitrogen species, the vapors of alkali metals and their salts (e.g., KCl and NaCl), ammonia, and phosphorous. Thus, it is essential to develop a fundamental understanding of poisoning/inhibition mechanisms before investing in the development of any costly mitigation technologies. We therefore investigated the impact of potential contaminants (H2S, NH3, HCN, AsH3, PH3, HCl, NaCl, KCl, AS3, NH4NO3, NH4OH, KNO3, HBr, HF, and HNO3) on the performance and lifetime of commercially available and generic (prepared in-house) WGS and FT catalysts.

  8. Energy-shifting formulae yield reliable reaction and capture probabilities

    NASA Astrophysics Data System (ADS)

    Diaz-Torres, A.; Adamian, G. G.; Sargsyan, V. V.; Antonenko, N. V.

    2014-12-01

    Predictions of energy-shifting formulae for partial reaction and capture probabilities are compared with coupled channels calculations. The quality of the agreement notably improves with increasing mass of the system and/or decreasing mass asymmetry in the heavy-ion collision. The formulae are reliable and useful for circumventing impracticable reaction calculations at low energies.

  9. Water gas furnace

    SciTech Connect

    Gallaro, C.

    1985-12-03

    A water gas furnace comprising an outer container to provide a housing in which coke is placed into its lower part. A water container is placed within the housing. The coke is ignited and heats the water in the container converting it into steam. The steam is ejected into the coke, which together with air, produces water gas. Preferably, pumice stones are placed above the coke. The water gas is accepted into the pores of the pumice stones, where the heated pumice stones ignite the water gas, producing heat. The heat is extracted by a heat exchanger provided about the housing.

  10. Investigation of the Reverse Water Gas Shift Reaction for Production of Oxygen From Mars Atmospheric Carbon Dioxide

    NASA Technical Reports Server (NTRS)

    Meyer, Tom; Zubrin, Robert

    1997-01-01

    The first phase of the research includes a comprehensive analytical study examining the potential applications for engineering subsystems and mission strategies made possible by such RWGS based subsystems, and will include an actual experimental demonstration and performance characterization of a full-scale brassboard RWGS working unit. By the time of this presentation the laboratory demonstration unit will not yet be operational but we will present the results of our analytical studies to date and plans for the ongoing work.

  11. CO2 SELECTIVE CERAMIC MEMBRANE FOR WATER-GAS SHIFT REACTION WITH CONCOMITANT RECOVERY OF CO2

    SciTech Connect

    Paul K.T. Liu

    2002-08-01

    As part of our optimization effort, we have conducted a comprehensive study to investigate the morphology and crystal growth kinetics of hydrotalcite powder formation. Based upon the information obtained from this study, we resumed the membrane optimization activities. Although the selectivity of the membrane remains in the Knudsen regime, the permeance decreases along with the number of impregnation. Thus, the permeance could be reduced to a minimum through repeated impregnation. Then, the membrane can be sealed with chemical vapor deposition technique. More characterization results on the membranes prepared will be available in the next quarterly report.

  12. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burton Davis; Gary Jacobs; Wenping Ma; Dennis Sparks; Khalid Azzam; Janet Chakkamadathil Mohandas; Wilson Shafer; Venkat Ramana Rao Pendyala

    2011-09-30

    There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased. Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations. In the second and third years, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H

  13. Low Temperature Water-Gas Shift: Type and Loading Impacts Forward Decomposition of Pseudo-Stabilized Formate over Metal/Ceria Catalysts

    SciTech Connect

    Jacobs,G.; Ricote, S.; Graham, U.; Patterson, P.; Davis, B.

    2005-01-01

    A similar degree of surface shell reduction of ceria was obtained for a series of metal/ceria catalysts. Surface formate species were generated by reaction of CO with bridging OH groups associated with the Ce{sup 3+} defects. Forward decomposition of the pseudo-stable formates was followed in flowing H{sub 2}O, leading to the production of surface carbonate species. The forward formate decomposition rate was enhanced changing the promoter from Au to Pt, and by increasing the promoter loading (from 0.5 to 2.5%). Results suggest that formate C{single_bond}H bond breaking is not only facilitated by H{sub 2}O, but it is further enhanced by type and loading of metal promoter. From earlier kinetic isotope effect and isotopic tracer studies, the rate-limiting step of the forward formate decomposition (WGS reaction) was considered to be associated with C{single_bond}H bond rupture of the formate. The results can explain the promotion in the WGS rates observed for these samples by changing from Au to Pt and by increasing the promoter loading.

  14. Low Temperature Water-Gas Shift: Type and Loading of Metal Impacts Decomposition and Hydrogen Exchange Rates of Pseudo-stabilized Formate over Metal/ceria Catalysts

    SciTech Connect

    Jacobs,G.; Ricote, S.; Davis, B.

    2006-01-01

    In this investigation, a similar degree of surface shell reduction among a series of metal promoted ceria catalysts was established by diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) and X-ray absorption near-edge spectroscopy (XANES) measurements. Surface formate species were generated by reaction of CO with bridging OH groups associated with the Ce{sup 3+} defect sites. The thermal decomposition of the pseudo-stable formates was followed in the absence of H2O. Decomposition and exchange from H to D of the pseudo-stabilized formate was enhanced by changing the promoter from Au to Pt. Likewise, an increase was observed in both decomposition and exchange rates by increasing the promoter loading from 0.5 to 2.5 wt.%. The results suggest that C{single_bond}H bond breaking is facilitated during this thermal decomposition (i.e., reverse decomposition to CO and {single_bond}OH). Therefore, since the rate limiting step of the forward formate decomposition (i.e., the WGS reaction) is strongly suggested to be associated with C{single_bond}H bond cleaving in the formate intermediate (based on earlier kinetic isotope effect and isotopic tracer studies), the results can explain the promotion in the WGS rates as observed by changing from Au to Pt and by increased promoter loading.

  15. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, April 1, 1990--June 30, 1990

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1990-12-31

    Experiments on cobalt-catalyzed reactions of light 1-alkenes added to synthesis gas were performed. Data have been collected at 220C, 0.45 to 1.48 MPa and a synthesis gas flow rate between 0.015 and 0.030 Nl/(gcat{center_dot}min) with H{sub 2}/CO of 1.45 to 2.25. Ethylene, propene, and butene were added to synthesis gas feed from 0.5 to 1.2 mole% of total feed. For each material balance in which 1-alkenes were added, a material balance was performed at similar process conditions without 1-alkenes added, as ``base case``. Material balances without added 1-alkenes were also repeated to verify of catalyst selectivity stability. 49 material balances were performed during a single run lasting over 2,500 hours-on-stream. The hydrocarbon data have been completely analyzed; data correlations are still being made. Since C{sub 3}/C{sub 1} ratios by ethene addition, C{sub 4}/C{sub 1} ratios by propene addition, and C{sub 5}/C{sub 1} ratios by 1-butene addition, it appears that 1-alkenes may incorporate into growing chains on the surface of the catalyst. Further evidence for incorporation can be seen by comparing selectivity to n-alcohol one carbon number higher than added 1-alkene. Yield of this n-alcohol increases when alkenes are present. Sensitivity of hydrocarbon distribution to process variables seems to be greater on Co than on Fe catalysts.

  16. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalystes to Poisons form High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burton Davis; Gary Jacobs; Wenping Ma; Khalid Azzam; Janet ChakkamadathilMohandas; Wilson Shafer

    2009-09-30

    There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased. Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations.

  17. Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

    SciTech Connect

    Burtron Davis; Gary Jacobs; Wenping Ma; Khalid Azzam; Dennis Sparks; Wilson Shafer

    2010-09-30

    The successful adaptation of conventional cobalt and iron-based Fischer-Tropsch synthesis catalysts for use in converting biomass-derived syngas hinges in part on understanding their susceptibility to byproducts produced during the biomass gasification process. With the possibility that oil production will peak in the near future, and due to concerns in maintaining energy security, the conversion of biomass-derived syngas and syngas derived from coal/biomass blends to Fischer-Tropsch synthesis products to liquid fuels may provide a sustainable path forward, especially considering if carbon sequestration can be successfully demonstrated. However, one current drawback is that it is unknown whether conventional catalysts based on iron and cobalt will be suitable without proper development because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using an entrained-flow oxygen-blown gasifier) than solely from coal, other byproducts may be present in higher concentrations. The current project examines the impact of a number of potential byproducts of concern from the gasification of biomass process, including compounds containing alkali chemicals like the chlorides of sodium and potassium. In the second year, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H{sub 2}S and NH{sub 3}. Cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts were also subjected to a number of the same compounds in order to evaluate their sensitivities.

  18. Three model space experiments on chemical reactions. [Gibbs adsorption, equilibrium shift and electrodeposition

    NASA Technical Reports Server (NTRS)

    Grodzka, P.; Facemire, B.

    1977-01-01

    Three investigations conducted aboard Skylab IV and Apollo-Soyuz involved phenomena that are of interest to the biochemistry community. The formaldehyde clock reaction and the equilibrium shift reaction experiments conducted aboard Apollo Soyuz demonstrate the effect of low-g foams or air/liquid dispersions on reaction rate and chemical equilibrium. The electrodeposition reaction experiment conducted aboard Skylab IV demonstrate the effect of a low-g environment on an electrochemical displacement reaction. The implications of the three space experiments for various applications are considered.

  19. Density Functional Theory and Reaction Kinetics Studies of the Water–Gas Shift Reaction on Pt–Re Catalysts

    SciTech Connect

    Carrasquillo-Flores, Ronald; Gallo, Jean Marcel R.; Hahn, Konstanze; Dumesic, James A.; Mavrikakis, Manos

    2013-11-05

    Periodic, self-consistent density functional theory calculations (DFT-GGA-PW91) on Pt(111) and Pt3Re(111) surfaces, reaction kinetics measurements, and microkinetic modeling are employed to study the mechanism of the water–gas shift (WGS) reaction over Pt and Pt–Re catalysts. The values of the reaction rates and reaction orders predicted by the model are in agreement with the ones experimentally determined; the calculated apparent activation energies are matched to within 6% of the experimental values. The primary reaction pathway is predicted to take place through adsorbed carboxyl (COOH) species, whereas formate (HCOO) is predicted to be a spectator species. We conclude that the clean Pt(111) is a good representation of the active site for the WGS reaction on Pt catalysts, whereas the active sites on the Pt–Re alloy catalyst likely contain partially oxidized metal ensembles.

  20. Theoretical Investigation of Intramolecular Hydrogen Shift Reactions in 3-Methyltetrahydrofuran (3-MTHF) Oxidation.

    PubMed

    Parab, Prajakta R; Sakade, Naoki; Sakai, Yasuyuki; Fernandes, Ravi; Heufer, K Alexander

    2015-11-01

    3-Methyltetrahydrofuran (3-MTHF) is proposed to be a promising fuel component among the cyclic oxygenated species. To have detailed insight of its combustion kinetics, intramolecular hydrogen shift reactions for the ROO to QOOH reaction class are studied for eight ROO isomers of 3-MTHF. Rate constants of all possible reaction paths that involve formation of cyclic transition states are computed by employing the CBS-QB3 composite method. A Pitzer-Gwinn-like approximation has been applied for the internal rotations in reactants, products, and transition states for the accurate treatment of hindered rotors. Calculated relative barrier heights highlight that the most favorable reaction channel proceeds via a six membered transition state, which is consistent with the computed rate constants. Comparing total rate constants in ROO isomers of 3-MTHF with the corresponding isomers of methylcyclopentane depicts faster kinetics in 3-MTHF than methylcyclopentane reflecting the effect of ring oxygen on the intramolecular hydrogen shift reactions. PMID:26444499

  1. Evaluation of C-14 as a natural tracer for injected fluids at theAidlin sector of The Geysers geothermal system through modeling ofmineral-water-gas Reactions

    SciTech Connect

    Dobson, Patrick; Sonnenthal, Eric; Lewicki, Jennifer; Kennedy, Mack

    2006-06-01

    A reactive-transport model for 14C was developed to test its applicability to the Aidlin geothermal system. Using TOUGHREACT, we developed a 1-D grid to evaluate the effects of water injection and subsequent water-rock-gas interaction on the compositions of the produced fluids. A dual-permeability model of the fracture-matrix system was used to describe reaction-transport processes in which the permeability of the fractures is many orders of magnitude higher than that of the rock matrix. The geochemical system included the principal minerals (K-feldspar, plagioclase, calcite, silica polymorphs) of the metagraywackes that comprise the geothermal reservoir rocks. Initial simulation results predict that the gas-phase CO2 in the reservoir will become more enriched in 14C as air-equilibrated injectate water (with a modern carbon signature) is incorporated into the system, and that these changes will precede accompanying decreases in reservoir temperature. The effects of injection on 14C in the rock matrix will be lessened somewhat because of the dissolution of matrix calcite with ''dead'' carbon.

  2. Evaluation of C-14 as a natural tracer for injected fluids at theAidlin sector of The Geysers geothermal system through modeling ofmineral-water-gas Reactions

    SciTech Connect

    Dobson, Patrick; Sonnenthal, Eric; Lewicki, Jennifer; Kennedy, Mack

    2006-06-01

    A reactive-transport model for 14C was developed to test itsapplicability to the Aidlin geothermal system. Using TOUGHREACT, wedeveloped a 1-D grid to evaluate the effects of water injection andsubsequent water-rock-gas interaction on the compositions of the producedfluids. A dual-permeability model of the fracture-matrix system was usedto describe reaction-transport processes in which the permeability of thefractures is many orders of magnitude higher than that of the rockmatrix. The geochemical system included the principal minerals(K-feldspar, plagioclase, calcite, silica polymorphs) of themetagraywackes that comprise the geothermal reservoir rocks. Initialsimulation results predict that the gas-phase CO2 in the reservoir willbecome more enriched in 14C as air-equilibrated injectate water (with amodern carbon signature) is incorporated into the system, and that thesechanges will precede accompanying decreases in reservoir temperature. Theeffects of injection on 14C in the rock matrix will be lessened somewhatbecause of the dissolution of matrix calcite with "dead"carbon.

  3. Electronic shift register memory based on molecular electron-transfer reactions

    NASA Technical Reports Server (NTRS)

    Hopfield, J. J.; Onuchic, Jose Nelson; Beratan, David N.

    1989-01-01

    The design of a shift register memory at the molecular level is described in detail. The memory elements are based on a chain of electron-transfer molecules incorporated on a very large scale integrated (VLSI) substrate, and the information is shifted by photoinduced electron-transfer reactions. The design requirements for such a system are discussed, and several realistic strategies for synthesizing these systems are presented. The immediate advantage of such a hybrid molecular/VLSI device would arise from the possible information storage density. The prospect of considerable savings of energy per bit processed also exists. This molecular shift register memory element design solves the conceptual problems associated with integrating molecular size components with larger (micron) size features on a chip.

  4. High-Throughput Electrophoretic Mobility Shift Assays for Quantitative Analysis of Molecular Binding Reactions

    PubMed Central

    2015-01-01

    We describe a platform for high-throughput electrophoretic mobility shift assays (EMSAs) for identification and characterization of molecular binding reactions. A photopatterned free-standing polyacrylamide gel array comprised of 8 mm-scale polyacrylamide gel strips acts as a chassis for 96 concurrent EMSAs. The high-throughput EMSAs was employed to assess binding of the Vc2 cyclic-di-GMP riboswitch to its ligand. In optimizing the riboswitch EMSAs on the free-standing polyacrylamide gel array, three design considerations were made: minimizing sample injection dispersion, mitigating evaporation from the open free-standing polyacrylamide gel structures during electrophoresis, and controlling unit-to-unit variation across the large-format free-standing polyacrylamide gel array. Optimized electrophoretic mobility shift conditions allowed for 10% difference in mobility shift baseline resolution within 3 min. The powerful 96-plex EMSAs increased the throughput to ∼10 data/min, notably more efficient than either conventional slab EMSAs (∼0.01 data/min) or even microchannel based microfluidic EMSAs (∼0.3 data/min). The free-standing polyacrylamide gel EMSAs yielded reliable quantification of molecular binding and associated mobility shifts for a riboswitch–ligand interaction, thus demonstrating a screening assay platform suitable for riboswitches and potentially a wide range of RNA and other macromolecular targets. PMID:25233437

  5. Combining steam-methane reforming, water-gas shift, and CO{sub 2} removal in a single-step process for hydrogen production. Final report for period March 15, 1997 - December 14, 2000

    SciTech Connect

    Alejandro Lopez Ortiz; Bhaskar Balasubramanian; Douglas P. Harrison

    2001-02-01

    The objective of the research project was to determine the feasibility of a simpler, more energy-efficient process for the production of 95+% H{sub 2} from natural gas, and to collect sufficient experimental data on the effect of reaction parameters to guide additional larger-scale process development. The overall objectives were accomplished. 95+% H{sub 2} was produced in a single reaction step by adding a calcium-based CO{sub 2} acceptor to standard Ni-based reforming catalyst. The spent acceptor was successfully regenerated and used in a number of reaction steps with only moderate loss in activity as the number of cycles increased. Sufficient experimental data were collected to guide further larger-scale experimental work designed to investigate the economic feasibility of the process.

  6. Unusually Facile Thermal Homodienyl-[1,5]-Hydrogen Shift Reactions in Photochemically Generated Vinyl Aziridines.

    PubMed

    Knowles, Jonathan P; Booker-Milburn, Kevin I

    2016-08-01

    A range of photochemically generated tri- and tetracyclic vinyl aziridines have been found to undergo a general and surprisingly low temperature ring opening through a [1,5]-hydrogen shift reaction. The rate of the process was found to be highly dependent on the structure and substitution around the azirdine ring and the alkene terminus, with some substrates being observed to undergo ring opening at temperatures as low as 25 °C. The rigid nature of these polycyclic systems precludes a conformational explanation of these rate differences, and an Eyring study confirmed a negligible entropic barrier to the reaction. However, the Eyring plots for two different aziridines systems showed a significant difference in their enthalpies of activation. It is therefore believed that the levels of aziridine ring strain, as well as electronic effects, are the dominant factors in this sequence. PMID:27380942

  7. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts

    SciTech Connect

    Klier, K.; Herman, R.G.; Deemer, M.

    1992-12-01

    During this quarter, the surface areas of various catalysts were determined. The surface area of the catalyst tested last quarter was determined for the undoped catalyst, the doped catalyst before testing, and the doped catalyst after testing. These surface areas were then compared with ones reported earlier. After testing under high temperature and high pressure conditions for 551 hours, there was a loss of surface area. This might be due possibly to agglomeration of cesium formate on the surface. Higher surface area catalysts were also produced. Two samples of MoS[sub 2] were synthesized with surface areas of 96 m2/g and 91 m2/g. These were obtained by varying the heating rate of MoS[sub 3] and the calcination temperature.

  8. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts

    SciTech Connect

    Klier, K.; Herman, R.G.; Richards-Babb, M.

    1992-06-01

    During this quarter, the high pressure (up to 100 atm), high temperature (up to 350{degrees}C) catalyst testing system was rebuilt with clean tubing, etc. A new preparation of MoS{sub 2} catalyst was carried out, and this catalyst will be doped with alkali and tested during the next quarter of research.

  9. Difunctionalization of Alkenes via the Visible-Light-Induced Trifluoromethylarylation/1,4-Aryl Shift/Desulfonylation Cascade Reactions.

    PubMed

    Zheng, Lewei; Yang, Chao; Xu, ZhaoZhong; Gao, Fei; Xia, Wujiong

    2015-06-01

    A novel visible-light-induced trifluoromethylarylation/1,4-aryl shift/desulfonylation cascade reaction using CF3SO2Cl as CF3 source was described. The protocol provides an efficient approach for the synthesis of α-aryl-β-trifluoromethyl amides and/or CF3-containing oxindoles as well as the isoquinolinediones under benign conditions. PMID:25955879

  10. Lamb shift in radical-ion pairs produces a singlet-triplet energy splitting in photosynthetic reaction centers

    NASA Astrophysics Data System (ADS)

    Vitalis, K. M.; Kominis, I. K.

    2014-09-01

    Radical-ion pairs, fundamental for understanding photosynthesis and the avian magnetic compass, were recently shown to be biological open quantum systems. We here show that the coupling of the radical-pair spin degrees of freedom to its decohering vibrational reservoir leads to a shift of the radical-pair magnetic energy levels. The Lamb shift Hamiltonian is diagonal in the singlet-triplet basis, and results in a singlet-triplet energy splitting physically indistinguishable from an exchange interaction. This could have significant implications for understanding the energy level structure and the dynamics of photosynthetic reaction centers.

  11. A surface-plasmon resonance phase modulation bio-reaction detection system with (5,1) phase-shifting algorithm

    NASA Astrophysics Data System (ADS)

    Chen, Yi-Hung; Lee, Shu-Sheng; Hsu, I.-Hung; Tseng, Eddie; Lee, Chih-Kung

    2007-12-01

    Surface plasmon resonance (SPR) is a very important metrology in biology detection. Phase modulation is one of the SPR detection technologies and the sample changes can be recognized from the phase variation. It is able to detect very tiny bio sample variation due to its high sensitivity. In this study, the optical system design based on a paraboloidal lens-based surface plasmon resonance instrument will be used to control the SPR critical angle. The charge coupled device camera (CCD camera) will be used to record the images of the bio-reaction and (5,1) phase-shifting algorithm will be adopted to retrieve the phase fringes of the whole spot from the intensity maps. The combination of the angle control SPR system and the (5,1) phase-shifting algorithm will expand the whole spot detection ability from the intensity to phase modulation because the intensity maps are going to be recorded for the (5,1) phase-shifting algorithm calculation. The difference between (5,1) phase-shifting algorithm and Five-Step Algorithm1 is that (5,1) phase-shifting algorithm only needs one image map at one time during the bio reaction and Five-Step Algorithm requires five image maps. Therefore, (5,1) phase-shifting algorithm will reduce the process of experiment and the requirement of the memory. The different concentration alcohols were measured by the optical system to verify the (5,1) phase-shifting algorithm applied in SPR phase modulation measurement and to prove the idea is workable and successful.

  12. Features of the reaction of heterocyclic analogs of chalcone with lanthanide shift reagents

    SciTech Connect

    Turov, A.V.; Khilya, V.P.

    1994-10-01

    The PMR spectra of heterocyclic analogs of 2-hydroxychalcone containing thiazole, benzofuran, triazole, imidazole, benzodioxane, or pyridine rings in the presence of lanthanide shift reagents are studied. It is found that the most effective reagent for modifying the spectra of these compounds is Yb(fod)3. The broadening of the spectra of 2-hydroxy chalcones in the presence of lanthanide shift reagents is explained by the dynamic effects of complex formation. An example is given of the determination of the conformation of molecules of 2-hydroxychalcone by the simultaneous use of lanthanide shift reagents and the homonuclear Overhauser effect. 9 refs., 1 fig., 1 tab.

  13. Nanoconfined nitrogen hydrogenation on Ru(0001): Prediction of entropy related shifts in the reaction equilibria

    NASA Astrophysics Data System (ADS)

    Polak, Micha; Rubinovich, Leonid

    2015-11-01

    Remarkable variations in NHx (x = 1,2,3) equilibrium molecular fractions are revealed by statistical-mechanical computations for a system composed of only few reactant atoms that are confined to nanoscale Ru(0001) surface. Using one of two sets of reported DFT-based reaction energetics as input, NH formation on the flat surface is enhanced up to ~ 50% compared to the thermodynamic limit (TL) of the macroscopic system. This nanoconfinement entropic effect on chemical equilibrium (NCECE), introduced and demonstrated by us before for some hypothetical reactions, originates from mixing entropy reduction in the small-system that increases the product molecular fraction in exothermic reactions, as is fully elucidated here for the case of NH. The other input set gives an opposite effect due to the reaction endothermicity on both flat and stepped surfaces. For concurrent ND and NH formation, including H - D exchange, the temperature and coverage dependent superposition of the three NCECE contributions have a significant effect on two of the three equilibrium constants of the coupled reactions, and increase/decrease the ND/NH fractions. The computed TL low fractions of NH2 and NH3 in the coupled three hydrogenation steps are further diminished by the NCECE, suggesting that from this aspect ammonia synthesis on smaller particles is expected to be less effective.

  14. Enhancement of Equilibrium Shift in Dehydrogenation Reactions Using A Novel Membrane Reactor

    SciTech Connect

    Franklin G. King; Shamsuddin Ilias

    1998-05-27

    Electroless deposition of palladium thin-films on a surface of microporous ceramic substrate has been used to develop a new class of perm-selective inorganic membrane. In our previous two reports, we presented mathematical models to describe transport of hydrogen the palladium-ceramic composite membrane in single-stage permeation cell in cocurrent and countercurrent flow configurations. Analysis shows that the model equations have a singular point. In this report, a method is described how to avoid the singular point in order to solve the model equations numerically. To show the usefulness of the new method, a single-stage gas permeation for a three component system, without chemical reaction under cocurrent flow configuration has been used as an example.

  15. Rh(II)-catalyzed reaction of alpha-diazocarbonyl compounds bearing beta-trichloroacetylamino substituent: C-H insertion versus 1,2-H shift.

    PubMed

    Zhang, Zhenhua; Shi, Weifeng; Zhang, Jian; Zhang, Bo; Liu, Bingge; Liu, Yiyang; Fan, Bo; Xiao, Fengping; Xu, Feng; Wang, Jianbo

    2010-05-01

    The Rh(II)-carbene reaction is dramatically affected by the neighboring substituents. If the neighboring substituent is an OH group, a1,2-H shift is the exclusive pathway. If it is an OAc group, a 1,2-acetoxy migration is observed. If it is p-toluenesulfonyl group, 1,3 and 1,5-C-H insertion are the major pathways, and the 1,2-H shift is completely suppressed. If the adjacent substituent is a trichloroacetyl amino group, 1,5-C-H insertion competes with the 1,2-hydride shift, and no 1,3-C-H insertion can be observed. Both electronic and steric factors are responsible for the switching of the Rh(II)-carbene reaction pathway. The highly stereoselective 1,5-C-H insertions in Rh(II)-catalyzed reaction of alpha-diazocarbonyl compounds, bearing beta-trichloroacetylamino substituent, can be utilized as a novel way to synthesize five-membered cyclic beta-amino acid derivatives. PMID:20013998

  16. Characterization of reaction between ZnO and COS

    SciTech Connect

    Sasaoka, Eiji; Taniguchi, Kazuo; Uddin, M.A.; Hirano, Shigeru; Kasaoka, Shigeaki; Sakata, Yusaku

    1996-07-01

    In order to understand the behavior of COS in a ZnO desulfurization reactor, the reaction between ZnO and COS was studied in the presence of gases which compose a coal-derived gas. The behavior of COS in the reaction zone of a ZnO packed bed can be predicted as follows: H{sub 2}S in coal-derived gas reacts more easily with ZnO than COS; most of COS is converted to H{sub 2}S by catalytic hydrolysis and then reacts with ZnO, although a part of COS may react directly with ZnO; H{sub 2} accelerates the conversion of COS to H{sub 2}S; the water-gas shift reaction accelerates the reaction between ZnO and COS; and CO{sub 2} does not affect the reaction.

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

    NASA Astrophysics Data System (ADS)

    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.

  18. Computational Chemistry-Based Identification of Ultra-Low Temperature Water-Gas-Shift Catalysts

    SciTech Connect

    Manos Mavrikakis

    2008-08-31

    The current work seeks to identify novel, catalytically-active, stable, poison-resistant LWGS catalysts that retain the superior activity typical of conventional Cu catalysts but can be operated at similar or lower temperatures. A database for the Binding Energies (BEs) of the LWGS relevant species, namely CO, O and OH on the most-stable, close-packed facets of a set of 17 catalytically relevant transition metals was established. This BE data and a database of previously established segregation energies was utilized to predict the stability of bimetallic NSAs that could be synthesized by combinations of the 17 parent transition metals. NSAs that were potentially stable both in vacuo and under the influence of strong-binding WGS intermediates were then selected for adsorption studies. A set of 40 NSAs were identified that satisfied all three screener criteria and the binding energies of CO, O and OH were calculated on a set of 66, 43 and 79 NSA candidates respectively. Several NSAs were found that bound intermediates weaker than the monometallic catalysts and were thus potentially poison-resistant. Finally, kinetic studies were performed and resulted in the discovery of a specific NSA-based bimetallic catalyst Cu/Pt that is potentially a promising LWGS catalyst. This stable Cu/Pt subsurface alloy is expected to provide facile H{sub 2}O activation and remain relatively resistant from the poisoning by CO, S and formate intermediates.

  19. Preparation of neuroprotective condensed 1,4-benzoxazepines by regio- and diastereoselective domino Knoevenagel-[1,5]-hydride shift cyclization reaction.

    PubMed

    Tóth, László; Fu, Yan; Zhang, Hai Yan; Mándi, Attila; Kövér, Katalin E; Illyés, Tünde-Zita; Kiss-Szikszai, Attila; Balogh, Balázs; Kurtán, Tibor; Antus, Sándor; Mátyus, Péter

    2014-01-01

    Condensed O,N-heterocycles containing tetrahydro-1,4-benzoxazepine and tetrahydroquinoline moieties were prepared by a regio- and diastereoselective domino Knoevenagel-[1,5]-hydride shift cyclization reaction of a 4-aryl-2-phenyl-1,4-benzoxazepine derivative obtained from flavanone. The relative configuration of products were determined by the correlation of (3) J H,H coupling data with the geometry of major conformers accessed by DFT conformational analysis. Separated enantiomers of the products were characterized by HPLC-ECD data, which allowed their configurational assignment on the basis of TDDFT-ECD calculation of the solution conformers. Two compounds showed neuroprotective activities against hydrogen peroxide (H2O2) or β-amyloid25-35 (Aβ25-35)-induced cellular injuries in human neuroblastoma SH-SY5Y cells in the range of those of positive controls. PMID:25550721

  20. Preparation of neuroprotective condensed 1,4-benzoxazepines by regio- and diastereoselective domino Knoevenagel–[1,5]-hydride shift cyclization reaction

    PubMed Central

    Tóth, László; Fu, Yan; Zhang, Hai Yan; Mándi, Attila; Kövér, Katalin E; Illyés, Tünde-Zita; Kiss-Szikszai, Attila; Balogh, Balázs; Kurtán, Tibor

    2014-01-01

    Summary Condensed O,N-heterocycles containing tetrahydro-1,4-benzoxazepine and tetrahydroquinoline moieties were prepared by a regio- and diastereoselective domino Knoevenagel–[1,5]-hydride shift cyclization reaction of a 4-aryl-2-phenyl-1,4-benzoxazepine derivative obtained from flavanone. The relative configuration of products were determined by the correlation of 3 J H,H coupling data with the geometry of major conformers accessed by DFT conformational analysis. Separated enantiomers of the products were characterized by HPLC-ECD data, which allowed their configurational assignment on the basis of TDDFT-ECD calculation of the solution conformers. Two compounds showed neuroprotective activities against hydrogen peroxide (H2O2) or β-amyloid25–35 (Aβ25–35)-induced cellular injuries in human neuroblastoma SH-SY5Y cells in the range of those of positive controls. PMID:25550721

  1. Thermal cyclization of phenylallenes that contain ortho-1,3-dioxolan-2-yl groups: new cascade reactions initiated by 1,5-hydride shifts of acetalic H atoms.

    PubMed

    Alajarin, Mateo; Bonillo, Baltasar; Marin-Luna, Marta; Sanchez-Andrada, Pilar; Vidal, Angel

    2013-11-18

    A series of 2-(1,3-dioxolan-2-yl)phenylallenes that contained a range of substituents (alkyl, aryl, phosphinyl, alkoxycarbonyl, sulfonyl) at the cumulenic C3 position were prepared by using a diverse range of synthetic strategies and converted into their respective 1-(2-hydroxy)-ethoxy-2-substituted naphthalenes by smooth thermal activation in toluene solution. Electron-withdrawing groups at the C3 position accelerated these tandem processes, which consisted of 1) an initial hydride-like [1,5]-H shift of the acetalic H atom onto the central cumulene carbon atom; 2) a subsequent 6π-electrocyclic ring-closure of the resulting reactive ortho-xylylenes; and 3) a final aromatization step with concomitant ring-opening of the 1,3-dioxolane fragment. If the 1,3-dioxolane ring of the starting allenes was replaced by a dimethoxymethyl group, the reactions led to mixtures of two disubstituted naphthalenes, which were formed by the migration of either the acetalic H atom or the methoxy group, with the latter migration occurring to a lesser extent. Two of the final 1,2-disubstituted naphthalenes were converted into their corresponding naphtho-fused dioxaphosphepine or dioxepinone through an intramolecular transesterification reaction. A DFT computational study accounted for the beneficial influence of the 1,3-dioxolane fragment on the carbon atom from which the H-shift took place and also of the electron-withdrawing substituents on the allene terminus. Remarkably, in the processes that contained a sulfonyl substituent, the conrotatory 6π-electrocyclization step was of lower activation energy than the alternative disrotatory mode. PMID:24123192

  2. Shift of reaction pathway by added chloride ions in the oxidation of aromatic ketones by dichloroisocyanuric acid—A kinetic study

    NASA Astrophysics Data System (ADS)

    Kumar, Y. Lakshman; Nadh, R. Venkata; Radhakrishnamurti, P. S.

    2016-03-01

    Role of added chloride ions on the shift of reaction pathway of oxidation of aromatic ketones (acetophenone, desoxybenzoin) by dichloroisocyanuric acid (DCICA) was studied in aqueous acetic acid—perchloric acid medium. Participation of enolic and protonated forms of ketones in the rate determining steps is manifested from zero and first orders with respect to the oxidant in absence and presence of added chloride ions, respectively. Positive and negative effects of acid and dielectric constant on the reaction rate were observed. The observations deduce plausible mechanisms involving (i) rate-determining formation of enol from the conjugate acid of the ketone (SH+) in the absence of added chloride ions and (ii) rapid formation of molecular chlorine species from HOCl (hydrolytic species of DCICA) in the presence of added chloride ions, which then interacts with SH+ in a rate-determining step prior to the rapid steps of product formation. The order of Arrhenius parameters substantiate the proposed plausible mechanisms based on order of reactants both in presence and absence of added chloride ions.

  3. SurfKin: an ab initio kinetic code for modeling surface reactions.

    PubMed

    Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

    2014-10-01

    In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. PMID:25111729

  4. On the Importance of Metal–Oxide Interface Sites for the Water–Gas Shift Reaction Over Pt/CeO2 Catalysts

    SciTech Connect

    Aranifard, Sara; Ammal, Salai Cheettu; Heyden, Andreas

    2014-01-01

    The mechanism of water–gas shift reaction at the three-phase boundary of Pt/CeO2 catalysts has been investigated using density functional theory and microkinetic modeling to better understand the importance of metal–oxide interface sites in heterogeneous catalysis. Analysis of a microkinetic model based on parameters obtained from first principles suggests that both the “Redox pathway” and the “Associative carboxyl pathway with redox regeneration” could operate on Pt/CeO2 catalysts. Although (1) only few interfacial Pt atoms are found to be catalytically active at low temperatures due to strong adsorption of CO and (2) interfacial O–H bond breakage is difficult due to the high reducibility of ceria, interface sites are 2–3 orders of magnitude more active than Pt (1 1 1) and stepped Pt surface sites and therefore effectively determine the overall activity of Pt/CeO2. The high activity of Pt/CeO2 interface sites originates from a significantly enhanced water activation and dissociation at interfacial oxygen vacancies.

  5. A model to assess the feasibility of shifting reaction equilibrium by acetone removal in the transamination of ketones using 2-propylamine.

    PubMed

    Tufvesson, Pär; Bach, Christian; Woodley, John M

    2014-02-01

    Acetone removal by evaporation has been proposed as a simple and cheap way to shift the equilibrium in the biocatalytic asymmetric synthesis of optically pure chiral amines, when 2-propylamine is used as the amine donor. However, dependent on the system properties, this may or may not be a suitable strategy. To avoid excessive laboratory work a model was used to assess the process feasibility. The results from the current study show that a simple model of the acetone removal dependence on temperature and sparging gas flowrate can be developed and fits the experimental data well. The model for acetone removal was then coupled to a simple model for biocatalyst kinetics and also for loss of substrate ketone by evaporation. The three models were used to simulate the effects of varying the critical process parameters and reaction equilibrium constants (K eq) as well as different substrate ketone volatilities (Henry's constant). The simulations were used to estimate the substrate losses and also the maximum yield that could be expected. The approach was seen to give a clear indication for which target amines the acetone evaporation strategy would be feasible and for which amines it would not. The study also shows the value of a modeling approach in conceptual process design prior to entering a biocatalyst screening or engineering program to assess the feasibility of a particular process strategy for a given target product. PMID:23904347

  6. Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeOx–TiO2(110) surfaces: Effects of high ceria coverage

    DOE PAGESBeta

    Grinter, D. C.; Park, J. B.; Agnoli, S.; Evans, J.; Hrbek, J.; Stacchiola, D. J.; Senanayake, S. D.; Rodriguez, J. A.

    2016-08-01

    We used scanning tunnelling microscopy to study the morphology of an overlayer of ceria in contact with a TiO2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO2(110)-(1 × 1). For the other half of the surface, it comprised CeOx nanoparticles and reconstructed TiOx supported on TiO2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film and TiO2(110)-(1 × 1) areas,more » which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeOx/TiO2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO2(110) and Au/CeO2(111) systems. Finally, for Au/CeOx/TiO2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce3 + formed during WGS reaction conditions.« less

  7. The Effect of Rain on Air-Water Gas Exchange

    NASA Technical Reports Server (NTRS)

    Ho, David T.; Bliven, Larry F.; Wanninkhof, Rik; Schlosser, Peter

    1997-01-01

    The relationship between gas transfer velocity and rain rate was investigated at NASA's Rain-Sea Interaction Facility (RSIF) using several SF, evasion experiments. During each experiment, a water tank below the rain simulator was supersaturated with SF6, a synthetic gas, and the gas transfer velocities were calculated from the measured decrease in SF6 concentration with time. The results from experiments with IS different rain rates (7 to 10 mm/h) and 1 of 2 drop sizes (2.8 or 4.2 mm diameter) confirm a significant and systematic enhancement of air-water gas exchange by rainfall. The gas transfer velocities derived from our experiment were related to the kinetic energy flux calculated from the rain rate and drop size. The relationship obtained for mono-dropsize rain at the RSIF was extrapolated to natural rain using the kinetic energy flux of natural rain calculated from the Marshall-Palmer raindrop size distribution. Results of laboratory experiments at RSIF were compared to field observations made during a tropical rainstorm in Miami, Florida and show good agreement between laboratory and field data.

  8. Shifting tools

    SciTech Connect

    Fisher, E.P.; Welch, W.R.

    1984-03-13

    An improved shifting tool connectable in a well tool string and useful to engage and position a slidable sleeve in a sliding sleeve device in a well flow conductor. The selectively profiled shifting tool keys provide better fit with and more contact area between keys and slidable sleeves. When the engaged slidable sleeve cannot be moved up and the shifting tool is not automatically disengaged, emergency disengagement means may be utilized by applying upward force to the shifting tool sufficient to shear pins and cause all keys to be cammed inwardly at both ends to completely disengage for removal of the shifting tool from the sliding sleeve device.

  9. Shifting Attention

    ERIC Educational Resources Information Center

    Ingram, Jenni

    2014-01-01

    This article examines the shifts in attention and focus as one teacher introduces and explains an image that represents the processes involved in a numeric problem that his students have been working on. This paper takes a micro-analytic approach to examine how the focus of attention shifts through what the teacher and students do and say in the…

  10. Fluid Shifts

    NASA Technical Reports Server (NTRS)

    Stenger, Michael B.; Hargens, Alan R.; Dulchavsky, Scott A.; Ebert, Douglas J.; Lee, Stuart M. C.; Laurie, Steven S.; Garcia, Kathleen M.; Sargsyan, Ashot E.; Martin, David S.; Liu, John; Macias, Brandon R.; Arbeille, Philippe; Danielson, Richard; Chang, Douglas; Gunga, Hanns-Christian; Johnston, Smith L.; Westby, Christian M.; Ploutz-Snyder, Robert J.; Smith, Scott M.

    2016-01-01

    We hypothesize that microgravity-induced cephalad fluid shifts elevate intracranial pressure (ICP) and contribute to VIIP. We will test this hypothesis and a possible countermeasure in ISS astronauts.

  11. KINETIC UNDERSTANDING OF THE SYNGAS-TO-DME REACTION SYSTEM AND ITS IMPLICATIONS TO PROCESS AND ECONOMICS

    SciTech Connect

    Xiang-Dong Peng

    2002-12-01

    In a single-step synthesis gas-to-dimethyl ether process, synthesis gas (or syngas, a mixture of H{sub 2} and CO) is converted into dimethyl ether (DME) in a single reactor. The three reactions involved in this process, methanol synthesis, methanol dehydration and water gas shift, form an interesting reaction network. The interplay among these three reactions results in excellent syngas conversion or reactor productivity. A fundamental understanding of this interplay helps to explain many experimental and simulation observations, to identify optimal reaction conditions, and to provide guidelines for process development. The higher syngas conversion or reactor productivity in the syngas-to-DME reaction system, compared to that in the syngas-to-methanol reaction system, is referred to as chemical synergy. This synergy exhibits a strong dependence on the composition of the reactor feed. To demonstrate the extent of this dependence, simulations with adjusted activity for each reaction were performed to reveal the relative rate of each reaction. The results show that the water gas shift reaction is the most rapid, being practically controlled by the equilibrium. Both methanol synthesis and methanol dehydration reactions are kinetically controlled. The kinetics of the dehydration reactions is greater than that of the methanol synthesis reaction in the CO-rich regime. However, the rates of these two reactions come closer as the H{sub 2} concentration in the reactor feed increases. The role of the dehydration reaction is to remove the equilibrium barrier for the methanol synthesis reaction. The role of the water gas shift reaction is more complex; it helps the kinetics of methanol dehydration by keeping the water concentration low, which in turn enhances methanol synthesis. It also readjusts the H{sub 2}:CO ratio in the reactor as the reactions proceed. In the CO-rich regime, the water gas shift reaction supplements the limiting reactant, H{sub 2}, by reacting water with

  12. Fluid Shifts

    NASA Technical Reports Server (NTRS)

    Stenger, M. B.; Hargens, A.; Dulchavsky, S.; Ebert, D.; Lee, S.; Laurie, S.; Garcia, K.; Sargsyan, A.; Martin, D.; Lui, J.; Macias, B.; Arbeille, P.; Danielson, R.; Chang, D.; Gunga, H.; Johnston, S.; Westby, C.; Ribeiro, L.; Ploutz-Snyder, R.; Smith, S.

    2015-01-01

    INTRODUCTION: Mechanisms responsible for the ocular structural and functional changes that characterize the visual impairment and intracranial pressure (ICP) syndrome (VIIP) are unclear, but hypothesized to be secondary to the cephalad fluid shift experienced in spaceflight. This study will relate the fluid distribution and compartmentalization associated with long-duration spaceflight with VIIP symptoms. We also seek to determine whether the magnitude of fluid shifts during spaceflight, as well as the VIIP-related effects of those shifts, can be predicted preflight with acute hemodynamic manipulations, and also if lower body negative pressure (LBNP) can reverse the VIIP effects. METHODS: Physiologic variables will be examined pre-, in- and post-flight in 10 International Space Station crewmembers including: fluid compartmentalization (D2O and NaBr dilution); interstitial tissue thickness (ultrasound); vascular dimensions and dynamics (ultrasound and MRI (including cerebrospinal fluid pulsatility)); ocular measures (optical coherence tomography, intraocular pressure, ultrasound); and ICP measures (tympanic membrane displacement, otoacoustic emissions). Pre- and post-flight measures will be assessed while upright, supine and during 15 deg head-down tilt (HDT). In-flight measures will occur early and late during 6 or 12 month missions. LBNP will be evaluated as a countermeasure during HDT and during spaceflight. RESULTS: The first two crewmembers are in the preflight testing phase. Preliminary results characterize the acute fluid shifts experienced from upright, to supine and HDT postures (increased stroke volume, jugular dimensions and measures of ICP) which are reversed with 25 millimeters Hg LBNP. DISCUSSION: Initial results indicate that acute cephalad fluid shifts may be related to VIIP symptoms, but also may be reversible by LBNP. The effect of a chronic fluid shift has yet to be evaluated. Learning Objectives: Current spaceflight VIIP research is described

  13. Bridging silyl groups in sigma-bond metathesis and [1, 2] shifts. An experimental and computational study of the reaction between cerium metallocenes and MeOSiMe3

    SciTech Connect

    Werkema, Evan; Yahia, Ahmed; Maron, Laurent; Eisenstein, Odile; Andersen, Richard

    2010-04-21

    The reaction of Cp'2CeH (Cp' = 1,2,4-(Me3C)3C5H2 ) with MeOSiMe3 gives Cp'2CeOMe and HSiMe3 and the reaction of the metallacycle, Cp'[(Me3C)2C5H2C(Me) 2CH2]Ce, with MeOSiMe3 yields Cp'2CeOCH2SiMe3, formed from hypothetical Cp'2CeCH2OSiMe3 by a [1, 2] shift also known as a silyl-Wittig rearrangement. Although both cerium products are alkoxides, they are formed by different pathways. DFT calculations on the reaction of the model metallocene, Cp2CeH, and MeOSiMe3 show that the lowest energy pathway is a H for OMe exchange at Ce that occurs by way of a sigma-bond metathesis transition state as SiMe3 exchanges partners. The formation of Cp2CeOCH2SiMe3 occurs by way of a low activation barrier [1, 2]shift of the SiMe3 group in Cp2CeCH2OSiMe3. Calculations on a model metallacycle, Cp[C5H4C(Me)2CH2]Ce, show that the metallacycle favors CH bond activation over sigma-bond metathesis involving the transfer of the SiMe3 group in good agreement with experiment. The sigma-bond metathesis involving the transfer of SiMe3 and the [1, 2]shift of SiMe3 reactions have in common a pentacoordinate silicon at the transition states. A molecular orbital analysis illustrates the connection between these two Si-O bond cleavage reactions and traces the reason why they occur for a silyl but not for an alkyl group to the difference in energy required to form a pentacoordinate silicon or carbon atom in the transition state. This difference clearly distinguishes a silyl from an alkyl group as shown in the study of"Pyrolysis of Tetramethylsilane Yielding Free d-orbitals by Seyferth and Pudvin in ChemTech 1981, 11, 230-233".

  14. Fluid Shifts

    NASA Technical Reports Server (NTRS)

    Stenger, M.; Hargens, A.; Dulchavsky, S.; Ebert, D.; Lee, S.; Lauriie, S.; Garcia, K.; Sargsyan, A.; Martin, D.; Ribeiro, L.; Lui, J.; Macias, B.; Arbeille, P.; Danielson, R.; Chang, D.; Johnston, S.; Ploutz-Snyder, R.; Smith, S.

    2016-01-01

    NASA is focusing on long-duration missions on the International Space Station (ISS) and future exploration-class missions beyond low-Earth orbit. Visual acuity changes observed after short-duration missions were largely transient, but more than 50% of ISS astronauts experienced more profound, chronic changes with objective structural and functional findings such as papilledema and choroidal folds. Globe flattening, optic nerve sheath dilation, and optic nerve tortuosity also are apparent. This pattern is referred to as the visual impairment and intracranial pressure (VIIP) syndrome. VIIP signs and symptoms, as well as postflight lumbar puncture data, suggest that elevated intracranial pressure (ICP) may be associated with the spaceflight-induced cephalad fluid shifts, but this hypothesis has not been tested. The purpose of this study is to characterize fluid distribution and compartmentalization associated with long-duration spaceflight, and to correlate these findings with vision changes and other elements of the VIIP syndrome. We also seek to determine whether the magnitude of fluid shifts during spaceflight, as well as the VIIP-related effects of those shifts, is predicted by the crewmember's preflight conditions and responses to acute hemodynamic manipulations (such as head-down tilt). Lastly, we will evaluate the patterns of fluid distribution in ISS astronauts during acute reversal of fluid shifts through application of lower body negative pressure (LBNP) interventions to characterize and explain general and individual responses. METHODS: We will examine a variety of physiologic variables in 10 long-duration ISS crewmembers using the test conditions and timeline presented in the Figure below. Measures include: (1) fluid compartmentalization (total body water by D2O, extracellular fluid by NaBr, intracellular fluid by calculation, plasma volume by CO rebreathe, interstitial fluid by calculation); (2) forehead/eyelids, tibia, calcaneus tissue thickness (by

  15. A novel reaction-based colorimetric and ratiometric fluorescent sensor for cyanide anion with a large emission shift and high selectivity.

    PubMed

    Wang, Shaodan; Fei, Xiaoliang; Guo, Jing; Yang, Qingbiao; Li, Yaoxian; Song, Yan

    2016-02-01

    A hybrid carbazole-hemicyanine dye (Cac) has been developed as a novel colorimetric and ratiometric fluorescent sensor for cyanide detection. Upon treatment with cyanide, Cac displayed a remarkable fluorescence ratiometric response, with the emission wavelength displaying a very large emission shift (214 nm). The detection of cyanide was performed via the nucleophilic addition of cyanide anion to the indolium group of the sensor, which resulted in the blocking of the intramolecular charge transfer (ICT) process in the sensor, inducing a ratiometric fluorescence change and simultaneously an obvious color change. Furthermore, competitive anions did not showed any significant changes both in color and emission intensity ratio (I381/I595), indicating the high selectivity of the sensor to CN(-). PMID:26653444

  16. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Technical progress report, September 1992--November 1992

    SciTech Connect

    Klier, K.; Herman, R.G.; Deemer, M.

    1992-12-01

    During this quarter, the surface areas of various catalysts were determined. The surface area of the catalyst tested last quarter was determined for the undoped catalyst, the doped catalyst before testing, and the doped catalyst after testing. These surface areas were then compared with ones reported earlier. After testing under high temperature and high pressure conditions for 551 hours, there was a loss of surface area. This might be due possibly to agglomeration of cesium formate on the surface. Higher surface area catalysts were also produced. Two samples of MoS{sub 2} were synthesized with surface areas of 96 m2/g and 91 m2/g. These were obtained by varying the heating rate of MoS{sub 3} and the calcination temperature.

  17. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Technical progress report, March 1993--May 1993

    SciTech Connect

    Klier, K.; Herman, R.G.; Richards-Babb, M.

    1993-06-01

    Study of preparation of MoS{sub 3}, decomposition to form MoS{sub 2}, and the Cs-containing reagents and techniques to achieve surface doping of the MoS{sub 2} with Cs was begun. Goal is to achieve a high surface area catalyst containing lower quantities of the Cs promoter in a highly dispersed state. Using high resolution electron spectroscopy for chemical analysis and solid state Extended Hueckel (EH) theory investigation and interpretation of electronic structure of MoS{sub 2} (hexagonal 2H form, 2 MoS{sub 2} molecules/unit cell) was carried out. The theoretical valence band of MoS{sub 2} was obtained by modification of density of states. Qualitative agreement theoretical and experimental MoS{sub 2} valence bands was obtained after parameterization of EH input ionization potentials H{sub ii} and Slater-type orbital (STO) double zeta coefficients c{sub i}. Theoretical energy dispersion curves 2-D and 3-D MoS{sub 2} also compared well with experimental energy dispersion curves. Highest occupied band of valence band is shown to consist of contributions not only from Mo 4d{sub z2} orbitals but also from Mo 4d{sub xy} and Mo 4d{sub x2-y2} orbitals. The theoretical systems 2-D MoS{sub 2} and 3-D MoS{sub 2}, containing zero for the former and an infinite number of Van der Waals gaps for the latter, exhibit direct and indirect gaps, respectively. Nature of 2H-MoS{sub 2} indirect gap is found to be directly linked to the interaction of crystal orbitals across Van der Waals gap between adjacent layers of MoS{sub 2} in the realistic 3-D model. Thus, the electronic properties and ability of adsorbing and activating hydrogen of very small and thin particles of MoS{sub 2} might be expected to be different from large bulk particles of MoS{sub 2}.

  18. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Technical progress report, June 1993--August 1993

    SciTech Connect

    Klier, K.; Herman, R.G.; Deemer, M.; Carr, T.

    1993-09-01

    Various preparation methods of synthesizing molybdenum disulfide and various alkali doping procedures were studied to determine if various preparation paramenters affected catalyst activity. Testing was performed on an undoped molybdenum disulfide sample with H{sub 2}/CO = 1 synthesis gas at 8.1 MPa and at temperatures of 245, 255, 265, 275, 280, 300, 320, and 295C, and only hydrocarbons were formed. A methanol injection experiment with undoped catalyst showed that homologation of methanol did not occur over the undoped MOS{sub 2}. Catalytic testing on a cesium formate doped molybdenum disulfide catalyst corresponding to 9 wt% Cs/MoS{sub 2} at 8.1 MPa and temperatures of 245, 255, 265, 275, 285, and 295C, mostly linear alcohols. The CS/MOS{sub 2} sample was protected from air exposure during preparation and testiag. As with the other recently tested alkali-promoted MOS{sub 2} catalysts, this cataylst was not as active as previous CS/MOS{sub 2} catalysts [1], and some deactivation during these systematic studies was observed. X-Ray powder diffraction and BET surface area measurements are being used to characterize the catalysts, and electron microscopy analyses are being carried out.

  19. Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

    DOEpatents

    Bamberger, C.E.; Robinson, P.R.

    A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cyclic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

  20. Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

    DOEpatents

    Bamberger, Carlos E.; Robinson, Paul R.

    1980-01-01

    A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

  1. Fluid Shifts

    NASA Technical Reports Server (NTRS)

    Stenger, Michael; Hargens, A.; Dulchavsky, S.; Ebert, D.; Lee, S.; Sargsyan, A.; Martin, D.; Lui, J.; Macias, B.; Arbeille, P.; Platts, S.

    2014-01-01

    NASA is focusing on long-duration missions on the International Space Station (ISS) and future exploration-class missions beyond low Earth orbit. Visual acuity changes observed after short-duration missions were largely transient, but more than 30% of ISS astronauts experience more profound, chronic changes with objective structural and functional findings such as papilledema and choroidal folds. Globe flattening, optic nerve sheath dilation, and optic nerve tortuosity also are apparent. This pattern is referred to as the visual impairment and intracranial pressure (VIIP) syndrome. VIIP signs and symptoms, as well as postflight lumbar puncture data, suggest that elevated intracranial pressure (ICP) may be associated with the space flight-induced cephalad fluid shifts, but this hypothesis has not been tested. The purpose of this study is to characterize fluid distribution and compartmentalization associated with long-duration space flight, and to correlate these findings with vision changes and other elements of the VIIP syndrome. We also seek to determine whether the magnitude of fluid shifts during space flight, as well as the VIIP-related effects of those shifts, is predicted by the crewmember's pre-flight condition and responses to acute hemodynamic manipulations (such as head-down tilt). Lastly, we will evaluate the patterns of fluid distribution in ISS astronauts during acute reversal of fluid shifts through application of lower body negative pressure (LBNP) interventions to characterize and explain general and individual responses. We will examine a variety of physiologic variables in 10 long-duration ISS crewmembers using the test conditions and timeline presented in the Figure below. Measures include: (1) fluid compartmentalization (total body water by D2O, extracellular fluid by NaBr, intracellular fluid by calculation, plasma volume by CO rebreathe, interstitial fluid by calculation); (2) forehead/eyelids, tibia, calcaneus tissue thickness (by ultrasound

  2. Effect of intramolecular Paternò-Büchi reaction on the thermodynamics and kinetics of nearly degenerate [3,3]-sigmatropic shift in fluxional polycycles.

    PubMed

    Valiulin, Roman A; Dressen, Donald G; Riggs, Jennifer R; Habte, Faven M; Kutateladze, Andrei G

    2009-05-01

    In reactions with weak dienophiles, cyclooctatetraene (COT) often yields 2:1 adducts possessing the fluxional bicyclo[5.1.0]octadiene moiety. They undergo fast, nearly degenerate Cope rearrangement with an activation barrier similar to that of the parent dihydrobullvalene. Irradiation to excite the carbonyl moiety induces an intramolecular Paterno-Buchi cyclization yielding endo-oxetanes and significantly changing the Cope-averaged NMR spectra. In this paper we examine the effect of skeletal distortion caused by intramolecular [2 + 2]-photoaddition on thermodynamics and the activation barrier of the [3,3]-sigmatropic tautomerism. Our finding is that such a distortion lifts the energetic degeneracy of the two valence tautomers, while not affecting the activation barrier. PMID:19344135

  3. The reaction of European lobster larvae (Homarus gammarus) to different quality food: effects of ontogenetic shifts and pre-feeding history.

    PubMed

    Schoo, Katherina L; Aberle, Nicole; Malzahn, Arne M; Schmalenbach, Isabel; Boersma, Maarten

    2014-02-01

    Young larval stages of many organisms represent bottlenecks in the life-history of many species. The high mortality commonly observed in, for example, decapod larvae has often been linked to poor nutrition, with most studies focussing on food quantity. Here, we focus instead on the effects of quality and have investigated its effects on the nutritional condition of lobster larvae. We established a tri-trophic food chain consisting of the cryptophyte Rhodomonas salina, the calanoid copepod Acartia tonsa and larvae of the European lobster Homarus gammarus. In a set of experiments, we manipulated the C:N:P stoichiometry of the primary producers, and accordingly those of the primary consumer. In a first experiment, R. salina was grown under N- and P-limitation and the nutrient content of the algae was manipulated by addition of the limiting nutrient to create a food quality gradient. In a second experiment, the effect on lobster larvae of long- and short-term exposure to food of varying quality during ontogenetic development was investigated. The condition of the lobster larvae was negatively affected even by subtle N- and P-nutrient limitations of the algae. Furthermore, younger lobster larvae were more vulnerable to nutrient limitation than older ones, suggesting an ontogenetic shift in the capacity of lobster larvae to cope with low quality food. The results presented here might have substantial consequences for the survival of lobster larvae in the field, as, in the light of future climate change and re-oligotrophication of the North Sea, lobster larvae might face marked changes in temperature and nutrient conditions, thus significantly altering their condition and growth. PMID:24072442

  4. Laboratory support for in situ gasification: reaction kinetics. Annual report October 1977-September 1978

    SciTech Connect

    Young, J.E.; Wong, S.H.; Johnson, J.E.; Sikand, N.; Jonke, A.A.

    1980-02-01

    This work is directed toward support studies for the national program for the development and demonstration of in situ coal gasification processes. The objective of this work is to determine the reaction-controlling variables and reaction kinetics for the gasification of chars obtained by pyrolyzing coal in simulated underground gasification conditions. The reactions being studied and to be studied include steam-char, CO/sub 2/-char, H/sub 2/-char, the water-gas shift reaction, and the methanation reaction. In this report are presented data regarding the kinetics of the reaction of steam with chars prepared from Pittsburgh seam high-volatile bituminous coal. In addition, a reaction model is described correlating the steam-char reaction rates measured earlier for Hanna subbituminous coal with operating conditions including temperature, partial pressures of steam and hydrogen, and extent of carbon gasification. Partial results are presented and discussed for an investigation of structural parameters of Hanna char as a function of pyrolysis conditions and extent of carbon gasified.

  5. Acetic Acid Reforming over Rh Supported on La2O3/CeO2-ZrO2: Catalytic Performance and Reaction Pathway Analysis

    SciTech Connect

    Lemonidou, Angeliki A.; Vagia, Ekaterini C.; Lercher, Johannes A.

    2013-07-11

    Reforming of acetic acid was investigated on Rh supported on CeO2-ZrO2 modified with 3 wt % La. The active catalyst converted acetic acid to H-2-rich gas and hardly formed coke. The low rate of coke formation is concluded to be related to the presence of redox-active oxygen limiting the concentration of coke precursors. Temperature-programmed O-18(2)) isotope exchange measurements showed that the La2O3 and Rh enhanced the mobility of lattice oxygen compared with that of the parent CeO2-ZrO2. Ketonization and decarboxylation of acetic acid are the dominating reactions over the latter up to 600 degrees C, whereas above 600 degrees C, steam reforming and water gas shift also contribute. Over 0.5 wt % Rh on La2O3/CeO2-ZrO2, reforming and water gas shift reactions dominate, even below 300 degrees C, producing mostly H-2 and CO2. Using isotope labeling, it is shown that acetic acid adsorbs dissociatively on Rh, forming acetates, which sequentially decarboxylate and form surface methyl groups. The latter are in turn converted to CO, CO2, and H-2.

  6. A fully coupled model for water-gas-heat reactive transport with methane oxidation in landfill covers.

    PubMed

    Ng, C W W; Feng, S; Liu, H W

    2015-03-01

    Methane oxidation in landfill covers is a complex process involving water, gas and heat transfer as well as microbial oxidation. The coupled phenomena of microbial oxidation, water, gas, and heat transfer are not fully understood. In this study, a new model is developed that incorporates water-gas-heat coupled reactive transport in unsaturated soil with methane oxidation. Effects of microbial oxidation-generated water and heat are included. The model is calibrated using published data from a laboratory soil column test. Moreover, a series of parametric studies are carried out to investigate the influence of microbial oxidation-generated water and heat, initial water content on methane oxidation efficiency. Computed and measured results of gas concentration and methane oxidation rate are consistent. It is found that the coupling effects between water-gas-heat transfer and methane oxidation are significant. Ignoring microbial oxidation-generated water and heat can result in a significant difference in methane oxidation efficiency by 100%. PMID:25489976

  7. The adsorption behavior of octafluoropropane at the water/gas interface

    SciTech Connect

    Giebel, Friederike; Paulus, Michael; Nase, Julia Bieder, Steffen; Kiesel, Irena; Tolan, Metin

    2014-12-14

    We studied the adsorption behavior of the gas octafluoropropane at the water/gas interface as a function of different pressures. In a custom-made measurement cell, the gas pressure was varied in a range between 1 bar and close to the condensation pressure of octafluoropropane. The electron density profiles of the adsorption layers show that the layer thickness increases with pressure. The evolution of the layer electron density indicates that the bulk electron density is reached if a layer consisting of more than one monolayer of octafluoropropane is adsorbed on the water surface.

  8. Integrated reformer and shift reactor

    SciTech Connect

    Bentley, Jeffrey M.; Clawson, Lawrence G.; Mitchell, William L.; Dorson, Matthew H.

    2006-06-27

    A hydrocarbon fuel reformer for producing diatomic hydrogen gas is disclosed. The reformer includes a first reaction vessel, a shift reactor vessel annularly disposed about the first reaction vessel, including a first shift reactor zone, and a first helical tube disposed within the first shift reactor zone having an inlet end communicating with a water supply source. The water supply source is preferably adapted to supply liquid-phase water to the first helical tube at flow conditions sufficient to ensure discharge of liquid-phase and steam-phase water from an outlet end of the first helical tube. The reformer may further include a first catalyst bed disposed in the first shift reactor zone, having a low-temperature shift catalyst in contact with the first helical tube. The catalyst bed includes a plurality of coil sections disposed in coaxial relation to other coil sections and to the central longitudinal axis of the reformer, each coil section extending between the first and second ends, and each coil section being in direct fluid communication with at least one other coil section.

  9. Fischer-Tropsch synthesis over iron-based catalysts in slurry reactors. Reaction rates, kinetics and implications for improving hydrocarbon productivity

    SciTech Connect

    Raje, A.P.; Davis, B.H.

    1996-10-01

    The Fischer-Tropsch (FT) synthesis is carried out over a high activity precipitated iron catalyst promoted with silica and potassium in a slurry reactor. Reaction rates (FTS and water gas shift) and partial pressures are evaluated over a wide range of CO conversions (10 to 90%) and space velocities at 270{degrees}C, 175 psig and a H{sub 2}/CO ratio of 0.67. The partial pressure of water exhibits a maximum at intermediate CO conversion. Both the fraction of CO converted to hydrocarbons and the hydrocarbon space time yield decrease with increasing CO conversion. This implies that it would be beneficial to have lower conversion per pass in the reactor with recycle to achieve a high overall conversion. The data as well as experiments with water and CO{sub 2} addition enable us to determine a kinetic expression for the catalyst which shows negligible inhibition of the reaction rate by water or CO{sub 2}.

  10. Unusual 1H NMR chemical shifts support (His) C(epsilon) 1...O==C H-bond: proposal for reaction-driven ring flip mechanism in serine protease catalysis.

    PubMed

    Ash, E L; Sudmeier, J L; Day, R M; Vincent, M; Torchilin, E V; Haddad, K C; Bradshaw, E M; Sanford, D G; Bachovchin, W W

    2000-09-12

    13C-selective NMR, combined with inhibitor perturbation experiments, shows that the C(epsilon)(1)H proton of the catalytic histidine in resting alpha-lytic protease and subtilisin BPN' resonates, when protonated, at 9.22 ppm and 9.18 ppm, respectively, which is outside the normal range for such protons and approximately 0.6 to 0.8 ppm further downfield than previously reported. They also show that the previous alpha-lytic protease assignments [Markley, J. L., Neves, D. E., Westler, W. M., Ibanez, I. B., Porubcan, M. A. & Baillargeon, M. W. (1980) Front. Protein Chem. 10, 31-61] were to signals from inactive or denatured protein. Simulations of linewidth vs. pH demonstrate that the true signal is more difficult to detect than corresponding signals from inactive derivatives, owing to higher imidazole pK(a) values and larger chemical shift differences between protonated and neutral forms. A compilation and analysis of available NMR data indicates that the true C(epsilon)(1)H signals from other serine proteases are similarly displaced downfield, with past assignments to more upfield signals probably in error. The downfield displacement of these proton resonances is shown to be consistent with an H-bond involving the histidine C(epsilon)(1)H as donor, confirming the original hypothesis of Derewenda et al. [Derewenda, Z. S., Derewenda, U. & Kobos, P. M. (1994) J. Mol. Biol. 241, 83-93], which was based on an analysis of literature x-ray crystal structures of serine hydrolases. The invariability of this H-bond among enzymes containing Asp-His-Ser triads indicates functional importance. Here, we propose that it enables a reaction-driven imidazole ring flip mechanism, overcoming a major dilemma inherent in all previous mechanisms, namely how these enzymes catalyze both the formation and productive breakdown of tetrahedral intermediates. PMID:10984533

  11. Unusual 1H NMR chemical shifts support (His) Cɛ1—H⋅⋅⋅O⩵C H-bond: Proposal for reaction-driven ring flip mechanism in serine protease catalysis

    PubMed Central

    Ash, Elissa L.; Sudmeier, James L.; Day, Regina M.; Vincent, Matthew; Torchilin, Ekaterina V.; Haddad, Kristin Coffman; Bradshaw, Elizabeth M.; Sanford, David G.; Bachovchin, William W.

    2000-01-01

    13C-selective NMR, combined with inhibitor perturbation experiments, shows that the Cɛ1—H proton of the catalytic histidine in resting α-lytic protease and subtilisin BPN′ resonates, when protonated, at 9.22 ppm and 9.18 ppm, respectively, which is outside the normal range for such protons and ≈0.6 to 0.8 ppm further downfield than previously reported. They also show that the previous α-lytic protease assignments [Markley, J. L., Neves, D. E., Westler, W. M., Ibanez, I. B., Porubcan, M. A. & Baillargeon, M. W. (1980) Front. Protein Chem. 10, 31–61] were to signals from inactive or denatured protein. Simulations of linewidth vs. pH demonstrate that the true signal is more difficult to detect than corresponding signals from inactive derivatives, owing to higher imidazole pKa values and larger chemical shift differences between protonated and neutral forms. A compilation and analysis of available NMR data indicates that the true Cɛ1—H signals from other serine proteases are similarly displaced downfield, with past assignments to more upfield signals probably in error. The downfield displacement of these proton resonances is shown to be consistent with an H-bond involving the histidine Cɛ1—H as donor, confirming the original hypothesis of Derewenda et al. [Derewenda, Z. S., Derewenda, U. & Kobos, P. M. (1994) J. Mol. Biol. 241, 83–93], which was based on an analysis of literature x-ray crystal structures of serine hydrolases. The invariability of this H-bond among enzymes containing Asp-His-Ser triads indicates functional importance. Here, we propose that it enables a reaction-driven imidazole ring flip mechanism, overcoming a major dilemma inherent in all previous mechanisms, namely how these enzymes catalyze both the formation and productive breakdown of tetrahedral intermediates. PMID:10984533

  12. Psychopathology of Shift Work.

    ERIC Educational Resources Information Center

    Akinnawo, Ebenezer Olutope

    1989-01-01

    Examined incidence and nature of general psychopathology among Nigerian shift workers (N=320). Found shift workers more significantly psychopathological than non-shift workers (p<0.001). Prominent disorders among shift workers were intellectual, sleep, mood, and general somatic disorders. No significant difference could be attributed to gender and…

  13. Sorption enhanced reaction process (SERP) for production of hydrogen

    SciTech Connect

    Sircar, S.; Anand, M.; Carvill, B.

    1995-09-01

    Sorption Enhanced Reaction (SER) is a novel process that is being developed for the production of lower cost hydrogen by steam-methane reforming (SMR). In this process, the reaction of methane with steam is carried out in the presence of an admixture of a catalyst and a selective adsorbent for carbon dioxide. The consequences of SER are: (1) reformation reaction at a significantly lower temperature (300-500{degrees}C) than conventional SMR (800-1100{degrees}C), while achieving the same conversion of methane to hydrogen, (2) the product hydrogen is obtained at reactor pressure (200-400 psig) and at 99+% purity directly from the reactor (compared to only 70-75% H{sub 2} from conventional SMR reactor), (3) downstream hydrogen purification step is either eliminated or significantly reduced in size. The early focus of the program will be on the identification of an adsorbent/chemisorbent for CO{sub 2} and on the demonstration of the SER concept for SMR in our state-of-the-art bench scale process. In the latter stages, a pilot plant will be built to scale-up the technology and to develop engineering data. The program has just been initiated and no significant results for SMR will be reported. However, results demonstrating the basic principles and process schemes of SER technology will be presented for reverse water gas shift reaction as the model reaction. If successful, this technology will be commercialized by Air Products and Chemicals, Inc. (APCI) and used in its existing hydrogen business. APCI is the world leader in merchant hydrogen production for a wide range of industrial applications.

  14. Tandem pseudopericyclic reactions: [1,5]-X sigmatropic shift/6pi-electrocyclic ring closure converting N-(2-X-carbonyl)phenyl ketenimines into 2-X-quinolin-4(3H)-ones.

    PubMed

    Alajarín, Mateo; Ortín, María-Mar; Sanchez-Andrada, Pilar; Vidal, Angel

    2006-10-13

    N-(2-X-Carbonyl)phenyl ketenimines undergo, under mild thermal conditions, [1,5]-migration of the X group from the carbonyl carbon to the electron-deficient central carbon atom of the ketenimine fragment, followed by a 6pi-electrocyclic ring closure of the resulting ketene to provide 2-X-substituted quinolin-4(3H)-ones in a sequential one-pot manner. The X groups tested are electron-donor groups, such as alkylthio, arylthio, arylseleno, aryloxy, and amino. When involving alkylthio, arylthio, and arylseleno groups, the complete transformation takes place in refluxing toluene, whereas for aryloxy and amino groups the starting ketenimines must be heated at 230 degrees C in a sealed tube in the absence of solvent. The mechanism for the conversion of these ketenimines into quinolin-4(3H)-ones has been studied by ab initio and DFT calculations, using as model compounds N-(2-X-carbonyl)vinyl ketenimines bearing different X groups (X = F, Cl, OH, SH, NH(2), and PH(2)) converting into 4(3H)-pyridones. This computational study afforded two general reaction pathways for the first step of the sequence, the [1,5]-X shift, depending on the nature of X. When X is F, Cl, OH, or SH, the migration occurs in a concerted mode, whereas when X is NH(2) or PH(2), it involves a two-step sequence. The order of migratory aptitudes of the X substituents at the acyl group is predicted to be PH(2) > Cl > SH > NH(2) > F> OH. The second step of the full transformation, the 6pi-electrocyclic ring closure, is calculated to be concerted and with low energy barriers in all the cases. We have included in the calculations an alternative mode of cyclization of the N-(2-X-carbonyl)vinyl ketenimines, the 6pi-electrocyclic ring closure leading to 1,3-oxazines that involves its 1-oxo-5-aza-1,3,5-hexatrienic system. Additionally, the pseudopericyclic topology of the transition states for some of the [1,5]-X migrations (X = F, Cl, OH, SH), for the 6pi-electrocyclization of the ketene intermediates to the 4

  15. Near-surface physics during convection affecting air-water gas transfer

    NASA Astrophysics Data System (ADS)

    Fredriksson, S. T.; Arneborg, L.; Nilsson, H.; Handler, R. A.

    2016-05-01

    The gas flux at the water surface is affected by physical processes including turbulence from wind shear, microscale wave breaking, large-scale breaking, and convection due to heat loss at the surface. The main route in the parameterizations of the gas flux has been to use the wind speed as a proxy for the gas flux velocity, indirectly taking into account the dependency of the wind shear and the wave processes. The interest in the contributions from convection processes has increased as the gas flux from inland waters (with typically lower wind and sheltered conditions) now is believed to play a substantial role in the air-water gas flux budget. The gas flux is enhanced by convection through the mixing of the mixed layer as well as by decreasing the diffusive boundary layer thickness. The direct numerical simulations performed in this study are shown to be a valuable tool to enhance the understanding of this flow configuration often present in nature.

  16. Energy phase shift as mechanism for catalysis

    NASA Astrophysics Data System (ADS)

    Beke-Somfai, Tamás; Feng, Bobo; Nordén, Bengt

    2012-05-01

    Catalysts are agents that by binding reactant molecules lower the energy barriers to chemical reaction. After reaction the catalyst is regenerated, its unbinding energy recruited from the environment, which is associated with an inevitable loss of energy. We show that combining several catalytic sites to become energetically and temporally phase-shifted relative to each other provides a possibility to sustain the overall reaction by internal 'energy recycling', bypassing the need for thermal activation, and in principle allowing the system to work adiabatically. Using an analytical model for superimposed, phase-shifted potentials of F1-ATP synthase provides a description integrating main characteristics of this rotary enzyme complex.

  17. Gear shift control mechanism

    SciTech Connect

    Janson, D.A.

    1987-03-10

    A gear shift control mechanism is described comprising: multiple shift rods directed substantially parallel to one another, each rod carrying a shift fork for axial movement; a shift lever supported for pivotal movement about a first axis directed parallel to the axes of the shift rods and for pivotal movement about a second axis directed substantially perpendicular to the axes of the shift rods. The lever is moveable about the first axis and the second axis into engagement with a selected shift fork; interlock means located on each lateral side of the shift lever and mounted for pivotal movement about the first axis for blocking engagement with the shift forks; detent means for holding the shift lever in multiple predetermined angular positions about the second axis; and spring means located on a lateral side of the shift lever and mounted for pivotal movement about the first axis into interference contact with the shift forks for producing a force tending to resiliently bias the shift lever out of engagement with the selected shift fork.

  18. Theoretical study on the reaction mechanism of the gas-phase H2/CO2/Ni(3D) system.

    PubMed

    Qin, Song; Hu, Changwei; Yang, Huaqing; Su, Zhishan

    2005-07-28

    The ground-state potential energy surface (PES) in the gas-phase H2/CO2/Ni(3D) system is investigated at the CCSD(T)//B3LYP/6-311+G(2d,2p) levels in order to explore the possible reaction mechanism of the reverse water gas shift reaction catalyzed by Ni(3D). The calculations predict that the C-O bond cleavage of CO2 assisted by co-interacted H2 is prior to the dissociation of the H2, and the most feasible reaction path for Ni(3D) + H2 + CO2 --> Ni(3D) + H2O + CO is endothermic by 12.5 kJ mol(-1) with an energy barrier of 103.9 kJ mol(-1). The rate-determining step for the overall reaction is predicted to be the hydrogen migration with water formation. The promotion effect of H2 on the cleavage of C-O bond in CO2 is also discussed and compared with the analogous reaction of Ni(3D) + CO2 --> NiO + CO, and the difference between triplet and singlet H2/CO2/Ni systems is also discussed. PMID:16833994

  19. Methanol synthesis via CO2 hydrogenation over a Au/ZnO catalyst: an isotope labelling study on the role of CO in the reaction process.

    PubMed

    Hartadi, Yeusy; Widmann, Daniel; Behm, R Jürgen

    2016-04-20

    Methanol synthesis for chemical energy storage, via hydrogenation of CO2 with H2 produced by renewable energies, is usually accompanied by the undesired formation of CO via the reverse water-gas shift reaction. Aiming at a better mechanistic understanding of methanol formation from CO2/H2 on highly selective supported Au/ZnO catalysts we have investigated the role of CO in the reaction process using isotope labelling experiments. Using (13)C-labelled CO2, we found for reaction at 5 bar and 240 °C that (i) the methanol formation rate is significantly higher in CO2-containing gas mixtures than in a CO2-free mixture and (ii) in mixtures containing both CO2 and CO methanol formation from CO increases with the CO content up to 1% CO, and then remains at 20% of the total methanol formation up to a CO2/CO ratio of 1/1, making CO2 the preferred carbon source in these mixtures. A shift in the preferred carbon source for MeOH from CO2 towards CO is observed with increasing reaction temperatures between 240 °C and 300 °C. At even higher temperatures CO is expected to become the dominant carbon source. The consequences of these findings for the application of Au/ZnO catalysts for chemical storage of renewable energies are discussed. PMID:26923815

  20. Air-Water Gas Exchange in Wetland Water Columns Due To Wind and Thermal Convection

    NASA Astrophysics Data System (ADS)

    Poindexter, C.; Variano, E. A.

    2011-12-01

    The goal of this work is to provide a parameterization of the air-water gas transfer rate in wetlands, and do so in terms of easily measured environmental variables. This parameterization is intended to support biogeochemical modeling in wetlands by providing an interfacial flux of key importance. Our approach uses laboratory experiments describe the oxygen transfer across an air-water interface in a model wetland. The oxygen transfer is sensitive to the externally imposed wind, vegetation characteristics, and vertical thermal convection. We vary these systematically, determining the gas transfer (or "piston") velocity that describes interfacial gas flux. We measure velocity vector fields near the air-water interface using particle image velocimetry, and use these measurements to help explain the mechanisms behind the measured trends in oxygen transfer. The explanatory power of these measurements includes the relationship between plant geometry and surface divergence. We explore the potential impact of our results on wetland modeling and management, for issues such as carbon sequestration and methane emission.

  1. In-water gas combustion in linear and annular gas bubbles

    NASA Astrophysics Data System (ADS)

    Teslenko, V. S.; Drozhzhin, A. P.; Medvedev, R. N.; Batraev, I. S.

    2014-08-01

    A new pulsed-cyclic method of in-water gas combustion was developed with separate feed of fuel gas and oxygen with the focus on development of new technologies for heat generators and submerged propellers. The results of calorimetric and hydrodynamic measurements are presented. In-water combustion of acetylene, hydrogen, and propane was tested with the operation frequency of 2-2.5 Hz and with a linear injector. The combustion dynamics of combustion of stoichiometric mixture with propane (C3H8+5O2) was studied for a bubble near a solid wall; the produced gas bubble continues expansion and oscillations (for the case of linear and annular bubbles). It was demonstrated that gas combustion in annular bubbles produces two same-magnitude pulses of force acting on the wall. The first pulse is produced due to expansion of combustion products, and the second pulse is produced due to axial cumulative processes after bubble collapse. This process shapes an annular vortex which facilitates high-speed convective processes between combustion products and liquid; and this convection produces small-size bubbles.

  2. Molecular implementation of molecular shift register memories

    NASA Technical Reports Server (NTRS)

    Beratan, David N. (Inventor); Onuchic, Jose N. (Inventor)

    1991-01-01

    An electronic shift register memory (20) at the molecular level is described. The memory elements are based on a chain of electron transfer molecules (22) and the information is shifted by photoinduced (26) electron transfer reactions. Thus, multi-step sequences of charge transfer reactions are used to move charge with high efficiency down a molecular chain. The device integrates compositions of the invention onto a VLSI substrate (36), providing an example of a molecular electronic device which may be fabricated. Three energy level schemes, molecular implementation of these schemes, optical excitation strategies, charge amplification strategies, and error correction strategies are described.

  3. Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis

    NASA Astrophysics Data System (ADS)

    Stottlemyer, Alan L.; Kelly, Thomas G.; Meng, Qinghe; Chen, Jingguang G.

    2012-09-01

    Historically the interest in the catalytic properties of transition metal carbides (TMC) has been inspired by their "Pt-like" properties in the transformation reactions of hydrocarbon molecules. Recent studies, however, have revealed that the reaction pathways of oxygen-containing molecules are significantly different between TMCs and Pt-group metals. Nonetheless, TMCs demonstrate intriguing catalytic properties toward oxygen-containing molecules, either as the catalyst or as the catalytically active substrate to support metal catalysts, in several important catalytic and electrocatalytic applications, including water electrolysis, alcohol electrooxidation, biomass conversion, and water gas shift reactions. In the current review we provide a summary of theoretical and experimental studies of the interaction of TMC surfaces with oxygen-containing molecules, including both inorganic (O2, H2O, CO and CO2) and organic (alcohols, aldehydes, acids and esters) molecules. We will discuss the general trends in the reaction pathways, as well as future research opportunities in surface science studies that would facilitate the utilization of TMCs as catalysts and electrocatalysts.

  4. Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis

    NASA Astrophysics Data System (ADS)

    Stottlemyer, Alan L.; Kelly, Thomas G.; Meng, Qinghe; Chen, Jingguang G.

    2012-09-01

    Historically the interest in the catalytic properties of transition metal carbides (TMC) has been inspired by their “Pt-like” properties in the transformation reactions of hydrocarbon molecules. Recent studies, however, have revealed that the reaction pathways of oxygen-containing molecules are significantly different between TMCs and Pt-group metals. Nonetheless, TMCs demonstrate intriguing catalytic properties toward oxygen-containing molecules, either as the catalyst or as the catalytically active substrate to support metal catalysts, in several important catalytic and electrocatalytic applications, including water electrolysis, alcohol electrooxidation, biomass conversion, and water gas shift reactions. In the current review we provide a summary of theoretical and experimental studies of the interaction of TMC surfaces with oxygen-containing molecules, including both inorganic (O2, H2O, CO and CO2) and organic (alcohols, aldehydes, acids and esters) molecules. We will discuss the general trends in the reaction pathways, as well as future research opportunities in surface science studies that would facilitate the utilization of TMCs as catalysts and electrocatalysts.

  5. Shifting scintillator neutron detector

    SciTech Connect

    Clonts, Lloyd G; Cooper, Ronald G; Crow, Jr., Morris Lowell; Hannah, Bruce W; Hodges, Jason P; Richards, John D; Riedel, Richard A

    2014-03-04

    Provided are sensors and methods for detecting thermal neutrons. Provided is an apparatus having a scintillator for absorbing a neutron, the scintillator having a back side for discharging a scintillation light of a first wavelength in response to the absorbed neutron, an array of wavelength-shifting fibers proximate to the back side of the scintillator for shifting the scintillation light of the first wavelength to light of a second wavelength, the wavelength-shifting fibers being disposed in a two-dimensional pattern and defining a plurality of scattering plane pixels where the wavelength-shifting fibers overlap, a plurality of photomultiplier tubes, in coded optical communication with the wavelength-shifting fibers, for converting the light of the second wavelength to an electronic signal, and a processor for processing the electronic signal to identify one of the plurality of scattering plane pixels as indicative of a position within the scintillator where the neutron was absorbed.

  6. Slurry phase Fischer-Tropsch synthesis: Cobalt plus a water-gas shift catalyst. [Quarterly] report, October 1, 1989--December 31, 1989

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1989-12-31

    The rate of synthesis gas consumption over a cobalt FischerTropsch catalyst was measured in a well-mixed, continuous-flow, slurry reactor at 220 to 240{degrees}C, 0.5 to 1.5 MPa, H{sub 2}/CO feed ratios of 1.5 to 3.5 and conversions of 7 to 68% of hydrogen and 11 to 73% of carbon monoxide. The inhibiting effect of carbon monoxide was determined quantitatively and a Langmuir-Hinshelwood-type equation of the following form was found to best represent the results: -R{sub H{sub 2+Co}} = (a P{sub CO}P{sub H{sub 2}})/(1 + b P{sub CO}){sup 2}. The apparent activation energy was 93 to 95 kJ/mol. Data from previous studies on cobalt-based Fischer-Tropsch catalysts are also well correlated with this rate expression.

  7. Data for phase angle shift with frequency.

    PubMed

    Paul, T; Banerjee, D; Kargupta, K

    2016-06-01

    Phase angle shift between the current and voltage with frequency has been reported for a single phosphoric acid fuel cell in the cell temperature from 100 °C to 160 °C and the humidifier temperature from 40 °C to 90 °C. An electrochemical workbench is employed to find the shift. The figure of phase angle shift shows a peak in high humidifier temperatures. The peak in phase angle shift directs to lower frequency side with decreasing humidifier temperature. The estimation of electrochemical reaction time is also evaluated in the humidifier temperature zone from 50 °C to 90 °C. PMID:27158655

  8. Data for phase angle shift with frequency

    PubMed Central

    Paul, T.; Banerjee, D.; Kargupta, K.

    2016-01-01

    Phase angle shift between the current and voltage with frequency has been reported for a single phosphoric acid fuel cell in the cell temperature from 100 °C to 160 °C and the humidifier temperature from 40 °C to 90 °C. An electrochemical workbench is employed to find the shift. The figure of phase angle shift shows a peak in high humidifier temperatures. The peak in phase angle shift directs to lower frequency side with decreasing humidifier temperature. The estimation of electrochemical reaction time is also evaluated in the humidifier temperature zone from 50 °C to 90 °C. PMID:27158655

  9. Shape-Shifting Plastic

    SciTech Connect

    2015-05-20

    A new plastic developed by ORNL and Washington State University transforms from its original shape through a series of temporary shapes and returns to its initial form. The shape-shifting process is controlled through changes in temperature

  10. Our World: Fluid Shift

    NASA Video Gallery

    Learn about the circulatory system and how gravity aids blood flow in our bodies here on Earth. Find out how NASA flight surgeons help the astronauts deal with the fluid shift that happens during s...

  11. Molecular Electronic Shift Registers

    NASA Technical Reports Server (NTRS)

    Beratan, David N.; Onuchic, Jose N.

    1990-01-01

    Molecular-scale shift registers eventually constructed as parts of high-density integrated memory circuits. In principle, variety of organic molecules makes possible large number of different configurations and modes of operation for such shift-register devices. Several classes of devices and implementations in some specific types of molecules proposed. All based on transfer of electrons or holes along chains of repeating molecular units.

  12. Kinetics of the Fischer-Tropsch reaction on a precipitated promoted iron catalyst. 1. Experimental procedure and results

    SciTech Connect

    Lox, E.S.; Froment, G.F. )

    1993-01-01

    The Fischer-Tropsch reaction on a commercial promoted precipitated iron catalyst was studied in a tubular reactor under non-deactivating conditions of temperatures between 523 and 623 K, pressures between 0.6 and 2.1 MPa, hydrogen to carbon monoxide feed ratios between 3.0 and 6.0 mol/mol, and W/F[degree][sub CO] values between 9.2 and 63.0 kg[center dot]s/mol. The selectivity for carbon dioxide, methane, and hydrocarbons of different functionality with 2-15 carbon atoms in the molecule was obtained as a function of the carbon monoxide conversion, the reactor temperature, and the total pressure. The initial rate of formation of these products was measured as a function of the total pressure and the partial pressures of hydrogen and carbon monoxide at the reactor inlet. These experiments, combined with the information gained from the catalyst characterization, indicated that carbon dioxide is formed by the water gas shift reaction. Methane, n-paraffins, and 1-olefins with two and more carbon atoms in the molecule are all primary products of the Fischer-Tropsch reaction. The composition of the hydrocarbon product fraction, as a function of the number of carbon atoms in the hydrocarbon molecule, could be described by the Schulz-Flory distribution, although it is shown that the latter only approximately holds for the effluent of an integral reactor.

  13. Ammonia reactions with the stored oxygen in a commercial lean NOx trap catalyst

    DOE PAGESBeta

    Bartova, Sarka; Mracek, David; Koci, Petr; Marek, Milos; Choi, Jae -Soon

    2014-10-12

    Ammonia is an important intermediate of the NOx reduction in a NOx storage and reduction catalyst (aka lean NOx trap). NH3 formed under rich conditions in the reduced front part of the catalyst is transported by convection downstream to the unregenerated (still oxidized) zone of the catalyst, where it further reacts with the stored oxygen and NOx. In this paper, the kinetics and selectivity of NH3 reactions with the stored oxygen are studied in detail with a commercial Ba-based NOx storage catalyst containing platinum group metals (PGM), Ba and Ce oxides. Furthermore, steady-state NH3 decomposition, NH3 oxidation by O2 andmore » NO, and N2O decomposition are examined in light-off experiments. Periodic lean/rich cycling is measured first with O2 and NH3, and then with NOx + O2 and NH3 to discriminate between the NH3 reactions with the stored oxygen and the stored NOx. The reaction of NH3 with the stored O2 is highly selective towards N2, however a certain amount of NOx and N2O is also formed. The formed NOx by-product is efficiently adsorbed on the NOx storage sites such that the NOx is not detected at the reactor outlet except at high temperatures. The stored NOx reacts with NH3 feed in the next rich phase, contributing to the N2O formation. Water inhibits the reactions of NH3 with the stored oxygen. On the contrary, the presence of CO2 increases the NH3 consumption. Furthermore, CO2 is able to provide additional oxygen for NH3 oxidation, forming –CO in analogy to the reverse water gas shift reaction.« less

  14. Hot compressed water—a suitable and sustainable solvent and reaction medium?

    NASA Astrophysics Data System (ADS)

    Dinjus, E.; Kruse, A.

    2004-04-01

    cobalt-catalysed cyclotrimerization of acetylenes to form benzene derivatives or hydroformylation to produce aldehydes from olefins. There, only the addition of CO is necessary, the H2 required being formed by the equilibrium of the water-gas-shift reaction. After a homogeneous reaction in the supercritical state, the reaction mixture can be separated at subcritical conditions. In support of the chemical and technical developments and to principally understand the experimental findings fundamental aspects have to be investigated as well. Intensive studies have been devoted to chemical kinetics including the modelling with elementary reaction steps, e.g. to separate ionic and radical reaction pathways. Depending on the reaction conditions, ionic or radical reaction pathways can be favoured or suppressed, allowing for control selectivity. Furthermore, corrosion of relevant reactor materials has been investigated.

  15. Absorption driven focus shift

    NASA Astrophysics Data System (ADS)

    Harrop, N.; Wolf, S.; Maerten, O.; Dudek, K.; Ballach, S.; Kramer, R.

    2016-03-01

    Modern high brilliance near infrared lasers have seen a tremendous growth in applications throughout the world. Increased productivity has been achieved by higher laser power and increased brilliance of lasers. Positive impacts on the performance and costs of parts are opposed to threats on process stability and quality, namely shift of focus position over time. A high initial process quality will be reduced by contamination of optics, eventually leading to a focus shift or even destruction of the optics. Focus analysis at full power of multi-kilowatt high brilliance lasers is a very demanding task because of high power densities in the spot and the high power load on optical elements. With the newly developed high power projection optics, the High-Power Micro-Spot Monitor High Brilliance (HP-MSM-HB) is able to measure focus diameter as low as 20 μm at power levels up to 10 kW at very low internal focus shift. A main driving factor behind thermally induced focus shift is the absorption level of the optical element. A newly developed measuring system is designed to determine the relative absorption level in reference to a gold standard. Test results presented show a direct correlation between absorption levels and focus shift. The ability to determine the absorption level of optical elements as well as their performance at full processing power before they are put to use, enables a high level of quality assurance for optics manufacturers and processing head manufacturers alike.

  16. Predicting catastrophic shifts.

    PubMed

    Weissmann, Haim; Shnerb, Nadav M

    2016-05-21

    Catastrophic shifts are known to pose a serious threat to ecology, and a reliable set of early warning indicators is desperately needed. However, the tools suggested so far have two problems. First, they cannot discriminate between a smooth transition and an imminent irreversible shift. Second, they aimed at predicting the tipping point where a state loses its stability, but in noisy spatial system the actual transition occurs when an alternative state invades. Here we suggest a cluster tracking technique that solves both problems, distinguishing between smooth and catastrophic transitions and to identify an imminent shift in both cases. Our method may allow for the prediction, and thus hopefully the prevention of such transitions, avoiding their destructive outcomes. PMID:26970446

  17. Isotope shift in chromium

    NASA Astrophysics Data System (ADS)

    Furmann, B.; Jarosz, A.; Stefańska, D.; Dembczyński, J.; Stachowska, E.

    2005-01-01

    Thirty-three spectral lines of chromium atom in the blue-violet region (425-465 nm) have been investigated with the method of laser-induced resonance fluorescence on an atomic beam. For all the lines, the isotope shifts for every pair of chromium isotopes have been determined. The lines can be divided into six groups, according to the configuration of the upper and lower levels. Electronic factors of the field shift and the specific mass shift ( Fik and MikSMS, respectively) have been evaluated and the values for each pure configuration involved have been determined. Comparison of the values Fik and MikSMS to the ab initio calculations results has been performed. The presence of crossed second order (CSO) effects has been observed.

  18. AUDITORY-VISUAL PERCEPTUAL SHIFTING IN SPEECH HANDICAPPED CHILDREN.

    ERIC Educational Resources Information Center

    FLOWERS, ARTHUR

    INTERACTION BETWEEN VISION AND HEARING WERE STUDIED IN 35 SPEECH HANDICAPPED FIRST-GRADE CHILDREN. THE ABILITY TO SHIFT ATTENTION FROM ONE SENSORY MODALITY TO ANOTHER WAS LABELED AS "PERCEPTUAL SHIFTING." A DEVICE DEVELOPED BY EXPERIMENTAL PSYCHOLOGISTS PRESENTED VARIOUS STIMULI TO EACH SUBJECT AND RECORDED THE SUBJECT'S REACTION TIME. STIMULI…

  19. Design of a Molecular Memory Device: The Electron Transfer Shift Register Memory

    NASA Technical Reports Server (NTRS)

    Beratan, D.

    1993-01-01

    A molecular shift register memory at the molecular level is described. The memory elements consist of molecules can exit in either an oxidized or reduced state and the bits are shifted between the cells with photoinduced electron transfer reactions.

  20. Development of a mechanistic model for predicting corrosion rate in multiphase oil/water/gas flows

    SciTech Connect

    Zhang, R.; Gopal, M.; Jepson, W.P.

    1997-09-01

    A mechanistic model has been developed to predict corrosion rates in multiphase (water/oil/CO{sub 2}) flow conditions. The model takes into account electrochemistry, reaction kinetics, and, mass transport effects. This paper describes the equations used to determine pH and bulk concentrations of various ions, which are then used to calculate the mass transfer rates to the corrosion surface. The result includes the determination of the mass transfer coefficients of various ionic species and corrosion rates. Details of relations used for determination of mass transfer coefficients for multiphase flows, and rates of electrochemical reaction kinetics are discussed and predicted results are compared with experimental observations. Agreement between model results and experimental data is good.

  1. Eluding catastrophic shifts

    PubMed Central

    Villa Martín, Paula; Bonachela, Juan A.; Levin, Simon A.; Muñoz, Miguel A.

    2015-01-01

    Transitions between regimes with radically different properties are ubiquitous in nature. Such transitions can occur either smoothly or in an abrupt and catastrophic fashion. Important examples of the latter can be found in ecology, climate sciences, and economics, to name a few, where regime shifts have catastrophic consequences that are mostly irreversible (e.g., desertification, coral reef collapses, and market crashes). Predicting and preventing these abrupt transitions remains a challenging and important task. Usually, simple deterministic equations are used to model and rationalize these complex situations. However, stochastic effects might have a profound effect. Here we use 1D and 2D spatially explicit models to show that intrinsic (demographic) stochasticity can alter deterministic predictions dramatically, especially in the presence of other realistic features such as limited mobility or spatial heterogeneity. In particular, these ingredients can alter the possibility of catastrophic shifts by giving rise to much smoother and easily reversible continuous ones. The ideas presented here can help further understand catastrophic shifts and contribute to the discussion about the possibility of preventing such shifts to minimize their disruptive ecological, economic, and societal consequences. PMID:25825772

  2. Eluding catastrophic shifts.

    PubMed

    Villa Martín, Paula; Bonachela, Juan A; Levin, Simon A; Muñoz, Miguel A

    2015-04-14

    Transitions between regimes with radically different properties are ubiquitous in nature. Such transitions can occur either smoothly or in an abrupt and catastrophic fashion. Important examples of the latter can be found in ecology, climate sciences, and economics, to name a few, where regime shifts have catastrophic consequences that are mostly irreversible (e.g., desertification, coral reef collapses, and market crashes). Predicting and preventing these abrupt transitions remains a challenging and important task. Usually, simple deterministic equations are used to model and rationalize these complex situations. However, stochastic effects might have a profound effect. Here we use 1D and 2D spatially explicit models to show that intrinsic (demographic) stochasticity can alter deterministic predictions dramatically, especially in the presence of other realistic features such as limited mobility or spatial heterogeneity. In particular, these ingredients can alter the possibility of catastrophic shifts by giving rise to much smoother and easily reversible continuous ones. The ideas presented here can help further understand catastrophic shifts and contribute to the discussion about the possibility of preventing such shifts to minimize their disruptive ecological, economic, and societal consequences. PMID:25825772

  3. Trophic shift, not collapse

    USGS Publications Warehouse

    Madenjian, Charles P.; Rutherford, Edward S.; Stow, Craig A.; Roseman, Edward F.; He, Ji X.

    2013-01-01

    scientists who are closely monitoring Lake Huron’s food web, we believe that the ongoing changes are more accurately characterized as a trophic shift in which benthic pathways have become more prominent. While decreases in abundance have occurred for some species, others are experiencing improved reproduction resulting in the restoration of several important native species.

  4. Shifting Up a Gear.

    ERIC Educational Resources Information Center

    Palmer, Martin

    1997-01-01

    Shift workers are often excluded from educational opportunities on and off the job. General education and leisure learning needs are addressed less than job-specific training needs. Providers should consider open/distance learning, creative marketing, targeted funding, and consortia of employer-developed programs. (SK)

  5. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

    NASA Astrophysics Data System (ADS)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.

    2015-04-01

    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

  6. Ambiguous red shifts

    NASA Astrophysics Data System (ADS)

    Wulfman, Carl E.

    2010-12-01

    A one-parameter conformal invariance of Maxwell's equations allows the wavelengths of electromagnetic waves to change as they propagate, and do so even in otherwise field-free space. This produces an ambiguity in interpretations of stellar red shifts. Experiments that will determine the value of the group parameter, and thereby remove the ambiguity, are proposed. They are based on an analysis of the anomalous frequency shifts uncovered in the Pioneer 10 and 11 spacecraft studies, and physical interpretation of an isomorphism discovered by E.L. Hill. If the group parameter is found to be non-zero, Hubble's relations will have to be reinterpreted and space-time metrics will have to be altered. The cosmological consequences of the transformations are even more extensive because, though they change frequencies they do not alter the energy and momentum conservation laws of classical and quantum-electrodynamical fields established by Cunningham and by Białynicki-Birula.

  7. Shifts that divide population

    NASA Astrophysics Data System (ADS)

    Muneepeerakul, Rachata; Qubbaj, Murad; Aggarwal, Rimjhim; Anderies, John M.; Janssen, Marco

    2014-05-01

    How does a population of organisms in an ecosystem or of people in a society respond to rapid shifts in the environment? Answers to this question are critical to our ability to anticipate and cope with a changing ecohydrological system. We have developed a generic model of adaptation mechanisms, based on replicator dynamics, in which we derive a simple and insightful threshold condition that separates two important types of responses: 'cohesive transition' in which the whole population changes gradually together, and 'population-dividing transition' in which the population splits into two groups with one eventually dominating the other. The threshold depends on the magnitude of the shift and the shape of the fitness landscape. Division in populations can fundamentally alter the functioning of and induce subsequent feedbacks within the system; knowing the condition that gives rise to such division is thus fundamentally important.

  8. The shifted penalty method

    NASA Astrophysics Data System (ADS)

    Zavarise, Giorgio

    2015-07-01

    The method presented here is a variation of the classical penalty one, suited to reduce penetration of the contacting surfaces. The slight but crucial modification concerns the introduction of a shift parameter that moves the minimum point of the constrained potential toward the exact value, without any penalty increase. With respect to the classical augmentation procedures, the solution improvement is embedded within the original penalty contribution. The problem is almost consistently linearized, and the shift is updated before each Newton's iteration. However, adding few iterations, with respect to the original penalty method, a reduction of the penetration of several orders of magnitude can be achieved. The numerical tests have shown very attractive characteristics and very stable solution paths. This permits to foresee a wide area of applications, not only in contact mechanics, but for any problem, like e.g. incompressible materials, where a penalty contribution is required.

  9. Quantitative Real-Time Polymerase Chain Reaction Measurement of HLA-DRA Gene Expression in Whole Blood Is Highly Reproducible and Shows Changes That Reflect Dynamic Shifts in Monocyte Surface HLA-DR Expression during the Course of Sepsis

    PubMed Central

    Tina, Elisabet; Bäckman, Anders; Magnuson, Anders; Strålin, Kristoffer; Söderquist, Bo; Källman, Jan

    2016-01-01

    Introduction A decrease in the expression of monocyte surface protein HLA-DR (mHLA-DR), measured by flow cytometry (FCM), has been suggested as a marker of immunosuppression and negative outcome in severe sepsis. However, FCM is not always available due to sample preparation that limits its use to laboratory operational hours. In this prospective study we evaluated dynamic changes in mHLA-DR expression during sepsis in relation to changes in HLA-DRA gene expression and Class II transactivator (CIITA), measured by quantitative Real-Time Polymerase Chain Reaction (qRT-PCR). Aims The aims of this study were: 1. to validate the robustness of qRT-PCR measurement of HLA-DRA- and CIITA–mRNA expression, in terms of reproducibility; and 2. to see if changes in expression of these genes reflect changes in mHLA-DR expression during the course of severe and non-severe bacteraemic sepsis. Methods and Findings Blood samples were collected from 60 patients with bacteraemic sepsis on up to five occasions during Days 1–28 after hospital admission. We found the reproducibility of the qRT-PCR method to be high by demonstrating low threshold variations (<0.11 standard deviation (SD)) of the qRT-PCR system, low intra-assay variation of Ct-values within triplicates (≤0.15 SD) and low inter-assay variations (12%) of the calculated target gene ratios. Our results also revealed dynamic HLA-DRA expression patterns during the course of sepsis that reflected those of mHLA-DR measured by FCM. Furthermore, HLA-DRA and mHLA-DR recovery slopes in patients with non-severe sepsis differed from those in patients with severe sepsis, shown by mixed model for repeated measurements (p<0.05). However, during the first seven days of sepsis, PCR-measurements showed a higher magnitude of difference between the two sepsis groups. Mean differences (95% CI) between severe sepsis (n = 20) and non-severe sepsis (n = 40) were; on day 1–2, HLA-DRA 0.40 (0.28–0.59) p<0.001, CIITA 0.48 (0.32–0.72) p = 0

  10. 2DCOR-GC: an application of the generalized two-dimensional correlation analysis as a route to optimization of continuous flow supercritical fluid reactions.

    PubMed

    Hyde, Jason R; Bourne, Richard A; Noda, Isao; Stephenson, Phil; Poliakoff, Martyn

    2004-11-01

    A new approach for optimization and monitoring of continuous reactions has been developed using 2D correlation methods for the analysis of GC data (2DCOR-GC). 2DCOR-GC maps are obtained following perturbation of the system that allow the effect of changing reaction parameters such as time, temperature, pressure, or concentration to be both monitored and sequenced with regard to changes in the raw GC data. In this paper, we describe the application of the 2DCOR-GC technique to monitoring the reverse water-gas shift reaction in scCO(2). 2DCOR-GC is combined with FT-IR data to validate the methodology. We also report the application of 2DCOR-GC to probe the mechanism of the alkylation of m-cresol with isopropyl alcohol in scCO(2) using Nafion SAC-13 as the catalyst. These results identify coeluting peaks that could easily be missed without exhaustive method development. PMID:15516110

  11. 20 Years of Air-Water Gas Exchange Observations for Pesticides in the Western Arctic Ocean.

    PubMed

    Jantunen, Liisa M; Wong, Fiona; Gawor, Anya; Kylin, Henrik; Helm, Paul A; Stern, Gary A; Strachan, William M J; Burniston, Deborah A; Bidleman, Terry F

    2015-12-01

    The Arctic has been contaminated by legacy organochlorine pesticides (OCPs) and currently used pesticides (CUPs) through atmospheric transport and oceanic currents. Here we report the time trends and air-water exchange of OCPs and CUPs from research expeditions conducted between 1993 and 2013. Compounds determined in both air and water were trans- and cis-chlordanes (TC, CC), trans- and cis-nonachlors (TN, CN), heptachlor exo-epoxide (HEPX), dieldrin (DIEL), chlorobornanes (ΣCHBs and toxaphene), dacthal (DAC), endosulfans and metabolite endosulfan sulfate (ENDO-I, ENDO-II, and ENDO SUL), chlorothalonil (CHT), chlorpyrifos (CPF), and trifluralin (TFN). Pentachloronitrobenzene (PCNB and quintozene) and its soil metabolite pentachlorothianisole (PCTA) were also found in air. Concentrations of most OCPs declined in surface water, whereas some CUPs increased (ENDO-I, CHT, and TFN) or showed no significant change (CPF and DAC), and most compounds declined in air. Chlordane compound fractions TC/(TC + CC) and TC/(TC + CC + TN) decreased in water and air, while CC/(TC + CC + TN) increased. TN/(TC + CC + TN) also increased in air and slightly, but not significantly, in water. These changes suggest selective removal of more labile TC and/or a shift in chlordane sources. Water-air fugacity ratios indicated net volatilization (FR > 1.0) or near equilibrium (FR not significantly different from 1.0) for most OCPs but net deposition (FR < 1.0) for ΣCHBs. Net deposition was shown for ENDO-I on all expeditions, while the net exchange direction of other CUPs varied. Understanding the processes and current state of air-surface exchange helps to interpret environmental exposure and evaluate the effectiveness of international protocols and provides insights for the environmental fate of new and emerging chemicals. PMID:26196214

  12. Influence of current velocity and wind speed on air-water gas exchange in a mangrove estuary

    NASA Astrophysics Data System (ADS)

    Ho, David T.; Coffineau, Nathalie; Hickman, Benjamin; Chow, Nicholas; Koffman, Tobias; Schlosser, Peter

    2016-04-01

    Knowledge of air-water gas transfer velocities and water residence times is necessary to study the fate of mangrove derived carbon exported into surrounding estuaries and ultimately to determine carbon balances in mangrove ecosystems. For the first time, the 3He/SF6 dual tracer technique, which has been proven to be a powerful tool to determine gas transfer velocities in the ocean, is applied to Shark River, an estuary situated in the largest contiguous mangrove forest in North America. The mean gas transfer velocity was 3.3 ± 0.2 cm h-1 during the experiment, with a water residence time of 16.5 ± 2.0 days. We propose a gas exchange parameterization that takes into account the major sources of turbulence in the estuary (i.e., bottom generated shear and wind stress).

  13. Effects of surface concentration on the porphine monolayers: Molecular simulations at the nanoscale water-gas interface

    NASA Astrophysics Data System (ADS)

    Krongsuk, Sriprajak; Kerdcharoen, Teerakiat

    2011-05-01

    The effect of surface concentration on the structure and stability of porphine (PH 2) monolayers at the water-gas interface was studied by using molecular dynamics simulation. Five monolayer systems having different surface concentrations were investigated in order to cover a full range of the experimental π- A isotherm. The simulation results show that increment of a number of the PH 2 molecules not only affects the significantly decreasing water density at the interface but also the monolayer surface tensions. The calculated surface tensions of the five systems indicate that the monolayer phase transfer corresponding to gaseous, expanded, condensed, and collapsed phases are observed. The hydrogen bonding between water and the PH 2 molecules at the interface plays an important role on the monolayer film formation, especially at the lower surface concentrations. The PH 2 orientations for all surface concentrations, except the highest one, are favored to be the β-structure as observed in the copper porphyrazine (CuPz) monolayer.

  14. Shift of meaning and students' alternative concepts

    NASA Astrophysics Data System (ADS)

    Schmidt, Hans-Jürgen; Volke, Dagmar

    2003-11-01

    The purpose of the study was to establish a relationship between the shift of meaning of the concept oxidation that has taken place during the historical development, and students' alternative concepts. First Examination Board papers were examined. The result enabled us to specify the research question. In the main part of the study, multiple-choice items were given to 3074 senior high school students. They were asked to select the correct answer and to justify their choices. Additional illustrative material was collected in four interviews with senior high school students. The analysis of the data revealed the mechanism that some students used to interpret the reactions from NO3m to NO and from CO32m to CO2. Students' interpretations were based on the concept of a transfer of oxide ions. The mechanism explains some correct and incorrect answers to the problems. The interview study also revealed that students were reluctant to accept water as a Brønsted base. It is suggested to use students' alternative concepts about oxidation reactions in class, helping them to better understand the half-reaction method. Students should also understand that the meaning of the concept oxidation has shifted in the course of time. In the area of acid-base reactions, further research is needed.

  15. Shifted genus expanded W ∞ algebra and shifted Hurwitz numbers

    NASA Astrophysics Data System (ADS)

    Zheng, Quan

    2016-05-01

    We construct the shifted genus expanded W ∞ algebra, which is isomorphic to the central subalgebra A ∞ of infinite symmetric group algebra and to the shifted Schur symmetrical function algebra Λ* defined by Okounkov and Olshanskii. As an application, we get some differential equations for the generating functions of the shifted Hurwitz numbers; thus, we can express the generating functions in terms of the shifted genus expanded cut-and-join operators.

  16. [Characteristics of water-gas two-phase CO2 transport in unsaturated zone].

    PubMed

    Yu, Yanxin; Chen, Jiajun; Wang, Jinsheng; Yun, Ying; Li, Shushen; Wang, Zhiming

    2003-07-01

    The migration of CO2 in soil was simulated through use of soil column, especially the transformation of CO2 between water and gas phases at wetting front was studied. The soil column in the test was 1 m long and the concentration of CO2 solution was 748 mg/L. Through analysis, it was shown that CO2 migration in water phase was governed by advection, dispersion, reaction and mass transfer between water and gas phases, that in gas phase by advection, dispersion, mass transfer between two phases. Sampling method under dynamic condition of two phase flow in soil column was approached and mass transfer coefficient from water phase to gas phase was determined as 0.00061. This showed that there was certain mass transformation of CO2 from water phase to gas phase and yet it was not so significant. This study can provide the quantitative scientific bases for safety assessment of geological disposal of low and intermediate level radioactive waste and environmental impact assessment of solid waste disposal by landfilling. PMID:14551970

  17. Emission spectroscopy of a microhollow cathode discharge plasma in helium-water gas mixtures

    SciTech Connect

    Namba, S.; Yamasaki, T.; Hane, Y.; Fukuhara, D.; Kozue, K.; Takiyama, K.

    2011-10-01

    A dc microhollow cathode discharge (MHCD) plasma was generated inflowing helium gas containing water vapor. The cathode hole diameters were 0.3, 0.7, 1.0, and 2.0 mm, each with a length of 2.0 mm. Emission spectroscopy was carried out to investigate the discharge mode and to determine the plasma parameters. For the 0.3-mm cathode, stable MHCDs in an abnormal glow mode existed at pressures up to 100 kPa, whereas for larger diameters, a plasma was not generated at atmospheric pressure. An analysis of the lineshapes relevant to He at 667.8 nm and to H{alpha} at 656.3 nm implied an electron density and gas temperature of 2 x 10{sup 14} cm{sup -3} and 1100 K, respectively, for a 100-kPa discharge in the negative glow region. The dependence of the OH band, and H{alpha} intensities on the discharge current exhibited different behaviors. Specifically, the OH spectrum had a maximum intensity at a certain current, while the H atom intensity kept increasing with the discharge current. This observation implies that a high concentration of OH radicals results in quenching, leading to the production of H atoms via the reaction OH + e{sup -}{yields} O + H + e{sup -}.

  18. Shifted nondiffractive Bessel beams

    NASA Astrophysics Data System (ADS)

    Kovalev, Alexey A.; Kotlyar, Victor V.; Porfirev, Alexey A.

    2015-05-01

    Nondiffractive Bessel beams are well known to have infinite energy and infinite orbital angular momentum (OAM). However, when normalized to unity of energy, their OAM is finite. In this work, we derive an analytical relationship for calculating the normalized OAM of the superposition of off-axis Bessel beams characterized by the same topological charge. We show that if the constituent beams of the superposition have real-valued weight coefficients, the total OAM of the superposition of the Bessel beams equals that of an individual nonshifted Bessel beam. This property enables generating nondiffractive beams with different intensity distributions but identical OAM. The superposition of a set of identical Bessel beams centered on an arbitrary-radius circle is shown to be equivalent to an individual constituent Bessel beam put in the circle center. As a result of a complex shift of the Bessel beam, the transverse intensity distribution and OAM of the beam are also shown to change. We show that, in the superposition of two or more complex-shifted Bessel beams, the OAM may remain unchanged, while the intensity distribution is changed. Numerical simulation is in good agreement with theory.

  19. Transmission shift control assembly

    SciTech Connect

    Dzioba, D.L.

    1989-04-18

    This patent describes a transmission shift control assembly mounted on a steering column having a longitudinal axis comprising: bracket means secured to the steering column; transmission shift cable means having a portion secured to the bracket means and a portion linearly movable relative to the secured portion; mounting means on the bracket cable drive arm means having an axis and being rotatably mounted on the rotary axis on the mounting means oblique to the longitudinal axis and including a cable connecting portion secured to the movable portion of the cable means and lever mounting means adjacent the mounting means; operator control means including lever means, pin means for pivotally mounting the lever means on the lever mounting means on an axis substantially perpendicular to the rotary axis and positioning arm means formed on the lever means and extending from the pin means; and detent gate means disposed on the bracket means in position to abut the positioning arm means for limiting the extent of pivotal movement of the lever means.

  20. Strategies for improving the performance and stability of Ni-based catalysts for reforming reactions.

    PubMed

    Li, Shuirong; Gong, Jinlong

    2014-11-01

    Owing to the considerable publicity that has been given to petroleum related economic, environmental, and political problems, renewed attention has been focused on the development of highly efficient and stable catalytic materials for the production of chemical/fuel from renewable resources. Supported nickel nanoclusters are widely used for catalytic reforming reactions, which are key processes for generating synthetic gas and/or hydrogen. New challenges were brought out by the extension of feedstock from hydrocarbons to oxygenates derivable from biomass, which could minimize the environmental impact of carbonaceous fuels and allow a smooth transition from fossil fuels to a sustainable energy economy. This tutorial review describes the recent efforts made toward the development of nickel-based catalysts for the production of hydrogen from oxygenated hydrocarbons via steam reforming reactions. In general, three challenges facing the design of Ni catalysts should be addressed. Nickel nanoclusters are apt to sinter under catalytic reforming conditions of high temperatures and in the presence of steam. Severe carbon deposition could also be observed on the catalyst if the surface carbon species adsorbed on metal surface are not removed in time. Additionally, the production of hydrogen rich gas with a low concentration of CO is a challenge using nickel catalysts, which are not so active in the water gas shift reaction. Accordingly, three strategies were presented to address these challenges. First, the methodologies for the preparation of highly dispersed nickel catalysts with strong metal-support interaction were discussed. A second approach-the promotion in the mobility of the surface oxygen-is favored for the yield of desired products while promoting the removal of surface carbon deposition. Finally, the process intensification via the in situ absorption of CO2 could produce a hydrogen rich gas with low CO concentration. These approaches could also guide the design

  1. Phase shifting diffraction interferometer

    DOEpatents

    Sommargren, Gary E.

    1996-01-01

    An interferometer which has the capability of measuring optical elements and systems with an accuracy of .lambda./1000 where .lambda. is the wavelength of visible light. Whereas current interferometers employ a reference surface, which inherently limits the accuracy of the measurement to about .lambda./50, this interferometer uses an essentially perfect spherical reference wavefront generated by the fundamental process of diffraction. This interferometer is adjustable to give unity fringe visibility, which maximizes the signal-to-noise, and has the means to introduce a controlled prescribed relative phase shift between the reference wavefront and the wavefront from the optics under test, which permits analysis of the interference fringe pattern using standard phase extraction algorithms.

  2. Phase shifting interferometer

    DOEpatents

    Sommargren, G.E.

    1999-08-03

    An interferometer is disclosed which has the capability of measuring optical elements and systems with an accuracy of {lambda}/1000 where {lambda} is the wavelength of visible light. Whereas current interferometers employ a reference surface, which inherently limits the accuracy of the measurement to about {lambda}/50, this interferometer uses an essentially perfect spherical reference wavefront generated by the fundamental process of diffraction. Whereas current interferometers illuminate the optic to be tested with an aberrated wavefront which also limits the accuracy of the measurement, this interferometer uses an essentially perfect spherical measurement wavefront generated by the fundamental process of diffraction. This interferometer is adjustable to give unity fringe visibility, which maximizes the signal-to-noise, and has the means to introduce a controlled prescribed relative phase shift between the reference wavefront and the wavefront from the optics under test, which permits analysis of the interference fringe pattern using standard phase extraction algorithms. 11 figs.

  3. Phase shifting interferometer

    DOEpatents

    Sommargren, Gary E.

    1999-01-01

    An interferometer which has the capability of measuring optical elements and systems with an accuracy of .lambda./1000 where .lambda. is the wavelength of visible light. Whereas current interferometers employ a reference surface, which inherently limits the accuracy of the measurement to about .lambda./50, this interferometer uses an essentially perfect spherical reference wavefront generated by the fundamental process of diffraction. Whereas current interferometers illuminate the optic to be tested with an aberrated wavefront which also limits the accuracy of the measurement, this interferometer uses an essentially perfect spherical measurement wavefront generated by the fundamental process of diffraction. This interferometer is adjustable to give unity fringe visibility, which maximizes the signal-to-noise, and has the means to introduce a controlled prescribed relative phase shift between the reference wavefront and the wavefront from the optics under test, which permits analysis of the interference fringe pattern using standard phase extraction algorithms.

  4. Phase shifting diffraction interferometer

    DOEpatents

    Sommargren, G.E.

    1996-08-29

    An interferometer which has the capability of measuring optical elements and systems with an accuracy of {lambda}/1000 where {lambda} is the wavelength of visible light. Whereas current interferometers employ a reference surface, which inherently limits the accuracy of the measurement to about {lambda}/50, this interferometer uses an essentially perfect spherical reference wavefront generated by the fundamental process of diffraction. This interferometer is adjustable to give unity fringe visibility, which maximizes the signal-to-noise, and has the means to introduce a controlled prescribed relative phase shift between the reference wavefront and the wavefront from the optics under test, which permits analysis of the interference fringe pattern using standard phase extraction algorithms. 8 figs.

  5. Shifting epidemiology of Flaviviridae.

    PubMed

    Petersen, Lyle R; Marfin, Anthony A

    2005-04-01

    The dengue, West Nile, Japanese encephalitis and yellow fever viruses are important mosquito-borne viruses whose epidemiology is shifting in response to changing societal factors, such as increasing commerce, urbanization of rural areas, and population growth. All four viruses are expanding geographically, as exemplified by the emergence of West Nile virus in the Americas and Japanese encephalitis virus in Australasia. The large, recent global outbreaks of severe neurological disease caused by West Nile virus, the increasing frequency of dengue hemorrhagic fever outbreaks in the Americas, and the emergence of yellow fever virus vaccination-associated viscerotropic disease, are new clinical epidemiologic trends. These worrisome epidemiologic trends will probably continue in coming decades, as a reversal of their societal and biological drivers is not in sight. Nevertheless, the substantial reductions in Japanese encephalitis virus incidence resulting from vaccination programs and economic development in some Asian countries provide some encouragement within this overall guarded outlook. PMID:16225801

  6. Reactions involving shifting of the double bond in cyclic ethers

    SciTech Connect

    Ibatullin, U.G.; Petrushina, T.F.; Akhmadeeva, A.A.; Safarov, M.G.

    1985-09-01

    4-Methylenetetrahydropyran undergoes isomerization to 4-methyl-5,6-dihydropyran in the presence of sodium on aluminum oxide. Both pyrans are converted to a vinyl ether, viz., 4-methyl-2,3-dihydropyran, under the influence of iron pentacarbonyl.

  7. The origin of the "snap-in" in the force curve between AFM probe and the water/gas interface of nanobubbles.

    PubMed

    Song, Yang; Zhao, Binyu; Zhang, Lijuan; Lü, Junhong; Wang, Shuo; Dong, Yaming; Hu, Jun

    2014-02-24

    The long-range attractive force or "snap-in" is an important phenomenon usually occurring when a solid particle interacts with a water/gas interface. By using PeakForce quantitative nanomechanics the origin of snap-in in the force curve between the atomic force microscopy (AFM) probe and the water/gas interface of nanobubbles has been investigated. The snap-in frequently happened when the probe was preserved for a certain time or after being used for imaging solid surfaces under atmospheric conditions. In contrast, imaging in liquids rarely induced a snap-in. After a series of control experiments, it was found that the snap-in can be attributed to hydrophobic interactions between the water/gas interface and the AFM probe, which was either modified or contaminated with hydrophobic material. The hydrophobic contamination could be efficiently removed by a conventional plasma-cleaning treatment, which prevents the occurring of the snap-in. In addition, the adsorption of sodium dodecyl sulfate onto the nanobubble surface changed the water/gas interface into hydrophilic, which also eliminated the snap-in phenomenon. PMID:24478257

  8. Wind driven vertical transport in a vegetated, wetland water column with air-water gas exchange

    NASA Astrophysics Data System (ADS)

    Poindexter, C.; Variano, E. A.

    2010-12-01

    Flow around arrays of cylinders at low and intermediate Reynolds numbers has been studied numerically, analytically and experimentally. Early results demonstrated that at flow around randomly oriented cylinders exhibits reduced turbulent length scales and reduced diffusivity when compared to similarly forced, unimpeded flows (Nepf 1999). While horizontal dispersion in flows through cylinder arrays has received considerable research attention, the case of vertical dispersion of reactive constituents has not. This case is relevant to the vertical transfer of dissolved gases in wetlands with emergent vegetation. We present results showing that the presence of vegetation can significantly enhance vertical transport, including gas transfer across the air-water interface. Specifically, we study a wind-sheared air-water interface in which randomly arrayed cylinders represent emergent vegetation. Wind is one of several processes that may govern physical dispersion of dissolved gases in wetlands. Wind represents the dominant force for gas transfer across the air-water interface in the ocean. Empirical relationships between wind and the gas transfer coefficient, k, have been used to estimate spatial variability of CO2 exchange across the worlds’ oceans. Because wetlands with emergent vegetation are different from oceans, different model of wind effects is needed. We investigated the vertical transport of dissolved oxygen in a scaled wetland model built inside a laboratory tank equipped with an open-ended wind tunnel. Plastic tubing immersed in water to a depth of approximately 40 cm represented emergent vegetation of cylindrical form such as hard-stem bulrush (Schoenoplectus acutus). After partially removing the oxygen from the tank water via reaction with sodium sulfite, we used an optical probe to measure dissolved oxygen at mid-depth as the tank water re-equilibrated with the air above. We used dissolved oxygen time-series for a range of mean wind speeds to estimate the

  9. Quantized beam shifts in graphene

    NASA Astrophysics Data System (ADS)

    Kort-Kamp, Wilton; Sinitsyn, Nikolai; Dalvit, Diego

    We show that the magneto-optical response of a graphene-on-substrate system in the presence of an external magnetic field strongly affects light beam shifts. In the quantum Hall regime, we predict quantized Imbert-Fedorov, Goos-Hänchen, and photonic spin Hall shifts. The Imbert-Fedorov and photonic spin Hall shifts are given in integer multiples of the fine structure constant α, while the Goos-Hänchen ones in discrete multiples of α2. Due to time-reversal symmetry breaking the IF shifts change sign when the direction of the applied magnetic field is reversed, while the other shifts remain unchanged. We investigate the influence on these shifts of magnetic field, temperature, and material dispersion and dissipation. An experimental demonstration of quantized beam shifts could be achieved at terahertz frequencies for moderate values of the magnetic field. We acknowledge the LANL LDRD program for financial support.

  10. Hydraulically actuated well shifting tool

    SciTech Connect

    Roth, B.A.

    1992-10-20

    This patent describes a hydraulically actuated shifting tool for actuating a sliding member in a well tool. It comprises: a housing having a hydraulic fluid bore therein; shifting dog means positioned on the housing for movement away and toward the housing; locking dog means positioned on the housing for movement away and toward the body; shifting dog hydraulic actuating means in fluid communication with the bore for causing engagement of the shifting dogs with the sliding member; locking dog hydraulic actuating means in communication with the bore for causing engagement of the locking dogs with the locking means; and hydraulic shifting means in communication with the bore for causing relative movement between the shifting dog means and the locking dog means for shifting the sliding sleeve.